Silicone resins

Abstract

Also provided are a silicone resin and the like with which a cured product having a low dielectric loss tangent and a high glass transition temperature can be obtained. A silicone resin having a structural unit represented by formula (A-1), a structural unit represented by formula (A-2), and a structural unit represented by formula (A-3). 'NUMERATION 1' # IMGABS0 #

Description

Technical Field

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

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method using an assembly method in which an insulating layer and a conductor layer are alternately laminated is known.

[0003] As an insulating material for such an insulating layer of a printed wiring board, for example, a resin composition is disclosed in Patent Document 1. In addition, in Non-Patent Document 1, materials that can be used as insulating materials are disclosed.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2013-173841

[0007] Non-Patent Documents

[0008] Non-Patent Document 1: Composites Science and Technology 224(2022)109456 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] In recent years, with the high functionality of printed wiring boards, for the insulating layer of printed wiring boards, a low dielectric loss tangent and improved mechanical strength are required. In order to improve the mechanical strength, it is required to increase the glass transition temperature of the insulating layer.

[0011] The problem of the present invention is conceived in view of the above problems, and is to provide a silicone resin capable of obtaining a cured product having a low dielectric loss tangent and a high glass transition temperature; a resin composition containing the silicone resin; a resin sheet containing the above resin composition; a printed wiring board including an insulating layer formed by using the above resin composition, and a semiconductor device.

[0012] Means for Solving the Problems

[0013] The present inventors conducted in-depth research on the above problems, and as a result, found that by using a silicone resin having a specific structure, the above problems can be solved, and the present invention was completed.

[0014] That is, the present invention includes the following.

[0015] [1] The silicone resin has structural units represented by the following formula (A-1), structural units represented by the following formula (A-2), and structural units represented by the following formula (A-3).

[0016] [Chemical 1]

[0017]

[0018] In formula (A-1), R 1 represents a group represented by the following formula (A-1a) or a group represented by the following formula (A-1b). R 2 represents a monovalent hydrocarbon group which may have a substituent, and * represents a bonding end.

[0019] In formula (A-2), R 3 and R 4 each independently represent a monovalent hydrocarbon group which may have a substituent, and * represents a bonding end.

[0020] In formula (A-3), R 5 and R 6 each independently represent a monovalent hydrocarbon group which may have a substituent or a hydrogen atom, and * represents a bonding end. However, R 5 is a group different from R 3 and R 4 in formula (A-2).

[0021] [Chemical 2]

[0022]

[0023] In formula (A-1a), n1 represents an integer of 2 to 10, and * represents the bonding end to the silicon atom in formula (A-1).

[0024] In formula (A-1b), n2 represents an integer of 1 to 10, and * represents the bonding end to the silicon atom in formula (A-1).

[0025] [2] The silicone resin according to [1], wherein in formula (A-1), R 2 represents an alkyl group which may have a substituent.

[0026] [3] The silicone resin according to [1] or [2], wherein in formula (A-2), R 3 and R 4 each independently represent an aryl group which may have a substituent.

[0027] [4] The silicone resin according to any one of [1] to [3], wherein in formula (A-2), R 3 and R 4Each independently represents a phenyl group which may have a substituent, or a naphthyl group which may have a substituent.

[0028] [5] The silicone resin according to any one of [1] to [4], wherein in formula (A-3), R 5 represents a hydrogen atom, an aryl group which may have a substituent, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent.

[0029] [6] The silicone resin according to any one of [1] to [5], wherein in formula (A-3), R 6 represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.

[0030] [7] The silicone resin according to any one of [1] to [6], wherein the number average molecular weight is 10,000 or less.

[0031] [8] The silicone resin according to any one of [1] to [7], wherein the number average molecular weight is 7,000 or less.

[0032] [9] A resin composition, comprising:

[0033] (A) The silicone resin according to any one of [1] to [8],

[0034] (B) A curing agent, and

[0035] (C) An inorganic filler.

[0036]

[10] The resin composition according to [9], wherein the component (B) contains an active ester-based curing agent.

[0037]

[11] The resin composition according to [9] or

[10] , wherein the component (B) contains a phenolic curing agent.

[0038]

[12] The resin composition according to any one of [9] to

[11] , wherein the component (B) contains an acid anhydride-based curing agent.

[0039]

[13] The resin composition according to any one of [9] to

[12] , which further contains (E) a radically polymerizable compound.

[0040]

[14] The resin composition according to

[13] , wherein the component (E) contains a maleimide-based radically polymerizable compound.

[0041]

[15] A resin sheet, comprising: a support; and a resin composition layer provided on the support and containing the resin composition according to any one of [9] to

[14] .

[0042]

[16] The printed wiring board includes an insulating layer formed of a cured product of the resin composition according to any one of [9] to

[14] .

[0043]

[17] The semiconductor device includes the printed wiring board according to

[16] .

[0044] Effects of the Invention

[0045] According to the present invention, it is possible to provide a silicone resin capable of obtaining a cured product having a low dielectric loss tangent and a high glass transition temperature; a resin composition containing the above silicone resin; a resin sheet having a resin composition layer containing the above resin composition; a printed wiring board including an insulating layer formed of a cured product of the above resin composition; and a semiconductor device including the above printed wiring board. Detailed Description of the Invention

[0046] Hereinafter, the present invention will be described in detail with respect to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily changed and implemented without departing from the scope of the patent claims of the present invention and their equivalents. Hereinafter, the silicone resin having a structural unit represented by the formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3) may be simply referred to as "silicone resin".

[0047] [Silicone Resin]

[0048] The silicone resin of the present invention has a structural unit represented by the following formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3).

[0049] [Chemical Formula 3]

[0050]

[0051] In the formula (A-1), R 1 represents a group represented by the following formula (A-1a) or a group represented by the following formula (A-1b), and R 2 represents a monovalent hydrocarbon group which may have a substituent. * represents a bonding end.

[0052] In the formula (A-2), R 3 and R 4 each independently represent a monovalent hydrocarbon group which may have a substituent.

[0053] * represents a bonding end,

[0054] In the formula (A-3), R 5 and R 6Each independently represents a monovalent hydrocarbon group which may have a substituent, or a hydrogen atom. * represents a bonding end. However, in the case where R 5 represents a monovalent hydrocarbon group which may have a substituent, R 5 is a group different from R 3 and R 4 in formula (A-2).

[0055] [Chemical 4]

[0056]

[0057] In formula (A-1a), n1 represents an integer of 2 to 10. * represents the bonding end to the silicon atom in formula (A-1).

[0058] In formula (A-1b), n2 represents an integer of 1 to 10. * represents the bonding end to the silicon atom in formula (A-1).

[0059] The silicone resin of the present invention can provide a cured product with a low dielectric loss tangent and a high glass transition temperature. In addition, for the silicone resin of the present invention, generally, since it has a Si-O backbone, the stress of the resin composition is alleviated, and as a result, it can also provide a cured product in which the generation of cracks is suppressed. Hereinafter, the silicone resin of the present invention will be described in detail.

[0060] The silicone resin of the present invention is a resin having a structural unit represented by formula (A-1), a structural unit represented by formula (A-2), and a structural unit represented by formula (A-3). The silicone resin may be a random copolymer having a structural unit represented by formula (A-1), a structural unit represented by formula (A-2), and a structural unit represented by formula (A-3), may be a block copolymer, may be a graft copolymer, or may be an alternating copolymer. In addition, for the silicone resin of the present invention, in addition to the structural unit represented by formula (A-1), the structural unit represented by formula (A-2), and the structural unit represented by formula (A-3), other structural units may be included within the range not hindering the effects of the present invention.

[0061] In formula (A-1), R 1 represents a group represented by formula (A-1a) or a group represented by formula (A-1b).

[0062] In formula (A-1a), n1 represents an integer of 2 to 10, preferably an integer of 3 to 8, more preferably an integer of 3 to 6, still more preferably an integer of 3 to 5, and particularly preferably 3.

[0063] In formula (A-1b), n2 represents an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

[0064] In formula (A-1), R 2 represents a monovalent hydrocarbon group which may have substituents.

[0065] The so-called monovalent hydrocarbon group refers to a group obtained by removing one hydrogen atom from a hydrocarbon compound. The monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group. The monovalent hydrocarbon group may have an aromatic structure or may not have an aromatic structure. The monovalent hydrocarbon group is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and still more preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, etc.

[0066] The so-called alkyl group means a straight-chain or branched-chain monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2-methylpropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a tert-octyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, etc., and among them, a methyl group is preferred.

[0067] The so-called cycloalkyl group means a cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms, and still more preferably a cycloalkyl group having 5 or 6 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a bicyclopentyl group, etc., and among them, a cyclopentyl group and a cyclohexyl group are preferred.

[0068] The so-called alkenyl group means a straight-chain, branched-chain and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. Unless otherwise specified, the alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, and still more preferably an alkenyl group having 2 to 6 carbon atoms. Examples of the alkenyl group include a vinyl group, a propenyl group (allyl group, 1-propenyl group, isopropenyl group), a butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotyl group, etc.), a pentenyl group (1-pentenyl group, etc.), a hexenyl group (1-hexenyl group, etc.), a heptenyl group (1-heptenyl group, etc.), an octenyl group (1-octenyl group, etc.), a cyclopentenyl group (2-cyclopentenyl group, etc.), a cyclohexenyl group (3-cyclohexenyl group), etc.

[0069] As used herein, the term "aryl" means a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbocyclic ring. Unless otherwise specified, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, etc., with phenyl being preferred.

[0070] As used herein, the term "aralkyl" means an alkyl group substituted with one or more (preferably one) aryl groups. Unless otherwise specified, the aralkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, and still more preferably 7 to 11 carbon atoms. Examples of the aralkyl group include benzyl, phenethyl, hydrocinnamyl, α-methylbenzyl, α-cumyl, 1-naphthylmethyl, 2-naphthylmethyl, etc.

[0071] As used herein, the term "alkylaryl" means an aryl group substituted with one or more (preferably one) alkyl groups. Unless otherwise specified, the alkylaryl group preferably has 7 to 15 carbon atoms, more preferably 7 to 11 carbon atoms. Examples of the alkylaryl group include 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, etc., with 4-methylphenyl being preferred.

[0072] The monovalent hydrocarbon group may have substituents. Examples of the substituents include halogen atoms, -OH, -O-C 1-6 alkyl, -N(C 1-10 alkyl)2, C 1-20 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, C 6-10 aryl, cyano, -NH2, -CN, -C(O)O-C 1-10 alkyl, -COOH, -C(O)H, -NO2, etc. Among them, the expression "C p-q " (where p and q are positive integers and p < q) means that the number of carbon atoms in the organic group described after this expression 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 be bonded to each other to form a ring, and the ring structure also includes spiro rings and fused rings.

[0073] In formula (A-1), R 1 represents a monovalent hydrocarbon group which may have substituents, preferably an alkyl group which may have substituents or an aryl group which may have substituents, more preferably an alkyl group which may have substituents, and still more preferably a methyl group.

[0074] As specific examples of the structural unit represented by formula (A-1), the structural units represented by formulas (A-1-1) to (A-1-2) can be mentioned, but the present invention is not limited thereto. In the formulas, * represents a bonding end.

[0075] [Chemical 5]

[0076]

[0077] As the structural unit represented by formula (A-1), the structural unit represented by formula (A-1-1) is preferred.

[0078] In formula (A-2), R 3 and R 4 each independently represent a monovalent hydrocarbon group which may have a substituent. The monovalent hydrocarbon group is the same as the monovalent hydrocarbon group which may have a substituent represented by R 2 in formula (A-1).

