Resin composition

Abstract

To provide a resin composition from which a cured product that is excellent in adhesion to a conductor layer, suppresses occurrence of a warpage amount and is low in dielectric characteristics can be obtained.SOLUTION: A resin composition contains (A) a silicone resin having a structural unit represented by formula (A-1) and a structural unit represented by formula (A-2), (B) an epoxy resin, (C) an active ester-based curing agent, and (D) an inorganic filler.SELECTED DRAWING: None

Description

Technical Field

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

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 printed wiring boards used for such insulating layers, for example, a resin composition is disclosed in Patent Document 1.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, with the high functionality of printed wiring boards, the insulating layers of printed wiring boards are required to have high adhesion to conductor layers and suppression of warpage. Further, the insulating layers are also required to further improve the dissipation factor and the dielectric constant. Hereinafter, the dissipation factor and the relative dielectric constant may be collectively referred to as dielectric properties.

[0006]

Means for Solving the Problems

[0007] ​As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by combining and containing (A) a silicone resin having a specific structural unit, (B) an epoxy resin, (C) an active ester-based curing agent, and (D) an inorganic filler, and have completed the present invention.

[0008] That is, the present invention includes the following. [1] A resin composition containing (A) a silicone resin having a structural unit represented by the following formula (A-1) and a structural unit represented by the following formula (A-2), (B) an epoxy resin (excluding those corresponding to component (A)), (C) an active ester-based curing agent, and (D) an inorganic filler. [Chemical formula] 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 represent a monovalent hydrocarbon group which may have a substituent. * represents a bond. [Chemical formula] In formula (A-1a), n1 represents an integer of 2 to 10. * represents a bond to the silicon atom in formula (A-1). In formula (A-1b), n2 represents an integer of 1 to 10. * represents a bond to the silicon atom in formula (A-1). [2] The resin composition according to [1], wherein n1 in formula (A-1a) represents an integer of 3 to 8. [3] The resin composition according to [1] or [2], wherein in formula (A-1), R 2 represents an alkyl group which may have a substituent. [4] The resin composition according to [1], wherein in formula (A-2), R 3 and R 4The resin composition according to any one of [1] to [3], which independently represents an aryl group which may have a substituent. [5] In formula (A-2), R 3 and R 4 The resin composition according to any one of [1] to [4], which independently represents a phenyl group which may have a substituent. [6] The resin composition according to any one of [1] to [5], wherein the number average molecular weight of the component (A) is 10,000 or less. [7] The resin composition according to any one of [1] to [6], wherein the content of the component (D) exceeds 60% by mass when the non-volatile component of the resin composition is 100% by mass. [8] 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 [1] to [7]. [9] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [7].

[10] A semiconductor device including the printed wiring board according to [9]. [Advantages of the Invention]

[0009] According to the present invention, there can be provided a resin composition capable of obtaining a cured product having excellent adhesion to a conductor layer, suppressing the generation of warpage amount, and having low dielectric properties; a resin sheet including the resin composition; a printed wiring board provided with an insulating layer formed using the resin composition; and a semiconductor device. [Embodiments for Carrying Out the Invention]

[0010] Hereinafter, the present invention will be described in detail according 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.

[0011] [Resin Composition] The resin composition of the present invention contains (A) a silicone resin having a structural unit represented by formula (A-1) and a structural unit represented by formula (A-2), (B) an epoxy resin (excluding those corresponding to component (A)), (C) an active ester-based curing agent, and (D) an inorganic filler. In the present invention, by combining and containing components (A), (B), (C), and (D), a cured product excellent in adhesion to a conductor layer, with suppressed generation of warpage amount and low dielectric properties can be obtained. Further, usually, a cured product excellent in adhesion to a copper foil after a HAST test can also be obtained.

[0012] The resin composition may further contain an arbitrary component in combination with components (A) to (D). Examples of the arbitrary component include (E) a thermosetting resin, (F) a high molecular weight component, (G) a curing accelerator, (H) an organic filler, (I) other additives, and (J) a solvent, etc. Hereinafter, each component contained in the resin composition will be described in detail.

[0013] <(A) a silicone resin having a structural unit represented by formula (A-1) and a structural unit represented by formula (A-2)> The resin composition contains, as component (A), a silicone resin having a structural unit represented by formula (A-1) and a structural unit represented by formula (A-2). By containing component (A) in the resin composition, it becomes possible to obtain a cured product excellent in dielectric properties and adhesion. Further, since component (A) has a Si-O skeleton, the stress of the resin composition is relaxed. As a result, the elastic modulus of the cured product decreases, and the generation of the warpage amount of the cured product is suppressed. Component (A) may be used alone or in combination of two or more.

Chemical formula

Chemical formula

[0014] In formula (A-1), R 1 represents a group represented by formula (A-1a) or a group represented by formula (A-1b).

[0015] In formula (A-1a), n1 represents an integer from 2 to 10, preferably an integer from 3 to 8, more preferably an integer from 3 to 6, still more preferably an integer from 3 to 5, and particularly preferably 3.

[0016] In formula (A-1b), n2 represents an integer from 1 to 10, preferably an integer from 1 to 5, more preferably an integer from 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

[0017] In formula (A-1), R 2 represents a monovalent hydrocarbon group which may have a substituent. Also, in formula (A-2), R 3 and R 4 each independently represents a monovalent hydrocarbon group which may have a substituent.

[0018] 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, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, and the like.

[0019] The alkyl group means a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2-methylpropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a tert-octyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, and the like. Among them, the methyl group is preferred.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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 " (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.

[0025] 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.

[0026] In formula (A-2), R 3 and R 4The monovalent hydrocarbon group which may have a substituent represented by may each independently be preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably an aryl group which may have a substituent, and even more preferably a phenyl group.

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

Chemical formula

[0028] (In component (A), the number of the structural units represented by formula (A-1) is 1 or more, preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less. When there are a plurality of structural units represented by formula (A-1), the structural units represented by formula (A-1) may be linked to each other as repeating units, 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 formula (A-2) or another structural unit is interposed between the plurality of structural units represented by formula (A-1). Further, when there are a plurality of structural units represented by formula (A-1), R in formula (A-1) 1 and R 2 may be the same or different.

[0029] (With respect to 100 mol% of the whole molecule of component (A), the amount of the structural unit represented by formula (A-1) is preferably 35 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more, and preferably 65 mol% or less, more preferably 60 mol% or less, and even more preferably 55 mol% or less.

