TW202502877A - Resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a resin composition and the like which can obtain a cured product that has low dielectric properties and is capable of suppressing a halo phenomenon. A resin composition containing (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-forming atom.

Description

Resin composition

The present invention relates to a resin composition and further to an adhesive film, a printed wiring board and a semiconductor device obtained by using the resin composition.

As a manufacturing technology for printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductive layers are alternately stacked is known.

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 Patent document 1: International Publication No. 2022/038893.

Technical problem to be solved by the invention In recent years, there has been an increasing demand for resin compositions that can form insulating layers with low relative dielectric constants and dielectric tangents. Relative dielectric constants and dielectric tangents are sometimes collectively referred to as dielectric properties.

If the dielectric properties of the insulating layer are to be reduced, materials that reduce the dielectric properties, such as active ester-based hardeners, may be considered. However, it is known that hardened resin compositions containing materials that reduce the dielectric properties will produce a haloing phenomenon that reduces the conductivity. Here, the haloing phenomenon refers to interlayer peeling between the insulating layer around the through hole and the inner substrate. Such a haloing phenomenon is usually caused by the deterioration of the resin around the through hole when the through hole is formed, and the deteriorated part is eroded during the roughening process. Furthermore, the aforementioned deteriorated part is usually observed as a discolored part.

The present invention has been made in view of the above-mentioned problems, and the problem of the present invention is to provide a resin composition that can obtain a cured product with low dielectric properties and suppressed halo 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 technical problems The inventors of the present invention have conducted intensive research on the above-mentioned problems and found that the above-mentioned problems can be solved by combining (A) epoxy resin, (B) active ester hardener, (C) inorganic filler, and (D) silane compound having silicon atoms as ring atoms, thereby completing the present invention.

That is, the present invention includes the following contents. [1] A resin composition comprising: (A) an epoxy resin, (B) an active ester-based hardener, (C) an inorganic filler, and (D) a silane compound having silicon atoms as ring-forming atoms. [2] The resin composition according to [1], wherein the component (C) comprises any one of (C-1) a hollow inorganic filler and (C-2) a solid inorganic filler. [3] The resin composition according to [1] or [2], wherein the component (C) comprises (C-1) a hollow inorganic filler. [4] The resin composition according to any one of [1] to [3], wherein the component (C) is surface-treated by 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, based on 100% by mass of the non-volatile components in the resin composition. [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, based on 100% by mass of the resin components in the resin composition. [7] An adhesive film comprising: a support, and a resin composition layer disposed on the support and comprising the resin composition according to any one of [1] to [6]. [8] A printed wiring board comprising an insulating layer formed by a cured product of a resin composition as described in any one of [1] to [6]. [9] A semiconductor device comprising the printed wiring board as described in [8].

Effect of the invention According to the present invention, a resin composition that can obtain a cured product having low dielectric properties and suppressing haloing can be provided, an adhesive film containing the resin composition, a printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device.

The present invention is described in detail below based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any changes within the scope of the patent application of the present invention and its equivalent scope.

[Resin composition] The resin composition of the present invention contains (A) epoxy resin, (B) active ester curing agent, (C) inorganic filler, and (D) silane compound having silicon atoms as ring-forming atoms. In the present invention, by combining the components (A), (B), (C) and (D), a hardened material having low dielectric properties and suppressed haloing can be obtained. In addition, a hardened material having excellent elongation at break can also be obtained.

The resin composition may further contain an arbitrary component in combination with the components (A) to (D). Examples of the arbitrary component include (E) a hardener (excluding the hardener belonging to the component (B)), (F) a hardening accelerator, (G) a thermoplastic resin, (H) other additives, and (I) a solvent. The following describes each component contained in the resin composition in detail.

<(A) Epoxy resin> The resin composition contains (A) epoxy resin as the (A) component. By making the resin composition contain (A) epoxy resin, a cured product showing good mechanical strength and insulation reliability can be obtained. (A) Epoxy resins may be used alone or in combination of two or more.

Examples of the epoxy resin (A) include bixylene 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-butylcatechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, and glycidyl ester type epoxy resins. , glycidyl cyclohexane type epoxy resin, alkyl diglycidyl ether type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trihydroxymethyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalimidine type epoxy resin, etc. Epoxy resins may be used alone or in combination of two or more.

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

Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin as component (A), only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. Among them, from the viewpoint of significantly obtaining the effect of the present invention, a combination of a liquid epoxy resin and a solid epoxy resin is preferred.

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

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, aliphatic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, Glycidylamine type epoxy resin, epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenol benzopyrrolidone type epoxy resin, alkyl diglycidyl ether type epoxy resin, more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, alkyl diglycidyl ether type epoxy resin, and further preferably bisphenol A type epoxy resin.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-based epoxy resins) manufactured by DIC Corporation, and "828US", "jER828EL", "825", and "EPIKOTE" manufactured by Mitsubishi Chemical Corporation. 828EL" (bisphenol A type epoxy resin), "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd., "CELLOXIDE "2021P" (aliphatic epoxy resin with an ester skeleton), "PB-3600" manufactured by Daicel Co., Ltd. (epoxy resin with a butadiene structure), "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical Materials Co., Ltd. (liquid 1,4-glycidyl cyclohexane type epoxy resin), "YED216D" (alkyl diglycidyl ether type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. These resins may be used alone or in combination of two or more.

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 further preferred.

As the solid epoxy resin, preferred are biphenylol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, and more preferred is biphenyl type epoxy resin.

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", and "HP6000" manufactured by DIC Corporation. 、"HP6000L" (naphthyl ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd. (biphenylphenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "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), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "WHR-991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These resins may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as component (A), the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. By making the mass ratio of the liquid epoxy resin to the solid epoxy resin within this range, the desired effect of the present invention can be significantly obtained.

The epoxy equivalent of component (A) is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., further preferably 80 g/eq. to 2000 g/eq., and further preferably 110 g/eq. to 1000 g/eq. Within this range, a cured product of the resin composition can be obtained with a sufficient crosslinking density. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of 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 a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, when the non-volatile components in the resin composition are set to 100 mass %, the content of component (A) is preferably 10 mass % or more, more preferably 20 mass % or more, and even more preferably 30 mass % or more. The upper limit is preferably 55 mass % or less, more preferably 50 mass % or less, and particularly preferably 45 mass % or less.

In the present invention, unless otherwise specified, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is set to 100 mass %, and the non-volatile component refers to all non-volatile components in the resin composition except the solvent.

From the viewpoint of obtaining a cured product having good mechanical strength and insulation reliability, when the resin component in the resin composition is 100 mass %, the content of the component (A) is preferably 30 mass % or more, more preferably 40 mass % or more, further preferably 50 mass % or more, preferably 70 mass % or less, more preferably 65 mass % or less, further preferably 60 mass % or less.

In the present invention, the resin component in the resin composition refers to the component other than the (C) inorganic filler in the non-volatile components of the resin composition.

<(B) Active ester curing agent> The resin composition contains (B) active ester curing agent as (B) component. The (B) active ester curing agent as the (B) component does not include substances belonging to the above-mentioned (A) component. The (B) active ester curing agent can usually form a bond by reacting with the (A) epoxy resin and cure the resin composition. By making the resin composition contain (A) component and (B) active ester curing agent in combination, a cured product with low dielectric properties can be obtained. The (B) component can be used alone or in combination of two or more.

As the active ester curing agent (B), it is generally preferred to use a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. The active ester curing agent is preferably a compound obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, as the component (B), there can be mentioned dicyclopentadiene type active ester hardeners, naphthalene type active ester hardeners containing a naphthalene structure, active ester hardeners containing acetylated products of phenol novolac resins, active ester hardeners containing benzoylated products of phenol novolac resins, active ester hardeners which are acetylated products of phenol novolac resins, active ester hardeners containing styryl and naphthalene structures, etc., and dicyclopentadiene type active ester hardeners are preferred. As the dicyclopentadiene type active ester hardeners, active ester hardeners containing a dicyclopentadiene type diphenol structure are preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

As commercially available products of the component (B), as active ester curing agents containing a dicyclopentadiene-type diphenol structure, there are "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); as naphthalene-type active ester curing agents containing a naphthalene structure, there are "HP-B-8151-62T", "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Corporation), "PC1300-02-65T" (manufactured by Air Products Corporation), and "HP-B-8151-62T" (manufactured by Air Products Corporation). As an active ester compound containing phosphorus, "EXB9401" (manufactured by DIC Corporation) can be cited; as an active ester curing agent containing an acetylated product of phenol novolac resin, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; as an active ester curing agent containing a benzoyl acylated product of phenol novolac resin, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) can be cited; as an active ester curing agent containing an acetylated product of phenol novolac resin, "DC808 ” (Mitsubishi Chemical Co., Ltd.); as active ester hardeners which are benzoyl compounds of phenol novolac resins, there are “YLH1026” (Mitsubishi Chemical Co., Ltd.), “YLH1030” (Mitsubishi Chemical Co., Ltd.), “YLH1048” (Mitsubishi Chemical Co., Ltd.), and “EXB-8500-65T” (DIC Co., Ltd.); as active ester hardeners containing styrene and naphthalene structures, there are “PC1300-02-65MA” (Air Water Co., Ltd.), etc.

From the viewpoint of obtaining a cured product having excellent peel strength while reducing the dielectric tangent, 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-based curing agent containing 1 equivalent of active ester groups.

