Resin composition

Abstract

To provide a resin composition and the like capable of producing a cured product with enhanced crack resistance, elevated peel strength, and a reduced dielectric loss tangent.SOLUTION: A resin composition comprises (A) an epoxy resin, (B) an active ester-based curing agent, (C) a curing accelerator with a group represented by formula (C-1), and (D) a curing accelerator (excluding those corresponding to component (C)).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition. Further, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device obtained 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 laminated is known. In the manufacturing method by the build-up method, generally, the insulating layer is formed by curing a resin composition. As such a resin composition, for example, the resin composition disclosed in Patent Document 1 is known.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The insulating layer of a printed wiring board is required to have a low dielectric tangent from the viewpoint of improving electrical characteristics. For this reason, a method of containing an active ester-based curing agent in the resin composition can be considered, but when an active ester-based curing agent is contained, the crack resistance of the cured product may be inferior or the peel strength from the conductor layer may be inferior.

[0005] The present invention was devised in view of the above problems, and provides a resin composition capable of obtaining a cured product having excellent crack resistance, high peel strength, and low dielectric tangent; a resin sheet including a resin composition layer containing the resin composition; a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that, even when using (B) an active ester-based curing agent, by using in combination a (C) component having a specific structure in addition to the (D) component as a curing accelerator, it is possible to obtain a cured product having excellent crack resistance, high peel strength, and low dielectric tangent. Based on this unexpected and remarkable finding, the inventors have found that the above problems can be solved and have completed the present invention.

[0007] That is, the present invention includes the following. [1] (A) An epoxy resin, (B) An active ester-based curing agent, (C) A curing accelerator having a group represented by the formula (C-1), and (D) A resin composition containing a curing accelerator (excluding those corresponding to the (C) component). [Chemical formula] In the formula, R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms. * represents a bond. [2] Further, the resin composition according to [1], further containing (E) an inorganic filler. [3] The resin composition according to [1] or [2], wherein the content of the (B) component is 5% by mass or more and 25% by mass or less when the non-volatile components in the resin composition are 100% by mass. [4] The resin composition according to any one of [1] to [3], wherein the content of the (C) component is 0.01% by mass or more and 1.5% by mass or less when the non-volatile components in the resin composition are 100% by mass. [5] The resin composition according to any one of [1] to [4], wherein the content of the (D) component is 0.01% by mass or more and 0.5% by mass or less when the non-volatile components in the resin composition are 100% by mass. [6] The resin composition according to any one of [1] to [5], wherein the (C) component has a cyclic structure. [7] The resin composition according to any one of [1] to [6], wherein the (C) component has two or more groups represented by the formula (C-1). [8] The resin composition according to any one of [1] to [7], wherein the (D) component contains either an imidazole-based curing accelerator or an amine-based curing accelerator. [9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer.

[10] 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 [9].

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

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

[11] . [Advantages of the Invention]

[0008] According to the present invention, there can be provided a resin composition capable of obtaining a cured product excellent in crack resistance, having high peel strength, and low dielectric tangent; a resin sheet including a resin composition layer containing the resin composition; a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board. [Embodiments for Carrying Out the Invention]

[0009] Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0010] [Resin Composition] The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester-based curing agent, (C) a curing accelerator having a group represented by the formula (C-1), and (D) a curing accelerator (excluding those corresponding to the component (C)). According to such a resin composition, it is possible to obtain a cured product having excellent crack resistance, high peel strength, and low dielectric tangent. In addition, the resin composition can usually also obtain a cured product having a small surface roughness after roughening treatment.

Chemical formula

[0011] The resin composition may further optionally contain any components such as (E) an inorganic filler, (F) a thermoplastic resin, (G) a curing agent, (H) a radically polymerizable compound, and (I) other additives, as required. Hereinafter, each component contained in the resin composition will be described in detail.

[0012] In the present invention, the content of each component in the resin composition is a value when the non-volatile components in the resin composition are 100% by mass, unless otherwise specified. The non-volatile components mean the entire non-volatile components excluding the solvent in the resin composition. Further, in the present invention, the resin components in the resin composition represent the components excluding the (E) inorganic filler among the non-volatile components of the resin composition.

[0013] <(A) Epoxy resin> The resin composition contains (A) an epoxy resin as the component (A). By containing the (A) epoxy resin in the resin composition, a cured product having low dielectric properties and excellent peel strength can be obtained. The (A) epoxy resin may be used alone or in combination of two or more.

[0014] (A) Examples of the epoxy resin include bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, tris-phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, glycidyl cyclohexane type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalimide type epoxy resin, etc. The epoxy resin may be used alone or in combination of two or more.

[0015] The resin composition preferably contains, as the component (A), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more with respect to 100% by mass of the epoxy resin (A).

[0016] The epoxy resin includes an epoxy resin that is liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at 20°C (hereinafter sometimes referred to as "solid epoxy resin"). The resin composition may contain only the liquid epoxy resin, only the solid epoxy resin, or a combination of the liquid epoxy resin and the solid epoxy resin as the component (A).

[0017] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0018] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, and phenolphthalimide type epoxy resin are preferable, and bisphenol A type epoxy resin is more preferable.

[0019] 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" (glycidyl amine 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-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. etc. These may be used alone or in combination of two or more.

[0020] 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.

[0021] As the solid epoxy resin, a bicyclol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolac 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, a tetraphenylethane type epoxy resin are preferable, and a biphenyl type epoxy resin is more preferable.

[0022] 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" (phenolphthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. These may be used alone or in combination of two or more kinds.

[0023] When using a combination of a liquid epoxy resin and a solid epoxy resin as component (A), their quantitative ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.3 to 1:10, and particularly preferably 1:0.5 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.

