resin composition

Abstract

To provide a resin composition or the like in which, even if a via hole and a trench are formed by plasma treatment, generation of unevenness on a side face and a bottom face of the via hole or the trench can be suppressed, processing speed can be improved, and a cured product having excellent toughness and insulation reliability is obtained.SOLUTION: A resin composition contains (A) epoxy resin, (B) inorganic filler having the average particle diameter of 0.1 μm or less, (C) resin having an imide skeleton, and (D) resin having a phenylene ether skeleton. The content of component (B) is 69 mass% or less in the case where a nonvolatile component in the resin composition is 100 mass%, and the content of component (C) is 1 mass% or more and 15 mass% or less in the case where a nonvolatile component in the resin composition is 100 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, and further to a resin sheet, a printed wiring board, a semiconductor device, and a method for producing a printed wiring board, each of which uses the resin composition. [Background technology]

[0002] In recent years, in printed wiring boards, build-up layers have become multi-layered, and there is a demand for finer and denser wiring. The build-up layers are formed by a build-up method in which insulating layers and conductor layers are alternately stacked, and in manufacturing methods using the build-up method, the insulating layers are generally formed by thermally curing a resin composition.

[0003] Many resin compositions suitable for forming insulating layers of inner layer circuit boards have been proposed, including the resin composition described in Patent Document 1, for example. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-59779 Summary of the Invention [Problem to be solved by the invention]

[0005] When manufacturing a printed wiring board, a via hole or a trench may be formed in an insulating layer. A "via hole" usually refers to a hole that penetrates an insulating layer. A "trench" usually refers to a groove that does not penetrate an insulating layer. A method using a laser can be considered as a method for forming a via hole or a trench.

[0006] However, in the method using a laser, via holes or trenches are formed one by one, which takes time to form. Furthermore, it is difficult to make via holes and trenches small using a laser. Therefore, the present inventors focused on plasma treatment as a method that can simultaneously form multiple via holes or trenches and can also make the via holes and trenches small. However, after conducting research, the present inventors found that when via holes are formed using plasma treatment, the cured resin component and inorganic filler are excavated on the side and bottom surfaces of the via holes, resulting in unevenness and an uneven surface. Furthermore, the processing speed of plasma treatment can be slower than when using a laser. In particular, in resin compositions for obtaining insulating layers with excellent toughness and insulation reliability, it is particularly difficult to suppress the occurrence of unevenness and improve the processing speed when using plasma treatment.

[0007] An object of the present invention is to provide a resin composition that can suppress the occurrence of irregularities on the side and bottom surfaces of a via hole or trench even when the via hole or trench is formed by plasma treatment, can improve the processing speed, and can produce a cured product that is excellent in toughness and insulation reliability; and to provide a resin sheet, a printed wiring board, a semiconductor device, and a method for manufacturing a printed wiring board that use the resin composition. [Means for solving the problem]

[0008] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that by incorporating a resin composition in combination an epoxy resin, a predetermined amount of an inorganic filler having an average particle size of 0.1 μm or less, a predetermined amount of a resin having an imide skeleton represented by formula (C), and a resin having a phenylene ether skeleton represented by formula (D), it is possible to suppress the occurrence of unevenness on the side and bottom surfaces of a via hole or trench, improve the processing speed, and improve toughness and insulation reliability, even when the via hole or trench is formed by plasma treatment, and have thereby completed the present invention.

[0009] That is, the present invention includes the following. [1] (A) epoxy resin, (B) an inorganic filler having an average particle size of 0.1 μm or less; (C) a resin having an imide skeleton represented by the following formula (C), and (D) A resin composition containing a resin having a phenylene ether skeleton represented by the following formula (D): The content of the (B) component is 69% by mass or less, when the total amount of nonvolatile components in the resin composition is 100% by mass, A resin composition, wherein the content of component (C) is 1% by mass or more and 15% by mass or less, when the total amount of nonvolatile components in the resin composition is 100% by mass. [ka] (In formula (C), R a are each independently a halogen atom, a cyano group, a nitro group, or -X 13 -R 13 represents X 13 are each independently a single bond, -NR 13’ -, -O-, -S-, -CO-, -SO2-, -NR 13’ CO-, -CONR 13’ represents -, -OCO-, or -COO-; R 13 each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R 13’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. a1 represents an integer of 0 to 3. * indicates a binding site. In formula (D), R b each independently represents a substituent, b1 represents an integer of 0 to 4. * indicates a binding site. [2] The resin composition according to [1], wherein the content of component (D) is 5% by mass or more and 10% by mass or less, when the total amount of nonvolatile components in the resin composition is 100% by mass. [3] The resin composition according to [1] or [2], wherein the total content of the (C) component and the (D) component is 10% by mass or more and 25% by mass or less, when the non-volatile components in the resin composition are 100% by mass. [4] The resin composition according to any one of [1] to [3], wherein the resin composition has a minimum melt viscosity of 5000 poise or less. [5] The resin composition according to any one of [1] to [4], which is used for forming via holes or trenches in an insulating layer of a printed wiring board by plasma treatment. [6] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to [5]. [7] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [5]. [8] A semiconductor device comprising the printed wiring board according to [7]. [9] A step of forming an insulating layer containing a cured product of the resin composition according to any one of [1] to [5] on an inner layer circuit board; and A method for manufacturing a printed wiring board, comprising a step of performing plasma treatment on the surface of an insulating layer to form via holes or trenches. [Effects of the Invention]

[0010] According to the present invention, even when via holes and trenches are formed by plasma treatment, the occurrence of unevenness on the side and bottom surfaces of the via holes or trenches can be suppressed, the processing speed can be improved, and a cured product excellent in toughness and insulation reliability can be obtained; and methods for manufacturing a resin sheet, a printed wiring board, a semiconductor device, and a printed wiring board using the resin composition can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0012] [Resin composition] The resin composition of the present invention contains (A) an epoxy resin, (B) an inorganic filler having an average particle size of 0.1 μm or less, (C) a resin having an imide skeleton represented by the following formula (C), and (D) a resin having a phenylene ether skeleton represented by the following formula (D), wherein the content of the (B) component is 69% by mass or less, when the total nonvolatile components in the resin composition is 100% by mass, and the content of the (C) component is 1% by mass or more and 15% by mass or less, when the total nonvolatile components in the resin composition is 100% by mass. [ka] (In formula (C), R a are each independently a halogen atom, a cyano group, a nitro group, or -X 13 -R 13 represents X 13 are each independently a single bond, -NR 13’ -, -O-, -S-, -CO-, -SO2-, -NR 13’ CO-, -CONR 13’ represents -, -OCO-, or -COO-; R 13 each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R 13’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. a1 represents an integer of 0 to 3. * indicates a binding site. In formula (D), R b each independently represents a substituent, b1 represents an integer of 0 to 4. * indicates a binding site.

[0013] In the present invention, by containing component (A), a specific amount of component (B), specific amounts of component (C), and component (D), even when via holes and trenches are formed by plasma treatment, the occurrence of unevenness on the side and bottom surfaces of the via holes or trenches can be suppressed, and a resin composition can be obtained that can realize a cured product that can improve processing speed. That is, the present invention provides a resin composition that can give a cured product with excellent plasma processability. Furthermore, the present invention provides a resin composition that can give a cured product with excellent toughness and insulation reliability. Furthermore, the resin composition typically has a low minimum melt viscosity. Furthermore, the resin composition typically can also give a cured product with excellent pattern embedding ability and flatness.

[0014] The resin composition of the present invention may further contain optional components in combination with the components (A) to (D). Examples of optional components include a curing agent (E), a curing accelerator (F), and other additives (G). Each component contained in the resin composition of the present invention will be described in detail below.

[0015] <(A) Epoxy resin> The resin composition contains an epoxy resin (A) as component (A). Examples of the epoxy resin (A) include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, and tetraphenylethane-type epoxy resins. Among these, from the viewpoint of significantly achieving the effects of the present invention, component (A) is more preferably one or more selected from bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthylene ether-type epoxy resins, and cyclohexane-type epoxy resins, and even more preferably contains bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthylene ether-type epoxy resins, and cyclohexane-type epoxy resins. One type of epoxy resin may be used alone, or two or more types may be used in combination.

[0016] The resin composition preferably contains, as the (A) epoxy resin, an epoxy resin having two or more epoxy groups per molecule. From the viewpoint of significantly achieving the desired effects of the present invention, the proportion of the (A) epoxy resin having two or more epoxy groups per 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 non-volatile components of the epoxy resin.

[0017] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may use a liquid epoxy resin as the epoxy resin (A), or a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. From the viewpoint of significantly achieving the effects of the present invention, it is preferable to use a combination of a liquid epoxy resin and a solid epoxy resin.

[0018] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0019] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins; glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins such as alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure, with cyclohexane type epoxy resins being more preferred.

[0020] Specific examples of liquid epoxy resins include "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US," "jER828EL," "825," and "Epikote 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "630" and "630LSD" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation. ); "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (a glycidyl ester type epoxy resin); "Celloxide 2021P" manufactured by Daicel Corporation (an alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel Corporation (an epoxy resin having a butadiene structure); and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. These may be used alone or in combination of two or more.

[0021] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0022] Preferred solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and more preferred are bixylenol-type epoxy resins, naphthol-type epoxy resins, naphthalene-type epoxy resins, and naphthylene ether-type epoxy resins.

[0023] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC Corporation. type epoxy resin); DIC Corporation's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", and "HP6000L" (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", and "NC 3000L, "NC3100" (biphenyl-type epoxy resin); "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. Examples of epoxy resins include "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

[0024] When a liquid epoxy resin and a solid epoxy resin are used in combination as the (A) epoxy resin, the ratio by mass between them (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:1 to 1:15, and particularly preferably 1:1 to 1:10. When the ratio between the liquid epoxy resin and the solid epoxy resin is within this range, the desired effects of the present invention can be significantly achieved. Furthermore, when used in the form of a resin sheet, appropriate adhesiveness is usually imparted. Furthermore, when used in the form of a resin sheet, sufficient flexibility is usually obtained, improving handleability. Furthermore, a cured product having sufficient breaking strength can usually be obtained.

[0025] The epoxy equivalent of the (A) epoxy resin is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, even more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g / eq to 1000 g / eq. Within this range, the crosslink density of the cured product of the resin composition is sufficient, resulting in an insulating layer with low surface roughness. The epoxy equivalent is the mass of a resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0026] The weight average molecular weight (Mw) of the (A) epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500, from the viewpoint of significantly achieving the desired effects of the present invention. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene equivalent value.

[0027] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the (A) epoxy resin is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit of the epoxy resin content is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less. In the present invention, the content of each component in the resin composition is the value when the nonvolatile components in the resin composition are taken as 100% by mass, unless otherwise specified.

