JP7214981B2 - Resin composition, sheet laminate material, printed wiring board and semiconductor device - Google Patents

Description

The present invention relates to resin compositions. Furthermore, it relates to a sheet-like laminate material, a printed wiring board, and a semiconductor device.

As a technique for manufacturing a printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer substrate is known. An insulating layer is generally formed from a cured product of a resin composition.

For example, Patent Document 1 discloses (A) a phosphonate compound having one or more ethylenically unsaturated bonds in the molecule, (B) two or more ethylenically unsaturated bonds in the molecule and one or more aromatic Disclosed is a resin composition comprising a radically polymerizable compound having a hydrocarbon or an alicyclic hydrocarbon, and (C) an inorganic filler, wherein the (A) component and the (B) component are different compounds.

Further, Patent Document 2 discloses a resin composition characterized by containing (A) a radically polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component. .

JP 2016-210856 A JP 2014-034580 A

In recent years, there has been an increasing demand for a resin composition capable of forming an insulating layer with a low dielectric loss tangent. In addition, electronic devices are becoming more compact and higher in performance, and printed wiring boards are required to have multiple build-up layers and finer and higher density wiring.

In order to achieve further miniaturization and higher density of wiring, there is a demand for a resin composition that has a low dielectric loss tangent, excellent smear removability, and can provide a cured product with excellent adhesion to the conductor layer. be done. In addition, from the viewpoint of prolonging the adhesiveness, it is required that the adhesiveness is particularly excellent after a high-temperature high-humidity environment test (HAST). However, the current situation is that all of these are not fully satisfied.

Accordingly, an object of the present invention is to provide a resin composition that has a low dielectric loss tangent, is excellent in smear removal properties, and can provide a cured product having excellent adhesion to a conductor layer; a sheet-like laminate containing the resin composition The present invention provides a material; a printed wiring board provided with an insulating layer made of a cured product formed using the resin composition; and a semiconductor device containing the cured product of the resin composition.

As a result of extensive studies on the above problems, the present inventors have found that a combination of (A) an epoxy resin, (B) a resin having a radically polymerizable unsaturated group, and (C) an epoxy resin curing agent is blended in a specific amount. By doing so, the inventors have found that the above problems can be achieved, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a resin having a radically polymerizable unsaturated group, and (C) an epoxy resin curing agent, wherein the component (A) is (A-1) When the content of component (A) other than component (A-1) containing glycidylamine-type epoxy resin is 100 parts by mass, the content of component (A-1) is 2 to 250 parts by mass, ( A resin composition in which the content of component (A-1) is 3 to 250 parts by mass when the content of component B) is 100 parts by mass.
[2] The resin composition according to [1], wherein component (A-1) is a difunctional or trifunctional glycidylamine type epoxy resin.
[3] The resin composition according to [1] or [2], wherein the content of component (A-1) is 0.20 to 10 parts by mass when the non-volatile component in the resin composition is 100 parts by mass. thing.
[4] Any of [1] to [3], wherein component (C) is selected from the group consisting of active ester curing agents, phenolic curing agents, carbodiimide curing agents, and benzoxazine curing agents. The described resin composition.
[5] The resin composition according to any one of [1] to [4], wherein the component (B) is a (meth)acrylic acid ester.
[6] The resin composition according to any one of [1] to [5], wherein the content of component (A) is 100 to 1000 parts by mass when the content of component (B) is 100 parts by mass. .
[7] The resin composition according to any one of [1] to [6], further comprising (D) an inorganic filler.
[8] The resin composition according to [7], wherein the content of component (D) is 65 parts by mass or more based on 100 parts by mass of non-volatile components in the resin composition.
[9] The resin composition according to any one of [1] to [8], further comprising (E) a thermoplastic resin.
[10] The resin composition according to any one of [1] to [9], which is used for forming an insulating layer for forming a conductor layer.
[11] The resin composition according to any one of [1] to [9], which is for forming an insulating layer of a printed wiring board.
[12] A sheet-like laminate material containing the resin composition according to any one of [1] to [9].
[13] A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [9].
[14] A semiconductor device comprising a cured product of the resin composition according to any one of [1] to [9].

According to the resin composition of the present invention, a cured product having a low dielectric loss tangent, excellent smear removal properties, and excellent adhesion to a conductor layer; a sheet-like laminate material containing the resin composition; the resin composition and a semiconductor device comprising a cured product of the resin composition.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. 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 comprises (A) an epoxy resin, (B) a resin having a radically polymerizable unsaturated group, and (C) an epoxy resin curing agent, wherein the component (A) is When the content of component (A) other than component (A-1) containing (A-1) glycidylamine type epoxy resin is 100 parts by mass, the content of component (A-1) is 2 to 250 mass parts. When the content of component (B) is 100 parts by mass, the content of component (A-1) is 3 to 250 parts by mass.

By using such a resin composition, it is possible to obtain the desired effect of the present invention that it is possible to obtain a cured product having a low dielectric loss tangent, excellent adhesion to the conductor layer, and excellent smear removal properties. be done.

The resin composition of the present invention may further contain optional components in addition to (A) an epoxy resin, (B) a resin having a radically polymerizable unsaturated group, and (C) an epoxy resin curing agent. Examples of optional components include (D) an inorganic filler, (E) a thermoplastic resin, (F) a curing accelerator, (G) a polymerization initiator, and (H) other additives. Each component contained in the resin composition will be described in detail below.

<(A) Epoxy resin>
The resin composition of the present invention contains an epoxy resin as component (A). Component (A) contains (A-1) a glycidylamine type epoxy resin, and further contains other epoxy resins apart from component (A-1).

When the non-volatile component in the resin composition is 100 parts by mass, the content of component (A) in the resin composition is preferably 2 mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. parts or more, more preferably 5 parts by mass or more, and still more preferably 8 parts by mass or more. The upper limit is preferably 60 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

When the content of component (B) is 100 parts by mass, the content of component (A) in the resin composition is preferably 100 parts by mass or more, more preferably 100 parts by mass or more, from the viewpoint of obtaining a cured product having excellent adhesion. is 150 parts by mass or more, more preferably 200 parts by mass or more. The upper limit is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, and even more preferably 550 parts by mass or less from the viewpoint of obtaining a cured product with a low dielectric loss tangent.