[0079] In formula (A-2), as the monovalent hydrocarbon group which may have a substituent represented by R 3 and R 4 a monovalent aryl group which may have a substituent is preferred, and a phenyl group which may have a substituent or a naphthyl group which may have a substituent is more preferred.

[0080] As specific examples of the structural unit represented by formula (A-2), the structural units represented by formulas (A-2-1) to (A-2-3) can be mentioned, but the present invention is not limited thereto. In the formulas, * represents a bonding end.

[0081] [Chemical 6]

[0082]

[0083] As the structural unit represented by formula (A-2), the structural unit represented by formula (A-2-1) is preferred.

[0084] In formula (A-3), R 5 and R 6 each independently represent a monovalent hydrocarbon group which may have a substituent or a hydrogen atom. However, when R 5 and R 6 represent a monovalent hydrocarbon group which may have a substituent, R 5 is a group different from R 3 and R 4 in formula (A-2).

[0085] The monovalent hydrocarbon group represented by R 5 and R 6 which may have a substituent is the same as the monovalent hydrocarbon group which may have a substituent represented by R 2 in formula (A-1).

[0086] In formula (A-3), R 5 represents a monovalent hydrocarbon group which may have substituents, preferably an alkyl group which may have substituents, a cycloalkyl group which may have substituents, or an aryl group which may have substituents, more preferably a phenyl group which may have substituents, a cyclohexyl group which may have substituents, a cyclopentyl group which may have substituents, a methyl group which may have substituents, and still more preferably a methyl group.

[0087] In formula (A-3), as R 6 represents a monovalent hydrocarbon group which may have substituents, preferably an alkyl group which may have substituents, a cycloalkyl group which may have substituents, or an aryl group which may have substituents, more preferably a methyl group which may have substituents, a cyclopentyl group which may have substituents, a cyclohexyl group which may have substituents, or a phenyl group which may have substituents, and still more preferably a phenyl group or a cyclohexyl group.

[0088] In addition, in formula (A-3), R 5 preferably each independently represents a monovalent hydrocarbon group which may have substituents or a hydrogen atom, more preferably represents a hydrogen atom, an aryl group which may have substituents, an alkyl group which may have substituents, or a cycloalkyl group which may have substituents, still more preferably represents a cycloalkyl group which may have substituents or an alkyl group which may have substituents, and particularly preferably represents a methyl group.

[0089] Among them, in formula (A-3), R 6 preferably each independently represents a monovalent hydrocarbon group which may have substituents, more preferably represents an alkyl group which may have substituents, a cycloalkyl group which may have substituents, or an aryl group which may have substituents, and still more preferably represents a cyclohexyl group which may have substituents or a phenyl group which may have substituents.

[0090] As specific examples of the structural unit represented by formula (A-3), the structural units represented by formulae (A-3-1) to (A-3-13) can be cited, but the present invention is not limited to these. In the formula, * represents a bonding end.

[0091]

Chemical formula 7

[0092]

[0093]

Chemical formula 8

[0094]

[0095] As the structural unit represented by formula (A-1), the structural unit represented by formula (A-3-11) and the structural unit represented by formula (A-3-12) are preferred.

[0096] In the component (A), the number of structural units represented by the formula (A-1) is 1 or more, preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. When there are a plurality of structural units represented by the formula (A-1), the structural units represented by the formula (A-1) may be connected to each other as repeating units, or may not be connected to each other. When not connected to each other, for a plurality of structural units represented by the formula (A-1), preferably, a structural unit represented by the formula (A-2), a structural unit represented by the formula (A-3), or other structural units are interposed therebetween. Further, when there are a plurality of structural units represented by the formula (A-1), R 1 and R 2 in the formula (A-1) may be the same or different.

[0097] With respect to 100 mol% of the entire molecule of the component (A), the amount of the structural unit represented by the formula (A-1) is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, preferably 20 mol% or less, more preferably 15 mol% or less, and still more preferably 12 mol% or less.

[0098] In the component (A), the number of structural units represented by the formula (A-2) is 1 or more, preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. When there are a plurality of structural units represented by the formula (A-2), the structural units represented by the formula (A-2) may be connected to each other as repeating units, or may not be connected to each other. When not connected to each other, for a plurality of structural units represented by the formula (A-2), preferably, a structural unit represented by the formula (A-1), a structural unit represented by the formula (A-3), or other structural units are interposed therebetween. Further, when there are a plurality of structural units represented by the formula (A-2), R 3 and R 4 in the formula (A-2) may be the same or different.

[0099] With respect to 100% by mass of the entire molecule of the component (A), the amount of the structural unit represented by the formula (A-2) is preferably 40 mol% or more, more preferably 42 mol% or more, still more preferably 45 mol% or more, preferably 55 mol% or less, more preferably 53 mol% or less, and still more preferably 50 mol% or less.

[0100] In component (A), the number of structural units represented by formula (A-3) is 1 or more, preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. When there are a plurality of structural units represented by formula (A-3), the structural units represented by formula (A-3) may be connected to each other as repeating units, or may not be connected to each other. When not connected to each other, for a plurality of structural units represented by formula (A-3), preferably, a structural unit represented by formula (A-1), a structural unit represented by formula (A-2), or other structural units are interposed therebetween. Further, when there are a plurality of structural units represented by formula (A-3), R 5 and R 6 may be the same or different.

[0101] Relative to 100% by mass of the total mass of the molecule of component (A), the amount of the structural unit represented by formula (A-3) is preferably 40 mol% or more, more preferably 42 mol% or more, still more preferably 45 mol% or more, preferably 55 mol% or less, more preferably 53 mol% or less, and still more preferably 50 mol% or less.

[0102] In the total molecule of component (A), when the amount of the structural unit represented by formula (A-1) is a1, the amount of the structural unit represented by formula (A-2) is b1, and the amount of the structural unit represented by formula (A-3) is c1, preferably the relationship a1 < b1 + c1 is satisfied.

[0103] a1 / b1 is preferably 0.05 or more, more preferably 0.08 or more, still more preferably 0.1 or more, preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.2 or less.

[0104] a1 / c1 is preferably 0.05 or more, more preferably 0.08 or more, still more preferably 0.1 or more, preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.2 or less.

[0105] b1 / c1 is preferably 0.8 or more, more preferably 0.9 or more, still more preferably 1.0 or more, preferably 1.2 or less, more preferably 1.1 or less, and still more preferably 1.0 or less.

[0106] Further, (b1 + c1) / a1 is preferably 10 or more, more preferably 15 or more, still more preferably 20 or more, preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.

[0107] As the terminal structure of the silicone resin of the present invention, for example, R in formula (A-1) is preferably 2A monovalent hydrocarbyl group, hydroxy group, alkoxy group, alkenyloxy group, aryloxy group, or aralkyloxy group, more preferably an alkyl group, aryl group, hydroxy group, or alkoxy group, still more preferably an alkyl group, hydroxy group, alkoxy group, particularly preferably a hydroxy group or alkoxy group.

[0108] The so-called alkoxy group means a monovalent group formed by bonding an alkyl group and an oxygen atom (i.e., a group represented by R A1 -O-(R A1 is an alkyl group). As long as the alkoxy group is not particularly specified, an alkoxy group having 1 to 10 carbon atoms is preferred, more preferably 1 to 6 carbon atoms, and still more preferably an alkoxy group having 1 to 3 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc., and methoxy is preferred.

[0109] The so-called alkenyloxy group means a monovalent group formed by bonding an alkenyl group and an oxygen atom (i.e., a group represented by R A2 -O-(R A2 is an alkenyl group). As long as the alkenyloxy group is not particularly specified, an alkenyloxy group having 2 to 18 carbon atoms is preferred, more preferably 2 to 10 carbon atoms, and still more preferably an alkenyloxy group having 2 to 6 carbon atoms. Examples of the alkenyloxy group include vinyloxy, allyloxy (allyloxy, 1-propenyloxy, isopropenyloxy), etc.

[0110] The so-called aryloxy group means a monovalent group formed by bonding an aryl group and an oxygen atom (i.e., a group represented by R A3 -O-(R A3 is an aryl group). As long as the aryloxy group is not particularly specified, an aryloxy group having 6 to 18 carbon atoms is preferred, more preferably 6 to 10 carbon atoms. Examples of the aryloxy group include phenoxy, 1-naphthyloxy, 2-naphthyloxy, etc.

[0111] The so-called aralkyloxy group means a monovalent group formed by bonding an aralkyl group and an oxygen atom (i.e., a group represented by R A4 -O-(R A4 is an aralkyl group). As long as the aralkyloxy group is not particularly specified, an aralkyloxy group having 7 to 19 carbon atoms is preferred, more preferably 7 to 11 carbon atoms. Examples of the aralkyloxy group include benzyloxy, α-methylbenzyloxy, etc.

[0112] The alkoxy group, alkenyloxy group, aryloxy group, and aralkyloxy group may have substituents. The substituents are the same as those that the monovalent hydrocarbyl group represented by R in formula (A-1) may have. 2 can have.

[0113] As the silicone resin of the present invention, it may have a structural unit represented by the following formula (A-4).

[0114] [Chemical Formula 9]

[0115]

[0116] In formula (A-4), R 11 represents a group represented by formula (A-1a) or a group represented by formula (A-1b). R 12 , R 13 and R 14 each independently represent a monovalent hydrocarbon group which may have a substituent. R 15 and R 16 each independently represent a monovalent hydrocarbon group which may have a substituent or a hydrogen atom. a, b and c each independently represent an integer from 1 to 20, satisfying the relationship a < b + c. * represents a bonding end. However, R 15 is a group different from R 13 and R 14 .

[0117] In formula (A-4), R 11 represents a group represented by formula (A-1a) or a group represented by formula (A-1b). For the group represented by formula (A-1a) and the group represented by formula (A-1b), as described above.

[0118] In formula (A-4), R 12 , R 13 , R 14 each independently represent a monovalent hydrocarbon group which may have a substituent. R 12 is the same as the monovalent hydrocarbon group which may have a substituent represented by R 2 in formula (A-1). R 13 and R 14 are the same as the monovalent hydrocarbon groups which may have a substituent represented by R 3 , R 4 in formula (A-2).

[0119] In formula (A-4), R 15 and R 16 each independently represent a monovalent hydrocarbon group which may have a substituent or a hydrogen atom. The monovalent hydrocarbon groups represented by R 15 and R 16 are the same as the monovalent hydrocarbon groups which may have a substituent represented by R 5 , R 6 in formula (A-3).

[0120] In formula (A-4), a, b, and c each independently represent an integer from 1 to 20, satisfying the relationship a < b + c. a preferably represents an integer from 1 to 10, more preferably represents an integer from 1 to 6, further preferably represents an integer from 1 to 3, and particularly preferably 1. B and c preferably represent an integer from 1 to 18, more preferably represent an integer from 3 to 15. a, b, and c can be obtained from the feed ratio of the raw materials during the synthesis of the organosilicon resin.

[0121] As a specific example of the organosilicon resin, the organosilicon resins represented by (A1) to (A78) can be cited, but the present invention is not limited thereto. In the formula, * represents a bonding end.