The amount ratio of the epoxy resin (A) to the active ester curing agent (B) is preferably 0.01 or more, more preferably 0.3 or more, further preferably 0.5 or more, and preferably 5 or less, more preferably 4 or less, further preferably 3 or less in terms of the ratio of [the total number of active groups of the active ester curing agent]/[the total number of epoxy groups of the epoxy resin]. Here, the "number of epoxy groups of the epoxy resin" refers to the value obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, "the number of active groups of the active ester hardener" refers to the total value of all values obtained by dividing the mass of the non-volatile components of the active ester hardener present in the resin composition by the active ester group equivalent. By making the amount ratio of the epoxy resin to the active ester hardener within the above range, the effect of the present invention can be significantly obtained.

From the viewpoint of obtaining a cured product having excellent dielectric properties, when the non-volatile components in the resin composition are set to 100 mass %, the content of component (B) is preferably 1 mass % or more, more preferably 3 mass % or more, and further preferably 5 mass % or more. In addition, the upper limit is preferably 25 mass % or less, more preferably 20 mass % or less, and further preferably 15 mass % or less.

From the viewpoint of obtaining a cured product having excellent dielectric properties, when the resin component in the resin composition is 100 mass %, the content of the component (B) is preferably 10 mass % or more, more preferably 15 mass % or more, further preferably 20 mass % or more, preferably 40 mass % or less, more preferably 35 mass % or less, further preferably 30 mass % or less.

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

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

(C) Inorganic fillers can be classified into (C-1) hollow inorganic fillers having pores inside and (C-2) solid inorganic fillers having no pores inside. (C) Inorganic fillers preferably include either (C-1) hollow inorganic fillers or (C-2) solid inorganic fillers. From the perspective of obtaining a cured product with low dielectric properties, (C-1) hollow inorganic fillers are more preferably included.

The (C-1) hollow inorganic filler may be a single hollow particle having only one hole inside the particle, may be a multi-hollow particle having two or more holes inside the particle, or may be a combination of a single hollow particle and a multi-hollow particle.

The (C-1) hollow inorganic filler material has pores and therefore generally has a porosity greater than 0 volume %. The porosity of the (C-1) hollow inorganic filler material is preferably 10 volume % or more, more preferably 15 volume % or more, and particularly preferably 20 volume % or more. In addition, from the viewpoint of the mechanical strength of the cured product of the resin composition, the porosity of the (C-1) hollow inorganic filler material is preferably 80 volume % or less, more preferably 75 volume % or less, and particularly preferably 70 volume % or less.

The porosity P (volume %) of the inorganic filler is defined as the volume ratio of "the total volume of one or more pores existing inside the particle" to "the volume of the entire particle based on the outer surface of the particle" (total volume of pores/volume of the particle), and is calculated, for example, by using the measured value _DM (g/ ^cm3 ) of the actual density of the inorganic filler and the theoretical value _DT (g/ ^cm3 ) of the material density of the material forming the inorganic filler by the following formula (1): [Mathematical formula 1] .

(C-1) The hollow inorganic filling material generally has a hole formed in the particle and a shell formed by an inorganic material surrounding the hole. Usually, the hole is separated from the outside of the particle by the shell. In this case, the hole is preferably not connected to the outside of the particle. Therefore, the shell is preferably a shell without pores that connect the hole and the outside of the particle. The absence of pores in the shell can be confirmed by observation using a transmission electron microscope (TEM).

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, particularly preferably 0.3 μm or more, preferably 5 μm or less, more preferably 4 μm or less, particularly preferably 3 μm or less.

The average particle size of particles can be measured by laser diffraction scattering based on Mie scattering theory. Specifically, a particle size distribution of particles is prepared based on volume using a laser diffraction scattering particle size distribution measuring device, and the median diameter is used as the average particle size for measurement. The measurement sample of the inorganic filler can be a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. For the sample to be measured, a laser diffraction particle size distribution measuring device can be used. The particle size distribution of the inorganic filler can be measured by a flow cell method using blue and red light source wavelengths. The average particle size can be calculated based on the obtained particle size distribution as the median diameter. Examples of laser diffraction particle size distribution measuring devices include "LA-960" manufactured by Horiba, Ltd.

From the viewpoint of significantly obtaining the effects of the present invention, the BET specific surface area of the hollow inorganic filler (C-1) is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, particularly preferably 5 m ² /g or more, preferably 100 m ² /g or less, more preferably 50 m ² /g or less, particularly preferably 30 m ² /g or less. The BET specific surface area of the particles can be measured by adsorbing nitrogen on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and calculating the specific surface area by the BET multipoint method.

(C-1) A commercially available hollow inorganic filler can be used. Examples of commercially available hollow inorganic fillers (C-1) include "MG-005" manufactured by Pacific Cement Co., Ltd. and "LHP-208" manufactured by Ube Exsymo Co., Ltd.

In addition, the hollow inorganic filler (C-1) can be produced by, for example, the method described in Japanese Patent Gazette No. 5940188 or a method based thereon. As a specific example, hollow silica particles as an example of the hollow inorganic filler (C-1) can be produced by a method comprising the following steps: preparing an aqueous solution containing a substance capable of forming pores and an alkaline compound; mixing and stirring the aqueous solution with alkoxysilane to precipitate silica particles; removing the substance capable of forming pores from the silica particles to obtain a hollow silica precursor; and calcining the hollow silica precursor.

In addition, the hollow inorganic filler (C-1) can also be produced by, for example, the method described in Japanese Patent No. 5864299 or a method based thereon. To give a specific example, hollow silica particles as an example of a hollow inorganic filler (C-1) can be produced by a method comprising the following steps: (a) step of preparing an aqueous solution containing a substance capable of forming a hollow portion and an alkaline compound; (b) step of adding alkoxysilane to the aqueous solution and stirring the solution at 0°C to 100°C to precipitate silica particles; (c) step of removing the substance capable of forming a hollow portion from the silica particles obtained in step (b) to obtain a hollow silica precursor; and (c) step of calcining the hollow silica precursor obtained in step (c) at a temperature exceeding 900°C to obtain hollow silica.

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 later. Examples of the surface treatment agent other than the component (D) include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, butylsilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organic silazane compounds, and titanium ester-based coupling agents. The surface treatment agent may be used alone or in any combination of two or more.

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

From the viewpoint of improving dispersibility, the degree of surface treatment by a surface treatment agent other than component (D) is preferably within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface treated by 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).

The degree of surface treatment by 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 preferably 0.02 mg/ ^m2 or more, more preferably 0.1 mg/ ^m2 or more, and further preferably 0.2 mg/ ^m2 or more. On the other hand, from the viewpoint of preventing the increase in the melt viscosity of the resin composition, it is preferably 1.0 mg/m2 or ^less , more preferably 0.8 mg/ ^m2 or less, and further preferably 0.5 mg/ ^m2 or less.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added as a solvent 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 components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

From the viewpoint of significantly achieving the effect of the present invention, when the non-volatile components in the resin composition are set to 100 mass %, the content (mass %) of the hollow inorganic filler (C-1) is preferably 0 mass % or more, more preferably 15 mass % or more, further preferably 20 mass % or more, preferably 70 mass % or less, more preferably 65 mass % or less, and further preferably 60 mass % or less.

From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are set to 100 volume %, the content (volume %) of the hollow inorganic filler (C-1) is preferably 1 volume % or more, more preferably 3 volume % or more, further preferably 5 volume % or more, preferably 70 volume % or less, more preferably 60 volume % or less, further preferably 50 volume % or less.

From the viewpoint of significantly obtaining the effects of the present invention, the specific gravity of the component (C-1) is preferably 3.50 g/cm ³ or less, more preferably 3.00 g/cm ³ or less, and further preferably 2.50 g/cm ³ or less, and is preferably 0.05 g/cm ³ or more, more preferably 0.5 g/cm ³ or more, and further preferably 1.0 g/cm ³ or more. The specific gravity can be measured by the method described in the examples described later.

(C-2) Solid inorganic filler is an inorganic filler having a porosity of 0 volume %. (C-2) Solid inorganic filler can use commercial products. Commercial products of (C-2) solid inorganic filler include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd., "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd., "UFP-30", "DAW-03", "FB-105FD" manufactured by DENKA Co., Ltd., "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N" manufactured by Tokuyama Co., Ltd., "CellSpheres" and "MGH-005" manufactured by Pacific Cement Co., Ltd., etc.

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, further preferably 0.3 μm or more, and preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less. The average particle size of the component (C-2) can be measured by the same method as the average particle size of the hollow inorganic filler (C-1).

The BET specific surface area of the solid inorganic filler (C-2) is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, and further preferably 1 m ² /g or more, and is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, and further preferably 40 m ² /g or less. The BET specific surface area of the component (C-2) can be measured by the same method as the BET specific surface area of the component (C-1).

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

When the non-volatile components in the resin composition are set to 100 mass %, the content (mass %) of the solid inorganic filler (C-2) may be 0 mass % or greater than 0 mass %, preferably 10 mass % or greater, more preferably 20 mass % or greater, particularly preferably 30 mass % or greater, 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 set to 100 volume %, the content (volume %) of the (C-2) solid inorganic filler material can be 0 volume % or greater than 0 volume %, preferably 5 volume % or more, more preferably 10 volume % or more, further preferably 20 volume % or more, preferably 50 volume % or less, more preferably 40 volume % or less, further preferably 30 volume % or less.

The proportion of pores contained in the (C) inorganic filler material as a whole, including both (C-1) hollow inorganic filler material and (C-2) solid inorganic filler material, can be obtained as the porosity (volume %) of the (C) inorganic filler material. The porosity (volume %) of the (C) inorganic filler material is a representative value that expresses the proportion of pores in the volume of the (C) inorganic filler material on a volume basis, and is expressed as "total volume of pores/total volume of the (C) inorganic filler material". The specific range of the porosity of the (C) inorganic filler material is preferably 10 volume % or more, more preferably 15 volume % or more, further preferably 20 volume % or more, preferably 80 volume % or less, more preferably 70 volume % or less, and further preferably 60 volume % or less.