<Epoxy resin other than (A-1) component>
Epoxy resins other than component (A-1) (that is, component (A) other than component (A-1)) include, for example, bisphenol-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, and naphthol novolak. type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin , 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 resins, trimethylol-type epoxy resins, and tetraphenylethane-type epoxy resins. Epoxy resins other than component (A-1) may be used alone or in combination of two or more.

Bisphenol-type epoxy resins refer to epoxy resins having a bisphenol structure, and include, for example, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, and bisphenol AF-type epoxy resins.

A biphenyl-type epoxy resin refers to an epoxy resin having a biphenyl structure, where the biphenyl structure may have a substituent such as an alkyl group, an alkoxy group, or an aryl group. Therefore, bixylenol type epoxy resins and biphenyl aralkyl type epoxy resins are also included in biphenyl type epoxy resins.

As the epoxy resin other than the component (A-1), an aromatic epoxy resin is preferable. Here, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule. The aromatic ring includes not only monocyclic structures such as benzene ring but also polycyclic aromatic structures such as naphthalene ring and aromatic heterocyclic structures. Among them, from the viewpoint of achieving excellent adhesion in combination with components (A-1) and (B), epoxy resins other than component (A-1) are bisphenol type epoxy resins, biphenyl type epoxy resins, naphthyl One or more selected from the group consisting of rene ether-type epoxy resins, naphthalene-type tetrafunctional epoxy resins and naphthol-type epoxy resins is preferred, and one or more selected from the group consisting of bisphenol-type epoxy resins and naphthol-type epoxy resins is more preferred. , bisphenol A type epoxy resins and naphthol type epoxy resins.

Epoxy resins other than component (A-1) preferably have two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin other than the component (A-1) is 100% by mass, the ratio of the epoxy resin other than the component (A-1) having two or more epoxy groups in one molecule is preferably 50%. % by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.

Generally, epoxy resins include an epoxy resin that is liquid at a temperature of 20° C. (hereinafter also referred to as “liquid epoxy resin”) and an epoxy resin that is solid at a temperature of 20° C. (hereinafter also referred to as “solid epoxy resin”). be. The resin composition of the present invention may contain a liquid epoxy resin alone as an epoxy resin other than component (A-1), or may contain a solid epoxy resin alone. may be included in combination with a similar epoxy resin. Above all, the resin composition of the present invention preferably contains a solid epoxy resin alone or a combination of a solid epoxy resin and a liquid epoxy resin as the epoxy resin other than component (A-1).

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 biphenyl-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, and biphenyl-type epoxy resins. Epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol type epoxy resin, tetraphenylethane type epoxy resin are preferred, bixylenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, naphthalene type epoxy resin. Tetrafunctional epoxy resins and naphthol-type epoxy resins are more preferred, and naphthol-type epoxy resins are even more preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; DIC's "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl aralkyl type epoxy resin); Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin); Nippon Steel & Sumikin Chemical Co., Ltd. "ESN485" (naphthol Novolak type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin); "PG-100" and "CG-500" (bisphenol AF type epoxy resin) manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical Corporation (tetraphenylethane type epoxy resin) ; These may be used individually by 1 type, and may be used in combination of 2 or more type.

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.

Liquid epoxy resins include bisphenol-type epoxy resins, naphthalene-type epoxy resins, glycidyl ester-type epoxy resins, phenol novolak-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and butadiene structures are preferred, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferred, and bisphenol A type epoxy resin is particularly preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC; ", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin); Celoxide 2021P” (alicyclic epoxy resin having an ester skeleton); “PB-3600” manufactured by Daicel Corporation (epoxy resin having a butadiene structure); “ZX1658” and “ZX1658GS” manufactured by Nippon Steel & Sumikin Chemical Co. 4-glycidylcyclohexane type epoxy resin); These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a combination of a liquid epoxy resin and a solid epoxy resin is used as the epoxy resin other than the component (A-1), the mass ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1. to 1:15, more preferably 1:0.5 to 1:10, still more preferably 1:1 to 1:8, and particularly preferably 1:2 to 1:5. When the mass ratio of the liquid epoxy resin and the solid epoxy resin is within the above range, i) moderate adhesiveness is provided when used in the form of a sheet-like laminate material, and ii) the form of the sheet-like laminate material. When used in , sufficient flexibility can be obtained to improve handleability, and iii) an insulating layer having sufficient breaking strength can be obtained.

The epoxy equivalent of the epoxy resin other than component (A-1) is preferably 50 to 5000 g/eq, more preferably 50 to 3000 g/eq, still more preferably 80 to 2000 g/eq, and particularly preferably 110 to 1000 g/eq. be. When the epoxy equivalent of the epoxy resin is within the above range, the crosslink density of the cured product of the resin composition is sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent is the mass of a resin containing one equivalent of epoxy groups, and can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100-5000, more preferably 250-3000, and still more preferably 400-1500. In addition, a weight average molecular weight is a weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

When the non-volatile component in the resin composition is 100 parts by mass, the content of the epoxy resin other than the component (A-1) in the resin composition is from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability. Therefore, it is preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more, and still more preferably 2.5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

<(A-1) Glycidylamine type epoxy resin>
(A-1) Glycidylamine-type epoxy resin refers to an epoxy resin containing at least one glycidylamino group and/or diglycidylamino group. A glycidylamino group contains one epoxy group, and a diglycidylamino group contains two epoxy groups.

(A-1) The glycidylamine-type epoxy resin is preferably a bifunctional or more glycidylamine-type epoxy resin having two or more epoxy groups in one molecule from the viewpoint of obtaining a cured product having excellent heat resistance. , more preferably a bifunctional or trifunctional glycidylamine type epoxy resin having 2 or 3 epoxy groups in one molecule. Here, epoxy groups are not limited to those derived from glycidylamino groups and diglycidylamino groups. When the non-volatile component of the glycidylamine type epoxy resin is 100 parts by mass, the ratio of the difunctional or higher glycidylamine type epoxy resin is preferably 50 parts by mass or more, more preferably 60 parts by mass, from the viewpoint of increasing the heat resistance of the cured product. It is at least 70 parts by mass, more preferably at least 70 parts by mass. The component (A-1) may be used alone or in combination of two or more.

(A-1) The glycidylamine type epoxy resin preferably has an aromatic ring in the molecule from the viewpoint of further improving heat resistance and lowering the coefficient of linear thermal expansion. Aromatic rings include a benzene ring and a naphthalene ring.

Examples of preferred (A-1) glycidylamine type epoxy resins from the viewpoint of significantly obtaining the desired effects of the present invention include those represented by the following formula (a1).

