resin composition

Abstract

To provide a resin composition or the like that yields a cured product with low dielectric properties and resistance to haloing phenomenon.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an active ester-based curing agent, (C) an inorganic filler, and (D) a silane compound having a silicon atom as a ring-constitutive atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, and further to an adhesive film, a printed wiring board, and a semiconductor device obtained using the resin composition. [Background technology]

[0002] 2. Description of the Related Art A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked.

[0003] As an insulating material for a printed wiring board used in such an insulating layer, for example, Patent Document 1 discloses a resin composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2022 / 038893 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, there has been an increasing demand for resin compositions capable of forming insulating layers with low dielectric constants and dielectric loss tangents. The dielectric constant and dielectric loss tangent are sometimes collectively referred to as dielectric properties.

[0006] One possible way to lower the dielectric properties of the insulating layer is to include a material that lowers the dielectric properties, such as an active ester curing agent. However, it has been found that cured resin compositions containing materials that lower the dielectric properties exhibit a halo phenomenon, which reduces electrical conductivity reliability. Here, the halo phenomenon refers to delamination occurring between the insulating layer and the inner layer substrate around the via hole. This halo phenomenon typically occurs when the resin around the via hole deteriorates during via hole formation, and the deteriorated area is eroded during the roughening treatment. The deteriorated area is typically observed as a discolored area.

[0007] The present invention has been devised in view of the above-mentioned problems, and aims to provide a resin composition that can give a cured product that has low dielectric properties and can suppress the haloing phenomenon, an adhesive film containing the resin composition, a printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device. [Means for solving the problem]

[0008] As a result of extensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by incorporating a combination of (A) an epoxy resin, (B) an active ester-based curing agent, (C) an inorganic filler, and (D) a silane compound having a silicon atom as a ring-constituting atom, and have thus completed the present invention.

[0009] That is, the present invention includes the following. [1] (A) epoxy resin, (B) active ester curing agent, (C) inorganic fillers, and (D) A resin composition containing a silane compound having a silicon atom as a ring-constituting atom. [2] The resin composition according to [1], wherein the component (C) comprises either a hollow inorganic filler (C-1) or a solid inorganic filler (C-2). [3] The resin composition according to [1] or [2], wherein the component (C) contains a hollow inorganic filler (C-1). [4] The resin composition according to any one of [1] to [3], wherein the component (C) is surface-treated with the component (D). [5] The resin composition according to any one of [1] to [4], wherein the content of component (C) is 50% by mass or more, assuming that the total amount of non-volatile components in the resin composition is 100% by mass. [6] The resin composition according to any one of [1] to [5], wherein the content of component (D) is 0.1% by mass or more and 5% by mass or less, when the resin components in the resin composition are taken as 100% by mass. [7] An adhesive film 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 [6]. [8] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [6]. [9] A semiconductor device comprising the printed wiring board according to [8]. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a resin composition that can give a cured product that has low dielectric properties and can suppress the haloing phenomenon, an adhesive film that includes the resin composition, a printed wiring board that has an insulating layer formed using the resin composition, and a semiconductor device. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a cross-sectional view schematically showing an insulating layer obtained by curing a resin composition according to a first embodiment of the present invention into a sheet shape, together with an inner layer substrate. [Figure 2] FIG. 2 is a plan view schematically showing the surface of an insulating layer obtained by curing the resin composition according to the first embodiment of the present invention into a sheet shape, the surface opposite to the conductor layer. [Figure 3] FIG. 3 is a cross-sectional view schematically showing an insulating layer obtained by curing the resin composition according to the first embodiment of the present invention into a sheet form, after roughening treatment, together with an inner layer substrate. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0013] [Resin composition] The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester curing agent, (C) an inorganic filler, and (D) a silane compound having a silicon atom as a ring-constituting atom. In the present invention, by incorporating the components (A), (B), (C), and (D) in combination, a cured product having low dielectric properties and capable of suppressing haloing can be obtained. Furthermore, a cured product having excellent elongation at break can also be obtained.

[0014] The resin composition may further contain optional components in addition to the components (A) to (D). Examples of optional components include (E) a curing agent (excluding those corresponding to component (B)), (F) a curing accelerator, (G) a thermoplastic resin, (H) other additives, and (I) a solvent. Each component contained in the resin composition will be described in detail below.

[0015] <(A) Epoxy resin> The resin composition contains an epoxy resin (A) as component (A). By including the epoxy resin (A) in the resin composition, a cured product exhibiting good mechanical strength and insulating reliability can be obtained. The epoxy resin (A) may be used alone or in combination of two or more.

[0016] (A) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, and glycidyl ester type Examples of the epoxy resin include epoxy resins, glycidyl cyclohexane-type epoxy resins, alkyl diglycidyl ether-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and phenolphthalimidine-type epoxy resins. One type of epoxy resin may be used alone, or two or more types may be used in combination.

[0017] The resin composition preferably contains, as component (A), an epoxy resin having two or more epoxy groups per molecule. From the viewpoint of significantly achieving the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the epoxy resin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0018] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain, as component (A), only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. Of these, from the viewpoint of significantly achieving the effects of the present invention, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0019] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0020] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, 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, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure, glycidyl cyclohexane type epoxy resins, phenolphthalimidine type epoxy resins, and alkyl diglycidyl ether type epoxy resins, with bisphenol A type epoxy resins, bisphenol F type epoxy resins, and alkyl diglycidyl ether type epoxy resins being more preferred, and bisphenol A type epoxy resins being even more preferred.

[0021] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (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; "630" and "630LSD" (glycidyl amine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "ZX1" manufactured by Nippon Steel Chemical & Material Co., Ltd. Examples of epoxy resins that can be used include "EX-721" (a glycidyl ester epoxy resin) manufactured by Nagase ChemteX Corporation, "Celloxide 2021P" (an alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation, "PB-3600" (an epoxy resin having a butadiene structure) manufactured by Daicel Corporation, "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "YED216D" (an alkyl diglycidyl ether epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

[0022] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, a solid epoxy resin having three or more epoxy groups in one molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is even more preferred.

[0023] Preferred solid epoxy resins 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, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and biphenyl-type epoxy resins are more preferred.

[0024] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin), manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd.; Examples include "NC3100" (biphenyl-type epoxy resin); "ESN475V" (naphthalene-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR-991S" (phenolphthalimidine-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0025] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (A), the ratio by mass between them (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. When the ratio by mass between the liquid epoxy resin and the solid epoxy resin is within this range, the desired effects of the present invention can be significantly achieved.

[0026] The epoxy equivalent of component (A) 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. By keeping it within this range, a cured product of the resin composition can be obtained with sufficient crosslink density. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0027] From the viewpoint of significantly achieving the desired effects of the present invention, the weight average molecular weight (Mw) of the component (A) is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500. The weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0028] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulating reliability, the content of component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition, and the upper limit is preferably 55% by mass or less, more preferably 50% by mass or less, and particularly preferably 45% by mass or less.

[0029] In the present invention, unless otherwise specified, the content of each component in the resin composition is a value when the non-volatile components in the resin composition are taken as 100 mass%, and the non-volatile components mean all non-volatile components in the resin composition excluding the solvent.

[0030] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of component (A) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, and is preferably 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0031] In the present invention, the resin component in the resin composition refers to the non-volatile components of the resin composition excluding the inorganic filler (C).

[0032] <(B) Active ester curing agent> The resin composition contains an active ester curing agent (B) as component (B). This active ester curing agent (B) as component (B) does not include those corresponding to the above-mentioned component (A). The active ester curing agent (B) typically reacts with the epoxy resin (A) to form a bond, thereby curing the resin composition. By incorporating a combination of component (A) and active ester curing agent (B) into the resin composition, a cured product with low dielectric properties can be obtained. The component (B) may be used alone or in combination of two or more.

[0033] As the (B) active ester curing agent, 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 active ester curing agent 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, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents 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.

[0034] Specifically, examples of component (B) include dicyclopentadiene-type active ester curing agents, naphthalene-type active ester curing agents containing a naphthalene structure, active ester curing agents containing an acetylated product of phenol novolac, active ester curing agents containing a benzoylated product of phenol novolac, active ester curing agents that are acetylated products of phenol novolac, and active ester curing agents containing a styryl group and a naphthalene structure, with dicyclopentadiene-type active ester curing agents being preferred. As the dicyclopentadiene-type active ester curing agent, active ester curing agents containing a dicyclopentadiene-type diphenol structure are preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0035] Commercially available products of component (B) include active ester curing agents containing a dicyclopentadiene-type diphenol structure, such as "EXB9451," "EXB9460," "EXB9460S," "HPC-8000-65T," "HPC-8000H-65TM," and "EXB-8000L-65TM" (manufactured by DIC Corporation); naphthalene-type active ester curing agents containing a naphthalene structure, such as "HP-B-8151-62T," "EXB9416-70BK," "EXB-8100L-65T," "EXB-8150L-65T," "EXB-815065T," "HPC-815060T," and "HPC-8150-62T" (manufactured by DIC Corporation), and "PC1300-02-65T" (manufactured by Air Water Inc.); and a phosphorus-containing active ester compound, such as "EXB9401" (manufactured by DIC Corporation). "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent containing an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent which is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester-based curing agents which are benzoylated products of phenol novolac; "EXB-8500-65T" (manufactured by DIC Corporation); and "PC1300-02-65MA" (manufactured by Air Water Inc.) as an active ester-based curing agent containing a styryl group and a naphthalene structure.

