Silicone resin

Abstract

To provide a silicone resin from which a cured product having low dielectric loss tangent and high glass transition temperature can be obtained.SOLUTION: A silicone resin has three kinds of structural units, specifically, the following structural units.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked 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, Non-Patent Document 1 discloses materials that can be used as insulating materials.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Non-Patent Documents

[0005]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] In recent years, with the increasing functionality of printed wiring boards, the insulating layer of printed wiring boards is required to have a low dielectric tangent and improved mechanical strength. To improve mechanical strength, it is required to increase the glass transition temperature of the insulating layer.

[0007] The object of the present invention was 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 resin composition; a printed wiring board provided with an insulating layer formed using the resin composition, and a semiconductor device.

Means for Solving the Problems

[0008] As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a silicone resin having a predetermined structure, and have completed the present invention.

[0009] That is, the present invention includes the following. [1] A silicone resin having 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).

Chemical formula

Chemical formula

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

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

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

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

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

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

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

[14] The resin composition according to

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

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

[14] .

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

[14] .

[17] A semiconductor device including the printed wiring board according to

[16] . [Effects of the Invention]

[0010] According to the present invention, there can be provided a silicone resin capable of obtaining a cured product having a low dielectric tangent and a high glass transition temperature; a resin composition containing the silicone resin; a resin sheet including a resin composition layer containing the resin composition; a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board. [Embodiments for Carrying Out the Invention]

[0011] Hereinafter, the present invention will be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope. Hereinafter, the silicone resin having 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) may be simply referred to as "silicone resin".

[0012] [Silicone Resin] 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).

Chem.

Chem.

[0013] The silicone resin of the present invention can provide a cured product having a low dielectric loss tangent and a high glass transition temperature. Further, since the silicone resin of the present invention usually has a Si-O skeleton, the stress of the resin composition is relaxed, and as a result, a cured product in which the generation of cracks is suppressed can also be provided. Hereinafter, the silicone resin of the present invention will be described in detail.

[0014] 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, a block copolymer, a graft copolymer, or an alternating 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). Further, the silicone resin of the present invention may contain other structural units within a range that does not inhibit the effects 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).

[0015] In formula (A-1), R 1 represents a group represented by formula (A-1a) or a group represented by formula (A-1b).

[0016] 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.

[0017] 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.

[0018] In formula (A-1), R 2 represents a monovalent hydrocarbon group which may have a substituent. The 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 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, and the like.

[0019] The alkyl group means a monovalent aliphatic saturated hydrocarbon group that is linear or branched. 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. Among them, the methyl group is preferred.

[0020] The 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 dicyclopentanyl group, etc. Among them, the cyclopentyl group and the cyclohexyl group are preferred.

[0021] An alkenyl group means a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. Unless otherwise specified, an alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 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), and the like.

[0022] An aryl group means a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. Unless otherwise specified, an aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc., and among them, a phenyl group is preferred.

[0023] An aralkyl group means an alkyl group substituted with one or more (preferably one) aryl groups. Unless otherwise specified, an aralkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, and even more preferably 7 to 11 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, a hydrocinnamyl group, an α-methylbenzyl group, an α-cumyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, and the like.

[0024] An alkylaryl group means an aryl group substituted with one or more (preferably one) alkyl groups. Unless otherwise specified, the alkylaryl group is preferably an alkylaryl group having 7 to 15 carbon atoms, more preferably an alkylaryl group having 7 to 11 carbon atoms. Examples of the alkylaryl group include a 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-isopropylphenyl group, 3-isopropylphenyl group, 2-isopropylphenyl group, etc. Among them, a 4-methylphenyl group is preferred.

[0025] The monovalent hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom, -OH, -O-C 1-6 alkyl group, -N(C 1-10 alkyl group)2, C 1-20 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 6-10 aryl group, cyano group, -NH2, -CN, -C(O)O-C 1-10 alkyl group, -COOH, -C(O)H, -NO2, etc. Here, the term "C p-q " (where p and q are positive integers and p < q) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression "C 1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure includes spiro rings and fused rings.

[0026] In formula (A-1), the monovalent hydrocarbon group which may have a substituent represented by R 1 is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably an alkyl group which may have a substituent, and even more preferably a methyl group.

[0027] Specific examples of the structural unit represented by formula (A-1) include structural units represented by formulas (A-1-1) to (A-1-2), but the present invention is not limited thereto. In the formula, * represents a bond.

Chemical formula

[0028] As the structural unit represented by formula (A-1), the structural unit represented by formula (A-1-1) is preferred.

[0029] 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).

[0030] 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.

[0031] Specific examples of the structural unit represented by formula (A-2) include structural units represented by formulas (A-2-1) to (A-2-3), but the present invention is not limited thereto. In the formula, * represents a bond.

Chemical formula

[0032] As the structural unit represented by formula (A-2), the structural unit represented by formula (A-2-1) is preferred.

[0033] 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, R5 and R 6 When R represents a monovalent hydrocarbon group which may have a substituent, R 5 in formula (A-2) 3 and R 4 are different groups.

[0034] R 5 and R 6 The monovalent hydrocarbon group which may have a substituent represented by is the same as the monovalent hydrocarbon group which may have a substituent represented by R in formula (A-1). 2

[0035] In formula (A-3), the monovalent hydrocarbon group which may have a substituent represented by R 5 is preferably 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, more preferably a phenyl group which may have a substituent, a cyclohexyl group which may have a substituent, a cyclopentyl group which may have a substituent, or a methyl group which may have a substituent, and even more preferably a methyl group.

[0036] In formula (A-3), as the monovalent hydrocarbon group which may have a substituent represented by R 6 is preferably 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, more preferably a methyl group which may have a substituent, a cyclopentyl group which may have a substituent, a cyclohexyl group which may have a substituent, or a phenyl group which may have a substituent, and even more preferably a phenyl group or a cyclohexyl group.

[0037] Among them, in particular, R in formula (A-3) 5preferably represents a monovalent hydrocarbon group which may independently have a substituent, or a hydrogen atom, more preferably 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, still more preferably represents a cycloalkyl group which may have a substituent, or an alkyl group which may have a substituent, and particularly preferably represents a methyl group.

[0038] Among them, R in formula (A-3) 6 preferably represents a monovalent hydrocarbon group which may independently have a substituent, more preferably 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, and still more preferably represents a cyclohexyl group which may have a substituent, or a phenyl group which may have a substituent.

[0039] Specific examples of the structural unit represented by formula (A-3) include structural units represented by formulas (A-3-1) to (A-3-13), but the present invention is not limited thereto. In the formula, * represents a bond. [Chemical formula] [Chemical formula]

[0040] 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 preferable.

[0041] 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 or may not be linked to each other as repeating units. When they are not linked to each other, it is preferable that a structural unit represented by the formula (A-2), a structural unit represented by the formula (A-3), or another structural unit is interposed between the plurality of structural units represented by the formula (A-1). 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.

[0042] With respect to 100 mol% of the whole 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, and preferably 20 mol% or less, more preferably 15 mol% or less, and still more preferably 12 mol% or less.

[0043] 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 or may not be linked to each other as repeating units. When they are not linked to each other, it is preferable that a structural unit represented by the formula (A-1), a structural unit represented by the formula (A-3), or another structural unit is interposed between the plurality of structural units represented by the formula (A-2). 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.

[0044] With respect to 100% by mass of the total mass of the molecules of 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, and preferably 55 mol% or less, more preferably 53 mol% or less, still more preferably 50 mol% or less.