In formula (a1), each R ¹¹ independently represents a glycidyloxy group or an alkyl group. When R ¹¹ is a glycidyloxy group, R ¹¹ is preferably bonded at the para position relative to the bonding site between the nitrogen atom and the benzene ring. Moreover, when R ¹¹ is an alkyl group, it is preferably bonded at the ortho position with respect to the bonding site ^between the nitrogen atom and the benzene ring.

An alkyl group refers to a linear or branched monovalent aliphatic saturated hydrocarbon group. An alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl and the like.

In formula (a1), R ¹² represents a hydrogen atom or a monovalent to trivalent hydrocarbon group. Examples of hydrocarbon groups include monovalent hydrocarbon groups such as alkyl groups and aryl groups, and divalent hydrocarbon groups such as alkylene groups and arylene groups. Among them, when m is 1, from the viewpoint of obtaining the desired effects of the present invention, R ¹² is preferably an alkyl group, more preferably a methyl group. Further, when m is 2, from the viewpoint of obtaining the desired effect of the present invention, R ¹² is preferably an alkylene group, more preferably a methylene group.

An aryl group refers to a monovalent aromatic hydrocarbon group. An aryl group having 6 to 14 carbon atoms is preferred, and an aryl group having 6 to 10 carbon atoms is more preferred. Examples include phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, 2-anthryl and the like.

An alkylene group refers to a linear or branched divalent saturated aliphatic hydrocarbon group. An alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 1 to 5 carbon atoms is more preferred. Examples thereof include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 1,1-dimethylethylene group, etc., and the bonding positions thereof are not particularly limited.

An arylene group refers to a divalent aromatic hydrocarbon group. An arylene group having 6 to 14 carbon atoms is preferred, and an arylene group having 6 to 10 carbon atoms is more preferred. Examples include a phenylene group, a naphthylene group, a biphenylene group, and the like, and the bonding positions thereof are not particularly limited.

In formula (a1), each n independently represents an integer of 0 to 4. Among them, n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.

In formula (a1), m represents an integer of 1-3. Among them, m is preferably 1 or 2, more preferably 1.

(A-1) Specific examples of the glycidylamine type epoxy resin include "630" (according to the following formula) and "630LSD" manufactured by Mitsubishi Chemical Corporation, "EP3980S" (according to the following formula) manufactured by ADEKA, " EP3950S", "EP3950L", Sumitomo Chemical's "ELM-100" (according to the following formula), "ELM-100H", "ELM-434" (according to the following formula), "ELM-434L", etc. be done. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(A-1) The epoxy equivalent of the glycidylamine type epoxy resin is preferably 50 to 5000 g/eq, more preferably 50 to 3000 g/eq, still more preferably 60 to 2000 g/eq, and particularly preferably 70 to 1000 g/eq. be. When the epoxy equivalent of the glycidylamine type epoxy resin is within the above range, the crosslink density of the cured product of the resin composition is sufficient, and an insulating layer with a small surface roughness can be obtained.

(A-1) The weight average molecular weight (Mw) of the glycidylamine type epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500.

When the non-volatile component in the resin composition is 100 parts by mass, the content of the component (A-1) in the resin composition is preferably It is 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, and still more preferably 0.25 parts by mass or more. The upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, from the viewpoint of obtaining a cured product with a particularly low dielectric loss tangent.

When the content of component (A) other than component (A-1) in the resin composition is 100 parts by mass, the content of component (A-1) in the resin composition is the smear removal property and adhesion From the viewpoint of obtaining a cured product having excellent properties, the amount is 2 parts by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. The upper limit is 250 parts by mass or less, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, from the viewpoint of obtaining a cured product with a low dielectric loss tangent.

When the content of component (B) in the resin composition is 100 parts by mass, the content of component (A-1) in the resin composition is from the viewpoint of obtaining a cured product with excellent smear removal properties and adhesion. Therefore, it is 3 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. The upper limit is 250 parts by mass or less, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 50 parts by mass or less, from the viewpoint of obtaining a cured product with a low dielectric loss tangent. is.

<(B) Resin Having a Radically Polymerizable Unsaturated Group>
The resin composition of the present invention contains a resin having a radically polymerizable unsaturated group (hereinafter also referred to as “unsaturated resin”) as the component (B). By containing the component (B), the dielectric loss tangent can be lowered, and a cured product with excellent smear removability can be obtained.

A cured product of a resin composition containing (B) an unsaturated resin usually contains a molecular structure site formed by reaction of an unsaturated bond site of the (B) unsaturated resin. As a result, the polarity of the cured product is reduced, and the value of the dielectric loss tangent can be kept low.

One molecule of the (B) unsaturated resin may contain only one radically polymerizable unsaturated group, or a plurality thereof may be contained. (B) The unsaturated resin preferably has two or more radically polymerizable unsaturated groups per molecule from the viewpoint of obtaining a cured product having a low dielectric loss tangent and excellent smear removability.

The radically polymerizable unsaturated group is preferably a group having a carbon-carbon double bond. Examples of the radically polymerizable unsaturated group include an acryloyl group (--CO--CH=CH ₂ ), a methacryloyl group (--CO--C(CH ₃ )=CH ₂ ), a styryl group (--CH=CH--C ₆ H ₅ ), allyl group (--CH ₂ --CH=CH ₂ ), maleimide group (--NC ₄ O ₂ H ₂ ), and the like. Among them, an acryloyl group or a methacryloyl group is preferable. That is, the unsaturated resin is preferably a (meth)acrylic acid ester. The term "(meth)acrylic acid ester" includes acrylic acid esters, methacrylic acid esters, and combinations thereof.

(B) The unsaturated resin preferably has a cyclic group from the viewpoint of obtaining a cured product having a low dielectric loss tangent and excellent smear removability. The cyclic group may be either a non-aromatic cyclic group or an aromatic cyclic group. Among them, a non-aromatic cyclic group is preferable from the viewpoint of significantly obtaining the desired effects of the present invention.

From the viewpoint of significantly obtaining the desired effect of the present invention, the cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, and preferably a 25-membered ring or less. It is preferably a 20-membered ring or less, more preferably a 15-membered ring or less. Moreover, the cyclic group may have a monocyclic structure or a polycyclic structure.

The ring in the cyclic group may have a ring skeleton composed of heteroatoms other than carbon atoms. The heteroatom includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc., and an oxygen atom is preferred. The ring may have one heteroatom, or may have two or more.