[0030] Specific examples of the structural unit represented by formula (A-2) include the structural units represented by formulas (A-2-1) to (A-2-3), but the present invention is not limited thereto. In the formulas, * represents a bond.

Chemical formula

[0031] (In the (A) component, the number of structural units represented by the formula (A-2) 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-2) may be linked to each other as repeating units, 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) 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 may be the same or different.

[0032] With respect to 100 mol% of the whole molecule of the (A) component, the amount of the structural unit represented by the formula (A-2) is preferably 35 mol% or more, more preferably 40 mol% or more, still more preferably 45 mol% or more, and preferably 65 mol% or less, more preferably 60 mol% or less, still more preferably 55 mol% or less.

[0033] When the amount of the structural unit represented by the formula (A-1) is a1 and the amount of the structural unit represented by the formula (A-2) is b1 with respect to the whole molecule of the (A) component, a1 / b1 is preferably 0.8 or more, more preferably 0.9 or more, still more preferably 1.0 or more, and preferably 1.2 or less, more preferably 1.1 or less, still more preferably 1.0 or less.

[0034] As the (A) component, a resin having a structural unit represented by the formula (A-1) and a structural unit represented by the formula (A-2) can be used. The (A) component may be a random copolymer, a block copolymer, a graft copolymer, or an alternating copolymer having a structural unit represented by the formula (A-1) and a structural unit represented by the formula (A-2).

[0035] (A) As the terminal structure of the component, for example, R in formula (A-1) 2 represents a monovalent hydrocarbon group, a hydroxy group, an alkoxy group, an alkenyloxy group, an aryloxy group, or an aralkyloxy group, preferably an alkyl group, an aryl group, a hydroxy group, or an alkoxy group, more preferably an alkyl group, a hydroxy group, or an alkoxy group, still more preferably a hydroxy group or an alkoxy group, and particularly preferably a hydroxy group or an alkoxy group.

[0036] An alkoxy group means a monovalent group formed by an alkyl group bonded to an oxygen atom (that is, a group represented by R A1 -O-(R A1 is an alkyl group). Unless otherwise specified, an 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 still 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.

[0037] An alkenyloxy group means a monovalent group formed by an alkenyl group bonded to an oxygen atom (that is, a group represented by R A2 -O-(R A2 is an alkenyl group). Unless otherwise specified, an 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 still 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), and the like.

[0038] An aryloxy group means a monovalent group formed by an aryl group bonded to an oxygen atom (that is, a group represented by R A3 -O-(R A3means a group represented by an aryl group). 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, unless otherwise specified. Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and the like.

[0039] The aralkyloxy group means a monovalent group in which an aralkyl group is bonded to an oxygen atom (that is, R A4 -O-(R A4 is an aralkyl group). 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, unless otherwise specified. Examples of the aralkyloxy group include a benzyloxy group, an α-methylbenzyloxy group, and the like.

[0040] The alkoxy group, alkenyloxy group, or aryloxy group may have a substituent. The substituent is the same as the substituent that the monovalent hydrocarbon group represented by R 2 in the formula (A-1) may have.

[0041] (A) component may have other structural units as long as the effects of the present invention are not inhibited, in addition to the structural unit represented by the formula (A-1) and the structural unit represented by the formula (A-2). Examples of the other structural units include a structural unit represented by the following formula (A-4).

Chemical formula

[0042] In the formula (A-4), R 5 and R 6each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent. 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 3 and R 4 in formula (A-2).

[0043] Specific examples of component (A) include, but are not limited to, the compounds represented by (A1) to (A6). In the formula, a and b each independently represent an integer of 1 to 20, and * represents a bond.

Chemical formula

Chemical formula

[0044] There is no particular limitation on the method for synthesizing component (A). For example, component (A) can be synthesized by polymerizing a silanediol compound with a dialkoxysilane compound or a diaryloxysilane compound. The temperature condition is preferably 30 to 120°C, more preferably 50 to 100°C. The reaction time is preferably 1 hour to 7 days, more preferably 3 hours to 5 days.

[0045] The weight average molecular weight of component (A) is preferably 5000 or more, more preferably 6000 or more, still more preferably 7000 or more, and preferably 15000 or less, more preferably 14000 or less, still more preferably 13000 or less. The weight average molecular weight of component (A) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

[0046] The number average molecular weight of component (A) is preferably 10,000 or less, more preferably 9,500 or less, still more preferably 9,000 or less, 8,500 or less, and is 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 component (A) is the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

[0047] The active group equivalent of component (A) 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 is 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, 450 g / eq. or less.

[0048] 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, and is 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, 2% by mass or less.

[0049] 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, and is 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, 10% by mass or less, 8% by mass or less.

[0050] 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 (D) the inorganic filler among the non-volatile components of the resin composition.

[0051] <(B) Epoxy resin> The resin composition contains, as component (B), (B) an epoxy resin (excluding those corresponding to component (A)). The (B) epoxy resin as component (B) does not include those corresponding to component (A). By including the (B) epoxy resin in the resin composition, a cured product exhibiting good mechanical strength and insulation reliability can be obtained. The (B) epoxy resin may be used alone or in combination of two or more.

[0052] Examples of the (B) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, glycidyl cyclohexane type epoxy resin, alkyldiglycidyl ether type epoxy resin, cresol novolac 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, etc.

[0053] The resin composition preferably contains, as component (B), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the 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 (B) epoxy resin.

[0054] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin as component (B), may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. Among them, from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0055] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0056] 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, phenol phthalimide type epoxy resin, and alkyldiglycidyl ether type epoxy resin. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, and naphthalene type epoxy resin are more preferable.

[0057] 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; "Celoxide 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.

[0058] 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.

[0059] Examples of the solid epoxy resin include a biphenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin. Among them, a naphthalene type epoxy resin and a biphenyl type epoxy resin are preferred, and a naphthalene type epoxy resin is more preferred.

[0060] Specific examples of the solid epoxy resin 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" (phenol phthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like. These may be used alone or in combination of two or more.

[0061] When the liquid epoxy resin and the solid epoxy resin are used in combination as component (B), 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.

[0062] The epoxy equivalent of component (B) 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. When it is 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.

[0063] The weight average molecular weight (Mw) of component (B) 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.