From the viewpoint of significantly achieving the effect of the present invention, the average particle size of the (C) inorganic filler material as a whole, including both the (C-1) hollow inorganic filler material and the (C-2) solid inorganic filler material, is preferably greater than 0.01 μm, more preferably greater than 0.1 μm, further preferably greater than 0.3 μm, preferably less than 5 μm, more preferably less than 4 μm, further preferably less than 3 μm.

From the viewpoint of remarkably obtaining the effects of the present invention, the BET specific surface area of the (C) inorganic filler material as a whole including both the (C-1) hollow inorganic filler material and the (C-2) solid inorganic filler material is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, further preferably 5 m ² /g or more, and preferably 100 m ² /g or less, more preferably 50 m ² /g or less, further preferably 30 m ² /g or less.

When the (C) component includes both (C-1) hollow inorganic filler and (C-2) solid inorganic filler, from the viewpoint of significantly obtaining the effect of the present invention, when the content of all inorganic fillers is set to 100 volume %, the content (volume %) of the (C-1) hollow inorganic filler in all inorganic fillers is preferably 0 volume %, more preferably 0 volume % or more, further preferably 30 volume % or more, preferably 100 volume %, more preferably 100 volume % or less, and further preferably 75 volume % or less.

From the viewpoint of significantly achieving the effect of the present invention, when the non-volatile components in the resin composition are set to 100 mass %, the content (mass %) of the (C) inorganic filler is preferably 50 mass % or more, more preferably 55 mass % or more, further preferably 60 mass % or more, preferably 85 mass % or less, more preferably 80 mass % or less, and particularly preferably 75 mass % or less.

From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are set to 100 volume %, the content (volume %) of the (C) inorganic filler is preferably 20 volume % or more, more preferably 30 volume % or more, further preferably 40 volume % or more, preferably 80 volume % or less, more preferably 75 volume % or less, and particularly preferably 70 volume % or less.

<(D) Silane compound having silicon atoms as ring-forming atoms> The resin composition contains (D) a silane compound having silicon atoms as ring-forming atoms as the (D) component. The (D) silane compound having silicon atoms as ring-forming atoms as the (D) component does not include substances belonging to the above-mentioned (A) to (C) components. By making the resin composition contain the (D) component, the halo phenomenon can be suppressed. The (D) component may be used alone or in combination of two or more.

As component (D), a compound having a cyclic structure and containing silicon atoms as ring-forming atoms constituting the cyclic structure can be used. The cyclic structure may be a monocyclic, polycyclic, or condensed ring, and is preferably a monocyclic from the viewpoint of significantly obtaining the effect of the present invention. In addition, the cyclic structure may be a saturated cyclic structure or an unsaturated cyclic structure, and is preferably a saturated cyclic structure from the viewpoint of significantly obtaining the effect of the present invention. The cyclic structure is preferably a three- to ten-membered ring, more preferably a four- to six-membered ring, further preferably a five- or six-membered ring, and particularly preferably a five-membered ring.

The cyclic structure has carbon atoms as ring-forming atoms in addition to silicon atoms. In addition, the ring-forming atoms may have miscellaneous atoms such as nitrogen atoms, oxygen atoms, and sulfur atoms. From the viewpoint of significantly obtaining the effect of the present invention, the component (D) preferably has silicon atoms, carbon atoms, and nitrogen atoms as ring-forming atoms, and the component (D) is preferably a cyclic silazane compound.

The number of silicon atoms as ring-forming atoms is preferably 1 to 5, more preferably 1 or 2, and further preferably 1. When a heteroatom is included as a ring-forming atom, the number of the heteroatom is preferably 1 to 3, more preferably 1 or 2, and further preferably 1.

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

The silicon atom as a ring-forming atom in the component (D) is preferably bonded to an alkoxy group. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, and hexyloxy. Among them, the alkoxy group is preferably a methoxy group from the viewpoint of significantly obtaining the effect of the present invention.

As the component (D), a compound represented by the formula (D-1) is preferred, [Chemical Formula 1] In the formula, ^R1 and ^R2 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, A represents a heteroatom, and n represents an integer of 1 to 4.

^R1 and ^R2 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The monovalent hydrocarbon group having 1 to 20 carbon atoms is preferably a monovalent hydrocarbon group having 1 to 15 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and still more preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms. The carbon number does not include the carbon number of the substituent. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group. The alkyl group may be any of a linear, branched, and cyclic group, and the preferred carbon number is as described above. As the alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, iso-decyl, etc. can be cited. The alkenyl group can be any of a straight chain, a branched chain, and a ring, and the preferred number of carbon atoms is as described above. As the alkenyl group, for example, vinyl, allyl, butenyl, methallyl, etc. can be cited. As the aryl group, for example, phenyl, tolyl, xylyl, etc. can be cited. Preferably, it is an aryl group. From the viewpoint of remarkably obtaining the effect of the present invention, ^R1 is preferably an aryl group, and more preferably a phenyl group. Furthermore, from the viewpoint of remarkably obtaining the effect of the present invention, ^R2 is preferably an alkyl group, and more preferably a methyl group.

The monovalent alkyl group represented by ^R1 and ^R2 may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, _-OC1-6 alkyl, -N( _C1-10 alkyl) ₂ , _C1-20 alkyl, _C2-30 alkenyl, _C2-30 alkynyl, _C6-10 aryl, _-NH2 , -CN, -C(O) _OC1-10 alkyl, -COOH, -C(O)H, _-NO2 , etc. Here, the term " _Cpq " means that the number of carbon atoms of the organic group described immediately after the term is p to q, and p and q are positive integers satisfying p<q. For example, the expression " _C1-10 alkyl" means 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 may also include a spiro ring or a condensed ring.

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

n represents an integer of 1 to 4, preferably 2 or 3, more preferably 3.

Examples of the 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-Silylation cyclopentane, 2,2-dimethoxy-1-butyl-1-aza-2-silylation cyclopentane, 2-methoxy-2-methyl-1-butyl-1-aza-2-silylation cyclopentane, 2,2-dimethyl-1-butyl-1-aza-2-silylation cyclopentane, 2,2-diethoxy-1-butyl-1-aza-2-silylation cyclopentane, 2-ethoxy-2-methyl-1-butyl-1-aza-2-silylation cyclopentane Heterocyclopentane, 2,2-dimethoxy-1-cyclohexyl-1-aza-2-silycyclopentane, 2-methoxy-2-methyl-1-cyclohexyl-1-aza-2-silycyclopentane, 2,2-dimethyl-1-cyclohexyl-1-aza-2-silycyclopentane, 2,2-diethoxy-1-cyclohexyl-1-aza-2-silycyclopentane, 2-ethoxy-2-methyl-1-cyclohexyl-1-aza-2-silycyclopentane Silicylidene pentane, 2,2-dimethoxy-1-phenyl-1-aza-2-sililidene pentane, 2-methoxy-2-methyl-1-phenyl-1-aza-2-sililidene pentane, 2,2-dimethyl-1-phenyl-1-aza-2-sililidene pentane, 2,2-diethoxy-1-phenyl-1-aza-2-sililidene pentane, 2-ethoxy-2-methyl-1-phenyl-1-aza-2-sililidene pentane 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 Cyclopentane, 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 2,2-Dimethoxy-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 Pentane, 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-(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 Hetero-2-silycyclopentane, 2-methoxy-2-methyl-1-methyldimethoxysilylmethyl-1-aza-2-silycyclopentane, 2,2-dimethyl-1-methyldimethoxysilylmethylmethyl-1-aza-2-silycyclopentane, 2,2-diethoxy-1-methyldimethoxysilylmethylmethyl-1-aza-2-silycyclopentane, 2-ethoxy-2-methyl-1-methyldimethoxysilylmethyl 2-Methoxy-2-methyl-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 Pentane, 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 Azo-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-dimethylmethoxysilane 2-Methoxy-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-dimethylmethoxy 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 Pentane, 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 Hetero-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-triethoxymethyl)-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 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-methyldiethoxysilylmethyl Oxysilylmethylmethyl-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-methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, -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-Methoxy-2-methyl-1-(4-methyldiethoxysilylbutyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-1-(4-methyldiethoxysilylpropyl)-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-Dimethoxy-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-dimethoxysilylmethyl 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-dimethyl-1-dimethylethoxysilylmethyl-1-aza-2-silacyclopentane Oxy-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-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-(2-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-(2-(4-dimethylethoxysilylbutyl)-1-aza-2-silacyclopentane, 2-(2-(4-dimethylethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-(2-(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 Hetero-2-silycyclopentane, 2-methoxy-2-methyl-1-methyl-1-aza-2-silycyclopentane, 2,2-dimethyl-1-methyl-1-aza-2-silycyclopentane, 2,2-diethoxy-1-methyl-1-aza-2-silycyclopentane, 2-ethoxy-2-methyl-1-methyl-1-aza-2-silycyclopentane, 2,2-dimethoxy-1-butyl-1-aza-2- Silicylidene pentane, 2-methoxy-2-methyl-1-butyl-1-aza-2-sililidene pentane, 2,2-dimethyl-1-butyl-1-aza-2-sililidene pentane, 2,2-diethoxy-1-butyl-1-aza-2-sililidene pentane, 2-ethoxy-2-methyl-1-butyl-1-aza-2-sililidene pentane, 2,2-dimethoxy-1-cyclohexyl-1-aza-2-sililidene pentane Pentane, 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 Pentane, 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-dimethoxy-1-(2-methoxycarbonyl-2-methyl)ethyl-1-aza-2-silacyclopentane, Ethoxy-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-Silica cyclopentane, 2,2-dimethyl-1-trimethoxysilylmethyl-1-aza-2-silica cyclopentane, 2,2-diethoxy-1-trimethoxysilylmethyl-1-aza-2-silica cyclopentane, 2-ethoxy-2-methyl-1-trimethoxysilylmethyl-1-aza-2-silica cyclopentane, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1 -2-Aza-silycyclopentane, 2-methoxy-2-methyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silycyclopentane, 2,2-dimethyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silycyclopentane, 2,2-diethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silycyclopentane, 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 Cyclopentane, 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-methyldimethoxymethyl Silylmethyl-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-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-dimethylmethoxysilyl Alkylmethyl-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 Cyclopentane, 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-dimethyl-1-methyldiethoxysilylmethylmethyl-1-aza-2-silacyclopentane, 1-Aza-2-silacyclopentane, 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 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 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-(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 Cyclopentane, 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 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.