Specific examples of the cyclic group include the following divalent groups (i) to (xi). Among them, (x) or (xi) is preferable as the cyclic group.

The cyclic group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, A mercapto group, an oxo group and the like can be mentioned, and an alkyl group is preferred.

An alkoxy group refers to a monovalent group formed by bonding an alkyl group to an oxygen atom. An alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 5 carbon atoms is more preferred. Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy and the like.

An arylalkyl group refers to a monovalent group formed by replacing any hydrogen atom of an alkyl group with an aryl group. For example, a benzyl group and the like can be mentioned.

The acyl group refers to a group represented by RCO- (wherein R represents an alkyl group, an aryl group, an arylalkyl group, etc.). Examples include acetyl group and benzoyl group.

The radically polymerizable unsaturated group may be directly bonded to the cyclic group, or may be bonded via a divalent linking group. Examples of divalent linking groups include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, -C(=O)O-, -O-, -NHC(=O)-, and -NC(=O). Examples include N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, and -NH-, and may be a group combining a plurality of these.

An alkenylene group refers to a linear or branched divalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. An alkylene group having 2 to 10 carbon atoms is preferred, and an alkylene group having 2 to 5 carbon atoms is more preferred. For example, ethenyl, 1-propenyl, 2-propenyl (allyl), 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl , 3-pentenyl, 4-pentenyl and the like.

The heteroarylene group refers to a divalent aromatic heterocyclic group containing a heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom in the aromatic ring. A 5- or 6-membered heteroarylene group is preferred. The number of heteroatoms is preferably 1-4. pyridine-2,6-diyl, thiazole-5,4-diyl and the like.

(B) The unsaturated resin is preferably a compound represented by the following formula (1).

(In formula (1), R ¹ and R ⁴ each independently represent a radically polymerizable unsaturated group, R ² and R ³ each independently represent a divalent linking group, and Ring A represents a cyclic group. .)

R ¹ and R ⁴ each independently represent a radically polymerizable unsaturated group, preferably an acryloyl group or a methacryloyl group, more preferably an acryloyl group. R ² and R ³ each independently represent a divalent linking group. The divalent linking group is the same as the above divalent linking group. Ring A represents a cyclic group. Ring A is the same as the above cyclic group. Ring A may have a substituent. The substituent is the same as the substituent that the cyclic group may have.

Specific examples of the unsaturated resin represented by formula (1) include Shin-Nakamura Chemical Co., Ltd. "A-DOG" (dioxane acrylic monomer glycol diacrylate, number average molecular weight 326, represented by the following formula (2) compound), Shin-Nakamura Chemical Co., Ltd. "A-DCP" (tricyclodecanedimethanol diacrylate, number average molecular weight 304, compound represented by the following formula (3)), etc., but are limited to these not a thing

As a specific example of the unsaturated resin other than the unsaturated resin represented by formula (1), "YL7776" manufactured by Mitsubishi Chemical Corporation (bixylenol diallyl ether resin, number average molecular weight 331, represented by the following formula (4) compound), “MIR-3000-70MT” (biphenylmaleimide resin, compound represented by the following formula (5)) manufactured by Nippon Kayaku Co., Ltd., but not limited thereto.

In formula (5), n represents 1-5.

(B) The unsaturated resin preferably has a number average molecular weight of 100 or more, more preferably 200 or more, and preferably 10,000 or less, more preferably 3,000 or less. (B) When the number average molecular weight of the unsaturated resin is within the above range, volatilization of the resin varnish during drying can be suppressed, and excessive melt viscosity of the resin composition can be suppressed. The number average molecular weight can be measured in terms of polystyrene by gel permeation chromatography (GPC). Measurement of the number average molecular weight by the GPC method, for example, using "LC-9A / RID-6A" manufactured by Shimadzu Corporation as a measuring device, "Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Co., Ltd. as a column. ”, chloroform is used as a mobile phase, and the measurement can be performed at a column temperature of 40° C.

When the resin component in the resin composition is 100 parts by mass, the content of component (B) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, from the viewpoint of significantly obtaining the effects of the present invention. More preferably, it is 5 parts by mass or more. The upper limit is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less. The “resin component” of the resin composition refers to a non-volatile component contained in the resin composition, excluding (D) the inorganic filler.

When the non-volatile component in the resin composition is 100 parts by mass, the content of the component (B) in the resin composition is excellent in smear removal, from the viewpoint of obtaining a resin composition that provides a cured product with a low dielectric loss tangent. , preferably 1% by mass or more, more preferably 2% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, or 7% by mass, from the viewpoint of improving the compatibility of the resin composition and particularly enhancing the adhesion after HAST. % or less.

<(C) Epoxy resin curing agent>
The resin composition of the present invention contains (C) an epoxy resin curing agent as the (C) component. (C) The epoxy resin curing agent is not particularly limited as long as it has a function of curing the epoxy resin. hardeners and carbodiimide hardeners. The curing agent may be used singly or in combination of two or more.

The epoxy resin curing agent is preferably a curing agent selected from the group consisting of active ester curing agents, phenolic curing agents, carbodiimide curing agents, and benzoxazine curing agents.

From the viewpoint of obtaining a cured product with excellent heat resistance, low dielectric loss tangent, excellent smear removability, and excellent adhesion to the conductor layer, the component (C) contains an active ester curing agent. is preferred. When the total amount of component (C) is 100 parts by mass, the content of the active ester curing agent is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 75% by mass or more.

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. In addition, from the viewpoint of enhancing adhesion to the conductor layer, a nitrogen-containing phenolic curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer. Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, “MEH-7700”, “MEH-7810” and “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", Nippon Steel & Sumikin Chemical Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD2090" manufactured by DIC Corporation ” and the like.

The active ester-based curing agent is not particularly limited, but generally contains an ester group with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds in one molecule. A compound having two 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, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene type diphenol structure. ), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated phenol novolak, benzoyl of phenol novolac "YLH1026" (made by Mitsubishi Chemical Corporation) etc. are mentioned as an active-ester compound containing a compound.

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; -d”, “Fa”, and the like.

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- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate ester resins) and "BA230" (a part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. is triazined to form a trimer) and the like.