[0064] When the non-volatile components in the resin composition are regarded as 100% by mass, the content of component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

[0065] When the resin components in the resin composition are regarded as 100% by mass, the content of component (B) is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, 45% by mass or less, and 40% by mass or less.

[0066] <(C) Active ester-based curing agent> The resin composition contains, as component (C), an (C) active ester-based curing agent. The (C) active ester-based curing agent as this component (C) does not include those corresponding to the above-described components (A) to (B). The (C) active ester-based curing agent can usually form a bond by reacting with the (B) epoxy resin to cure the resin composition. Further, by combining the component (A) and the component (C) and including them in the resin composition, a cured product having excellent adhesion and a low elastic modulus can be obtained. The component (C) may be used alone or in combination of two or more.

[0067] (C) As the active ester-based curing agent, compounds having two or more highly reactive ester groups in one molecule, such as generally phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. 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. Particularly from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. 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. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, benzene triol, 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.

[0068] Specifically, examples of the component (C) include dicyclopentadiene-type active ester-based curing agents, naphthalene-type active ester-based curing agents containing a naphthalene structure, active ester-based curing agents containing an acetylated product of phenol novolak, active ester-based curing agents containing a benzoylated product of phenol novolak, active ester-based curing agents that are acetylated products of phenol novolak, phosphorus-containing active ester-based, active ester-based curing agents containing a styryl group and a naphthalene structure, etc. Among them, any one of a dicyclopentadiene-type active ester-based curing agent, a naphthalene-type active ester-based curing agent containing a naphthalene structure, and an active ester-based curing agent containing a styryl group and a naphthalene structure is preferable, and any one of a dicyclopentadiene-type active ester-based curing agent and a naphthalene-type active ester-based curing agent containing a naphthalene structure is more preferable. As the dicyclopentadiene-type active ester-based curing agent, an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure is preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

[0069] Examples of commercially available products of component (C) include, as active ester-based curing agents containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM", "HPC-8000H-65MT" (manufactured by DIC Corporation); as naphthalene type active ester-based curing agents containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as phosphorus-containing active ester-based curing agents, "EXB9401" (manufactured by DIC Corporation); as active ester-based curing agents containing an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); as active ester-based curing agents containing a benzoylated product of phenol novolak, "YLH1026" (manufactured by Mitsubishi Chemical Corporation); as active ester-based curing agents that are acetylated products of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); as active ester-based curing agents that are benzoylated products of phenol novolak, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "EXB-8500-65T" (manufactured by DIC Corporation); and as active ester-based curing agents containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water, Inc.), etc.

[0070] From the viewpoint of being able to lower the dielectric loss tangent and obtaining a cured product excellent in peel strength, the active ester group equivalent of component (C) is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and still more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester-based curing agent containing 1 equivalent of the active ester group.

[0071] (B) The quantitative ratio of the epoxy resin to (C) the active ester-based curing agent is the ratio of [total number of active groups of the active ester-based curing agent] / [total number of epoxy groups of the epoxy resin], preferably 0.01 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and preferably 5 or less, more preferably 4 or less, still more preferably 3 or less. Here, the "number of epoxy groups of the epoxy resin" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. Also, the "number of active groups of the active ester-based curing agent" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the active ester-based curing agent present in the resin composition by the active ester group equivalent. By setting the quantitative ratio of the epoxy resin to the active ester-based curing agent within such a range, it becomes possible to remarkably obtain the effects of the present invention.

[0072] When the non-volatile component in the resin composition is 100% by mass, the content of component (C) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more. The upper limit is 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.

[0073] When the resin component in the resin composition is 100% by mass, the content of component (C) is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, particularly preferably 60% by mass or less.

[0074] When the non-volatile component in the resin composition is 100% by mass, the total content of component (A), component (B), and component (C) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.

[0075] <(D) Inorganic filler> The resin composition contains a (D) inorganic filler as component (D). By including the (D) inorganic filler in the resin composition, a cured product with low dielectric properties can be obtained. The (D) inorganic filler is usually contained in the resin composition in the form of particles. Component (D) may be used alone or in combination of two or more.

[0076] As the material of the (D) inorganic filler, an inorganic compound is used. Examples of the material of the (D) inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Also, spherical silica is preferred as the silica.

[0077] Examples of commercially available products of the (D) inorganic filler include "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; "Celsospheres MGH-005" manufactured by Taiheiyo Cement Corporation; "Esferique BA-1" manufactured by JGC Catalysts & Chemicals Ltd., etc.

[0078] (D) 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, 0.4 μm or more, 0.5 μm or more, and preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less.

[0079] (D) The average particle size of the inorganic filler can be measured by the laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler based on volume using a laser diffraction scattering type particle size distribution measuring device and taking the median diameter thereof as the average particle size. 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 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 size 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.

[0080] (D) 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, and preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 40 m 2 / g or less.

[0081] (D) The specific surface area of the inorganic filler can be measured by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multipoint method.

[0082] (D) 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, and the like. The surface treatment agent may be used alone or in any combination of two or more kinds.

[0083] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc., all manufactured by Shin-Etsu Chemical Co., Ltd.

[0084] 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 0.2% to 3% by mass of the surface treatment agent, and even more preferably 0.3% to 2% by mass of the surface treatment agent.

[0085] 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, and preferably 0.1 mg / m 2The above is more preferable, 0.2 mg / m 2 The above is even more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, 1.0 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, 0.5 mg / m 2 or less is even more preferable.

[0086] (D) 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 (for example, 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.

[0087] 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, even more preferably 0.1% by mass or more, and preferably 1.0% by mass or less, more preferably 0.8% by mass or less, even more preferably 0.5% by mass or less. (D) The amount of carbon per unit mass of the inorganic filler can be measured using a carbon analyzer in the same manner as the amount of carbon per unit surface area of the (D) inorganic filler.

[0088] (D) The content of the inorganic filler, when the non-volatile components in the resin composition are 100% by mass, is preferably more than 60% by mass, more preferably 65% by mass or more, even more preferably 68% by mass or more, 70% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less.

[0089] <(E) Thermosetting resin> The resin composition may further contain, as an optional component, an (E) thermosetting resin as component (E). The (E) thermosetting resin as component (E) excludes those corresponding to components (A) to (D). The type of the (E) thermosetting resin is not particularly limited as long as it can be cured by heat. The (E) thermosetting resin may be used alone or in combination of two or more.

