Resin composition

Abstract

To provide a resin composition or the like that provides a cured product having a low dielectric loss tangent and excellent adhesion strength to a conductor layer after exposure to a high temperature and high humidity environment, and can exhibit good flexibility before curing.SOLUTION: The epoxy resin composition includes (A) epoxy resins and one or more resins selected from (B) active ester resins and (C) radical-polymerizable resins, wherein the (A) components include (a- 1) biphenol skeleton epoxy resins represented by the following general formula (1) and having epoxy equivalents of 200g / eq. or more and (a- 2) epoxy resins that are liquid at room temperature. [In the formula, R represents a hydrogen atom or a methyl group. N represents an integer of 0 to 10. ] SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] A known manufacturing technique for circuit boards such as printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked. In build-up manufacturing methods, the insulating layers are generally formed by curing a resin composition. Known examples of such resins include resin compositions in which an active ester resin or a radically polymerizable resin is added to an epoxy resin (Patent Document 1). On the other hand, tetramethylbiphenol-type epoxy resins are widely used as semiconductor encapsulants because they have excellent flame retardancy, heat resistance, and moisture absorption resistance, and also have a low melt viscosity at 150° C. (Patent Documents 2 and 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-44128 [Patent Document 2] Japanese Patent Application Publication No. 2017-48387 [Patent Document 3] Japanese Patent Application Publication No. 2017-48388 Summary of the Invention [Problem to be solved by the invention]

[0004] A cured product formed by curing a resin composition can be used as an insulating layer of a circuit board of a semiconductor device. With the recent increase in communication speeds, the insulating layer of a circuit board is required to have excellent dielectric properties (low dielectric dissipation factor) to reduce transmission loss when operating in a high-frequency environment. For example, as described in Patent Document 1, it is known that a resin composition obtained by adding an active ester resin or a radical polymerizable resin to an epoxy resin can produce a cured product with a low dielectric dissipation factor. However, the present inventors have found that a cured product of a resin composition obtained by adding an active ester resin or a radical polymerizable resin to an epoxy resin tends to exhibit a reduced adhesion strength with a conductor layer after exposure to a high-temperature, high-humidity environment. In the manufacture of circuit boards by the build-up method, the insulating layer is formed by laminating a resin sheet containing a resin composition layer onto an inner substrate so that the resin composition layer is bonded to the inner substrate, followed by curing. In this case, to achieve a resin sheet with good handleability, the resin composition layer before curing is required to have good flexibility.

[0005] The present invention has been made in view of the above-mentioned problems, and aims to provide a resin composition which provides a cured product having a low dielectric tangent and excellent adhesion strength with a conductor layer even after exposure to a high-temperature, high-humidity environment, and which can exhibit good flexibility before curing; a resin sheet having a resin composition layer containing the resin composition; a circuit board including an insulating layer formed from a cured product of the resin composition; and a semiconductor device including the circuit board. [Means for solving the problem]

[0006] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a resin composition containing a specific biphenol skeleton epoxy resin and an epoxy resin that is liquid at room temperature, and further containing one or more resins selected from active ester resins and radical polymerizable resins, and have completed the present invention.

[0007] That is, the present invention includes the following inventions. [1] (A) an epoxy resin; (B) one or more resins selected from an active ester resin and (C) a radical polymerizable resin; Including, (A) component (A-1) an epoxy resin represented by the following general formula (1) and having an epoxy equivalent of 200 g / eq. or more; (A-2) a resin composition comprising an epoxy resin that is liquid at room temperature.

[0008] [ka] [In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 10.] [2] The resin composition according to [1], wherein the content of the component (A-1) is 2 to 40% by mass, where the resin component in the resin composition is 100% by mass. [3] The resin composition according to [1] or [2], wherein the content of the component (A-2) is 4 to 60 mass % when the resin component in the resin composition is 100 mass %. [4] The resin composition according to any one of [1] to [3], which contains component (B), and in which the molar ratio of epoxy groups in component (A) to active ester groups in component (B) [active ester groups / epoxy groups] is 1.0 to 2.0. [5] The resin composition according to any one of [1] to [4], further comprising (D) an inorganic filler. [6] The resin composition according to [5], wherein the content of component (D) is 60 to 80 mass % when the total nonvolatile components in the resin composition is 100 mass %. [7] The resin composition according to any one of [1] to [6], further comprising (F) a curing accelerator. [8] The resin composition according to any one of [1] to [7], which is used to form an insulating layer. [9] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to [8].

[10] A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [8].

[11] A semiconductor device comprising the circuit board according to

[10] . [Effects of the Invention]

[0009] According to the present invention, there are provided a resin composition which provides a cured product having a low dielectric tangent and excellent adhesion strength with a conductor layer even after exposure to a high-temperature, high-humidity environment, and which can exhibit good flexibility before curing; a resin sheet having a resin composition layer containing the resin composition; a circuit board having an insulating layer formed from a cured product of the resin composition; and a semiconductor device including the circuit board. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0011] [Resin composition] The resin composition of the present invention comprises (A) an epoxy resin and one or more resins selected from (B) an active ester resin and (C) a radical polymerizable resin, (A) component (A-1) an epoxy resin represented by the above general formula (1) and having an epoxy equivalent of 200 g / eq. or more; (A-2) an epoxy resin that is liquid at room temperature. Such a resin composition can provide a cured product having a low dielectric loss tangent and excellent adhesive strength to a conductor layer even after exposure to a high-temperature, high-humidity environment. In addition, the uncured resin composition has excellent flexibility.