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

When the non-volatile component in the resin composition is 100 parts by mass, the content of component (C) in the resin composition is preferably 5% by mass or more, more It is preferably 8% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

The ratio of (A) the epoxy resin to (C) the epoxy resin curing agent is [total number of epoxy groups in the epoxy resin]:[total number of reactive groups in the curing agent], and is 1:0.2 to A range of 1:2 is preferred, 1:0.3 to 1:1.5 is more preferred, and 1:0.4 to 1:1.2 is even more preferred. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and varies depending on the type of curing agent. Further, the total number of epoxy groups in the epoxy resin is the sum of the values obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups in the curing agent is It is a value obtained by dividing the solid content mass of each curing agent by the reactive group equivalent and totaling all the curing agents. By setting the amount ratio of the epoxy resin to the curing agent within such a range, the heat resistance of the obtained insulating layer is further improved.

<(D) Inorganic filler>
The resin composition of the present invention may further contain an inorganic filler as component (D). By including an inorganic filler, a cured product having a lower coefficient of linear thermal expansion and a lower dielectric loss tangent can be achieved.

(D) The material of the inorganic filler is not particularly limited, but examples 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. Silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(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”; Admatechs “SC2500SQ”, “SO-C4”, “SO-C2”, “SO-C1”;

The average particle size of the inorganic filler is preferably 4 µm or less, more preferably 3 µm or less, still more preferably 2.5 µm or less, even more preferably 2 µm or less, and particularly preferably 1 µm or less, 0.7 µm or less, or 0.5 µm. It is below. The lower limit of the average particle size of the inorganic filler is preferably 0.01 µm or more, more preferably 0.03 µm or more, and still more preferably 0.05 µm or more, 0.07 µm or more, or 0.1 µm or more. 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 can be prepared on a volume basis using a laser diffraction particle size distribution measuring apparatus, and the median diameter can be used as the average particle size for measurement. As the measurement sample, one obtained by ultrasonically dispersing an inorganic filler in water can be preferably used. "LA-500", "LA-750", "LA-950" manufactured by Horiba, Ltd. and the like can be used as the laser diffraction particle size distribution analyzer.

Inorganic fillers include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, etc., from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents. 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. silane), Shin-Etsu Chemical 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 ), “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

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 preventing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, 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 specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 1.5 m ² /g or more, and particularly preferably 2 m ² /g or more, from the viewpoint of further improving the effects of the present invention. be. Although there is no particular upper limit, it is preferably 20 m ² /g or less, 10 m ² /g or less, or 5 m ² /g or less. The specific surface area of the inorganic filler can be measured by the BET method.

When the non-volatile component in the resin composition is 100 parts by mass, the content of the inorganic filler (D) in the resin composition is preferably 50 from the viewpoint of obtaining a cured product with a low linear thermal expansion coefficient and dielectric loss tangent. % by mass or more, more preferably 55% by mass or more, 60% by mass or more, or 65% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of the mechanical strength of the resulting cured product.

<(E) Thermoplastic resin>
The resin composition of the present invention may further contain (E) a thermoplastic resin as an optional component in addition to the components described above.

Examples of thermoplastic resins as component (E) 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 them, the phenoxy resin is preferable from the viewpoint of obtaining the desired effects of the present invention remarkably and from the viewpoint of obtaining an insulating layer having a small surface roughness and particularly 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.

(E) 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.

When the non-volatile component in the resin composition is 100 parts by mass, the content of (E) the thermoplastic resin is preferably 0.1 parts by mass or more, more preferably 0.1 part by mass or more, from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.3 parts by mass or more, more preferably 0.5 parts by mass or more. The upper limit is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less.

<(F) Curing accelerator>
The resin composition may further contain (F) a curing accelerator as an optional component in addition to the components described above.

Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, and metallic curing accelerators are preferred, and amine curing accelerators, imidazole curing accelerators, and metallic curing accelerators are more preferred. The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1, 8-diazabicyclo(5,4,0)-undecene, etc., and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

Examples of imidazole curing accelerators 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-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(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 isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

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

When the non-volatile component in the resin composition is 100 parts by mass, the content of (F) the curing accelerator is preferably 0.001 parts by mass or more, more preferably 0.001 part by mass or more, from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.01 parts by mass or more, more preferably 0.05 parts by mass or more. The upper limit is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.1 part by mass or less.

<(G) Polymerization initiator>
The resin composition may further contain (G) a polymerization initiator as an optional component in addition to the components described above. (G) The polymerization initiator usually has a function of promoting cross-linking of the radically polymerizable unsaturated groups in the component (B). (G) The polymerization initiator may be used singly or in combination of two or more.

(G) Polymerization initiators include, for example, t-butyl cumyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t -butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxybenzoate and other peroxides.

(G) Commercially available polymerization initiators include, for example, “Perbutyl C”, “Perbutyl A”, “Perbutyl P”, “Perbutyl L”, “Perbutyl O”, “Perbutyl ND” and “Perbutyl ND” manufactured by NOF Corporation. Perbutyl Z”, “Perbutyl P”, “Perkmyl D” and the like.

When the non-volatile component in the resin composition is 100 parts by mass, the content of the polymerization initiator (G) is preferably 0.001 parts by mass or more, more preferably 0.001 part by mass or more, from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 5 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.

<(H) Other Additives>
The resin composition may further contain other additives as optional components in addition to the components described above. Such additives include, for example, organic fillers; resin additives such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents; and the like. These additives may be used singly or in combination of two or more. Each content can be appropriately set by those skilled in the art.

<Preparation and physical properties of resin composition>
The method of preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a solvent or the like to the compounding ingredients, if necessary, and mixing and dispersing using a rotating mixer or the like.

According to the resin composition of the present invention, it is possible to obtain a cured product having a low dielectric loss tangent, excellent smear removability, and excellent adhesion to the conductor layer. The present inventor presumes that the mechanism by which such excellent effects are obtained is as follows. However, the technical scope of the present invention is not limited by the mechanism described below.

According to the studies of the present inventors, it has been found that combining (A) an epoxy resin with (B) an unsaturated resin can improve the dielectric loss tangent and the smear removability of the cured product. However, (A) the epoxy resin and (B) the unsaturated resin usually have different polarities, and thus have low compatibility and tend to separate at a minute level in the cured product. Therefore, a cured product of a resin composition containing a combination of (A) an epoxy resin and (B) an unsaturated resin generally has a reduced mechanical strength in a high-temperature, high-humidity environment test, and delamination is likely to occur. Therefore, conventionally, it has been difficult to obtain a cured product having excellent adhesion to the conductor layer after a high-temperature and high-humidity test.