[0024] The epoxy equivalent of component (A) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., still more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. By being within this range, a cured product with a sufficient crosslink density of the resin composition can be obtained. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0025] From the viewpoint of remarkably obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of component (A) 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.

[0026] Regarding the content of component (A), from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, when the resin component in the resin composition is 100% by mass, it is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, preferably 60% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, and still more preferably 65% by mass or less.

[0027] The content of component (A), from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more when the non-volatile components in the resin composition are taken as 100% by mass. The upper limit of the content of the epoxy resin is preferably 35% by mass or less, more preferably 30% by mass or less, particularly preferably 25% by mass or less from the viewpoint of significantly obtaining the desired effects of the present invention.

[0028] <(B) Active ester curing agent> The resin composition contains, as component (B), an (B) active ester curing agent. The (B) active ester curing agent as component (B) does not include those corresponding to the above-mentioned component (A). The (B) active ester curing agent can usually form a bond by reacting with the (A) epoxy resin to cure the resin composition. Since the resin composition contains component (B), a cured product with a small surface roughness after roughening treatment can be obtained. Further, in the present invention, by using component (A) and the (B) active ester curing agent in combination, a cured product excellent in peel strength with plating can be obtained, and the dielectric property can also be lowered. Component (B) may be used alone or in combination of two or more.

[0029] (B) As the active ester-based curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are generally 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, 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, 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.

[0030] Specifically, examples of component (B) 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 novolac, active ester-based curing agents containing a benzoylated product of phenol novolac, active ester-based curing agents that are acetylated products of phenol novolac, active ester-based curing agents containing a styryl group and a naphthalene structure, and the like. 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.

[0031] Among them, as component (B), it is more preferable that it is one or more selected from active ester-based curing agents containing a styryl group and a naphthalene structure, and naphthalene-type active ester-based curing agents containing a naphthalene structure, and a naphthalene-type active ester-based curing agent containing a naphthalene structure is even more preferable.

[0032] Examples of commercially available products of component (B) include, as active ester-based curing agents containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); as naphthalene-type active ester-based curing agents containing a naphthalene structure, "HP-B-8151-62T", "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Corporation), "PC1300-02-65T" (manufactured by Air Water, Inc.); as phosphorus-containing active ester compounds, "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.), and the like.

[0033] From the viewpoint of being able to reduce the dielectric loss tangent and obtaining a cured product excellent in peel strength, the active ester group equivalent of component (B) 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.

[0034] (A) The quantitative ratio of the epoxy resin to (B) the active ester-based curing agent is the ratio of [the total number of active groups of the active ester-based curing agent] / [the 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 3 or less, still more preferably 2 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 significantly obtain the effects of the present invention.

[0035] Regarding the content of component (B), from the viewpoint of obtaining a cured product having a small surface roughness after the roughening treatment and excellent peel strength and dielectric tangent, when the resin component in the resin composition is 100% by mass, it is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, and preferably 55% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less. Since the resin composition of the present invention contains components (C) and (D) in combination, even if the content of component (B) is increased to lower the dielectric tangent, a cured product excellent in crack resistance and peel strength can be obtained.

[0036] Regarding the content of component (B), from the viewpoint of obtaining a cured product having a small surface roughness after the roughening treatment and excellent peel strength and dielectric tangent, when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 8% by mass or more. Also, the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less. Since the resin composition of the present invention contains components (C) and (D) in combination, even if the content of component (B) is increased to lower the dielectric tangent, a cured product excellent in crack resistance and peel strength can be obtained.

[0037] <A curing accelerator having a group represented by formula (C-1)> The resin composition contains, as component (C), a curing accelerator having a group represented by formula (C-1). The curing accelerator having a group represented by formula (C-1) as component (C) does not include those corresponding to the above-described component (A) and component (B). Component (C) usually functions as a catalyst in the reaction between (A) an epoxy resin and a curing agent such as component (B) and component (G), and can accelerate the curing of the resin composition. In the present invention, by using component (C) in combination with component (D) described later, a cured product excellent in crack resistance and excellent in peel strength from plating can be obtained. Component (C) may be used alone or in combination of two or more.

Chemical formula

[0038] As component (C), a compound having a group represented by formula (C-1) and having a function as a curing catalyst for accelerating the curing of (A) an epoxy resin can be used. Component (C) preferably has one or more groups represented by formula (C-1) in one molecule, and more preferably has two or more. The upper limit is not particularly limited, but may be 10 or less, 5 or less, etc.

[0039] In formula (C-1), R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a naphthyl group, etc.

[0040] The alkyl group having 1 to 3 carbon atoms and the aryl group having 6 to 10 carbon atoms may have a substituent. Examples of the substituent include a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, a sulfo group and the like. The number of substituents is preferably 0 to 3, more preferably 0 or 1, and still more preferably 0.

[0041] Among them, R 1 and R 2 preferably represent an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R 3 preferably represents a hydrogen atom.

[0042] (C) component preferably has a cyclic structure from the viewpoint of significantly obtaining the effects of the present invention. As the cyclic structure, a divalent cyclic group is preferable.

[0043] The divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, preferably a 20-membered ring or less, more preferably a 15-membered ring or less, and still more preferably a 10-membered ring or less from the viewpoint of significantly obtaining the effects of the present invention. The divalent cyclic group may have a monocyclic structure or a polycyclic structure. Further, a plurality of divalent cyclic groups may be contained in one molecule.

[0044] The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure.

[0045] Examples of the cyclic group containing an alicyclic structure include a divalent cyclic group having a cyclopentane ring, a divalent cyclic group having a cyclohexane ring, etc., and a divalent cyclic group having a cyclohexane ring is preferable.