As the component (D), a commercial product may be used. Examples of the commercial product include "X-88-398" (2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KR-470", "X-40-2678", and "X-40-2728" manufactured by Shin-Etsu Silicon Co., Ltd.

The form of the component (D) contained in the resin composition of the present invention is not particularly limited. It is preferably contained in the resin composition in any of the following forms (i) to (iii), more preferably in any of the forms (ii) and (iii), and further preferably in the form (iii). (i) The component (D) is contained in the resin composition alone; (ii) The component (D) is contained as a surface treatment agent for the inorganic filler (C); (iii) The component (D) is contained in the resin composition alone while being contained as a surface treatment agent for the inorganic filler (C).

"(D) component is contained as a surface treatment agent for (C) inorganic filler" means that (C) inorganic filler is surface-treated with (D) component. In this case, (D) component is usually present on the surface of (C) inorganic filler. In addition, "(D) component is contained alone in the resin composition" means that (D) component is not contained as a surface treatment agent for (C) inorganic filler. Furthermore, when (D) component is not contained as a surface treatment agent for (C) inorganic filler, (D) component is free in the resin composition. In the present invention, the surface of (C) inorganic filler can be uniformly treated with (D) component, so the halo phenomenon can be effectively suppressed.

When the component (D) is contained as the surface treatment agent of the component (C), from the viewpoint of suppressing the halo phenomenon, when the non-volatile component in the resin composition is set to 100 mass%, the content of the component (D) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, further preferably 0.5 mass% or more, preferably 3 mass% or less, more preferably 2.5 mass% or less, and further preferably 2 mass% or less.

When the component (D) is contained as the surface treatment agent of the component (C), from the viewpoint of suppressing the halo phenomenon, when the resin component in the resin composition is 100 mass%, the content of the component (D) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 0.8 mass% or more, 1 mass% or more, 1.5 mass% or more, preferably 5 mass% or less, more preferably 4 mass% or less, and further preferably 3 mass% or less.

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

When the content (mass %) of the component (B) when the non-volatile components in the resin composition are 100 mass % is b, and the content (mass %) of the component (D) when the non-volatile components in the resin composition are 100 mass % is d, b/d is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, preferably 50 or less, more preferably 40 or less, further preferably 30 or less, 20 or less, 15 or less, or 10 or less. By adjusting the contents of the components (B) and (D) under the condition that b/d is within this range, a cured product having low dielectric properties can be obtained, and the halo phenomenon can be suppressed.

<(E) Hardener> In addition to the above-mentioned components, the resin composition may further contain (E) hardener as an arbitrary component. The (E) hardener as the (E) component does not include substances belonging to the above-mentioned (A) to (D) components. As the (E) hardener, a compound having a function of reacting with the (A) component to harden the resin composition can be used, for example, a phenol hardener, a naphthol hardener, a carbodiimide hardener, a benzoxazine hardener, a cyanate hardener, etc. can be cited. Among them, from the viewpoint of significantly obtaining the effect of the present invention, the (E) hardener preferably contains a phenol hardener. The (E) hardener may be used alone or in combination of two or more.

As the phenolic hardener and the naphthol hardener, a phenolic hardener having a phenolic structure or a naphthol hardener having a phenolic structure is preferred from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesion with the conductive layer, a nitrogen-containing phenolic hardener is preferred, and a triazine skeleton-containing phenolic hardener is more preferred.

Specific examples of the phenol-based hardener and the naphthol-based hardener include “MEH-7700”, “MEH-7810”, and “MEH-7851” manufactured by Meiwa Chemicals Co., Ltd., “NHN”, “CBN”, and “GPH” manufactured by Nippon Kayaku Co., Ltd., “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN495V”, “SN375”, and “SN395” manufactured by Nippon Steel & Sumitomo Chemicals Co., Ltd., and “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA3018-50P”, “EXB-9500”, and “KA-1163” manufactured by DIC Corporation.

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

As specific examples of the carbodiimide-based curing agent, commercially available carbodiimide-based 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 Co., Ltd., and Stabaxol P (carbodiimide group equivalent: 302 g/eq.) manufactured by LANXESS.

Specific examples of benzoxazine-based hardeners include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industries, Ltd.

Examples of the cyanate curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(2,6-dimethylphenyl cyanate ... Difunctional cyanate resins such as (4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac resins and cresol novolac resins; prepolymers obtained by triazinizing a part of these cyanate resins; and the like. Specific examples of cyanate-based curing agents include "PT30" and "PT60" (phenol novolac type multifunctional cyanate resins), "ULL-950S" (multifunctional cyanate resin), "BA230" and "BA230S75" (prepolymers in which a part or all of bisphenol A dicyanate is triazine-treated to form a trimer) manufactured by Arxada.

The amount ratio of component (A) to 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, in terms of the ratio of [the total number of epoxy groups in component (A)]:[the total number of active groups in component (E)]. Here, the "total number of epoxy groups in the epoxy resin" refers to the value obtained by adding up all the values obtained by dividing the mass of the non-volatile components of component (A) present in the resin composition by the epoxy equivalent. In addition, the "total number of active groups in component (E)" refers to the value obtained by adding up all the values obtained by dividing the mass of the non-volatile components of component (E) present in the resin composition by the active group equivalent. When the amount ratio of the component (E) to the component (A) is within the above range, the effect of the present invention can be significantly achieved.

The ratio of the amount of component (A) to the amount of component (B) and component (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, in terms of [the total number of epoxy groups in component (A)]:[the total number of active groups in component (B) and component (E)]. Here, "the total number of active groups in component (B) and component (E)" refers to the value obtained by summing up all values obtained by dividing the mass of the non-volatile components of component (B) and component (E) present in the resin composition by the active group equivalent. By making the ratio of the amount of component (A) to the amount of component (B) and component (E) within this range, the effect of the present invention can be significantly obtained.

From the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile components in the resin composition are set to 100 mass%, the content of the component (E) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and further preferably 0.5 mass% or more. The upper limit is preferably 8 mass% or less, more preferably 5 mass% or less, and further preferably 3 mass% or less.

From the viewpoint of remarkably obtaining the desired effect of the present invention, when the resin component in the resin composition is 100 mass %, the content of the component (E) is preferably 1 mass % or more, more preferably 3 mass % or more, further preferably 5 mass % or more, preferably 20 mass % or less, more preferably 15 mass % or less, further preferably 10 mass % or less.

<(F) Hardening accelerator> In addition to the above-mentioned components, the resin composition may further contain a hardening accelerator as a component (F) as an arbitrary component. The (F) hardening accelerator as the component (F) does not include substances belonging to the above-mentioned components (A) to (E). By including the (F) component, the hardening of the (A) component can be further accelerated. The (F) component may be used alone or in combination of two or more.

As the component (F), for example, phosphorus-based hardening accelerators, urea-based hardening accelerators, guanidine-based hardening accelerators, imidazole-based hardening accelerators, metal-based hardening accelerators, amine-based hardening accelerators, etc. Among them, hardening accelerators selected from amine-based hardening accelerators and metal-based hardening accelerators are preferred, and amine-based hardening accelerators are particularly preferred.

Phosphorus-based hardening accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-toluene; Aromatic phosphonium salts such as triphenylphosphonium tetra-p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenyl borate, tris(3-methylphenyl)ethylphosphonium tetraphenyl borate, tris(2-methoxyphenyl)ethylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-t-butylphosphine, trioctylphosphine, di-t-butylphosphine aliphatic phosphines such as (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, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6- Aromatic phosphines such as tri(3,5-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(2-methoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(4-ethoxyphenyl)phosphine, tri(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 are also included.

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, 3-(3,4-dimethylphenyl)-1,1 -dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] and the like.

Examples of the guanidine-based hardening accelerator 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

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

As the imidazole-based hardening accelerator, a commercially available product can be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW", "C11Z-A" manufactured by Shikoku Chemical Industries, Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc.

Examples of the metal hardening accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex 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 the organic metal salt include zinc octylate, tin octylate, zinc cycloalkanoate, cobalt cycloalkanoate, tin stearate, zinc stearate, and the like.

Examples of the amine-based 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.

As the amine-based hardening accelerator, a commercially available product can be used, and for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd. can be cited.

From the viewpoint of remarkably obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is 100 mass %, the content of the component (F) is preferably 0.01 mass % or more, more preferably 0.03 mass % or more, further preferably 0.05 mass % or more, preferably 1 mass % or less, more preferably 0.8 mass % or less, further preferably 0.5 mass % or less.