[0122]

Chemical formula 10

[0123]

[0124]

Chemical formula 11

[0125]

[0126]

Chemical formula 12

[0127]

[0128]

Chemical formula 13

[0129]

[0130]

Chemical formula 14

[0131]

[0132]

Chemical formula 15

[0133]

[0134]

Chemical formula 16

[0135]

[0136]

Chemical formula 17

[0137]

[0138]

Chemical formula 18

[0139]

[0140]

Chemical formula 19

[0141]

[0142]

Chemical formula 20

[0143]

[0144]

Chemical Formula 21

[0145]

[0146]

Chemical Formula 22

[0147]

[0148]

Chemical Formula 23

[0149]

[0150]

Chemical Formula 24

[0151]

[0152]

Chemical Formula 25

[0153]

[0154]

Chemical Formula 26

[0155]

[0156]

Chemical Formula 27

[0157]

[0158]

Chemical Formula 28

[0159]

[0160]

Chemical Formula 29

[0161]

[0162] There is no particular limitation on the method for synthesizing the silicone resin. For example, the silicone resin can be synthesized by polymerizing a silanediol compound capable of forming a structural unit represented by the formula (A-2) with 1) an alkoxysilane compound containing a glycidyl group, an aryloxysilane compound containing a glycidyl group, an alkoxysilane compound containing an epoxycyclohexyl group, or an aryloxysilane compound containing an epoxycyclohexyl group, which are capable of forming a structural unit represented by the formula (A-1), and 2) a dialkoxysilane compound or a diaryloxysilane compound capable of forming a structural unit represented by the formula (A-3). The temperature condition is preferably 30 to 120 °C, more preferably 50 to 100 °C. The reaction time is preferably 1 hour to 7 days, more preferably 3 hours to 5 days.

[0163] The weight-average molecular weight of the silicone resin is preferably 2,500 or more, more preferably 3,000 or more, still more preferably 4,000 or more, preferably 15,000 or less, more preferably 12,000 or less, and still more preferably 10,000 or less. The weight-average molecular weight of the silicone resin is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0164] The number-average molecular weight of the silicone resin is preferably 10,000 or less, more preferably 9,500 or less, still more preferably 9,000 or less, 8,500 or less, 8,000 or less, 7,000 or less, preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, 2,500 or more. The number-average molecular weight of the silicone resin is the number-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0165] The active group equivalent of the silicone resin is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, still more preferably 150 g / eq. or more, 200 g / eq. or more, 250 g / eq. or more, 300 g / eq. or more, 350 g / eq. or more, preferably 1,000 g / eq. or less, more preferably 900 g / eq. or less, still more preferably 800 g / eq. or less, 700 g / eq. or less, 600 g / eq. or less, 500 g / eq. or less, 400 g / eq. or less.

[0166] [Resin Composition]

[0167] The resin composition of the present invention contains: (A) a silicone resin having a structural unit represented by formula (A-1), a structural unit represented by formula (A-2), and a structural unit represented by formula (A-3), (B) a curing agent, and (C) an inorganic filler. In the present invention, by containing the components (A), (B), and (C) in combination, a cured product having a low dielectric loss tangent and a high glass transition temperature can be obtained. In addition, a cured product having excellent crack resistance can usually be obtained.

[0168] The resin composition may further contain optional components in combination with the components (A) to (C). Examples of the optional components include (D) an epoxy resin, (E) a radically polymerizable compound, (F) a high molecular weight component, (G) a curing accelerator, (H) a radical polymerization initiator, (I) an organic filler, (J) other additives, and (K) a solvent, etc. Hereinafter, each component that can be contained in the resin composition will be described in detail.

[0169] <(A) Silicone Resin>

[0170] Regarding the resin composition, as the component (A), it contains (A) silicone resin. The (A) silicone resin that can be contained in the resin composition is as described in the above [Silicone Resin] section. The component (A) can be used alone as one type, or two or more types can be used in combination.

[0171] When the non-volatile components in the resin composition are set to 100% by mass, the content of the component (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less.

[0172] When the resin components in the resin composition are set to 100% by mass, the content of the component (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, preferably 70% by mass or less, more preferably 65% by mass or less, further preferably 60% by mass or less, 50% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.

[0173] In the present invention, regarding the content of each component in the resin composition, unless otherwise specified, it is the value when the non-volatile components in the resin composition are set to 100% by mass. The so-called non-volatile components refer to the components other than the (K) solvent described later among the components constituting the resin composition. In addition, in the present invention, the so-called resin components in the resin composition refer to the components obtained by removing the (C) inorganic filler from the non-volatile components of the resin composition.

[0174] <(B) Curing Agent>

[0175] Regarding the resin composition, as the component (B), it contains (B) curing agent. The (B) curing agent as the component (B) does not contain components equivalent to the component (A). The component (B) generally has the function of reacting with the later-described component (D) to cure the resin composition. The component (B) can be used alone as one type, or two or more types can be combined and used at any ratio.

[0176] As the component (B), a compound capable of reacting with the component (D) to cure the resin composition can be used. For example, active ester-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, carbodiimide-based curing agents, benzoxazine-based curing agents, amine-based curing agents, cyanate ester-based curing agents, etc. can be cited. Among them, as the component (B), it is preferable to contain any one of an active ester-based curing agent, a phenol-based curing agent, an acid anhydride-based curing agent, and a carbodiimide-based curing agent, more preferably to contain an active ester-based curing agent, still more preferably to contain any one of an active ester-based curing agent, a phenol-based curing agent, and an acid anhydride-based curing agent, and further preferably to contain an active ester-based curing agent.

[0177] As the active ester-based curing agent, a curing agent having one or more active ester groups in one molecule can be cited. Among them, as the active ester-based curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, benzenethiol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferable. This active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.

[0178] As the carboxylic acid compound, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. can be cited.

[0179] As the phenol compound or naphthol compound, for example, 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, phenol novolac, etc. can be cited. Among them, the so-called "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol in 1 molecule of dicyclopentadiene.

[0180] As preferred specific examples of the active ester-based curing agent, there may be mentioned an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure, an active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent containing an acetylated product of phenol novolac, and an active ester-based curing agent containing a benzoylated product of phenol novolac. Among them, an active ester-based curing agent containing a naphthalene structure and an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" means a divalent structure composed of phenylene-subdicyclopentylidene-phenylene.

[0181] As commercially available products of the active ester-based curing agent, as the active ester-based curing agent containing a dicyclopentadiene-type diphenol structure, there may be mentioned "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "HPC-8000H", "EXB-8000L-65TM" (manufactured by DIC Corporation); as the active ester-based curing agent containing a naphthalene structure, there may be mentioned "EXB-9416-70BK", "EXB-8100L-65T", "HPC-8150-62T", "EXB-8150L-65T", "EXB-8100L-65T", "EXB-8" (manufactured by DIC Corporation); as the active ester-based curing agent containing phosphorus, there may be mentioned "EXB9401" (manufactured by DIC Corporation), as the active ester-based curing agent containing an acetylated product of phenol novolac, there may be mentioned "DC808" (manufactured by Mitsubishi Chemical Corporation); as the active ester-based curing agent containing a benzoylated product of phenol novolac, there may be mentioned "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), "EXB-8500-65T" (manufactured by DIC Corporation); as the active ester-based curing agent containing a styryl group and a naphthalene structure, there may be mentioned "PC1300-02-65T", "PC1300-02-65MA" (manufactured by AIRWATER Corporation), etc.

[0182] As the phenolic curing agent, there may be mentioned a curing agent having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) in one molecule. Among them, a compound having a hydroxyl group bonded to a benzene ring is preferred. In addition, from the viewpoints of heat resistance and water resistance, a phenolic curing agent having a novolac structure is preferred. Further, from the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferred, and a phenolic curing agent containing a triazine skeleton is more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a phenol novolac curing agent containing a triazine skeleton is preferred.

[0183] As specific examples of phenol-based curing agents and naphthol-based curing agents, there can be cited "MEH-7700", "MEH-7810", "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-495", "SN-495V", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "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 Corporation; "GDP-6115L", "GDP-6115H", "ELPC75", etc. manufactured by Gunei Chemical Industry Co., Ltd.

[0184] As specific examples of carbodiimide-based curing agents, there can be cited aliphatic biscarbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexane bis(methylene-tert-butylcarbodiimide); biscarbodiimides such as phenylenebis(xylenylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), poly(isophorone carbodiimide); aromatic polycarbodiimides such as poly(phenylene carbodiimide), poly(naphthylene carbodiimide), poly(m-tolylene carbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(benzylidene carbodiimide), poly(tetramethylbenzylidene carbodiimide), poly(methylenediphenylene carbodiimide), poly[methylene bis(methylphenylene)] carbodiimide, etc.

[0185] As commercially available products of carbodiimide-based curing agents, for example, there can be cited "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07" and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; "Stabaxol P", "Stabaxol P100", "Stabaxol P400", "Hycadil 510", etc. manufactured by LANXESS Corporation.

[0186] As the acid anhydride curing agent, a compound having one or more, preferably two or more, acid anhydride groups in one molecule can be used. 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, benzophenonetetracarboxylic anhydride, biphenyl Tetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride) (Ethylene Glycol Bis), styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid, and the like polymer type acid anhydrides, and the like.

[0187] Commercially available products of anhydride curing agents include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" manufactured by Lezonack Co., Ltd.; "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Cleaver Co., Ltd.; and "MHHPA" manufactured by Shigmar Drizzle Co., Ltd.

[0188] Specific examples of the benzoxazine-based curing agent include "ODA-BOZ" manufactured by JEE Chemical Co., Ltd., "HFB2006M" manufactured by Showa High Molecular Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0189] As the amine-based curing agent, curing agents having one or more amino groups in one molecule can be cited. For example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. can be cited. Among them, from the viewpoint of achieving the desired effects of the present invention, aromatic amines are preferred. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenylsulfone diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 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. The amine-based curing agent can be a commercially available product. For example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., "EPICURE W" manufactured by Mitsubishi Chemical Corporation, etc. can be cited.

[0190] As the cyanate ester-based curing agent, for example, bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylen-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanatephenyl)propane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) sulfide, and bis(4-cyanatephenyl) ether and other difunctional cyanate ester resins can be cited; polyfunctional cyanate ester resins derived from phenol novolac and cresol novolac, etc.; prepolymers in which a part of these cyanate ester resins is triazine-ized, etc. As specific examples of the cyanate ester-based curing agent, "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins) manufactured by arxada company; "ULL-950S" (polyfunctional cyanate ester resin); "BA230", "BA230S75" (prepolymers that are part or all of bisphenol A dicyanate triazine-ized trimers), etc. can be cited.

[0191] When the epoxy equivalent number of component (D) is 1, the number of active groups of curing agent (B) 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. Herein, the so-called "epoxy equivalent number of component (D)" is the total value obtained by dividing the mass of the non-volatile component of component (D) present in the resin composition by the epoxy equivalent. In addition, the so-called "number of active groups of curing agent (B)" is the total value obtained by dividing the mass of the non-volatile component of curing agent (B) present in the resin composition by the active group equivalent.

[0192] When the non-volatile component in the resin composition is set to 100% by mass, the content of curing agent (B) is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more or 10% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, 15% by mass or less, and further preferably 10% by mass or less.

[0193] (B) When the resin component in the resin composition is set to 100% by mass, the content of the curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, 15% by mass or more, 20% by mass or more, preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less.

[0194] <(C) Inorganic filler>

[0195] In the case of the resin composition, as the component (C), an (C) inorganic filler is contained. By containing the (C) inorganic filler in the resin composition, a cured product with a low dielectric loss tangent can be obtained. The (C) inorganic filler is usually contained in the resin composition in a particulate state. The component (C) can be used alone or in combination of two or more.

[0196] As the material of the (C) inorganic filler, an inorganic compound is used. As the material of the (C) inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate can be cited. Among these, silica is particularly preferred. As silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be cited. In addition, as silica, spherical silica is preferred.