[0012] The resin composition may further contain optional components such as (A-3) other epoxy resins other than component (A-1) and component (A-2), (D) inorganic fillers, (E) other curing agents, (F) curing accelerators, and (G) other additives, as necessary. Each component contained in the resin composition will be described in detail below.

[0013] (A) Epoxy resin The resin composition of the present invention contains an epoxy resin as component (A). In the present invention, component (A) contains (A-1) a biphenol-skeleton epoxy resin represented by the following general formula (1) and having an epoxy equivalent of 200 g / eq. or more, and (A-2) an epoxy resin that is liquid at room temperature. Component (A) may further contain (A-3) another epoxy resin.

[0014] <(A-1) Epoxy resin represented by general formula (1) and having an epoxy equivalent of 200 g / eq. or more> The component (A-1) is a biphenol-skeleton epoxy resin represented by the following general formula (1) and having an epoxy equivalent of 200 g / eq. or more.

[0015] [ka] [In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 10.] In general formula (1), n ​​is 0 to 10, and preferably 0 to 5. When the value of n is within the above range, it is easy to realize a resin composition that exhibits an appropriate melt viscosity, which is preferable.

[0016] Component (A-1) may be a mixture of multiple compounds having different values ​​of n in general formula (1). In addition, in such a mixture, it is not excluded that the mixture contains an epoxy resin in which the value of n in general formula (1) exceeds 10.

[0017] Here, the term "biphenol skeleton" refers to a skeleton that at least partially contains a divalent structure formed by removing two hydroxy groups from a biphenol that may have a substituent. Hereinafter, an epoxy resin containing a "biphenol skeleton" will also be referred to as a biphenol-type epoxy resin.

[0018] A specific example of the epoxy resin represented by the general formula (1) is "YX4000HS" (tetramethylbiphenol type epoxy resin, epoxy equivalent weight 210 g / eq.) manufactured by Mitsubishi Chemical Corporation.

[0019] In a combination of the (A-2) component described below with one or more of the (B) and (C) components, the epoxy equivalent of the (A-1) component is 200 g / eq or more, from the viewpoint of providing a resin composition that can provide a cured product with a low dielectric tangent and excellent adhesive strength to a conductor layer after exposure to a high-temperature, high-humidity environment, and that can exhibit good flexibility before curing. The upper limit of the epoxy equivalent is preferably 200 to 300 g / eq, from the viewpoint of being able to fully enjoy the effects of the present invention. The mechanism by which the adhesion strength to the conductor layer is improved after exposure to a high-temperature, high-humidity environment is not clear, but when the epoxy equivalent of component (A-1) is 200 g / eq. or more, the proportion of oligomer components contained in the epoxy resin of general formula (1) above is higher than when it is less than 200 g / eq., resulting in a higher concentration of secondary hydroxyl groups derived from the oligomer. These secondary hydroxyl groups have low reactivity and remain unreacted after curing, so it is thought that adhesion to copper can be maintained even after exposure to a high-temperature, high-humidity environment. In the present invention, the term "epoxy equivalent" is defined as "the mass of an epoxy resin containing one equivalent of epoxy groups" and can be measured in accordance with JIS K7236 (2001).

[0020] From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulating reliability, the content of component (A-1) is preferably 2% by mass or more, 4% by mass or more, 6% by mass or more, or 8% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, when the resin component in the resin composition is taken as 100% by mass. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit of the content of component (A-1) is preferably 40% by mass or less, more preferably 35% by mass or less, and particularly preferably 30% by mass or less. In the present invention, the term "resin component" in relation to the resin composition refers to the non-volatile components constituting the resin composition excluding the inorganic filler described below.

[0021] <(A-2) Epoxy resin that is liquid at room temperature> The component (A-2) is an epoxy resin that is liquid at room temperature (20°C) (hereinafter simply referred to as "liquid epoxy resin").

[0022] The component (A-2) is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule.

[0023] Examples of component (A-2) include bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol AF-type epoxy resins; naphthalene-type epoxy resins; glycidyl ester-type epoxy resins; glycidyl amine-type epoxy resins; phenol novolac-type epoxy resins; alicyclic epoxy resins having an ester skeleton; cyclohexane-type epoxy resins; cyclohexanedimethanol-type epoxy resins; glycidyl amine-type epoxy resins; and epoxy resins having a butadiene structure. Among these, from the viewpoint of significantly achieving the effects of the present invention, bisphenol-type epoxy resins and naphthalene-type epoxy resins are preferred, and bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and naphthalene-type epoxy resins are more preferred.

[0024] Specific examples of the component (A-2) include "HP-4032," "HP-4032D," and "HP-4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US," "jER828EL," "825," and "Epikote 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "630" and "630LSD" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation. Epoxy resins such as "ZX1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Chemical & Material Corporation, "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase ChemteX Corporation, "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation, "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation, and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane epoxy resin) manufactured by Nippon Steel Chemical & Material Corporation. These may be used alone or in combination of two or more.

[0025] The epoxy equivalent of component (A-2) is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, even more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g / eq to 1000 g / eq. When the epoxy equivalent is within this range, the crosslink density of the cured product of the resin composition layer is sufficient, and an insulating layer with low surface roughness can be obtained.

[0026] The weight average molecular weight (Mw) of the component (A-2) is preferably 100 to 5,000, more preferably 200 to 3,000, and even more preferably 250 to 1,500, from the viewpoint of significantly achieving the desired effects of the present invention.

[0027] From the viewpoint of being able to enjoy the effects of the present invention more effectively, particularly from the viewpoint of obtaining a resin composition that exhibits good flexibility when uncured, the content of component (A-2) is preferably 4% by mass or more, 6% by mass or more, or 8% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, when the resin components in the resin composition are taken as 100% by mass. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit of the content of component (A-2) is preferably 60% by mass or less, more preferably 40% by mass or less, and particularly preferably 20% by mass or less.