[0036] From the viewpoint of being able to reduce the dielectric tangent and obtaining a cured product with excellent peel strength, the active ester group equivalent of component (B) is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and even more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester curing agent containing one equivalent of active ester groups.

[0037] The quantitative ratio of (A) epoxy resin to (B) active ester curing agent, expressed as the ratio of [total number of active groups in active ester curing agent] / [total number of epoxy groups in epoxy resin], is preferably 0.01 or more, more preferably 0.3 or more, even more preferably 0.5 or more, and preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. Here, the "number of epoxy groups in the epoxy resin" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. Furthermore, the "number of active groups in the active ester curing agent" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the active ester curing agent present in the resin composition by the active ester group equivalent. By setting the quantitative ratio of the epoxy resin to the active ester curing agent within this range, the effects of the present invention can be significantly achieved.

[0038] From the viewpoint of obtaining a cured product with excellent dielectric properties, the content of component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition, and the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0039] From the viewpoint of obtaining a cured product with excellent dielectric properties, the content of component (B) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, assuming that the resin component in the resin composition is 100% by mass.

[0040] <(C) Inorganic filler> The resin composition contains an inorganic filler (C) as component (C). By including the inorganic filler (C) in the resin composition, a cured product with low dielectric properties can be obtained. The inorganic filler (C) is usually included in the resin composition in the form of particles. The component (C) may be used alone or in combination of two or more.

[0041] (C) Inorganic fillers are inorganic compounds. Examples of (C) 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.

[0042] (C) Inorganic fillers can be classified into (C-1) hollow inorganic fillers having internal voids and (C-2) solid inorganic fillers having no internal voids. The (C) inorganic filler preferably contains either the (C-1) hollow inorganic filler or the (C-2) solid inorganic filler, and more preferably contains the (C-1) hollow inorganic filler from the viewpoint of obtaining a cured product with low dielectric properties.

[0043] The hollow inorganic filler (C-1) may be a mono-hollow particle having only one void inside the particle, a poly-hollow particle having two or more voids inside the particle, or a combination of a mono-hollow particle and other hollow particles.

[0044] Since the hollow inorganic filler (C-1) has pores, it usually has a porosity of more than 0% by volume. The porosity of the hollow inorganic filler (C-1) is preferably 10% by volume or more, more preferably 15% by volume or more, and particularly preferably 20% by volume or more. Furthermore, from the viewpoint of the mechanical strength of the cured product of the resin composition, the porosity of the hollow inorganic filler (C-1) is preferably 80% by volume or less, more preferably 75% by volume or less, and particularly preferably 70% by volume or less.

[0045] The porosity P (vol %) of an inorganic filler is defined as the volume-based ratio of the total volume of one or more voids present inside the particle to the total volume of the particle based on the outer surface of the particle (total volume of voids / volume of particle). For example, the actual density measurement value D of the inorganic filler M (g / cm 3 ), and the theoretical value of the material density D of the material forming the inorganic filler T (g / cm 3 ) is used to calculate the following formula (1):

number

[0046] (C-1) Hollow inorganic filler generally has voids formed within the particle and an outer shell formed of an inorganic material surrounding the voids. Usually, the voids are separated from the outside of the particle by the outer shell. In this case, it is preferable that the voids do not communicate with the outside of the particle. Therefore, it is preferable that the outer shell is a non-porous shell that does not have pores that communicate the voids with the outside of the particle. The fact that the outer shell is non-porous can be confirmed by observation with a transmission electron microscope (TEM).

[0047] From the viewpoint of significantly obtaining the effects of the present invention, the average particle size of the hollow inorganic filler (C-1) is preferably 0.01 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.3 μm or more, and is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less.

[0048] The average particle size can be measured using a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution based on volume 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 of inorganic filler can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture ultrasonically for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution analyzer with blue and red light source wavelengths using a flow cell system to measure the volumetric particle size distribution of the inorganic filler, and the average particle size can be 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.

[0049] The BET specific surface area of ​​the hollow inorganic filler (C-1) is preferably 1 m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 5m 2 / g or more, preferably 100m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 30m 2 The BET specific surface area of ​​the particles can be measured in accordance with the BET method by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

[0050] The hollow inorganic filler (C-1) may be a commercially available product. Examples of commercially available hollow inorganic fillers (C-1) include "MG-005" manufactured by Taiheiyo Cement Corporation and "LHP-208" manufactured by Ube Exsymo Co., Ltd.

[0051] The (C-1) hollow inorganic filler may also be produced by, for example, the method described in Japanese Patent No. 5940188 or a method equivalent thereto. Specifically, hollow silica particles, which are an example of the (C-1) hollow inorganic filler, can be produced by a method including the steps of: preparing an aqueous solution containing a substance capable of forming pores and a basic compound; mixing the aqueous solution with an alkoxysilane and stirring to precipitate silica particles; removing the substance capable of forming pores from the silica particles to obtain hollow silica precursors; and calcining the hollow silica precursors.

[0052] The hollow inorganic filler (C-1) may also be produced by, for example, the method described in Japanese Patent No. 5864299 or a method equivalent thereto. Specifically, hollow silica particles, which are an example of the hollow inorganic filler (C-1), can be produced by a method including: (a) a step of preparing an aqueous solution containing a substance capable of forming hollow spaces and a basic compound; (b) a step of adding an alkoxysilane to the aqueous solution and stirring the mixture at 0°C to 100°C to precipitate silica particles; (c) a step of removing the substance capable of forming hollow spaces from the silica particles obtained in step (b) to obtain hollow silica precursors; and (c) a step of calcining the hollow silica precursor obtained in step (c) at a temperature exceeding 900°C to obtain hollow silica.

[0053] From the viewpoint of improving moisture resistance and dispersibility, the hollow inorganic filler (C-1) may be treated with a surface treatment agent other than the component (D) described below. Examples of surface treatment agents other than the component (D) include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

[0054] 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).

[0055] From the viewpoint of improving dispersibility, the degree of surface treatment with a surface treatment agent other than component (D) preferably falls within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 8% by mass of a surface treatment agent other than component (D), more preferably 0.2% to 5% by mass of a surface treatment agent other than component (D), and even more preferably 0.3% to 3% by mass of a surface treatment agent other than component (D).

[0056] The degree of surface treatment with a surface treatment agent other than component (D) 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 preventing an increase in the melt viscosity of the resin composition, it is more preferable that the content be 1.0 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:

[0057] The carbon amount per unit surface area of ​​the inorganic filler 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. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. The carbon analyzer that can be used is the "EMIA-320V" manufactured by Horiba, Ltd.

[0058] From the viewpoint of significantly achieving the effects of the present invention, the content (mass %) of the (C-1) hollow inorganic filler is preferably 0 mass % or more, more preferably 15 mass % or more, and even more preferably 20 mass % or more, and is preferably 70 mass % or less, more preferably 65 mass % or less, and even more preferably 60 mass % or less, when the non-volatile components in the resin composition are taken as 100 mass %, inclusive.

[0059] From the viewpoint of significantly achieving the effects of the present invention, the content (volume %) of the hollow inorganic filler (C-1) is preferably 1 volume % or more, more preferably 3 volume % or more, and even more preferably 5 volume % or more, when the non-volatile components in the resin composition are taken as 100 volume %, and is preferably 70 volume % or less, more preferably 60 volume % or less, and even more preferably 50 volume % or less.

[0060] The specific gravity of the component (C-1) is preferably 3.50 g / cm from the viewpoint of significantly achieving the effects of the present invention. 3 or less, more preferably 3.00 g / cm 3 or less, more preferably 2.50 g / cm 3 or less, preferably 0.05 g / cm 3 More preferably, 0.5 g / cm 3 More preferably, 1.0 g / cm 3 The specific gravity can be measured by the method described in the Examples below.

[0061] The (C-2) solid inorganic filler is an inorganic filler with a porosity of 0% by volume. Commercially available (C-2) solid inorganic fillers may be used. Examples of commercially available (C-2) solid inorganic fillers include "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 Co., Ltd.; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "CellSpheres" and "MGH-005" manufactured by Taiheiyo Cement Corporation; and "Spherique" and "BA-1" manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0062] The average particle size of the solid inorganic filler (C-2) is preferably 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 0.3 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The average particle size of the component (C-2) can be measured in the same manner as the average particle size of the hollow inorganic filler (C-1).

[0063] The BET specific surface area of ​​the (C-2) solid inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 40m 2 The BET specific surface area of ​​component (C-2) can be measured in the same manner as for the BET specific surface area of ​​component (C-2).

[0064] Like the hollow inorganic filler (C-1), the solid inorganic filler (C-2) may be treated with a surface treatment agent other than component (D). The surface treatment agent other than component (D), the degree of surface treatment, the amount of carbon, etc. are as described above.

[0065] The content (mass %) of the (C-2) solid inorganic filler may be 0 mass % or more, and is preferably 10 mass % or more, more preferably 20 mass % or more, and particularly preferably 30 mass % or more, and is preferably 85 mass % or less, more preferably 80 mass % or less, and particularly preferably 75 mass % or less, assuming that the non-volatile components in the resin composition are 100 mass %.