[0045] In component (A), the number of the structural units represented by the formula (A-3) is 1 or more, preferably 100 or less, more preferably 50 or less, 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-3) may be linked to each other using the structural unit represented by the formula (A-3) as a repeating unit, or may not be linked to each other. When they are not linked to each other, it is preferable that a structural unit represented by the formula (A-1), a structural unit represented by the formula (A-2), or another structural unit is interposed between the plurality of structural units represented by the formula (A-3). Further, when there are a plurality of structural units represented by the formula (A-3), R 5 and R 6 may be the same or different.

[0046] With respect to 100% by mass of the total mass of the molecules of component (A), the amount of the structural unit represented by the formula (A-3) is preferably 40 mol% or more, more preferably 42 mol% or more, still more preferably 45 mol% or more, and preferably 55 mol% or less, more preferably 53 mol% or less, still more preferably 50 mol% or less.

[0047] In the total molecules of component (A), when the amount of the structural unit represented by the formula (A-1) is a1, the amount of the structural unit represented by the formula (A-2) is b1, and the amount of the structural unit represented by the formula (A-3) is c1, it is preferable to satisfy the relationship of a1 < b1 + c1.

[0048] a1 / b1 is preferably 0.05 or more, more preferably 0.08 or more, still more preferably 0.1 or more, and preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.2 or less.

[0049] a1 / c1 is preferably 0.05 or more, more preferably 0.08 or more, even more preferably 0.1 or more, and is preferably 0.5 or less, more preferably 0.3 or less, even more preferably 0.2 or less.

[0050] b1 / c1 is preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 1.0 or more, and is preferably 1.2 or less, more preferably 1.1 or less, and even more preferably 1.0 or less.

[0051] In addition, (b1+c1) / a1 is preferably 10 or more, more preferably 15 or more, and even more preferably 20 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.

[0052] The terminal structure of the silicone resin of the present invention is, for example, R 2 Preferred is a monovalent hydrocarbon group, a hydroxy group, an alkoxy group, an alkenyloxy group, an aryloxy group, or an aralkyloxy group represented by the formula (I), more preferred is an alkyl group, an aryl group, a hydroxy group, or an alkoxy group, still more preferred is an alkyl group, a hydroxy group, or an alkoxy group, and particularly preferred is a hydroxy group or an alkoxy group.

[0053] An alkoxy group is a monovalent group formed by bonding an alkyl group to an oxygen atom (i.e., R A1 -O-(R A1 means a group represented by an alkyl group). Unless otherwise specified, the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and even more preferably an alkoxy group having 1 to 3 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, and the like, and a methoxy group is preferred.

[0054] An alkenyloxy group is a monovalent group formed by bonding an alkenyl group to an oxygen atom (i.e., R A2-O-(R A2 (wherein R is an alkenyl group). Unless otherwise specified, the alkenyloxy group is preferably an alkenyloxy group having 2 to 18 carbon atoms, more preferably an alkenyloxy group having 2 to 10 carbon atoms, and even more preferably an alkenyloxy group having 2 to 6 carbon atoms. Examples of the alkenyloxy group include a vinyloxy group, a propenyloxy group (allyloxy group, 1-propenyloxy group, isopropenyloxy group), etc.

[0055] The aryloxy group means a monovalent group formed by bonding an aryl group to an oxygen atom (i.e., R A3 -O-(R A3 is an aryl group). Unless otherwise specified, the aryloxy group is preferably an aryloxy group having 6 to 18 carbon atoms, more preferably an aryloxy group having 6 to 10 carbon atoms. Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, etc.

[0056] The aralkyloxy group means a monovalent group formed by bonding an aralkyl group to an oxygen atom (i.e., R A4 -O-(R A4 is an aralkyl group). Unless otherwise specified, the aralkyloxy group is preferably an aralkyloxy group having 7 to 19 carbon atoms, more preferably an aralkyloxy group having 7 to 11 carbon atoms. Examples of the aralkyloxy group include a benzyloxy group, an α-methylbenzyloxy group, etc.

[0057] The alkoxy group, alkenyloxy group, aryloxy group, and aralkyloxy group may have a substituent. The substituent is the same as the substituent that the monovalent hydrocarbon group represented by R in the formula (A-1) may have. 2 is the same as the substituent that the monovalent hydrocarbon group represented by R in the formula (A-1) may have.

[0058] The silicone resin of the present invention may have a structural unit represented by the following formula (A-4).

Chemical formula

[0059] In formula (A-4), R 11 represents a group represented by formula (A-1a) or a group represented by formula (A-1b). The groups represented by formula (A-1a) and formula (A-1b) are as described above.

[0060] 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 a 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 a monovalent hydrocarbon group which may have a substituent represented by R 3 , R 4 in formula (A-2).

[0061] 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 a monovalent hydrocarbon group which may have a substituent represented by R 5 , R 6 in formula (A-3).

[0062] In formula (A-4), a, b, and c each independently represent an integer from 1 to 20 and satisfy the relationship a < b + c. Preferably, a represents an integer from 1 to 10, more preferably an integer from 1 to 6, still more preferably an integer from 1 to 3, and particularly preferably 1. Preferably, b and c represent integers from 1 to 18, and more preferably integers from 3 to 15. a, b, and c can be determined from the charging ratio of the raw materials in synthesizing the silicone resin.

[0063] Specific examples of the silicone resin include silicone resins represented by (A1) to (A78), but the present invention is not limited thereto. In the formula, * represents a bond.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0064] The synthesis method of the silicone resin is not particularly limited. 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) a glycidyl group-containing alkoxysilane compound, a glycidyl group-containing aryloxysilane compound, an epoxycyclohexyl group-containing alkoxysilane compound, or an epoxycyclohexyl group-containing aryloxysilane compound 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 conditions are 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.

[0065] 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, and preferably 15,000 or less, more preferably 12,000 or less, 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 the gel permeation chromatography (GPC) method.

[0066] 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, and 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 the gel permeation chromatography (GPC) method.

[0067] 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, and 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.

[0068] [Resin Composition] 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 combining and containing the components (A), (B), and (C), a cured product having a low dielectric tangent and a high glass transition temperature can be obtained. Further, a cured product excellent in crack resistance can usually be obtained.

[0069] The resin composition may further contain optional components in combination with components (A) to (C). Examples of the optional components include (D) epoxy resin, (E) radically polymerizable compound, (F) high molecular weight component, (G) curing accelerator, (H) radical polymerization initiator, (I) organic filler, (J) other additives, and (K) solvent, etc. Hereinafter, each component contained in the resin composition will be described in detail.

[0070] <(A) silicone resin> The resin composition contains (A) silicone resin as component (A). The (A) silicone resin contained in the resin composition is as described in the above [Silicone Resin] section. Component (A) may be used alone or in combination of two or more.

[0071] When the non-volatile components in the resin composition are 100% by mass, the content of component (A) 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, 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, and preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less.

[0072] When the resin components in the resin composition are 100% by mass, the content of component (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more 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, still more preferably 50% by mass or more, and preferably 70% by mass or less, more preferably 65% by mass or less, still more 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.

[0073] In the present invention, unless otherwise specified, the content of each component in the resin composition is a value based on 100% by mass of the non-volatile components in the resin composition. The non-volatile components mean the entire non-volatile components excluding the solvent in the resin composition. Further, in the present invention, the resin component in the resin composition represents the component excluding the (C) inorganic filler among the non-volatile components of the resin composition.

