JP7206613B2 - resin composition - Google Patents

Description

The present invention relates to resin compositions. Furthermore, the present invention relates to resin sheets, printed wiring boards and semiconductor devices using the resin composition.

2. Description of the Related Art As a manufacturing technique for a multilayer printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by thermosetting a resin composition.

For example, Patent Document 1 discloses a resin composition containing (A) an epoxy resin, (B) an active ester curing agent, and (C) a curing accelerator, wherein the component (C) is an electron-withdrawing A resin composition containing one or more selected from the group consisting of a pyridine compound having a group and an imidazole compound having an electron-withdrawing group at the 1-position is disclosed.

JP 2015-59170 A

When manufacturing a multilayer printed wiring board, it is desirable that the resin composition for forming the insulating layer has excellent adhesion to the conductor layer even after an environmental test (HAST test) under a high-temperature and high-humidity environment. .

An object of the present invention is to provide a resin composition capable of obtaining a cured product having excellent adhesion to a conductor layer even after the HAST test; a resin sheet containing the resin composition; An object of the present invention is to provide a printed wiring board having an insulating layer formed thereon, and a semiconductor device.

As a result of intensive studies to solve the above-mentioned problems, the present inventors found that by including pyridine substituted with a cyclic amino group in the resin composition, the adhesion between the conductor layer and the conductor layer was improved even after the HAST test. The inventors have found that it is possible to obtain an excellent cured product, and have completed the present invention. That is, the present invention includes the following contents.

[1] (A) epoxy resin,
A resin composition containing (B) an active ester curing agent and (C) pyridine substituted with a cyclic amino group.
[2] The resin composition according to [1], wherein the cyclic amino group in component (C) is bonded to the 4-position of the pyridine ring.
[3] The resin composition according to [1] or [2], wherein the cyclic amino group in component (C) is a saturated cyclic amino group.
[4] The resin composition according to any one of [1] to [3], wherein the cyclic amino group in component (C) is a 5- or 6-membered cyclic amino group.
[5] The resin composition according to any one of [1] to [4], further comprising (D) an inorganic filler.
[6] The resin composition according to [5], wherein the content of component (D) is 50% by mass or more based on 100% by mass of non-volatile components in the resin composition.
[7] The resin composition according to any one of [1] to [6], which is used for insulation.
[8] The resin composition according to any one of [1] to [7], which is for forming an insulating layer.
[9] The resin composition according to any one of [1] to [8], which is used for forming an insulating layer for forming a conductor layer.
[10] The resin composition according to any one of [1] to [7], which is used for encapsulating semiconductor chips.
[11] A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [10] provided on the support.
[12] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [10].
[13] A semiconductor device including the printed wiring board according to [12].

According to the present invention, a resin composition capable of obtaining a cured product having excellent adhesion to a conductor layer even after the HAST test; a resin sheet containing the resin composition; A printed wiring board including the formed insulating layer and a semiconductor device can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

[Resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester curing agent, and (C) a pyridine substituted with a cyclic amino group. (C) By including pyridine substituted with a cyclic amino group in the resin composition, it is possible to obtain a cured product having excellent adhesion to a conductor layer such as a copper foil even after the HAST test. . Furthermore, the obtained cured product is excellent in peel strength between the normal plated conductor layer and peel strength between the conductor layer such as copper foil before the HAST test.

In addition, the resin composition may further contain optional components in combination with the components (A) to (C). Examples of optional components include (D) an inorganic filler, (E) a curing agent, (F) a thermoplastic resin, and (G) other additives. Each component contained in the resin composition of the present invention will be described in detail below.

<(A) Epoxy resin>
The resin composition contains (A) an epoxy resin. (A) Epoxy resins include, for example, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin. resins, naphthol novolak-type epoxy resins, phenol novolak-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 novolak 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, tetraphenylethane type epoxy resins and the like can be mentioned. Epoxy resins may be used singly or in combination of two or more.