[0028] <(B) Inorganic filler with an average particle size of 0.1 μm or less> The resin composition contains, as component (B), an inorganic filler (B) with an average particle size of 0.1 μm or less. When forming via holes and trenches by plasma treatment, the cured resin component is etched by plasma irradiation with a specific gas, exposing component (B). However, because component (B) has an average particle size of 0.1 μm or less, it is possible to reduce the irregularities (depth and length) of the bottom and sidewalls of the via hole, preventing the sidewalls and bottom from becoming uneven. As a result, it is possible to achieve a uniform thickness for the conductor layer, thereby improving flatness. Unless otherwise specified, the term "resin component" refers to the non-volatile components contained in the resin composition, excluding the inorganic filler.

[0029] From the viewpoint of improving plasma processability, the average particle size of component (B) is 0.1 μm or less, preferably 0.09 μm or less, more preferably 0.08 μm or less, and preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more.

[0030] The average particle size of component (B) can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a volumetric particle size distribution of the inorganic filler is created using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them ultrasonically for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution analyzer with blue and red light source wavelengths using a flow cell system to measure the volumetric particle size distribution of component (B). The average particle size can then be calculated as the median diameter from the particle size distribution obtained. Examples of laser diffraction particle size distribution analyzers include the LA-960 manufactured by Horiba, Ltd.

[0031] From the viewpoint of improving the minimum melt viscosity of the resin composition and the flatness, toughness, and plasma processability of the cured product, the content of component (B) is 69% by mass or less, preferably 64% by mass or less, and more preferably 63% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, 50% by mass or more, or 60% by mass or more.

[0032] (B) An inorganic compound is used as the inorganic filler material. Examples of inorganic filler materials include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, calcium carbonate and silica are preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Furthermore, spherical silica is preferred. The component (B) may be used alone or in combination of two or more.

[0033] Commercially available products of component (B) include, for example, "UFP-30" manufactured by Denka; "SP60-05," "SP507-05," and "SPH516-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," and "YA010C" manufactured by Admatechs Co., Ltd.; and "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation.

[0034] The specific surface area of ​​component (B) is preferably 10 m 2 / g or more, more preferably 15m 2 / g or more, particularly preferably 20m 2 / g or more, 30m 2 / g or more. There is no particular upper limit, but it is preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2The specific surface area is determined by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0035] From the viewpoint of improving moisture resistance and dispersibility, it is preferable that component (B) be treated with a surface treatment agent. Examples of surface treatment agents include vinylsilane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Among these, from the viewpoint of significantly achieving the effects of the present invention, vinylsilane coupling agents, (meth)acrylic coupling agents, and aminosilane coupling agents are preferred, and aminosilane coupling agents are more preferred. Furthermore, the surface treatment agents may be used alone or in any combination of two or more.

[0036] Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd.'s "KBM1003" (vinyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM503" (3-methacryloxypropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s "KBM1003" (vinyltriethoxysilane). Examples of suitable silane coupling agents include "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0037] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass.

[0038] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is more preferable that the amount of the resin varnish is 1 mg / m 2 Less than 0.8 mg / m is preferred 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0039] The carbon amount per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. The carbon analyzer that can be used is the "EMIA-320V" manufactured by Horiba, Ltd.

[0040] <(C) Polyimide resin> The resin composition contains, as component (C), a resin having an imide skeleton represented by formula (C): By including a specific amount of component (C) in the resin composition, it is possible to improve the toughness of the cured product of the resin composition and also to improve plasma processability. [ka] (In formula (C), R a are each independently a halogen atom, a cyano group, a nitro group, or -X 13 -R 13 represents X 13 are each independently a single bond, -NR 13’ -, -O-, -S-, -CO-, -SO2-, -NR 13’ CO-, -CONR 13’ represents -, -OCO-, or -COO-; R 13 each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R 13’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. a1 represents an integer of 0 to 3. * indicates a binding site.

[0041] a1 represents an integer of 0 to 3, and is preferably 0.

[0042] The substituents that the substituted or unsubstituted alkyl group and the substituted or unsubstituted alkenyl group may have include R 9 The substituents are the same as those that may be possessed by the substituted or unsubstituted alkyl group and the substituted or unsubstituted alkenyl group represented by the formula (I).

[0043] Component (C) is not particularly limited as long as it is a resin having an imide skeleton represented by formula (C) in the repeating unit. Component (C) generally includes those obtained by the imidization reaction of a diamine compound with an acid anhydride. Component (C) also includes modified polyimide resins such as siloxane-modified polyimide resins. Component (C) may be used alone or in combination of two or more types.

[0044] The diamine compound used to prepare the component (C) is not particularly limited, but examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

[0045] Examples of aliphatic diamine compounds include linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane, and 1,10-diaminodecane; branched aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5-diaminopentane; alicyclic diamine compounds such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4′-methylenebis(cyclohexylamine); and dimer acid diamines (hereinafter also referred to as “dimer diamines”), among which dimer acid diamines are preferred.

[0046] Dimer acid diamines refer to diamine compounds obtained by substituting the two terminal carboxylic acid groups (—COOH) of a dimer acid with aminomethyl groups (—CH—NH) or amino groups (—NH). Dimer acids are known compounds obtained by dimerizing unsaturated fatty acids (preferably those with 11 to 22 carbon atoms, particularly preferably those with 18 carbon atoms), and their industrial production processes are largely standardized in the industry. Dimer acids are particularly readily available, primarily consisting of 36-carbon dimer acids obtained by dimerizing 18-carbon unsaturated fatty acids such as oleic acid and linoleic acid, which are inexpensive and readily available. Depending on the production method, degree of purification, and other factors, dimer acids may contain arbitrary amounts of monomer acids, trimer acids, other polymerized fatty acids, and the like. Although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrogenated products obtained by further hydrogenation to reduce the degree of unsaturation are also included in the term dimer acids. Dimer acid type diamines are commercially available, for example, "PRIAMINE 1073," "PRIAMINE 1074," and "PRIAMINE 1075" manufactured by Croda Japan; "VERSAMINE 551" and "VERSAMINE 552" manufactured by Cognis Japan; and the like.

[0047] Examples of the aromatic diamine compound include a phenylenediamine compound, a naphthalenediamine compound, and a dianiline compound.

[0048] The phenylenediamine compound means a compound consisting of a benzene ring having two amino groups, and further, the benzene ring here may have any of 1 to 3 substituents.

[0049] Examples of the substituent include an unsaturated hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. The substituent may be contained alone or in combination of two or more kinds. The above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). Unless otherwise specified, the same secondary substituent as the above-mentioned substituent may be used. Examples of the unsaturated hydrocarbon group include an alkenyl group having 2 to 30 carbon atoms and an alkynyl group having 2 to 30 carbon atoms.

[0050] Examples of the alkenyl group having 2 to 30 carbon atoms include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a 1-octenyl group, a 2-octenyl group, a 1-undecenyl group, a 1-pentadecenyl group, and a 3-pentadecenyl group. Examples of the alkyl group include a 7-pentadecenyl group, a 1-octadecenyl group, a 2-octadecenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a 1,3-butadienyl group, a 1,4-butadienyl group, a hexa-1,3-dienyl group, a hexa-2,5-dienyl group, a pentadeca-4,7-dienyl group, a hexa-1,3,5-trienyl group, and a pentadeca-1,4,7-trienyl group.

[0051] Examples of the alkynyl group having 2 to 30 carbon atoms include an ethynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, and a 1,3-butadiynyl group.

[0052] Examples of the phenylenediamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

[0053] The naphthalene diamine compound refers to a compound consisting of a naphthalene ring having two amino groups, and the naphthalene ring may have one to three optional substituents. The substituents are the same as those that the phenylenediamine compound may have. Examples of the naphthalene diamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

[0054] A dianiline compound refers to a compound containing two aniline structures in the molecule, and each of the two benzene rings in the two aniline structures may further optionally have one to three substituents. The substituents here are the same as the substituents that a phenylenediamine compound may have. The two aniline structures in the dianiline compound may be bonded via a direct bond and / or one or two linker structures having 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur, and nitrogen atoms. Dianiline compounds also include those in which two aniline structures are bonded by two bonds.

[0055] Specific examples of the "linker structure" in the dianiline compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CH=CH-, -O-, -S-, -CO-, and -SO2- , -NH-, -Ph-, -Ph-Ph-, -C(CH3)2-Ph-C(CH3)2-, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, -Ph-CO-O-Ph-, -C(CH3)2-Ph-C(CH3)2-, groups represented by the following formulas (I) and (II), and groups consisting of combinations thereof. In this specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group.

[0056] [ka]

[0057] In one embodiment, specific examples of the dianiline compound include 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-biphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-biphenyl, 4,4'-diaminodiphenyl ether ... α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene)dianiline, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl Examples of the fluorene include 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, and 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan, and preferably 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan.

[0058] In another embodiment, examples of the dianiline compound include diamine compounds represented by the following formula (C-1).

[0059] [ka] (In formula (C-1), R 1 ~R 8are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X 9 -R 9 , or -X 10 -R 10 indicates R 1 ~R 8 At least one of the -X 10 -R 10 and X 9 are each independently a single bond, -NR 9’ -, -O-, -S-, -CO-, -SO2-, -NR 9’ CO-, -CONR 9’ -, -OCO-, or -COO-, and R 9 each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R 9’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group; X 10 each independently represents a single bond, -(substituted or unsubstituted alkylene group), -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO-, or -COO-; R 10 each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0060] R in formula (C-1) 9 and R 9’ The alkyl group represented by the formula (I) refers to a linear, branched, or cyclic monovalent aliphatic saturated hydrocarbon group. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred. Examples of such alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, and a cyclohexyl group.

[0061] R in formula (C-1) 9 and R 9’The alkenyl group represented by the formula (I) refers to a linear, branched, or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 or 3 carbon atoms. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, and 2-cyclohexenyl.

[0062] The substituent of the alkyl group in the "substituted or unsubstituted alkyl group" and the substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

[0063] An alkoxy group refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferable, and an alkoxy group having 1 to 3 carbon atoms is more preferable. Examples of such alkoxy groups include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group.

[0064] X in formula (C-1) 10The alkylene group represented by refers to a straight-chain, branched-chain, or cyclic divalent aliphatic saturated hydrocarbon group, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include -CH-, -CH-CH-, -CH(CH)-, -CH-CH-CH-, -CH-CH(CH)-, -CH(CH)-CH-, -C(CH)-, -CH-CH-CH-CH-, -CH-CH-CH(CH)-, -CH-CH(CH)-CH-, -CH(CH)-CH-CH-, -CH-C(CH)-, and -C(CH)-CH-. The substituent of the alkylene group in the "substituted or unsubstituted alkylene group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

[0065] R in formula (C-1) 10 The aryl group represented by is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group, and preferably a phenyl group. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, and examples include a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, and a sulfo group. The number of substituents is preferably 1 to 3, and more preferably 1.