[0074] <(B) curing agent> The resin composition contains a (B) curing agent as the (B) component. The (B) curing agent as the (B) component does not include those corresponding to the (A) component. The (B) component usually has a function of reacting with the (D) component described later to cure the resin composition. The (B) component may be used alone or in combination of two or more in any ratio.

[0075] As the (B) component, a compound capable of reacting with the (D) component 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 mentioned. Among them, as the (B) component, it is preferably included any one of active ester-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and carbodiimide-based curing agents, more preferably includes an active ester-based curing agent, even more preferably includes any one of active ester-based curing agents, phenol-based curing agents, and acid anhydride-based curing agents, and even more preferably includes an active ester-based curing agent.

[0076] Examples of the active ester-based curing agent include curing agents having one or more active ester groups in one molecule. Among them, as the active ester-based curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferable. The 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.

[0077] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc.

[0078] Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0079] Preferable specific examples of the active ester curing agent include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated product of phenol novolac, and an active ester curing agent containing a benzoylated product of phenol novolac. Among them, an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

[0080] Commercially available products of the active ester curing agent include, as an active ester curing agent containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC Corporation); as an active ester curing agent containing a naphthalene structure, "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T", "EXB9416-70BK", "EXB-8151-62T" (manufactured by DIC Corporation); as an active ester curing agent containing an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester curing agent containing a benzoylated product of phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation); as an active ester curing agent which is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester curing agent which is a benzoylated product of phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and the like.

[0081] Examples of phenolic curing agents include curing agents 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, compounds having a hydroxyl group bonded to a benzene ring are preferred. Also, from the viewpoints of heat resistance and water resistance, phenolic curing agents having a novolak structure are preferred. Further, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and phenolic curing agents containing a triazine skeleton are more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, phenolic novolak curing agents containing a triazine skeleton are preferred.

[0082] Specific examples of phenolic curing agents and naphtholic curing agents include "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 & Material 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.

[0083] Specific examples of the carbodiimide-based curing agent include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides like phenylene-bis(xilylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), and poly(isophorone carbodiimide); and aromatic polycarbodiimides such as poly(phenylene carbodiimide), poly(naphthylene carbodiimide), poly(tolylene carbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylylene carbodiimide), poly(tetramethylxylylene carbodiimide), poly(methylenediphenylene carbodiimide), and poly[methylenebis(methylphenylene) carbodiimide].

[0084] Commercially available products of the carbodiimide-based curing agent include, for example, "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", "Highcadil 510", etc. manufactured by LANXESS.

[0085] 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, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and the like. Examples of acid anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid.

[0086] Commercially available acid anhydride curing agents include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Japan Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" manufactured by Resonaq; "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Cray Valley Chemical Industries, Ltd.; and "MHHPA" manufactured by Sigma-Aldrich.

[0087] Specific examples of benzoxazine-based curing agents include "ODA-BOZ" manufactured by JFE Chemical Corporation, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0088] Examples of the amine curing agent include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, from the viewpoint of achieving the desired effects of the present invention, aromatic amines are preferred. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 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. Commercially available products may be used as the amine curing agent, 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.

[0089] Examples of the cyanate ester curing agent include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers in which a part of these cyanate resins is triazine-ized; and the like. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza; "ULL-950S" (polyfunctional cyanate ester resin); "BA230" and "BA230S75" (prepolymers in which a part or all of bisphenol A dicyanate is triazine-ized to form trimers); and the like.

[0090] When the epoxy group number of component (D) is taken as 1, the active group number of curing agent (B) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 10 or less, more preferably 5 or less, still more preferably 3 or less. Here, the "epoxy group number of component (D)" is the total value obtained by summing up all the values obtained by dividing the mass of the non-volatile component of component (D) present in the resin composition by the epoxy equivalent. Also, the "active group number of curing agent (B)" is the total value obtained by summing up all the values obtained by dividing the mass of the non-volatile component of curing agent (B) present in the resin composition by the active group equivalent.

[0091] (B) The content of the curing agent is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, or 10% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, 15% by mass or less, still more preferably 10% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0092] (B) When the resin component in the resin composition is taken as 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, and 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.

[0093] <(C) Inorganic filler> The resin composition contains (C) an inorganic filler as component (C). By including the (C) inorganic filler in the resin composition, a cured product with a low dielectric tangent can be obtained. The (C) inorganic filler is usually contained in the resin composition in the form of particles. Component (C) may be used alone or in combination of two or more.

[0094] (C) As the material of the inorganic filler, an inorganic compound is used. (C) As the material of the 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 tungstate phosphate, etc. may be mentioned. Among these, silica is particularly suitable. As silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. may be mentioned. Also, spherical silica is preferable as silica.

[0095] (C) As commercially available products of the 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; "Cellspheres", "MGH-005" manufactured by Taiheiyo Cement Corporation; "Esferique", "BA-1" manufactured by JGC Catalysts & Chemicals Ltd., etc. may be mentioned.

[0096] (C) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, and preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less.

[0097] (C) The average particle diameter of the inorganic filler can be measured by the laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter thereof is taken as the average particle diameter for measurement. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample can be used to measure the volume-based particle size distribution of the inorganic filler by using a laser diffraction type particle size distribution measuring device with the wavelengths of the light sources used being blue and red and in a flow cell method, and the average particle diameter can be calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0098] (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, still more preferably 1 m 2 / g or more, preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 40 m 2 / g or less.

[0099] (C) The specific surface area of the inorganic filler can be measured by adsorbing nitrogen gas on the sample surface in accordance with the BET method using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multi-point method.

[0100] (C) From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, etc. The surface treatment agent may be used alone or in any combination of two or more.

[0101] 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. manufactured by Shin-Etsu Chemical Co., Ltd.

[0102] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a specific range. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 3% by mass of the surface treatment agent, and even more preferably surface-treated with 0.3% to 2% by mass of the surface treatment agent.

[0103] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and even more preferably 0.5 mg / m 2 or less.

[0104] (C) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler 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 a surface treatment agent, and ultrasonic cleaning is performed at 25 °C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0105] Also, the degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit mass of the inorganic filler. The amount of carbon per unit mass of the inorganic filler is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and 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.

[0106] (C) When the non-volatile components in the resin composition are 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.

[0107] <(D) Epoxy resin> The resin composition may further contain, as an optional component and as component (D), (D) an epoxy resin. (D) The epoxy resin as component (D) does not include those corresponding to components (A) to (C). By including (D) the epoxy resin in the resin composition, a cured product showing good mechanical strength and insulation reliability can be obtained. (D) The epoxy resin may be used alone or in combination of two or more.

[0108] Examples of the 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, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, glycidyl cyclohexane type epoxy resin, alkyldiglycidyl 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, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalimide type epoxy resin, and the like.

[0109] The resin composition preferably contains, as the 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 with respect to 100% by mass of the epoxy resin (B).

[0110] Epoxy resins include liquid epoxy resins (hereinafter sometimes referred to as "liquid epoxy resins") that are liquid at a temperature of 20°C and solid epoxy resins (hereinafter sometimes referred to as "solid epoxy resins") that are solid at a temperature of 20°C. The resin composition may contain only a liquid epoxy resin as the component (B), 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 combination of a liquid epoxy resin and a solid epoxy resin.

[0111] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0112] Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenolphthalimide type epoxy resin, and alkyldiglycidyl ether type epoxy resin. Bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable.

[0113] Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "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 Mitsubishi Chemical Corporation; "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 may be used alone or in combination of two or more types.

[0114] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferable, a solid epoxy resin having three or more epoxy groups in one molecule is more preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0115] As the solid epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, tris-phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and biphenyl type epoxy resin is more preferred.