[0066] The content (vol %) of the (C-2) solid inorganic filler may be 0 vol % or more, and is preferably 5 vol % or more, more preferably 10 vol % or more, and even more preferably 20 vol % or more, and is preferably 50 vol % or less, more preferably 40 vol % or less, and even more preferably 30 vol % or less, assuming that the non-volatile components in the resin composition are 100 vol %.

[0067] The proportion of voids contained in the entire (C) inorganic filler, including both the (C-1) hollow inorganic filler and the (C-2) solid inorganic filler, is determined as the porosity (volume %) of the (C) inorganic filler. The porosity (volume %) of the (C) inorganic filler is a representative value that represents the proportion of voids in the volume of the (C) inorganic filler on a volume basis, and is expressed as "total volume of voids / total volume of the (C) inorganic filler." The specific range of the porosity of the (C) inorganic filler is preferably 10% by volume or more, more preferably 15% by volume or more, and even more preferably 20% by volume or more, and is preferably 80% by volume or less, more preferably 70% by volume or less, and even more preferably 60% by volume or less.

[0068] The average particle size of the entire inorganic filler (C), including both the hollow inorganic filler (C-1) and the solid inorganic filler (C-2), is preferably 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 0.3 μm or more, from the viewpoint of significantly obtaining the effects of the present invention, and is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less.

[0069] The BET specific surface area of ​​the entire inorganic filler (B) including both the hollow inorganic filler (C-1) and the solid inorganic filler (C-2) is preferably 1 m² from the viewpoint of significantly obtaining the effects of the present invention. 2 / g or more, more preferably 2m 2 / g or more, more preferably 5m 2 / g or more, preferably 100m 2 / g or less, more preferably 50m 2 / g or less, more preferably 30m 2 / g or less.

[0070] When the component (C) includes both a hollow inorganic filler (C-1) and a solid inorganic filler (C-2), the content (vol %) of the hollow inorganic filler (C-1) in all inorganic fillers is, from the viewpoint of significantly obtaining the effects of the present invention, preferably 0 vol %, more preferably 0 vol % or more, and even more preferably 30 vol % or more, when the content of all inorganic fillers is 100 vol %, and is preferably 100 vol %, more preferably 100 vol % or less, and even more preferably 75 vol % or less.

[0071] From the viewpoint of significantly achieving the effects of the present invention, the content (mass %) of the (C) inorganic filler is preferably 50 mass % or more, more preferably 55 mass % or more, and even more preferably 60 mass % or more, and is preferably 85 mass % or less, more preferably 80 mass % or less, and particularly preferably 75 mass % or less, when the non-volatile components in the resin composition are taken as 100 mass %.

[0072] From the viewpoint of achieving a significant effect of the present invention, the content (vol %) of (C) inorganic filler is preferably 20% by volume or more, more preferably 30% by volume or more, and even more preferably 40% by volume or more, and is preferably 80% by volume or less, more preferably 75% by volume or less, and particularly preferably 70% by volume or less, assuming that the non-volatile components in the resin composition are 100% by volume.

[0073] <(D) Silane Compound Having Silicon Atom as Ring-Constituting Atom> The resin composition contains, as component (D), a silane compound having a silicon atom as a constituent atom of the (D) ring. This silane compound having a silicon atom as a constituent atom of the (D) ring as component (D) does not include those corresponding to the above-mentioned components (A) to (C). By including component (D) in the resin composition, it is possible to suppress the haloing phenomenon. One type of component (D) may be used alone, or two or more types may be used in combination.

[0074] As component (D), a compound having a cyclic structure and containing a silicon atom as a ring-constituting atom constituting the cyclic structure can be used. The cyclic structure may be a monocyclic, polycyclic, or fused ring, but a monocyclic structure is preferred from the viewpoint of achieving a significant effect of the present invention. The cyclic structure may be a saturated or unsaturated cyclic structure, but a saturated cyclic structure is preferred from the viewpoint of achieving a significant effect of the present invention. The cyclic structure is preferably a 3- to 10-membered ring, more preferably a 4- to 6-membered ring, even more preferably a 5- or 6-membered ring, and particularly preferably a 5-membered ring.

[0075] The cyclic structure has a silicon atom and a carbon atom as ring-constituting atoms. The ring-constituting atoms may also have a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. From the viewpoint of achieving the effects of the present invention more significantly, component (D) preferably has a silicon atom, a carbon atom, and a nitrogen atom as ring-constituting atoms, and component (D) is preferably a cyclic silazane compound.

[0076] The number of silicon atoms as ring-constituting atoms is preferably 1 to 5, more preferably 1 or 2, and even more preferably 1. When a heteroatom is contained as a ring-constituting atom, the number of heteroatoms is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0077] The component (D) preferably has 1 to 3 cyclic structures in one molecule, more preferably 1 or 2 cyclic structures, and even more preferably 1 cyclic structure.

[0078] In component (D), the silicon atom as a ring-constituting atom is preferably bonded to an alkoxy group. Examples of the alkoxy group include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, and hexyloxy. Of these, the alkoxy group is preferably a methoxy group, from the viewpoint of achieving the most significant effects of the present invention.

[0079] The component (D) is preferably a compound represented by formula (D-1). [ka] In the formula, R 1 and R 2 each independently represents a monovalent hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, A represents a heteroatom, and n represents an integer of 1 to 4.

[0080] R 1 and R 2each independently represent a monovalent hydrocarbon group of 1 to 20 carbon atoms which may have a substituent. The monovalent hydrocarbon group of 1 to 20 carbon atoms is preferably a monovalent hydrocarbon group of 1 to 15 carbon atoms, more preferably a monovalent hydrocarbon group of 1 to 10 carbon atoms, and even more preferably a monovalent hydrocarbon group of 1 to 6 carbon atoms. This number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, and aryl groups. The alkyl group may be linear, branched, or cyclic, and the preferred number of carbon atoms is as described above. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. Alkenyl groups may be linear, branched, or cyclic, and the preferred number of carbon atoms is as described above. Examples of alkenyl groups include vinyl, allyl, butenyl, and methallyl groups. Examples of aryl groups include phenyl, tolyl, and xylyl groups. An aryl group is preferred, and R 1 From the viewpoint of significantly achieving the effects of the present invention, R is preferably an aryl group, more preferably a phenyl group. 2 From the viewpoint of significantly achieving the effects of the present invention, the alkyl group is preferred, and a methyl group is more preferred.

[0081] R 1 and R 2 The monovalent hydrocarbon group represented by may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, —OH, —OC 1-6 Alkyl group, -N(C 1-10 alkyl group)2, C 1-20 Alkyl group, C 2-30 Alkenyl group, C 2-30 Alkynyl group, C 6-10An aryl group, -NH2, -CN, -C(O)O-C 1-10 Examples include an alkyl group, -COOH, -C(O)H, -NO2, etc. Here, the term "C p-q " (where p and q are positive integers and p < q) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression "C 1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure includes spiro rings and fused rings as well.

[0082] A represents a heteroatom, and the heteroatom is as described above.

[0083] n represents an integer from 1 to 4, preferably 2 or 3, more preferably 3.