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

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). As the epoxy resin (A), the resin composition may contain only a liquid epoxy resin or only a solid epoxy resin, but may contain a combination of a liquid epoxy resin and a solid epoxy resin. is preferred. (A) By using a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin, it is possible to improve the flexibility of the resin composition layer, which will be described later, and to improve the breaking strength of the cured product of the resin composition. can

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups per molecule, more preferably an aromatic liquid epoxy resin having two or more epoxy groups per molecule. Here, the “aromatic” epoxy resin means an epoxy resin having an aromatic ring in its molecule.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin is more preferable.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC; "EXA-850CRP" (bisphenol A type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; F-type epoxy resin mixture); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); Daicel "PB-3600" (epoxy resin having a butadiene structure) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include 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, and naphthylene. Ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, tetraphenylethane-type epoxy resin are preferred, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, and dicyclopentadiene-type epoxy resin. is more preferred, and biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, and dicyclopentadiene-type epoxy resins are even more preferred. Biphenyl-type epoxy resins include biphenyl aralkyl-type epoxy resins and bixylenol-type epoxy resins.

Specific examples of solid epoxy resins include "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP7200" manufactured by DIC Corporation. ”, “HP7200HH”, “HP7200H” (dicyclopentadiene type epoxy resin); DIC “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S” ", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl aralkyl type epoxy resins) manufactured by Nippon Kayaku; bixylenol type epoxy resin); Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin); Nippon Steel & Sumikin Chemical Co., Ltd. "ESN485" (naphthol novolac type epoxy resin); type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" manufactured by Mitsubishi Chemical (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical (fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical; These may be used individually by 1 type, and may be used in combination of 2 or more types.

(A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the ratio by mass (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1:20. , more preferably 1:1 to 1:15, particularly preferably 1:1 to 1:10. The desired effect of the present invention can be remarkably obtained by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range. In addition, it usually provides moderate tackiness when used in the form of a resin sheet. In addition, when used in the form of a resin sheet, sufficient flexibility is usually obtained, and handleability is improved. Furthermore, usually, a cured product having sufficient breaking strength can be obtained.

(A) The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product of the resin composition layer is sufficient, and an insulating layer with a small surface roughness can be obtained. Epoxy equivalent weight is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention.
The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

(A) From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin is preferably 1% by mass or more, when the non-volatile component in the resin composition is 100% by mass. It is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit of the epoxy resin content is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

<(B) Active ester curing agent>
The resin composition contains (B) an active ester curing agent. (B) The active ester curing agent is an active ester compound having one or more active ester groups in one molecule.

(B) The active ester curing agent generally contains two highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. A compound having one or more is preferably used. The active ester curing agent is preferably 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, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, the (B) active ester curing agent includes a dicyclopentadiene type active ester curing agent, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated phenol novolac, and a phenol An active ester-based curing agent containing a benzoylated novolak is preferred, among which an active ester-based curing agent including a naphthalene structure and a dicyclopentadiene-type active ester-based curing agent are more preferred, and a dicyclopentadiene-type active ester-based curing agent is even more preferred. . As the dicyclopentadiene-type active ester-based curing agent, an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure is preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

(B) Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", and "HPC8000H" as active ester curing agents containing a dicyclopentadiene type diphenol structure. -65TM", "EXB8000L-65TM" (manufactured by DIC Corporation), "EXB8150-60T" and "EXB9416-70BK" (manufactured by DIC Corporation) as active ester curing agents containing a naphthalene structure, activity containing acetylated phenol novolak "DC808" (manufactured by Mitsubishi Chemical Corporation) as an ester curing agent, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing a benzoylated phenol novolak, and an active ester curing agent that is an acetylated phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical company) and the like.

The ratio of (B) active ester curing agent to (A) epoxy resin is [total number of epoxy groups in (A) epoxy resin]:[total number of reactive groups in (B) active ester curing agent]. is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.05 to 1:2, even more preferably 1:0.1 to 1:1.5. Here, the reactive group of (B) the active ester-based curing agent is an active ester group. In addition, (A) the total number of epoxy groups in the epoxy resin is the sum of all the values obtained by dividing the solid mass of each component by the epoxy equivalent, and (B) the total number of reactive groups in the active ester curing agent. The number is the total value obtained by dividing the solid content mass of each active ester curing agent by the reactive group equivalent for all the active ester curing agents. By setting the ratio between the epoxy resin and the active ester curing agent within this range, the heat resistance of the cured product of the resin composition is further improved.