From the viewpoint of remarkably obtaining the desired effect of the present invention, when the resin component in the resin composition is 100 mass %, the content of the component (F) is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, further preferably 0.1 mass % or more, preferably 1.5 mass % or less, more preferably 1 mass % or less, further preferably 0.5 mass % or less.

<(G) Thermoplastic resin> In addition to the above-mentioned components, the resin composition may further contain (G) thermoplastic resin as an arbitrary component. The (G) thermoplastic resin as the (G) component does not include substances belonging to the above-mentioned (A) to (F) components.

Examples of the thermoplastic resin (G) include polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamide imide resins, polyether imide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. In one embodiment, the thermoplastic resin (G) preferably includes a thermoplastic resin selected from the group consisting of polyimide resins and phenoxy resins, and more preferably includes a phenoxy resin. The thermoplastic resin may be used alone or in combination of two or more.

Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., and "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Chemical Co., Ltd.

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

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

Examples of the polyvinyl acetal resin include polyvinyl formaldehyde resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include 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.

Examples of the polyolefin resin include ethylene copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-methyl acrylate copolymers; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

Examples of the polybutadiene resin include resins containing a hydrogenated polybutadiene skeleton, polybutadiene resins containing a hydroxyl group, polybutadiene resins containing a phenolic hydroxyl group, polybutadiene resins containing a carboxyl group, polybutadiene resins containing an acid anhydride group, polybutadiene resins containing an epoxy group, polybutadiene resins containing an isocyanate group, polybutadiene resins containing a urethane group, and polyphenylene ether-polybutadiene resins.

Specific examples of polyamide imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide imide resins include modified polyamide imides such as "KS9100" and "KS9300" (polyamide imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

As a specific example of the polyether sulfide resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. can be cited.

As specific examples of the polyol resin, polyol "P1700", "P3500" and the like manufactured by Solvay Advanced Polymers Co., Ltd. can be cited.

Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC, and the like. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE, and the like.

Examples of the polycarbonate resin include hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, anhydride-containing carbonate resins, isocyanate-containing carbonate resins, and urethane-containing carbonate resins. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Co., Ltd., and "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd. Specific examples of the polyetheretherketone resin include "SUMIPLOY K" manufactured by Sumitomo Chemical Co., Ltd.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

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

From the viewpoint of remarkably obtaining the desired effect of the present invention, when the non-volatile components in the resin composition are set to 100 mass %, the content of the (G) thermoplastic resin is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, further preferably 1 mass % or more, preferably 5 mass % or less, more preferably 3 mass % or less, and further preferably 2 mass % or less.

From the viewpoint of remarkably obtaining the desired effect of the present invention, when the resin component in the resin composition is 100 mass %, the content of the thermoplastic resin (G) is preferably 1 mass % or more, more preferably 1.5 mass % or more, further preferably 2 mass % or more, preferably 10 mass % or less, more preferably 8 mass % or less, further preferably 5 mass % or less.

＜(H) Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. Examples of (H) other additives include free radical polymerizable compounds, elastomers, polymerization initiators, organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black, polymerization inhibitors such as hydroquinone, o-catechin, gallphenol, and phenothiazine, polysilicone levelers, and acrylic polymers. Leveling agents such as leveling agents, organic movers, montmorillonite and other viscosity increasing agents, silicone defoamers, acrylic defoamers, fluorine defoamers, vinyl resin defoamers and other defoaming agents, benzotriazole UV absorbers and other UV absorbers, urea silane and other adhesion enhancers, triazole adhesion enhancers, tetrazole adhesion enhancers, triazine adhesion enhancers and other adhesion enhancers, hindered phenol antioxidants Antioxidants such as stilbene derivatives, fluorescent whitening agents such as fluorine surfactants, polysilicone surfactants, phosphorus flame retardants (such as phosphate compounds, diphosphine nitrogen compounds, hypophosphorous acid compounds, red phosphorus), nitrogen flame retardants (such as melamine sulfate), halogen flame retardants, inorganic flame retardants (such as antimony trioxide), etc., phosphate dispersants, polyoxyalkylene dispersants , acetylene dispersants, silicone dispersants, anionic dispersants, cationic dispersants and other dispersants, borate stabilizers, titanium stabilizers, aluminum stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic anhydride stabilizers and other stabilizers, tertiary amine photopolymerization initiator, pyrazoline, anthracene, coumarin, xanthone, thioxanone and other photosensitizers. (H) Other additives may be used alone or in combination of two or more.

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

In order to significantly obtain the effect of the present invention, the resin composition preferably contains 0.5 mass % or more and 6 mass % or less of the (I) solvent relative to 100 mass % of all components of the resin composition. Specifically, the content of the (I) solvent relative to 100 mass % of all components of the resin composition is preferably 5 mass % or less, more preferably 4 mass % or less, preferably 0.5 mass % or more, more preferably 0.8 mass % or more, and even more preferably 1 mass % or more.

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a solvent is added to the ingredients as necessary, and the mixture is mixed and dispersed using a rotary mixer or the like.

<Physical properties and uses of resin composition> By hardening the resin composition of the present invention, an insulating layer formed of the hardened resin composition can be obtained. When a through hole is formed in the insulating layer and a roughening treatment is performed, the halo phenomenon can be suppressed. The above-mentioned effect is described below with reference to the attached figure.

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

As shown in FIG1 , the insulating layer 100 according to the first embodiment of the present invention is a layer obtained by hardening a resin composition layer formed on an inner substrate 200 including a conductive layer 210, and is formed of a hardened product of the resin composition layer. In addition, the insulating layer 100 is formed with a through hole 110. The through hole 110 is usually formed in the following shape, that is, a right cone whose diameter increases as it approaches a surface 100U of the insulating layer 100 on the opposite side of the conductive layer 210 and decreases as it approaches the conductive layer 210, and is preferably formed in a columnar shape having a certain diameter in the thickness direction of the insulating layer 100. The through hole 110 is usually formed by irradiating a surface 100U of the insulating layer 100 on the opposite side to the conductive layer 210 with laser light to remove a portion of the insulating layer 100 .

The bottom of the through hole 110 on the conductive layer 210 side is appropriately referred to as the "through hole bottom" and is indicated by the symbol 120. Therefore, the diameter of the through hole bottom 120 is called the bottom diameter Lb. In addition, the opening of the through hole 110 formed on the side opposite to the conductive layer 210 is appropriately referred to as the "through hole top" and is indicated by the symbol 130. Therefore, the diameter of the through hole top 130 is called the top diameter Lt. Usually, the through hole bottom 120 and the through hole top 130 are formed to have a circular planar shape observed from the thickness direction of the insulating layer 100, but may also be an elliptical shape. When the planar shape of the through hole bottom 120 and the through hole top 130 is an ellipse, the bottom diameter Lb and the top diameter Lt respectively represent the long diameter of the aforementioned ellipse.

At this time, the closer the taper ratio Lb/Lt (%) obtained by dividing the bottom diameter Lb by the top diameter Lt is to 100%, the better the shape of the through hole 110. If the resin composition layer of the present invention is used, the shape of the through hole 110 can be easily controlled, so the through hole 110 with a taper ratio Lb/Lt close to 100% can be realized.

For example, when the insulating layer 100 obtained by hardening the resin composition by heating it at 100°C for 30 minutes and then heating it at 180°C for 30 minutes is irradiated with a _CO2 laser under the conditions of a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ/shot, an irradiation number of 2, and a burst mode (10 kHz), a through hole 110 having a top diameter Lt of about 70 μm is formed, the tapered ratio Lb/Lt of the through hole 110 can be preferably 75% to 100%, more preferably 80% to 100%, and particularly preferably 85% to 100%.

The taper ratio Lb/Lt of the through hole 110 can be calculated from the bottom diameter Lb and the top diameter Lt of the through hole 110. In addition, the bottom diameter Lb and the top diameter Lt of the through hole 110 can be measured as follows: using FIB (focused ion beam), the insulating layer 100 is cut so that a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the through hole bottom 120 is revealed, and then the cross section is observed with an electron microscope.

FIG2 is a plan view schematically showing a surface 100U of an insulating layer 100 opposite to a conductive layer 210 (not shown in FIG2 ) obtained by curing the resin composition according to the first embodiment of the present invention into a sheet shape.

As shown in FIG. 2 , when observing the insulating layer 100 formed with the through hole 110, a discolored portion 140 of the insulating layer 100 may be observed around the through hole 110. The discolored portion 140 may be formed due to resin deterioration when forming the through hole 110, and is usually formed continuously from the through hole 110. In addition, in most cases, the discolored portion 140 is a whitened portion.

Fig. 3 is a cross-sectional view schematically showing the roughened insulating layer 100 obtained by hardening the resin composition related to the first embodiment of the present invention into a sheet shape together with the inner substrate 200. Fig. 3 shows a cross section of the insulating layer 100 cut along a plane passing through the center 120C of the through-hole bottom 120 of the through-hole 110 and parallel to the thickness direction of the insulating layer 100.

As shown in FIG. 3 , if the insulating layer 100 having the through hole 110 is roughened, a halo phenomenon occurs, and the insulating layer 100 of the discolored portion 140 is sometimes peeled off from the conductive layer 210, forming a gap portion 160 continuous from the edge 150 of the through hole bottom 120. The gap portion 160 is usually formed by etching the discolored portion 140 during the roughening process.

By using the resin composition of the present invention, the above-mentioned halo phenomenon can be suppressed. Therefore, the separation of the insulating layer 100 from the conductive layer 210 can be suppressed, so the size of the gap 160 can be reduced.