[0084] Examples of component (D) include 2,2-dimethoxy-1-methyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-methyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-methyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-methyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-methyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-butyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-butyl-1-aza-2-silacyclopentane, 2,2-Dimethyl-1-butyl-1-aza-2-silacyclopentane, 2,2-Diethoxy-1-butyl-1-aza-2-silacyclopentane, 2-Ethoxy-2-methyl-1-butyl-1-aza-2-silacyclopentane, 2,2-Dimethoxy-1-cyclohexyl-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-1-cyclohexyl-1-aza-2-silacyclopentane, 2,2-Dimethyl-1-cyclohexyl-1-aza-2-silacyclopentane, 2,2-Diethoxy-1 -Cyclohexyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-cyclohexyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-phenyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-phenyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-phenyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-phenyl-1-aza-2-silacyclopentane 2,2-dimethoxy-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane, 2,2-Dimethoxy-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, 2,2-Dimethyl-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, 2,2-Diethoxy-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, 2-Ethoxy-2-methyl-1-(2-methoxycarbonyl-2- Methyl)ethyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane , 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane 2,2-dimethoxy-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-1-methyldimethoxysilylmethyl-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-1-methyldimethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-Dimethyl-1-methyldimethoxysilylmethylmethyl-1-aza-2-silacyclopentane, 2,2-Diethoxy-1-methyldimethoxysilylmethyl-1-aza-2-silacyclopentane, 2-Ethoxy-2-methyl-1-methyldimethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-Dimethoxy-1 -(3-Methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane 2,2-Dimethoxy-1-(4-methyldimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-1-(4-methyldimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-Dimethyl-1-(4-methyldimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy-1-(4-methyldimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-Ethoxy-2-methyl-1-(4-methyldimethoxysilylbutyl)-1-aza-2- Silacyclopentane, 2,2-dimethoxy-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-Dimethoxy-1-(3-dimethylmethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-1-(3-dimethylmethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-Dimethyl-1-(3-dimethylmethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy-1-(3-dimethylmethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-Ethoxy-2-methyl-1-(3-dimethylmethoxysilylpropyl)-1-aza-2 -Silacyclopentane, 2,2-dimethoxy-1-(4-dimethylmethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-dimethylmethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-dimethylmethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(4-dimethylmethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-dimethylmethoxysilylbutyl) -1-Aza-2-silacyclopentane, 2,2-dimethoxy-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2- Dimethoxy-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl 2-Methoxy-1-methyldiethoxysilylmethyl-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-1-methyldiethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-Dimethyl-1-methyldiethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-Diethoxy-1-methyldiethoxysilylmethyl-1-aza-2-silacyclopentane, 2-Ethoxy-2-methyl-1-methyldiethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-Dimethoxy-1-(3-methyl) 2-Methoxy-2-methyl-1-(3-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimeth 2-methoxy-2-methyl-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-dimethylethoxysilylpropyl, )-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-dimethylethoxysilylbutyl)-1 -Aza-2-silacyclopentane, 2,2-diethoxy-1-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-methyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-methyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-methyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-methyl-1-aza-2-silacyclopentane, 2 -Ethoxy-2-methyl-1-methyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-butyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-butyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-butyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-butyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-butyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-cyclohexyl-1-aza-2-silacyclopentane, 2-methoxy-2 -methyl-1-cyclohexyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-cyclohexyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-cyclohexyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-cyclohexyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-phenyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-phenyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-phenyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-phenyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane 2-ethoxy-2-methyl-1-(2-methoxycarbonyl)ethyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, 2, 2-diethoxy-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane , 2,2-diethoxy-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-trimethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2- Diethoxy-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-methyldimethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-methyldimethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-methyldimethoxysilylmethylmethyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1 -Methyldimethoxysilylmethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-methyldimethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(3-methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy- 1-(3-methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-methyldimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-methyldimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-methyldimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(4-methyldimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-methyldimethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-di Ethoxy-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-dimethylmethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(3-dimethylmethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-dimethylmethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-dimethylmethoxysilylpropyl)-1-aza-2-silacyclopentane, 2, 2-diethoxy-1-(3-dimethylmethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-dimethylmethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-dimethylmethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-dimethylmethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-dimethylmethoxysilylbutyl)-1-aza-2-silacyclopentane Cyclopentane, 2,2-diethoxy-1-(4-dimethylmethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-dimethylmethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-triethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-triethoxysilylmethyl-1-aza-2-silacyclopentane 2-ethoxy-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2- Diethoxy-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-triethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-methyldiethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-methyldiethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-methyldiethoxysilylmethylmethyl-1-aza-2-silacyclopentane, 2,2-diethoxy 2-ethoxy-2-methyl-1-methyldiethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(3-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(3-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane 2,2-Dimethyl-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-Dimethyl-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-Ethoxy-2-methyl-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-Di, Methoxy-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-dimethyl-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-dimethylethoxysilylmethyl 2,2-Dimethoxy-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-Dimethyl-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, -Aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(3-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-dimethylethoxysilylbutyl)-1-aza 2-silacyclopentane, 2,2-diethoxy-1-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, tetrakis(3,4-epoxycyclohexylethyl)-tetramethylcyclotetrasiloxane, bis(3-glycidyloxypropyl)-hexaalkylcyclotetrasiloxane, and the like.

[0085] Component (D) may be a commercially available product, such as "X-88-398" (2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane) manufactured by Shin-Etsu Chemical Co., Ltd., or "KR-470," "X-40-2678," or "X-40-2728" manufactured by Shin-Etsu Silicones Co., Ltd.

[0086] The form of component (D) contained in the resin composition of the present invention is not particularly limited, but it is preferably contained in the resin composition in any of the following forms (i) to (iii), more preferably in the resin composition in either form (ii) or (iii), and even more preferably in the resin composition in form (iii). (i) The resin composition contains only the component (D). (ii) Component (D) is contained as a surface treatment agent for inorganic filler (C). (iii) The component (D) is contained as a surface treatment agent for the inorganic filler (C), and the component (D) is contained alone in the resin composition.

[0087] "Containing component (D) as a surface treatment agent for inorganic filler (C)" means that the inorganic filler (C) has been surface-treated with component (D). In this case, component (D) is usually present on the surface of inorganic filler (C). Furthermore, "containing component (D) alone in the resin composition" means that component (D) is not contained as a surface treatment agent for inorganic filler (C). Note that when component (D) is not contained as a surface treatment agent for inorganic filler (C), component (D) is free in the resin composition. In the present invention, component (D) can uniformly treat the surface of inorganic filler (C), thereby effectively suppressing the haloing phenomenon.

[0088] When the component (D) is contained as a surface treatment agent for the component (C), the content of the component (D) is, from the viewpoint of suppressing the haloing phenomenon, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, and is preferably 3% by mass or less, more preferably 2.5% by mass or less, and even more preferably 2% by mass or less.

[0089] When the component (D) is contained as a surface treatment agent for the component (C), from the viewpoint of suppressing the haloing phenomenon, the content of the component (D), relative to the resin component in the resin composition taken as 100% by mass, is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, 1% by mass or more, or 1.5% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0090] When component (D) is contained as a surface treatment agent for component (C), the degree of surface treatment with component (D) (content of component (D)), relative to 100% by mass of inorganic filler (C), from the viewpoint of suppressing haloing, is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, or 0.6% by mass or more, and is preferably 8% by mass or less, more preferably 5% by mass or less, and even more preferably 4% by mass or less.

[0091] When the content (% by mass) of the (B) component when the nonvolatile components in the resin composition are taken as 100% by mass is b, and the content (% by mass) of the (D) component when the nonvolatile components in the resin composition are taken as 100% by mass is d, b / d is preferably at least 1, more preferably at least 2, and even more preferably at least 3, and is preferably at most 50, more preferably at most 40, and even more preferably at most 30, 20, 15, or 10. By adjusting the contents of the (B) and (D) components so that b / d falls within this range, a cured product with low dielectric properties can be obtained, and the haloing phenomenon can also be suppressed.

[0092] <(E) Hardener> In addition to the above-mentioned components, the resin composition may further contain a (E) curing agent as an optional component. The (E) curing agent as this component (E) does not include those corresponding to the above-mentioned components (A) to (D). As the (E) curing agent, a compound having the function of reacting with the (A) component to cure the resin composition can be used, and examples thereof include phenol-based curing agents, naphthol-based curing agents, carbodiimide-based curing agents, benzoxazine-based curing agents, and cyanate ester-based curing agents. Among these, it is preferable that the (E) curing agent contains a phenol-based curing agent from the viewpoint of achieving the effects of the present invention more significantly. The (E) curing agents may be used alone or in combination of two or more.

[0093] 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.

[0094] 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 & Sumikin Chemical Co., Ltd.; and "TD-2090," "LA-7052," "LA-7054," "LA-1356," "LA3018-50P," "EXB-9500," and "KA-1163" manufactured by DIC Corporation.

[0095] The carbodiimide curing agent is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule, and the carbodiimide curing agent is preferably a compound having two or more carbodiimide groups in one molecule.

[0096] Specific examples of commercially available carbodiimide curing agents include Carbodilite V-03 (carbodiimide group equivalent: 216 g / eq., V-05 (carbodiimide group equivalent: 262 g / eq.), V-07 (carbodiimide group equivalent: 200 g / eq.), and V-09 (carbodiimide group equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Inc.; and Stavaxol P (carbodiimide group equivalent: 302 g / eq.) manufactured by Rhein Chemie AG.

[0097] 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.

[0098] 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 Japan.

[0099] The quantitative ratio of component (A) to component (E), expressed as the ratio of [total number of epoxy groups in component (A)] to [total number of active groups in component (E)], is preferably in the range of 1:0.01 to 1:10, more preferably 1:0.05 to 1:8, and even more preferably 1:0.08 to 1:5. Here, the "total number of epoxy groups in the epoxy resin" refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of component (A) present in the resin composition by the epoxy equivalent. Furthermore, the "total number of active groups in component (E)" refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of component (E) present in the resin composition by the active group equivalent. By maintaining the quantitative ratio of component (E) to component (A) within this range, the effects of the present invention can be significantly achieved.

[0100] The quantitative ratio of component (A) to components (B) and (E), expressed as the ratio of [total number of epoxy groups in component (A)] to [total number of active groups in components (B) and (E)], is preferably in the range of 1:0.01 to 1:10, more preferably 1:0.3 to 1:5, and even more preferably 1:0.4 to 1:4. Here, the "total number of active groups in components (B) and (E)" refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components (B) and (E) present in the resin composition by the active group equivalent. By maintaining the quantitative ratio of component (A) to components (B) and (E) within this range, the effects of the present invention can be significantly achieved.

[0101] To significantly achieve the desired effects of the present invention, the content of component (E) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit is preferably 8% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0102] From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (E) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0103] <(F) Curing accelerator> In addition to the above-mentioned components, the resin composition may further contain a curing accelerator as an optional component (F). This curing accelerator as component (F) does not include those corresponding to the above-mentioned components (A) to (E). By including component (F), it becomes possible to further accelerate the curing of component (A). Component (F) may be used alone or in combination of two or more.

[0104] Examples of component (F) include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. Among these, curing accelerators selected from amine-based curing accelerators and metal-based curing accelerators are preferred, with amine-based curing accelerators being particularly preferred.