[0028] <(A-3) Other epoxy resins> The resin composition of the present invention may further contain (A-3) another epoxy resin, i.e., an epoxy resin other than components (A-1) and (A-2). As component (A-3), an epoxy resin that is solid at room temperature (20°C) (hereinafter simply referred to as "solid epoxy resin") can be preferably used.

[0029] The epoxy resin of component (A-3) is preferably a solid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having two or more epoxy groups in one molecule.

[0030] Examples of component (A-3) include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, naphthol aralkyl-skeleton epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, tetraphenylethane-type epoxy resins, biphenyl aralkyl-type epoxy resins, biphenyl novolac-type epoxy resins, and biphenol-type epoxy resins with an epoxy equivalent of less than 200 g / eq. Among these, naphthalene-type epoxy resins and biphenol-type epoxy resins with an epoxy equivalent of less than 200 g / eq. are preferred.

[0031] Specific examples of the component (A-3) include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadiene-type epoxy resins) manufactured by DIC Corporation. epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", and "NC31" manufactured by Nippon Kayaku Co., Ltd. 00" (biphenyl-type epoxy resin); "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121HA", and YL6677" (biphenylol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. Examples of epoxy resins include "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

[0032] The epoxy equivalent of the component (A-3), excluding biphenol-type epoxy resins, is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent of the biphenol-type epoxy resin used as the component (A-3) is preferably 150 g / eq. or more and less than 200 g / eq., and more preferably 155 g / eq. to 198 g / eq. When the resin composition of the present invention contains the component (A-3), if the epoxy equivalent of the component (A-3) is within this range, the crosslink density of the cured product of the resin composition layer will be sufficient, resulting in an insulating layer with low surface roughness.

[0033] The weight average molecular weight (Mw) of the component (A-3) is preferably 100 to 5,000, more preferably 200 to 3,000, and even more preferably 250 to 1,500, from the viewpoint of significantly achieving the desired effects of the present invention.

[0034] The content of component (A-3) may be 0% by mass when the resin component in the resin composition is taken as 100% by mass, but from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulating reliability, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit of the content of component (A-3) is preferably 30% by mass or less, more preferably 28% by mass or less, and particularly preferably 25% by mass or less.

[0035] The components (A-1) and (A-3) are usually solid epoxy resins, and the component (A-2) is a liquid epoxy resin. In the present invention, a solid epoxy resin and a liquid epoxy resin are used in combination as the component (A), and the mass ratio thereof (solid epoxy resin:liquid epoxy resin) is preferably 1:0.5 to 1:15, more preferably 1:1 to 1:12, and particularly preferably 1:1.5 to 1:10.

[0036] The resin composition of the present invention contains, in addition to (A) an epoxy resin, one or more resins selected from (B) an active ester resin and (C) a radically polymerizable resin.

[0037] (B) Active ester resin When the resin composition of the present invention contains (B) an activated ester resin, the activated ester resin is contained as a curing agent for the epoxy resin. While there are no particular limitations on the activated ester resin, compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The activated ester resin is preferably one obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of improving heat resistance, activated ester resins obtained from a carboxylic acid compound and a hydroxy compound are preferred, and activated ester resins obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound are more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0038] Specifically, active ester resins containing a dicyclopentadiene-type diphenol structure, active ester resins containing a naphthalene structure, active ester resins containing an acetylated product of phenol novolac, and active ester resins containing a benzoylated product of phenol novolac are preferred, and among these, active ester resins containing a naphthalene structure and active ester resins containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0039] Commercially available activated ester resins can be used. For example, activated ester resins containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation). Activated ester resins containing a naphthalene structure include "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-8150-63T", "EXB-8150-64T", "EXB-8150-65T", "EXB-8150-66T", "EXB-8150-67T", "EXB-8150-68T", "EXB-8150-69T", "EXB-8150-70T", "EXB-8150-71T", ​​"EXB-8150-72T", "EXB-8150-73T", "EXB-8150-74T", "EXB-8150-75T", "EXB-8150-75T", "EXB-8150-76T", "EXB-8150-77T", "EXB-8150-78T", "EXB-8150-79 ... Examples of active ester resins that contain phenol novolac include "EXB-9416-70BK," "HPC-8150-60T," "HPC-8150-62T," and "HP-B-8151-62T" (manufactured by DIC Corporation), a phosphorus-containing active ester resin is "EXB9401" (manufactured by DIC Corporation), an active ester resin that is an acetylated product of phenol novolac is "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester resins that are benzoylated products of phenol novolac are "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and an active ester resin containing a styryl group and a naphthalene structure is "PC1300-02-65MA" (manufactured by Air Water Inc.).

[0040] When the resin composition of the present invention contains the active ester resin (B), the ratio of the amount of the epoxy resin (A) (component (A-1), component (A-2), and component (A-3)) to the amount of the active ester resin (B) is The molar ratio of [total number of active ester groups in component (B)] / [total number of epoxy groups in component (A)] is preferably in the range of 1.0 to 2.0, more preferably 1.0 to 1.8, and even more preferably 1.1 to 1.3. By keeping the quantitative ratio of component (A) to component (B) within this range, it tends to be easier to realize a resin composition that provides a cured product that exhibits excellent adhesion strength to a conductor layer after exposure to a high-temperature, high-humidity environment.