[0116] Specific examples of solid epoxy resins include "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" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-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" (bixylenol-type epoxy resin), "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR-991S" (phenolphthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. These may be used alone or in combination of two or more.

[0117] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (D), their quantitative ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5 in terms of mass ratio. When the quantitative ratio of the liquid epoxy resin and the solid epoxy resin is within such a range, the desired effects of the present invention can be remarkably obtained.

[0118] The epoxy equivalent of component (D) is preferably 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 product of the resin composition with a sufficient crosslink density 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 according to JIS K7236.

[0119] The weight average molecular weight (Mw) of component (D) is preferably 100 to 5000, more preferably 150 to 3000, and 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) method.

[0120] When the non-volatile components in the resin composition are taken as 100% by mass, the content of component (D) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

[0121] When the resin components in the resin composition are taken as 100% by mass, the content of component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and 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.

[0122] <(E) Radical polymerizable compound> The resin composition may further contain, as an optional component, an (E) radical polymerizable compound as the (E) component. The (E) thermosetting resin as the (E) component excludes those corresponding to the (A) to (D) components. The (E) radical polymerizable compound may be used alone or in combination of two or more.

[0123] (E) The radical polymerizable compound can be, for example, a compound having a radical polymerizable group. The radical polymerizable group is not particularly limited as long as it is radically polymerizable, but an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or inside is preferable. For example, unsaturated hydrocarbon groups such as vinyl group, allyl group, 1-propenyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group; α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) and the like can be mentioned. The (E) radical polymerizable compound preferably has one or more radical polymerizable unsaturated groups, and more preferably has two or more.

[0124] (E) As the radical polymerizable compound, known radical polymerizable compounds can be widely used and are not particularly limited. For example, (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, maleimide radical polymerizable compounds and the like can be mentioned. As the (E) component, it is preferable to contain a maleimide radical polymerizable compound.

[0125] (Meth)acrylic radical polymerizable compounds are, for example, compounds having one or more, preferably two or more acryloyl groups and / or methacryloyl groups. Examples of (meth)acrylic radical polymerizable compounds include low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds 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, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate; low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as dioxane glycol 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; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate; high molecular weight (molecular weight 1000 or more) acrylate compounds such as (meth)acrylic-modified polyphenylene ether resin, and the like.Examples of commercially available (meth)acrylic radical polymerizable compounds include, for example, "A-DOG" (dioxane glycol 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 glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd., "SA9000", "SA9000-111" (methacryl-modified polyphenylene ether) manufactured by SABIC, etc.

[0126] Styrene-based 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 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, bis(4-vinylphenyl) ether; high molecular weight (molecular weight 1000 or more) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resin, styrene-divinylbenzene copolymer, etc. Examples of commercially available styrene-based radical polymerizable compounds include, for example, "ODV-XET(X03)", "ODV-XET(X04)", "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemical & Material Co., Ltd., "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Company, Inc. Also, examples of styrene-based radical polymerizable compounds include copolymer A described in International Publication No. 2017 / 115813, etc.

[0127] An allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more, allyl groups. Examples of the allyl radical polymerizable compound include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenedicarboxylate; allyl ester compounds of isocyanuric acid such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyl diphenylsilane. Commercially available products of the allyl radical polymerizable compound include, for example, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshin 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 Nisshin 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 Co., Ltd.

[0128] 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" (maleimide compound containing a dimer diamine structure) manufactured by Designer Molecules Inc., "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules Inc., "MIR-5000-60T", "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound) 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., and the like. Further, as the maleimide-based radically polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in Invention Association Public Technical Report Publication No. 2020-500211 may be used.

[0129] (E) The ethylene unsaturated bond equivalent of the component is preferably 20 g / eq. to 3,000 g / eq., more preferably 50 g / eq. to 2,500 g / eq., still more preferably 70 g / eq. to 2,000 g / eq., and particularly preferably 90 g / eq. to 1,500 g / eq. The ethylene unsaturated bond equivalent represents the mass of the radically polymerizable compound per equivalent of the ethylene unsaturated bond.

[0130] (E) The weight average molecular weight (Mw) of the component 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. The lower limit is not particularly limited, but may be, for example, 150 or more. The weight average molecular weight can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC) method.

[0131] When the content of component (E) is based on 100% by mass of the non-volatile components in the resin composition, it 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, and 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.

[0132] When the content of component (E) is based on 100% by mass of the resin components in the resin composition, it 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, and 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.

[0133] <(F) polymer component> The resin composition may further contain, as an optional component, an (F) polymer component as component (F). The (F) polymer component as component (F) excludes those corresponding to components (A) to (E). By incorporating component (F) into the resin composition, the stress of the resin composition is relaxed and the elastic modulus is lowered. As a result, even when the content of component (A) is small, it is possible to obtain a cured product excellent in crack resistance. Component (F) may be used alone or in combination of two or more.

[0134] As component (F), those having a high weight-average molecular weight can be used. Examples of such components include polyimide resins, phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, and the like.

[0135] (F) The weight average molecular weight (Mw) of the component is preferably greater than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

[0136] The polyimide resin represents a resin containing a repeating unit containing an imide bond. Usually, the polyimide resin contains a repeating unit having a structure obtained by reacting a diamine compound with an acid anhydride (imidization reaction).

[0137] Examples of the diamine compound include aliphatic diamine compounds and aromatic diamine compounds. Among them, aromatic diamine compounds are preferred. Examples of the aromatic diamine compound include phenylenediamine compounds, naphthalenediamine compounds, dianiline compounds, etc. Among them, dianiline compounds are preferred.

[0138] The dianiline compound represents a compound containing two aniline structures in the molecule. Each benzene ring in the aniline structure may optionally have 1 to 3 substituents. The two aniline structures in the dianiline compound may be directly bonded or may be bonded via a linker structure having 1 to 100 skeletal atoms selected from the group consisting of carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

[0139] Specific examples of the "linker structure" in the dianiline 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-, a group represented by the following formula (I), a group represented by (II), and a group composed of a combination thereof. In this specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group unless otherwise specified. In the following formulas (I) and (II), "*" represents a bond.

Chemical formula

[0140] Examples of the dianiline compound include 4,4'-diamino-2,2'-ditrifuluoromethyl-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)dianiline, 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)dianiline, 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, and the like. The diamine compound may be used alone or in combination of two or more.

[0141] As the acid anhydride, an acid dianhydride can usually be used, and an aromatic tetracarboxylic dianhydride is preferred. Examples of the aromatic tetracarboxylic dianhydride include benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride, phthalic dianhydride, and the like, and phthalic dianhydride is preferred.

[0142] Diphthalic dianhydride refers to a compound containing two phthalic anhydride structures in the molecule. Each benzene ring in the phthalic anhydride structure may optionally have 1 to 3 substituents. The two phthalic anhydride structures in diphthalic dianhydride may be directly bonded or may be bonded via a linker structure having 1 to 100 backbone atoms selected from the group consisting of carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0143] Examples of the "linker structure" in diphthalic dianhydride include -[R e -Ph] me -R e -[Ph-R e ne The divalent group represented by -. In this formula, R e each independently represents a single bond, -(substituted or unsubstituted alkylene group)-, -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 linker 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.

[0144] ​Examples of the diphthalic anhydride 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-ethynylidene-4,4’-diphthalic dianhydride, 2,2-propylidene-4,4’-diphthalic dianhydride, 1,2-ethylene-4,4’-diphthalic dianhydride, 1,3-trimethylene-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 may be used alone or in combination of two or more kinds.