[0046] Examples of the cyclic group containing an aromatic ring structure include a divalent cyclic group having a benzene ring, a divalent cyclic group having a naphthalene ring, etc., and a divalent cyclic group having a benzene ring is preferable.

[0047] The divalent cyclic group may have a substituent. Examples of the substituent include, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, an oxo group, etc. Among them, the substituent is preferably an alkyl group, more preferably a methyl group. The number of substituents is preferably 1 to 3.

[0048] Specific examples of the divalent cyclic group include the following groups. In the following divalent cyclic groups, * represents a bond.

Chemical formula

[0049] Component (C) is preferably a compound represented by the following formula (C-2).

Chemical formula

[0050] R 11 , R 21 , R 31 , R 41 , R 51 , and R 61 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R 11 , R 21 , R 41 , and R 51 are the same as R 1 in formula (C-1). R 31 and R 61 are the same as R 3 in formula (C-1).

[0051] Ring C represents a divalent cyclic group, and the divalent cyclic group is as described above.

[0052] Specific examples of the component (C) include the following compounds. However, the component (C) is not limited to these specific examples. [Chemical formula]

[0053] As the component (C), commercially available products may be used. Examples of commercially available products include "U-CAT 3512T", "U-CAT 3513N", etc. manufactured by San-Apro Ltd.

[0054] Regarding the content of the component (C), from the viewpoint of obtaining a cured product with excellent crack resistance, when the resin component in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 60% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1.5% by mass or less.

[0055] Regarding the content of the component (C), from the viewpoint of obtaining a cured product with excellent crack resistance, when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more. The upper limit of the content of the component (C) is preferably 1.5% by mass or less, more preferably 1% by mass or less, particularly preferably 0.8% by mass or less from the viewpoint of significantly obtaining the desired effects of the present invention.

[0056] When the content of component (A) is a and the content of component (C) is c based on 100% by mass of the non-volatile components in the resin composition, (c / a)×100 is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, 1.5 or more from the viewpoint of significantly obtaining the effects of the present invention, and is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less, 3.5 or less.

[0057] When the content of component (B) is b based on 100% by mass of the non-volatile components in the resin composition, (c / b)×100 is preferably 0.1 or more, more preferably 1 or more, still more preferably 2.5 or more from the viewpoint of significantly obtaining the effects of the present invention, and is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.

[0058] <(D) Curing accelerator> In addition to the above-described components, the resin composition further contains, as an optional component, a curing accelerator ((excluding those corresponding to component (C))) as component (D). The (D) curing accelerator as component (D) does not include those corresponding to the above-described components (A), (B), and (C). Component (D) usually functions as a catalyst in the reaction between (A) epoxy resin and a curing agent such as component (B) and component (G) to promote the curing of the resin composition. By using the resin composition of the present invention in combination with a curing accelerator having a group represented by formula (C-1) having a specific structure in addition to the (D) curing accelerator, it is possible to obtain a cured product excellent in crack resistance.

[0059] Examples of component (D) include imidazole-based curing accelerators, amine-based curing accelerators, guanidine-based curing accelerators, phosphorus-based curing accelerators, metal-based curing accelerators, and the like. Among them, as component (D), either an imidazole-based curing accelerator or an amine-based curing accelerator is preferable. Component (D) may be used alone or in combination of two or more.

[0060] 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 other imidazole compounds and adducts of imidazole compounds and epoxy resins. 2-Ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0061] As the imidazole-based curing accelerator, commercially available products may be used. Examples include "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd. and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0062] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene, etc. Among them, 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)undecene are preferred.

[0063] As the amine-based curing accelerator, commercially available products may be used. For example, "DMAP" manufactured by Tokyo Chemical Industry Co., Ltd. can be mentioned.

[0064] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. Among them, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0065] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

[0066] 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.

[0067] (D) component content, from the viewpoint of significantly obtaining the desired effects of the present invention, when the resin component in the resin composition is 100% by mass, 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 is preferably 60% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, 1.5% by mass or less.

[0068] (D) component content, from the viewpoint of significantly obtaining the desired effects of the present invention, when the non-volatile component in the resin composition is 100% by mass, 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 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.2% by mass or less.

[0069] When the content of the (D) component when the non-volatile component in the resin composition is 100% by mass is d, and the content of the (C) component when the non-volatile component in the resin composition is 100% by mass is c, c / d is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, 1.5 or more, from the viewpoint of obtaining a cured product with excellent crack resistance, and is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less, 4 or less, 3 or less.

[0070] When the content of component (B) is b with the non-volatile components in the resin composition being 100% by mass, b / (c + d) is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, 15 or more, and preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, 25 or less. Since the resin composition of the present invention contains components (C) and (D) in combination, even if the content of component (B) is increased to lower the dielectric loss tangent, a cured product excellent in crack resistance and peel strength can be obtained.

[0071] <(E) Inorganic filler> The resin composition may contain an (E) inorganic filler as an optional component in addition to the above-described components. By including the (E) inorganic filler in the resin composition, it becomes possible to obtain a cured product having excellent dielectric properties.

[0072] As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, 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. The (E) inorganic filler may be used alone or in combination of two or more.

[0073] (E) Examples of commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "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; "Selfiers" and "MGH-005" manufactured by Taiheiyo Cement Corporation; "Esferic" and "BA-S" manufactured by JGC Catalysts & Chemicals Ltd., and the like.

[0074] (E) From the viewpoint of significantly obtaining the desired effects of the present invention, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less.

[0075] (E) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a volume-based particle size distribution of the inorganic filler with a laser diffraction / scattering type particle size distribution measuring device and using 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 is measured for 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 is 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. and "SALD-2200" manufactured by Shimadzu Corporation.

