TWI869397B - Resin composition, prepreg, resin sheet with support, metal foil-clad laminate, and printed wiring board - Google Patents

Abstract

A resin composition containing an epoxy compound (A), a curing agent (B), and zirconium nitride (C), wherein the amount of zirconium nitride (C) is within a range from 1 to 30 parts by mass per 100 parts by mass of the total amount of the epoxy compound (A) and the curing agent (B).

Description

Resin composition, prepreg, resin sheet with support, metal-clad laminate, and printed wiring board

The present invention relates to a resin composition, a prepreg, a resin sheet with a support, a metal-clad laminate, and a printed wiring board.

In terms of the use of printed wiring boards, in recent years, for the orientation of display and sensor substrates, materials with excellent light shielding properties from visible light to near-infrared light (wavelength 400~2000nm) are required. [Prior technical literature] [Patent literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-172114

[The problem that the invention wants to solve]

As for black powders with excellent light-shielding properties from visible light to near-infrared light, there are carbon particles. For example, Patent Document 1 discloses a thermosetting resin composition with excellent light-shielding properties, which has a thermosetting resin, carbon particles, and a thermosetting catalyst as essential components. On the other hand, carbon particles have high electrical conductivity, so if they are used directly, short circuits may occur between surrounding conductive devices. In response to this, Patent Document 1 discloses a method for improving insulation by coating the surface of carbon particles with a thermosetting resin, but such processing will become a major cause of increased product costs. In addition, Patent Document 1 also discloses that when the surface of carbon particles is not coated and a prepreg is made, the light-shielding property is poor.

Therefore, the present invention provides a resin composition, a prepreg, a resin sheet with a support, a metal-clad laminate, and a printed wiring board that have excellent formability, light-shielding properties from visible light to near-infrared light, and insulation resistance. [Means for solving the problem]

The inventors of the present invention have repeatedly conducted in-depth research to solve the above-mentioned problems and have found that a resin composition containing an epoxy compound (A), a hardener (B), and a specific amount of zirconium nitride (C) can solve the above-mentioned problems and thus complete the present invention.

That is, the present invention is as follows. [1] A resin composition comprising: an epoxy compound (A), a hardener (B), and zirconium nitride (C); the content of the zirconium nitride (C) is 1 to 30 parts by mass relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). [2] The resin composition as described in [1], wherein the zirconium nitride (C) comprises particles having a primary particle size of 20 to 50 nm. [3] The resin composition as described in [1] or [2], wherein the epoxy compound (A) comprises a compound represented by the following formula (I). [Chemical 1] In formula (I), n1 represents an integer greater than 1. [4] The resin composition as described in any one of [1] to [3], wherein the curing agent (B) comprises a phenol compound (D) and/or a cyanate compound (E). [5] The resin composition as described in [4], wherein the phenol compound (D) comprises a compound represented by the following formula (II) or formula (III). [Chemical 2] In formula (II), n2 represents an integer greater than 1. In formula (III), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n3 represents an integer greater than 1. [6] The resin composition as described in [4], wherein the cyanate ester compound (E) comprises a naphthol aralkyl type cyanate ester compound represented by the following formula (VI) and/or a novolac type cyanate ester compound represented by the following formula (VII). [Chemical 4] In the formula (VI), R ⁵ each independently represents a hydrogen atom or a methyl group, and n6 represents an integer greater than 1. In the formula (VII), R ⁶ each independently represents a hydrogen atom or a methyl group, and n7 represents an integer greater than or equal to 1. [7] The resin composition as described in any one of [1] to [6], further comprising a maleimide compound (F). [8] The resin composition as described in [7], wherein the maleimide compound (F) comprises one or more selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2'-bis{4-(4-maleimidophenoxy)phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V). [Chemistry 6] In formula (IV), R ³ each independently represents a hydrogen atom or a methyl group, and n4 represents an integer greater than 1. [Chemistry 7] In formula (V), ^R4 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n5 is an average value and represents 1＜n5≦5. [9] The resin composition as described in any one of [1] to [8], further comprising an inorganic filler (G). [10] The resin composition as described in [9], wherein the inorganic filler (G) comprises at least one selected from the group consisting of silica, aluminum hydroxide, aluminum oxide, alumina, magnesium oxide, molybdenum oxide, zinc molybdate, and magnesium hydroxide. [11] The resin composition as described in any one of [1] to [10], for use in a printed wiring board. [12] A prepreg comprising: a substrate, and a resin composition as described in any one of [1] to [11] impregnated or coated on the substrate. [13] A resin sheet with a support, comprising: a support, and a resin composition as described in any one of [1] to [11] laminated on one or both sides of the support. [14] A metal foil-clad laminate comprising: a laminate formed of one or more selected from the group consisting of a prepreg as described in [12] and a resin sheet with a support as described in [13], and metal foil disposed on one or both sides of the laminate. [15] A metal-clad laminate as described in [14], wherein the transmittance of the substrate obtained by removing the metal foil from the metal-clad laminate is less than 0.1% in the wavelength range of 400 to 2000 nm. [16] A printed wiring board is produced using the prepreg as described in [12] as a stacking material. [17] A printed wiring board is produced using the resin sheet with a support as described in [13] as a stacking material. [18] A printed wiring board is produced using the metal-clad laminate as described in [14] or [15] as a stacking material. [19] A printed wiring board comprising: an insulating layer, and a conductive layer formed on a surface of the insulating layer; the insulating layer contains the resin composition described in any one of [1] to [11]. [Effects of the Invention]