[0197] As commercially available products of the (C) inorganic filler, for example, "SP60-05", "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", "FB-105FD" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "Celsifers MGH-005" manufactured by Taiheiyo Cement Corporation, etc. can be cited.

[0198] (C) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, further preferably 0.3 μm or more, preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less.

[0199] (C) The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a laser diffraction / scattering type particle size distribution measuring device can be used to create a particle size distribution of the inorganic filler based on volume, and the median diameter is measured as the average particle diameter. For the measurement sample, a product obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them ultrasonically for 10 minutes can be used. For the measurement sample, using a laser diffraction type particle size distribution measuring device, with the light source wavelengths of cyan and red, the volume-based particle size distribution of the inorganic filler is measured in a flow cell manner, and the average particle diameter can be calculated as the median diameter from the obtained particle size distribution. As a laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba, Ltd. can be cited.

[0200] (C) The BET specific surface area of the inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, further preferably 1 m 2 / g or more, preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, further preferably 40 m 2 / g or less.

[0201] (C) The specific surface area of the inorganic filler can be measured by adsorbing nitrogen on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method and calculating the specific surface area using the BET multi-point method.

[0202] (C) Regarding the inorganic filler, from the viewpoints of improving moisture resistance and dispersibility, it is preferably treated with a surface treatment agent. As the surface treatment agent, for example, fluorosilane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. can be cited. The surface treatment agent can be used alone as 1 type, or 2 types or more can be arbitrarily combined and used.

[0203] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc., all manufactured by Shin-Etsu Chemical Co., Ltd.

[0204] Regarding the degree of surface treatment using the surface treatment agent, from the viewpoint of improving the dispersibility of the inorganic filler, it is preferably within a specific range. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 3% by mass of the surface treatment agent, and further preferably surface-treated with 0.3% to 2% by mass of the surface treatment agent.

[0205] The degree of surface treatment using the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Regarding the amount of carbon per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, it is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and further preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and further preferably 0.5 mg / m 2 or less.

[0206] (C) The amount of carbon per unit surface area of the inorganic filler can be measured after subjecting the surface-treated inorganic filler to a cleaning treatment with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the 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 can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. etc. can be used.

[0207] In addition, the degree of surface treatment using the surface treatment agent can be evaluated by the amount of carbon per unit mass of the inorganic filler. The amount of carbon per unit mass of the inorganic filler is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more. In addition, it is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less. (C) The amount of carbon per unit mass of the inorganic filler can be measured using a carbon analyzer in the same manner as (D) the amount of carbon per unit surface area of the inorganic filler.

[0208] (C) When the non-volatile components in the resin composition are set to 100% by mass, the content of the inorganic filler is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, or 55% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.

[0209] <(D) Epoxy resin>

[0210] Regarding the resin composition, as an optional component, (D) epoxy resin can be further contained as component (D). The (D) epoxy resin as component (D) does not contain substances corresponding to components (A) to (C). By containing (D) epoxy resin in the resin composition, a cured product having good mechanical strength and insulation reliability can be obtained. (D) Epoxy resin can be used alone as one type, or two or more types can be used in combination.

[0211] Examples of the (D) epoxy resin include bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, glycidyl cyclohexane type epoxy resin, alkyl diglycidyl ether type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing a spiro ring, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthalene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalimide type epoxy resin, etc.

[0212] The resin composition preferably contains, as component (D), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the 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 (B) epoxy resin.

[0213] Among epoxy resins, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). Regarding the resin composition, as component (B), it may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. Among them, from the viewpoint of obtaining a cured product with excellent crack resistance, it is preferable to contain a liquid epoxy resin and a solid epoxy resin in combination.

[0214] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0215] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, epoxy resin having a butadiene structure, glycidylcyclohexane type epoxy resin, phenolphthaleimide type epoxy resin, alkyl diglycidyl ether type epoxy resin are preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable.

[0216] As specific examples of the liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation can be cited; "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" (glycidylamine-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YED216D" (alkyl diglycidyl ether-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used alone or in combination of two or more.

[0217] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, a solid epoxy resin having three or more epoxy groups in one molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is further preferred.

[0218] As the solid epoxy resin, bisxylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthyl ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, tetraphenylethane-type epoxy resin are preferred, and biphenyl-type epoxy resin is more preferred.

[0219] As specific examples of solid epoxy resins, there can be cited "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (tetrafunctional naphthalene-type epoxy resin), "N-690" (cresol novolak-type epoxy resin), "N-695" (cresol novolak-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" (naphthalene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (triphenol-type epoxy resin), "NC7000L" (naphthol novolak-type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthalene-type epoxy resin), "ESN485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bisdimethylphenol-type epoxy resin), "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500", "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 Osaka Gas Chemical Co., Ltd.; "WHR-991S" (phenolphthaleimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. These can be used alone or in combination of two or more.

[0220] When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (D), their quantitative ratio (liquid epoxy resin: solid epoxy resin) is expressed by mass ratio, 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 the quantitative ratio of the liquid epoxy resin and the solid epoxy resin being within this range, the desired effects of the present invention can be significantly obtained.

[0221] (D) component preferably has an epoxy equivalent of 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., still more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. By being within this range, a cured body with sufficient crosslinking density of the cured product of the resin composition can be obtained. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

[0222] (D) component preferably has a weight average molecular weight (Mw) of 100 to 5000, more preferably 150 to 3000, still more preferably 200 to 1500. The weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0223] (D) component content, when the non-volatile components in the resin composition are set to 100% by mass, is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

[0224] (D) component content, when the resin components in the resin composition are set to 100% by mass, is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, 30% by mass or less, or 25% by mass or less.

[0225] <(E) Free radical polymerizable compound>

[0226] For the resin composition, as an optional component, (E) free radical polymerizable compound can be further contained as (E) component. The (E) thermosetting resin as this (E) component does not contain substances corresponding to (A) to (D) components. The (E) free radical polymerizable compound can be used alone or in combination of two or more.

[0227] Regarding the (E) radically polymerizable compound, for example, it may be a compound having a radically polymerizable group. As the radically polymerizable group, as long as it can be radically polymerized, there is no particular limitation, and an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or inside is preferred. For example, unsaturated hydrocarbon groups such as vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl can be cited; α,β-unsaturated carbonyls such as acryloyl, methacryloyl, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) and the like. The (E) radically polymerizable compound preferably has one or more radically polymerizable unsaturated groups, and more preferably has two or more.

[0228] As the (E) radically polymerizable compound, known radically polymerizable compounds can be widely used and there is no particular limitation. For example, (meth)acrylic acid-based radically polymerizable compounds, styrene-based radically polymerizable compounds, allyl-based radically polymerizable compounds, maleimide-based radically polymerizable compounds and the like can be cited. As the (E) component, a maleimide-based radically polymerizable compound is preferably included.

[0229] (Meth)acrylic radical-polymerizable compounds are, for example, compounds having one or more, preferably two or more acryloyl groups and / or methacryloyl groups. Examples of the (meth)acrylic radical-polymerizable compounds include aliphatic (meth)acrylate compounds with 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, pentaerythritol tetra(meth)acrylate; (meth)acrylate compounds with low molecular weight (molecular weight less than 1000) containing ethers such as dioxane diol di(meth)acrylate, 3,6-dioxa-1,8-octanediol 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; (meth)acrylate compounds with low molecular weight (molecular weight less than 1000) containing isocyanurates such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate; acrylate compounds with high molecular weight (molecular weight 1000 or more) such as (meth)acrylic acid-modified polyphenylene ether resin. Examples of commercially available products of (meth)acrylic radical-polymerizable compounds include "A-DOG" (dioxane diol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxane diol diacrylate) manufactured by Nippon Kayaku Co., Ltd., "SA9000", "SA9000-111" (methacrylic acid-modified polyphenylene ether) manufactured by SABIC, etc.

[0230] Styrene-based free-radical polymerizable compounds are, for example, compounds having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based free-radical polymerizable compounds 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 1000 or more) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Examples of commercially available products of styrene-based free-radical polymerizable compounds include "ODV-XET(X03)", "ODV-XET(X04)", "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel & Chemical & Material Co., Ltd., and "OPE-2St1200", "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Company, Inc. In addition, examples of styrene-based free-radical polymerizable compounds include copolymer A described in International Publication No. 2017 / 115813, etc.

[0231] Allyl-based radically polymerizable compounds are, for example, compounds having one or more, preferably two or more allyl groups. Examples of allyl-based radically polymerizable compounds include aromatic carboxylic acid allyl ester compounds such as diallyl phthalate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenedicarboxylate; allyl isocyanurate compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; aromatic allyl compounds containing epoxy 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 ether such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyl diphenylsilane. Examples of commercially available allyl-based radically polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., "DAD" (diallyl phthalate) manufactured by Nisshu Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the product name "DAND" (diallyl 2,3-naphthalenedicarboxylate) manufactured by Nisshu Techno Fine Chemical Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Kasei Kogyo 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 Kasei Kogyo Co., Ltd.

[0232] The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Examples of commercially available maleimide-based radically polymerizable compounds include "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (a maleimide compound containing a dimer diamine structure) manufactured by DesignerMolecules Inc., "BMI-6100" (an aromatic maleimide compound) manufactured by Designer Molecules Inc., "MIR-5000-60T", "MIR-3000-70MT" (biphenyl aralkyl-type maleimide compounds) manufactured by Nippon Kayaku Co., Ltd., "BMI-70", "BMI-80" manufactured by K.I. Kasei Co., Ltd., "BMI-2300", "BMI-TMH" manufactured by Yamato Kasei Kogyo Co., Ltd., etc. In addition, as the maleimide-based radically polymerizable compound, a maleimide resin (a maleimide compound containing an indane ring skeleton) disclosed in Technical Report Publication No. 2020-500211 of the Japan Institute of Invention and Innovation can be used.

[0233] The vinyl unsaturated bond equivalent of component (E) is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., still more preferably 70 g / eq. to 2000 g / eq., and particularly preferably 90 g / eq. to 1500 g / eq. The vinyl unsaturated bond equivalent represents the mass of the vinyl unsaturated bond per 1 equivalent of the radically polymerizable compound.

[0234] The weight average molecular weight (Mw) of component (E) is preferably 40,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, and particularly preferably 3,000 or less. There is no particular limitation on the lower limit, and it can be, for example, 150 or more. The weight average molecular weight can be measured by gel permeation chromatography (GPC) as a polystyrene conversion value.

[0235] When the non-volatile components in the resin composition are set to 100% by mass, the content of component (E) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 20% by mass or less, 10% by mass or less, 5% by mass or less.

[0236] When the resin component in the resin composition is set to 100% by mass, the content of component (E) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, preferably 90% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, 8% by mass or less.

[0237] <(F) Polymer Component>

[0238] In the case of the resin composition, as an optional component, (F) polymer component can be further contained as component (F). The (F) polymer component as this (F) component does not contain a substance corresponding to component (A) to

[0239] component (E). By containing component (F) in the resin composition, the stress of the resin composition is alleviated and the elastic modulus is reduced. As a result, even when the content of component (A) is small, a cured product with excellent crack resistance can be obtained. Component (F) can be used alone or in combination of two or more.

[0240] Component (F) can use a component with a high molecular weight in terms of weight average molecular weight. As such a component, for example, polyimide resin, phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc. can be cited.

[0241] The weight average molecular weight (Mw) of component (F) is preferably greater than 5000, more preferably 8000 or more, still more preferably 10000 or more, particularly preferably 20000 or more, preferably 100000 or less, more preferably 70000 or less, still more preferably 60000 or less, particularly preferably 50000 or less.