[0041] When the resin composition of the present invention contains component (B), from the viewpoint of being able to enjoy the effects of the present invention more effectively in combination with the aforementioned components (A-1) and (A-2), the content of component (B) is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the resin components in the resin composition. The upper limit is preferably 70% by mass or less, more preferably 68% by mass or less or 66% by mass or less, and even more preferably 65% ​​by mass or less.

[0042] (C) Radical polymerizable resin The (C) radical polymerizable resin that may be included in the resin composition of the present invention is a compound having a radical polymerizable unsaturated group in the molecule. This radical polymerizable unsaturated group is not particularly limited as long as it is a group containing an unsaturated bond that exhibits radical polymerizability, and examples thereof include groups containing ethylenic double bonds. Component (C) containing such a radical polymerizable unsaturated group can undergo radical polymerization by heat or active energy rays, thereby curing the resin composition.

[0043] Examples of radically polymerizable unsaturated groups include maleimide, vinyl, styryl, vinylphenyl, acryloyl, methacryloyl, fumaroyl, maleoyl, benzocyclobutene, and allyl groups. Among these, from the viewpoint of achieving the effects of the present invention more effectively when combined with components (A-1) and (A-2), one or more selected from maleimide, styryl, vinylphenyl, acryloyl, methacryloyl, and allyl groups are preferred. The number of radically polymerizable unsaturated groups contained in one molecule of component (C) is typically 1 or more, preferably 2 or more. When component (C) contains two or more radically polymerizable unsaturated groups, these two or more radically polymerizable unsaturated groups may be the same or different. There is no particular upper limit to the number of radically polymerizable unsaturated groups, but it may typically be 10 or less, 8 or less, or 6 or less.

[0044] In particular, from the viewpoint of significantly achieving the effects of the present invention, the component (C) is preferably at least one selected from a styryl resin, a (meth)acrylic resin, a maleimide resin, and an allyl resin, and more preferably at least one selected from a styryl resin, a (meth)acrylic resin, and a maleimide resin.

[0045] (Styryl resin) The styryl resin may be a monomer or an oligomer, and may be any type, as long as it contains one or more (preferably two or more) styryl or vinylphenyl groups in one molecule. Examples of the styryl resin include low-molecular-weight (molecular-weight less than 1000) styryl resins such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; and high-molecular-weight (molecular-weight 1000 or more) styryl resins such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Commercially available styryl resins include, for example, "ODV-XET(X03)," "ODV-XET(X04)," and "ODV-XET(X05)" (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "OPE-2St," "OPE-2St 1200," and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company, Inc.; and "H1041," "Tuftec H1043," "Tuftec P2000," and "Tuftec MP10" (hydrogenated styrene-based thermoplastic resins) manufactured by Asahi Kasei Corporation.

[0046] ((Meth)acrylic resin) The (meth)acrylic resin is not particularly limited in type as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, and may be a monomer or oligomer. Examples of the (meth)acrylic resin include 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, and the like. (meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and other low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylic acid ester resins; dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester resins such as 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, and propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester resins such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate; and high molecular weight (molecular weight 1000 or more) acrylic acid ester resins such as (meth)acrylic-modified polyphenylene ether resins. Examples of commercially available (meth)acrylic resins include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate) and "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC.

[0047] (maleimide resin) The type of maleimide resin is not particularly limited as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule. Examples of maleimide resins include (1) "BMI-3000J," "BMI-5000," "BMI-1400," "BMI-1500," "BMI-1700," and "BMI-689" (all manufactured by Designer Molecules). (1) Maleimide resins containing an aliphatic skeleton (preferably a divalent aliphatic group having 10 or more carbon atoms, particularly preferably an aliphatic skeleton having 36 carbon atoms derived from dimer acid or dimer diamine), such as "SLK-6895" (manufactured by Shin-Etsu Chemical Co., Ltd.), "SLK-1500" (manufactured by Shin-Etsu Chemical Co., Ltd.); (2) Maleimide resins containing an indane skeleton, as described in the Technical Journal Disclosure No. 2020-500211 of the Japan Institute of Invention and Innovation; and (3) Maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group, such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), and "BMI-80" (manufactured by Keiai Kasei Co., Ltd.).

[0048] (allyl resin) The allyl resin is not particularly limited in type, and may be a monomer or oligomer, as long as it has one or more (preferably two or more) allyl groups in one molecule. Examples of allyl resins include aromatic carboxylic acid allyl ester resins such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate; isocyanuric acid allyl ester resins such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl resins such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl resins such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl resins such as 1,3,5-triallyl ether benzene; allyl silane resins such as diallyl diphenyl silane; and resins containing multiple benzene rings and multiple allyl groups. Commercially available allyl resins include, for example, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "DAND" (2,3-naphthalenecarboxylic acid diallyl) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., and "ALP-d" (bis[3-allyl isocyanurate) manufactured by Shikoku Chemical Industry Co., Ltd. Examples include "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 Chemicals Corporation, and "NE-V-1100-70T" (a resin containing multiple benzene rings and multiple allyl groups) manufactured by DIC Corporation.

[0049] When the resin composition of the present invention contains the component (C), from the viewpoint of being able to enjoy the effects of the present invention more effectively in combination with the aforementioned components (A-1) and (A-2), the content of the component (C) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and is preferably 65% ​​by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, based on 100% by mass of the resin components in the resin composition.

[0050] (D) Inorganic filler The resin composition of the present invention may contain an inorganic filler as component (D). By containing the inorganic filler (D) in the resin composition, it is possible to obtain a cured product with even more excellent dielectric properties.

[0051] Inorganic compounds are used as inorganic fillers. Examples of inorganic filler materials 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred. Component (D) may be used alone or in combination of two or more.