According to the present invention, a resin composition, a prepreg, a metal-clad laminate, a resin sheet, and a printed wiring board having excellent formability, light-shielding property (transmittance) from visible light to near-infrared light, and insulation resistance (insulation resistance value) can be provided.

Hereinafter, a form for implementing the present invention (hereinafter referred to as "this embodiment") is described in detail, but the present invention is not limited thereto and various modifications are possible within the scope not departing from the gist thereof.

[Resin composition] The resin composition of the present embodiment contains an epoxy compound (A), a hardener (B), and zirconium nitride (C), and the content of zirconium nitride (C) is 1 to 30 parts by mass relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). With such a composition, the resin composition of the present embodiment has excellent moldability, light shielding properties (transmittance) from visible light to near-infrared light, and insulation resistance (insulation resistance value). In addition, the resin composition of the present embodiment also has excellent insulation resistance after a moisture and heat resistance test. The following is a description of each component constituting the resin composition of the present embodiment.

(Zirconium nitride (C)) The resin composition of this embodiment contains zirconium nitride (C). Zirconium nitride (C) is not particularly limited, and preferably contains particles with a primary particle size of 20 to 50 nm. By containing particles with a primary particle size of 20 nm or more, there is a tendency for the zirconium nitride (C) particles to have excellent dispersibility, and by containing particles with a primary particle size of 50 nm or less, there is a tendency for excellent formability. The primary particle size can be measured by electron microscope observation or other methods.

Such zirconium nitride (C) can be a commercially available product, for example, "NITRBLACK (registered trademark) UB-1" manufactured by Mitsubishi Materials Corporation can be used.

The content of zirconium nitride (C) in the resin composition of this embodiment is 1 to 30 parts by mass relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). The content of zirconium nitride (C) in the resin composition is preferably 5 to 25 parts by mass, and more preferably 5 to 20 parts by mass. When the content of zirconium nitride (C) is 1 part by mass or more, light shielding property tends to be excellent. When the content of zirconium nitride (C) is 30 parts by mass or less, formability tends to be excellent.

(Epoxy compound (A)) The resin composition of this embodiment contains an epoxy compound (A). The epoxy compound (A) is not particularly limited, and epoxy compounds having two or more epoxy groups in one molecule are preferred. Examples of such epoxy compounds include bisphenol type epoxy resins (e.g., bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin), diallyl bisphenol type epoxy resins (e.g., diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.), phenol novolac type epoxy resins (e.g., phenol novolac type epoxy resins, etc.), and the like. Epoxy resins, bisphenol A novolac type epoxy resins, cresol novolac type epoxy resins), aralkyl type epoxy resins, biphenyl type epoxy resins containing a biphenyl skeleton, naphthalene type epoxy resins containing a naphthalene skeleton, anthracene type epoxy resins containing anthracene skeleton, glycidyl ester type epoxy resins, polyol type epoxy resins, epoxy resins containing isocyanurate epoxy, dicyclopentadiene type epoxy resins, epoxy resins composed of bisphenol A type structural units and hydrocarbon structural units, and halogen compounds thereof. These epoxy compounds may be used alone or in combination of two or more.