[0242] Polyimide resin means a resin containing a repeating unit containing an imide bond. Generally, polyimide resin contains a repeating unit having a structure obtained by reacting a diamine compound with an acid anhydride (imide-forming reaction).

[0243] As the diamine compound, for example, aliphatic diamine compounds and aromatic diamine compounds can be cited. Among them, aromatic diamine compounds are preferred. As the aromatic diamine compound, for example, benzene diamine compounds, naphthalene diamine compounds, diphenylamine compounds, etc. can be cited. Among them, diphenylamine compounds are preferred.

[0244] The so-called diphenylamine compound refers to a compound containing two aniline structures in the molecule. Each benzene ring in the aniline structure may arbitrarily have 1 to 3 substituents. The two aniline structures in the diphenylamine compound may be directly bonded or bonded via a linking structure having 1 to 100 backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0245] Specific examples of the "linking structure" in the diphenylamine compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CH=CH-, -O-, -S-, -CO-, -SO2-, -NH-, -Ph-, -Ph-Ph-, -C(CH3)2-Ph-C(CH3)2-, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, -Ph-CO-O-Ph-, -C(CH3)2-Ph-C(CH3)2-, the group represented by the following formula (I), the group represented by (II), and the group composed of their combinations. In this specification, "Ph", unless otherwise specified, represents 1,4-phenylene, 1,3-phenylene, or 1,2-phenylene. In the following formulas (I) and (II), "*" represents a bonding end.

[0246]

Chemical Formula 30

[0247]

[0248] As the diphenylamine compound, for example, 4,4'-diamino-2,2'-bis(trifluoromethyl)-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, etc. can be cited. The diamine compound can be used alone as 1 kind, or 2 or more kinds can be used in combination.

[0249] As the acid anhydride, generally acid dianhydride can be used, and aromatic tetracarboxylic dianhydride is preferred. As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic dianhydride, etc. can be cited, and diphthalic dianhydride is preferred.

[0250] The so-called diphthalic dianhydride means a compound containing 2 phthalic anhydride structures in the molecule. The benzene rings in the phthalic anhydride structure can each optionally have 1 to 3 substituents. The 2 phthalic anhydride structures in the diphthalic dianhydride can be directly bonded, or can be bonded via a linking structure having 1 to 100 backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

[0251] As an example of the "linking structure" in the diphthalic dianhydride, a divalent group represented by -[R e -Ph] me -R e -[Ph-R e ne - can be cited. In this formula, R e ​Each independently represents a single bond, -(substituted or unsubstituted alkylene)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; me and ne each independently represent an integer from 0 to 2 (preferably 0 or 1). Specific examples of the linking structure include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CO-, -SO2-, -Ph-, -O-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, etc.

[0252] Examples of the dianhydride of diphthalic acid include 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylidene-4,4'-diphthalic dianhydride, 1,3-trimethylen-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl) benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy) bisphthalic dianhydride, etc. The acid anhydride can be used alone or in combination of two or more.

[0253] The polyimide resin can be manufactured by methods known in the past. For example, the polyimide resin can be manufactured by a method including heating a mixture of a diamine compound, an acid anhydride, and a solvent to cause a reaction. In addition, as the polyimide resin, commercially available products can be used. Specific examples of commercially available polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Rika Coat SN20" and "Rika Coat PN20" manufactured by Nippon Rika Kako Co., Ltd., etc.

[0254] As the phenoxy resin, for example, phenoxy resins having one or more skeletons selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton can be cited. The terminal of the phenoxy resin can be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; "YX8100" (a phenoxy resin containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation; "YX6954" (a phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation, etc.

[0255] As the polyvinyl acetal resin, for example, polyvinyl formal resin and polyvinyl butyral resin can be cited, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include the ESREC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Co., Ltd.

[0256] As the polyolefin resin, for example, ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin-based polymers such as polypropylene and ethylene-propylene block copolymer, etc.

[0257] As the polybutadiene resin, for example, resins containing a hydrogenated polybutadiene backbone, polybutadiene resins containing hydroxyl groups, polybutadiene resins containing phenolic hydroxyl groups, polybutadiene resins containing carboxyl groups, polybutadiene resins containing acid anhydride groups, polybutadiene resins containing epoxy groups, polybutadiene resins containing isocyanate groups, polybutadiene resins containing urethane groups, polyphenylene ether-polybutadiene resins, etc. can be cited.

[0258] As specific examples of the polyamideimide resin, "Vylon Max HR11NN" and "Vylon Max HR16NN" manufactured by Toyobo Co., Ltd. can be cited. As other specific examples of the polyamideimide resin, modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane backbone) manufactured by Resona Co., Ltd. can be cited.

[0259] As a specific example of the polyethersulfone resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. can be cited.

[0260] As specific examples of the polysulfone resin, polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers can be cited.

[0261] As a specific example of the polyphenylene ether resin, "NORYL SA90" manufactured by SABIC can be cited. As a specific example of the polyetherimide resin, "ULTEM" manufactured by GE can be cited.

[0262] As the polycarbonate resin, for example, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing urethane groups, etc. can be cited. As specific examples of the polycarbonate resin, "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., etc. can be cited. As a specific example of the polyetheretherketone resin, "Sumipro EK" manufactured by Sumitomo Chemical Co., Ltd. can be cited.

[0263] As the polyester resin, for example, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, polycyclohexanedimethanol terephthalate resin, etc. can be cited.

[0264] (F) When the non-volatile components in the resin composition are set to 100% by mass, the content of the polymer component is 0% by mass, preferably 0% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1.5% by mass or less, 1% by mass or less.

[0265] (F) When the resin components in the resin composition are set to 100% by mass, the content of the polymer component is 0% by mass, preferably 0% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less, 3% by mass or less, or 1% by mass or less.

[0266] <(G) Curing accelerator>

[0267] In the case of the resin composition, as an optional component, (G) a curing accelerator can be further contained as the (G) component. In the (G) curing accelerator as the (G) component, substances conforming to the above (A) to (F) components are not contained. By containing the (G) component, the curing of the (B) component can be further promoted. The (G) component can be used alone as 1 type, or 2 types or more can be used in combination.

[0268] As the (G) component, for example, phosphorous curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metal curing accelerators, amine curing accelerators, etc. can be cited. Among them, curing accelerators selected from amine curing accelerators and metal curing accelerators are preferred, and amine curing accelerators are particularly preferred.

[0269] As phosphorus-based curing accelerators, for example, there can be mentioned aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyl dimethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetrakis(p-tolyl)borate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrakis(p-tolyl)borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine·triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine·p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine; aromatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether, etc.

[0270] As the urea-based curing accelerator, for example, 1,1-dimethylurea can be cited; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea], etc.

[0271] As the guanidine-based curing accelerator, for example, 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-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. can be cited.

[0272] As imidazole-based curing accelerators, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate or ester, 1-cyanoethyl-2-phenylimidazolium trimellitate or ester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-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 other imidazole compounds and adducts of imidazole compounds and epoxy resins can be cited.

[0273] As imidazole-based curing accelerators, commercially available products can be used. For example, "1B2PZ", "2MZA-PW", "2PHZ-PW", "C11Z-A", "C11Z", "2P4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. can be cited.

[0274] As metal-based curing accelerators, for example, metal, organometallic complexes or organometallic salts of cobalt, copper, zinc, iron, nickel, manganese, tin, etc. can be cited. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, organomanganese complexes such as manganese(II) acetylacetonate, etc. As organometallic salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

[0275] As amine-based curing accelerators, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. can be cited.

[0276] As the amine-based curing accelerator, commercially available products can be used. For example, “MY-25” manufactured by Ajinomoto Fine-Techno Co., Inc. etc. can be cited.

[0277] (G) component content, when the non-volatile components in the resin composition are set to 100% by mass, is preferably 0.01% by mass or more, more preferably 0.002% by mass or more, further preferably 0.03% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less.

[0278] (G) component content, when the resin components in the resin composition are set to 100% by mass, is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1.5% by mass or less.

[0279] <(H) Radical polymerization initiator>

[0280] Regarding the resin composition, as an optional component, (H) radical polymerization initiator can be included. The (H) radical polymerization initiator of this (H) component does not contain substances that conform to components (A) to (G). Regarding the (H) radical polymerization initiator, for example, it can be a thermal polymerization initiator that generates radicals when heated. The (H) radical polymerization initiator can be a polymerization initiator for radical-reactive groups. The (H) radical polymerization initiator can be used alone as 1 type, or 2 types or more can be arbitrarily combined and used.

[0281] As the (H) radical polymerization initiator, for example, peroxide-based radical polymerization initiators, azo-based radical polymerization initiators, etc. can be cited. Among them, peroxide-based radical polymerization initiators are preferred.

[0282] As a peroxide-based radical polymerization initiator, for example, hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide can be cited; dialkyl peroxide compounds such as tert-butyl cumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate; peroxyester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl) 2-ethylhexanoate, tert-butyl 2-ethylhexanoate, tert-butyl 3,5,5-trimethylhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, peroxy maleic acid tert-butyrate, etc.

[0283] As an azo-based radical polymerization initiator, for example, azonitrile compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile can be cited; azoamide compounds such as 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); alkyl azo compounds such as 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), etc.

[0284] Examples of commercially available products as the (H) radical polymerization initiator include "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", "Perbutyl ND", "Perbutyl Z", "Perbutyl I", "Parkmill P", "Parkmill D", "Perhexyl D", "Perhexyl A", "Perhexyl I", "Perhexyl Z", "Perhexyl ND", "Perhexyl O", "Perhexyl PV", etc. manufactured by NOF Corporation.

[0285] When the non-volatile components in the resin composition are set to 100% by mass, the content of the (H) component is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.

[0286] When the resin components in the resin composition are set to 100% by mass, the content of the (H) component is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, preferably 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

[0287] <(I) Organic filler>

[0288] In the resin composition, as an optional component, (I) organic filler may be further contained as the (I) component. In the (I) organic filler as the (I) component, substances corresponding to the above (A) to (H) components are not contained. The (I) component may be used alone or in combination of two or more.

[0289] The (I) component exists in the resin composition in a particulate form. Examples of the (I) component include rubber particles, polyamide fine particles, silicone particles, core-shell type particles, etc. In the present invention, from the viewpoint of significantly obtaining the desired effects of the present invention, either rubber particles or core-shell type particles are preferably used, and rubber particles are more preferably used.

[0290] As the rubber component contained in the rubber particles, for example, polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutene copolymer, isobutene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butene terpolymer and other olefin-based thermoplastic elastomers can be cited; poly(meth)acrylate propyl ester, poly(meth)acrylate butyl ester, poly(meth)acrylate cyclohexyl ester, poly(meth)acrylate octyl ester and other acrylic-based thermoplastic elastomers and other thermoplastic elastomers are preferred, olefin-based thermoplastic elastomers are more preferred, and styrene-butadiene copolymer is even more preferred. Further, in the rubber component, silicone-based rubbers such as polyorganosiloxane rubber can be mixed. The glass transition temperature of the rubber component contained in the rubber particles is, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower.

[0291] As the rubber particles, commercially available products can be used. For example, "EXL2655" manufactured by Dow Chemical Japan Co., Ltd., "AC3401N", "AC3816N" manufactured by Aika Industries Co., Ltd. and the like can be cited.

[0292] The so-called core-shell type particles are particulate organic filler materials composed of core particles containing the above-listed rubber components and one or more shell parts covering them. Further, the core-shell type particles are preferably core-shell type graft copolymer particles composed of core particles containing the above-listed rubber components and a shell part formed by graft copolymerizing a monomer component copolymerizable with the rubber component contained in the core particles. The so-called core-shell type here does not necessarily mean only the type in which the core particles and the shell part can be clearly distinguished, and also includes the type in which the boundary between the core particles and the shell part is unclear, and the core particles may not be completely covered by the shell part.