(B) The content of the active ester curing agent is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more, when the non-volatile component in the resin composition is 100% by mass. is. Also, the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. By setting the content of component (B) within this range, the heat resistance of the cured product of the resin composition is further improved.

<(C) Pyridine Substituted with a Cyclic Amino Group>
The resin composition contains (C) pyridine substituted with a cyclic amino group. This component (C) has a molecular structure in which one or more hydrogen atoms of pyridine are substituted with cyclic amino groups. A cyclic amino group is superior in electron-donating property to a non-cyclic amino group, so that the curing acceleration effect of the epoxy resin is improved as compared with a curing accelerator having a non-cyclic amino group. Therefore, when curing the resin composition, it can be cured in a state in which the reaction between (A) the epoxy resin and (B) the active ester curing agent is further accelerated, and even after the HAST test, the adhesion between the resin composition and the conductor layer can be effectively improved.

Component (C) can improve adhesion to the conductor layer even after the HAST test if the cyclic amino group is directly bonded to the pyridine ring. From the viewpoint of further improving the adhesion between the conductor layer even after the HAST test, the cyclic amino group is preferably bonded to any one of the 2 to 6 positions of the pyridine ring, and is bonded to the 4 position of the pyridine ring. It is more preferable to have The number of cyclic amino groups substituted on one pyridine ring may be one, or two or more. In pyridine substituted with two or more cyclic amino groups, one type of cyclic amino group or two or more types of cyclic amino groups may be bonded to the pyridine ring. Among them, from the viewpoint of effectively improving adhesion, it is preferable that one cyclic amino group is substituted for each pyridine ring.

As the cyclic amino group, one that can be substituted with pyridine can be used. An amino group is preferred.

The number of nitrogen atoms possessed by the cyclic amino group is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, still more preferably 1 or more, from the viewpoint of further improving the adhesion to the conductor layer even after the HAST test. 2 or less, preferably 1.

The number of atoms forming one ring of the cyclic amino group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, from the viewpoint of further improving adhesion to the conductor layer even after the HAST test. It is preferably a 5-membered ring or more, preferably a 10-membered ring or less, more preferably an 8-membered ring or less, still more preferably a 6-membered ring or less. The number of atoms forming one ring of the cyclic amino group is particularly preferably a 5-membered ring or a 6-membered ring.

Atoms that form the ring in the cyclic amino group can be atoms that can improve adhesion to the conductor layer even after the HAST test. Specifically, the ring in the cyclic amino group preferably has a ring skeleton composed of nitrogen atoms, carbon atoms, and heteroatoms, and more preferably has a ring skeleton composed of nitrogen atoms and carbon atoms. . Heteroatoms include, for example, an oxygen atom, a sulfur atom, and the like. The ring may have one heteroatom, or may have two or more.

Such cyclic amino groups include, for example, a pyrrolidino group, a piperidino group, a morpholino group, a piperazino group and the like. Among them, a pyrrolidino group and a piperidino group are preferable from the viewpoint of further improving the adhesion to the conductor layer even after the HAST test.

Specific examples of component (C) include 4-pyrrolidinopyridine, 4-piperidinopyridine, 4-morpholinopyridine, 4-(1-piperazinyl)pyridine and the like. Among them, 4-pyrrolidinopyridine and 4-piperidinopyridine are preferred. (C) component may be used individually by 1 type, and may be used in combination of 2 or more types.

(C) Component may have a substituent. The substituent may be substituted on the pyridine ring or may be substituted on the cyclic amino group. Examples of such substituents include halogen atoms, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, mercapto groups, An oxo group and the like can be mentioned.

The content of component (C) is preferably 0.1% by mass when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of improving the adhesion between the conductor layer even after the HAST test. Above, more preferably 0.5% by mass or more, still more preferably 1% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

The content (% by mass) of component (A), the content (% by mass) of component (B), and the content (% by mass) of component (C) when the non-volatile component in the resin composition is 100% by mass ) are a, b, and c respectively, a/(b+c) is preferably 0.5 or more, more preferably 1 or more, from the viewpoint of improving the adhesion between the conductor layer even after the HAST test. , and more preferably 1.3 or more. The upper limit is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less.