Among them, the epoxy compound (A) preferably includes a biphenyl aralkyl type epoxy resin from the viewpoint of better formability, linear thermal expansion coefficient (CTE), glass transition temperature (Tg), copper foil peeling strength, and heat resistance. The biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (I). [Chemical 8] In formula (I), n1 represents an integer greater than 1. The upper limit of n1 is preferably 10, more preferably 7.

The content of the epoxy compound (A) in the resin composition of the present embodiment is not particularly limited. Considering the formability, glass transition temperature (Tg), heat resistance, and coefficient of linear thermal expansion (CTE), the content is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, and particularly preferably 40 to 60 parts by mass, relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). In addition, when two or more epoxy compounds (A) are used in combination, their total amount preferably meets the above value.

(Hardener (B)) The curing agent (B) in this embodiment is not particularly limited if it is a compound commonly used as a curing agent for epoxy compounds. For example, one or more selected from the group consisting of phenol compounds (D), cyanate compounds (E), acid anhydrides, and amine compounds can be appropriately used. Among them, it is more preferable that the curing agent (B) contains a phenol compound (D) and/or a cyanate compound (E).

(Phenol compound (D)) The phenol compound (D) is not particularly limited, and is preferably a phenol compound having two or more phenol groups in one molecule. Examples of such phenol compounds include: bisphenols (e.g., bisphenol A, bisphenol E, bisphenol F, bisphenol S, etc.), diallyl bisphenols (e.g., diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, diallyl bisphenol S, etc.), bisphenol-type phenolic resins (e.g., bisphenol A resins, bisphenol E resins, bisphenol F resins, bisphenol S resins, etc.), benzene Phenolic novolac resins (e.g., phenol novolac resins, naphthol novolac resins, cresol novolac resins, etc.), glycidyl ester type phenolic resins, naphthalene type phenolic resins, anthracene type phenolic resins, dicyclopentadiene type phenolic resins, biphenyl type phenolic resins, alicyclic phenolic resins, polyol type phenolic resins, aralkyl type phenolic resins, phenol-modified aromatic hydrocarbon resins, etc. These phenolic compounds may be used alone or in combination of two or more.

Among them, the phenol compound (D) preferably includes a biphenyl aralkyl type phenolic resin and/or a naphthalene type phenolic resin from the viewpoint of being superior in formability, coefficient of linear thermal expansion (CTE), glass transition temperature (Tg), heat resistance, and low water absorption.

The biphenyl aralkyl type phenolic resin or the naphthalene type phenolic resin preferably contains a compound represented by the following formula (II) or the following formula (III). [Chemistry 9] In formula (II), n2 represents an integer greater than 1. The upper limit of n2 is preferably 10, more preferably 7, and even more preferably 6. In formula (III), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n3 represents an integer greater than 1. The upper limit of n3 is preferably 10, more preferably 7, and even more preferably 6.

The content of the phenol compound (D) in the resin composition of the present embodiment is not particularly limited. Considering the moldability, linear thermal expansion coefficient (CTE), glass transition temperature (Tg), heat resistance, and low water absorption, the content is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, and particularly preferably 40 to 60 parts by mass relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). In addition, when two or more phenol compounds (D) are used in combination, their total amount preferably meets the above value.

(Cyanate compound (E)) The cyanate compound (E) is not particularly limited if it is a compound in which a cyanate group (cyano group) is directly bonded to an aromatic ring. Examples thereof include naphthol aralkyl cyanate compounds (naphthol aralkyl cyanate), naphthyl ether cyanate compounds, xylene resin cyanate compounds, phenol methane cyanate compounds, and adamantane skeleton cyanate compounds. Among them, in view of further improving the coating adhesion and low water absorption, the cyanate compound (E) preferably includes one or more selected from the group consisting of naphthol aralkyl cyanate compounds, naphthyl ether cyanate compounds, novolac cyanate compounds, and xylene resin cyanate compounds, and is preferably a naphthol aralkyl cyanate compound or a novolac cyanate compound. These cyanate compounds may be used alone or in combination of two or more. These cyanate ester compounds can be prepared by known methods, or commercially available products can be used.