[0052] Commercially available products of component (D) 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," and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30," "DAW-03," and "FB-105FD" manufactured by Denka Company, Limited; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; and "Cellspheres" and "MGH-005" manufactured by Taiheiyo Cement Corporation.

[0053] From the viewpoint of significantly achieving the desired effects of the present invention, the average particle size of component (D) is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more, and is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0054] The average particle size of component (D) can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a volumetric particle size distribution of the inorganic filler is created using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them ultrasonically for 10 minutes. The volumetric particle size distribution of the inorganic filler was measured using a laser diffraction particle size distribution analyzer with blue and red light source wavelengths using a flow cell system, and the average particle size was calculated as the median diameter from the particle size distribution obtained. Examples of laser diffraction particle size distribution analyzers include the LA-960 manufactured by Horiba, Ltd.

[0055] From the viewpoint of significantly achieving the desired effects of the present invention, the specific surface area of ​​component (D) is preferably 1 m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m 2 / g or more. There is no particular upper limit, but it is preferably 60m 2 / g or less, 50m2 / g or less or 40m 2 The specific surface area is measured by using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) to adsorb nitrogen gas onto the surface of the sample and calculate the specific surface area using the BET multipoint method.

[0056] From the viewpoint of improving moisture resistance and dispersibility, component (D) is preferably treated with a surface treatment agent. Examples of surface treatment agents include fluorine-containing silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane; aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; epoxysilane coupling agents such as 3-glycidoxypropyltrimethoxysilane; mercaptosilane coupling agents such as 3-mercaptopropyltrimethoxysilane; silane coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane; and titanate coupling agents. Furthermore, the surface treatment agents may be used alone or in any combination of two or more.

[0057] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0058] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. 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 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass.

[0059] 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 set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is more preferable that the amount of the resin varnish is 1 mg / m 2 Less than 0.8 mg / m is preferred 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0060] The carbon content per unit surface area of ​​component (D) can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. The supernatant is removed, the solid content is dried, and then the carbon content per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. An "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used as the carbon analyzer.

[0061] From the viewpoint of significantly achieving the effects of the present invention, the content of component (D) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and is preferably 85% by mass or less, more preferably 83% by mass or less or 81% by mass or less, even more preferably 80% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0062] (E) Other hardeners The resin composition of the present invention may contain a compound that functions as a curing agent for epoxy resins as the other curing agent (E). However, component (E) does not include those that fall under components (B) and (C). Examples of other curing agents (E) include phenolic curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents. Of these, from the viewpoint of improving insulation reliability, component (E) is preferably one or more of carbodiimide curing agents, phenolic curing agents, and naphthol curing agents. Component (E) may be used alone or in combination of two or more.

[0063] As the phenol-based curing agent and naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferred from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred.

[0064] Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700," "MEH-7810," and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170," "SN180," "SN190," "SN475," "SN485," "SN495," "SN-495V," "SN375," and "SN395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "TD-2090," "LA-7052," "LA-7054," "LA-1356," "LA3018-50P," and "EXB-9500" manufactured by DIC Corporation.

[0065] Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0066] 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'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; multifunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resin), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer), all of which are manufactured by Lonza.

[0067] Specific examples of carbodiimide curing agents include "V-03," "V-05," and "V-07" manufactured by Nisshinbo Chemical Inc.

[0068] When the resin composition of the present invention contains component (E), the content of component (E) is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more, based on 100% by mass of the resin components in the resin composition, from the viewpoint of significantly achieving the desired effects of the present invention. The upper limit is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and even more preferably 3.0% by mass or less.

[0069] (F) Curing accelerator The resin composition of the present invention may further contain a curing accelerator as component (F). Examples of the component (F) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Radical polymerization initiators are also examples of the curing accelerator. The component (F) may be used alone or in combination of two or more.

[0070] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0071] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0072] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium 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-4,5-dihydroxymethylimidazole, Examples of the imidazole compound include imidazole compounds such as 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0073] As the imidazole-based curing accelerator, commercially available products may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation and "1B2PZ" manufactured by Shikoku Chemicals Corporation.

[0074] 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, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of suitable biguanide include 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0075] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0076] The radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated. The radical polymerization initiator may be a polymerization initiator with a radical reactive group. The radical polymerization initiator may be used alone or in any combination of two or more.

[0077] Examples of the radical polymerization initiator include peroxide radical polymerization initiators, azo radical polymerization initiators, etc. Among these, peroxide radical polymerization initiators are preferred.

[0078] Examples of the peroxide radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide compounds such as tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; and diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl)peroxydicarbonate. peroxyester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl) 2-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butylperoxy-2-ethylhexyl monocarbonate, and tert-butylperoxymaleic acid; and the like.

[0079] Examples of the azo radical polymerization initiator include azonitrile compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], and 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide]. azoamide compounds such as 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); alkyl azo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane); and the like.

[0080] Commercially available radical polymerization initiators include, for example, "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," "Perbutyl Z," "Perbutyl I," "Percumyl P," "Percumyl D," "Perhexyl D," "Perhexyl A," "Perhexyl I," "Perhexyl Z," "Perhexyl ND," "Perhexyl O," and "Perhexyl PV," all manufactured by NOF Corporation.

[0081] When the resin composition of the present invention contains component (F), the content of component (F) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and preferably 1.5 mass% or less, more preferably 1.2 mass% or less, based on 100 mass% of the resin components in the resin composition, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0082] (G) Other additives The resin composition of the present invention may further contain other additives as optional components in addition to the components described above. Examples of such additives include thermoplastic resins, elastomers, organic fillers, thickeners, antifoaming agents, leveling agents, adhesion promoters, and flame retardants. These may be used alone or in combination of two or more in any ratio.