<(D) Inorganic filler>
The resin composition may contain (D) an inorganic filler. An inorganic compound is used as the material of the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. (D) The inorganic filler may be used singly or in combination of two or more.

(D) Commercially available inorganic fillers include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo; “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; 5N"; "SC2500SQ", "SOC4", "SOC2", "SOC1" manufactured by Admatechs;

(D) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more, from the viewpoint of significantly obtaining the desired effects of the present invention, It is preferably 5 µm or less, more preferably 2 µm or less, and still more preferably 1 µm or less.

(D) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, and the volume-based particle size distribution of the inorganic filler (D) is measured by the flow cell method. The average particle size was calculated as the median size from the size distribution. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(D) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 5 m ² /g or more, and particularly preferably 10 m ² /g or more, from the viewpoint of significantly obtaining the desired effects of the present invention. be. Although there is no particular upper limit, it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method. .

(D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds. A coupling agent etc. are mentioned. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination.

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

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

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

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

(D) The content of the inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of improving insulation properties. It is preferably 65% by mass or more, more preferably 70% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. Usually, when the content of (D) inorganic filler is large, the adhesion tends to decrease. However, since the resin composition contains the component (C), even if the content of the inorganic filler (D) is large, the adhesion does not decrease, and it is possible to improve the adhesion after HAST. Become.

<(E) Curing agent>
The resin composition may contain (E) a curing agent. However, the (B) active ester curing agent is not included in the (E) curing agent. (E) Curing agents include, for example, phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, amine-based curing agents, and acid anhydride-based curing agents. mentioned. Among them, from the viewpoint of improving insulation reliability, the (E) curing agent is preferably one or more of a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. , a phenol-based curing agent, and a carbodiimide-based curing agent. A single curing agent may be used alone, or two or more curing agents may be used in combination.

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

Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd., "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. , "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol Polyfunctional cyanate resins derived from novolacs, cresol novolaks, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resins) and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer), and the like.

Specific examples of carbodiimide curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., and the like.

Amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′. -diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 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, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents may be used. Kayahard AS", Mitsubishi Chemical's "Epicure W", and the like.

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, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 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), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid.

The ratio of (A) epoxy resin to (B) active ester curing agent and (E) curing agent is [total number of epoxy groups in component (A)]:[reaction of components (B) and (E) total number of groups], the range is preferably from 1:0.01 to 1:5, more preferably from 1:0.05 to 1:2, and even more preferably from 1:0.1 to 1:1. The reactive group of the curing agent is a phenolic hydroxyl group or the like, and varies depending on the type of curing agent. The total number of reactive groups in the curing agent is the sum of the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents. By setting the ratio of these amounts to such a range, the heat resistance of the cured product of the resin composition is further improved.

(E) The content of the curing agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass when the non-volatile component in the resin composition is 100% by mass. That's it. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less. (E) By setting the content of the curing agent within this range, the heat resistance of the cured product of the resin composition is further improved.

<(F) Thermoplastic resin>
The resin composition may contain (F) a thermoplastic resin. Examples of thermoplastic resins as component (F) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, and polyphenylene ether resins. , polycarbonate resins, polyetheretherketone resins, polyester resins, and the like. Among these resins, phenoxy resins and polyvinyl acetal resins are preferable from the viewpoints of significantly obtaining the desired effect of the present invention and obtaining an insulating layer having a small surface roughness and excellent adhesion to the conductor layer. Further, the thermoplastic resin may be used singly or in combination of two or more.

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

Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482";

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP manufactured by Sekisui Chemical Co., Ltd. S-LEC BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series;

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika. Specific examples of polyimide resins also include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in JP-A-2006-37083), and polysiloxane skeletons. Examples include modified polyimides such as polyimide containing (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

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

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polyphenylene ether resin include oligophenylene ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

(F) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more, from the viewpoint of significantly obtaining the desired effects of the present invention. is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

(F) The content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.5% by mass or more, more preferably 1% by mass or more, preferably 5% by mass or less, more preferably 2.5% by mass or less, and even more preferably 2% by mass or less.

<(G) Optional Additives>
The resin composition may further contain optional additives as optional components in addition to the components described above. Such additives include, for example, curing accelerators (excluding those corresponding to component (C)); organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; flame retardants, Resin additives such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents; These additives may be used singly or in combination of two or more.