The naphthol aralkyl type cyanate compound is not particularly limited, and is preferably a compound represented by the following formula (VI). In formula (VI), R ⁵ each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In formula (VI), n6 represents an integer greater than 1. The upper limit of n6 is preferably 10, more preferably 6.

The novolac-type cyanate compound is not particularly limited, and is preferably, for example, a compound represented by the following formula (VII). In the formula (VII), R6 each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In the formula (VII), n7 represents an integer greater than 1. The upper limit of n7 is preferably 10, more preferably 7.

The content of the cyanate compound (E) in the resin composition of this embodiment is not particularly limited. Considering the moldability, coating adhesion, and low water absorption, the content is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, and particularly preferably 40 to 60 parts by mass, relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). In addition, when two or more cyanate compounds (E) are used in combination, their total amount preferably meets the above value.

The resin composition of this embodiment may also contain both of a phenol compound (D) and a cyanate compound (E) as a hardener (B). In this case, the total content of the phenol compound (D) and the cyanate compound (E) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, and particularly preferably 40 to 60 parts by mass, relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). When the total content of the phenol compound (D) and the cyanate compound (E) falls within the above range, the moldability tends to be improved.

(Maleimide compound (F)) The resin composition of this embodiment preferably further contains a maleimide compound (F). The maleimide compound (F) is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, and examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2'-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V). The maleimide compound may be in the form of not only a monomer but also a prepolymer, or a prepolymer of a maleimide compound and an amine compound. These maleimide compounds (F) may be used alone or in combination of two or more as appropriate.

Among them, from the viewpoint of heat resistance, the maleimide compound (F) is preferably one or more selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2'-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V). [Chemical 13] In formula (IV), R ³ each independently represents a hydrogen atom or a methyl group, and is particularly preferably a methyl group. n4 represents an integer greater than 1. The upper limit of n4 is preferably 10, more preferably 7, and even more preferably 6. [Chemical 14] In formula (V), R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, preferably a hydrogen atom, a methyl group, or a phenyl group. n5 is an average value and represents 1＜n5≦5.

The content of the maleimide compound (F) in the resin composition of this embodiment is not particularly limited, but is preferably 5 to 35 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 20 parts by mass, relative to 100 parts by mass of the total content of the epoxy compound (A) and the hardener (B). In addition, when two or more maleimide compounds (F) are used in combination, their total amount preferably meets the above value.

(Other resins) The resin composition of this embodiment may contain other resins as shown below as long as it does not hinder the effects of the present invention. Other resins include compounds with polymerizable unsaturated groups other than the above-mentioned epoxy compound (A), hardener (B), and maleimide compound (F), cyclohexane resins, benzophenone compounds, etc. Examples of compounds having polymerizable unsaturated groups include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; (meth)acrylates of mono- or polyols such as methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trihydroxymethylpropane di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and benzocyclobutene resins. Examples of the cyclohexane resin include cyclohexane, 2-methylcyclohexane, 2,2-dimethylcyclohexane, 3-methylcyclohexane, 3,3-dimethylcyclohexane and other alkylcyclohexanes; 3-methyl-3-methoxymethylcyclohexane, 3,3'-bis(trifluoromethyl)perfluorocyclohexane, 2-chloromethylcyclohexane, 3,3-bis(chloromethyl)cyclohexane, biphenyl-type cyclohexane, and "OXT-101" and "OXT-121" of Toagosei Co., Ltd., etc. The benzophenone compound may be a compound having two or more dihydrobenzophenone rings in one molecule, for example, "Bisphenol F-type benzophenone BF-BXZ" and "Bisphenol S-type benzophenone BS-BXZ" produced by Konishi Chemical Co., Ltd.