[0076] (E) From the viewpoint of significantly obtaining the desired effects of the present invention, the specific surface area of the inorganic filler is preferably 1 m 2 / g or more, more preferably 2 m 2 / g or more, particularly preferably 3 m2 / g or more. There is no particular limitation on the upper limit, but preferably 60 m 2 / g or less, 50 m 2 / g or less or 40 m 2 / g or less. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a BET full-automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multi-point method to measure the specific surface area of the inorganic filler.

[0077] (E) 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 such as 3,3,3-trifluoropropyltrimethoxysilane; aminosilane-based coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; epoxy silane-based coupling agents such as 3-glycidoxypropyltrimethoxysilane; mercapto silane-based coupling agents such as 3-mercaptopropyltrimethoxysilane; silane-based coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane; titanate-based coupling agents, etc. Further, the surface treatment agent may be used alone or in any combination of two or more.

[0078] Examples of commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0079] 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 predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, more preferably surface-treated with 0.2 to 3 parts by mass, and still more preferably surface-treated with 0.3 to 2 parts by mass.

[0080] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and still more preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and still more preferably 0.5 mg / m 2 or less.

[0081] (E) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0082] (E) As the content of the inorganic filler, from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, it is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, preferably 90% by mass or less, preferably 85% by mass or less, and preferably 80% by mass or less.

[0083] <(F) Thermoplastic resin> The resin composition of the present invention may further contain (F) a thermoplastic resin as an optional component. The (F) thermoplastic resin as this (F) component does not include those corresponding to the above-mentioned (A) to (D) components.

[0084] (F) Examples of the thermoplastic resin include polyimide resin, phenoxy 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. In one embodiment, the (F) thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and more preferably contains phenoxy resin. Also, the thermoplastic resin may be used alone or in combination of two or more.

[0085] Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Lica Coat SN20" and "Lica Coat PN20" manufactured by Nippon Rika Kogyo Co., Ltd., and the like.

[0086] Examples of the phenoxy resin include a phenoxy resin having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0087] 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.

[0088] Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Kabushiki Kaisha; 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.

[0089] 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, and the like.

[0090] Examples of polybutadiene resins include, for example, 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.

[0091] Specific examples of polyamideimide resins include "Vyromax HR11NN" and "Vyromax 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 Hitachi Chemical Co., Ltd.

[0092] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0093] Specific examples of polysulfone resins include polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers, LLC.

[0094] Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE.

[0095] Examples of the polycarbonate resin include hydroxy group-containing carbonate resin, phenolic hydroxyl group-containing carbonate resin, carboxy group-containing carbonate resin, acid anhydride group-containing carbonate resin, isocyanate group-containing carbonate resin, 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 Chemicals 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.

[0096] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethylene terephthalate resin, and the like.

[0097] (F) From the viewpoint of significantly obtaining the effects of the present invention, the weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

[0098] (F) From the viewpoint of significantly obtaining the desired effects of the present invention, when the resin components in the resin composition are 100% by mass, the content of the thermoplastic resin is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and is preferably 6% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less.

[0099] (F) From the viewpoint of significantly obtaining the desired effects of the present invention, when the content of the thermoplastic 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 0.2% by mass or more, still more preferably 0.3% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less.

[0100] <(G) Curing agent> In addition to the above-described components, the resin composition may further contain, as an optional component, (G) a curing agent. The (G) curing agent as this (G) component does not include those corresponding to the above-described components (A) to (F). The (G) curing agent can usually form a bond by reacting with the (A) epoxy resin to cure the resin composition. Examples of the (G) curing agent include phenolic curing agents, naphtholic curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents. Among them, from the viewpoint of improving insulation reliability, the (G) curing agent is preferably any one or more of phenolic curing agents, naphtholic curing agents, and carbodiimide curing agents, more preferably any one of phenolic curing agents and naphtholic curing agents, and still more preferably contains a phenolic curing agent. The (G) curing agent may be used alone or in combination of two or more.

[0101] From the viewpoints of heat resistance and water resistance, the phenolic curing agent and the naphtholic curing agent are preferably a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure. Also, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a phenolic curing agent containing a triazine skeleton is more preferable.

[0102] Specific examples of phenolic curing agents and naphthol curing agents include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA3018-50P", "EXB-9500" manufactured by DIC Corporation, etc.

[0103] Specific examples of benzoxazine curing agents include "HFB2006M" manufactured by Showa Highpolymer Co., Ltd., "P-d", "F-a" manufactured by Shikoku Kasei Kogyo Co., Ltd.

[0104] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-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 triazinized, etc. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", "BA230S75" (prepolymer in which some or all of bisphenol A dicyanate is triazinized to form a trimer) manufactured by Lonza Japan Co., Ltd., etc.

[0105] Specific examples of the carbodiimide-based curing agent include "V-03", "V-07", etc. manufactured by Nisshinbo Chemical Inc.

[0106] When the curing agent is contained as the (G) component, the quantitative ratio of the (A) epoxy resin, (B) active ester-based curing agent, and (G) curing agent is preferably in the range of [total number of epoxy groups of the epoxy resin]:[total number of active groups of the (B) active ester-based curing agent and (G) curing agent] at a ratio of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and even more preferably 1:0.5 to 1:2. 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 (B) active ester-based curing agent and (G) 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 and the curing agent present in the resin composition by the active group equivalent. By setting the quantitative ratio of the (B) component and the (G) component to be within such a range with respect to the epoxy resin, the effects of the present invention can be significantly obtained.