[0090] Examples of the (E) thermosetting resin include radical polymerizable resins, phenol resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. Hereinafter, phenol resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins may be collectively referred to as "curing agents".

[0091] The type of the radical polymerizable resin as component (E) is not particularly limited as long as it has one or more (preferably two or more) radical polymerizable unsaturated groups in one molecule. Examples of the radical polymerizable resin include resins having, as the radical polymerizable unsaturated group, one or more selected from maleimide groups, vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, and maleoyl groups. Among them, the radical polymerizable resin is preferably a maleimide resin, a (meth)acrylic resin, or a styrene resin.

[0092] As the maleimide resin, as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule, its type is not particularly limited. Examples of the maleimide resin include: (1) maleimide resins containing an aliphatic skeleton (preferably an aliphatic skeleton having 36 carbon atoms derived from a dimer diamine), such as "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", "BMI-689" (all manufactured by Designer Molecules Inc.), "SLK6895-T90" (manufactured by Shin-Etsu Chemical Co., Ltd.); (2) maleimide resins containing an indane skeleton described in JP-A No. 2020-500211 of the Japan Institute of Invention and Innovation; (3) maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group, such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), "BMI-80" (manufactured by KAI Chemical Co., Ltd.).

[0093] (As the (meth)acrylic resin, as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, its type is not particularly limited, and it may be a monomer or an oligomer. Here, the term "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group. Examples of the methacrylic resin include, in addition to (meth)acrylate monomers, (meth)acrylic resins such as "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "SA9000" (manufactured by SABIC), "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0094] A styrene resin is, for example, a compound having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene resins include low molecular weight (molecular weight less than 1000) styrene compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; and high molecular weight (molecular weight 1000 or more) styrene resins such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Commercially available styrene resins include, for example, "ODV-XET(X03)", "ODV-XET(X04)", "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Company, Inc.

[0095] (E) When the content of the radical polymerizable resin as the thermosetting resin 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, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

[0096] (E) When the content of the radical polymerizable resin as the thermosetting resin is based on 100% by mass of the resin components in the resin composition, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

[0097] As the phenolic resin, a compound having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. Since the phenolic resin can react with an epoxy resin to cure the resin composition when combined with the epoxy resin, it is sometimes referred to as a "phenolic curing agent". From the viewpoint of significantly obtaining the effects of the present invention, a phenolic resin having a novolak structure is preferable. Further, from the viewpoint of adhesion, a nitrogen-containing phenolic resin is preferable, and a phenolic resin containing a triazine skeleton is more preferable. Among them, from the viewpoint of significantly obtaining the effects of the present invention, a phenolic novolak resin containing a triazine skeleton is preferable. Specific examples of the phenolic resin include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M", "KA-1163" manufactured by DIC Corporation, etc.

[0098] As the active ester resin, generally, 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 preferably used. Since the active ester resin can react with the epoxy resin when combined with the epoxy resin to cure the resin composition, it is sometimes referred to as an "active ester-based curing agent". The active ester resin 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. Particularly from the viewpoint of improving the high-temperature reflow bulge resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenolic compound and / or a naphthol compound is more preferred. 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. Examples of the phenolic 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 compounds, phenol novolac, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0099] Specifically, as the active ester resin, a dicyclopentadiene type active ester resin, a naphthalene type active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolak, and an active ester resin containing a benzoylated product of phenol novolak are preferred. Among them, at least one selected from a dicyclopentadiene type active ester resin and a naphthalene type active ester resin is more preferred. As the dicyclopentadiene type active ester resin, an active ester resin containing a dicyclopentadiene type diphenol structure is preferred.

[0100] Examples of commercially available active ester resins include, for example, as an active ester resin containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000L-65T", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as an active ester resin containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as a phosphorus-containing active ester resin, "EXB9401" (manufactured by DIC Corporation); as an active ester resin that is an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester resin that is a benzoylated product of phenol novolak, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation); as an active ester resin containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), and the like.

[0101] As the cyanate resin, a compound having one or more, preferably two or more cyanate groups in one molecule can be used. Since the cyanate resin can react with an epoxy resin to cure the resin composition when combined with the epoxy resin, it is sometimes referred to as a "cyanate-based curing agent". Examples of the cyanate resin 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-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers in which some of these cyanate resins are partially triazine-ized, and the like. Specific examples of the cyanate resin include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate resins), "BA230", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazine-ized to form a trimer), etc. manufactured by Lonza.

[0102] As the carbodiimide resin (excluding those corresponding to the component (A)), a compound having one or more, preferably two or more carbodiimide structures in one molecule and not having a radically polymerizable group can be used. Since the carbodiimide resin can react with an epoxy resin to cure the resin composition when combined with the epoxy resin, it is sometimes referred to as a "carbodiimide-based curing agent".

[0103] Specific examples of the carbodiimide resin 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].

[0104] Commercially available carbodiimide resins include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stabaxol P", "Stabaxol P100", "Stabaxol P400", "Highcadil 510" manufactured by LANXESS Corporation, etc.

[0105] As the acid anhydride resin, a compound having one or more, preferably two or more acid anhydride groups in one molecule can be used. Since the acid anhydride resin can react with an epoxy resin to cure the resin composition when combined with an epoxy group, it is sometimes referred to as an "acid anhydride-based curing agent". Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as a styrene-maleic acid resin copolymerized from styrene and maleic acid. Commercially available products of the acid anhydride resin include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd.; "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200", "HN-5500" manufactured by Resonaak Co., Ltd.; "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Cray Valley Co., Ltd., etc.

[0106] As the amine resin, a compound having one or more, preferably two or more amino groups in one molecule can be used. Since the amine resin can react with an epoxy resin to cure the resin composition when combined with an epoxy group, it is sometimes referred to as an "amine-based curing agent". Examples of the amine resin include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred. The amine resin preferably contains a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine resin include 4,4'-methylenebis(2,6-dimethylaniline), 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 of the amine resin include, for example, "SEIKACURE-S" manufactured by Seika Corporation; "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; "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd., etc.

[0107] Benzoxazine resins, when combined with epoxy resins, can react with the epoxy resin to harden the resin composition, and are therefore sometimes called "benzoxazine-based hardeners." Specific examples of benzoxazine resins include "JBZ-OP100D" and "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.