[0066] R in formula (C-1) 10The heteroaryl group represented by the formula (I) is an aromatic heterocyclic group having 1 to 4 heteroatoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom. The heteroaryl group is preferably a 5- to 12-membered (preferably 5- or 6-membered) monocyclic, bicyclic, or tricyclic (preferably monocyclic) aromatic heterocyclic group. Examples of such heteroaryl groups include a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, a 1,2,3-oxadiazolyl group, a 1,2,4-oxadiazolyl group, a 1,3,4-oxadiazolyl group, a furazanyl group, a 1,2,3-thiadiazolyl group, a 1,2,4-thiadiazolyl group, a 1,3,4-thiadiazolyl group, a 1,2,3-triazolyl group, a 1,2,4-triazolyl group, a tetrazolyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, etc. Substituents of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" are the same as the substituents of the aryl group in the "substituted or unsubstituted aryl group".

[0067] R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X 9 -R 9 , or -X 10 -R 10 Indicates R 1 ~R 8 are preferably each independently a hydrogen atom or -X 10 -R 10 is.

[0068] R 1 ~R 8 At least one of the -X 10 -R 10 Preferably, R 1 ~R 8 One or two of them are -X 10 -R 10 and more preferably, R 5 ~R 8 One or two of them are -X 10 -R 10and more preferably, R 5 and R 7 One or two of them are -X 10 -R 10 is.

[0069] In one embodiment, preferably, R 1 ~R 8 One or two of them are -X 10 -R 10 and R 1 ~R 8 The other is a hydrogen atom, and more preferably, R 5 ~R 8 One or two of them are -X 10 -R 10 and R 1 ~R 8 The other is a hydrogen atom, and more preferably, R 5 and R 7 One or two of them are -X 10 -R 10 and R 1 ~R 8 The rest are hydrogen atoms.

[0070] X 9 are each independently a single bond, -NR 9’ -, -O-, -S-, -CO-, -SO2-, -NR 9’ CO-, -CONR 9’ -, -OCO-, or -COO-. R 9 X each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. 9 is preferably a single bond.

[0071] R 9’ R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. 9 is preferably a substituted or unsubstituted alkyl group.

[0072] X 10X each independently represents a single bond, -(substituted or unsubstituted alkylene group), -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO-, or -COO-. 10 is preferably a single bond.

[0073] R 10 R each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. 10 is preferably a substituted or unsubstituted aryl group.

[0074] In one embodiment, the diamine compound represented by formula (C-1) is preferably a compound represented by the following formula (C-2), and more preferably a compound represented by the following formula (C-3) (5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate). [ka] (In the formula, R 1 ~R 6 and R 8 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X 9 -R 9 These symbols are as explained above.) [ka]

[0075] The diamine compound may be commercially available or may be synthesized by a known method. For example, the diamine compound represented by formula (C-1) can be synthesized by the synthesis method described in Japanese Patent No. 6240798 or a method equivalent thereto. The diamine compound may be used alone or in combination of two or more.

[0076] The acid anhydride used to prepare component (C) is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of aromatic tetracarboxylic dianhydrides include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, and diphthalic dianhydride, with diphthalic dianhydride being preferred.

[0077] Benzenetetracarboxylic dianhydride means a dianhydride of benzene having four carboxy groups, and further, the benzene ring here may have 1 to 3 optional substituents, such as a halogen atom, a cyano group, and -X 13 -R 13 (The same definition as in the following formula (C-4)) Specific examples of the benzenetetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

[0078] Naphthalenetetracarboxylic dianhydride refers to a dianhydride of naphthalene having four carboxy groups, and the naphthalene ring here may optionally have 1 to 3 substituents, such as halogen atoms, cyano groups, and -X 13 -R 13 (The same definition as in the following formula (C-4)) Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

[0079] Anthracenetetracarboxylic dianhydride refers to a dianhydride of anthracene having four carboxy groups, and the anthracene ring here may optionally have 1 to 3 substituents, such as halogen atoms, cyano groups, and -X 13 -R 13(The same definition as in the following formula (C-4)) is preferred. Specific examples of the anthracenetetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride.

[0080] Diphthalic dianhydride refers to a compound containing two phthalic anhydrides in the molecule, and each of the two benzene rings in the two phthalic anhydrides may have one to three optional substituents. The substituents include halogen atoms, cyano groups, and -X 13 -R 13 (the same as the definition in the following formula (C-4)) is preferred. The two phthalic anhydrides in the diphthalic dianhydride can be bonded to each other by a direct bond or via a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0081] An example of the diphthalic dianhydride is a compound represented by formula (C-4). [ka] (In the formula, R 11 and R 12 are each independently a halogen atom, a cyano group, a nitro group, or -X 13 -R 13 indicates, X 13 are each independently a single bond, -NR 13’ -, -O-, -S-, -CO-, -SO2-, -NR 13’ CO-, -CONR 13’ -, -OCO-, or -COO-; R 13 each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R 13’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y represents a single bond or a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms; n1 and m1 each independently represent an integer of 0 to 3.

[0082] Y is preferably a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. n1 and m1 are preferably 0.

[0083] The "linker structure" in Y has 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The "linker structure" is preferably -[A-Ph] a -A-[Ph-A] b - (wherein each A independently represents a single bond, -(substituted or unsubstituted alkylene group)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-, and each a and b independently represents an integer of 0 to 2 (preferably 0 or 1).)

[0084] Specific examples of the "linker structure" for Y include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CO-, -SO2-, -Ph-, -O-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, etc.

[0085] Specific examples of diphthalic dianhydrides include 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethynylidene-4,4'-diphthalic Acid dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, and the like.

[0086] The aromatic tetracarboxylic dianhydride may be a commercially available product, or may be synthesized by a known method or a method similar thereto. The aromatic tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0087] In one embodiment, the acid anhydride used to prepare the component (C) may include other acid anhydrides in addition to the aromatic tetracarboxylic dianhydride.

[0088] Specific examples of other acid anhydrides include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, cyclohexane-1,2,3,4-tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic acid dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, and sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride.

[0089] The proportion of structures derived from aromatic tetracarboxylic dianhydride in 100 mol% of all structures derived from acid anhydrides constituting component (C) is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, even more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 100 mol%.

[0090] The component (C) preferably has a structural unit represented by the following general formula (C-5). [ka] (In general formula (C-5), R 51 represents a single bond or a residue derived from an acid anhydride, and R 52 represents a single bond or a residue derived from a diamine compound.

[0091] R 51 represents a single bond or a residue derived from an acid anhydride, and is preferably a residue derived from an acid anhydride. 51The residue derived from an acid anhydride represented by the formula (I) refers to a divalent group obtained by removing two oxygen atoms from an acid anhydride. The acid anhydride is as described above.

[0092] R 52 represents a single bond or a residue derived from a diamine compound, and is preferably a residue derived from a diamine compound. 52 The residue derived from a diamine compound represented by the formula (I) refers to a divalent group obtained by removing two amino groups from a diamine compound. The diamine compound is as described above.

[0093] Component (C) can be prepared by a conventionally known method. For example, a method of heating a mixture of a diamine compound, an acid anhydride, and a solvent to cause the mixture to react is exemplified. The amount of the diamine compound added is typically 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents, relative to the acid anhydride.

[0094] Examples of solvents used in preparing component (C) include amide solvents such as N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone; ketone solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ester solvents such as γ-butyrolactone; and hydrocarbon solvents such as cyclohexane and methylcyclohexane. Furthermore, in preparing component (C), an imidization catalyst, an azeotropic dehydrating solvent, an acid catalyst, and the like may be used as needed. Examples of imidization catalysts include tertiary amines such as triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N,N-dimethyl-4-aminopyridine, and pyridine. Examples of azeotropic dehydrating solvents include toluene, xylene, and ethylcyclohexane. Examples of acid catalysts include acetic anhydride. The amounts of the imidization catalyst, azeotropic dehydrating solvent, acid catalyst, and the like used can be determined appropriately by those skilled in the art. The reaction temperature for preparing the component (C) is usually 100 to 250°C.

[0095] The weight average molecular weight of component (C) is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less.

[0096] From the viewpoint of improving the minimum melt viscosity of the resin composition and the pattern embedding ability, flatness, toughness, and plasma processability of the cured product, the content of component (C) is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, 10% by mass or more, and 15% by mass or less, more preferably 14.5% by mass or less, and even more preferably 14% by mass or less, based on 100% by mass of nonvolatile components in the resin composition.

[0097] <(D) Resin having a phenylene ether skeleton represented by formula (D)> The resin composition contains, as component (D), a resin having a phenylene ether skeleton represented by formula (D). By including component (D) in the resin composition, the insulating reliability of the cured product can be improved. In addition, plasma processability can be improved. [ka] (In formula (D), R b each independently represents a substituent, b1 represents an integer of 0 to 4. * indicates a binding site.

[0098] R b each independently represents a substituent. The substituent is the same as the substituent that the above-mentioned phenylenediamine compound may have, and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0099] b1 represents an integer of 0 to 4, preferably 1 to 4, more preferably 2 or 3, and even more preferably 2.

[0100] The component (D) is not particularly limited as long as it is a resin having a phenylene ether skeleton represented by formula (D). From the viewpoint of significantly achieving the effects of the present invention, the component (D) is preferably a resin having, in addition to the phenylene ether skeleton represented by formula (D), a radically polymerizable unsaturated group or a hydroxyl group that contributes to the curing reaction. Phenyl It is preferable that the component (D) contains two or more radically polymerizable unsaturated groups. Examples of radically polymerizable unsaturated groups include vinyl groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, and maleoyl groups. It is preferable that the component (D) contains two or more radically polymerizable unsaturated groups.

[0101] In one embodiment, the component (D) includes a compound represented by the following formula (D-1): [ka] (In formula (D-1), X's each independently represent a monovalent group having a radically polymerizable unsaturated group or a hydroxyphenyl group which may have a substituent; L 3 represents a divalent linking group, R D11 and R D12 each independently represents a substituent, nD11 and nD12 each independently represent an integer of 0 to 4, nD1 and nD2 each independently represent an integer of 0 to 300, provided that at least one of them is an integer of 1 or more. Multiple Xs may be the same or different, and R D11 If there are multiple, they may be the same or different, and R D12 If there are multiple, they may be the same or different.)

[0102] Each X independently represents a monovalent group having a radically polymerizable unsaturated group or a hydroxyphenyl group which may have a substituent. The monovalent group having a radically polymerizable unsaturated group represented by X is not particularly limited as long as it has a radically polymerizable unsaturated group, but from the viewpoint of significantly achieving the effects of the present invention, it is preferably a monovalent group represented by the following formula (D-2):

[0103] [ka] (In formula (D-2), R D1 , R D2 and R D3 each independently represents a hydrogen atom or an alkyl group, R D4 represents an alkylene group, R D13 represents a substituent, nD3 and nD4 each independently represent 0 or 1; nD13 represents an integer of 0 to 4, * indicates the binding site. D1 , R D2 , R D3 and R D4 Each of R may independently have a substituent. D13 If there are multiple, they may be the same or different.)