[0293] In the core-shell type graft copolymer particles, the rubber component is preferably contained in an amount of 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more. There is no particular limitation on the upper limit of the content of the rubber component in the core-shell type graft copolymer particles. From the viewpoint of sufficiently covering the core particles with the shell part, for example, it is preferably 95% by mass or less, 90% by mass.

[0294] Examples of the monomer component for forming the shell portion of the core-shell graft copolymer particles include (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, and glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; (meth)acrylonitrile, etc. (meth)acrylate esters are preferred, and methyl (meth)acrylate is more preferred.

[0295] Examples of commercially available core-shell graft copolymer particles include "CHT" manufactured by Samsung SDI Co., Ltd.; "B602" manufactured by Techno UMG Co., Ltd.; "Paraloid EXL2602", "Paraloid EXL2603", "Paraloid EXL2655", "Paraloid EXL2311", "Paraloid EXL2313", "Paraloid EXL2315", "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.; "Kaneka Ace M-511", "Kaneka Ace M-600", "Kaneka Ace M-400", "Kaneka Ace M-580", "Kaneka MR-01" manufactured by Kaneka Corporation, etc. These can be used alone or in combination of two or more.

[0296] There is no particular limitation on the average particle diameter (average primary particle diameter) of the core-shell graft copolymer particles. It 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 5000 nm or less, more preferably 2000 nm or less, further preferably 1000 nm or less, and particularly preferably 500 nm or less. The average particle diameter (average primary particle diameter) of the core-shell graft copolymer particles can be measured using a ζ-potential particle size distribution measuring device, etc.

[0297] When the non-volatile content in the resin composition is set to 100% by mass, the content of the component (I) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less.

[0298] When the resin component in the resin composition is 100% by mass, the content of the (I) component is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, preferably 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

[0299] <(J) Other Additives>

[0300] In the case of the resin composition, in addition to the above components, as optional components, other additives may be further contained. As the (J) other additives, for example, 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-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as ureidosilane; 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; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate ester-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photoinitiator assistants such as tertiary amines; and photosensitizers such as pyrarizone-based compounds, anthracene-based compounds, coumarin-based compounds, xanthone-based compounds, and thioxanthone-based compounds. The (J) other additives may be used alone or in combination of two or more.

[0301] <(K) Solvent>

[0302] Regarding the resin composition, in addition to the above-mentioned non-volatile components, as volatile components, any solvent can be further contained. As the (K) solvent, known solvents can be appropriately used, and there is no particular limitation on its type, and an organic solvent is preferred. As the (K) solvent, for example, ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone can be listed; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isopentyl 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; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diethylene glycol acetate, 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. The (K) solvent can be used alone or two or more kinds can be used in any ratio in combination.

[0303] Regarding the resin composition, relative to 100% by mass of all the components of the resin composition, it is preferably to contain 0.5% by mass or more and 3% by mass or less of the (K) solvent. Specifically, the (K) solvent is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1.5% by mass or less, preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and further preferably 1% by mass or more relative to 100% by mass of all the components of the resin composition.

[0304] There is no particular limitation on the method for preparing the resin composition of the present invention. For example, methods such as adding compounding components, solvents as needed, and using a rotary mixer to perform mixing and dispersion can be listed.

[0305] <Physical properties and uses of the resin composition>

[0306] Regarding the resin composition, since the components (A) to (C) are contained in combination, a cured product with a low dielectric loss tangent and a high glass transition temperature can be obtained. In addition, a cured product with excellent crack resistance can usually be obtained.

[0307] The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of low dielectric loss tangent. Therefore, the above-mentioned cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.008 or less, more preferably 0.004 or less, and further preferably 0.003 or less, 0.0025 or less. The lower limit value of the dielectric loss tangent can be 0.0001 or more, etc. The measurement of the dielectric loss tangent can be carried out according to the method described in the examples below.

[0308] Regarding the cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes, since the component (A) can relieve stress, it generally exhibits excellent crack resistance. Therefore, the above-mentioned cured product can form an insulating layer with excellent crack resistance. In one example, by the method described in the examples below, an insulating layer is formed on a circuit board having a conductor layer with a wiring pattern formed on its surface, and a roughening treatment is carried out to obtain a yield. In this case, the yield can be increased. The specific range of the yield is preferably 40% or more, more preferably 60% or more, and further preferably 80% or more.

[0309] Regarding the cured product obtained by thermally curing the resin composition at 190°C for 90 minutes, it exhibits the characteristic of a high glass transition temperature (Tg). Therefore, it provides an insulating layer with a high glass transition temperature. The glass transition temperature is preferably 80°C or more, more preferably 145°C or more, and further preferably 150°C or more. There is no particular limitation on the upper limit of the glass transition temperature of the cured product, and it can be 300°C or less, etc. The glass transition temperature can be measured by the method described in the examples below.

[0310] The resin composition of the present invention can obtain a cured product with a low dielectric loss tangent and a high glass transition temperature. Furthermore, a cured product with excellent crack resistance can generally be obtained. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, it can be suitably used as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for a conductor layer) for forming a conductor layer (including a rewiring layer) formed on an insulating layer.

[0311] In addition, in the multilayer printed wiring board described below, 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).

[0312] Further, for example, in the case of manufacturing a semiconductor chip package 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 formation layer (a resin composition for forming a rewiring formation layer) for an insulating layer for forming a rewiring layer and a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer can be further formed on the sealing layer.

[0313] (1) A step of laminating a temporary fixing film on a substrate,

[0314] (2) A step of temporarily fixing a semiconductor chip on the temporary fixing film,

[0315] (3) A step of forming a sealing layer on the semiconductor chip,

[0316] (4) A step of peeling the substrate and the temporary fixing film from the semiconductor chip,

[0317] (5) A step of 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 are peeled, and

[0318] (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0319] [Resin sheet]

[0320] The resin sheet of the present invention includes: a support; and a resin composition layer provided on the support and formed of the resin composition of the present invention.

[0321] Regarding the thickness of the resin composition layer, from the viewpoints of thinning of the printed wiring board and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film, it is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 50 μm or less. There is no particular limitation on the lower limit of the thickness of the resin composition layer, and it can generally be 5 μm or more, etc.

[0322] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

[0323] When using a film made of a plastic material as the support, examples of the plastic material include polyethyleneterephthalate (hereinafter sometimes simply referred to as "PET"), polyethylene naphthalate (hereinafter sometimes simply referred to as "PEN"), etc. polyesters, polycarbonate (hereinafter sometimes simply referred to as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfone (PES), polyetherketone, polyimide, etc. Among them, polyethyleneterephthalate and polyethylene naphthalate are preferred, and polyethyleneterephthalate with a low price is particularly preferred.

[0324] When using a metal foil as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of single metal of copper can be used, or a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0325] Regarding the support, the surface joined to the resin composition layer can be subjected to matting treatment, corona treatment, antistatic treatment.

[0326] In addition, as the support, a support with a release layer having a release layer on the surface joined to the resin composition layer can be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products can be used as the support with a release layer. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purelex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc., which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0327] The thickness of the support is not particularly limited, and the range of 5 μm to 75 μm is preferred, and the range of 10 μm to 60 μm is more preferred. It should be noted that when using a support with a release layer, it is preferred that the overall thickness of the support with a release layer is within the above range.

[0328] In one embodiment, the resin sheet may further contain other layers as needed. Examples of the other layer include a protective film based on the support provided on the surface of the resin composition layer that is not joined to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, for example, it is 1 μm to 40 μm. By laminating the protective film, the adhesion of garbage, etc. and scratches on the surface of the resin composition layer can be suppressed.

[0329] Regarding the resin sheet, for example, it can be manufactured by preparing a resin varnish in which a resin composition is dissolved in a solvent, coating the resin varnish on a support using a die coater or the like, and then drying it to form a resin composition layer. Regarding the solvent, as described above.

[0330] Drying can be carried out by known methods such as heating and jetting hot air. There are no particular limitations on the drying conditions, and it is dried in such a way that the content of the solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. It also varies depending on the boiling point of the solvent in the resin varnish. For example, in the case of using a resin varnish containing 30% to 60% by mass of the solvent, a resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0331] The resin sheet can be wound into a roll for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0332] [Printed Wiring Board]

[0333] The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention.

[0334] Regarding the printed wiring board, for example, it can be manufactured by a method including the following steps (I) and (II) using the above resin sheet.

[0335] (I) A step of laminating the resin composition layer of the resin sheet on the inner layer substrate in a manner to be joined to the inner layer substrate

[0336] (II) A step of thermally curing the resin composition layer to form an insulating layer

[0337] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board. For example, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. can be cited. In addition, the substrate can have a conductor layer on one or both sides thereof, and the conductor layer can be patterned. Sometimes the inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is called an "inner layer circuit substrate". In addition, in the manufacture of a printed wiring board, an intermediate product for further forming an insulating layer and / or a conductor layer is also included in the "inner layer substrate" as referred to in the present invention. In the case where the printed wiring board is a component-embedded circuit board, an inner layer substrate with components embedded can be used.

[0338] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (such as a SUS mirror plate) or a metal roller (SUS roller) can be cited. It should be noted that it is preferable not to directly press the thermocompression bonding member against the resin sheet, but to press the resin sheet against the surface unevenness of the inner layer substrate through an elastic material such as heat-resistant rubber so that the resin sheet follows sufficiently.

[0339] The lamination of the inner layer substrate and the resin sheet can be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under a reduced pressure condition of 26.7 hPa or less.

[0340] The lamination can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum booster manufactured by Niko Materials Co., Ltd., an intermittent vacuum pressure laminator, etc. can be cited.

[0341] After lamination, the smoothing treatment of the laminated resin sheet can be carried out by pressing the thermocompression bonding member from the support side under normal pressure (atmospheric pressure), for example. The pressing conditions for the smoothing treatment can be set to the same conditions as the thermocompression bonding conditions for the above lamination. The smoothing treatment can be carried out using a commercially available laminator. It should be noted that the lamination and the smoothing treatment can be continuously carried out using the above-mentioned commercially available vacuum laminator.

[0342] The support can be removed between process (I) and process (II), or can be removed after process (II).

[0343] In process (II), the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions for the resin composition layer are not particularly limited, and the conditions usually used when forming the insulating layer of a printed wiring board can be used.

[0344] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, etc., the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and further preferably 170°C to 210°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 100 minutes.

[0345] Before thermally curing the resin composition layer, the resin composition layer can be preheated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin composition layer can be preheated at a temperature of 50°C or higher and less than 120°C (preferably 60°C or higher and 115°C or lower, more preferably 70°C or higher and 110°C or lower) 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).

[0346] When manufacturing a printed wiring board, the processes of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer can be further implemented. These processes (III) to (V) can be implemented according to various methods well-known to those skilled in the art for manufacturing printed wiring boards. It should be noted that when removing the support after process (II), the removal of the support can be carried out between process (II) and process (III), between process (III) and process (IV), or between process (IV) and process (V). Additionally, if necessary, the formation of the insulating layer and the conductor layer in processes (II) to (V) can be repeatedly implemented to form a multilayer wiring board.

[0347] Process (III) is a process of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Regarding process (III), it can be implemented using, for example, a drill bit, a laser, or a plasma according to the composition of the resin composition used in the formation of the insulating layer, etc. The size and shape of the holes can be appropriately determined according to the design of the printed wiring board.