[0083] The resin composition can be produced, for example, by mixing the above-mentioned components in any order. Furthermore, heating and / or cooling may be performed by appropriately adjusting the temperature during the process of mixing the components. Furthermore, stirring may be performed using a stirring device such as a mixer during or after mixing the components to uniformly disperse the components. Furthermore, the resin composition may be subjected to a degassing treatment, if necessary.

[0084] <Physical properties and applications of resin compositions> The resin composition of the present invention contains a combination of components (A-1) and (A-2) and one or more of components (B) and (C), and therefore can produce a cured product with a low dielectric tangent and excellent adhesion strength to a conductor layer after exposure to a high-temperature, high-humidity environment. Furthermore, the uncured resin composition has excellent flexibility.

[0085] The resin composition of the present invention is characterized by producing a cured product exhibiting a low dielectric loss tangent. Therefore, when an insulating layer is formed using the resin composition of the present invention, an insulating layer with a low dielectric loss tangent can be obtained. For example, the dielectric loss tangent Df of the cured product obtained by curing the resin composition under the conditions described in the Examples below (thermal curing at 190°C for 90 minutes) is preferably 0.010 or less, more preferably 0.005 or less, and even more preferably 0.003 or less. The lower limit of the dielectric loss tangent of the cured product is not particularly limited, but can be 0.0001 or more. The dielectric loss tangent of the cured product can be measured by the method described in the Examples.

[0086] The resin composition of the present invention is characterized by producing a cured product with good adhesion strength to a conductor layer. Therefore, when an insulating layer is formed using the resin composition of the present invention, an insulating layer with good adhesion strength to the conductor layer can be obtained. For example, when an insulating layer and copper foil are formed by the method described in the Examples below, the adhesion strength to the conductor layer can be preferably 0.60 kgf / cm or more, more preferably 0.65 kgf / cm or more. The upper limit of the adhesion strength is not particularly limited, but can be, for example, 10.0 kgf / cm or less. The adhesion strength to the conductor layer can be measured by the method described in the Examples.

[0087] The resin composition of the present invention is characterized by producing a cured product with good adhesion strength to a conductor layer after exposure to a high-temperature, high-humidity environment. Therefore, when an insulating layer is formed using the resin composition of the present invention, an insulating layer with good adhesion strength to a conductor layer after exposure to a high-temperature, high-humidity environment can be obtained. For example, an insulating layer and a conductor layer are formed by the method described in the Examples below, and the HAST test is performed by leaving the layer at 130°C and 85% RH for 100 hours. The adhesion strength to the conductor layer after the HAST test is preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, and particularly preferably 0.40 kgf / cm or more. The upper limit of the adhesion strength is not particularly limited, but can be, for example, 10.0 kgf / cm or less. The adhesion strength to the conductor layer after the HAST test can be measured by the method described in the Examples.

[0088] The resin composition of the present invention is characterized by having good flexibility before curing. Therefore, when a resin sheet is formed using the resin composition of the present invention, it is possible to realize a resin sheet that is easy to handle in the production of circuit boards. For example, a resin sheet obtained by applying the resin composition to a support and drying the resin composition at 80°C to 100°C (average 90°C) for 2 minutes has good flexibility, and even when bent at an angle of 180 degrees with the support on the inside and the resin composition layer on the outside, no cracks occur in the resin composition layer. Flexibility can be evaluated, for example, by the method described in the Examples.

[0089] The resin composition of the present invention is suitable as a resin composition for insulating purposes, and particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition of the present invention is suitable as a resin composition for forming an insulating layer of a circuit board (a resin composition for forming an insulating layer of a circuit board). The resin composition is suitable as a resin composition for forming an interlayer insulating layer of a circuit board (a resin composition for forming an interlayer insulating layer of a circuit board). The resin composition of the present invention is also suitable as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer) to form a conductor layer (including a rewiring layer) formed on an insulating layer. The resin composition of the present invention can also be used in a wide range of applications where resin compositions can be used, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, and system-in-packages. In the present invention, the circuit board includes a printed wiring board and a rewiring board.

[0090] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is also suitable as a resin composition for forming a rewiring formation layer as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation layer), and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the encapsulation layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0091] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention and provided on the support.

[0092] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, from the viewpoint of making the circuit board thinner and being able to provide a cured product of the resin composition that has excellent insulating properties even when the cured product is thin. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0093] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0094] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0095] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0096] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0097] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0098] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0099] When a metal foil is used as the support, a metal foil with a support substrate may be used, which is a thin metal foil with a peelable support substrate attached thereto. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When a metal foil with a support substrate is used as the support, the resin composition layer is provided on the metal foil.

[0100] In the metal foil with a supporting substrate, the material of the supporting substrate is not particularly limited, but examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When copper foil is used as the supporting substrate, it may be electrolytic copper foil or rolled copper foil. Furthermore, the release layer is not particularly limited as long as it allows the metal foil to be released from the supporting substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic coating, etc.

[0101] In the metal foil with a supporting substrate, the material of the metal foil is preferably, for example, copper foil or copper alloy foil.

[0102] In the metal foil with a supporting substrate, the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. The thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0103] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite 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, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0104] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying this resin varnish to a support using a die coater or the like, and then drying it to form a resin composition layer.

[0105] Examples of organic solvents 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; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

[0106] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0107] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0108] [Circuit board] The resin composition of the present invention can be used to form an insulating layer for a circuit board. The present invention also provides such a circuit board, i.e., a circuit board comprising an insulating layer made of a cured product of the resin composition of the present invention.