The edge 150 of the through-hole bottom 120 corresponds to the edge of the inner peripheral side of the gap 160. Therefore, the distance Wb from the edge 150 of the through-hole bottom 120 to the end 170 of the outer peripheral side of the gap 160 (i.e., the end on the side farther from the center 120C of the through-hole bottom 120) corresponds to the dimension of the gap 160 in the in-plane direction. Here, the in-plane direction refers to the direction perpendicular to the thickness direction of the insulating layer 100. In addition, in the following description, the distance Wb is sometimes referred to as the halo distance Wb of the through-hole 110 from the edge 150 of the through-hole bottom 120. The degree of suppression of the halo phenomenon can be evaluated by the halo distance Wb from the edge 150 of the through hole bottom 120. Specifically, the smaller the halo distance Wb from the edge 150 of the through hole bottom 120, the more effectively the halo phenomenon can be suppressed.

For example, the insulating layer 100 obtained by heating the resin composition layer containing the resin composition at 100°C for 30 minutes and then heating it at 180°C for 30 minutes to harden it is irradiated with _CO2 laser under the conditions of mask diameter 1 mm, pulse width 16μs, energy 0.2 mJ/time, irradiation number 2, burst mode (10 kHz) to form a through hole 110 with a top diameter Lt of about 70μm. Then, it is immersed in a swelling liquid at 60°C for 5 minutes, then immersed in an oxidizing agent solution at 80°C for 10 minutes, then immersed in a neutralizing liquid at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

The halo distance Wb from the edge 150 of the through-hole bottom 120 can be measured by cutting the insulating layer 100 using FIB (focused ion beam) to reveal a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the through-hole bottom 120, and then observing the cross section with an electron microscope.

Furthermore, by using the resin composition of the present invention, the shape of the through hole 110 of the insulating layer 100 before the roughening treatment can be easily controlled, so generally, even in the insulating layer 100 after the roughening treatment, the shape of the through hole 110 can be easily controlled. Therefore, even after the roughening treatment, the shape of the through hole 110 can be made good as before the roughening treatment. Therefore, if the resin composition of the present invention is used, in the insulating layer after the roughening treatment, the through hole 110 with a taper ratio Lb/Lt close to 100% can be realized.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100°C for 30 minutes and then heating it at 180°C for 30 minutes to harden it is irradiated with _CO2 laser under the conditions of mask diameter 1 mm, pulse width 16μs, energy 0.2 mJ/time, irradiation number 2, burst mode (10 kHz) to form a through hole 110 with a top diameter Lt of about 70μm. Then, it is immersed in a swelling liquid at 60°C for 5 minutes, then immersed in an oxidizing agent solution at 80°C for 10 minutes, then immersed in a neutralizing liquid at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. If the resin composition of the present invention is used, the taper ratio Lb/Lt of the through 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%.

The taper ratio Lb/Lt of the through hole 110 can be calculated from the bottom diameter Lb and the top diameter Lt of the through hole 110. In addition, the bottom diameter Lb and the top diameter Lt of the through hole 110 can be measured by cutting the insulating layer 100 using FIB (focused ion beam) to reveal a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the through hole bottom 120, and then observing the cross section with an electron microscope.

Furthermore, according to the research of the inventors, it is found that generally, the larger the diameter of the through hole 110, the easier it is for the size of the discoloration portion 140 to become larger, so the size of the gap portion 160 also tends to become larger. Therefore, the ratio of the size of the gap portion 160 to the diameter of the through hole 110 can be used to evaluate the degree of suppression of the halo phenomenon. For example, the halo ratio Hb of the through hole 110 relative to the bottom radius Lb/2 can be used for evaluation. Here, the bottom radius Lb/2 of the through hole 110 refers to the radius of the through hole bottom 120 of the through hole 110. In addition, the halo ratio Hb of the through hole 110 relative to the bottom radius Lb/2 refers to the ratio obtained by dividing the halo distance Wb from the edge 150 of the through hole bottom 120 by the bottom radius Lb/2 of the through hole 110. The smaller the halo ratio Hb of the through hole 110 relative to the bottom radius Lb/2, the more effectively the halo phenomenon can be suppressed.

For example, the insulating layer 100 obtained by heating the resin composition at 100°C for 30 minutes and then heating it at 180°C for 30 minutes to harden it is irradiated with _CO2 laser under the conditions of mask diameter 1 mm, pulse width 16μs, energy 0.2 mJ/time, irradiation times 2, and burst mode (10 kHz) to form a through hole 110 with a top diameter Lt of 30μm±2μm. Then, it is immersed in a swelling liquid at 60°C for 5 minutes, then immersed in an oxidizing agent solution at 80°C for 10 minutes, then immersed in a neutralizing liquid at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. If the resin composition of the present invention is used, the halo ratio Hb of the through hole 110 formed in the insulating layer 100 obtained in this way relative to the bottom radius Lb/2 can be preferably less than 35%, more preferably less than 30%, and further preferably less than 25%.

The halo ratio Hb of the through hole 110 relative to the bottom radius Lb/2 may be calculated by the bottom diameter Lb of the through hole 110 and the halo distance Wb of the through hole 110 from the edge 150 of the through hole bottom 120 .

Furthermore, generally, by using the resin composition of the present invention, the formation of the discolored portion 140 when the through hole 110 is formed can be suppressed. Therefore, as shown in FIG. 2 , the size of the discolored portion 140 can be reduced, and ideally, the discolored portion 140 can be eliminated. The size of the discolored portion 140 can be evaluated using the halo distance Wt of the through hole 110 from the edge 180 of the through hole top 130.

The edge 180 of the through-hole top 130 is equivalent to the edge of the inner peripheral side of the discoloration portion 140. The halo distance Wt from the edge 180 of the through-hole top 130 represents the distance from the edge 180 of the through-hole top 130 to the edge 190 of the outer peripheral side of the discoloration portion 140. The smaller the halo distance Wt from the edge 180 of the through-hole top 130, the more effectively the formation of the discoloration portion 140 can be evaluated.

The halo distance Wt from the edge 180 of the through hole top 130 can be measured by observation using an optical microscope.

Furthermore, according to the research of the inventors, it is found that the larger the diameter of the through hole 110 is, the easier it is for the size of the discoloration portion 140 to become larger. Therefore, the ratio of the size of the discoloration portion 140 to the diameter of the through hole 110 can be used to evaluate the degree of suppression of the formation of the discoloration portion 140. For example, the halo ratio Ht of the through hole 110 relative to the top radius Lt/2 can be used for evaluation. Here, the top radius Lt/2 of the through hole 110 refers to the radius of the through hole top 130 of the through hole 110. In addition, the halo ratio Ht of the through hole 110 relative to the top radius Lt/2 refers to the ratio obtained by dividing the halo distance Wt from the edge 180 of the through hole top 130 by the top radius Lt/2 of the through hole 110. The smaller the halo ratio Ht of the through hole 110 relative to the top radius Lt/2, the more effectively the formation of the discoloration portion 140 can be suppressed.

For example, when the insulating layer 100 obtained by heating the resin composition layer at 100°C for 30 minutes and then heating it at 180°C for 30 minutes to harden it is irradiated with a _CO2 laser under the conditions of a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ/time, an irradiation number of 2, and a burst mode (10 kHz) to form a through hole 110 with a top diameter Lt of about 70 μm, the halo ratio Ht of the through hole 110 relative to the top radius Lt/2 can be preferably less than 45%, more preferably less than 40%, and further preferably less than 35%.

The halo ratio Ht of the through hole 110 relative to the top radius Lt/2 can be calculated by the top diameter Lt of the through hole 110 and the halo distance Wt of the through hole 110 from the edge 180 of the through hole top 130.

In the manufacturing process of the printed wiring board, the through hole 110 is usually formed in a state where no other conductive layer (not shown) is provided on the surface 100U of the insulating layer 100 on the side opposite to the conductive layer 210. Therefore, if the manufacturing process of the printed wiring board is known, it can be clearly recognized that there is a structure in which the through hole bottom 120 exists on the conductive layer 210 side and the through hole top 130 is opened on the side opposite to the conductive layer 210. However, in the completed printed wiring board, the conductive layer may be provided on both sides of the insulating layer 100. In this case, it may be difficult to distinguish the through hole bottom 120 and the through hole top 130 by the positional relationship with the conductive layer. However, usually, the top diameter Lt of the through hole top 130 is larger than the bottom diameter Lb of the through hole bottom 120. Therefore, in the above case, the through hole bottom 120 and the through hole top 130 can be distinguished by the size of the diameter.

The resin composition of the present invention can suppress the halo phenomenon and can also obtain a cured product with low dielectric properties. In addition, by hardening the resin composition of the present invention, an insulating layer with excellent elongation at break can usually be obtained.

The cured product obtained by heat curing the resin composition at 200°C for 90 minutes shows the property of low dielectric tangent. Therefore, the cured product provides an insulating layer with low dielectric tangent. The dielectric tangent is preferably 0.008 or less, more preferably 0.005 or less, and further preferably 0.004 or less. The lower limit of the dielectric tangent can be set to 0.0001 or more. The dielectric tangent can be measured according to the method described in the embodiments described below.

The cured product obtained by heat curing the resin composition at 200°C for 90 minutes shows the characteristic of low relative dielectric constant. Therefore, the cured product provides an insulating layer with low relative dielectric constant. The relative dielectric constant is preferably 4 or less, more preferably 3.5 or less, and further preferably 3 or less. The lower limit of the relative dielectric constant can be set to 1 or more. The relative dielectric constant can be measured according to the method described in the embodiments described below.