[0348] Process (IV) is a process for roughening the insulating layer. Usually, in this process (IV), removal of stains is also carried out. There are no particular limitations on the steps and conditions of the roughening treatment, and known steps and conditions commonly used when forming the insulating layer of a printed wiring board can be adopted. For example, swelling treatment using a swelling liquid, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing liquid can be sequentially carried out to roughen the insulating layer. There are no particular limitations on the swelling liquid used for the roughening treatment, and examples include an alkali solution, a surfactant solution, etc. An alkali solution is preferred, and as this alkali solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferred. As commercially available swelling liquids, for example, "Swelling Dip Security Gun P", "Swelling Dip Security Gun SBU", "Swelling Dip Security Gun P" manufactured by Atotech Japan Co., Ltd. can be cited. There are no particular limitations on the swelling treatment using the swelling liquid. For example, it can be carried out by immersing the insulating layer in the swelling liquid 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 at an appropriate level, it is preferred to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes. There are no particular limitations on the oxidizing agent used for the roughening treatment. For example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be cited. For the roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution, it is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, for example, alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Security Gun P" manufactured by Atotech Japan Co., Ltd. can be cited. In addition, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferred. As commercially available products, for example, "Reduction Solution Security Gun P" manufactured by Atotech Japan Co., Ltd. can be cited. For the treatment using the neutralizing liquid, it can be carried out by immersing the treated surface that has undergone the roughening treatment using the oxidizing agent in the neutralizing liquid at 30°C to 80°C for 1 minute to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object that has undergone the roughening treatment using the oxidizing agent in the neutralizing liquid at 40°C to 70°C for 5 minutes to 20 minutes is preferred.

[0349] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the roughened insulating layer is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 200 nm or less. There is no particular limitation on the lower limit, and it is preferably 30 nm or more, more preferably 40 nm or more, and still more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

[0350] Process (V) is a process of forming a conductor layer, and a conductor layer is formed on the insulating layer. There is no particular limitation on the conductor material used in the conductor layer. In a preferred embodiment, the conductor layer contains 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 of an alloy of two or more metals selected from the above group (such as nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) can be cited. Among them, from the viewpoints of the versatility of conductor layer formation, cost, ease of patterning, etc., 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 is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single metal layer of copper is still more preferred.

[0351] The conductor layer can be a single-layer structure, or a multilayer structure in which two or more single metal layers or alloy layers composed of different metals or alloys are laminated. In the case where the conductor layer is a multilayer 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.

[0352] The thickness of the conductor layer depends on the design of the desired printed wiring board, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0353] In one embodiment, the conductor layer can be formed by plating. For example, by using a conventionally known technique such as semi-additive method or full-additive method to plate on the surface of the insulating layer, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming a conductor layer by the semi-additive method is shown.

[0354] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Secondly, on the formed plating seed layer, a mask pattern is formed according to the desired wiring pattern so that a part of the plating seed layer is exposed. After forming a metal layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[0355] [Semiconductor Device]

[0356] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0357] Examples of semiconductor devices include various semiconductor devices for electrical products (such as computers, mobile phones, digital cameras, and televisions, etc.) and transportation means (such as motorcycles, automobiles, trams, ships, and aircraft, etc.).

[0358] The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on the conductive parts of the printed wiring board. The so-called "conductive part" is "the part in the printed wiring board that transmits electrical signals", and its location can be on the surface or an embedded part, either is acceptable. In addition, for semiconductor chips, as long as they are circuit elements made of semiconductors, there is no particular limitation.

[0359] Regarding the method of mounting semiconductor chips when manufacturing semiconductor devices, as long as the semiconductor chips function effectively, there is no particular limitation. Specifically, examples include wire bonding mounting methods, flip chip mounting methods, mounting methods using a bump-less build-up layer (BBUL), mounting methods using an anisotropic conductive film (ACF), mounting methods using a non-conductive film (NCF), etc. Among them, the so-called "mounting method using a bump-less build-up layer (BBUL)" refers to "a mounting method of directly embedding a semiconductor chip in the recess of a printed wiring board and connecting the semiconductor chip to the wiring on the printed wiring board".

[0360] Examples

[0361] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. It should be noted that in the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0362] The conditions of GPC used in the measurement of number average molecular weight, etc. are as described below.

[0363] Measuring device: "HLC-8420GPC" manufactured by Tosoh Corporation

[0364] Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ2000" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ2000" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ3000" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ4000" manufactured by Tosoh Corporation

[0365] Detector: RI (differential refractometer)

[0366] Data processing: "GPC Workstation Eco SEC-Work Station" manufactured by Tosoh Corporation

[0367] Column temperature: 40 °C

[0368] Developing solvent: Tetrahydrofuran

[0369] Flow rate: 0.35 mL / min

[0370] Standard: According to the measurement manual of the above-mentioned "GPC Workstation Eco SEC-Work Station", for molecular weight, the following known monodisperse polystyrene is used.

[0371] TSKgel F-10, F-4, F-1, A-5000, A-1000, A-500 (manufactured by Tosoh Corporation)

[0372] Sample: The product obtained by filtering a tetrahydrofuran solution containing 0.2% by mass of resin solid content with a microfilter (10 μL)

[0373] <Example 1A: Synthesis of silicone resin 1>

[0374] In a eggplant-shaped flask equipped with a Dean-Stark apparatus, 3.5 g of diphenylsilanediol, 0.71 g of 3-glycidoxypropyl(dimethoxy)methylsilane, 3.0 g of dimethoxy(methyl)phenylsilane, and 153 mg of barium hydroxide monohydrate were added, and the mixture was stirred at 85 °C for 5 hours under an argon atmosphere. After cooling to room temperature, toluene was added, and the unnecessary substances were filtered off. By concentration under reduced pressure, 6 g of a colorless transparent oily silicone resin 1 was obtained. It was dissolved in toluene to obtain the target silicone-based epoxy resin 1 with a solid content concentration of 50% by mass (number average molecular weight 2690, active group equivalent about 1345 g / eq., non-volatile component ratio 50%). Silicone resin 1 was identified using an NMR apparatus (nuclear magnetic resonance apparatus: Bruker AVANCE 400 (400 MHz)), and it was confirmed to have the following three structural units (where * represents the bonding end).

[0375] 1 H-NMR (400 MHz, chloroform-d) δ 7.71~7.12 (m, 100H), 7.12~6.72 (m, 50H), 3.51~2.84 (m, 8H), 2.82~2.62 (m, 3H), 2.61~2.41 (m, 3H), 1.82~1.42 (m, 6H), 0.48~0.17 (m, 6H), 0.06~ -0.33 (m, 30H).

[0376]

Chemical formula 31

[0377]

[0378] <Example 2A: Synthesis of Silicone Resin 2>

[0379] In a eggplant-shaped flask equipped with a Dean-Stark apparatus, 5.0 g of diphenylsilanediol, 1.02 g of 3-glycidoxypropyl(dimethoxy)methylsilane, 4.2 g of dimethoxy(methyl)phenylsilane, and 219 mg of barium hydroxide monohydrate were added, and the mixture was stirred at 85 °C for 3 days under an argon atmosphere. After cooling to room temperature, toluene was added, and unnecessary substances were filtered off. By concentration under reduced pressure, 10 g of a colorless transparent oily silicone resin 2 was obtained. It was dissolved in toluene to obtain the target silicone resin 2 with a solid content concentration of 50% by mass (number average molecular weight 7870, active group equivalent about 393 g / eq., non-volatile content rate 50%). The silicone resin 2 was identified using an NMR apparatus (nuclear magnetic resonance apparatus: Bruker AVANCE 400 (400 MHz)), and it was confirmed to have the following three structural units (where * represents the bonding end in the formula).

[0380] 1 H-NMR (400 MHz, chloroform-d) δ 7.72 - 7.13 (m, 100H), 7.12 - 6.73 (m, 50H), 3.49 - 2.85 (m, 3H), 2.82 - 2.61 (m, 1H), 2.60 - 2.42 (m, 1H), 1.83 - 1.42 (m, 2H), 0.50 - 0.15 (m, 2H), 0.07 - -0.34 (m, 30H).

[0381] [Chemical Formula 32]

[0382]

[0383] <Example 3A: Synthesis of Silicone Resin 3>

[0384] In a round-bottomed flask equipped with a Dean-Stark apparatus, 3.5 g of diphenylsilanediol, 0.71 g of 3-glycidoxypropyl(dimethoxy)methylsilane, 3.0 g of cyclohexyl(dimethoxy)methylsilane, and 153 mg of barium hydroxide monohydrate were added, and the mixture was stirred at 85 °C for 8 hours under an argon atmosphere. After cooling to room temperature, toluene was added, and the unnecessary substances were filtered off. By concentration under reduced pressure, 6.2 g of a colorless transparent oily silicone resin 3 was obtained. It was dissolved in toluene to obtain the target silicone-based epoxy resin 3 (number average molecular weight 3105, active group equivalent about 1553 g / eq., non-volatile content rate 50%) with a solid component concentration of 50% by mass. The silicone-based resin 3 was identified using an NMR apparatus (nuclear magnetic resonance apparatus: Bruker AVANCE 400 (400 MHz)), and it was confirmed to have the following three structural units (where * represents the bonding end in the formula).

[0385] 1 H-NMR (400 MHz, chloroform-d) δ 7.6 - 7.02 (m, 100H), 3.75 - 2.85 (m, 50H), 2.81 - 2.60 (m, 10H), 2.59 - 2.41 (m, 10H), 1.86 - 1.66 (m, 6H), 1.66 - 1.02 (m, 26H), 0.98 - 0.76 (m, 2H), 0.65 - 0.18 (m, 21H), 0.17 - -0.33 (m, 35H).

[0386]

Chemical formula 33

[0387]

[0388] <Synthesis Example 1: Synthesis of GPR (Glycidyl Epoxy / Phenyl Linear Siloxane Matrix Resin)>

[0389] Diphenylsilanediol and 3-glycidoxypropyl(dimethoxy)methylsilane were mixed at a molar ratio of 1:1, and barium hydroxide monohydrate was mixed at a ratio of 0.2 mol% relative to the silicone resin. The mixture was mixed at 80 °C for several hours under a nitrogen atmosphere to obtain the target GPR. GPR has the following structural units.

[0390]

Chemical formula 34

[0391]

[0392] <Synthesis Example 2: Synthesis of Maleimide A>

[0393] Prepare a MEK solution of maleimide A synthesized by the method described in Synthesis Example 1 of the Invention Association's Technical Bulletin Publication No. 2020-500211 (non-volatile component: 62% by mass, t” = 1.47 (mainly 1, 2, or 3), Mw / Mn = 1.81). This maleimide A has a structure represented by the following formula (1).

[0394]

Chemical Formula 35

[0395]

[0396] <Synthesis Example 3: Synthesis of Polyimide B>

[0397] Prepare a 500 mL separable flask equipped with a moisture quantitative receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer. Into this flask, add 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane. Stir at 45 °C for 2 hours under a nitrogen stream to carry out the reaction. Next, raise the temperature of this reaction solution and azeotropically remove the condensed water together with toluene while maintaining at about 160 °C under a nitrogen stream. Confirm that a specified amount of water accumulates in the moisture quantitative receiver and no water flows out. After confirmation, further raise the temperature of the reaction solution and stir at 200 °C for 1 hour. Then, cool 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.

[0398]

Chemical Formula 36

[0399]

[0400] <Manufacture of Resin Varnish>

[0401] Weigh each component in the mass parts described in the table, and further mix 15 parts of MEK and 2 parts of cyclohexanone, and disperse uniformly using a high-speed rotary mixer to obtain a resin varnish.