[0104] R D1 , R D2 and R D3 The number of carbon atoms in the alkyl group represented by R is preferably 1 to 10, more preferably 1 to 6 or 1 to 4, and even more preferably 1 or 2. The number of carbon atoms does not include the number of carbon atoms in the substituent. D1 is preferably a hydrogen atom or an alkyl group, and R D2 and R D3 is preferably a hydrogen atom.

[0105] R D4 The number of carbon atoms in the alkylene group represented by the following formula is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0106] nD13 is preferably 0 to 2, more preferably 0 or 1. When nD13 is an integer of 1 or more, R D13 The substituent represented by the formula (I) is preferably an alkyl group.

[0107] R D1 When R is a hydrogen atom, nD3 is preferably 0. D1 When is an alkyl group, nD3 is preferably 1.

[0108] Furthermore, when nD3 is 0, nD4 is preferably 1, and when nD3 is 1, nD4 is preferably 0.

[0109] The optionally substituted hydroxyphenyl group represented by X is preferably a monovalent group represented by the following formula (D-3), from the viewpoint of achieving the effects of the present invention more significantly. [ka] (In formula (D-3), R D130 represents a substituent, nD130 represents an integer of 0 to 4, * indicates the binding site. D130 If there are multiple, they may be the same or different.)

[0110] nD130 represents an integer of 0 to 4, preferably 0 to 2, more preferably 1 or 2, and even more preferably 2. When nD130 is an integer of 1 or more, R D130 The substituent represented by the formula (I) is preferably an alkyl group, more preferably a methyl group.

[0111] In formula (D-1), L 3 The divalent linking group represented by the formula (D-4) is not particularly limited as long as it is a divalent group consisting of one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. Specifically, the divalent linking group is preferably a divalent linking group represented by the following formula (D-4):

[0112] [ka]

[0113] In formula (D-4), Y1 represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; Ring Z 2 represents an optionally substituted non-aromatic ring or an optionally substituted aromatic ring, nB15 represents an integer of 0 to 5 (preferably 0 to 3), * indicates the binding site. Y 1 Yakan Z 2 Each of Y may independently have a substituent. 1 When there are multiple rings, they may be the same or different, and the ring Z 2 When there are multiple, they may be the same or different.

[0114] Specific examples of divalent linking groups include, but are not limited to, -CH2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH2CH3)2-, -O-, -CO-, -S-, -SO-, and -SO2-, as well as divalent organic groups represented by the following: [ka]

[0115] In formula (D-1), R D11 and R D12 each independently represents a substituent. The substituent is the same as the substituent that the above-mentioned phenylenediamine compound may have, and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0116] In formula (D-1), nD11 and nD12 are each independently preferably 1 to 4, more preferably 2 or 3, and even more preferably 2. When nD11 and nD12 are integers of 1 or more, R D11 and RD12 The substituent represented by the formula (I) is preferably an alkyl group.

[0117] In formula (D-1), nD1 and nD2 are each independently preferably 1 or more, and preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less or 10 or less.

[0118] From the viewpoint of achieving the remarkable effects of the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) of component (D) are preferably 2500 or less, more preferably 2300 or less, and even more preferably 2200, 2000 or less, or 1900 or less. There are no particular restrictions on the lower limit of the molecular weight, and it can be, for example, 500 or more, 700 or more, etc. The Mw and Mn of component (D) can be measured as polystyrene equivalent values ​​by gel permeation chromatography (GPC).

[0119] A preferred example of the component (D) is a compound represented by the following formula (D-5).

[0120] [ka] (In formula (D-5), R D4 , R D11 , R D12 , L 3 , nD1 and nD2 are as explained above.)

[0121] Among them, L 3 is preferably a divalent group represented by the following formula (D-6).

[0122] [ka] (In formula (D-6), R D14 and R D15 each independently represents an alkyl group or a phenyl group, nD14 and nD15 each independently represent an integer of 0 to 4, * indicates the binding site.)

[0123] R D14 and R D15 The number of carbon atoms in the alkyl group represented by R is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2. D14 and R D15 is preferably an alkyl group.

[0124] nD14 and nD15 are each independently preferably 1 to 4, more preferably 2 or 3.

[0125] An example of the compound represented by formula (D-5) is a compound represented by the following formula (D-7): In the formula, nD1 and nD2 are as explained above. An example of a commercially available product of the compound represented by formula (D-7) is "OPE-2St" manufactured by Mitsubishi Gas Chemical Company, Inc.

[0126] [ka]

[0127] Another preferred example of the component (D) is a compound represented by the following formula (D-8).

[0128] [ka]

[0129] In formula (D-8), R D2 , R D11 , R D12 , R D13 , L 3 , nD1 and nD2 are as explained above.

[0130] Among them, L 3is preferably selected from the group consisting of an alkylene group, an alkenylene group, -O-, -CO-, -CS-, -SO-, and -SO2-, more preferably an alkylene group, and even more preferably an isopropylidene group (-C(CH3)2-).

[0131] Examples of the compound represented by formula (D-8) include compounds represented by the following formula (D-9): 3 , nD1 and nD2 are as explained above. Commercially available products of the compound represented by formula (D-9) include, for example, "NORYL SA9000" manufactured by SABIC.

[0132] [ka]

[0133] Another preferred example of the component (D) is a compound represented by the following formula (D-10): 3 , nD1 and nD2 are as explained above. Commercially available products of the compound represented by formula (D-10) include, for example, "NORYL SA90" manufactured by SABIC.

[0134] [ka]

[0135] From the viewpoint of improving insulation reliability and plasma processability, the content of component (D) is preferably 5% by mass or more, more preferably 5.5% by mass or more, and even more preferably 6% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 7% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0136] From the viewpoint of significantly achieving the effects of the present invention, the total content of the (C) component and the (D) component is preferably 10% by mass or more, more preferably 12% by mass or more, and even more preferably 15% by mass or more, and is preferably 25% by mass or less, more preferably 23% by mass or less, and even more preferably 20% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0137] <(E) Hardener> The resin composition may contain a curing agent (E) as component (E). Component (E) typically has the function of reacting with component (A) to cure the resin composition. Component (E) may be used alone or in combination of two or more types in any ratio.

[0138] As the component (E), a compound capable of reacting with the component (A) to cure the resin composition can be used, and examples thereof include active ester curing agents, phenolic curing agents, benzoxazine curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, cyanate ester curing agents, etc. Among these, from the viewpoint of significantly obtaining the effects of the present invention, any of the active ester curing agents, phenolic curing agents, benzoxazine curing agents, and carbodiimide curing agents is preferred, and any of the active ester curing agents, phenolic curing agents, and carbodiimide curing agents is more preferred.

[0139] Examples of active ester curing agents include curing agents having one or more active ester groups per molecule. Among these, preferred active ester curing agents are compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound are more preferred.

[0140] 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.

[0141] Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0142] Preferred specific examples of active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and active ester compounds containing a benzoylated product of phenol novolac. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

[0143] Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451," "EXB9460," "EXB9460S," "HPC-8000," "HPC-8000H," "HPC-8000-65T," "HPC-8000H-65TM," "EXB-8000L," and "EXB-8000L-65TM" (manufactured by DIC Corporation); and active ester compounds containing a naphthalene structure, such as "HPC-8150-60T," "HPC-8150-62T," "EXB-8150-65T," "EXB-8100L-65T," "EXB9416- 70BK" and "EXB-8151-62T" (manufactured by DIC Corporation); an active ester compound containing an acetylated phenol novolac is "DC808" (manufactured by Mitsubishi Chemical Corporation); an active ester compound containing a benzoylated phenol novolac is "YLH1026" (manufactured by Mitsubishi Chemical Corporation); an active ester-based curing agent which is an acetylated phenol novolac is "DC808" (manufactured by Mitsubishi Chemical Corporation); and active ester-based curing agents which are benzoylated phenol novolac are "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

[0144] Examples of phenolic curing agents include curing agents having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (such as a benzene ring or a naphthalene ring) per molecule. Among these, compounds having a hydroxyl group bonded to a benzene ring are preferred. Furthermore, from the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac structure are preferred. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred. In particular, from the viewpoint of achieving high levels of heat resistance, water resistance, and adhesion, triazine skeleton-containing phenolic novolac curing agents are preferred.

[0145] Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700," "MEH-7810," "MEH-7851," and "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-495V," and "SN-375" manufactured by Nippon Steel Chemical & Material Co., Ltd. and "SN-395" manufactured by DIC Corporation; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", and "KA-1165" manufactured by Gun-ei Chemical Co., Ltd.; and "GDP-6115L", "GDP-6115H", and "ELPC75" manufactured by Gun-ei Chemical Co., Ltd.

[0146] Specific examples of benzoxazine curing agents include "ODA-BOZ" manufactured by JFE Chemical Corporation, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemicals Corporation.

[0147] Specific examples of carbodiimide curing agents include "V-03", "V-05", and "V-07" manufactured by Nisshinbo Chemical Inc.; and Stavaxol (registered trademark) P manufactured by Rhein Chemie.

[0148] Examples of acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone. Examples of suitable curing agents include tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resins (copolymers of styrene and maleic acid). Commercially available acid anhydride curing agents are also available, such as "MH-700" manufactured by New Japan Chemical Co., Ltd.

[0149] Examples of the amine curing agent include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among these, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxybenzoyl). Examples of suitable amine curing agents include 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone. Commercially available amine curing agents may be used, such as "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0150] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac, cresol novolac, etc.; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both are phenol novolac type multifunctional cyanate ester resins); "ULL-950S" (multifunctional cyanate ester resin); "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer); and the like.

[0151] From the viewpoint of significantly obtaining the effects of the present invention, the content of the (E) curing agent is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of non-volatile components in the resin composition.

[0152] When the number of epoxy groups in component (A) is taken as 1, the number of active groups in the (E) curing agent is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and preferably 1 or less, more preferably 0.5 or less, even more preferably 0.2 or less. Here, "the number of epoxy groups in component (A)" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of component (A) present in the resin composition by the epoxy equivalent. Furthermore, "the number of active groups in the (E) curing agent" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the (E) curing agent present in the resin composition by the active group equivalent. When the number of epoxy groups in component (A) is taken as 1, the desired effects of the present invention can be significantly achieved by having the number of active groups in the (E) curing agent within the above range.

[0153] <(F) Curing accelerator> The resin composition may contain a curing accelerator (F) as component (F). Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Amine-based curing accelerators and imidazole-based curing accelerators are preferred, and amine-based curing accelerators are more preferred. One type of curing accelerator may be used alone, or two or more types may be used in combination.