[0145] The polyimide resin can be produced by a conventionally known method. For example, the polyimide resin may be produced by a method including heating and reacting a mixture of a diamine compound, an acid anhydride, and a solvent. Also, a commercially available product may be used as the polyimide resin. Specific examples of commercially available polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Ricacote SN20" and "Ricacote PN20" manufactured by Nippon Rika Kasei Co., Ltd., and the like.

[0146] Examples of the phenoxy resin include a phenoxy resin having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac 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. The terminal of the phenoxy resin may 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 bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical Corporation; "YX8100" (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin) 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; and the like.

[0147] Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and the 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 manufactured by Sekisui Chemical Co., Ltd.; and the like.

[0148] Examples of polyolefin resins include 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; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0149] Examples of polybutadiene resins include resins containing a hydrogenated polybutadiene backbone, hydroxy group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, and the like.

[0150] Specific examples of polyamideimide resins include "Vylon Max HR11NN" and "Vylon Max HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane backbone) manufactured by Resona Co., Ltd.

[0151] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0152] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers, LLC.

[0153] Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE.

[0154] Examples of the polycarbonate resin include a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, a urethane group-containing carbonate resin, and the like. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., and the like. Specific examples of the polyether ether ketone resin include "Sumipro EK" manufactured by Sumitomo Chemical Company, and the like.

[0155] Examples of the polyester resin include a polyethylene terephthalate resin, a polyethylene naphthalate resin, a polybutylene terephthalate resin, a polybutylene naphthalate resin, a polytrimethylene terephthalate resin, a polytrimethylene naphthalate resin, a polycyclohexane dimethyl terephthalate resin, and the like.

[0156] (F) When the non-volatile components in the resin composition are 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, still more 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, and preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1.5% by mass or less, 1% by mass or less.

[0157] (F) When the resin components in the resin composition are 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, still more 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, and preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, 3% by mass or less, or 1% by mass or less.

[0158] <(G) Curing accelerator> The resin composition may further contain, as an optional component, a (G) curing accelerator as the (G) component. The (G) curing accelerator as the (G) component does not include those corresponding to the above-described (A) to (F) components. By containing the (G) component, it becomes possible to further accelerate the curing of the (B) component. The (G) component may be used alone or in combination of two or more.

[0159] Examples of the (G) component include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. Among them, curing accelerators selected from amine-based curing accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators are particularly preferable.

[0160] Examples of phosphorus-based hardening accelerators include 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-butyldimethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, 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)diphenylether, etc. are included.;

[0161] Examples of the urea-based curing accelerators include aliphatic dimethylureas such as 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; and 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].

[0162] Examples of the guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]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.

[0163] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

[0164] As the imidazole-based curing accelerator, commercially available products may 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 mentioned.

[0165] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc.

[0166] Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

[0167] As the amine-based hardening accelerator, commercially available products may be used. For example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc. can be mentioned.

[0168] When the non-volatile components in the resin composition are 100% by mass, the content of component (G) is preferably 0.01% by mass or more, more preferably 0.002% by mass or more, still more preferably 0.03% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less.

[0169] When the resin components in the resin composition are 100% by mass, the content of component (G) 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, and is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1.5% by mass or less.

[0170] <(H) Radical polymerization initiator> The resin composition may contain an (H) radical polymerization initiator as an optional component. The (H) radical polymerization initiator as this (H) component excludes those corresponding to the components (A) to (G). The (H) radical polymerization initiator can be, for example, a thermal polymerization initiator that generates free radicals upon heating. The (H) radical polymerization initiator can be a polymerization initiator for radical-reactive groups. The (H) radical polymerization initiator may be used alone or in any combination of two or more.

[0171] Examples of the (H) radical polymerization initiator include peroxide-based radical polymerization initiators, azo-based radical polymerization initiators, etc. Among them, peroxide-based radical polymerization initiators are preferred.

[0172] Examples of the peroxide-based radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; 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-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxymaleic acid; etc.

[0173] Examples of azo radical polymerization initiators include 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, and 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 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), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); alkylazo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane); and the like.

[0174] Examples of commercially available products of the radical polymerization initiator (H) include, for example, "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", "Perbutyl ND", "Perbutyl Z", "Perbutyl I", "Parkmyl P", "Parkmyl D", "Perhexyl D", "Perhexyl A", "Perhexyl I", "Perhexyl Z", "Perhexyl ND", "Perhexyl O", "Perhexyl PV", etc. manufactured by NOF Corporation.

[0175] When the content of component (H) is based on 100% by mass of the non-volatile components in the resin composition, it 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, and preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less.

[0176] When the content of component (H) is based on 100% by mass of the resin components in the resin composition, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

[0177] <(I) Organic filler> The resin composition may further contain, as an optional component, (I) an organic filler as component (I). The (I) organic filler as component (I) does not include those corresponding to the above-described components (A) to (H). Component (I) may be used alone or in combination of two or more.

[0178] Component (I) exists in a particulate form in the resin composition. Examples of component (I) 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, it is preferable to use either rubber particles or core-shell type particles, and it is more preferable to use rubber particles.

[0179] Examples of the rubber component contained in the rubber particles include olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer; and thermoplastic elastomers such as acrylic-based thermoplastic elastomers like poly(propyl (meth)acrylate), poly(butyl (meth)acrylate), poly(cyclohexyl (meth)acrylate), and poly(octyl (meth)acrylate). Preferably, it is an olefin-based thermoplastic elastomer, and more preferably, it is a styrene-butadiene copolymer. Furthermore, a silicone-based rubber such as polyorganosiloxane rubber may be mixed into the rubber component. The rubber component contained in the rubber particles has a glass transition temperature of, for example, 0 °C or lower, preferably -10 °C or lower, more preferably -20 °C or lower, and even more preferably -30 °C or lower.

[0180] As the rubber particles, commercially available products may be used. Examples include "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aika Industries Co., Ltd.

[0181] The core-shell type particles are particulate organic fillers composed of core particles containing a rubber component as described above and one or more shell portions covering the core particles. Furthermore, the core-shell type particles are preferably core-shell type graft copolymer particles composed of core particles containing a rubber component as described above and a shell portion obtained by graft copolymerizing a monomer component copolymerizable with the rubber component contained in the core particles. Here, the core-shell type does not necessarily refer only to those in which the core particles and the shell portion can be clearly distinguished. It also includes those in which the boundary between the core particles and the shell portion is unclear, and the core particles do not have to be completely covered by the shell portion.

[0182] The rubber component is preferably contained in the core-shell type graft copolymer particles in an amount of 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. The upper limit of the content of the rubber component in the core-shell type graft copolymer particles is not particularly limited, but from the viewpoint of sufficiently coating the core particles with the shell portion, for example, it is preferably 95% by mass or less, and preferably 90% by mass.

[0183] Examples of the monomer component forming the shell portion of the core-shell type graft copolymer particles include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, and glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; and (meth)acrylonitrile. Among them, (meth)acrylic acid esters are preferred, and methyl (meth)acrylate is more preferred.

[0184] Examples of commercially available products of the core-shell type 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.; "Kanekaes M-511", "Kanekaes M-600", "Kanekaes M-400", "Kanekaes M-580", "Kanekaes MR-01" manufactured by Kaneka Corporation. These may be used alone or in combination of two or more.