(Inorganic filler (G)) The resin composition of this embodiment may also contain inorganic fillers (G) other than the above-mentioned zirconium nitride (C). Such inorganic fillers (G) include: silicon dioxide, silicon compounds (such as white carbon, etc.), metal oxides (such as aluminum oxide, titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides other than zirconium nitride (C) (such as boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, etc.), metal sulfates (such as barium sulfate, etc.), metal hydroxides (such as aluminum hydroxide, aluminum hydroxide heat-treated products (such as aluminum hydroxide is heat-treated and a portion of crystal water is removed), soft alumina, magnesium hydroxide, etc. ), molybdenum compounds (such as molybdenum oxide, zinc molybdate, etc.), zinc molybdate supported on talc, zinc oxide or calcium carbonate, zinc compounds (such as zinc borate, zinc stannate, etc.), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass fine powders such as E-glass, T-glass, D-glass, S-glass, Q-glass, etc.), hollow glass, spherical glass, etc. These inorganic fillers can be used alone or in combination of two or more.

Among them, from the viewpoint of better coefficient of thermal expansion (CTE), flexural modulus, and flame retardancy, the inorganic filler (G) preferably includes at least one selected from the group consisting of silica, metal hydroxide, and metal oxide, more preferably includes at least one selected from the group consisting of silica, aluminum hydroxide, aluminum oxide, alumina, magnesium oxide, molybdenum oxide, zinc molybdate, and magnesium hydroxide, even more preferably includes at least one selected from the group consisting of silica, alumina, zinc molybdate, and aluminum oxide, and silica is particularly preferred.

Examples of silica include natural silica, fused silica, synthetic silica, amorphous silica, fumed silica (AEROSIL), hollow silica, etc. Among them, fused silica is preferred.

The content of the inorganic filler (G) is not particularly limited, and is preferably 100 to 250 parts by mass relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). When the content of the inorganic filler (G) is 100 parts by mass or more, the linear thermal expansion coefficient (CTE), bending modulus, and flame retardancy tend to be excellent. When the content of the inorganic filler (G) is 250 parts by mass or less, the flow characteristics and formability tend to be excellent, and it is suitable for use as a printed wiring board. Considering the same point of view, the content of the inorganic filler (G) is preferably 110 to 200 parts by mass, and more preferably 110 to 150 parts by mass. In addition, when two or more inorganic fillers (G) are used in combination, their total amount should preferably meet the above value.

(Silane coupling agent) The resin composition of this embodiment may further contain a silane coupling agent. By containing a silane coupling agent, the resin composition of this embodiment tends to have better dispersibility of the aforementioned zirconium nitride (C) and inorganic filler (G), or better bonding strength between the components of the resin composition of this embodiment and the substrate described below.

Examples of the silane coupling agent include silane coupling agents commonly used for surface treatment of inorganic substances, such as aminosilane compounds (e.g., γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyl trimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloyloxypropyl trimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyl trimethoxysilane hydrochloride, etc.), and phenylsilane compounds. These silane coupling agents may be used alone or in combination of two or more. Among them, the silane coupling agent is preferably an epoxysilane compound. Examples of epoxysilane compounds include "KBM-403", "KBM-303", "KBM-402", and "KBE-403" produced by Shin-Etsu Chemical Co., Ltd.

The content of the silane coupling agent is not particularly limited, and can be about 0.1 to 10.0 parts by mass, preferably 0.5 to 8.0 parts by mass, and more preferably 1.0 to 6.0 parts by mass, relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B).

(Wetting dispersant) The resin composition of this embodiment may further contain a wetting dispersant. The resin composition of this embodiment may contain a wetting dispersant, which tends to improve the dispersibility of the aforementioned zirconium nitride (C) and inorganic filler (G).

The wet dispersant may be any known dispersant (dispersion stabilizer) for dispersing the inorganic filler (G), for example, BYK Co., Ltd. products such as "DISPERBYK-110", "DISPERBYK-111", "DISPERBYK-118", "DISPERBYK-180", "DISPERBYK-161", "BYK-W996", "BYK-W9010", "BYK-W903", etc.

The content of the wetting dispersant is not particularly limited. Considering the better dispersibility of the zirconium nitride (C) and the inorganic filler (G), the content is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, and even more preferably 0.5 to 1.5 parts by mass, relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B).