[0154] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0155] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0156] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, Examples of the imidazole compound include imidazole compounds such as 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0157] As the imidazole-based curing accelerator, commercially available products may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0158] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of suitable biguanide include 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0159] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0160] From the viewpoint of significantly achieving the effects of the present invention, the content of the (F) curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more, and is preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0161] <(G) Other additives> In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include resin additives such as thermoplastic resins; flame retardants; organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; thickeners; antifoaming agents; leveling agents; adhesion promoters; and colorants. These additives may be used alone or in combination of two or more in any ratio. The content of each additive can be determined appropriately by those skilled in the art.

[0162] The method for preparing the resin composition is not particularly limited, and examples thereof include a method in which the ingredients are mixed and dispersed, if necessary, together with a solvent, using a rotary mixer or the like.

[0163] <Physical properties and applications of resin compositions> The resin composition contains (A) an epoxy resin, (B) an inorganic filler having an average particle size of 0.1 μm or less, (C) a resin having an imide skeleton represented by formula (C), and (D) a resin having a phenylene ether skeleton represented by the following formula (D), wherein the content of component (B) is 69% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition, and the content of component (C) is 1% by mass or more and 15% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. Because the resin composition contains a combination of components (A) to (D), it is possible to obtain a cured product that exhibits excellent toughness, insulation reliability, and plasma processability. Furthermore, the resin composition typically exhibits a low minimum melt viscosity. Furthermore, the cured product of the resin composition typically exhibits excellent pattern embedding ability and flatness.

[0164] The resin composition of the present invention typically exhibits the characteristic of a low minimum melt viscosity. Therefore, it typically results in an insulating layer with excellent pattern embedding properties and flatness. The minimum melt viscosity of the resin composition is preferably 5,000 poise or less, more preferably 4,500 poise or less, and even more preferably 4,000 poise or less, and is preferably 100 poise or more, more preferably 500 poise or more, and even more preferably 1,000 poise or more. Here, the term "minimum melt viscosity" refers to the minimum melt viscosity at 60°C to 200°C. The minimum melt viscosity can be measured using a dynamic viscoelasticity measuring device. The minimum melt viscosity can be measured according to the method described in the Examples below.

[0165] A cured product obtained by thermally curing a resin composition at 100°C for 30 minutes and then at 180°C for 30 minutes typically exhibits excellent pattern embedding properties. Therefore, the cured product typically produces an insulating layer with excellent pattern embedding properties. Specifically, a resin composition layer of a resin sheet, as described below, is laminated onto an inner layer circuit board. After laminating the resin composition layer onto the inner layer circuit board, the resin composition layer is thermally cured under the above-described thermal curing conditions to obtain an insulating layer. At this time, the insulating layer is typically sufficiently embedded in the inner layer circuit board. Pattern embedding properties can be evaluated by measuring the method described in the Examples section below.

[0166] A cured product obtained by thermally curing a resin composition at 100°C for 30 minutes and then at 180°C for 30 minutes typically exhibits excellent flatness. Therefore, the cured product typically produces an insulating layer with a low maximum cross-sectional height Rt of the surface of the cured product. The maximum cross-sectional height Rt is preferably less than 1.6 μm, more preferably 1.3 μm or less, and even more preferably less than 1.3 μm. The lower limit is not particularly limited, but may be 0.01 μm or more. Flatness can be measured according to the method described in the Examples below.

[0167] A cured product obtained by thermally curing the resin composition at 180°C for 90 minutes exhibits excellent toughness. Therefore, the cured product provides an insulating layer with excellent toughness. Toughness is measured by measuring the number of folding times in the MIT test. The number of folding times is preferably 300 times or more, more preferably 320 times or more, and even more preferably 350 times or more. There is no particular upper limit, but it can be 10,000 times or less. Toughness can be evaluated according to the method described in the Examples below.

[0168] The cured product obtained by thermally curing the resin composition at 100°C for 30 minutes and then at 180°C for 30 minutes exhibits excellent insulating reliability. Therefore, the cured product provides an insulating layer with excellent insulating reliability. The insulating reliability is preferably 1.00 x 10 8 Ω or more, preferably 5.00×10 8 Ω or more, more preferably 1.00×10 9 Ω or more. There is no particular upper limit, but it is 1.00×10 50 The insulation reliability can be evaluated by measurement according to the method described in the examples below.

[0169] The cured product obtained by thermally curing the resin composition at 100°C for 30 minutes and then at 180°C for 30 minutes exhibits excellent plasma processability. Therefore, the cured product can form a uniform and continuous conductor layer in a via hole or trench. Observation of the cross section of the insulating layer using an SEM confirms that a copper layer is formed uniformly and continuously on the wall surfaces of the trench and via hole formed in the insulating layer. Furthermore, the processing speed is preferably 0.5 μm / min or more, more preferably 0.6 μm / min or more. Plasma processability can be evaluated according to the method described in the Examples below.

[0170] The resin composition of the present invention is suitable as a resin composition for forming via holes or trenches in an insulating layer of a printed wiring board by plasma treatment. The resin composition of the present invention is also suitable as a resin composition for insulating purposes, and particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition is also suitable as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer) to form a conductor layer (including a rewiring layer) formed on the insulating layer. The resin composition can also be used in a wide range of applications where a resin composition can be used, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, and system-in-packages.

[0171] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to this embodiment is also suitable as a resin composition for forming a rewiring formation layer as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation layer), and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the encapsulation layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0172] The above-mentioned resin composition has excellent pattern embedding properties and can therefore be used when the printed wiring board is a circuit board with built-in components.

[0173] [Resin sheet] The resin sheet includes a support and a resin composition layer formed from a resin composition provided on the support. The resin composition is as described above.

[0174] The resin composition layer contains a resin composition with excellent insulating reliability, so it can be made thin. The thickness of the resin composition layer is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 40 μm or less, 30 μm or less, or 20 μm or less, from the viewpoint of being able to provide a cured product with excellent insulating properties even when it is thin. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 1 μm or more, 5 μm or more, etc.

[0175] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0176] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0177] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0178] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0179] The support may also be a support with a release layer, which has a release layer on the surface that bonds with the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including PET films with a release layer primarily composed of an alkyd resin-based release agent, such as "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited; and "U2-NR1" manufactured by DuPont Films.

[0180] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0181] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0182] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying this resin varnish to a support using a die coater or the like, and then drying it to form a resin composition layer.

[0183] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

[0184] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0185] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0186] [Printed wiring board manufacturing method] The method for producing a printed wiring board of the present invention comprises: (A) forming an insulating layer containing a cured product of a resin composition on an inner layer circuit board; and (B) A step of performing plasma treatment on the surface of the insulating layer to form via holes or trenches.

[0187] In the printed wiring board of the present invention, the insulating layer contains a cured product of the resin composition of the present invention, so that via holes or trenches can be formed in the insulating layer by plasma treatment, thereby suppressing the occurrence of irregularities on the side and bottom surfaces of the via holes and trenches and improving the processing speed.

[0188] In addition to the steps (A) and (B), the method for producing a printed wiring board of the present invention may further include, as needed, (C) a step of roughening the surface of the insulating layer; (D) forming a conductive layer on the surface of the insulating layer.

[0189] It is preferable to perform steps (A) and (B) in this order, and more preferable to perform steps in the order of steps (A), (B), (C), and (D). Each step of the method for producing a printed wiring board will be described below.

[0190] <Process (A)> Step (A) is a step of forming an insulating layer containing a cured product of a resin composition on an inner layer circuit board. In step (A), the insulating layer is usually formed on a main surface of the inner layer circuit board. The main surface of the inner layer circuit board refers to the surface of the inner layer circuit board on which the insulating layer is provided.

[0191] Step (A) may include (A-1) preparing an inner circuit board. The inner circuit board typically comprises a support substrate and a metal layer provided on the surface of the support substrate. The metal layer is exposed on the main surface of the inner circuit board.

[0192] Examples of materials for the support substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, etc. Examples of materials for the metal layer include copper foil, copper foil with a carrier, and materials for the conductor layer described below, with copper foil being preferred.

[0193] Furthermore, the step (A) may include the step (A-2) of preparing a resin sheet. The resin sheet is as described above.

[0194] In step (A), for example, a resin composition layer of a resin sheet is laminated on a main surface of an inner layer circuit board, and the resin composition layer is thermally cured to form an insulating layer.

[0195] The lamination of the inner layer circuit board and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer circuit board from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer circuit board (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS end plate) or a metal roll (SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer circuit board.

[0196] The lamination of the inner layer circuit board and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of 26.7hPa or less.

[0197] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0198] After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0199] The support may be removed after laminating the resin sheet and before thermal curing, or may be removed after step (A).

[0200] After laminating the resin sheet on the inner layer circuit board, the resin composition layer is heat-cured to form an insulating layer. The heat-curing conditions for the resin composition layer are not particularly limited, and conditions typically employed for forming insulating layers for printed wiring boards may be used.

[0201] For example, although the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0202] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C or higher but lower than 120°C (preferably 60°C or higher but 115°C or lower, more preferably 70°C or higher but 110°C or lower) for 5 minutes or longer (preferably 5 to 150 minutes, more preferably 15 to 120 minutes, and even more preferably 15 to 100 minutes).

[0203] The thickness of the insulating layer is preferably 100 μm or less, more preferably 50 μm or less, further preferably 40 μm or less, 30 μm or less, or 20 μm or less, and is preferably 1 μm or more, more preferably 5 μm or more.

[0204] Instead of forming an insulating layer using a resin sheet, an insulating layer may be formed by applying a resin composition directly to the main surface of the inner layer circuit board. The conditions for forming the insulating layer in this case are the same as those for forming an insulating layer using a resin sheet. The resin composition to be applied is as described above.

[0205] After step (A) is completed and before step (B) is performed, a step of forming a mask for plasma treatment on the insulating layer may be performed to effectively form via holes or trenches in the insulating layer. The step of forming the mask may include, for example, (A-3) a step of laminating a dry film on the insulating layer or a support, and (A-4) a step of exposing and developing the dry film using a photomask to obtain a patterned dry film.

[0206] In step (A-3), a dry film is laminated onto the insulating layer or support formed on the main surface of the inner layer circuit board. The lamination conditions for the insulating layer and the dry film may be the same as the lamination conditions for the inner layer circuit board and the resin sheet.

[0207] The dry film used in step (A-3) may be any film that can be patterned by exposure and development, and preferably is resistant to the plasma treatment in step (B). A photosensitive dry film made of a photoresist composition may be used as the dry film. Examples of such dry films include dry films made of resins such as novolac resins and acrylic resins.

[0208] From the viewpoint of improving the processability of via holes, the thickness of the dry film is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more, and is preferably 100 μm or less, more preferably 70 μm or less, and even more preferably 50 μm or less.