[0108] Thiol resins, when combined with epoxy resins, can react with the epoxy resin to harden the resin composition, and are therefore sometimes called "thiol-based hardeners." Examples of thiol resins include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0109] The active group equivalent of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent is the mass of the curing agent per equivalent of the active group.

[0110] The weight average molecular weight (Mw) of the curing agent is preferably from 100 to 5,000, more preferably from 250 to 3,000, and further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0111] (B) When the epoxy equivalent of the epoxy resin is set to 1, the active hydrogen equivalent of the curing agent is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 5 or less, more preferably 3 or less, particularly preferably 2 or less. The "epoxy equivalent of the epoxy resin" represents the total value obtained by summing up the values obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. Further, the "active hydrogen equivalent of the curing agent" represents the total value obtained by summing up the values obtained by dividing the mass of the non-volatile components of the curing agent present in the resin composition by the active hydrogen equivalent.

[0112] (E) When the non-volatile components in the resin composition are 100% by mass, the content of the curing agent as a thermosetting resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

[0113] (E) When the resin components in the resin composition are 100% by mass, the content of the curing agent as a thermosetting resin is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% 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.

[0114] (E) When the non-volatile components in the resin composition are 100% by mass, the content of the thermosetting resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

[0115] (E) When the resin components in the resin composition are 100% by mass, the content of the thermosetting resin is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% 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.

[0116] <(F) Polymer Component> The resin composition may further contain, as an optional component, a (F) polymer component as the (F) component. The (F) polymer component as the (F) component excludes those corresponding to the (A) to (E) components. By including the (F) component in the resin composition, the stress of the resin composition is relaxed, and as a result, it becomes possible to obtain a cured product with a low elastic modulus. The (F) component may be used alone or in combination of two or more.

[0117] As the (F) component, those having a high weight-average molecular weight can be used. Examples of such components include polyimide resin, phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc.

[0118] The weight-average molecular weight (Mw) of the (F) 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.

[0119] 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).

[0120] Examples of the diamine compound include aliphatic diamine compounds and aromatic diamine compounds, and among them, aromatic diamine compounds are preferred. Examples of the aromatic diamine compound include phenylenediamine compounds, naphthalenediamine compounds, dianiline compounds, etc., and among them, dianiline compounds are preferred.

[0121] The dianiline compound refers to 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 a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom.

[0122] 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-, the group represented by the following formula (I), the group represented by (II), and groups composed of combinations 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

[0123] Examples of the dianiline compound include 4,4'-diamino-2,2'-ditrifluoromethyl-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.

[0124] As the acid anhydride, usually, an acid dianhydride can 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.

[0125] Diphthalic anhydride 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 anhydride 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.

[0126] Examples of the "linker structure" in diphthalic anhydride include -[R e -Ph] me -R e -[Ph-R e ne -represents a divalent group. 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.

[0127] ​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, and the like. The acid anhydride may be used alone or in combination of two or more.

[0128] 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., "Lica Coat SN20" and "Lica Coat PN20" manufactured by Nippon Rika Kasei Co., Ltd., and the like.

[0129] Examples of the phenoxy resin include phenoxy resins 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 novolak skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. 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.

[0130] 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, and BM series manufactured by Sekisui Chemical Co., Ltd.; and the like.

[0131] 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; polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0132] Examples of polybutadiene resins include resins containing a hydrogenated polybutadiene skeleton, 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.

[0133] Specific examples of polyamideimide resins include "Vironmax HR11NN" and "Vironmax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Resona Co., Ltd.

[0134] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0135] Specific examples of polysulfone resins include polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers, LLC.

[0136] Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE.

[0137] Examples of the polycarbonate resin include a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy 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 polyetheretherketone resin include "Sumipro EK" manufactured by Sumitomo Chemical Company, and the like.

[0138] 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 polycyclohexanedimethylene terephthalate resin, and the like.

[0139] (F) When the non-volatile components in the resin composition are 100% by mass, the content of the polymer component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% 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.

[0140] (F) When the resin components in the resin composition are 100% by mass, the content of the polymer component is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less.

[0141] <(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-mentioned components (A) to (F). 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.

[0142] 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 preferred, and amine-based curing accelerators are particularly preferred.

[0143] Examples of phosphorus-based curing 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 mentioned.;

[0144] Examples of urea-based curing accelerators include, for example, 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N’,N’-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluene bisdimethylurea], etc.

[0145] Examples of guanidine-based curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc.

[0146] 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.

[0147] As the imidazole-based curing accelerator, commercially available products may be used. Examples include "1B2PZ", "C11Z", "2P4MZ", "2MZA-PW", "2PHZ-PW", "C11Z-A" manufactured by Shikoku Kasei Kogyo Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, and the like.

[0148] Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex 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 the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0149] Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and the like.

[0150] As the amine-based hardening accelerator, commercially available products may be used. For example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc. may be mentioned.

[0151] When the non-volatile component in the resin composition is 100% by mass, the content of the component (G) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, and preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.8% by mass or less.

[0152] When the resin component in the resin composition is 100% by mass, the content of the 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 preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1.5% by mass or less.

[0153] <(H) Organic filler> The resin composition may further contain, as an optional component, an (H) component, i.e., an (H) organic filler. The (H) organic filler as the (H) component does not include those corresponding to the above-described components (A) to (G). The (H) component may be used alone or in combination of two or more.

[0154] The (H) component exists in the form of particles in the resin composition. Examples of the (H) component include rubber particles, polyamide fine particles, silicone particles, core-shell type particles, etc. In the present invention, from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable to use either rubber particles or core-shell type particles, and it is more preferable to use rubber particles.

[0155] 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, 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), 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.

[0156] As the rubber particles, commercially available products may be used. For example, "EXL2655" manufactured by Dow Chemical Japan, "AC3401N", "AC3816N" manufactured by Aica Industries Co., Ltd., etc. may be mentioned.

[0157] The core-shell type particle is a particulate organic filler composed of core particles containing a rubber component as described above and one or more shell portions covering the core particles. Further, the core-shell type particle is preferably a core-shell type graft copolymer particle 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.

[0158] 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 covering the core particles with the shell portion, for example, it is preferably 95% by mass or less, and 90% by mass.

[0159] 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.