[0185] The average particle diameter (average primary particle diameter) of the core-shell type graft copolymer particles is not particularly limited, but is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 80 nm or more, particularly preferably 100 nm or more, preferably 5,000 nm or less, more preferably 2,000 nm or less, still more preferably 1,000 nm or less, and particularly preferably 500 nm or less. The average particle diameter (average primary particle diameter) of the core-shell type graft copolymer particles can be measured using a zeta potential particle size distribution measuring device or the like.

[0186] (I) When the non-volatile components in the resin composition are 100% by mass, the content of the 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, and preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less.

[0187] (I) When the resin components in the resin composition are 100% by mass, the content of the component is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

[0188] <(J) Other Additives> In addition to the above-described components, the resin composition may further contain other additives as optional components. (J) Examples of other additives include 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 benton and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; 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 ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photoinitiator aids such as tertiary amines; photosensitizers such as pyralizones, anthracenes, coumarins, xanthones, and thioxanthones. (J) Other additives may be used alone or in combination of two or more.

[0189] <(K) Solvent> In addition to the non-volatile components described above, the resin composition may further contain an arbitrary solvent as a volatile component. (K) As the solvent, known solvents can be appropriately used, the type thereof is not particularly limited, and it is preferably an organic solvent. (K) Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol 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. (K) The solvent may be used alone or in combination of two or more in any ratio.

[0190] The resin composition preferably contains 0.5% by mass or more and 3% by mass or less of the (K) solvent with respect to 100% by mass of all components of the resin composition. Specifically, the (K) solvent is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1.5% by mass or less, and preferably 0.5% by mass or more, more preferably 0.8% by mass or more, still more preferably 1% by mass or more with respect to 100% by mass of all components of the resin composition.

[0191] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing and dispersing the compounding components using a rotary mixer or the like, with a solvent or the like added as necessary.

[0192] <Physical properties and uses of the resin composition> Since the resin composition contains the components (A) to (C) in combination, a cured product having a low dielectric loss tangent and a high glass transition temperature can be obtained. Further, usually, a cured product excellent in crack resistance can also be obtained.

[0193] The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of having a low dielectric loss tangent. Therefore, the cured product provides an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably 0.008 or less, more preferably 0.004 or less, still more 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 dielectric loss tangent can be measured according to the method described in the examples below.

[0194] The cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes exhibits the characteristic of being usually excellent in crack resistance because the component (A) can relieve stress. Therefore, the cured product can form an insulating layer excellent in crack resistance. In one example, an insulating layer is formed on a circuit board having a conductor layer with a wiring pattern formed on its surface by the method described in the examples below, and a roughening treatment is performed to determine the 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, still more preferably 80% or more.

[0195] The cured product obtained by thermosetting the resin composition at 190 °C for 90 minutes exhibits the characteristic of having 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 higher, more preferably 145 °C or higher, and still more preferably 150 °C or higher. The upper limit of the glass transition temperature of the cured product is not particularly limited, and can be, for example, 300 °C or lower. The glass transition temperature can be measured by the method described in the examples below.

[0196] 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, it is usually possible to obtain a cured product with excellent crack resistance. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, it can be suitably used as a resin composition for forming an insulating layer (including a resin composition for forming an insulating layer for a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer.

[0197] Also, in a multilayer printed wiring board described below, it can be suitably used as a resin composition for forming an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of the multilayer printed wiring board), and a resin composition for forming an interlayer insulating layer of the printed wiring board (resin composition for forming an interlayer insulating layer of the printed wiring board).

[0198] Also, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a resin composition for a rewiring formation layer as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation layer), and a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When manufacturing a semiconductor chip package, a further rewiring layer may be formed on the encapsulation layer. (1) A step of laminating a temporary fixing film on a base material, (2) A step of temporarily fixing a semiconductor chip on the temporary fixing film, (3) Step of forming a sealing layer on the semiconductor chip (4) Step of peeling the base material and the temporary fixing film from the semiconductor chip (5) Step of forming a redistribution formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer

[0199] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

[0200] From the viewpoints of thinning the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0201] 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 preferable.

[0202] When using a film made of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

[0203] 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 copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0204] The support may be subjected to matting treatment, corona treatment, or antistatic treatment on the surface that joins the resin composition layer.

[0205] Also, as the support, a support with a release layer having a release layer on the surface that joins the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, commercially available products may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc.

[0206] The thickness of the support is not particularly limited, but the range of 5 μm to 75 μm is preferred, and the range of 10 μm to 60 μm is more preferred. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0207] In one embodiment, the resin sheet may further include other layers as needed. Examples of such other layers include a protective film similar to the support provided on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and scratches to the surface of the resin composition layer.

[0208] The resin sheet can be produced, for example, by preparing a resin varnish in which a resin composition is dissolved in a solvent, applying this resin varnish onto a support using a die coater or the like, and further drying it to form a resin composition layer. The solvent is as described above.

[0209] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but it is dried so that the solvent content in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of the solvent, a resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0210] The resin sheet can be stored by being wound into a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0211] [Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

[0212] The printed wiring board can be produced, for example, by a method including the following steps (I) and (II) using the above-described resin sheet. (I) A step of laminating on an inner layer substrate such that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of thermally curing the resin composition layer to form an insulating layer

[0213] The "inner layer substrate" used in step (I) is a member serving as the substrate of a printed wiring board. Examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Further, the substrate may have conductor layers on one or both of its sides, and these conductor layers may be pattern-processed. An inner layer substrate having conductor layers (circuits) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board". Further, in the production of a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate incorporating components can be used.

[0214] The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet onto the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet onto the inner layer substrate (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). Note that it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate, rather than directly pressing the heat-pressing member against the resin sheet.

[0215] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat-pressing 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 reduced pressure conditions of a pressure of 26.7 hPa or less.

[0216] The lamination can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurization type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichco Materials Co., Ltd., a batch type vacuum pressurization laminator, and the like.

[0217] After lamination, under normal pressure (atmospheric pressure), for example, by pressing the heat-bonding member from the support side, a smoothing process of the laminated resin sheet may be performed. The pressing conditions for the smoothing process can be the same as the heat-bonding conditions for the above lamination. The smoothing process can be performed by a commercially available laminator. Note that lamination and the smoothing process may be continuously performed using the above-mentioned commercially available vacuum laminator.

[0218] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0219] In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions of the resin composition layer are not particularly limited, and the conditions usually employed when forming an insulating layer of a printed wiring board may be used.

[0220] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition and the like, but the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and still more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

[0221] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, at a temperature of 50°C or higher and lower than 120°C (preferably 60°C or higher and 115°C or lower, more preferably 70°C or higher and 110°C or lower), the resin composition layer may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes).

[0222] When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing printed wiring boards. When removing the support after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

[0223] Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0224] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smears are also removed. The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples include an alkaline solution and a surfactant solution, preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Commercially available swelling liquids include, for example, "Swelling Dip Security Gun P", "Swelling Dip Security SBU", and "Swelling Dip Security Agent P" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, and examples include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Also, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security Gun P" manufactured by Atotech Japan Co., Ltd. Further, the neutralizing liquid used for the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction Solution Security Agent P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing liquid can be performed by immersing the treated surface that has been roughened with the oxidizing agent in a 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 an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0225] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

[0226] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, etc. of conductor layer formation, 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 preferable, 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 preferable, and a single metal layer of copper is even more preferable.

[0227] The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has 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.

[0228] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0229] In one embodiment, the conductor layer may be formed by plating. For example, by a conventionally known technique such as a semi-additive method or a full-additive method, plating can be performed on the surface of the insulating layer to form a conductor layer having a desired wiring pattern. From the viewpoint of manufacturing simplicity, it is preferable to form it by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

[0230] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0231] [Semiconductor device] 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.