[0209] In step (A-4), exposure is performed by irradiating the dry film with active energy rays through a photomask having a predetermined pattern. The details of exposure are usually to irradiate the surface of the dry film with active energy rays through a photomask to photocure the exposed portion of the dry film. Examples of active energy rays include ultraviolet rays, visible light, electron beams, and X-rays, with ultraviolet rays being preferred. The dose and duration of ultraviolet irradiation can be appropriately set depending on the dry film. Examples of exposure methods include contact exposure, in which a mask pattern is brought into close contact with the dry film and exposed, and non-contact exposure, in which a mask pattern is not brought into close contact with the dry film and exposed using parallel light.

[0210] After exposure, development is performed to remove either the exposed or unexposed portions of the dry film (usually the unexposed portions) to form a patterned dry film as a mask. Development may be performed by either wet development or dry development. Examples of development methods include dipping, puddling, spraying, brushing, and scraping.

[0211] In step (B) described below, plasma treatment is carried out using the patterned dry film as a mask to form via holes or trenches.

[0212] <Process (B)> Step (B) is a step of performing a plasma treatment on the surface of the insulating layer to form a via hole or a trench in the insulating layer. Since the insulating layer contains a cured product of the resin composition of the present invention, even if the via hole or trench is formed by the plasma treatment, the occurrence of unevenness on the side and bottom surfaces of the via hole or trench can be suppressed. It is also possible to improve the processing speed of the plasma treatment.

[0213] In the plasma treatment, the surface of the insulating layer is treated with plasma generated by introducing a gas into a plasma generator, thereby forming a via hole or a trench on the surface of the insulating layer. The method of generating plasma is not particularly limited, and examples thereof include microwave plasma in which plasma is generated by microwaves, high-frequency plasma using high frequency waves, atmospheric pressure plasma generated under atmospheric pressure, and atmospheric pressure plasma generated in a vacuum, with atmospheric pressure plasma generated in a vacuum being preferred.

[0214] The plasma used in step (B) is preferably RF plasma excited by high frequency waves.

[0215] The gas to be converted into plasma can be a gas that etches only the cured resin component in the insulating layer and removes the inorganic filler. Such gases are preferably CF4, Ar, O2, N2, or a gas consisting of a combination thereof, more preferably a mixed gas containing O2 and CF4, Ar, and N2, and even more preferably a mixed gas of CF4 and O2.

[0216] The mixing ratio of the mixed gas containing O2 and CF4, Ar, and N2 (CF4, Ar, N2 / O2: unit: sccm) is preferably 0.1 / 10 to 1 / 1, more preferably 0.5 / 10 to 1 / 2, and more preferably 1 / 10 to 1 / 2, from the viewpoint of making the thickness of the conductive layer formed in the via hole or trench uniform.

[0217] In order to obtain the effects of the present invention significantly, the pressure inside the chamber during plasma treatment is preferably 50 Pa or more, more preferably 75 Pa or more, even more preferably 100 Pa or more, and is preferably 300 Pa or less, more preferably 250 Pa or less, even more preferably 200 Pa or less.

[0218] The irradiation time in the plasma treatment is preferably 1 minute or more, more preferably 2 minutes or more, and even more preferably 3 minutes or more, since the insulating layer contains a resin composition that is excellent in plasma processability. The upper limit is not particularly limited, but is preferably 20 minutes or less, more preferably 15 minutes or less, and even more preferably 10 minutes or less.

[0219] In the present invention, the via hole or trench is formed by plasma treatment, so the opening diameter of the via hole or trench can be made small. The opening diameter is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, or 20 μm or less. The lower limit is not particularly limited, but can be 1 μm or more.

[0220] <Process (C)> Step (C) is a step of roughening the surface of the insulating layer, and more specifically, a step of removing foreign matter, such as inorganic filler, that has fallen off in step (B) from the via hole or trench using a treatment liquid. Foreign matter may be present on the surface of the insulating layer after step (B). This foreign matter may include, for example, inorganic filler that has been excavated by plasma treatment. This foreign matter may cause a decrease in the adhesion strength of the conductor layer. Therefore, step (C) is performed to remove these foreign matter. More specifically, step (C) is a step of contacting the surface of the insulating layer with a treatment liquid after step (B) to remove the foreign matter. Step (C) may be performed once or multiple times.

[0221] The procedure and conditions for step (C) are not particularly limited, and known procedures and conditions commonly used in forming insulating layers for printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid, in that order. The swelling liquid used for the roughening treatment is not particularly limited, but examples include alkaline solutions and surfactant solutions. Alkaline solutions are preferred, and sodium hydroxide solutions and potassium hydroxide solutions are more preferred. Commercially available swelling liquids include "Swelling Dip Securigans P," "Swelling Dip Securigans SBU," and "Swelling Dip Securigant P" manufactured by Atotech Japan. The swelling treatment with a swelling liquid is not particularly limited, but 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. To minimize swelling of the resin in the insulating layer, the insulating layer is preferably immersed in a swelling solution at 40°C to 80°C for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan. The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be cited. Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 1 to 30 minutes. From the standpoint of workability, a preferred method is to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0222] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. There is no particular lower limit, but it is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0223] <Process (D)> Step (D) is a step of forming a conductor layer on the surface of the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, 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 a nickel-chromium alloy, is more preferred, and a single metal layer of copper is even more preferred.

[0224] The conductor layer may be a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the cured body is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

[0225] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0226] In a preferred embodiment of step (D), the conductor layer is formed by sputtering. In the present invention, the resin composition contains an inorganic filler having an average particle size of 0.1 μm or less, which reduces unevenness at the bottom and sidewall of the via hole where the inorganic filler is dug out. As a result, the thickness of the conductor layer formed in the via hole or trench can be made uniform.

[0227] When forming a conductive layer by sputtering, a conductive seed layer is usually first formed on the surface of an insulating layer by sputtering, and then a conductive sputtered layer is formed on the conductive seed layer by sputtering. Before forming the conductive seed layer by sputtering, the surface of the insulating layer may be cleaned by reverse sputtering. Various gases can be used for the reverse sputtering, with Ar, O2, and N2 being preferred. When the seed layer is made of Cu or a Cu alloy, Ar or O2 or an Ar / O2 mixed gas is preferred. When the seed layer is made of Ti, Ar or N2 or an Ar / N2 mixed gas is preferred. When the seed layer is made of Cr or a Cr alloy (such as nichrome), Ar or O2 or an Ar / O2 mixed gas is preferred. Sputtering can be performed using various sputtering devices, such as magnetron sputtering and mirror tron ​​sputtering. Metals that form the conductive seed layer include Cr, Ni, Ti, and nichrome. Cr and Ti are particularly preferred. The conductive seed layer is typically formed to a thickness of preferably 5 nm or more, more preferably 10 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less. Examples of metals that form the sputtered conductor layer include Cu, Pt, Au, and Pd. Cu is particularly preferred. The sputtered conductor layer is generally formed to a thickness of preferably 50 nm or more, more preferably 100 nm or more, and preferably 3000 nm or less, more preferably 1000 nm or less.

[0228] After forming a conductor layer by sputtering, a copper plating layer may be further formed on the conductor layer by electrolytic copper plating. The thickness of the copper plating layer is usually preferably 5 μm or more, more preferably 8 μm or more, and is preferably formed to be 75 μm or less, more preferably 35 μm or less. Known methods such as subtractive and semi-additive methods can be used to form the circuit.

[0229] [Semiconductor Devices] The semiconductor device of the present invention includes a printed wiring board, and can be manufactured using a printed wiring board obtained by the manufacturing method of the present invention.

[0230] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft).

[0231] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of the printed wiring board that transmits an electrical signal, and the portion may be either on the surface or embedded. The semiconductor chip is not particularly limited as long as it is an electrical circuit element made of a semiconductor material.

[0232] The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include wire bonding mounting, flip chip mounting, bumpless buildup layer (BBUL) mounting, anisotropic conductive film (ACF) mounting, non-conductive film (NCF) mounting, etc. Here, the "bumpless buildup layer (BBUL) mounting method" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess in a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board." [Example]

[0233] The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0234] <Synthesis Example 1: Synthesis of Polyimide Resin 1> A 500 ml separable flask equipped with a nitrogen inlet tube and a stirrer was charged with 9.13 g (30 mmol) of 5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate (compound of formula (C-3)), 15.61 g (30 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, 94.64 g of N-methyl-2-pyrrolidone, 0.47 g (6 mmol) of pyridine, and 10 g of toluene. The imidization reaction was carried out under a nitrogen atmosphere at 180 °C for 4 hours while removing the toluene from the system, yielding a polyimide solution (20% nonvolatile content by mass) containing polyimide resin 1. No precipitation of the synthesized polyimide resin 1 was observed in the polyimide solution. The weight-average molecular weight of polyimide resin 1 was 45,000.

[0235] <Synthesis Example 2: Synthesis of Polyimide Resin 2> A reaction vessel equipped with a stirrer, a water divider, a thermometer, and a nitrogen gas inlet tube was charged with 65.0 g of aromatic tetracarboxylic dianhydride (SABIC Japan "BisDA-1000", 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane, and the solution was heated to 60 °C. Next, 43.7 g of dimer diamine (Croda Japan "PRIAMINE 1075") and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were added dropwise, and the imidization reaction was carried out at 140 °C for 1 hour. This resulted in a polyimide solution (non-volatile content 30% by mass) containing polyimide resin 2. The weight-average molecular weight of polyimide resin 2 was 25,000.

[0236] <Synthesis Example 3: Synthesis of Polyimide Resin 3> A 500 mL separable flask was prepared, equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to the flask and stirred at 45°C for 2 hours under a nitrogen stream. The reaction solution was then heated and maintained at approximately 160°C, while the condensed water was azeotropically removed with toluene under a nitrogen stream. It was confirmed that the specified amount of water had accumulated in the water content receiver and that no water was leaking out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. The mixture was then cooled to obtain a polyimide solution (non-volatile content 20% by mass) containing polyimide resin 3 having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 3 had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight-average molecular weight of the polyimide resin 3 was 12,000.

[0237] [ka]

[0238] [ka]

[0239] <Inorganic filler used> Inorganic filler 1: Spherical silica (Denka "UFP-30", average particle size 0.078 μm, specific surface area 30.7 m 2 The surface was treated with 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts of the silica gel (100 parts per 100g). Inorganic filler 2: Spherical silica (Admatechs "SC2500SQ", average particle size 0.63 μm, specific surface area 11.2 m) 2The surface was treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts of the silica gel (100 parts per 100g).

[0240] Example 1: Preparation of resin composition 1 Five parts of a bixylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: approximately 185), five parts of a naphthalene-type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight: approximately 332), ten parts of a naphthylene ether-type epoxy resin ("HP6000L" manufactured by DIC Corporation, epoxy equivalent weight: approximately 213), two parts of a cyclohexane-type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: approximately 135), and 100 parts of the polyimide solution (non-volatile component: 20% by mass) obtained in Synthesis Example 1 were dissolved in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone under heating with stirring. After cooling to room temperature, 6 parts of an active ester curing agent ("EXB-8151-62T" manufactured by DIC Corporation, active group equivalent weight 238, toluene solution with solids content of 62%), 10 parts of a polyphenylene ether resin ("NORYL SA90" manufactured by SABIC Corporation), and 0.2 parts of an amine curing accelerator (4-dimethylaminopyridine (DMAP)) were mixed thereto, and the mixture was uniformly dispersed using a high-speed rotary mixer. After that, the mixture was filtered through a cartridge filter ("SHP020" manufactured by ROKITECHNO Corporation) to prepare Resin Composition 1.