[0107] When the curing agent is contained as the (G) component, the quantitative ratio of the epoxy resin and all of the (G) curing agent is preferably in the range of [total number of epoxy groups of the epoxy resin]:[total number of active groups of the (G) curing agent] at a ratio of 1:0.01 to 1:1, more preferably 1:0.03 to 1:0.5, and even more preferably 1:0.05 to 1:0.3. Here, the "number of active groups of the (G) curing agent" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the (G) curing agent present in the resin composition by the active group equivalent. By setting the quantitative ratio of the epoxy resin and the curing agent as the (G) component to be within such a range, the effects of the present invention can be significantly obtained.

[0108] Regarding the content of the (G) component, from the viewpoint of significantly obtaining the desired effects of the present invention, when the resin component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and preferably 60% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7.5% by mass or less.

[0109] (G) From the viewpoint of significantly obtaining the desired effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, the content of the curing agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2.5% by mass or less.

[0110] <(H) Radical polymerizable compound> The resin composition of the present invention may further contain (H) a radical polymerizable compound as an optional component. The (H) radical polymerizable resin as this (H) component does not include those corresponding to the above-mentioned components (A) to (G). The (H) radical polymerizable compound may be used alone or in any combination of two or more.

[0111] (H) In one embodiment, the radical polymerizable compound is a radical polymerizable compound having an ethylenically unsaturated bond. The (H) radical polymerizable compound is not particularly limited, and examples thereof include unsaturated hydrocarbon groups such as an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a p-vinylphenyl group, an m-vinylphenyl group, and an o-vinylphenyl group; and α,β-unsaturated carbonyl groups such as an acryloyl group, a methacryloyl group, and a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), which may have a radical polymerizable group. The (H) radical polymerizable compound preferably has two or more radical polymerizable groups.

[0112] Examples of the (H) radical polymerizable compound may include (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, maleimide radical polymerizable compounds, and the like.

[0113] (Meth)acrylic radical polymerizable compounds are, for example, compounds having one or more, preferably two or more acryloyl groups and / or methacryloyl groups. Examples of (meth)acrylic radical polymerizable compounds include low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds such as cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate; low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate; high molecular weight (molecular weight 1000 or more) acrylate compounds such as (meth)acryl-modified polyphenylene ether resin, and the like.Examples of commercially available (meth)acrylic radical polymerizable compounds include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd., "SA9000", "SA9000-111" (methacrylic modified polyphenylene ether) manufactured by SABIC Innovative Plastics, etc.

[0114] Styrene-based radical polymerizable compounds are, for example, compounds having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based radical polymerizable compounds include low molecular weight (molecular weight less than 1000) styrene-based compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether; high molecular weight (molecular weight 1000 or more) styrene-based compounds such as vinylbenzyl modified polyphenylene ether resin, styrene-divinylbenzene copolymer, etc. Examples of commercially available styrene-based radical polymerizable compounds include "ODV-XET(X03)", "ODV-XET(X04)", "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemical & Material Co., Ltd., "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Company, Inc.

[0115] An allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more allyl groups. Examples of the allyl radical polymerizable compound include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, diallyl 2,3-naphthalenedicarboxylate; allyl isocyanurate ester compounds such as 1,3,5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; allyl silane compounds such as diallyl diphenylsilane and the like. Commercially available products of allyl radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshin Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., the product name "DAND" (diallyl 2,3-naphthalenedicarboxylate) manufactured by Nippon Distillation Industry Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Kasei Kogyo Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Co., Ltd., and the like.

[0116] The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Examples of commercially available products include "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (a maleimide compound containing a dimer diamine structure) manufactured by Designer Molecules, Inc., "BMI-6100" (an aromatic maleimide compound) manufactured by Designer Molecules, Inc., "MIR-5000-60T", "MIR-3000-70MT" (biphenyl aralkyl type maleimide compounds) manufactured by Nippon Kayaku Co., Ltd., "BMI-70", "BMI-80" manufactured by K.I. Kasei Co., Ltd., "BMI-2300", "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd., and the like. Further, as the maleimide-based radically polymerizable compound, a maleimide resin (a maleimide compound containing an indane ring skeleton) disclosed in Invention Association Public Technical Report Publication No. 2020-500211 may be used.

[0117] (H) The ethylene unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., still more preferably 70 g / eq. to 2000 g / eq., and particularly preferably 90 g / eq. to 1500 g / eq. The ethylene unsaturated bond equivalent is the mass of the radically polymerizable compound per equivalent of the ethylene unsaturated bond.

[0118] (H) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, but can be, for example, 150 or more.

[0119] The content of the (H) component, from the viewpoint of remarkably obtaining the desired effects of the present invention, when the resin component in the resin composition is 100% by mass, is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less.

[0120] The content of the (H) component, from the viewpoint of remarkably obtaining the desired effects of the present invention, when the non-volatile component in the resin composition is 100% by mass, 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 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less.

[0121] <(I) Other Additives> In addition to the above-described components, the resin composition may further contain other additives as optional components. Examples of such additives include elastomers (excluding those corresponding to the (F) component), organic fillers, thickeners, defoaming agents, leveling agents, adhesion-imparting agents, flame retardants, and the like. These may be used alone or in combination of two or more in any ratio.

[0122] The resin composition can be produced, for example, by mixing the above-described components in any order. Further, in the process of mixing each component, heating and / or cooling may be performed by appropriately adjusting the temperature. Also, during or after the mixing of each component, stirring may be performed using a stirring device such as a mixer to uniformly disperse each component. Furthermore, if necessary, a defoaming treatment may be performed on the resin composition.