(Hardening accelerator) The resin composition of this embodiment may further contain a hardening accelerator. The hardening accelerator is not particularly limited, and examples thereof include: the imidazole compounds described below; organic peroxides such as benzoyl peroxide, lauryl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di(tertiary)butyl diperphthalate; azo compounds such as azobisnitrile; tertiary amines such as N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylthiophene, triethanolamine, triethylenediamine, tetramethylbutylenediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and o-catechin; cycloalkane acids (naphthenic acid) Organic metal salts such as lead bis(2-nitrogen)sulfuric acid, lead stearate, zinc cycloalkanoate, zinc octoate, tin oleate, dibutyltin maleate, manganese cycloalkanoate, cobalt cycloalkanoate, iron acetylacetonate, etc.; those obtained by dissolving these organic metal salts in phenol, bisphenol and other hydroxyl-containing compounds; inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride, etc.; organic tin compounds such as dioctyltin oxide, other alkyltins, alkyltin oxide, etc.

The resin composition of the present embodiment preferably contains an imidazole compound as a hardening accelerator. Considering the excellent hardening property, the imidazole compound can be exemplified as follows: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4,5-triphenylimidazole, 2-phenyl-4-methylimidazole, etc. Among them, the imidazole compound is preferably 2,4,5-triphenylimidazole and/or 2-phenyl-4-methylimidazole, and more preferably 2,4,5-triphenylimidazole.

The content of the imidazole compound is not particularly limited. It can be about 0.1 to 10 parts by mass relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). From the perspective of more effectively and surely exerting the effects of the present invention, it is preferably 0.2 to 5.0 parts by mass, and more preferably 0.3 to 1.0 parts by mass.

(Solvent) The resin composition of this embodiment may also contain a solvent. By containing a solvent, the resin composition of this embodiment has a tendency to have a lower viscosity during preparation of the resin composition, better operability, and better impregnation into a substrate.

The solvent is not particularly limited as long as it can dissolve part or all of the components in the resin composition, and examples thereof include ketones (acetone, methyl ethyl ketone, methyl cellulose, etc.), aromatic hydrocarbons (such as toluene, xylene, etc.), aldehydes (such as dimethyl formaldehyde, etc.), propylene glycol monomethyl ether and its acetate, etc. These solvents can be used alone or in combination of two or more.

(Transmittance) For the resin composition of this embodiment, the transmittance of the substrate obtained by removing the metal foil from the metal foil-clad laminate obtained using the resin composition is preferably 0.1% or less in the wavelength range of 400 to 2000nm. There is no particular restriction on the lower limit of the transmittance, and it is preferably below the detection limit. A transmittance of 0.1% or less will have sufficient light-shielding properties. The transmittance can be adjusted according to the content of zirconium nitride (C) and the particle size of zirconium nitride (C). The transmittance can be measured using the measurement method described in the embodiment.

(Manufacturing method of resin composition) The manufacturing method of the resin composition of this embodiment is not particularly limited. For example, each component is mixed into a solvent at once or successively and stirred. At this time, in order to make each component dissolve or disperse uniformly, a known process such as stirring, mixing, kneading treatment is used.

[Application] The resin composition of this embodiment can be suitably used as a prepreg, a resin sheet, a laminate, a metal-clad laminate, or a printed wiring board. The following describes the prepreg, the resin sheet, the laminate, the metal-clad laminate, and the printed wiring board.

[Prepreg] The prepreg of the present embodiment comprises: a substrate, and the resin composition of the present embodiment impregnated or coated on the substrate. The prepreg of the present embodiment can be a prepreg obtained by using the resin composition of the present embodiment and using a known method. Specifically, it can be obtained by impregnating or coating the resin composition of the present embodiment on the substrate and then heating and drying it at 100-200°C to semi-harden (B-stage).

The prepreg of the present embodiment also includes a cured product obtained by thermally curing a semi-cured prepreg at a heating temperature of 200 to 230° C. and a heating time of 60 to 180 minutes.

The content of the resin composition of the present embodiment in the prepreg of the present embodiment is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and even more preferably 40 to 80% by mass relative to the total amount of the prepreg, in terms of solid content. When the content of the resin composition falls within the above range, the moldability tends to be further improved. In addition, the solid content of the prepreg refers to the component after the solvent is removed from the prepreg, for example, the filler is included in the solid content of the prepreg.