[0105] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, and tetraphenylphosphonium tetra-p-tolylborate. aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine aromatic phosphines such as benzene, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether;

[0106] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as toluene bis(dimethylurea), 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0107] Examples of guanidine curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0108] 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, and 1-benzyl-2-methylimidazole. 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-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and other imidazole compounds, as well as adducts of imidazole compounds with epoxy resins.

[0109] As the imidazole-based curing accelerator, commercially available products may be used, such as "1B2PZ", "2MZA-PW", "2PHZ-PW", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0110] 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.

[0111] 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.

[0112] As the amine-based curing accelerator, commercially available products may be used, for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0113] From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (F) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.05% by mass or more, and is preferably 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0114] From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (F) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is preferably 1.5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0115] <(G)Thermoplastic resin> In addition to the components described above, the resin composition may further contain a (G) thermoplastic resin as an optional component. The (G) thermoplastic resin as component (G) does not include those corresponding to the above-described components (A) to (F).

[0116] Examples of (G) thermoplastic resins include polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. In one embodiment, the (G) thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resins and phenoxy resins, and more preferably contains a phenoxy resin. Furthermore, one type of thermoplastic resin may be used alone, or two or more types may be used in combination.

[0117] Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., and "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

[0118] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, bisphenolacetophenone, novolac, biphenyl, fluorene, dicyclopentadiene, norbornene, naphthalene, anthracene, adamantane, terpene, and trimethylcyclohexane. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0119] Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; and "YL7500BH30," "YX6954BH30," "YX7553," "YX7553BH30," "YL7769BH30," "YL6794," "YL7213," "YL7290," "YL7482," and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation.

[0120] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP, manufactured by Denki Kagaku Kogyo Co., Ltd.; and S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series, manufactured by Sekisui Chemical Co., Ltd.

[0121] Examples of polyolefin resins include ethylene copolymer resins such as low-density polyethylene, very low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0122] Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxy group-containing polybutadiene resins, phenolic hydroxy group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

[0123] Specific examples of polyamide-imide resins include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imides) manufactured by Hitachi Chemical Co., Ltd.

[0124] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0125] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0126] A specific example of the polyphenylene ether resin is NORYL SA90 manufactured by SABIC, etc. A specific example of the polyetherimide resin is ULTEM manufactured by GE, etc.

[0127] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, Inc., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. Specific examples of polyether ether ketone resins include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd.

[0128] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

[0129] From the viewpoint of significantly achieving the effects of the present invention, the weight average molecular weight (Mw) of the (G) thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.

[0130] From the viewpoint of significantly achieving the desired effects of the present invention, the content of the (G) thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0131] From the viewpoint of significantly achieving the desired effects of the present invention, the content of the (G) thermoplastic resin is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0132] <(H) Other Additives> In addition to the components described above, the resin composition may further contain other additives as optional components. Examples of (H) other additives include radically polymerizable compounds; elastomers; polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silanes; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; hindered forms. surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photopolymerization initiation aids such as tertiary amines; and photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones. (H) Other additives may be used singly or in combination of two or more.

[0133] <(I) Solvent> The resin composition may further contain an arbitrary solvent as a volatile component in addition to the nonvolatile components described above. (I) As the solvent, any known solvent can be used appropriately, and the type is not particularly limited, but an organic solvent is preferred. (I) Solvents include, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of suitable solvents include ether ester solvents such as ethyl acetate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) The solvents may be used alone or in combination of two or more in any ratio.

[0134] From the viewpoint of achieving the effects of the present invention more significantly, the resin composition preferably contains 0.5% by mass or more and 6% by mass or less of (I) solvent, relative to 100% by mass of all components of the resin composition. Specifically, the (I) solvent is preferably contained in an amount of 5% by mass or less, more preferably 4% by mass or less, and more preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1% by mass or more, relative to 100% by mass of all components of the resin composition.

[0135] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the blending components are mixed and dispersed using a rotary mixer or the like, with the addition of a solvent or the like as necessary.

[0136] <Physical properties and applications of resin compositions> By curing the resin composition of the present invention, an insulating layer formed of the cured product of the resin composition can be obtained. When via holes are formed in this insulating layer and the layer is subjected to a roughening treatment, the haloing phenomenon can be suppressed. These effects will be described below with reference to the drawings.

[0137] 1 is a cross-sectional view schematically showing an insulating layer 100 obtained by curing a resin composition according to a first embodiment of the present invention into a sheet form, together with an inner layer substrate 200. Fig. 1 shows a cross section of the insulating layer 100 cut along a plane that passes through the center 120C of the bottom 120 of the via hole 110 and is parallel to the thickness direction of the insulating layer 100.

[0138] As shown in FIG. 1 , the insulating layer 100 according to the first embodiment of the present invention is a layer obtained by curing a resin composition layer formed on an inner substrate 200 including a conductor layer 210, and is made of a cured product of the resin composition layer. The insulating layer 100 also has a via hole 110 formed therein. The via hole 110 is generally formed in a forward tapered shape, with the diameter increasing toward the surface 100U of the insulating layer 100 opposite the conductor layer 210 and decreasing toward the conductor layer 210, and ideally formed in a columnar shape with a constant diameter in the thickness direction of the insulating layer 100. The via hole 110 is typically formed by irradiating the surface 100U of the insulating layer 100 opposite the conductor layer 210 with laser light to remove a portion of the insulating layer 100.

[0139] The bottom of the via hole 110 on the conductor layer 210 side is referred to as the "via bottom" as appropriate and is indicated by the reference numeral 120. The diameter of this via bottom 120 is referred to as the bottom diameter Lb. The opening formed on the opposite side of the via hole 110 from the conductor layer 210 is referred to as the "via top" as appropriate and is indicated by the reference numeral 130. The diameter of this via top 130 is referred to as the top diameter Lt. Usually, the via bottom 120 and the via top 130 are formed so that their planar shapes are circular when viewed from the thickness direction of the insulating layer 100, but they may also be elliptical. When the planar shapes of the via bottom 120 and the via top 130 are elliptical, the bottom diameter Lb and the top diameter Lt respectively represent the major axes of the elliptical shapes.

[0140] In this case, the closer to 100% the taper ratio Lb / Lt (%) obtained by dividing the bottom diameter Lb by the top diameter Lt is, the better the shape of the via hole 110. By using the resin composition layer of the present invention, it is possible to easily control the shape of the via hole 110, and therefore it is possible to realize a via hole 110 with a taper ratio Lb / Lt close to 100%.

[0141] For example, when an insulating layer 100 is obtained by heating a resin composition at 100°C for 30 minutes and then curing it at 180°C for 30 minutes, and then irradiating the resulting insulating layer 100 with CO2 laser light under the following conditions: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, number of shots 2, burst mode (10 kHz), to form a via hole 110 with a top diameter Lt of approximately 70 μm, the taper ratio Lb / Lt of the via hole 110 can be preferably 75% to 100%, more preferably 80% to 100%, and particularly preferably 85% to 100%.

[0142] The taper ratio Lb / Lt of the via hole 110 can be calculated from the bottom diameter Lb and top diameter Lt of the via hole 110. The bottom diameter Lb and top diameter Lt of the via hole 110 can be measured by using a focused ion beam (FIB) to cut out the insulating layer 100 so as to reveal a cross section that is parallel to the thickness direction of the insulating layer 100 and passes through the center 120C of the via bottom 120, and then observing the cross section with an electron microscope.

[0143] Figure 2 is a plan view schematically showing the surface 100U of the insulating layer 100 obtained by curing the resin composition in the first embodiment of the present invention into a sheet form, opposite the conductor layer 210 (not shown in Figure 2).

[0144] 2, when observing an insulating layer 100 having a via hole 110 formed therein, a discolored area 140, where the insulating layer 100 has discolored, may be observed around the via hole 110. This discolored area 140 can be formed by resin deterioration during the formation of the via hole 110, and is usually formed continuously from the via hole 110. In many cases, the discolored area 140 is a whitened area.

[0145] 3 is a cross-sectional view schematically showing a roughening-treated insulating layer 100 obtained by curing the resin composition according to the first embodiment of the present invention into a sheet, together with an inner layer substrate 200. This Fig. 3 shows a cross section of the insulating layer 100 cut along a plane that passes through the center 120C of the via bottom 120 of the via hole 110 and is parallel to the thickness direction of the insulating layer 100.

[0146] 3, when a roughening treatment is performed on the insulating layer 100 in which the via hole 110 is formed, a haloing phenomenon occurs, and the insulating layer 100 in the discolored portion 140 peels off from the conductor layer 210, and a gap 160 may be formed that continues from the edge 150 of the via bottom 120. This gap 160 is usually formed by erosion of the discolored portion 140 during the roughening treatment.

[0147] By using the resin composition of the present invention, the haloing phenomenon can be suppressed, and therefore, peeling of the insulating layer 100 from the conductor layer 210 can be suppressed, and the size of the gap 160 can be reduced.