[0160] Examples of commercially available core-shell graft copolymer particles include, for example, "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 The Dow Chemical Company Japan; "Metablen C-223A", "Metablen E-901", "Metablen S-2001", "Metablen W-450A", "Metablen SRK-200" manufactured by Mitsubishi Rayon Co., Ltd.; "Kaneka Ace M-511", "Kaneka Ace M-600", "Kaneka Ace M-400", "Kaneka Ace M-580", "Kaneka MR-01" manufactured by Kaneka Corporation, etc. These may be used alone or in combination of two or more kinds.

[0161] The average particle diameter (average primary particle diameter) of the core-shell 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, particularly preferably 500 nm or less. The average particle diameter (average primary particle diameter) of the core-shell graft copolymer particles can be measured using a zeta potential particle size distribution measuring device or the like.

[0162] When the non-volatile components in the resin composition are 100% by mass, the content of the (H) component is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less.

[0163] When the resin components in the resin composition are 100% by mass, the content of the (H) component is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

[0164] <(I) Other additives> In addition to the above-described components, the resin composition may further contain other additives as optional components. Examples of (I) other additives include polymerization initiators; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as 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; photopolymerization initiation aids such as tertiary amines; photosensitizers such as pyralizones, anthracenes, coumarins, xanthones, and thioxanthones. (I) Other additives may be used alone or in combination of two or more.

[0165] <(J) Solvent> In addition to the non-volatile components described above, the resin composition may further contain an arbitrary solvent as a volatile component. (J) As the solvent, known solvents can be appropriately used, the type thereof is not particularly limited, and it is preferably an organic solvent. (J) Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, 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, methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile, propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. (J) The solvent may be used alone or in combination of two or more in any ratio.

[0166] The resin composition preferably contains 0.5% by mass or more and 3% by mass or less of a solvent (J) based on 100% by mass of all components of the resin composition. Specifically, the solvent (J) 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 based on 100% by mass of all components of the resin composition.

[0167] The method for preparing the resin composition of the present invention is not particularly limited. For example, there are methods such as adding compounding components and, if necessary, a solvent or the like, and mixing and dispersing them using a rotary mixer or the like.

[0168] <Physical properties and uses of the resin composition> Since the resin composition contains components (A) to (D) in combination, a cured product having excellent adhesion to the conductor layer, suppressed generation of warpage amount, and low dielectric properties can be obtained. Further, usually, a cured product having excellent adhesion to the copper foil after the HAST test can also be obtained.

[0169] The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits the characteristic of excellent adhesion to the copper foil before the accelerated environmental test (HAST). Therefore, the cured product provides an insulating layer having excellent adhesion (peel strength) to the copper foil before the HAST test. The peel strength is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more, still more preferably 0.6 kgf / cm or more. The upper limit of the peel strength can be, for example, 10 kgf / cm or less. The peel strength can be measured according to the method described in the examples below.

[0170] The cured product obtained by thermosetting the resin composition at 200°C for 90 minutes usually exhibits the property of excellent adhesion to copper foil after the accelerated environmental test (HAST). Therefore, the cured product provides an insulating layer with excellent adhesion (peel strength) to copper foil after the HAST test. The peel strength after the HAST test is preferably 0.3 kgf / cm or more, more preferably 0.4 kgf / cm or more, and even more preferably 0.5 kgf / cm or more. The upper limit of the peel strength after the HAST test can be 10 kgf / cm or less, etc. The peel strength can be measured according to the method described in the examples below.

[0171] The cured product obtained by thermosetting the resin composition at 190°C for 90 minutes exhibits the property of low dielectric tangent. Therefore, the cured product provides an insulating layer with a low dielectric tangent. The dielectric tangent is preferably 0.005 or less, more preferably 0.0045 or less, and even more preferably 0.004 or less. The lower limit value of the dielectric tangent can be 0.0001 or more, etc. The dielectric tangent can be measured according to the method described in the examples below.

[0172] The cured product obtained by thermosetting the resin composition at 190°C for 90 minutes exhibits the property of low dielectric constant (relative permittivity). Therefore, the cured product provides an insulating layer with a low relative permittivity. The relative permittivity is preferably 5 or less, more preferably 4 or less, even more preferably 3.5 or less, 3.3 or less. The lower limit value of the relative permittivity can be 1 or more, etc. The relative permittivity can be measured according to the method described in the examples below.

[0173] Since the cured product obtained by thermosetting the resin composition at 190°C for 90 minutes exhibits the property of low elastic modulus at 23°C, it exhibits the property of suppressing the generation of warpage amount. Therefore, the cured product provides an insulating layer with suppressed generation of warpage amount. The elastic modulus at 23°C is preferably 20 GPa or less, more preferably 15 GPa or less, and even more preferably 13 GPa or less. The lower limit can be 0.1 GPa or more, etc. The elastic modulus can be measured according to the method described in the examples below.

[0174] The resin composition of the present invention has excellent adhesion to a conductor layer, suppresses the generation of warpage amount, and enables the formation of a cured product with low dielectric properties. Furthermore, it is possible to obtain a cured product having excellent adhesion after the HAST test. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation 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 an insulating layer.

[0175] Also, in a multilayer printed wiring board described later, 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).

[0176] 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 rewiring layer may be further 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) A step of forming an encapsulation layer on the semiconductor chip, (4) A step of peeling the base material and the temporary fixing film from the semiconductor chip, (5) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0177] [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.

[0178] From the viewpoints of thinning the printed wiring board and providing a cured product excellent in insulation 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 may be usually 5 μm or more.

[0179] 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.

[0180] 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, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

[0181] When using a metal foil as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable. 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.

[0182] The support may be subjected to a mat treatment, a corona treatment, or an antistatic treatment on the surface that joins the resin composition layer.

[0183] Further, as the support, a support with a release layer having a release layer on the surface that bonds to 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., and the like can be mentioned.

[0184] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. 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.

[0185] In one embodiment, the resin sheet may further contain other layers as necessary. 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 bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and the like and scratches on the surface of the resin composition layer.

[0186] The resin sheet can be manufactured, for example, by preparing a resin varnish in which the resin composition is dissolved in a solvent, applying this resin varnish onto the support using a die coater or the like, and further drying to form a resin composition layer. The solvent is as described above.

[0187] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but drying is carried out so that the content of the solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it 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, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0188] The resin sheet can be wound up and stored in a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0189] [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.

[0190] The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the above resin sheet. (I) A step of laminating on an inner layer substrate so 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

[0191] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board, and examples include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Further, the substrate may have a conductor layer on one or both sides thereof, and this conductor layer may be pattern-processed. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Also, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components can be used.