[0241] Example 2: Preparation of resin composition 2 In Example 1, 10 parts of the polyphenylene ether resin (NORYL SA90 manufactured by SABIC) was replaced with 10 parts of an oligophenylene ether-styrene resin (OPE-2st1200 manufactured by Mitsubishi Gas Chemical Company, Inc.). Resin composition 2 was prepared in the same manner as in Example 1, except for the above-mentioned changes.

[0242] Example 3: Preparation of resin composition 3 In Example 1, the amount of the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 1 was changed from 100 parts to 30 parts. Resin composition 3 was prepared in the same manner as in Example 1 except for the above.

[0243] Example 4: Preparation of resin composition 4 In Example 1, the amount of polyphenylene ether resin (NORYL SA90 manufactured by SABIC) was changed from 10 parts to 7 parts. Resin composition 4 was prepared in the same manner as in Example 1 except for the above-mentioned points.

[0244] Example 5: Preparation of resin composition 5 In Example 1, 100 parts of the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 1 was changed to 67 parts of the polyimide solution (non-volatile component 30% by mass) obtained in Synthesis Example 2. Resin composition 5 was prepared in the same manner as in Example 1 except for the above-mentioned points.

[0245] Example 6: Preparation of resin composition 6 In Example 1, 100 parts of the polyimide solution (20% by mass of non-volatile components) obtained in Synthesis Example 1 was changed to 100 parts of the polyimide solution (20% by mass of non-volatile components) obtained in Synthesis Example 3. Resin composition 6 was prepared in the same manner as in Example 1 except for the above.

[0246] <Comparative Example 1: Preparation of Resin Composition 7> In Example 1, The amount of inorganic filler 1 was changed from 90 parts to 75 parts. The amount of the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 1 was changed from 100 parts to 85 parts. Polyphenylene ether resin (NORYL SA90 manufactured by SABIC) was not used. Resin composition 7 was prepared in the same manner as in Example 1 except for the above.

[0247] Comparative Example 2: Preparation of Resin Composition 8 In Example 1, the amount of inorganic filler 1 was changed from 90 parts to 130 parts. Resin composition 8 was prepared in the same manner as in Example 1 except for the above-mentioned points.

[0248] Comparative Example 3: Preparation of Resin Composition 9 In Example 1, The amount of inorganic filler 1 was changed from 90 parts to 125 parts. The amount of the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 1 was changed from 100 parts to 225 parts. Resin composition 9 was prepared in the same manner as in Example 1 except for the above.

[0249] Comparative Example 4: Preparation of Resin Composition 10 In Example 1, The amount of inorganic filler 1 was changed from 90 parts to 55 parts. Without using 100 parts of the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 1, The amount of polyphenylene ether resin (NORYL SA90 manufactured by SABIC) was changed from 10 parts to 7 parts. Resin composition 10 was prepared in the same manner as in Example 1 except for the above points.

[0250] Comparative Example 5: Preparation of Resin Composition 11 In Example 1, Without using 100 parts of the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 1, 100 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of cyclohexanone and methyl ethyl ketone (MEK) with a solid content of 30% by mass) was used in place of 10 parts of a polyphenylene ether resin ("NORYL SA90" manufactured by SABIC). Resin composition 11 was prepared in the same manner as in Example 1, except for the above-mentioned changes.

[0251] <Comparative Example 6: Preparation of Resin Composition 12> In Example 1, 90 parts of Inorganic Filler 1 was changed to 90 parts of Inorganic Filler 2. Resin composition 12 was prepared in the same manner as in Example 1 except for the above-mentioned points.

[0252] <Preparation of resin sheet> A PET film (Toray Industries, Inc., "Lumirror R80," 38 μm thick, softening point 130°C, "release PET") that had been release-treated with an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared as a support. Resin compositions 1 to 12 were each uniformly applied to the release agent on the support using a die coater so that the thickness of the resin composition layer after drying would be 20 μm. The resulting film was then dried at 70 to 95°C for 2 minutes to obtain a resin composition layer on the release PET. Next, a roughened surface of a polypropylene film (Oji F-Tex Co., Ltd., "Alphan MA-411," 15 μm thick) was laminated as a protective film on the side of the resin composition layer not bonded to the support, so as to be bonded to the resin composition layer. This resulted in a resin sheet A consisting of the release PET (support), the resin composition layer, and the protective film in that order. Similarly, a resin sheet B was produced, having a resin composition layer with a thickness of 10 μm after drying.

[0253] <Test Example 1: Evaluation of minimum melt viscosity, pattern embedding ability, and flatness> (Test Example 1-1: Measurement of minimum melt viscosity) The minimum melt viscosity of the resin composition layer of each resin sheet A prepared in advance was measured using a dynamic viscoelasticity measuring device (Rheosol-G3000 manufactured by UBM). 1 g of a sample resin composition taken from the resin composition layer was heated using parallel plates with a diameter of 18 mm from a starting temperature of 60°C to 200°C at a heating rate of 5°C / min. The dynamic viscoelasticity was measured under the following conditions: temperature interval: 2.5°C, frequency: 1 Hz, strain: 1 deg. The minimum melt viscosity (poise) was measured and evaluated according to the following criteria. Good: Minimum melt viscosity is 5000 poise or less. ×: The minimum melt viscosity exceeds 5000 poise.

[0254] (Test Example 1-2: Evaluation of pattern embedding) An inner layer circuit board was prepared using a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company, Inc. "HL832NSF LCA", 255 × 340 mm size) with circuit conductors (copper) formed on both sides in a 1 mm square lattice wiring pattern (remaining copper ratio 59%). Both sides of the inner layer circuit board were subjected to a copper surface roughening treatment (copper etching amount 0.5 μm) using MEC's ​​"CZ8201".

[0255] Resin sheet A was laminated onto both sides of the inner layer circuit board using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700) so that the resin composition layer was in contact with the inner layer circuit board. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing the sheets at 130°C and a pressure of 0.74 MPa for 45 seconds. This was followed by a heat press at 120°C and a pressure of 0.5 MPa for 75 seconds.

[0256] The inner layer circuit board laminated with resin sheet A was placed in a 100°C oven for 30 minutes at 100°C, and then transferred to a 180°C oven for 30 minutes at 180°C, where it was thermally cured to form an insulating layer. This was designated "Evaluation Board A."

[0257] The support was peeled off from evaluation substrate A, and the surface of the insulating layer was observed with a micro-optical microscope to evaluate the pattern embedding property according to the following criteria. ◯: The insulating layer is sufficiently embedded in the inner layer circuit board. ×: The insulating layer is not sufficiently embedded.

[0258] (Test Example 1-3: Evaluation of Flatness) The flatness of the exposed insulating layer of evaluation board A in the area above the circuit conductor of the wiring pattern was measured using a non-contact surface roughness meter (Beeco Instruments' "WYKO NT3300"). The maximum cross-sectional height (Rt) was measured at 10x magnification in four areas of 0.82mm x 1.1mm, and the average value was calculated and evaluated according to the following criteria. ○: The average value of Rt is less than 1.3 μm. △: The average value of Rt is 1.3 μm or more and less than 1.6 μm. ×: The average value of Rt is 1.6 μm or more.

[0259] <Test Example 2: Evaluation of toughness> (1) Preparation of the cured product for evaluation A release PET film ("501010" manufactured by Lintec Corporation, 38 μm thick, 240 mm square) was placed on a glass cloth-based epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Panasonic Electric Works, Ltd., 0.7 mm thick, 255 mm square) so that the untreated surface of the release PET film was in contact with the laminate, and the four sides of the release PET film were fixed with polyimide adhesive tape (10 mm wide).

[0260] Each resin sheet A (167 x 107 mm square) prepared in the Examples and Comparative Examples was centrally laminated using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700) so that the resin composition layer was in contact with the release surface of a release PET film. The lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, followed by pressure bonding at 100°C and a pressure of 0.74 MPa for 30 seconds. The support was then peeled off, and the resin composition layer was thermally cured at 180°C for 90 minutes.

[0261] After thermal curing, the polyimide adhesive tape was peeled off, and the cured layer obtained by thermally curing the resin composition layer was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate. The release PET film was then peeled off from the cured layer to obtain a sheet-like cured product (cured product for evaluation).

[0262] (2) MIT Exam The cured product for evaluation was cut into test pieces 15 mm wide and 110 mm long, and the number of folding cycles until breakage of the cured product for evaluation was measured using an MIT testing device (MIT folding fatigue tester "MIT-DA" manufactured by Toyo Seiki Seisakusho, Ltd.) in accordance with JIS C-5016 under the measurement conditions of a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / minute. Measurements were performed on five samples, and the average of the top three was calculated and evaluated according to the following criteria. 〇: Can withstand folding over 300 times. ×: The number of folding times is less than 300.

[0263] <Test Example 3: Evaluation of insulation reliability> (1) Surface treatment of inner layer circuit board An inner layer circuit board was prepared using a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company, Inc. "HL832NSF LCA", 255 × 340 mm size) with a 1 mm square lattice wiring pattern (copper remaining rate 59%) on both sides. Both sides of the inner layer circuit board were treated with an organic coating on the copper surface using MEC's ​​"FlatBOND-FT".

[0264] (2) Laminating resin sheets The protective film was removed from each resin sheet B prepared in the Examples and Comparative Examples, and the resin composition layer was laminated onto both sides of the inner layer circuit board using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700) so that the resin composition layer was in contact with the inner layer circuit board. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing at 130°C and a pressure of 0.74 MPa for 45 seconds. This was then followed by a heat press at 120°C and a pressure of 0.5 MPa for 75 seconds.

[0265] (3) Thermal curing of the resin composition layer The inner layer circuit board laminated with Resin Sheet B was placed in an oven at 100°C for 30 minutes, then transferred to an oven at 180°C for 30 minutes to heat cure and form an insulating layer, and the release PET was then peeled off.

[0266] (4) Roughening treatment The inner layer circuit board on which the insulating layer was formed was subjected to a desmear treatment as a roughening treatment. The desmear treatment was the following wet desmear treatment. Wet desmearing: The substrate was immersed in a swelling solution (Atotech Japan's "Swelling Dip Securigant P," an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, then in an oxidizing solution (Atotech Japan's "Concentrate Compact CP," an aqueous solution of potassium permanganate approximately 6% and sodium hydroxide approximately 4%) at 80°C for 10 minutes, and finally in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P," an aqueous sulfuric acid solution) at 40°C for 5 minutes, followed by drying at 80°C for 15 minutes. This was designated "roughened substrate A."