[0148] The edge 150 of the via bottom 120 corresponds to the inner peripheral edge of the gap 160. Therefore, the distance Wb from the edge 150 of the via bottom 120 to the outer peripheral end 170 of the gap 160 (i.e., the end farther from the center 120C of the via bottom 120) corresponds to the in-plane size of the gap 160. Here, the in-plane direction refers to the direction perpendicular to the thickness direction of the insulating layer 100. In the following description, the distance Wb may be referred to as the halo distance Wb of the via hole 110 from the edge 150 of the via bottom 120. The halo distance Wb from the edge 150 of the via bottom 120 can be used to evaluate the degree of suppression of the halo phenomenon. Specifically, it can be evaluated that the smaller the halo distance Wb from the edge 150 of the via bottom 120, the more effectively the halo phenomenon can be suppressed.

[0149] For example, a resin composition layer containing a resin composition is heated at 100°C for 30 minutes, then heated at 180°C for 30 minutes to harden, to obtain an insulating layer 100. The insulating layer 100 is then irradiated with CO2 laser light under the following conditions: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot count 2, burst mode (10 kHz), to form a via hole 110 with a top diameter Lt of approximately 70 μm. The resulting layer is then immersed in a swelling solution at 60°C for 5 minutes, then immersed in an oxidizing agent solution at 80°C for 10 minutes, then immersed in a neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

[0150] The halo distance Wb from the edge 150 of the via bottom 120 can be measured by using a FIB (focused ion beam) to remove the insulating layer 100 so as to reveal a cross section that is parallel to the thickness direction of the insulating layer 100 and passes through the center 120C of the via bottom 120, and then observing the cross section with an electron microscope.

[0151] Furthermore, by using the resin composition of the present invention, the shape of the via hole 110 in the insulating layer 100 before the roughening treatment can be easily controlled, and therefore, it is usually possible to easily control the shape of the via hole 110 in the insulating layer 100 after the roughening treatment. Therefore, even after the roughening treatment, the shape of the via hole 110 can be made as good as before the roughening treatment. Therefore, by using the resin composition of the present invention, it is possible to realize a via hole 110 with a taper ratio Lb / Lt of nearly 100% in the insulating layer after the roughening treatment.

[0152] For example, a resin composition layer is heated at 100°C for 30 minutes, then heated at 180°C for 30 minutes to cure the resulting insulating layer 100. The resulting insulating layer 100 is then irradiated with CO2 laser light under the following conditions: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot count 2, burst mode (10 kHz) to form a via hole 110 with a top diameter Lt of approximately 70 μm. The resulting insulating layer 100 is then immersed in a swelling solution at 60°C for 5 minutes, then immersed in an oxidizing agent solution at 80°C for 10 minutes, then immersed in a neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. By using the resin composition of the present invention, the taper ratio Lb / Lt of the via hole 110 formed in the insulating layer 100 thus obtained can be preferably 76% to 100%, more preferably 80% to 100%, and particularly preferably 85% to 100%.

[0153] The taper ratio Lb / Lt of the via hole 110 can be calculated from the bottom diameter Lb and top diameter Lt of the via hole 110. The bottom diameter Lb and top diameter Lt of the via hole 110 can be measured by using a focused ion beam (FIB) to cut out the insulating layer 100 so as to reveal a cross section that is parallel to the thickness direction of the insulating layer 100 and passes through the center 120C of the via bottom 120, and then observing the cross section with an electron microscope.

[0154] Furthermore, according to the inventor's research, it has been found that, in general, the larger the diameter of the via hole 110, the larger the size of the discolored portion 140 tends to be, and therefore the larger the size of the gap 160 tends to be. Therefore, the degree of suppression of the halo phenomenon can be evaluated by the ratio of the size of the gap 160 to the diameter of the via hole 110. For example, the evaluation can be performed by the halo ratio Hb to the bottom radius Lb / 2 of the via hole 110. Here, the bottom radius Lb / 2 of the via hole 110 refers to the radius of the via bottom 120 of the via hole 110. The halo ratio Hb to the bottom radius Lb / 2 of the via hole 110 is the ratio obtained by dividing the halo distance Wb from the edge 150 of the via bottom 120 by the bottom radius Lb / 2 of the via hole 110. A smaller halo ratio Hb to the bottom radius Lb / 2 of the via hole 110 indicates that the halo phenomenon is more effectively suppressed.

[0155] For example, a resin composition is heated at 100°C for 30 minutes, then heated at 180°C for 30 minutes to cure the resulting insulating layer 100. The resulting insulating layer 100 is then irradiated with CO2 laser light under the following conditions: a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, two shots, and burst mode (10 kHz) to form a via hole 110 with a top diameter Lt of 30 μm ± 2 μm. The resulting insulating layer 100 is then immersed in a swelling solution at 60°C for 5 minutes, then in an oxidizing agent solution at 80°C for 10 minutes, then in a neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. Using the resin composition of the present invention, the haloing ratio Hb of the via hole 110 formed in the insulating layer 100 thus obtained to the bottom radius Lb / 2 can be preferably 35% or less, more preferably 30% or less, and even more preferably 25% or less.

[0156] The halo ratio Hb to the bottom radius Lb / 2 of the via hole 110 can be calculated from the bottom diameter Lb of the via hole 110 and the halo distance Wb of the via bottom 120 of the via hole 110 from the edge 150.

[0157] Furthermore, by using the resin composition of the present invention, it is usually possible to suppress the formation of discolored portion 140 during the formation of via hole 110. Therefore, as shown in Fig. 2, the size of discolored portion 140 can be reduced, and ideally, discolored portion 140 can be eliminated. The size of discolored portion 140 can be evaluated by the halo distance Wt from edge 180 of via top 130 of via hole 110.

[0158] The edge 180 of the via top 130 corresponds to the inner peripheral edge of the discoloration portion 140. The halo distance Wt from the edge 180 of the via top 130 represents the distance from the edge 180 of the via top 130 to the outer peripheral edge 190 of the discoloration portion 140. It can be evaluated that the smaller the halo distance Wt from the edge 180 of the via top 130, the more effectively the formation of the discoloration portion 140 can be suppressed.

[0159] The halo distance Wt from the edge 180 of the via top 130 can be measured by observation with an optical microscope.

[0160] Furthermore, according to the inventor's research, it has been found that, in general, the larger the diameter of the via hole 110, the larger the size of the discolored portion 140 tends to be. Therefore, the degree of suppression of the formation of the discolored portion 140 can be evaluated by the ratio of the size of the discolored portion 140 to the diameter of the via hole 110. For example, the evaluation can be performed by the halo ratio Ht to the top radius Lt / 2 of the via hole 110. Here, the top radius Lt / 2 of the via hole 110 refers to the radius of the via top 130 of the via hole 110. The halo ratio Ht to the top radius Lt / 2 of the via hole 110 is the ratio obtained by dividing the halo distance Wt from the edge 180 of the via top 130 by the top radius Lt / 2 of the via hole 110. A smaller halo ratio Ht to the top radius Lt / 2 of the via hole 110 indicates that the formation of the discolored portion 140 is more effectively suppressed.

[0161] For example, when an insulating layer 100 is obtained by heating a resin composition layer at 100°C for 30 minutes and then curing it by heating at 180°C for 30 minutes, and then irradiating the insulating layer 100 with CO2 laser light under the conditions of a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, two shots, and burst mode (10 kHz), to form a via hole 110 with a top diameter Lt of approximately 70 μm, the haloing ratio Ht of the via hole 110 to the top radius Lt / 2 can be preferably 45% or less, more preferably 40% or less, and even more preferably 35% or less.

[0162] The halo ratio Ht to the top radius Lt / 2 of the via hole 110 can be calculated from the top diameter Lt of the via hole 110 and the halo distance Wt from the edge 180 of the via top 130 of the via hole 110.

[0163] In the manufacturing process of a printed wiring board, the via hole 110 is usually formed without another conductor layer (not shown) being provided on the surface 100U of the insulating layer 100 opposite the conductor layer 210. Therefore, if the manufacturing process of the printed wiring board is understood, it is possible to clearly recognize the structure in which the via bottom 120 is located on the conductor layer 210 side and the via top 130 opens on the opposite side of the conductor layer 210. However, in a completed printed wiring board, conductor layers may be provided on both sides of the insulating layer 100. In this case, it may be difficult to distinguish between the via bottom 120 and the via top 130 due to their positional relationship with the conductor layers. However, the top diameter Lt of the via top 130 is usually greater than or equal to the bottom diameter Lb of the via bottom 120. Therefore, in the above case, it is possible to distinguish between the via bottom 120 and the via top 130 based on their diameters.

[0164] In addition to suppressing the haloing phenomenon, the resin composition of the present invention can also provide a cured product with low dielectric properties. Furthermore, by curing the resin composition of the present invention, an insulating layer with excellent elongation at break is usually obtained.

[0165] A cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits the characteristic of a low dielectric loss tangent. Therefore, the cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.008 or less, more preferably 0.005 or less, and even more preferably 0.004 or less. The lower limit of the dielectric loss tangent may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in the Examples below.

[0166] A cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits the characteristic of a low dielectric constant. Therefore, the cured product provides an insulating layer with a low dielectric constant. The dielectric constant is preferably 4 or less, more preferably 3.5 or less, and even more preferably 3 or less. The lower limit of the dielectric constant may be 1 or more. The dielectric constant can be measured according to the method described in the examples below.