<Physical properties and applications of the resin composition>
A 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 adhesion (peel strength) to the plated conductor layer. Therefore, the cured product provides an insulating layer with excellent peel strength to the plated conductor layer. The peel strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and still more preferably 0.5 kgf/cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 2 kgf/cm or less. The evaluation of the peel strength can be measured according to the method described in Examples below.

A cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits excellent adhesion to the copper foil (copper foil peeling strength) before the HAST test. Therefore, the cured product provides an insulating layer having excellent adhesion to the copper foil before the HAST test. The adhesion strength to the copper foil before the HAST test is preferably 0.5 kgf/cm or more, more preferably 0.6 kgf/cm or more, and still more preferably 0.7 kgf/cm or more. On the other hand, the upper limit of the adhesion strength before the HAST test is not particularly limited, but may be 5 kgf/cm or less. The adhesion strength evaluation before the HAST test can be measured according to the method described in the examples below.

A cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits excellent adhesion to the copper foil (copper foil peeling strength) after the HAST test. Therefore, the cured product provides an insulating layer having excellent adhesion to the copper foil after the HAST test. The adhesion strength to the copper foil after the HAST test is preferably 0.4 kgf/cm or more, more preferably 0.41 kgf/cm or more, and still more preferably 0.42 kgf/cm or more. On the other hand, the upper limit of the adhesion strength after the HAST test is not particularly limited, but may be 5 kgf/cm or less. The adhesion strength after the HAST test can be evaluated according to the method described in Examples below.

The resin composition of the present invention can provide an insulating layer with excellent adhesion to the conductor layer even after the HAST test. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition).
Further, in the multilayer printed wiring board described later, the resin composition for forming the insulating layer of the multilayer printed wiring board (the resin composition for forming the insulating layer of the multilayer printed wiring board) and the interlayer insulating layer of the printed wiring board are formed. (a resin composition for forming an interlayer insulating layer of a printed wiring board).

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is used as an insulating layer for forming a rewiring layer. (a resin composition for forming a rewiring layer) and a resin composition for sealing a semiconductor chip (a resin composition for semiconductor chip sealing). In some cases, a rewiring layer may be further formed on the sealing layer.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the base material and the temporary fixing film from the semiconductor chip;
(5) forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed; and (6) forming a rewiring layer as a conductor layer on the rewiring layer. forming process

Moreover, since the resin composition of the present invention provides an insulating layer having good part-embedding properties, it can be suitably used when the printed wiring board is a component-embedded circuit board.

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

The thickness of the resin composition layer is preferably 50 μm or less, more It is preferably 40 μm or less, more preferably 35 μm or less, 30 μm or less, or 20 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain other layers as necessary. Such other layers include, for example, a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

For the resin sheet, for example, a resin varnish is prepared by dissolving a resin composition in an organic solvent, the resin varnish is applied onto a support using a die coater or the like, and dried to form a resin composition layer. It can be manufactured by

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol; carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

A printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) Step of laminating the resin composition layer of the resin sheet on the inner layer substrate such that the resin composition layer is bonded to the inner layer substrate (II) Step of thermally curing the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed 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., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

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 bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

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

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. or higher and less than 120° C. (preferably 60° C. or higher and 115° C. or lower, more preferably 70° C. or higher and 110° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (II) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.

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

Step (IV) is a step of roughening the insulating layer. Smear is usually also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of 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 neutralizing treatment with a neutralizing liquid in this order. The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 80° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer after roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

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

The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

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

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

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

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

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

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. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

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

[Measurement of peeling strength (peel strength) of plated conductor layer]
<Preparation of sample for peel strength measurement>
(1) Surface treatment of inner layer circuit board Both sides of the glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, R1515A manufactured by Panasonic Corporation) on which the inner layer circuit is formed are coated with a microetching agent. (Mec Etch Bond "CZ-8101" manufactured by MEC Co.) was etched by 1 μm to roughen the copper surface.