On the other hand, (A-1) glycidylamine type epoxy resin is compatible with both (A) epoxy resin other than the (A-1) glycidylamine type epoxy resin and (B) unsaturated resin. Excellent for Therefore, by using (A-1) glycidylamine type epoxy resin, separation of (A) epoxy resin other than (A-1) glycidylamine type epoxy resin and (B) unsaturated resin can be suppressed. A decrease in the mechanical strength of the cured product due to a high-humidity test can be suppressed. Furthermore, (A-1) the glycidylamine type epoxy resin has the effect of improving the smear removability and adhesion of the cured product. Therefore, according to the combination of (A) epoxy resin other than (A-1) glycidylamine type epoxy resin, (A-1) glycidylamine type epoxy resin, and (B) unsaturated resin in appropriate amounts, Since delamination can be suppressed without impairing good dielectric loss tangent and smear removability, a cured product excellent in all of dielectric loss tangent, smear removability and adhesion can be realized.

An insulating layer made of a cured product of the resin composition of the present invention exhibits excellent adhesion (peel strength) to a conductor layer such as a copper foil. The copper foil adhesion (adhesion strength) before the high temperature and high humidity environment test (HAST) is preferably 0.62 kgf/cm or more, more preferably 0.65 kgf/cm or more, and still more preferably 0.70 kgf/cm or more. be. The copper foil adhesion after HAST is preferably 0.25 kgf/cm or more, more preferably 0.30 kgf/cm or more, still more preferably 0.35 kgf/cm or more, and particularly preferably 0.40 kgf/cm or more. . On the other hand, the upper limit of adhesion (adhesion strength) is not particularly limited, but may be 5 kgf/cm or less. The copper foil adhesion can be measured according to the method described in the examples below.

A cured product of the resin composition of the present invention is characterized by a low dielectric loss tangent. The dielectric loss tangent of the cured product is preferably less than 0.0054, more preferably less than 0.0052, still more preferably less than 0.0050 and less than 0.0048. On the other hand, the lower limit of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be evaluated according to the method described in Examples below.

Moreover, the cured product of the resin composition of the present invention exhibits excellent smear removability. The maximum smear length of the cured product is preferably less than 5 µm. "Maximum smear length" means the maximum length of smear from the circumference of the bottom surface of the via to the center of the circle. The maximum smear length can be evaluated according to the method described in Examples below.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can reduce the dielectric loss tangent and can provide an insulating layer with excellent smear removal properties and adhesion. 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). Moreover, in the printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention also includes adhesive films, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, component-embedding resins, and the like. Can be used for a wide range of applications.

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). A rewiring layer may be further formed on the encapsulation layer when the semiconductor chip package is manufactured.
(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.

<Sheet-like laminated material>
Although the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminate material, an adhesive film (hereinafter also referred to as a "resin sheet") and a prepreg are preferable.

In one embodiment, the adhesive film comprises a support and a resin composition layer (adhesive layer) bonded to the support, wherein the resin composition layer (adhesive layer) is the resin composition of the present invention. formed from

The thickness of the resin composition layer is preferably 50 μm or less, more It is preferably 40 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 adhesive film may further contain optional layers as needed. Examples of such an optional layer include 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 adhesive film, 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 adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

In one embodiment, a prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 μm or more.

A prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

In the present invention using a resin composition containing a combination of components (A), (B), and (C) in a specific content, the glass transition temperature is high, the dielectric loss tangent is low, and the conductor layer and It is possible to realize a sheet-like laminated material that gives a cured product with good adhesion and is extremely useful in the production of printed wiring boards.

The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for interlayer insulating layers of wiring boards).

<Printed wiring board>
The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

A printed wiring board can be produced, for example, using the above-described adhesive film by a method including the following steps (I) and (II).
(I) Step of laminating an adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) Curing (for example, thermosetting) the resin composition layer to form an insulating layer process

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 may be used.

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

Lamination of the inner layer substrate and the adhesive film 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., 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 adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression 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 cured (for example, thermally cured) to form an insulating layer. Curing conditions for the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer of a printed wiring board 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 lower than 120° C., preferably 60° C. or higher and lower than 115° C., more preferably 70° C. or higher and lower than 110° C. Minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes, may be preheated.

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.

In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as in the case of using an adhesive film.

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 100° 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.

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.

When producing a printed wiring board using the resin composition of the present invention containing a combination of components (A), (B), and (C) in a specific content, the conductor layer is formed by plating, or Adhesion between the conductor layer and the insulating layer can be remarkably improved regardless of whether or not they are formed using metal foil.

<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 examples shown below. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

First, the measurement/evaluation methods in the evaluation of physical properties in this specification will be described.

<Preparation of sample for measuring copper foil adhesion>
(1) Surface treatment of copper foil Electrolytic copper foil (“3EC-III” manufactured by Mitsui Kinzoku Mining Co., Ltd., thickness 35 μm) is immersed in a micro-etching agent (“CZ-8101” manufactured by MEC Co., Ltd.). Then, the copper surface was subjected to roughening treatment (Ra value=1 μm), and then to antirust treatment using an antirust solution (“CL8300” manufactured by MEC Co., Ltd.). The obtained copper foil is called CZ copper foil. Further, heat treatment was performed in an oven at 130° C. for 30 minutes.

(2) Lamination of copper foil and formation of insulating layer As an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Co., Ltd.) on which an inner layer circuit was formed was used. "R1515A") was prepared. Then, the resin sheets obtained in the following Examples and Comparative Examples were processed using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) so that the resin composition layer became the inner layer circuit board. It laminated|stacked on both surfaces of the inner layer circuit board so that it might join. Lamination 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. After lamination, the PET film was peeled off. The treated surface of the CZ copper foil was laminated on the exposed resin composition layer under the same conditions as above. After that, the resin composition layer was cured under curing conditions of 190° C. for 90 minutes to form an insulating layer, thereby obtaining a sample having a structure of CZ copper foil/insulating layer/inner layer circuit board/insulating layer/CZ copper foil. made.

<Measurement of copper foil adhesion (adhesion 1) before high temperature and high humidity environment test (HAST)>
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. SL"), and using an Instron universal testing machine, the load when peeling off 35 mm in the vertical direction at a speed of 50 mm/min at room temperature was measured according to JIS C6481. The load thus measured is referred to as "adhesion 1".