[0402]

Table 1

[0403]

[0404]

[0405] The details of each component described in the table are as follows.

[0406] (A) Component

[0407] · Silicone resin 1: The product synthesized in Example 1A

[0408] · Silicone resin 2: The product synthesized in Example 2A

[0409] · Silicone resin 3: The product synthesized in Example 3A

[0410] (B) Component

[0411] · HPC-8150-62T: An active ester curing agent, an active ester resin having a naphthalene structure, functional group equivalent 223 g / eq., manufactured by DIC Corporation

[0412] · HPC-8000L-65MT: An active ester resin containing a dicyclopentadiene-type diphenol structure, functional group equivalent 229 g / eq., manufactured by DIC Corporation

[0413] · PC1300-02-65MA: An active ester resin having a naphthalene structure, functional group equivalent 199 g / eq., manufactured by Air Water

[0414] · LA-3018-50P: A 1-methoxy-2-propanol solution with a functional group equivalent of 151 g / eq. and a non-volatile content of 50% by mass, manufactured by DIC Corporation

[0415] · V-03: A toluene solution with a functional group equivalent of 216 g / eq. and a non-volatile content of 50% by mass, manufactured by Nisshinbo Chemicals, Inc.

[0416] · BA230S75: A prepolymer of bisphenol A dicyanate, functional group equivalent 232 g / eq., manufactured by arxada

[0417] · MHHPA: Methylhexahydrophthalic anhydride (manufactured by Sigma-Aldrich)

[0418] (C) Component

[0419] · SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm, specific surface area 5.8 m 2 / g, manufactured by Admatechs

[0420] · UFP-30: Spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.3 μm, specific surface area 30.7 m 2 / g, manufactured by Denka

[0421] (D) Component

[0422] · NC-3000-L: Biphenyl type epoxy resin (functional group equivalent: 269 g / eq., manufactured by Nippon Kayaku Co., Ltd.)

[0423] · ZX-1059: 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent: 169 g / eq.)

[0424] · 840-S: Bisphenol A type epoxy resin (functional group equivalent: 180 - 190 g / eq., manufactured by DIC Corporation)

[0425] · GPR: Glycidyl epoxy / phenyl linear silicone matrix resin, the product synthesized in Synthesis Example 1

[0426] (Component (E))

[0427] · Maleimide A: The product synthesized in Synthesis Example 4, a maleimide-based free radical polymerizable compound

[0428] · ODV-XET-X04: Styrene-based free radical polymerizable compound, manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0429] · OPE-2St: Vinylbenzyl-modified polyphenylene ether (manufactured by Mitsubishi Gas Chemical Company, toluene solution with non-volatile content rate of 65%)

[0430] · A-DOG: Dioxane diol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0431] (Component (F))

[0432] · YX7553BH30: Phenoxy resin, 1:1 solution of MEK and cyclohexanone with 30 mass% non-volatile content, manufactured by Mitsubishi Chemical Corporation

[0433] · Polyimide B: The product synthesized in Synthesis Example 3

[0434] (Component (G))

[0435] · 2-Methylimidazole: Imidazole-based reaction accelerator

[0436] · 1B2PZ: Imidazole-based reaction accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd.

[0437] · DMAP: Amine-based curing accelerator, manufactured by Tokyo Chemical Industry Co., Ltd.

[0438] · Co(III): Metal-based curing accelerator, manufactured by Tokyo Chemical Industry Co., Ltd.

[0439] (Component (H))

[0440] · Perbutyl C: A free radical polymerization initiator, tert-butyl cumyl peroxide (manufactured by NOF Corporation)

[0441] (I) component

[0442] · EXL2655: Core-shell graft copolymer rubber particles, manufactured by The Dow Chemical Company

[0443] <Measurement of the average particle diameter of the inorganic filler>

[0444] Weigh 100 mg of the inorganic filler, 0.1 g of the dispersant ("SN9228" manufactured by San Nopco Limited), and 10 g of methyl ethyl ketone in a vial, and disperse them ultrasonically for 20 minutes. Using a laser diffraction particle size distribution analyzer ("SALD-2200" manufactured by Shimadzu Corporation), measure the particle size distribution in the batch cell method, and calculate the average particle diameter based on the median diameter.

[0445] <Measurement of the dielectric loss tangent and glass transition temperature>

[0446] (1) Preparation of resin sheet A with a resin composition layer thickness of 40 μm

[0447] As the support, prepare a polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm). On the release layer of this support, uniformly coat the resin varnishes obtained in the examples and comparative examples so that the thickness of the dried resin composition layer becomes 40 μm. Then, dry the resin composition at 80°C to 100°C (average 90°C) for 2 minutes to obtain resin sheet A containing the support and the resin composition layer.

[0448] (2) Preparation of the cured product of the resin composition layer

[0449] Cure the prepared resin sheet A in an oven at 190°C for 90 minutes. Peel off the support from the resin sheet A taken out of the oven to obtain the cured product of the resin composition layer.

[0450] (3) Measurement of the dielectric loss tangent (dielectric properties)

[0451] Cut the cured product of the resin composition layer into 80 mm in length and 2 mm in width, and use "HP8362B" manufactured by Agilent Technologies to measure the value of the dielectric loss tangent (Df value) at a measurement frequency of 5.8 GHz, measurement temperatures of 23°C and 90°C by the cavity resonance perturbation method (hollow resonance perturbation method). Perform the measurement using 2 test pieces and calculate their average.

[0452] (4) Measurement of the glass transition temperature

[0453] The cured product of the resin composition layer was cut to obtain a test piece approximately 5 mm wide and 15 mm long. For this test piece, a thermomechanical analysis was performed using a thermomechanical analyzer (manufactured by RIGAKU CORPORATION, "Thermo Plus TMA8310") by the tensile loading method. Specifically, after mounting the test piece on the above thermomechanical analyzer, two consecutive measurements were carried out under the measurement conditions of a load of 1 g and a heating rate of 5 °C / minute. Then, in the second measurement, the glass transition temperature Tg (°C) was calculated.

[0454]

Table 3

[0455] (Table 3)

[0456]

[0457] <Evaluation of crack resistance>

[0458] (1) Lamination of resin sheet A

[0459] Prepare an inner layer substrate (manufactured by Resonac Corporation, "MCL-E700G") with circuit conductors (copper) formed with a wiring pattern of L / S = 8 μm / 8 μm on both sides. The thickness of the conductor layer is 35 μm, the total thickness is 0.4 mm, and the residual copper rate is 40%). Resin sheet A was laminated on both sides of this inner layer substrate in such a way that the resin composition layer was in contact with the inner layer substrate. For this laminate, after evacuating for 30 seconds at 120 °C using a vacuum pressure laminator (manufactured by Meiki Seisakusho Co., Ltd., "MVLP-500"), it was pressed for 30 seconds from the support body via a heat-resistant rubber at 120 °C and a pressure of 7.0 kg / cm 2 under the conditions. Next, under atmospheric pressure, using a SUS mirror plate, it was pressed for 60 seconds at 120 °C and a pressure of 5.5 kg / cm 2 under the conditions.

[0460] (2) Thermal curing of the resin composition layer

[0461] The inner layer substrate laminated with resin sheet A was heated at 130 °C for 30 minutes, and then at 170 °C for 30 minutes to thermally cure the resin composition layer to obtain an insulating layer. Then, the support body was peeled off to obtain a sample substrate having a layer structure of insulating layer / inner layer substrate / insulating layer.

[0462] (3) Roughening treatment

[0463] The insulating layer of the test substrate is roughened. Specifically, the test substrate is immersed in Swelling Dip & Securigant P manufactured by Atotech Japan Co., Ltd. as a swelling liquid at 60 °C for 10 minutes. Next, it is immersed in Concentrate Compact P (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) manufactured by Atotech Japan Co., Ltd. as a roughening liquid at 80 °C for 20 minutes. Finally, it is immersed in Reduction Solution & Securigant P manufactured by Atotech Japan Co., Ltd. as a neutralizing liquid at 40 °C for 5 minutes.

[0464] (4) Evaluation of crack resistance

[0465] In the surface of the insulating layer after the roughening treatment, the part on the L / S pattern of the inner substrate is observed. Along the pattern shapes of 100 inner substrates, it is confirmed whether cracks (cracking) are generated on the surface, and the ratio of the number of parts on the pattern where no cracks are generated is counted. This ratio is calculated as the "yield". In addition, for the calculated yield, the following criteria are used for scoring.

[0466] 1 point: 0% or more and less than 20%.

[0467] 2 points: 20% or more and less than 40%.

[0468] 3 points: 40% or more and less than 60%.

[0469] 4 points: 60% or more and less than 80%.

[0470] 5 points: 80% or more.

[0471] A score of 3 points or more is recorded as "○", and a score of 2 points or less is recorded as "×" for evaluation.

[0472]

[0473] For Example 1, the crack resistance was also evaluated in the same manner as in Example 2. As a result, it was confirmed that the same results as in Example 2 were obtained.

Claims

1. A silicone resin comprising: a structural unit represented by the following formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3), In formula (A-1), R 1 represents a group represented by the following formula (A-1a) or a group represented by the following formula (A-1b), R 2 represents a monovalent hydrocarbon group which may have a substituent, * represents a bonding end, In formula (A-2), R 3 and R 4 Each independently represents a monovalent hydrocarbon group which may have a substituent, * represents a bonding end, In formula (A-3), R 5 and R 6 Each independently represents a monovalent hydrocarbon group which may have a substituent, or a hydrogen atom, and * represents a bonding end. However, R 5 is the same as R in formula (A-2) 3 and R 4 Different groups, In formula (A-1a), n1 represents an integer of 2 to 10, * represents a bonding end to the silicon atom in formula (A-1), In the formula (A-1b), n2 represents an integer of 1 to 10, and * represents a bonding end to the silicon atom in the formula (A-1).

2. The organic silicone resin according to claim 1, wherein In formula (A-1), R 2 It represents an alkyl group which may have a substituent.

3. The organic silicone resin according to claim 1, wherein In formula (A-2), R 3 and R 4 Each independently represents an aryl group which may have a substituent.

4. The organic silicone resin according to claim 1, wherein In formula (A-2), R 3 and R 4 Each independently represents a phenyl group which may have a substituent, or a naphthyl group which may have a substituent.

5. The organic silicone resin according to claim 1, wherein In formula (A-3), R 5 represents a hydrogen atom, an aryl group which may have a substituent, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent.

6. The organic silicone resin according to claim 1, wherein In formula (A-3), R 6 It represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.

7. The organic silicone resin according to claim 1, wherein The number average molecular weight is 10,000 or less.

8. The organic silicone resin according to claim 1, wherein The number average molecular weight is 7,000 or less.

9. A resin composition comprising: (A) the silicone resin according to any one of claims 1 to 8, (B) curing agent, and (C) Inorganic filling materials.

10. The resin composition according to claim 9, wherein The component (B) contains an active ester-based curing agent.

11. The resin composition according to claim 9, wherein The component (B) contains a phenolic curing agent.

12. The resin composition according to claim 9, wherein The component (B) contains an acid anhydride-based curing agent. 13 . The resin composition according to claim 9 , further comprising (E) a radical polymerizable compound.

14. The resin composition according to claim 13, wherein The component (E) contains a maleimide-based radical polymerizable compound. 15 . A resin sheet comprising: a support; and a resin composition layer provided on the support and comprising the resin composition according to claim 9 . 16 . A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to claim 9 .

17. A semiconductor device comprising: the printed wiring board according to claim 16.

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