[0167] A cured product obtained by thermally curing a resin composition at 200°C for 90 minutes typically exhibits the property of high elongation at break. Therefore, the cured product provides an insulating layer with high elongation at break. The elongation at break is measured by a tensile test in accordance with JIS K7127. The elongation at break is preferably 1% or more, more preferably 1.3% or more, and even more preferably 1.7% or more. The upper limit of the elongation at break can be set to 10% or less. The elongation at break can be measured according to the method described in the examples below.

[0168] The resin composition of the present invention makes it possible to obtain a cured product that has low dielectric properties and can suppress the haloing phenomenon. Furthermore, it makes it possible to obtain a cured product that has excellent elongation at break. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation applications. Specifically, it can be suitably used as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer) that forms a conductor layer (including a rewiring layer) to be formed on the insulating layer.

[0169] Furthermore, in the multilayer printed wiring board described below, the resin composition can be suitably used as a resin composition for forming an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board) and as a resin composition for forming an interlayer insulating layer of the printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board).

[0170] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring 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 encapsulating 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.

[0171] [Adhesive film] The adhesive film of the present invention comprises a support and a resin composition layer formed from the resin composition of the present invention provided on the support.

[0172] The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less, from the viewpoint of making the printed wiring 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.

[0173] 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.

[0174] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0175] 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.).

[0176] 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.

[0177] 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.

[0178] 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.

[0179] In one embodiment, the adhesive film 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.

[0180] The adhesive film can be produced, for example, by preparing a resin varnish by dissolving the resin composition in a solvent, applying the resin varnish to a support using a die coater or the like, and then drying the applied resin varnish to form a resin composition layer. The solvent is as described above.

[0181] 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 solvent content 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 solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0182] The adhesive film can be stored by being wound up in a roll. When the adhesive film has a protective film, it can be used by peeling off the protective film.

[0183] [Printed wiring board] The printed wiring board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention.

[0184] The printed wiring board can be produced, for example, by using the above-mentioned adhesive film by a method including the following steps (I) and (II). (I) A step of laminating the adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate. (II) Step of thermally curing the resin composition layer to form an insulating layer

[0185] 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 (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board." Furthermore, the "inner layer substrate" of the present invention also includes 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. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0186] The inner layer substrate and the adhesive film can be laminated, for example, by thermocompression bonding the adhesive film to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the adhesive film to the inner layer substrate (hereinafter also referred to as a "thermocompression member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). Note that rather than pressing the thermocompression member directly onto the adhesive film, it is preferable to press it via an elastic material such as heat-resistant rubber so that the adhesive film can sufficiently follow the surface irregularities of the inner layer substrate.

[0187] The inner layer substrate and the adhesive film may be laminated 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 is preferably carried out under reduced pressure conditions of 26.7hPa or less.

[0188] 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.

[0189] After lamination, the laminated adhesive film may be smoothed under normal pressure (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 lamination. The smoothing treatment may be carried out using a commercially available laminator. Note that lamination and smoothing treatment may be carried out consecutively using the commercially available vacuum laminator.

[0190] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0191] In step (II), the resin composition layer is thermally cured to form an insulating layer. The conditions for thermally curing the resin composition layer are not particularly limited, and conditions typically employed for forming insulating layers for printed wiring boards may be used.

[0192] For example, although the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, 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.

[0193] 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 or higher but lower than 120°C (preferably 60°C or higher but 115°C or lower, more preferably 70°C or higher but 110°C or lower) for 5 minutes or longer (preferably 5 to 150 minutes, more preferably 15 to 120 minutes, and even more preferably 15 to 100 minutes).

[0194] When manufacturing a printed wiring board, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. These steps (III) to (V) may be performed according to various methods known to those skilled in the art and used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

[0195] 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.

[0196] Step (IV) is a step of roughening the insulating layer. Smear removal is usually also performed in this step (IV). The roughening procedure and conditions are not particularly limited, and known procedures and conditions commonly used in forming insulating layers for printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used in the roughening treatment is not particularly limited, but examples include alkaline solutions and surfactant solutions. Alkaline solutions are preferred, and sodium hydroxide solutions and potassium hydroxide solutions are more preferred. Commercially available swelling liquids include "Swelling Dip Securigans P," "Swelling Dip Securigans SBU," and "Swelling Dip Securigant P," both manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 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 liquid at 40°C to 80°C for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an 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 Securiganth P" manufactured by Atotech Japan. The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and a commercially available product thereof is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan. Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in the neutralizing solution at 30°C to 80°C for 1 to 30 minutes.From the viewpoint of workability, a preferred method is to immerse the object that has been subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0197] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. There is no particular lower limit, but it is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] In one embodiment, the conductor layer may be 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 conventionally known technique such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, it is preferable to form the conductor layer by a semi-additive method. An example of forming the conductor layer by a semi-additive method will be described below.

[0202] First, a plating seed layer is formed on the surface of an 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. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, 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.

[0203] [Semiconductor Devices] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0204] 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).

[0205] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of the printed wiring board that transmits an electrical signal, and the portion may be either on the surface or embedded. The semiconductor chip is not particularly limited as long as it is an electrical circuit element made of a semiconductor material.

[0206] The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include wire bonding mounting, flip chip mounting, bumpless buildup layer (BBUL) mounting, anisotropic conductive film (ACF) mounting, non-conductive film (NCF) mounting, etc. Here, the "bumpless buildup layer (BBUL) mounting method" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess in a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board." [Example]

[0207] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0208] <Measurement of the average particle size of inorganic fillers> 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed into a vial and dispersed ultrasonically for 10 minutes. Using a laser diffraction particle size distribution analyzer (HORIBA, Ltd., "LA-960"), blue and red light sources were used, and the particle size distribution of the inorganic filler was measured on a volume basis using a flow cell system. From the particle size distribution obtained, the average particle size of the inorganic filler was calculated as the median diameter.

[0209] <Measurement of the average porosity of inorganic fillers> The density of the inorganic filler was measured using a true density measuring device (QUANTACHROME's "ULTRAPYCNOMETER 1000"). In this measurement, nitrogen was used as the measurement gas. The measured density (measured value) D M (g / cm 3 ) and the material density (theoretical value) D of the inorganic material (silica) that forms the inorganic filler T (g / cm 3) and the average porosity of the inorganic filler was measured according to the above formula (I). In the above formula (I), the material density (theoretical value) of silica as an inorganic material is 2.2 g / cm 3 It was decided.

[0210] <Synthesis Example 1: Production of Hollow Silica Particles 1> Hollow silica particles 1 were synthesized according to the description in Japanese Patent No. 5864299. The obtained hollow silica particles 1 had an average particle size of 2.0 μm and a porosity of 50% by volume.

[0211] Example 1 280 parts of solid silica (average particle size 0.5 μm, "SO-C2" manufactured by Admatechs Co., Ltd.) and 1.68 parts of an aminosilane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with 100 parts of MEK and 20 parts of solvent naphtha, and the mixture was heated and stirred at 60°C for 2 hours, and then cooled to room temperature. This produced a stirred liquid containing solid silica surface-treated with an aminosilane coupling agent. The stirred solution was mixed with 30 parts of bisphenol A epoxy resin (Mitsubishi Chemical Corporation "828US", epoxy equivalent weight approximately 180 g / eq.), 30 parts of biphenyl epoxy resin (Nippon Kayaku Co., Ltd. "NC3000H", epoxy equivalent weight approximately 269 g / eq.), 14 parts of a triazine skeleton-containing phenolic hardener (DIC Corporation "LA-3018-50P", hydroxyl group equivalent weight approximately 151 g / eq., 2-methoxypropanol solution with 50% non-volatile components), and 14 parts of an active ester compound. A resin varnish was prepared by mixing 40 parts of a resin (DIC Corporation's "HPC-8000-65T," active group equivalent weight approximately 223 g / eq., toluene solution with 65% nonvolatile content by mass), 10 parts of a phenoxy resin (Mitsubishi Chemical Corporation's "YX6954BH30," a 1:1 solution of MEK and cyclohexanone with 30% nonvolatile content by mass), and 6 parts of a curing accelerator ("DMAP," 4-dimethylaminopyridine, MEK solution with 5% solids by mass), and dispersing the mixture uniformly using a high-speed rotating mixer.

[0212] A PET film (Toray Industries, Inc., "Lumirror R80," thickness 38 μm) that had been treated with an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared as a support. A resin varnish was uniformly applied to the release layer of the support using a die coater so that the thickness of the resin composition layer after drying would be 40 μm, and the resulting film was dried at 80 to 120°C (average 100°C) for 4 minutes to produce an adhesive film.

[0213] <Example 2> In Example 1, the stirred liquid containing the solid silica surface-treated with an aminosilane coupling agent was replaced with a stirred liquid containing the solid silica surface-treated with an aminosilane coupling agent and the hollow silica surface-treated with an aminosilane coupling agent. Except for the above, a resin varnish and an adhesive film were prepared in the same manner as in Example 1.

[0214] A stirred liquid containing solid silica surface-treated with an aminosilane coupling agent and hollow silica surface-treated with an aminosilane coupling agent was obtained by the following method. 140 parts of solid silica (average particle size 0.5 μm, Admatechs "SO-C2"), 70 parts of hollow silica (average particle size 0.5 μm, porosity 50 vol%, Ube Exsymo "LHP-208"), and 2.24 parts of aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "X-88-398") were mixed with 100 parts of MEK and 20 parts of solvent naphtha, heated and stirred at 60 ° C for 2 hours, and then cooled to room temperature. This produced a stirred liquid containing solid silica surface-treated with an aminosilane coupling agent and hollow silica surface-treated with an aminosilane coupling agent.