<Measurement of copper foil adhesion (adhesion 2) after high temperature and high humidity environment test (HAST)>
A high-temperature, high-humidity environment test was performed on the prepared samples under conditions of 130° C. and 85% RH for 100 hours using a highly accelerated life tester (“PM422” manufactured by Kusumoto Kasei Co., Ltd.). After that, in the same manner as in the measurement of adhesion 1, a cut was made and one end in the length direction of the copper foil was peeled off and gripped with a gripper ("AC-50C-SL" manufactured by TSE Co., Ltd.). Using a tester, the load was measured in accordance with JIS C6481 when a 35 mm strip was vertically peeled off at a rate of 50 mm/min at room temperature. The load thus measured is referred to as "adhesion 2".

When the measurement result in adhesion 2 was less than 0.25 kgf/cm, it was evaluated as "x", and when it was 0.25 kgf/cm or more, it was evaluated as "good".

<Measurement of dielectric loss tangent>
The resin sheets obtained in Examples and Comparative Examples were thermally cured at 200° C. for 90 minutes, and then the PET film was peeled off to prepare samples for evaluation of cured physical properties.

A test piece having a width of 2 mm and a length of 80 mm was cut from the cured physical property evaluation sample. The dielectric loss tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated.

A case where the average value of the dielectric loss tangent was less than 0.0054 was evaluated as "good", and a case where it was 0.0054 or more was evaluated as "poor".

<Evaluation of Smear Removability and Arithmetic Average Roughness (Ra)>
(1) Surface treatment of interior substrate As an inner layer substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, manufactured by Panasonic “R1515A” ”) was prepared. The copper foil on the surface of the inner layer substrate was roughened by etching with a microetching agent (“CZ8101” manufactured by MEC Co., Ltd.) at a copper etching amount of 1 μm. After that, drying was performed at 190° C. for 30 minutes.

(2) Lamination and curing of resin sheet The resin sheets obtained in the above-described Examples and Comparative Examples are laminated using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). Both surfaces of the inner layer substrate were laminated so that the composition layer was bonded to the inner layer substrate. This lamination was carried out by pressure bonding for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds.

Then, the laminated resin sheet was hot-pressed for 60 seconds at 100° C. under atmospheric pressure and a pressure of 0.5 MPa for smoothing. Further, this was put into a 130° C. oven and heated for 30 minutes, then transferred to a 170° C. oven and heated for 30 minutes.

(3) Via hole formation Using a CO ₂ laser processing machine (LK-2K212/2C) manufactured by Via Mechanics Co., Ltd., the insulating layer was processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and the number of shots of 3. , a via hole having a top diameter (diameter) of 50 μm on the surface of the insulating layer and a diameter of 40 μm on the bottom surface of the insulating layer. The top diameter represents the diameter of the opening of the via hole. After that, the PET film was peeled off.

(4) Roughening Treatment The inner layer substrate was immersed in a swelling liquid, Swelling Dip Securigant P manufactured by Atotech Japan, at 60° C. for 10 minutes. Next, it was immersed at 80° C. for 20 minutes in a roughening liquid Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by Atotech Japan. Finally, it was immersed at 40° C. for 5 minutes in Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd., which is a neutralizing solution. The obtained substrate was designated as an evaluation substrate A.

<Evaluation of Smear Removability>
The periphery of the bottom of the via hole of evaluation substrate A was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image and evaluated according to the following criteria.
Good: The maximum smear length is less than 5 μm.
x: The maximum smear length is 5 μm or more.

<Example 1>
Bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 g / eq) 5 parts, naphthol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent 330 g / eq) 15 parts, glycidylamine type epoxy 3 parts of resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g/eq) was dissolved in 30 parts of methyl ethyl ketone (MEK) by heating with stirring, and then cooled to room temperature. The resulting resin solution was added with 30 parts of an active ester resin ("HPC-8000-65T" manufactured by DIC, active ester group equivalent of 223 g/eq, a toluene solution with a non-volatile content of 65% by mass), a phenol resin ("LA -3018-50P", phenolic hydroxyl equivalent 151 g / eq, 2-methoxypropanol solution with a non-volatile content of 50% by mass) 5 parts, acrylic acid ester (manufactured by Shin-Nakamura Chemical Co., Ltd. "A-DOG", acrylic equivalent 156 g / eq ) 10 parts, phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YL7553BH30", 1:1 solution of MEK and cyclohexanone with a nonvolatile content of 30% by mass) 5 parts, curing accelerator (4-dimethylaminopyridine (DMAP), nonvolatile content 5 mass % MEK solution) 3 parts, 0.6 parts of dicumyl peroxide (“Percumyl D” manufactured by NOF Corporation), spherical silica surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) ( 120 parts of "SO-C2" manufactured by Admatechs, average particle size 0.5 μm) are mixed, and after uniformly dispersing with a high-speed rotating mixer, filtered through a cartridge filter ("SHP020" manufactured by ROKITECHNO) to obtain a resin varnish. 1 was prepared.

Next, on the release layer of a PET film with an alkyd resin release layer (“AL-5” manufactured by Lintec Corporation, thickness 38 μm), resin varnish was applied so that the thickness of the resin composition layer after drying was 40 μm. 1 was uniformly applied with a die coater and dried at 80 to 110° C. (average 95° C.) for 5 minutes to prepare a resin sheet 1.

<Example 2>
Further carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216 g / eq, non-volatile content 50 wt% toluene solution) was added in the same manner as in Example 1 except that 5 parts of resin varnish 2 and resin Sheet 2 was produced.

<Example 3>
Further, resin varnish 3 and resin sheet 3 were produced in the same manner as in Example 1, except that 3 parts of a benzoxazine-based curing agent ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.) was added.

<Example 4>
Resin varnish 4 and resin sheet were prepared in the same manner as in Example 1, except that the amount of glycidylamine-type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 95 g/eq) was changed from 3 parts to 0.5 parts. 4 was produced.

<Example 5>
No bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 g/eq) was added, and the amount of glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g/eq) was added to 3. Same as in Example 1, except that the amount of acrylic acid ester ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., acrylic equivalent 156 g / eq) was changed from 10 parts to 5 parts. Then, resin varnish 5 and resin sheet 5 were produced.

<Example 6>
The amount of naphthol-type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent 330 g / eq) was changed from 15 parts to 5 parts, and active ester resin (manufactured by DIC "HPC-8000-65T", active ester A resin varnish 6 and a resin sheet 6 were produced in the same manner as in Example 5, except that the amount of the toluene solution having a base equivalent of 223 g/eq and a non-volatile content of 65% by mass was changed from 30 parts to 50 parts.