The cured product obtained by heat curing the resin composition at 200°C for 90 minutes generally shows the characteristic 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 based on 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 embodiments described below.

The resin composition of the present invention can obtain a hardened material having low dielectric properties and capable of suppressing the halo phenomenon. Furthermore, a hardened material having excellent elongation at the fracture point can be obtained. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, it can be suitably used as: a resin composition for forming an insulating layer, and the insulating layer is used to form a conductive layer (including a redistribution layer) formed on the insulating layer (a resin composition for forming an insulating layer for forming a conductive layer).

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

In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a resin composition for a redistribution forming layer as an insulating layer for forming a redistribution layer (resin composition for redistribution forming layer formation), and a resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing). When manufacturing a semiconductor chip package, a redistribution layer can be further formed on the sealing layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on the temporary fixing film; (3) a step of forming a sealing layer on the semiconductor chip; (4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip; (5) a step of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film are peeled; and (6) a step of forming a redistribution layer as a conductive layer on the redistribution layer.

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

From the viewpoint of thinning the printed wiring board and providing a cured product of the resin composition having excellent insulation even in the form of a thin film, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and can generally be set to 5 μm or more.

As the support, for example, a film formed of a plastic material, a metal foil, and a release paper can be cited, and a film formed of a plastic material and a metal foil are preferred.

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

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. The copper foil may be a foil made of copper alone or an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

For the support body, the surface that is bonded to the resin composition layer may be subjected to matte treatment, corona discharge treatment, and antistatic treatment.

In addition, as the support body, a support body with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used for the release layer of the support body with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, urethane resins and silicone resins can be cited. The support body with a release layer can use commercially available products, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Co., Ltd., "LUMIRROR T60" manufactured by Toray Industries, Ltd., "Purex" manufactured by Teijin Co., Ltd., and "Unipeel" manufactured by UNITIKA Co., Ltd., which are PET films having a release layer with an alkyd resin-based release agent as a main component.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Furthermore, when a support with a release layer is used, the thickness of the entire support with a release layer is preferably within the above range.

In one embodiment, the adhesive film may further include other layers as needed. As the other layers, for example, a protective film that is provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the side opposite to the support) and serves as a support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust or the like on the surface of the resin composition layer or the formation of damage.

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

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

The adhesive film can be stored in a roll. If the adhesive film has a protective film, it can be used by peeling off the protective film.

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

For example, a printed wiring board can be manufactured using the above-mentioned bonding film by a method including the following steps (I) and (II): (I) a step of stacking the bonding film on the inner substrate in such a manner that the resin composition layer is bonded to the inner substrate; (II) a step of thermally curing the resin composition layer to form an insulating layer.

The "inner layer substrate" used in step (I) refers to a component that becomes the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. In addition, the substrate may have a conductive layer on one or both sides thereof, and the conductive layer may have been subjected to pattern processing. An inner layer substrate having a conductive layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, intermediate products that require further formation of an insulating layer and/or a conductive layer when manufacturing a printed wiring board are also included in the "inner layer substrate" referred to in the present invention. In the case where the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components can be used.

The inner substrate and the bonding film can be stacked, for example, by heating and pressing the bonding film to the inner substrate from the side of the support. As a component for heating and pressing the bonding film to the inner substrate (hereinafter also referred to as a "heating and pressing component"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) can be cited. Furthermore, it is preferred not to press the heating and pressing component directly to the bonding film, but to press it through an elastic material such as heat-resistant rubber so that the bonding film fully conforms to the surface unevenness of the inner substrate.

The lamination of the inner substrate and the adhesive film can be performed by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum press laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko-Materials Co., Ltd., and a batch vacuum press laminator.

After lamination, the laminated bonding film can be smoothed by, for example, pressing a heat-pressing member from the side of the support under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be the same as the heat-pressing conditions for the lamination described above. The smoothing treatment can be performed by a commercially available laminating press. Furthermore, the lamination and smoothing treatment can be performed continuously using the commercially available vacuum laminating press described above.

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

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

For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition, and the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and further preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 100 minutes.

Before the resin composition layer is heat-hardened, the resin composition layer may be preheated at a temperature lower than the hardening temperature. For example, before the resin composition layer is heat-hardened, the resin composition layer may be preheated at a temperature of 50°C or higher and lower than 120°C (preferably 60°C or higher and 115°C or lower, more preferably 70°C or higher and 110°C or lower) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, the step (III) of opening holes in the insulating layer, the step (IV) of roughening the insulating layer, and the step (V) of forming a conductive layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art in the art used in the manufacture of printed wiring boards. Furthermore, when the support is removed after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Furthermore, the formation of the insulating layer and the conductive layer in steps (II) to (V) can be repeated as needed to form a multi-layer wiring board.

Step (III) is a step of opening holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) can be performed using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, in step (IV), contamination is also removed. The steps and conditions of the roughening treatment are not particularly limited, and the known steps and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by swelling treatment using a swelling liquid, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing liquid in sequence. The swelling liquid used in the roughening treatment is not particularly limited, and an alkaline solution, a surfactant solution, etc. can be cited. An alkaline solution is preferred, and a sodium hydroxide solution or a potassium hydroxide solution is more preferred as the alkaline solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", and "Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd. The swelling treatment using the swelling liquid is not particularly limited, and can be performed, 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 controlling the swelling of the resin of the insulating layer to an appropriate level, it is preferred 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, and an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be cited. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. In addition, as the neutralizing solution used in the roughening treatment, an acidic aqueous solution is preferred, and as a commercially available product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. The treatment using the neutralizing solution can be performed by immersing the surface treated by the roughening treatment using the oxidizing agent in the neutralizing solution at 30°C to 80°C for 1 minute to 30 minutes. From the perspective of operability, etc., it is preferred to immerse the object treated by the roughening treatment using the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

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

Step (V) is a step of forming a conductive layer, and the conductive layer is formed on the insulating layer. The conductive material used for the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer contains one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductive layer can be a single metal layer or an alloy layer. As an alloy layer, for example, a layer formed of an alloy of two or more metals selected from the above metals (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be cited. Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of pattern formation, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred; a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferred; and a single metal layer of copper is further preferred.

The conductive layer may be a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers formed of different types of metals or alloys are stacked. When the conductive layer is a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

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

In one embodiment, the conductive layer can be formed by plating. For example, the conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. From the perspective of manufacturing simplicity, it is preferably formed by a semi-additive method. An example of forming a conductive layer by a semi-additive method is shown below.

First, a coating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed coating seed layer to expose a portion of the coating seed layer in accordance with the desired wiring pattern. After a metal layer is formed on the exposed coating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary coating seed layer is removed by etching or the like, thereby forming a conductive layer having the desired wiring pattern.

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

As semiconductor devices, there can be cited various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and transportation vehicles (such as motorcycles, automobiles, trains, ships, and aircraft).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conductive position of a printed wiring board. The "conductive position" refers to "a position in a printed wiring board where an electrical signal is conducted", and the position can be a surface or an embedded position. In addition, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor.

The semiconductor chip mounting method when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip can function effectively. Specifically, there can be cited a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. Here, "a mounting method using a bumpless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly buried in a recess of a printed wiring board to connect the semiconductor chip to the wiring on the printed wiring board." Implementation Example

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

<Measurement of average particle size of inorganic filler> 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasound for 10 minutes. Using a laser diffraction particle size distribution measuring device ("LA-960" manufactured by Horiba, Ltd.), the particle size distribution of the inorganic filler was measured on a volume basis using a flow cell method with the wavelength of the light source set to blue and red. Based on the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median diameter.

<Measurement of Average Porosity of Inorganic Filler> The density of the inorganic filler was measured using a true density measuring device ("ULTRAPYCNOMETER 1000" manufactured by QUANTACHROME). In this measurement, nitrogen was used as the measuring gas. Then, using the measured density (measured value) _DM (g/ ^cm3 ) and the material density (theoretical value) _DT (g/ ^cm3 ) of the inorganic material (silicon dioxide) forming the inorganic filler, 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 silicon dioxide as the inorganic material is set to 2.2 g/ ^cm3 .

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

<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 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, heated and stirred at 60°C for 2 hours, and then cooled to room temperature. Thus, a stirred liquid containing solid silica surface-treated with an aminosilane coupling agent was obtained. Into the stirred liquid, 30 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 180 g/eq.), 30 parts of biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.), 14 parts of a phenolic curing agent containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Co., Ltd., hydroxyl equivalent of about 151 g/eq., 2-methoxypropanol solution containing 50% of non-volatile components), 40 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Co., Ltd., active group equivalent of about 223 g/eq.) were mixed. g/eq., a toluene solution with a non-volatile content of 65% by mass), 10 parts of phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Co., Ltd., a 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass), and 6 parts of a curing accelerator ("DMAP", 4-dimethylaminopyridine, a MEK solution with a solid content of 5% by mass), were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

As a support, a PET film ("LUMIRROR R80" manufactured by Toray Industries, Ltd., thickness 38μm) that had been subjected to mold release treatment with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Co., Ltd.) was prepared. A resin varnish was uniformly applied to the mold release layer of the support using a die coater so that the thickness of the resin composition layer after drying would be 40μm, and dried at 80 to 120°C (average 100°C) for 4 minutes to prepare an adhesive film.

<Example 2> In Example 1, the mixing liquid containing solid silica surface-treated with an aminosilane coupling agent is changed to a mixing liquid containing solid silica surface-treated with an aminosilane coupling agent and hollow silica surface-treated with an aminosilane coupling agent. Except for the above matters, the same operation as Example 1 is performed to prepare a resin varnish and a bonding film.