[0232] Examples of the semiconductor device include various semiconductor devices used in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, airplanes, etc.).

[0233] The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) at the conductive portions of the printed wiring board. The "conductive portion" is a "portion for transmitting an electrical signal in the printed wiring board", and the location may be either on the surface or an embedded portion. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of semiconductor.

[0234] The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, examples include wire bonding mounting methods, flip chip mounting methods, mounting methods using bump-less build-up layers (BBUL), mounting methods using anisotropic conductive films (ACF), mounting methods using non-conductive films (NCF), and the like. Here, the "mounting method using bump-less build-up layers (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board."

Example

[0235] Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "mass%", respectively.

[0236] The conditions of GPC used for measuring the number average molecular weight and the like are as follows. Measuring device: "HLC-8420GPC" manufactured by Tosoh Corporation 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 Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Column temperature: 40 °C Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL / min Standard: In accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene with a known molecular weight was used. TSKgel F-10, F-4, F-1, A-5000, A-1000, A-500 (manufactured by Tosoh Corporation) Sample: A 0.2 mass% tetrahydrofuran solution in terms of resin solid content, filtered through a microfilter (10 μL)

[0237] <Example 1A: Synthesis of silicone resin 1> Into a eggplant flask equipped with a Dean-Stark apparatus, 3.5 g of diphenylsilanediol, 0.71 g of 3-glycidyloxypropyl(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 to filter off impurities, and 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 epoxy resin 1 with a solid content concentration of 50 mass% (number average molecular weight 2,690, active group equivalent of about 1,345 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 a bond in the formula). 1 H-NMR(400MHz,Chloroform-d)δ7.71~7.12(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).

Chemical formula

[0238] <Example 2A: Synthesis of silicone resin 2> To a eggplant flask equipped with a Dean-Stark apparatus, 5.0 g of diphenylsilanediol, 1.02 g of 3-glycidyloxypropyl(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, insoluble matters were filtered off, and the filtrate was concentrated under reduced pressure to obtain 10 g of a colorless transparent oily silicone resin 2. The obtained silicone resin 2 was dissolved in toluene to obtain a target silicone resin 2 having a solid content concentration of 50 mass% (number average molecular weight 7870, active group equivalent of about 393 g / eq., non-volatile component ratio 50%). The silicone-based resin 2 was identified using an NMR apparatus (nuclear magnetic resonance apparatus: Bruker AVANCE 400 (400 MHz)), and it was confirmed that it had the following three structural units (in the formula, * represents a bond). 1 H-NMR(400MHz,Chloroform-d)δ7.72~7.13(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).

Chemical formula

[0239] <Example 3A: Synthesis of Silicone Resin 3> To a round-bottom flask equipped with a Dean-Stark apparatus, 3.5 g of diphenylsilanediol, 0.71 g of 3-glycidyloxypropyl(dimethoxy)methylsilane, 3.0 g of cyclohexyl(dimethoxy)methylsilane, and 153 mg of barium hydroxide monohydrate were added. The mixture was stirred at 85 °C for 8 hours under an argon atmosphere. After cooling to room temperature, toluene was added, and the insoluble matter was filtered off. The filtrate was concentrated under reduced pressure to obtain 6.2 g of a colorless transparent oily silicone resin 3. The silicone resin 3 was dissolved in toluene to obtain the target silicone-based epoxy resin 3 (number average molecular weight 3,105, active group equivalent about 1,553 g / eq., non-volatile component ratio 50%) with a solid content 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 a bond in the formula). 1 H-NMR(400MHz,Chloroform-d)δ7.6~7.02(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).

Chemical formula

[0240] <Synthesis Example 1: Synthesis of GPR (glycidyl epoxy / phenyl linear siloxane matrix resin)> Diphenylsilanediol and 3-glycidyloxypropyl(dimethoxy)methylsilane were mixed in a molar ratio of 1:1, and barium hydroxide monohydrate was mixed at a ratio of 0.2 mol% with respect to the silicone resin. The mixture was mixed at 80 °C for several hours under a nitrogen atmosphere to obtain the target GPR. GPR had the following structural units.

Chemical formula

[0241] <Synthesis Example 2: Synthesis of Maleimide A> A MEK solution of maleimide compound A (non-volatile component: 62% by mass, t’’ = 1.47 (mainly 1, 2, or 3), Mw / Mn = 1.81) synthesized by the method described in Synthesis Example 1 of Publication No. 2020-500211 of the Invention Association's Technical Report was prepared. This maleimide compound A has a structure represented by the following formula (1).

Chemical formula

[0242] <Synthesis Example 3: Synthesis of Polyimide B> A 500 mL separable flask equipped with a water quantitative receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. Into this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added, and the mixture was stirred at 45°C for 2 hours under a nitrogen stream to carry out the reaction. Next, the temperature of this reaction solution was raised, and while maintaining it at about 160°C, the condensed water was removed by azeotropic distillation together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the water quantitative receiver and that the outflow of water was no longer observed. After confirmation, the temperature of the reaction solution was further raised, and it was stirred at 200°C for 1 hour. Then, it was cooled to obtain a polyimide solution (non-volatile content: 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). Also, the weight average molecular weight of the said polyimide resin was 12,000.

Chemical formula

[0243] <Production of Resin Varnish> Each component was weighed in the parts by mass described in the table, and further 15 parts of MEK and 2 parts of cyclohexanone were mixed and uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish. [Table 1] [Table 2] *1: Represents the content when the resin component in the resin composition is 100% by mass. *2: Represents the content when the non-volatile component in the resin composition is 100% by mass.

[0244] Details of each component described in the table are as follows. Component (A) · Silicone resin 1: Synthesized in Example 1A · Silicone resin 2: Synthesized in Example 2A · Silicone resin 3: Synthesized in Example 3A Component (B) · HPC-8150-62T: Active ester-based curing agent, active ester resin having a naphthalene structure, functional group equivalent 223 g / eq., manufactured by DIC Corporation · HPC-8000L-65MT: Active ester resin containing a dicyclopentadiene-type diphenol structure, functional group equivalent 229 g / eq., manufactured by DIC Corporation · PC1300-02-65MA: Active ester resin having a naphthalene structure, functional group equivalent 199 g / eq., manufactured by Air Water Inc. · LA-3018-50P: 1-methoxy-2-propanol solution with a functional group equivalent of 151 g / eq. and a non-volatile content of 50% by mass, manufactured by DIC Corporation · V-03: Toluene solution with a functional group equivalent of 216 g / eq. and a non-volatile content of 50% by mass, manufactured by Nisshinbo Chemical Inc. · BA230S75: Prepolymer of bisphenol A dicyanate, functional group equivalent 232 g / eq., manufactured by Lonza · MHHPA: Methylhexahydrophthalic anhydride (manufactured by Sigma-Aldrich) Component (C) · SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573"), average particle size 0.5 μm, specific surface area 5.8 m 2 / g, manufactured by Admatechs · 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 (Component (D)) · NC-3000-L: Biphenyl-type epoxy resin (functional group equivalent 269 g / eq., manufactured by Nippon Kayaku Co., Ltd.) · ZX-1059: A 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.) · 840-S: Bisphenol A-type epoxy resin (functional group equivalent 180 - 190 g / eq., manufactured by DIC Corporation) · GPR: glycidyl epoxy / phenyl linear siloxane matrix resin, synthesized in Synthesis Example 1 (Component (E)) · Maleimide A: Synthesized in Synthesis Example 4, a maleimide-based radical polymerizable compound · ODV-XET-X04: Styrene-based radical polymerizable compound, manufactured by Nippon Steel Chemical & Material Co., Ltd. · OPE-2St: Vinylbenzyl-modified polyphenylene ether (manufactured by Mitsubishi Gas Chemical Company, a toluene solution with a non-volatile component ratio of 65%) · A-DOG: Dioxane glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) (Component (F)) · YX7553BH30: Phenoxy resin, a 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass, manufactured by Mitsubishi Chemical Corporation · Polyimide B: Synthesized in Synthesis Example 3 (Component (G)) · 2-methylimidazole: An imidazole-based reaction accelerator · 1B2PZ: An imidazole-based reaction accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd. · DMAP: An amine-based curing accelerator, manufactured by Tokyo Chemical Industry Co., Ltd. · Co(III): A metal-based curing accelerator, manufactured by Tokyo Chemical Industry Co., Ltd. (Component (H)) · Perbutyl C: Radical polymerization initiator, t-butyl cumyl peroxide (manufactured by NOF Corporation) Component (I) · EXL2655: Core-shell graft copolymer rubber particles, manufactured by The Dow Chemical Company