<Example 7>
Acrylic ester (manufactured by Shin-Nakamura Chemical Co., Ltd. "A-DOG", acrylic equivalent 156 g / eq) instead of 10 parts of acrylic ester (manufactured by Kyoeisha Chemical Co., Ltd. "A-DCP", acrylic equivalent 152 g / eq) 10 parts A resin varnish 7 and a resin sheet 7 were prepared in the same manner as in Example 1, except that .

<Example 8>
Instead of 3 parts of glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g/eq), 3 parts of glycidylamine type epoxy resin (ADEKA "EP3980S", epoxy equivalent 115 g/eq) was used. A resin varnish 8 and a resin sheet 8 were produced in the same manner as in Example 1 except for the above.

<Example 9>
Glycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "630", epoxy equivalent 95 g / eq) instead of 3 parts, glycidyl amine type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd. "ELM-434", epoxy equivalent 98 g / eq) 3 parts A resin varnish 9 and a resin sheet 9 were produced in the same manner as in Example 1, except that .

<Example 10>
Glycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation "630", epoxy equivalent 95 g / eq) instead of 3 parts, glycidylamine type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd. "ELM-100", epoxy equivalent 105 g / eq) 3 parts A resin varnish 10 and a resin sheet 10 were produced in the same manner as in Example 1, except that .

<Comparative Example 1>
A resin varnish 11 and a resin sheet 11 were produced in the same manner as in Example 1, except that a glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 95 g/eq) was not added.

<Comparative Example 2>
Resin varnish 12 and resin sheet were prepared in the same manner as in Example 1, except that the amount of glycidylamine-type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 95 g/eq) was changed from 3 parts to 0.1 parts. 12 was produced.

<Comparative Example 3>
The amount of glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 95 g / eq) was changed from 3 parts to 0.5 parts, and acrylic acid ester ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd. , Acrylic equivalent 156 g / eq) was changed from 10 parts to 50 parts, and the amount of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) was changed from 120 parts to 200 parts. A resin varnish 13 and a resin sheet 13 were produced in the same manner as in Example 1, except that the amount of methyl ethyl ketone (MEK) used was changed from 30 parts to 60 parts.

<Comparative Example 4>
The amount of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "828US", epoxy equivalent 180 g / eq) was changed from 5 parts to 15 parts, and glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630", epoxy equivalent 95 g /eq) was changed from 3 parts to 0.1 parts, and the amount of acrylic acid ester (“A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., acrylic equivalent 156 g / eq) was changed from 10 parts to 2 parts. A resin varnish 14 and a resin sheet 14 were produced in the same manner as in Example 1, except for the change.

<Comparative Example 5>
The amount of naphthol-type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 330 g / eq) was changed from 15 parts to 5 parts, and glycidylamine-type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g) was added. /eq) was changed from 3 parts to 30 parts, and the amount of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) was changed from 120 parts to 150 parts. A resin varnish 15 and a resin sheet 15 were prepared in the same manner as in Example 1.

<Comparative Example 6>
The amount of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "828US", epoxy equivalent 180 g / eq) was changed from 5 parts to 15 parts, and glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630", epoxy equivalent 95 g /eq) was changed from 3 parts to 30 parts, and the amount of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) was changed from 120 parts to 200 parts. A resin varnish 16 and a resin sheet 16 were prepared in the same manner as in Example 1.

<Comparative Example 7>
The amount of naphthol-type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 330 g / eq) was changed from 15 parts to 5 parts, and glycidylamine-type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g) was added. /eq) was changed from 3 parts to 30 parts, and the amount of acrylic acid ester ("A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., acrylic equivalent 156 g / eq) was changed from 10 parts to 30 parts. , Resin varnish 17 and resin sheet 17 in the same manner as in Example 1, except that the amount of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) was changed from 120 parts to 200 parts. was made.

Table 1 shows the evaluation results of Examples and Comparative Examples.

From the above results, when using a resin composition containing a combination of components (A), (B), and (C) in a specific content, the dielectric loss tangent is low, the smear removal property is excellent, and the conductor It can be seen that a cured product having excellent adhesion to the layer can be obtained.

In Examples 1 to 10, it has been confirmed that the same results as in the above Examples are obtained even when the components (D) to (G) are not contained, although there are differences in degree.

Claims (12)

(A) an epoxy resin, (B) a resin having two or more radically polymerizable unsaturated groups per molecule selected from acryloyl groups and methacryloyl groups and having a cyclic group , (C) an epoxy resin curing agent, and ( D) A resin composition containing an inorganic filler,
component (A) contains (A-1) a glycidylamine type epoxy resin and an epoxy resin other than component (A-1),
When the content of component (A) other than component (A-1) is 100 parts by mass, the content of component (A-1) is 2 to 250 parts by mass,
When the content of component (B) is 100 parts by mass, the content of component (A-1) is 3 to 250 parts by mass,
When the non-volatile component in the resin composition is 100 parts by mass, the content of component (A-1) is 0.20 to 10 parts by mass,
A resin composition in which the content of component (D) is 50 to 90 parts by mass when the non-volatile component in the resin composition is 100 parts by mass. 2. The resin composition according to claim 1, wherein component (A-1) is a difunctional or trifunctional glycidylamine type epoxy resin. 3. The resin composition according to claim 1, wherein component (C) is selected from the group consisting of active ester curing agents, phenolic curing agents, carbodiimide curing agents, and benzoxazine curing agents. 4. The resin composition according to any one of claims 1 to 3 , wherein the component (B) is a (meth)acrylic acid ester. The resin composition according to any one of claims 1 to 4 , wherein the content of component (A) is 100 to 1000 parts by mass when the content of component (B) is 100 parts by mass. 6. The resin composition according to any one of claims 1 to 5 , wherein the content of component (D) is 65 parts by mass or more based on 100 parts by mass of non-volatile components in the resin composition. The resin composition according to any one of claims 1 to 6 , further comprising (E) a thermoplastic resin. The resin composition according to any one of claims 1 to 7 , which is used for forming an insulating layer for forming a conductor layer. The resin composition according to any one of claims 1 to 7 , which is used for forming an insulating layer of a printed wiring board. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 7 . A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 7 . A semiconductor device comprising a cured product of the resin composition according to any one of claims 1 to 7 .