A stirred liquid containing solid silica surface-treated with an aminosilane coupling agent and hollow silica surface-treated with an aminosilane coupling agent is obtained by the following method: 140 parts of solid silica (average particle size 0.5 μm, "SO-C2" manufactured by Admatechs Co., Ltd.), 70 parts of hollow silica (average particle size 0.5 μm, porosity 50 volume %, "LHP-208" manufactured by Ube Exsymo Co., Ltd.) and 2.24 parts of aminosilane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) are 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. Thus, a mixing liquid containing solid silica surface-treated with an aminosilane coupling agent and hollow silica surface-treated with an aminosilane coupling agent is obtained.

<Example 3> In Example 2, 1) 70 parts of hollow silica (average particle size 0.5 μm, porosity 50 volume %, "LHP-208" manufactured by Ube Exsymo Co., Ltd.) were changed to 70 parts of hollow silica particles 1 (average particle size 2.0 μm, porosity 50 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; Except for the above matters, the same operation as in Example 2 was performed to prepare a resin varnish and a bonding film.

<Example 4> In Example 1, 1) 280 parts of solid silica (average particle size 0.5 μm, "SO-C2" manufactured by Admatechs Co., Ltd.) were changed to 140 parts of hollow silica particles 1 (average particle size 2.0 μm, porosity 50 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; Except for the above matters, the same operation as in Example 1 was performed to prepare a resin varnish and an adhesive film.

<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. Except for the above matters, the same operation as Example 1 was carried out to prepare a resin varnish and an adhesive film.

<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. Except for the above matters, the same operation as Example 4 was carried out to prepare a resin varnish and an adhesive film.

<Comparative Example 1> In Example 1, 1.68 parts of silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was replaced with 1.68 parts of aminosilane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above matters, the same operation as Example 1 was performed to prepare a resin varnish and an adhesive film.

<Comparative Example 2> In Example 4, 4.48 parts of silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) were replaced with 4.48 parts of aminosilane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above matters, the same operation as Example 4 was performed to prepare a resin varnish and an adhesive film.

<Comparative Example 3> In Example 4, 4.48 parts of silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) were replaced with 8.96 parts of aminosilane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above matters, the same operation as Example 4 was carried out to prepare a resin varnish and an adhesive film.

<Comparative Example 4> In Example 1, 1.68 parts of silane coupling agent ("X-88-398" manufactured by Shin-Etsu Chemical Co., Ltd.) was not used. Except for the above matters, the same operation as Example 1 was carried out to prepare a resin varnish and an adhesive film.

<Preparation of a cured product for evaluation> The 40 μm thick adhesive film prepared in the examples and comparative examples was heated at 200°C for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The resulting cured product is referred to as a "cured product for evaluation".

<Measurement of relative dielectric constant and dielectric tangent> The evaluation hardened material was cut into a specimen with a width of 2 mm and a length of 80 mm. For this specimen, the relative dielectric constant and dielectric tangent were measured by the resonant cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C using the "HP8362B" manufactured by Agilent Technologies. The two specimens were measured and the average value was calculated.

<Measurement of elongation at break> For the evaluation hardened material, a tensile test was performed in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.), and the elongation at break was measured.

<Preparation of samples for halo evaluation> (1) Base treatment of inner circuit substrate The copper surface of a glass cloth-based epoxy resin laminate (copper foil thickness 18μm, substrate thickness 0.4 mm, R1515A manufactured by Panasonic Co., Ltd.) with inner circuits was roughened by etching 1μm on both sides with a micro-etchant (CZ8101 manufactured by MEC Co., Ltd.).

(2) Lamination of adhesive films with supports The prepared adhesive films were pressed onto both sides of the inner circuit board using a batch vacuum pressure laminating press (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds until the air pressure reached 13 hPa or less, and then laminating at 100°C and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of the resin composition layer The adhesive film after lamination is cured at 130°C for 30 minutes and then at 170°C for 30 minutes to form an insulating layer.

(4) Formation of through holes A _CO2 laser processing machine (manufactured by Hitachi Via Mechanics Co., Ltd., LC-2E21B/1C) was used to open holes in the insulating layer under the conditions of mask diameter 1.60 mm, focus offset 0.050, pulse width 25 μs, power 0.66 W, aperture 13, irradiation times 2, and burst mode (10 kHz). A plurality of through holes were formed under the condition that the top diameter of the through holes in the surface of the insulating layer was about 50 μm. Then, the support body was peeled off.

(5) Roughening treatment The inner circuit substrate with the insulating layer formed thereon was immersed in Swelling Dip Securiganth P (glycol ether, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd. as a swelling liquid at 60°C for 10 minutes, then immersed in Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan Co., Ltd. as a roughening liquid at 80°C for 20 minutes, and finally immersed in Reduction Solution Securiganth P (aqueous solution of sulfuric acid) manufactured by Atotech Japan Co., Ltd. as a neutralizing liquid at 40°C for 5 minutes, and then dried at 80°C for 30 minutes. This substrate is referred to as an evaluation substrate.

<Measurement of the size, halo distance, and halo ratio of the through hole after roughening> For the evaluation substrate, a cross-sectional observation was performed using a FIB-SEM composite device ("SMI3050SE" manufactured by SIINanotechnology Co., Ltd.). Specifically, the insulating layer was cut using a FIB (focused ion beam) to reveal a cross section parallel to the thickness direction of the insulating layer and passing through the center of the bottom of the through hole. The cross section was observed using an SEM. From the observed image, the bottom diameter and top diameter of the through hole were measured.

In addition, in the image observed by SEM, it can be seen that the insulating layer is continuously peeled off from the edge of the bottom of the through hole by the copper foil layer of the inner substrate to form a gap. Therefore, from the observed image, the distance r1 from the center of the bottom of the through hole to the edge of the bottom of the through hole (equivalent to the inner radius of the gap) and the distance r2 from the center of the bottom of the through hole to the end of the farther side of the aforementioned gap (equivalent to the outer radius of the gap) are measured, and the difference between the distance r1 and the distance r2 (r2-r1) is calculated as the halo distance from the edge of the bottom of the through hole at the measured point.

The above measurements were performed at 5 randomly selected through holes. The average value of the top diameters of the 5 through holes was used as the top diameter Lt of the sample after the roughening treatment. In addition, the average value of the bottom diameters of the 5 through holes was used as the bottom diameter Lb of the sample after the roughening treatment. Furthermore, the average value of the halo distances of the 5 through holes was used as the halo distance Wb from the edge of the bottom of the through hole of the sample.

Based on the above measurement results, the taper ratio (the ratio of the bottom diameter Lb and the top diameter Lt of the through hole after roughening treatment "Lb/Lt") and the halo ratio Hb (the ratio of the halo distance Wb from the edge of the through hole bottom after roughening treatment to the radius of the through hole bottom (Lb/2) of the through hole after roughening treatment "Wb/(Lb/2)") were calculated and evaluated according to the following standards. ○: The halo ratio Hb is less than 35%; △: The halo ratio Hb is greater than 35% and less than 50%; ×: The halo ratio Hb is greater than 50%.

* In the table, the content of component (C) (mass %) indicates the content when the non-volatile components in the resin composition are set to 100 mass %, and the content of component (C) (volume %) indicates the content when the non-volatile components in the resin composition are set to 100 volume %. The content of component (D) indicates the content when the resin components in the resin composition are set to 100 mass %.

100: Insulating layer 100U: Surface of insulating layer opposite to the conductive layer 110: Through hole 120: Bottom of through hole 120C: Center of bottom of through hole 130: Top of through hole 140: Discolored portion 150: Edge of bottom of through hole 160: Gap portion 170: End portion 180: Edge of top of through hole 190: End portion of peripheral side 200: Inner substrate 210: Conductive layer (first conductive layer) Lb: Bottom diameter of through hole Lt: Top diameter of through hole Wt: Halo distance from the edge of top of through hole Wb: halo distance from the edge of the bottom of the through hole

[FIG. 1] is a cross-sectional view schematically showing an insulating layer obtained by hardening the resin composition related to the first embodiment of the present invention into a sheet shape together with an inner substrate. [FIG. 2] is a top view schematically showing the surface of the insulating layer obtained by hardening the resin composition related to the first embodiment of the present invention into a sheet shape on the side opposite to the conductive layer. [FIG. 3] is a cross-sectional view schematically showing the insulating layer obtained by hardening the resin composition related to the first embodiment of the present invention into a sheet shape after roughening treatment together with an inner substrate.

Claims (9)

A resin composition comprising: (A) epoxy resin, (B) active ester hardener, (C) inorganic filler, and (D) silane compound having silicon atoms as ring atoms. The resin composition of claim 1, wherein the component (C) comprises any one of (C-1) a hollow inorganic filler and (C-2) a solid inorganic filler. The resin composition of claim 1, wherein the component (C) comprises (C-1) a hollow inorganic filler. The resin composition of claim 1, wherein the component (C) is surface treated with the component (D). The resin composition of claim 1, wherein the content of the component (C) is 50% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass. The resin composition of claim 1, wherein the content of the component (D) is 0.1% by mass or more and 5% by mass or less, based on 100% by mass of the resin component in the resin composition. A bonding film comprising: a support, and a resin composition layer disposed on the support and comprising a resin composition as described in any one of claims 1 to 6. A printed wiring board comprising an insulating layer formed using a cured product of the resin composition according to any one of claims 1 to 6. A semiconductor device comprising a printed wiring board as claimed in claim 8.

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