(Substrate) The substrate is not particularly limited, and for example, the known substrates used in the materials of various printed wiring boards can be listed. Specific examples of the substrate include: glass substrates, inorganic substrates other than glass (for example, inorganic substrates composed of inorganic fibers other than glass such as quartz), organic substrates (for example, organic substrates composed of organic fibers such as wholly aromatic polyamides, polyesters, poly(p-phenylene benzobisazole), and polyimides), etc. These substrates can be used alone or in combination of two or more. Among them, from the perspective of further improving rigidity or making the thermal dimensional stability better, a glass substrate is preferably used.

The fiber constituting the glass substrate may be, for example, E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, HME glass, etc. Among them, the fiber constituting the glass substrate is preferably one or more fibers selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass from the viewpoint of having better strength and low water absorption.

There is no particular restriction on the form of the substrate, and examples thereof include: woven fabric, non-woven fabric, coarse yarn, chopped strand felt, surface-processed felt, etc. There is no particular restriction on the weaving method of the woven fabric, and for example, plain weave, twill weave, and twill weave are known, and it can be appropriately selected from these known ones depending on the intended use and performance. In addition, glass fabrics obtained by opening the fibers or surface-treating the fibers with a silane coupling agent can be appropriately used. There is no particular restriction on the thickness and mass of the substrate, and generally, about 0.01 to 0.3 mm is appropriately used.

[Resin sheet] The resin sheet of the present embodiment contains the resin composition of the present embodiment. The method for producing the resin sheet is not particularly limited, and examples thereof include: a method in which the resin composition of the present embodiment is applied to a support and dried, and after drying, the support is peeled off or etched to obtain a resin sheet, or a method in which the resin composition of the present embodiment is supplied to a mold having a sheet-shaped mold groove and dried to form a sheet.

Furthermore, the resin sheet of the present embodiment may also be a resin sheet having a support and a resin composition of the present embodiment laminated on one or both sides of the support. Such a resin sheet is also called a resin sheet with a support. The resin sheet with a support is used as a means of thinning, and can be manufactured by, for example, directly applying a resin composition (including a filler) used in a prepreg or the like on a support such as a metal foil or a film and drying it.

The support is not particularly limited, and any known support used for various printed wiring board materials can be used. For example, polyimide film, polyamide film, polyester film, polycarbonate film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, aluminum foil, copper foil, gold foil, glass plate, SUS plate, etc. Among them, electrolytic copper foil and PET film are preferred.

The method of applying the resin composition includes, for example, applying the resin composition of the present embodiment in a solution state containing a solvent onto a support using a coating rod, a die coater, a scraper, a Baker applicator, or the like.

The resin sheet with a support is preferably formed by applying the resin composition of the present embodiment to a support and semi-hardening it (B-stage). Specifically, for example, a method of applying the resin composition of the present embodiment to a support such as copper foil and then heating it in a dryer at 20 to 200°C for 1 to 90 minutes to semi-harden it and produce the resin sheet with a support. The amount of the composition attached to the support is preferably within the range of 0.1 to 500 μm in terms of the thickness of the resin layer.

[Laminate] The laminate of this embodiment has a prepreg or a resin sheet with a support of this embodiment. The laminate of this embodiment contains one or more layers of prepreg or a resin sheet with a support, and when it contains multiple layers, it has a shape in which prepregs and/or resin sheets with a support are stacked. The laminate of this embodiment has excellent heat resistance, chemical resistance, low water absorption and electrical properties by having a prepreg or a resin sheet with a support of this embodiment. The manufacturing method of the laminate can appropriately use a generally known method without special restrictions. For example, a laminated plate can be obtained by laminating the above-mentioned prepregs or the prepregs and other layers and performing heating and pressurizing molding. At this time, the heating temperature is not particularly limited, and is preferably 65 to 300°C, and more preferably 120 to 270°C. In addition, the pressing pressure is not particularly limited, and is preferably 2 to 5 MPa, and more preferably 2.5 to 4 MPa. The laminated plate of this embodiment can be appropriately used as a metal foil-clad laminated plate described later by further providing a layer composed of metal foil.