(2) Lamination of resin sheets The resin sheets prepared in Examples and Comparative Examples were laminated on both sides of an inner layer circuit board using a batch-type vacuum pressure laminator (MVLP-500 manufactured by Meiki Co., Ltd.). The lamination was carried out by reducing the pressure to 13 hPa or less for 30 seconds, and then press bonding for 30 seconds at 100° C. and a pressure of 0.74 MPa.

(3) Curing of Resin Composition The laminated resin sheet was cured at 100° C. for 30 minutes and then at 180° C. for 30 minutes to cure the resin composition to form an insulating layer.

(4) Roughening treatment After peeling off the polyethylene terephthalate film as the support from the inner layer circuit board on which the insulating layer is formed, the swelling liquid Swelling Dip Securigant P (glycol) containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd. It was immersed in an aqueous solution of ethers and sodium hydroxide) at 60°C for 10 minutes. Next, as a roughening liquid, it was immersed in Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by Atotech Japan Co., Ltd. at 80° C. for 20 minutes. Finally, as a neutralizing solution, it was immersed in Reduction Shoryusin Securigant P (aqueous solution of sulfuric acid) manufactured by Atotech Japan Co., Ltd. at 40° C. for 5 minutes. After that, it was dried at 80° C. for 30 minutes.

(5) Plating by semi-additive method This inner layer circuit board was immersed in an electroless plating solution containing PdCl ₂ at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. After annealing by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm. Annealing was then performed at 200° C. for 60 minutes. This substrate was used as an evaluation substrate.

<Measurement of peel strength>
A 10 mm wide and 100 mm long cut was made in the conductor layer of the evaluation board, and one end was peeled off and gripped with a gripper (Autocom type testing machine AC-50C-SL manufactured by TSE), At room temperature, the load (kgf/cm) when 35 mm was peeled off vertically at a rate of 50 mm/min was measured.

[Measurement of Copper Foil Peeling Strength and Copper Foil Peeling Strength After Environmental Resistance Test (HAST)]
<Preparation of sample for measuring copper foil peel strength>
(1) Surface treatment of copper foil The glossy surface of “3EC-III” (electrolytic copper foil, 35 μm) manufactured by Mitsui Kinzoku Mining Co., Ltd. is immersed in a micro-etching agent (Mec Etch Bond “CZ-8101” manufactured by MEC Co., Ltd.). The surface was subjected to roughening treatment (Ra value=1 μm) and further to antirust treatment (CL8300). Further, heat treatment was performed in an oven at 130° C. for 30 minutes. This copper foil is called CZ copper foil.

(2) Lamination of copper foil and formation of an insulating layer Each resin sheet prepared in Examples and Comparative Examples is subjected to a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.) to form a resin composition layer. The laminate is bonded to a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) on which an inner layer circuit is formed. Laminated on both sides. The lamination process was carried out by pressure bonding for 30 seconds at 100° C. and pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. A polyethylene terephthalate film as a support was peeled off from the laminated resin sheet. The treated surface of the CZ copper foil was laminated on the resin composition layer under the same conditions as above. Then, a sample was produced by curing the resin composition layer under curing conditions of 200° C. for 90 minutes to form an insulating layer.

<Measurement of copper foil peel strength (adhesion 1)>
The prepared samples were cut into 150 x 30 mm pieces. Using a cutter, cut the copper foil portion of the small piece with a width of 10 mm and a length of 100 mm. AC-50C-SL"), and using an Instron universal testing machine, at room temperature, the load when peeling off 35 mm in the vertical direction at a speed of 50 mm / min was measured in accordance with JIS C6481. .

<Measurement of copper foil peel strength (adhesion 2) after environmental resistance test (HAST)>
The prepared sample was subjected to an accelerated environmental test for 100 hours under conditions of 130° C. and 85% RH using a highly accelerated life tester (“PM422” manufactured by Kusumoto Kasei Co., Ltd.). After that, as in the measurement of adhesion 1, one end of the copper foil was peeled off and gripped with a gripper (manufactured by TSE Co., Autocom type testing machine, "AC-50C-SL"), and the Instron universal test Using a machine, the load was measured in accordance with JIS C6481 when a 35 mm strip was vertically peeled off at a speed of 50 mm/min at room temperature.