[0109] [Printed wiring board] In one embodiment, the circuit board of the present invention is a printed wiring board. Such a printed wiring board includes an insulating layer formed of a cured product obtained by curing the above-described resin composition.

[0110] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) Step of curing the resin composition layer to form an insulating layer

[0111] The "inner layer substrate" used in step (I) is a member that will become the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. 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 board." Furthermore, intermediate products on which an insulating layer and / or a conductor layer is to be further formed during the production of a printed wiring board are 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.

[0112] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (such as a SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0113] 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 temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination may be carried out under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0114] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0115] After lamination, the laminated resin sheets may be smoothed under atmospheric pressure, for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. Note that the lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0116] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0117] 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 for the resin composition layer are not particularly limited, and the conditions employed for forming an 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.

[0118] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0119] 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 even more preferably 15 minutes to 100 minutes.

[0120] The method for producing a printed wiring board may further include the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. When the support is removed after step (II), the support may be removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0121] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be determined appropriately depending on the design of the printed wiring board.

[0122] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also performed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0123] Examples of swelling solutions used in the roughening treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Examples of alkaline solutions include sodium hydroxide solutions and potassium hydroxide solutions. Examples of commercially available swelling solutions include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment using a swelling solution is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0124] Examples of oxidizing agents used in the roughening treatment include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0125] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be cited. Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, a preferred method is to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0126] 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 alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a 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 a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0127] The conductor layer may have a single layer structure, or 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 a nickel-chromium alloy.

[0128] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0129] The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a method such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, the conductor layer is preferably formed by a semi-additive method. An example of forming a conductor layer by a semi-additive method will be described below.

[0130] 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, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having the desired wiring pattern.

[0131] [Semiconductor Devices] A semiconductor device according to one embodiment of the present invention includes the above-described printed wiring board, and can be manufactured using the above-described printed wiring board.

[0132] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0133] The present invention will be specifically described below 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 "% by mass", respectively, unless otherwise specified. Furthermore, the operations described below were carried out in an environment of normal temperature and pressure, unless otherwise specified.

[0134] (Examples 1 to 14, Comparative Examples 1 to 7) <Production of Resin Composition> Each component was weighed out in the parts by mass shown in Table 1, and then mixed with 10 parts of MEK and 2 parts of cyclohexanone, and the mixture was uniformly dispersed using a high-speed rotating mixer to obtain a varnish-like resin composition.

[0135] <Test Example 1: Measurement of dielectric loss tangent> (1) Preparation of a resin sheet having a resin composition layer thickness of 40 μm A polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) with a release layer was prepared as a support. The varnish-like resin compositions obtained in the Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying would be 40 μm. The resin composition was then dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet including a support and a resin composition layer. (2) Preparation of hardened product The obtained resin sheet was cured for 90 minutes in an oven at 190° C. Resin sheet A was taken out of the oven and the support was peeled off to obtain a cured product of the resin composition for evaluation. (3) Measurement of dielectric loss tangent The cured product for evaluation was cut into a piece of 80 mm long and 2 mm wide, and the dielectric loss tangent (Df value) was measured by the cavity resonance perturbation method using an Agilent Technologies HP8362B at a measurement frequency of 5.8 GHz and measurement temperatures of 23°C and 90°C. Measurements were performed on two test pieces, and the average was calculated.

[0136] <Test Example 2: Measurement of adhesion strength with conductor layer (copper foil peel strength) and adhesion strength with conductor layer after HAST test> The adhesive strength to the conductor layer was evaluated by measuring the copper foil peel strength according to the following procedure.

[0137] (1) Copper foil surface preparation The shiny side of an electrolytic copper foil (Mitsui Mining & Smelting Co., Ltd., "3EC-III," 35 μm thick) was etched to a depth of 1 μm with a microetching agent (Mec Co., Ltd., "CZ8101") to roughen the copper surface, followed by a rust-proofing treatment (CL8300). The copper foil whose surface had been etched with the microetching agent in this manner is hereinafter sometimes referred to as "CZ copper foil." Furthermore, this copper foil was heat-treated in an oven at 130°C for 30 minutes to obtain copper foil I having a roughened treated surface.

[0138] (2) Preparation of inner layer board A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with copper foil on the surface and inner layer circuitry was prepared. Both sides of this glass cloth-based epoxy resin double-sided copper-clad laminate were etched to a depth of 1 μm using a microetching agent (MEC "CZ8101") to roughen the copper foil surface. This resulted in an inner layer substrate with a treated CZ copper foil on its surface.

[0139] (3) Lamination of resin composition layer The resin sheet prepared in Test Example 1(1) was laminated on both sides of the inner layer substrate. This lamination was performed using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700") so that the resin composition layer was in contact with the inner layer substrate. The lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, followed by pressure bonding at 120°C and a pressure of 0.74 MPa for 30 seconds. The laminated resin sheet was then heat-pressed at 100°C and a pressure of 0.5 MPa for 60 seconds. The support was then peeled off to expose the resin composition layer.

[0140] (4) Lamination of copper foil and curing of resin composition layer The treated surface of copper foil I was laminated onto the exposed resin composition layer under the same conditions as in "(3) Lamination of Resin Composition Layer" above. The resin composition layer was then cured at 200°C for 90 minutes to form an insulating layer containing a cured resin composition. This procedure yielded evaluation substrate C, in which CZ copper foil was laminated on both sides of the insulating layer. This evaluation substrate C had a layer structure of copper foil I / insulating layer / inner layer substrate / insulating layer / copper foil I.