[0245] <Measurement of average particle diameter of inorganic filler> 100 mg of inorganic filler, 0.1 g of dispersant (SN9228 manufactured by San Nopco Ltd.), and 10 g of methyl ethyl ketone were weighed into a vial and dispersed by ultrasonic waves for 20 minutes. Using a laser diffraction particle size distribution analyzer (SALD-2200 manufactured by Shimadzu Corporation), the particle size distribution was measured by the batch cell method, and the average particle diameter based on the median diameter was calculated.

[0246] <Measurement of dielectric loss tangent and glass transition temperature> (1) Preparation of resin sheet A with a resin composition layer thickness of 40 μm As a support, a polyethylene terephthalate film with a release layer (AL5 manufactured by Lintec Corporation, thickness 38 μm) was prepared. Onto the release layer of this support, the resin varnishes obtained in the examples and comparative examples were uniformly coated so that the thickness of the resin composition layer after drying would be 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain resin sheet A including the support and the resin composition layer.

[0247] (2) Preparation of cured product of resin composition layer The prepared resin sheet A was cured in an oven at 190°C for 90 minutes. By peeling off the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained.

[0248] (3) Measurement of dielectric loss tangent (dielectric property) The cured product of the resin composition layer was cut into pieces 80 mm long and 2 mm wide, and using "HP8362B" manufactured by Agilent Technologies, the value of dielectric loss tangent (Df value) was measured at a measurement frequency of 5.8 GHz, measurement temperatures of 23°C and 90°C by the cavity resonance perturbation method. The measurement was carried out on two test pieces, and the average was calculated.

[0249] (4) Measurement of glass transition temperature The cured product of the resin composition layer was cut to obtain a test piece with a width of about 5 mm and a length of about 15 mm. For this test piece, thermomechanical analysis was performed by the tensile loading method using a thermomechanical analyzer (Thermo Plus TMA8310 manufactured by Rigaku Corporation). Specifically, after mounting the test piece on the thermomechanical analyzer, measurements were continuously performed twice under the measurement conditions of a load of 1 g and a heating rate of 5 °C / min. Then, in the second measurement, the glass transition temperature Tg (°C) was calculated.

[0250]

Table 3

[0251] <Evaluation of crack resistance> (1) Lamination of resin sheet A An inner layer substrate (MCL-E700G manufactured by Resonac Co., Ltd., conductor layer thickness 35 μm, total thickness 0.4 mm, residual copper ratio 40%) having circuit conductors (copper) formed with a wiring pattern of L / S = 8 μm / 8 μm on both sides was prepared. Resin sheet A was laminated on both sides of this inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. Such lamination was performed using a vacuum pressure laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.). After vacuum suction at 120 °C for 30 seconds, pressing was performed from the support through a heat-resistant rubber for 30 seconds under the conditions of a temperature of 120 °C and a pressure of 7.0 kg / cm 2 Then, under the conditions of a temperature of 120 °C and a pressure of 5.5 kg / cm 2 pressing was performed for 60 seconds under atmospheric pressure using a SUS mirror plate.

[0252] (2) Thermal curing of resin composition layer The inner layer substrate laminated with resin sheet A was heated at 130 °C for 30 minutes, and then heated at 170 °C for 30 minutes to thermally cure the resin composition layer to obtain an insulating layer. Then, the support was peeled off to obtain a sample substrate having a layer structure of insulating layer / inner layer substrate / insulating layer.

[0253] (3) Roughening treatment The insulating layer of the sample substrate was subjected to roughening treatment. Specifically, the sample substrate was immersed in Swelling Dip Securigant P manufactured by Atotech Japan Co., Ltd., which is a swelling liquid, at 60°C for 10 minutes. Next, it was immersed in Concentrate Compact P manufactured by Atotech Japan Co., Ltd., which is a roughening liquid (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L), at 80°C for 20 minutes. Finally, it was immersed in Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd., which is a neutralizing liquid, at 40°C for 5 minutes.

[0254] (4) Evaluation of crack resistance Among the surfaces of the insulating layer after roughening treatment, the portion on the L / S pattern of the inner layer substrate was observed. It was confirmed whether cracks (fissures) occurred on the surface along the pattern shapes of 100 inner layer substrates, and the ratio of the number of portions on the patterns where no cracks occurred was counted. This ratio was calculated as the "yield". Also, the calculated yield was scored according to the following criteria. 1 point: 0% or more and less than 20%. 2 points: 20% or more and less than 40%. 3 points: 40% or more and less than 60%. 4 points: 60% or more and less than 80%. 5 points: 80% or more. Those with 3 points or more were evaluated as "○", and those with 2 points or less were evaluated as "×".

[0255]

Table 4

[0256] In Examples 1 to 13, even when the components (E) to (H) are not contained, although there are differences to some extent, it has been confirmed that the results are the same as those of the above examples. Also, when the crack resistance of Example 1 was evaluated in the same manner as Example 2, it was confirmed that the results were equivalent to those of Example 2.

Claims

1. A silicone resin having 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). 【Chemical 1】 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), and R ２ represents a monovalent hydrocarbon group which may have a substituent. * represents a bond. In formula (A-2), R ３ and R ４ each independently represents a monovalent hydrocarbon group which may have a substituent. * represents a bond. 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. * represents a bond. However, R ５ is a group different from R ３ and R ４ in formula (A-2). [Chemical 2] In formula (A-1a), n1 represents an integer from 2 to 10. * represents a bond to a silicon atom in formula (A-1). In formula (A-1b), n2 represents an integer from 1 to 10. * represents a bond to a silicon atom in formula (A-1).

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

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

4. 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, the silicone resin according to claim 1.

5. 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. The silicone resin according to claim 1.

6. 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. The silicone resin according to claim 1.

7. The silicone resin according to claim 1, having a number average molecular weight of 10,000 or less.

8. The silicone resin according to claim 1, having a number average molecular weight of 7,000 or less.

9. A resin composition containing: (A) the silicone resin according to any one of claims 1 to 8; (B) a curing agent; and (C) an inorganic filler.

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

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

12. The resin composition according to claim 9, wherein component (B) contains an acid anhydride-based curing agent.

13. The resin composition according to claim 9, further containing (E) a radically polymerizable compound.

14. The resin composition according to claim 13, wherein component (E) contains a maleimide-based radically polymerizable compound.

15. A resin sheet including a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 9 to 14.

16. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 9 to 14.

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

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