[0192] The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter, also referred to as "thermocompression bonding member"), for example, a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll) can be mentioned. In addition, rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the inner layer substrate.

[0193] The lamination of the inner layer substrate and the resin sheet may be carried out by the vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0194] The lamination can be carried out by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikkō Materials Co., Ltd., a batch type vacuum pressure laminator, and the like.

[0195] After the lamination, under normal pressure (atmospheric pressure), for example, by pressing the thermocompression bonding member from the support side, a smoothing treatment of the laminated resin sheet may be performed. The pressing conditions for the smoothing treatment can be the same as the thermocompression bonding conditions for the above lamination. The smoothing treatment can be carried out by a commercially available laminator. In addition, the lamination and the smoothing treatment may be continuously carried out using the above-mentioned commercially available vacuum laminator.

[0196] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0197] In step (II), the resin composition layer is thermoset to form an insulating layer. The thermosetting 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.

[0198] For example, the thermosetting 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.

[0199] Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer may be preheated 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) for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes).

[0200] When manufacturing a printed wiring board, steps (III) of drilling holes in the insulating layer, (IV) of roughening the insulating layer, and (V) of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art and used for manufacturing a printed wiring board. 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.

[0201] 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., depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

[0202] 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, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer. 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", "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 carried out, for example, by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the 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 carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. 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. The neutralizing liquid used for the roughening treatment is preferably an acidic aqueous solution. 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 carried out by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing liquid at 30°C to 80°C for 1 minute to 30 minutes.From the viewpoint of workability and the like, a method of immersing an object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0203] 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 still 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 still more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

[0204] 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 general applicability, 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 still more preferable.

[0205] 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.

[0206] 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.

[0207] In one embodiment, the conductor layer may be formed by plating. For example, a plating seed layer can be formed on the surface of the insulating layer by a conventionally known technique such as semi-additive method or full-additive method 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.

[0208] 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. Then, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0209] [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.

[0210] 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.).

[0211] 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" means "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 a semiconductor.

[0212] 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, 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), etc. can be mentioned. 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 and the wiring on the printed wiring board are connected."

Example

[0213] 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 "% by mass", respectively.

[0214] The conditions of GPC used for measuring the number average molecular weight, etc. 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 Method for measuring molecular weight: 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)

[0215] <Synthesis Example 1: Synthesis of Silicone Resin 1> To a round-bottom flask equipped with a Dean-Stark apparatus, 2.95 g of diphenylsilanediol, 3.00 g of 3-glycidyloxypropyl(dimethoxy)methylsilane, and 128 mg of barium hydroxide monohydrate were added, and the mixture was stirred at 85 °C for 6 hours under an argon atmosphere. After cooling to room temperature, toluene was added to filter off impurities, and the filtrate was concentrated under reduced pressure to obtain 6 g of a colorless transparent oily silicone resin 1. The resin was dissolved in toluene to obtain the target silicone epoxy resin 1 with a solid content concentration of 50 mass% (number average molecular weight 3468, active group equivalent weight approximately 385 g / eq., non-volatile component ratio 50%). The silicone epoxy resin 1 was identified using an NMR apparatus (nuclear magnetic resonance apparatus: Bruker AVANCE 400 (400 MHz)), and it was confirmed to have a structural unit represented by the following formula (A-1-1) and a structural unit represented by formula (A-2-1) (where * represents a bond in the formula). 1 H-NMR(400MHz,Chloroform-d)δ 7.67 - 7.01(m,10H),3.76 - 2.84(m,5H),2.82 - 2.62(m,1H),2.61 - 2.41(m,1H),1.67 - 1.03(m,2H),0.64 - 0.17(m,2H),0.16 - 0.35(m,3H) [Chemical formula]

[0216] <Synthesis Example 2: Synthesis of Silicone Resin 2> To a round-bottomed flask equipped with a Dean-Stark apparatus, 4.91 g of diphenylsilanediol, 5.00 g of 3-glycidyloxypropyl(dimethoxy)methylsilane, and 215 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-based epoxy resin 2. The obtained product was dissolved in toluene to obtain a target silicone resin 2 having a solid content concentration of 50% by mass (number average molecular weight 7,869, active group equivalent of about 393 g / eq., nonvolatile component ratio of 50%). The silicone-based epoxy resin 2 was identified using an NMR apparatus (Bruker AVANCE 400 (400 MHz)), and it was confirmed that it had a structural unit represented by the following formula (A-1-1) and a structural unit represented by formula (A-2-1) (where * represents a bond in the formula). 1 H-NMR(400MHz,Chloroform-d)δ 7.68-7.02(m,10H),3.75-2.85(m,5H),2.81-2.60(m,1H),2.59-2.41(m,1H),1.66-1.02(m,2H),0.65-0.18(m,2H),0.17-0.33(m,3H)

Chemical formula

[0217] <Synthesis Example 3: Synthesis of maleimide A> A MEK solution of maleimide compound A (nonvolatile component 62% by mass, t’’ = 1.47 (mainly 1, 2, or 3), Mw / Mn = 1.81) synthesized by the method described in Synthesis Example 1 of JP-A 2020-500211 was prepared. This maleimide compound A has a structure represented by the following formula (1).

Chemical formula

[0218] <Synthesis Example 4: Synthesis of polyimide B> A 500 mL separable flask equipped with a reflux cooler, a moisture metering receiver, a nitrogen inlet tube, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to this flask, and the mixture was stirred at 45 °C for 2 hours under a nitrogen stream to carry out the reaction. Next, the temperature of this reaction solution was raised, and while maintaining it at about 160 °C, the condensed water was removed by azeotropic distillation together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the moisture metering receiver and that the outflow of water was no longer visible. 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). Further, the weight average molecular weight of the polyimide resin was 12,000. [Chemical formula]

[0219] <Production of resin varnish> Each component was weighed in the parts by mass shown 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] *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.