[0141] (5) Measurement of adhesion strength with the conductor layer (copper foil) (copper foil peel strength) and adhesion strength with the conductor layer after HAST test Evaluation board C was cut into small pieces measuring 150 mm x 30 mm. A cutter was used to make a slit in the copper foil I piece, enclosing a section 10 mm wide and 100 mm long. One end of this section was peeled off and gripped with the gripping tool of a tensile tester (TSE Autocom Universal Tester "AC-50C-SL"). The piece was pulled vertically at a rate of 50 mm / min at room temperature (25°C), and the load [kgf / cm] when 35 mm was peeled off was measured as the adhesion strength to the conductor layer. After the measurement, the samples were subjected to a highly accelerated life test (HAST test) at 130°C and 85% RH for 100 hours using a highly accelerated life tester (Kusumoto Chemicals Co., Ltd., "PM422"). The adhesion strength with the conductor layer after HAST was then measured in the same manner as the initial adhesion strength with the conductor layer. The measurement was performed in accordance with Japanese Industrial Standard JIS C6481.

[0142] <Test Example 3: Evaluation of flexibility when uncured> The resin sheet prepared in Test Example 1(1) was bent at an angle of 180 degrees with the support facing inward and the resin composition layer facing outward to check its flexibility. Those in which the resin composition layer was not cracked were marked with a circle, and those in which it was cracked were marked with an x.

[0143] The results of Test Examples 1 to 3 are shown in Tables 1 and 2.

[0144] [Table 1]

[0145] [Table 2]

[0146] Details of each component listed in Tables 1 and 2 are as follows. (A-1) Biphenol-based epoxy resin with an epoxy equivalent of 200 g / eq or more YX4000HS: Biphenol-based epoxy resin, epoxy equivalent weight 210g / eq, manufactured by Mitsubishi Chemical Corporation (A-2) Liquid epoxy resin 828US: Bisphenol A epoxy resin, epoxy equivalent 186g / eq, manufactured by Mitsubishi Chemical Corporation HP-4032US: Naphthalene-type epoxy resin, epoxy equivalent weight 144g / eq, manufactured by DIC Corporation (A-3) Other epoxy resins ESN-475V: Naphthol-type epoxy resin, epoxy equivalent 332g / eq, manufactured by Nippon Steel Chemical & Material Co., Ltd. YX4000H: Biphenol-based epoxy resin, epoxy equivalent weight 194g / eq, manufactured by Mitsubishi Chemical Corporation (B) Active ester resin HPC-8000-65T: Active ester curing agent containing dicyclopentadiene-type diphenol structure, ester equivalent weight 223g / eq, non-volatile content 65% in toluene solution, manufactured by DIC Corporation HP-B-8151-62T: Active ester curing agent containing naphthalene structure, ester equivalent weight 238g / eq, manufactured by DIC Corporation (C) Radical polymerizable resin OPE-2St: Vinylbenzyl-modified polyphenylene ether resin, toluene solution with 65% non-volatile content, manufactured by Mitsubishi Gas Chemical Company, Inc. P2000: Hydrogenated styrene-based thermoplastic elastomer, manufactured by Asahi Kasei Corporation A-DOG: (meth)acrylate resin, manufactured by Shin-Nakamura Chemical Co., Ltd. BMI-689: Aliphatic maleimide compound containing an aliphatic amine skeleton, manufactured by Designer Molecules Inc. MIR-3000-70MT: Aromatic maleimide compound containing an aromatic amine skeleton, toluene / MEK mixed solution with 70% non-volatile content, manufactured by Nippon Kayaku Co., Ltd. (D) Inorganic filler SO-C2: Spherical silica surface-treated with an amine-based silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573"), average particle size 0.5 μm, specific surface area 5.8 m 2 / g, manufactured by Admatechs Co., Ltd. (E) Other hardeners LA-3018-50P: Triazine skeleton-containing phenolic curing agent, 1-methoxy-2-propanol solution with 50% non-volatile content, manufactured by DIC Corporation V-03: Carbodiimide curing agent, carbodiimide equivalent: 216 g / eq., toluene solution with 50% nonvolatile content, manufactured by Nisshinbo Chemical Co., Ltd. (F) Curing accelerator Perbutyl C: Peroxide radical polymerization initiator, manufactured by NOF Corporation 1B2PZ: Imidazole curing accelerator, manufactured by Shikoku Chemicals Corporation

Claims

1. (A) an epoxy resin; (B) one or more resins selected from an active ester resin or (C) a radical polymerizable resin; Including, Component (A) (A-1) an epoxy resin represented by the following general formula (1) and having an epoxy equivalent of 200 g / eq. or more; (A-2) A resin composition containing an epoxy resin that is liquid at room temperature. 【Chemistry 1】 [In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 10.]

2. The resin composition according to claim 1, wherein the content of the component (A-1) is 2 to 40% by mass, when the resin component in the resin composition is 100% by mass.

3. The resin composition according to claim 1, wherein the content of the component (A-2) is 4 to 60% by mass, when the resin component in the resin composition is 100% by mass.

4. 2. The resin composition according to claim 1, comprising component (B), wherein the molar ratio of epoxy groups in component (A) to active ester groups in component (B) [active ester groups / epoxy groups] is 1.0 to 2.

0.

5. The resin composition according to claim 1 , further comprising (D) an inorganic filler.

6. The resin composition according to claim 5, wherein the content of the component (D) is 60 to 80 mass% when the total amount of nonvolatile components in the resin composition is 100 mass%.

7. The resin composition according to claim 1 , further comprising (F) a curing accelerator.

8. The resin composition according to claim 1, which is used to form an insulating layer.

9. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition comprising the resin composition according to any one of claims 1 to 8.

10. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 8.

11. A semiconductor device comprising the circuit board according to claim 10.

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