[0123] <Physical Properties and Uses of Resin Composition> Since the resin composition contains the (A) component, (B) component, (C) component, and (D) component in combination, it is possible to obtain a cured product having excellent crack resistance, high peel strength, and low dielectric tangent. In addition, the resin composition can usually also obtain a cured product having a small surface roughness after roughening treatment.

[0124] The cured product obtained by curing the resin composition at 100°C for 30 minutes, 170°C for 30 minutes, and further 190°C for 1 hour exhibits the property of excellent crack resistance. Therefore, it provides an insulating layer with excellent crack resistance. Specifically, a layer made of the cured product of the resin composition is formed on the inner layer circuit board on which 25 copper patterns are formed. The layer made of the cured product is roughened, and a copper plating layer is formed on the roughened surface. At this time, the number of cracks in the 25 copper patterns is preferably 2 or less, more preferably 1 or less, and even more preferably 0. The crack resistance can be measured by the method described in the examples below.

[0125] The cured product obtained by curing the resin composition at 100°C for 30 minutes, 170°C for 30 minutes, and further 190°C for 1 hour can increase the peel strength with plating. Therefore, when an insulating layer is formed with this cured product, an insulating layer with high peel strength between the conductor layer can be obtained. The peel strength between the insulating layer and the conductor layer is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more. The upper limit value of the peel strength is not particularly limited, but can be, for example, 10.0 kgf / cm or less. The peel strength can be measured by the method described in the examples below.

[0126] The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes has a low dielectric tangent. Therefore, when an insulating layer is formed with this cured product, an insulating layer with a low dielectric tangent can be obtained. The dielectric tangent of the cured product is preferably less than 0.0035, more preferably less than 0.0030, even more preferably 0.0030 or less, 0.0025 or less. The lower limit is not particularly limited, but can be 0.0001 or more. The dielectric tangent can be measured by the method described in the examples below.

[0127] The cured product of the resin composition exhibits the property that the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is low. The arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably less than 200 nm, still more preferably 100 nm or less, and even more preferably less than 100 nm. The lower limit is not particularly limited, and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) can be measured by the method described in the examples below.

[0128] The resin composition of the present invention is suitable as a resin composition for insulating applications, and among them, it is particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition is suitable as a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board). Further, the resin composition is suitable as a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer (a resin composition for forming an insulating layer for forming a conductor layer). The resin composition can also be widely used in applications where resin compositions can be used, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, multi-chip packages, package-on-package, wafer-level packages, panel-level packages, system-in-package, etc.

[0129] Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment is a resin composition for forming a rewiring formation layer as an insulating layer for forming a rewiring layer (a resin composition for forming a rewiring formation layer), and a resin composition for encapsulating a semiconductor chip (a resin composition for encapsulating a semiconductor chip) is also suitable. When manufacturing a semiconductor chip package, a further rewiring layer may be formed on the encapsulation layer. (1) A step of laminating a temporary fixing film on a substrate, (2) Step of temporarily fixing the semiconductor chip on the temporary fixing film, (3) Step of forming a sealing layer on the semiconductor chip, (4) Step of peeling the substrate and the temporary fixing film from the semiconductor chip, (5) Step of forming a redistribution formation layer as an insulating layer on the surface of the substrate and the temporary fixing film of the semiconductor chip from which they are peeled, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer

[0130] The above-described resin composition can also be used when the printed wiring board is a component-built-in circuit board.

[0131] [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.

[0132] From the viewpoints of thinning the printed wiring board and providing a cured product having excellent insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0133] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

[0134] 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"), 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 preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0135] When using a metal foil as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0136] The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface that joins the resin composition layer.

[0137] Further, as the support, a support with a release layer having a release layer on the surface that joins the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, commercially available products may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., and the like.

[0138] 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 the release layer is within the above range.

[0139] In one embodiment, the resin sheet may further contain other layers as necessary. Such other layers include, for example, a protective film similar to the support provided on the surface of the resin composition layer that is not joined to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, 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.

[0140] The resin sheet can be produced, for example, by preparing a resin varnish in which the resin composition is dissolved in an organic solvent, applying this resin varnish onto the support using a die coater or the like, and further drying to form a resin composition layer.

[0141] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

[0142] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic 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 organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0143] The resin sheet can be wound up and stored in a roll shape. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0144] [Printed Wiring Board] The printed wiring board according to one embodiment of the present invention includes an insulating layer formed of a cured product obtained by curing the above-described resin composition.

[0145] The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the above-described resin sheet. (I) A step of laminating a resin sheet 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 curing the resin composition layer to form an insulating layer

[0146] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. 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 formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". Also, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "inner layer substrate". When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0147] 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 (such as a SUS roll) can be mentioned. Note that, 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.

[0148] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the 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 can preferably be carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0149] 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.

[0150] After the lamination, under atmospheric pressure, for example, a smoothing process of the laminated resin sheet may be performed by pressing the thermocompression bonding member from the support side. The pressing conditions for the smoothing process can be the same as the thermocompression bonding conditions for the above lamination. The smoothing process can be carried out by a commercially available laminator. Note that the lamination and the smoothing process may be continuously carried out using the above-mentioned commercially available vacuum laminator.

[0151] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0152] In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions employed when forming the insulating layer of a printed wiring board may be used. The resin composition layer may be cured by irradiation with active energy rays such as ultraviolet rays, but is usually thermally cured by heating.

[0153] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition. In one embodiment, 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.

[0154] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes.

[0155] The method for manufacturing a printed wiring board may further include (III) a step of drilling holes in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. 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 (I) to (V) may be repeated to form a multilayer wiring board.

[0156] 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 shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0157] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal is also carried out. The procedures and conditions of the roughening treatment are not particularly limited. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.