[0220] Details of each component described in the table are as follows. Component (A) ·Silicone resin 1: Synthesized and prepared in Synthesis Example 1 ·Silicone resin 2: Synthesized and prepared in Synthesis Example 2 (B) component · HP-4032-SS: Naphthalene-type epoxy resin (functional group equivalent: 144 g / eq., manufactured by DIC Corporation) · NC-3000-L: Biphenyl-type epoxy resin (functional group equivalent: 269 g / eq., manufactured by Nippon Kayaku Co., Ltd.) · ZX-1059: 1:1 mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent: 169 g / eq.) · ESN-475V: Naphthalene-type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent: 332 g / eq.) · 828EL: Bisphenol A-type liquid epoxy resin, functional group equivalent: 189 g / eq., manufactured by Mitsubishi Chemical Corporation

Chem.

Chem.

[0221] (Measurement of Dielectric Constant, Dissipation Factor, and Elastic Modulus) (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 applied 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 a resin sheet A including the support and the resin composition layer.

[0222] (2) Preparation of the cured product of the resin composition layer The resin sheet A obtained in the examples and comparative examples was cured in an oven at 190°C for 90 minutes. By peeling off the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained.

[0223] (3) Measurement of dielectric constant and dielectric loss tangent (dielectric properties) The cured product was cut out into pieces with a length of 80 mm and a width of 2 mm, and using 「HP8362B」manufactured by Agilent Technologies, the values of dielectric constant and dielectric loss tangent (Dk value and Df value) were measured at a measurement frequency of 5.8 GHz, measurement temperatures of 23°C and 90°C by the cavity resonance perturbation method. The measurement was carried out on two test pieces, and the average value was calculated.

[0224] (4) Measurement of elastic modulus Tensile strength measurement was performed using a tensile testing machine 「RTC-1250A」manufactured by Orientec, and the elastic modulus at 23°C was measured. The measurement was carried out in accordance with JIS K7127. The measurement was carried out 5 times, and the average value of the top 3 data points was calculated.

[0225] <Evaluation of adhesion> (1) Substrate treatment of copper foil The shiny surface of an electrolytic copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., "3EC-III", thickness 35 μm) was etched by 1 μm using a micro-etching agent (manufactured by Meck Co., Ltd., "CZ8101") to roughen the copper surface, and then a rust prevention treatment (CL8300) was applied. The copper foil whose surface was etched with the above micro-etching agent is sometimes hereinafter referred to as "CZ copper foil". Further, this copper foil was heat-treated in an oven at 130 °C for 30 minutes to obtain copper foil I having a treated surface subjected to the roughening treatment.

[0226] (2) Preparation of inner layer substrate A glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, manufactured by Panasonic Corporation, "R1515A") having a copper foil on the surface and an inner layer circuit formed thereon was prepared. Both surfaces of this glass cloth base epoxy resin double-sided copper-clad laminate were etched by 1 μm using a micro-etching agent (manufactured by Meck Co., Ltd., "CZ8101") to roughen the copper foil surface. Thereby, an inner layer substrate having a CZ copper foil having a treated surface on the surface was obtained.

[0227] (3) Lamination of resin composition layer The resin sheets prepared in the examples and comparative examples were laminated on both surfaces of the inner layer substrate. This lamination was performed using a batch type vacuum pressure laminator (manufactured by Nichco Materials Co., Ltd., 2-stage build-up laminator "CVP700") so that the resin composition layer was in contact with the above inner layer substrate. Further, the above lamination was carried out by reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then pressure-bonding at 120 °C and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was subjected to a hot press at 100 °C and a pressure of 0.5 MPa for 60 seconds. Thereafter, the support was peeled off to expose the resin composition layer.

[0228] (4) Lamination of copper foil and curing of resin composition layer The treated surface of copper foil I was laminated on the exposed resin composition layer under the same conditions as in the above-mentioned "(3) Lamination of the resin composition layer". Then, the resin composition layer was cured under the curing conditions of 200°C for 90 minutes to form an insulating layer containing a cured product of the resin composition. Through the above operations, an evaluation substrate C with CZ copper foil laminated on both sides of the insulating layer was obtained. This evaluation substrate C had a layer structure of copper foil I / insulating layer / inner substrate / insulating layer / copper foil I.

[0229] (5) Measurement of the adhesion (peel strength) with the copper foil before the HAST test The evaluation substrate C was cut into small pieces of 150 mm × 30 mm. A cut was made in the copper foil I of the small piece using a cutter to surround a portion with a width of 10 mm and a length of 100 mm. One end of this portion was peeled off and grasped with the gripper of a tensile testing machine (Autocom universal testing machine "AC-50C-SL" manufactured by T.S.E. Co., Ltd.). At room temperature (25°C), it was pulled vertically at a speed of 50 mm / min, and the load [kgf / cm] when 35 mm was peeled off was measured as the copper foil peel strength. The measurement was carried out in accordance with Japanese Industrial Standard JIS C6481.

[0230] (6) Measurement of the copper foil peel strength after the accelerated environmental test (HAST) The evaluation substrate C was subjected to an accelerated environmental test for 100 hours under the conditions of 130°C and 85% RH using a highly accelerated life test device ("PM422" manufactured by Kusumoto Chemical Co., Ltd.). Then, similar to the measurement of adhesion 1, one end of the copper foil was peeled off and grasped with a gripper (manufactured by T.S.E. Co., Ltd., Autocom type testing machine, "AC-50C-SL"), and the load when 35 mm was peeled off vertically at a speed of 50 mm / min at room temperature was measured in accordance with JIS C6481 using an Instron universal testing machine.

[0231]

Table 2

[0232] In Examples 1 to 10, 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 in the above examples.

Claims

1. A silicone resin having a structural unit represented by the following formula (A-1) and a structural unit represented by the following formula (A-2), An epoxy resin (excluding those corresponding to component (A)), An active ester-based curing agent, and An inorganic filler, a resin composition containing. 【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 represent a monovalent hydrocarbon group which may have a substituent. * represents a bond. 【Chemical Formula 2】 In formula (A-1a), n1 represents an integer of 2 to 10. * represents a bond to a silicon atom in formula (A-1). In formula (A-1b), n2 represents an integer of 1 to 10. * represents a bond to a silicon atom in formula (A-1).

2. The resin composition according to claim 1, wherein n1 in formula (A-1a) represents an integer of 3 to 8.

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

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

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

6. The resin composition according to claim 1, wherein the number average molecular weight of component (A) is 10,000 or less.

7. The resin composition according to claim 1, wherein the content of component (D) exceeds 60% by mass when the non-volatile component of the resin composition is 100% by mass.

8. 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 1 to 7.

9. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 7.

10. A semiconductor device including the printed wiring board according to claim 9.

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