[0267] (5) Formation of via holes (5-1) Dry film pattern formation A 20 μm-thick dry film (Nikko Materials Co., Ltd., "ALPHO 20A263") was laminated onto the insulating layer surface of the roughened substrate A. The dry film was laminated using a batch-type vacuum pressure laminator (Meiki Seisakusho Co., Ltd., "MVLP-500"), which was depressurized for 30 seconds to a pressure of 13 hPa or less, and then pressurized at a pressure of 0.1 MPa and a temperature of 70°C for 20 seconds. A glass mask with a via pattern was then placed on the polyethylene terephthalate film, which was the protective layer of the dry film, and a UV lamp was used to irradiate the film at an intensity of 150 mJ / cm. 2 After UV irradiation, the substrate was sprayed with a 1% aqueous sodium carbonate solution at 30°C at a spray pressure of 0.15 MPa for 30 seconds. After that, the substrate was washed with water and patterned to form a via pattern with a wiring width of 20 μm, thereby obtaining a via-processed substrate.

[0268] (5-2) Plasma processing Using a vacuum plasma etching device (M120W manufactured by Nissin Co., Ltd.), processing was performed for 5 minutes under conditions of a CF4 / O2 mixture ratio of 1:7 (sccm) and a pressure of 120 Pa, creating a trench structure approximately 20 μm wide in the insulating layer on the via-processed substrate, and processing was continued for 15 minutes to form a via hole with a top diameter of approximately 15 μm in the insulating layer of the via-processed substrate.The etching resist was then peeled off to obtain the via substrate.

[0269] (6) Conductor layer formation (6-1) Electroless plating In order to form a conductor layer on the roughened surface of the via substrate, a plating process (copper plating process using a chemical solution manufactured by Atotech Japan) including the following steps 1 to 6 was carried out to form the conductor layer.

[0270] 1. Alkaline cleaning (cleaning the surface of the insulating layer and adjusting the charge) The surface of the roughened substrate A was cleaned with Cleaning Cleaner Securiganth 902 (trade name) at 60° C. for 5 minutes. 2. Soft etching (cleaning inside via holes) The surface of the roughened substrate A was treated with an aqueous solution of sodium peroxodisulfate acidified with sulfuric acid at 30° C. for 1 minute. 3. Pre-dip (adjusting the surface charge of the insulating layer for Pd deposition) The surface of the roughened substrate A was treated with Pre. Dip Neoganth B (trade name) at room temperature for 1 minute. 4. Adding activator (adding Pd to the surface of the insulating layer) The surface of the roughened substrate A was treated with Activator Neoganth 834 (trade name) at 35° C. for 5 minutes. 5. Reduction (reducing Pd attached to the insulating layer) The surface of the roughened substrate A was treated with a mixed solution of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (trade name) at 30° C. for 5 minutes. 6. Electroless copper plating (Cu is deposited on the surface of the insulating layer (Pd surface)) The surface of the roughened substrate A was treated with a mixed solution of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) at 35°C for 20 minutes to form an electroless copper plating layer. The thickness of the formed electroless copper plating layer was 0.8 μm.

[0271] (6-2) Electroplating Next, an electrolytic copper plating process was performed using a chemical solution manufactured by Atotech Japan under conditions that filled the via holes with copper. Subsequently, a 10 μm-thick conductor layer having lands and conductor patterns was formed on the surface of the insulating layer using a resist pattern for etching: a 1 mm diameter land pattern that was conductive to the underlying conductor, and a 10 mm diameter circular conductor pattern that was not connected to the underlying conductor. Next, an annealing treatment was performed at 200°C for 90 minutes. This substrate was designated "Evaluation Substrate B."

[0272] (7) Evaluation of the insulation reliability of the insulating layer The 10 mm diameter circular conductor side of evaluation board B was used as the positive electrode, and the lattice circuit conductor (copper) side of the inner layer circuit board connected to the 1 mm diameter land was used as the negative electrode. A highly accelerated life tester (ETAC Corporation, "PM422") was used. Test pieces were left at 110°C, 85% relative humidity, and 20 V DC for 100 hours. The insulation resistance was measured using an electrochemical migration tester (J-RAS Corporation, "ECM-100"). This measurement was performed six times and evaluated according to the following criteria. The insulation resistance values ​​listed in the table below are the minimum insulation resistance values ​​of the six test pieces. ○: The resistance value of all six test pieces was 1.00 × 10 8 More than Ω. ×: The resistance value of at least one of the six test pieces is 1.00 × 10 8 Less than Ω.

[0273] <Test Example 4: Evaluation of plasma processability> (1) Preparation of copper clad laminate As the copper-clad laminate, a glass cloth-based epoxy resin double-sided copper-clad laminate with copper foil layers laminated on both sides (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company, Inc. "HL832NSF LCA", size 255 × 340 mm) was prepared.

[0274] (2) Laminating resin sheets The protective film was removed from each resin sheet B prepared in the Examples and Comparative Examples, and the resin composition layer was laminated onto both sides of a copper-clad laminate using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700) so that the resin composition layer was in contact with the copper-clad laminate. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing the laminate at 130°C and a pressure of 0.74 MPa for 45 seconds. The laminate was then heat-pressed at 120°C and a pressure of 0.5 MPa for 75 seconds.

[0275] (3) Thermal curing of the resin composition layer The copper-clad laminate with the resin sheet laminated thereon was placed in an oven at 100°C for 30 minutes, then transferred to an oven at 180°C for 30 minutes to heat cure the laminate to form an insulating layer, and the support was then peeled off, yielding a copper-clad laminate A with a 10 μm insulating layer.

[0276] (4) Dry film pattern formation A 20 μm-thick dry film (Nikko Materials Co., Ltd., "ALPHO 20A263") was laminated to the surface of the insulating layer of copper-clad laminate A on which the insulating layer had been formed. The dry film was laminated using a batch-type vacuum pressure laminator (Meiki Seisakusho Co., Ltd., "MVLP-500"), which was depressurized for 30 seconds to a pressure of 13 hPa or less, and then pressurized at a pressure of 0.1 MPa and a temperature of 70°C for 20 seconds. A glass mask with a trench pattern was then placed on the polyethylene terephthalate film, which was the protective layer of the dry film, and a UV lamp was used to irradiate the film at an irradiation intensity of 150 mJ / cm. 2The substrate was then subjected to UV irradiation at 100°C. After UV irradiation, the substrate was sprayed with a 1% aqueous sodium carbonate solution at 30°C for 30 seconds at a spray pressure of 0.15 MPa. The substrate was then washed with water and patterned to form a trench pattern with a wiring width of 20 μm, thereby obtaining a trench-processed substrate. Furthermore, using a glass mask with a via pattern, patterning was performed in the same manner as in the preparation of the trench-processed substrate, to form via holes with a top diameter of 15 μm, thereby obtaining a via-processed substrate.

[0277] (5) Plasma processing Using a vacuum plasma etching device (M120W manufactured by Nissin), processing was performed for 5 minutes at a CF4 / O2 mixture ratio of 1:7 (sccm) and a pressure of 120 Pa to form a trench structure approximately 20 μm wide in the insulating layer on the trench-processed substrate. Processing was continued for 15 minutes to form a via hole with a top diameter of approximately 15 μm in the insulating layer of the via-processed substrate, and the etching resist was then peeled off to obtain a trench evaluation substrate and a via evaluation substrate.

[0278] (6) Observation of trench and via wall surfaces after plasma processing The trench evaluation substrate and via evaluation substrate were heated at 150°C for 30 minutes, and then a copper layer (200 nm thick) was formed on the insulating layer using a sputtering device (Canon Anelva "E-400S").Then, cross-sections were observed using a FIB-SEM hybrid device (SII Nano Technology "SMI3050SE") and evaluated according to the following criteria. ◯: A copper layer is formed uniformly and without interruption on the wall surfaces of the trench and via hole formed in the insulating layer. ×: The copper layer was not formed uniformly due to unevenness on the wall surfaces of the trench and via hole formed in the insulating layer.

[0279] (7) Evaluation of processing speed of plasma treatment The processing speed was observed when processing a via evaluation board using a vacuum plasma etching device. The time required to process 10 μm in the depth direction was measured and evaluated according to the following criteria. 〇: Machining speed is 0.6μm / min or more. △: Machining speed is 0.5 μm / min or more and less than 0.6 μm / min. ×: Processing speed is less than 0.5 μm / min.

[0280] [Table 1]

[0281] In Examples 1 to 6, it was confirmed that even when components (E) to (F) were not contained, the same results as in the above Examples were obtained, although to different degrees.

Claims

1. (A) an epoxy resin, (B) an inorganic filler having an average particle size of 0.1 μm or less; (C) a resin having an imide skeleton represented by the following formula (C) (excluding epoxy resins), and (D) A resin composition containing a resin having a phenylene ether skeleton represented by the following formula (D) and further having a radical polymerizable unsaturated group or a hydroxyphenyl group (excluding epoxy resins and resins having an imide skeleton represented by formula (C)): The weight average molecular weight (Mw) or number average molecular weight (Mn) of component (D) is 2,500 or less, The content of the component (B) is 69% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass, A resin composition, wherein the content of component (C) is 5% by mass or more and 15% by mass or less, when the total amount of nonvolatile components in the resin composition is 100% by mass. 【Chemistry 1】 (In formula (C), R ａ each independently represents a halogen atom, a cyano group, a nitro group, or —X １３ -R １３ represents X １３ are each independently a single bond, —NR １３’ -, -O-, -S-, -CO-, -SO ２ -, -NR １３’ CO-, -CONR １３’ represents -, -OCO-, or -COO-; R １３ each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R １３’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. a1 represents an integer of 0 to 3. * indicates a binding site. In formula (D), R ｂ each independently represents a substituent, b1 represents an integer of 0 to 4. * indicates a binding site.

2. The resin composition according to claim 1, wherein the content of the component (D) is 5% by mass or more and 10% by mass or less, when the total amount of nonvolatile components in the resin composition is 100% by mass.

3. 3. The resin composition according to claim 1, wherein the total content of the components (C) and (D) is 10% by mass or more and 25% by mass or less, when the total amount of nonvolatile components in the resin composition is 100% by mass.

4. The resin composition according to any one of claims 1 to 3, wherein the resin composition has a minimum melt viscosity of 5000 poise or less.

5. The resin composition according to any one of claims 1 to 4, which is used for forming via holes or trenches in an insulating layer of a printed wiring board by plasma treatment.

6. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition comprising the resin composition according to any one of claims 1 to 5.

7. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 5.

8. A semiconductor device comprising the printed wiring board according to claim 7.

9. A step of forming an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 5 on an inner layer circuit board; and A method for manufacturing a printed wiring board, comprising a step of performing plasma treatment on the surface of an insulating layer to form via holes or trenches.

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