[0158] Examples of the swelling liquid used for the roughening treatment include an alkaline solution, a surfactant solution, etc., and an alkaline solution is preferred. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include "Swelling Dip Security Gun P" and "Swelling Dip Security Gun SBU" 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 a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0159] Examples of the oxidizing agent used for the roughening treatment include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in 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. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0160] As the neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferable. Examples of commercially available products include "Reduction Solution Security Guard P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object that has been roughened with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0161] In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment can preferably be 500 nm or less, more preferably less than 200 nm, still more preferably 100 nm or less, and even more preferably less than 100 nm. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. Also, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0162] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single-metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, etc. of forming the conductor layer, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single-metal layer of copper is even more preferred.

[0163] The conductor layer may have a single-layer structure, or may have a multi-layer 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 multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0164] 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.

[0165] The conductor layer is preferably formed by plating. For example, by plating on the surface of the insulating layer by methods such as semi-additive method and full-additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0166] 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 a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Then, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0167] [Semiconductor device] The semiconductor device according to an embodiment of the present invention includes the printed wiring board described above. This semiconductor device can be manufactured using the printed wiring board described above.

[0168] 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.).

Example

[0169] Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "mass%", respectively, unless otherwise specified. Also, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

[0170] <Example 1> 15 parts of a biphenyl type epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd.), 5 parts of a bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical & Material Co., Ltd.), 2 parts of an aminotriazine skeleton cresol novolak resin (“LA-3018-50P” manufactured by DIC Corporation), 26 parts of an active ester type curing agent (“HP-B-8151-62T” manufactured by DIC Corporation, containing 62% by mass of solid content and 38% by mass of toluene), 3 parts of a phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation), 150 parts of spherical silica (spherical silica obtained by surface-treating 100 parts of “SOC2” manufactured by Admatechs Co., Ltd. with 0.6 parts of a silane coupling agent having an N-phenyl-3-aminopropyl group (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5 μm), 0.2 part of 4-dimethylaminopyridine (“DMAP” manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.5 part of a curing accelerator (“U-CAT 3513N” manufactured by San-Apro Ltd.) were mixed and stirred at room temperature until a uniform solution was obtained to obtain a resin varnish.

[0171] Using an applicator, the resin varnish obtained above was coated on the release-treated surface of a PET film (thickness 38 μm), and then dried in a gear oven at 100 °C for 180 seconds to volatilize the solvent. Thus, a resin sheet having a resin composition with a thickness of 25 μm was obtained on the PET film.

[0172] <Examples 2 to 17, Comparative Examples 1 to 3> Each component was blended at the blending ratios shown in the following table and stirred at room temperature until a uniform solution was obtained to prepare a resin varnish. Also, a resin sheet was obtained in the same manner as in Example 1.

[0173]

Table 1

[0174]

Table 2

[0175] The abbreviations and the like in the table are as follows. (A) component · ZX1059: Bisphenol type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd.) · NC3000H: Biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd.) (B) component · HP-B-8151-62T: Active ester type curing agent ("HP-B-8151-62T" manufactured by DIC Corporation, containing 62% by mass of solid content and 38% by mass of toluene) · PC-1300-02-65MA: Active ester type curing agent ("PC-1300-02-65MA" manufactured by Air Water Inc., containing 65% by mass of solid content and 35% by mass of toluene) (C) component · U-CAT 3512T: (manufactured by San-Apro Ltd. "U-CAT 3512T"), a compound represented by the following structural formula

Chemical formula

Chemical formula

[0176] [Evaluation of Crack Resistance, Peel Strength, and Arithmetic Mean Roughness (Ra)] <Preparation of Samples> Etch the copper foils on both sides of a glass cloth base epoxy resin double-sided laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, size 500 mm × 500 mm, "R5715ES" manufactured by Panasonic) with an inner layer circuit formed, and produce 25 copper patterns with an L / S of 1 mm / 1 mm and a length of 5 cm to obtain a concavo-convex substrate. Then, perform roughening treatment on the copper surface by etching 1 μm with "CZ8100" manufactured by Meck to obtain an inner layer circuit board.

[0177] Lay the resin sheets obtained in each example and each comparative example on both sides of the inner layer circuit board using a batch-type vacuum pressure laminator (two-stage build-up laminator CVP700 manufactured by Nichigo-Morton). The lamination was carried out by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then crimping at 100 °C and a pressure of 0.74 MPa for 30 seconds. Subsequently, thermal pressing was performed at 100 °C and a pressure of 0.5 MPa for 60 seconds.

[0178] The laminated resin sheet was heated at 100 °C for 30 minutes and then at 170 °C for 30 minutes to thermoset the resin composition layer and form an insulating layer. The obtained laminated sample was designated as "Laminated Sample A".

[0179] Next, the following swelling treatment, roughening treatment, and electroless plating treatment were performed on the obtained Laminated Sample A.

[0180] Swelling treatment: The above Laminated Sample A was placed in a swelling solution at 60 °C (an aqueous solution containing "Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd. and "Sodium Hydroxide" manufactured by Wako Pure Chemical Industries, Ltd.) and shaken at a swelling temperature of 60 °C for 10 minutes. Then, it was washed with pure water.

[0181] Roughening treatment (permanganate treatment): The swollen laminated sample was placed in a sodium permanganate roughening aqueous solution at 80 °C (containing "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd. and "Sodium Hydroxide" manufactured by Wako Pure Chemical Industries, Ltd.) and shaken at a roughening temperature of 80 °C for 20 minutes. Then, it was washed with a cleaning solution at 40 °C (containing "Reduction Securigant P" manufactured by Atotech Japan Co., Ltd. and "Sulfuric Acid" manufactured by Wako Pure Chemical Industries, Ltd.) for 10 minutes, and then further washed with pure water to obtain Laminated Sample B.