In addition, when the measurement result in adhesion 2 was less than 0.40 kgf/cm, it was evaluated as "x", and when it was 0.40 kgf/cm or more, it was evaluated as "good".

[Measurement of average particle size and specific surface area of inorganic filler]
<Method for measuring average particle size of inorganic filler>
100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed into a vial and dispersed with ultrasonic waves for 10 minutes. Using a laser diffraction particle size distribution analyzer ("LA-960" manufactured by Horiba Ltd.), the wavelength of the light source used was set to blue and red, and the particle size distribution of the inorganic filler was measured on a volume basis by a flow cell method. From the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median size.

<Method for measuring specific surface area of inorganic filler>
Using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co.), nitrogen gas is adsorbed on the sample surface, and the specific surface area is calculated using the BET multipoint method to determine the specific surface area of the inorganic filler. was measured.

[Example 1]
Bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 180) 10 parts, biphenyl aralkyl type epoxy resin (Nippon Kayaku "NC3000L", epoxy equivalent about 269) 20 parts, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) 10 parts, 10 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), solvent naphtha 25 The mixture was heated and dissolved while stirring. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenolic curing agent (DIC's "LA-3018-50P", 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%), active ester type curing. Agent ("HPC8000-65T" manufactured by DIC Corporation, a toluene solution with an active group equivalent of about 223 and a nonvolatile content of 65% by mass) 40 parts, a pyridine substituted with a cyclic amino group (4-pyrrolidinopyridine, solid content of 5% by mass) 1-Methoxy-2-propanol solution) 8 parts, spherical silica surface-treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") (average particle size 0.5 μm, specific surface area 11.2 m ² /g, "SOC2" manufactured by Admatechs Co., Ltd.) was mixed and uniformly dispersed by a high-speed rotating mixer to prepare a resin varnish.

Next, a resin varnish was evenly applied onto the release surface of a release-treated polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) so that the thickness of the resin composition layer after drying would be 30 μm. , 80 to 120° C. (average 100° C.) for 4 minutes to prepare a resin sheet.

The structure of 4-pyrrolidinopyridine is shown below.

[Example 2]
In Example 1, 40 parts of an active ester curing agent ("HPC8000-65T" manufactured by DIC, a toluene solution with an active group equivalent of about 223 and a nonvolatile content of 65% by mass) was added to an active ester curing agent ("EXB9416" manufactured by DIC). -70BK", a methyl isobutyl ketone solution with an active group equivalent weight of about 330 and a non-volatile content of 70% by mass), replaced by 38 parts of a pyridine substituted with a cyclic amino group (4-pyrrolidinopyridine, 1-methoxy with a solid content of 5% by mass -2-propanol solution) was changed from 8 parts to 12 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

[Example 3]
In Example 1,
1) Change the amount of biphenyl aralkyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269) from 20 parts to 10 parts,
2) 10 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed to 20 parts of naphthylene ether type epoxy resin ("HP6000" manufactured by DIC Corporation, epoxy equivalent of about 250),
3) Furthermore, 5 parts of a dicyclopentadiene type epoxy resin (manufactured by DIC, "HP7200HH", epoxy equivalent: about 283) was added.
A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

[Example 4]
In Example 1, 12 parts of a carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent weight: about 216, solid content: 50% by mass, toluene solution) was added. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

[Example 5]
In Example 1, 8 parts of pyridine substituted with a cyclic amino group (4-pyrrolidinopyridine, 1-methoxy-2-propanol solution with a solid content of 5% by mass) were added to pyridine substituted with a cyclic amino group (4- piperidinopyridine, 1-methoxy-2-propanol solution with a solid content of 5% by mass)) was changed to 8 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

The structure of 4-piperidinopyridine is shown below.

[Example 6]
In Example 5, spherical silica (average particle diameter 0.5 μm, specific surface area 11.2 m ² /g, Admatechs Co., Ltd.) surface-treated with a phenylaminosilane-based coupling agent (Shin-Etsu Chemical Co., Ltd., “KBM573”) "SOC2") was changed from 200 parts to 100 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 5 except for the above matters.