[0215] Example 3 In Example 2, 1) 70 parts of hollow silica (average particle size 0.5 μm, porosity 50% by volume, "LHP-208" manufactured by Ube Exsymo Co., Ltd.) were replaced with 70 parts of hollow silica particles 1 (average particle size 2.0 μm, porosity 50% by volume), 2) The amount of silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 2.24 parts to 3.08 parts. A resin varnish and an adhesive film were prepared in the same manner as in Example 2, except for the above.

[0216] Example 4 In Example 1, 1) 280 parts of solid silica (average particle size 0.5 μm, Admatechs "SO-C2") was replaced with 140 parts of hollow silica particles 1 (average particle size 2.0 μm, porosity 50% by volume), 2) The amount of silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 1.68 parts to 4.48 parts. A resin varnish and an adhesive film were prepared in the same manner as in Example 1 except for the above.

[0217] <Example 5> In Example 1, the amount of silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 1.68 parts to 0.84 parts. A resin varnish and an adhesive film were prepared in the same manner as in Example 1 except for the above.

[0218] Example 6 In Example 4, the amount of silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 4.48 parts to 2.24 parts. A resin varnish and an adhesive film were prepared in the same manner as in Example 4 except for the above.

[0219] <Comparative Example 1> In Example 1, 1.68 parts of a silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 1.68 parts of an aminosilane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) In addition to the above, a resin varnish and an adhesive film were prepared in the same manner as in Example 1.

[0220] <Comparative Example 2> In Example 4, 4.88 parts of a silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 4.48 parts of an aminosilane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) In addition to the above, a resin varnish and an adhesive film were prepared in the same manner as in Example 4.

[0221] <Comparative Example 3> In Example 4, 4.88 parts of a silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 8.96 parts of an aminosilane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) Except for the above, a resin varnish and an adhesive film were prepared in the same manner as in Example 4.

[0222] <Comparative Example 4> The 4.88 parts of silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was not used in Example 1. A resin varnish and an adhesive film were prepared in the same manner as in Example 1 except for the above points.

[0223] <Preparation of cured product for evaluation> The adhesive films with a thickness of 40 μm produced in the examples and comparative examples were heated at 200° C. for 90 minutes to thermally cure the resin composition layers, and then the support was peeled off. The resulting cured products are referred to as "cured products for evaluation."

[0224] <Measurement of relative permittivity and dielectric loss tangent> The cured product for evaluation was cut into test pieces measuring 2 mm in width and 80 mm in length. The dielectric constant and dielectric loss tangent of the test pieces were measured using an Agilent Technologies HP8362B by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on two test pieces, and the average values ​​were calculated.

[0225] <Measurement of elongation at break> The cured product for evaluation was subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.) to measure the elongation at break.

[0226] <Preparation of a sample for halo evaluation> (1) Surface treatment of inner layer circuit board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic R1515A) with an inner layer circuit formed on it were etched 1 μm deep with a microetching agent (MEC CZ8101) to roughen the copper surface.

[0227] (2) Laminating adhesive film with a support Using a batch-type vacuum pressure laminator (MVLP-500 manufactured by Meiki Co., Ltd.), each adhesive film was laminated onto both sides of the inner layer circuit board. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing for 30 seconds at 100°C and a pressure of 0.74 MPa.

[0228] (3) Curing of the resin composition layer The laminated adhesive film was cured at 130°C for 30 minutes, followed by 170°C for 30 minutes to cure the resin composition layer, thereby forming an insulating layer.

[0229] (4) Via hole formation Using a CO2 laser processing machine (Hitachi Via Mechanics, LC-2E21B / 1C), the insulating layer was drilled under the following conditions: mask diameter 1.60 mm, focus offset value 0.050, pulse width 25 μs, power 0.66 W, aperture 13, shot number 2, burst mode (10 kHz), forming multiple via holes so that the top diameter (diameter) of the via holes on the insulating layer surface was approximately 50 μm. The support was then peeled off.

[0230] (5) Roughening treatment The inner layer circuit board with the insulating layer formed was immersed in a swelling solution, Swelling Dip Securigant P (aqueous solution of glycol ethers and sodium hydroxide) containing diethylene glycol monobutyl ether (manufactured by Atotech Japan) at 60°C for 10 minutes, then in a roughening solution, Concentrate Compact P (aqueous solution of KMnO4: 60g / L, NaOH: 40g / L) (manufactured by Atotech Japan) at 80°C for 20 minutes, and finally in a neutralizing solution, Reduction Shoreusin Securigant P (aqueous solution of sulfuric acid) (manufactured by Atotech Japan) for 5 minutes at 40°C, and then dried for 30 minutes at 80°C. This substrate is referred to as the evaluation substrate.

[0231] <Measurement of via hole dimensions, halo distance, and halo ratio after roughening treatment> The evaluation substrate was subjected to cross-sectional observation using a FIB-SEM hybrid device ("SMI3050SE" manufactured by SII Nano Technology Co., Ltd.). Specifically, the insulating layer was scraped using a FIB (focused ion beam) so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole was revealed. This cross section was observed using an SEM. The bottom diameter and top diameter of the via hole were measured from the observed image.

[0232] Furthermore, in the image observed by SEM, a gap was observed that continued from the edge of the via bottom, where the insulating layer had peeled off from the copper foil layer of the inner layer substrate. From the observed image, the distance r1 from the center of the via bottom to the edge of the via bottom (corresponding to the inner radius of the gap) and the distance r2 from the center of the via bottom to the far end of the gap (corresponding to the outer radius of the gap) were measured, and the difference between these distances r1 and r2 (r2 - r1) was calculated as the halo distance from the edge of the via bottom at that measurement point.

[0233] The above measurement was performed on five randomly selected via holes. The average of the top diameters of the five measured via holes was used as the top diameter Lt of the sample after the roughening treatment. The average of the bottom diameters of the five measured via holes was used as the bottom diameter Lb of the sample after the roughening treatment. Furthermore, the average of the halo distances of the five measured via holes was used as the halo distance Wb from the edge of the via bottom of the sample.

[0234] From the measurement results, the taper ratio (the ratio of the top diameter Lt of the via hole after roughening treatment to the bottom diameter Lb, "Lb / Lt") and the halo ratio Hb (the ratio of the halo distance Wb from the edge of the via bottom after roughening treatment to the radius (Lb / 2) of the via bottom of the via hole after roughening treatment, "Wb / (Lb / 2)") were calculated and evaluated according to the following criteria. ○: Haloing ratio Hb is 35% or less. △: Haloing ratio Hb is greater than 35% and less than 50%. ×: Haloing ratio Hb is greater than 50%.

[0235] [Table 1] *In the table, the content (mass%) of component (C) represents the content when the nonvolatile components in the resin composition are taken as 100 mass%, the content (volume%) of component (C) represents the content when the nonvolatile components in the resin composition are taken as 100 volume%, and the content of component (D) represents the content when the resin components in the resin composition are taken as 100 mass%.

[0236] In Examples 1 to 6, it was confirmed that even when components (E) to (G) were not contained, the same results as in the above Examples were obtained, although to different degrees. [Explanation of symbols]

[0237] 100 insulating layer 100U The surface of the insulating layer opposite to the conductor layer 110 Beer Hall 120 Beer Bottom 120C Center of via bottom 130 Beer Top 140 Discolored area 150 Via bottom edge 160 Gap 170 End 180 Via top edge 190 outer edge 200 inner layer board 210 Conductor layer (first conductor layer) Lb Bottom diameter of via hole Lt Top diameter of via hole Wt Halo distance from the edge of the via top Wb Halo distance from the edge of the via bottom

Claims

1. (A) an epoxy resin, (B) an active ester curing agent, (C) an inorganic filler, and (D) a silane compound having a silicon atom as a ring-constituting atom, the content (mass%) of the (B) component when the total amount of nonvolatile components in the resin composition is taken as 100 mass%, is taken as b, and the content (mass%) of the (D) component when the total amount of nonvolatile components in the resin composition is taken as 100 mass%, is taken as d, and b / d is 1 or more and 50 or less; A resin composition, wherein the component (D) contains a compound represented by formula (D-1): 【Chemistry 1】 In the formula, R 1 and R 2 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, A represents a nitrogen atom, and n represents an integer of 1 to 4.

2. 2. The resin composition according to claim 1, wherein the component (C) comprises either a hollow inorganic filler (C-1) or a solid inorganic filler (C-2).

3. The resin composition according to claim 1, wherein the component (C) comprises a hollow inorganic filler (C-1).

4. The resin composition according to claim 1, wherein the component (C) has been surface-treated with the component (D).

5. The resin composition according to claim 1, wherein the content of the component (C) is 50% by mass or more, based on 100% by mass of nonvolatile components in the resin composition.

6. The resin composition according to claim 1, wherein the content of the component (D) is 0.1% by mass or more and 5% by mass or less, when the resin component in the resin composition is 100% by mass.

7. An adhesive film 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 6.

8. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 6.

9. A semiconductor device comprising the printed wiring board according to claim 8.

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