[0182] Electroless plating treatment: The surface of Laminated Sample B was treated with an alkaline cleaner at 60 °C (Atotech Japan Co., Ltd.'s "Cleaner Securigant 902") for 5 minutes for degreasing and cleaning. After washing, the cured product was treated with a pre-dip solution at 25 °C (Atotech Japan Co., Ltd.'s "Pre-dip Neogant B") for 2 minutes. Then, the cured product was treated with an activator solution at 40 °C (Atotech Japan Co., Ltd.'s "Activator Neogant 834") for 5 minutes to attach a palladium catalyst. Next, Laminated Sample B was treated with a reducing solution at 30 °C (Atotech Japan Co., Ltd.'s "Reducer Neogant WA") for 5 minutes.

[0183] Next, the laminated sample B was placed in a electroless copper solution (all from Atotech Japan Co., Ltd., namely "Basic Print Gun MSK-DK", "Copper Print Gun MSK", "Stabilizer Print Gun MSK", "Reducer Cu"), and electroless plating was carried out until the plating thickness reached about 0.1 μm. After electroless plating, in order to remove the remaining hydrogen gas, annealing was performed at a temperature of 120 °C for 30 minutes. All processes up to the electroless plating process were carried out in a beaker scale with 2 L of the treatment solution, while oscillating the laminated sample B.

[0184] Next, electrolytic plating was carried out on the electroless-plated laminated sample B until the plating thickness reached 25 μm. Using a copper sulfate solution (copper sulfate pentahydrate from Wako Pure Chemical Industries, Ltd., sulfuric acid from Wako Pure Chemical Industries, Ltd., Basic Leveler Caparacid HL from Atotech Japan Co., Ltd., and Corrector Caparacid GS from Atotech Japan Co., Ltd.) for electrolytic copper plating, an electric current of 0.6 A / cm2 was passed until the plating thickness reached about 25 μm. After the copper plating treatment, the cured product was heated at 190 °C for 1 hour to further cure the cured product. In this way, a laminated sample C with a copper plating layer laminated on the upper surface was obtained.

[0185] <Evaluation of crack resistance> Regarding the laminated sample C, the presence or absence of cracks on the surface was confirmed using an optical microscope and evaluated according to the following criteria. 〇: There are no cracks in 25 copper patterns. △: There are 1 or 2 cracks in 25 copper patterns. ×: There are 3 or more cracks in 25 copper patterns.

[0186] <Evaluation of peel strength> In the laminated sample C, a notch was made with a width of 10 mm on the surface of the copper plating layer. Then, using a tensile testing machine (AC-50C-SL manufactured by TSE), at room temperature, the load (kgf / cm) when peeling 35 mm vertically at a speed of 50 mm / min was measured and evaluated according to the following criteria. ◎: Peel strength is 0.5 kgf / cm or more ○: Peel strength is less than 0.4 kgf / cm and less than 0.5 kgf / cm ×: Peel strength is less than 0.4 kgf / cm

[0187] [Measurement of arithmetic mean roughness (Ra)] The arithmetic mean roughness of the insulating layer surface of the laminated sample B was measured using a non-contact surface roughness meter (「WYKO NT3300」manufactured by Veeco Instruments Inc.) in VSI mode with a 50x lens, and the Ra value was determined by the numerical value obtained with a measurement range of 121 μm × 92 μm. The average value of 10 randomly selected points was determined as the measured value and evaluated according to the following criteria. ◎: Arithmetic mean roughness (Ra) is less than 100 nm ○: Arithmetic mean roughness (Ra) is 100 nm or more and less than 200 nm △: Arithmetic mean roughness (Ra) is 200 nm or more and less than 400 nm ×: Arithmetic mean roughness (Ra) is 400 nm or more

[0188] [Evaluation of dielectric loss tangent] [Preparation of evaluation samples] The resin compositions obtained in each example and each comparative example were uniformly coated on a release-treated PET film (「PET501010」manufactured by Lintec Corporation) with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and dried at 90 to 130 °C (average 110 °C) for 5 minutes. Then, heat treatment was performed at 200 °C for 90 minutes in a nitrogen atmosphere, and the cured product (thickness 40 μm) was obtained by peeling from the support. The cured product was cut into pieces with a length of 80 mm and a width of 2 mm to obtain evaluation samples.

[0189] [Evaluation of dielectric loss tangent] For the evaluation samples, the dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method (ASTM D2520) using HP8362B manufactured by Agilent Technologies. Measurements were performed on two test pieces and the average value was calculated and evaluated according to the following criteria. ◎: Dielectric loss tangent is less than 0.0025 〇: Dielectric tangent is 0.0025 or more and less than 0.0030 △: Dielectric tangent is 0.0030 or more and less than 0.0035 ×: Dielectric tangent is 0.0035 or more

[0190]

Table 3

[0191]

Table 4

[0192] In Examples 1 to 17, even when the components (E) to (G) are not contained, although there are differences to some extent, it has been confirmed that the results are the same as those of the above examples.

Claims

1. (A) an epoxy resin, (B) an active ester-based curing agent, (C) a curing accelerator having a group represented by formula (C-1), (D) a curing accelerator (excluding those corresponding to component (C)), and (E) an inorganic filler, wherein component (C) has a cyclohexane ring, the resin composition. 【Chemical 1】 In the formula, R １ , R ２ , and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms. * represents a bond.

2. A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to claim 1.

3. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to claim 1.

4. A semiconductor device comprising the printed wiring board according to claim 3.

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