[Example 7]
In Example 6,
1) Spherical silica (average particle diameter 0.5 μm, specific surface area 11.2 m ² /g, Admatechs “SOC2”) surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) ) was added to 100 parts of spherical silica (average particle diameter 0.3 μm, specific surface area 30.7 m ² /g, Denki Kagaku Kogyo Co., Ltd.) surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) made "UFP-30") changed to 81 parts,
2) changing the amount of pyridine substituted with a cyclic amino group (4-piperidinopyridine, 1-methoxy-2-propanol solution with a solid content of 5% by mass) from 8 parts to 12 parts;
3) Further, 12 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution having an active group equivalent of about 216 and a solid content of 50% by mass) was added.
A resin varnish and a resin sheet were produced in the same manner as in Example 6 except for the above matters.

[Comparative Example 1]
In Example 1, 8 parts of pyridine substituted with a cyclic amino group (4-pyrrolidinopyridine, 1-methoxy-2-propanol solution with a solid content of 5% by mass) was added to a curing accelerator (N,N-dimethyl-4 - Aminopyridine (DMAP), MEK solution with a solids content of 5% by weight)) was changed to 8 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

The structure of N,N-dimethyl-4-aminopyridine is shown below.

[Comparative Example 2]
In Example 1, 8 parts of pyridine substituted with a cyclic amino group (4-pyrrolidinopyridine, 1-methoxy-2-propanol solution with a solid content of 5% by mass) were added to a curing accelerator (4-benzoylpyridine, solid content 5 mass % MEK solution) was changed to 8 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

The structure of 4-benzoylpyridine is shown below.

[Comparative Example 3]
In Example 7, 12 parts of pyridine substituted with a cyclic amino group (4-piperidinopyridine, 1-methoxy-2-propanol solution with a solid content of 5% by mass) was added to a curing accelerator (N,N-dimethyl- 4-aminopyridine, MEK solution with a solid content of 5% by mass)) was changed to 12 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 7 except for the above matters.

[Comparative Example 4]
In Example 7, 12 parts of pyridine substituted with a cyclic amino group (4-piperidinopyridine, 1-methoxy-2-propanol solution with a solid content of 5% by mass) was added to a curing accelerator (4-benzoylpyridine, solid 5% by weight MEK solution) was changed to 12 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 7 except for the above matters.

表中、「（Ｄ）成分の含有量（質量％）」は、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｄ）成分の含有量を表す。

In the table, "Content (% by mass) of component (D)" represents the content of component (D) when the non-volatile component in the resin composition is 100% by mass.

In Examples 1 to 7, even if the components (D) to (F) are not contained, it has been confirmed that the same results as in the above Examples are obtained, although there is a difference in degree.

Claims (14)

(A) an epoxy resin,
(B) an active ester curing agent, and (C) a pyridine substituted with a cyclic amino group, a resin composition containing
(A) component contains a liquid epoxy resin that is liquid at a temperature of 20 ° C.,
A resin composition in which the content of component (B) is 1% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is taken as 100% by mass. 2. The resin composition according to claim 1, further comprising (D) an inorganic filler. 3. The resin composition according to claim 2, wherein the content of component (D) is 50% by mass or more based on 100% by mass of non-volatile components in the resin composition. (A) an epoxy resin,
(B) an active ester curing agent,
(C) a pyridine substituted with a cyclic amino group, and (D) an inorganic filler, a resin composition containing
(A) component contains a liquid epoxy resin that is liquid at a temperature of 20 ° C.,
A resin composition in which the content of component (D) is 50% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass. The resin composition according to any one of claims 1 to 4, wherein the cyclic amino group in component (C) is bonded to the 4-position of the pyridine ring. The resin composition according to any one of claims 1 to 5, wherein the cyclic amino group in component (C) is a saturated cyclic amino group. 7. The resin composition according to any one of claims 1 to 6, wherein the cyclic amino group in component (C) is a 5- or 6-membered cyclic amino group. The resin composition according to any one of claims 1 to 7, which is used for insulation. The resin composition according to any one of claims 1 to 8, which is used for forming an insulating layer. The resin composition according to any one of claims 1 to 9, which is used for forming an insulating layer for forming a conductor layer. The resin composition according to any one of claims 1 to 8, which is used for encapsulating semiconductor chips. A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 11 provided on the support. 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 11. A semiconductor device comprising the printed wiring board according to claim 13 .