[Metal foil-clad laminate] The metal foil-clad laminate of the present embodiment has: a laminate formed of one or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and metal foil arranged on one or both sides of the laminate. The metal foil-clad laminate of the present embodiment contains one or more selected from the group consisting of the prepreg and the resin sheet with a support. When the number of selected from the group consisting of the prepreg and the resin sheet with a support is one, the metal foil-clad laminate has a form in which metal foil is arranged on one or both sides of the prepreg or the resin sheet with a support. When the number of the materials selected from the group consisting of a prepreg and a resin sheet with a support is plural, the metal foil-clad laminate has a form in which metal foil is arranged on one or both sides of a laminate (e.g., a laminate of prepregs, a laminate of prepregs and a resin sheet with a support) formed of one or more materials selected from the group consisting of a prepreg and a resin sheet with a support. The metal foil-clad laminate of this embodiment has excellent heat resistance, chemical resistance, low water absorption and electrical characteristics by having one or more materials selected from the group consisting of a prepreg and a resin sheet with a support of this embodiment.

The metal foil (conductor layer) may be any metal foil used for various printed wiring board materials, such as copper, aluminum, etc. The copper metal foil may be rolled copper foil, electrolytic copper foil, etc. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

The forming method and forming conditions of the metal-clad laminate are not particularly limited, and the methods and conditions for forming laminates and multi-layer laminates for general printed wiring boards can be used. For example, a multi-layer press, a multi-layer vacuum press, a continuous forming machine, a high-temperature and high-pressure (autoclave) forming machine, etc. can be used when forming the metal-clad laminate. In addition, when forming (laminate forming) the metal-clad laminate, generally speaking, the temperature falls within the range of 100 to 300°C, the pressure falls within the range of 2 to 100 kgf/ ^cm2 in terms of surface pressure, and the heating time falls within the range of 0.05 to 5 hours. In addition, post-hardening can also be performed at a temperature of 150 to 300°C as needed. When a multi-layer press is used, in order to fully promote the curing of the prepreg or the resin sheet with a support, the temperature is preferably 200°C to 250°C, the pressure is 10 to 40 kgf/cm ² , and the heating time is 80 to 130 minutes. The temperature is more preferably 215°C to 235°C, the pressure is 25 to 35 kgf/cm ² , and the heating time is 90 to 120 minutes. In addition, a multi-layer board can be produced by combining the above-mentioned prepreg or the resin sheet with a support with a separately produced inner layer wiring board and laminating them.

With respect to the metal foil-clad laminate of this embodiment, the transmittance of the substrate obtained by removing the metal foil from the metal foil-clad laminate is preferably 0.1% or less in the wavelength range of 400 to 2000 nm. The lower limit of the transmittance is not particularly limited, and it is preferably below the detection limit. A transmittance of 0.1% or less will have sufficient light-shielding properties. The transmittance can be adjusted according to the content of zirconium nitride (C) and the particle size of zirconium nitride (C). The transmittance can be measured using the measurement method described in the embodiment. In addition, from the perspective of specific measurement conditions, the transmittance measurement in the embodiment is implemented using a metal foil-clad laminate using E-glass cloth, but there is no particular limitation on the substrate when forming a prepreg using the resin composition of this embodiment, and the above-mentioned various substrates can be used.

[Printed wiring board] The printed wiring board of this embodiment includes: an insulating layer and a conductive layer formed on the surface of the insulating layer, and the insulating layer includes the resin composition of this embodiment. The printed wiring board of this embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of this embodiment into a predetermined wiring pattern and forming a conductive layer.

Furthermore, the printed wiring board of the present embodiment can be manufactured using the prepreg of the present embodiment as a stacking material. Furthermore, the printed wiring board of the present embodiment can be manufactured using the resin sheet of the present embodiment as a stacking material. Furthermore, the printed wiring board of the present embodiment can be manufactured using the metal-clad laminate of the present embodiment as a stacking material. That is, the printed wiring board of the present embodiment can also have one or more selected from the group consisting of the prepreg of the present embodiment and a resin sheet with a support. In this case, the insulating layer is composed of one or more selected from the group consisting of the prepreg of the present embodiment and a resin sheet with a support.

Specifically, the printed wiring board of the present embodiment can be manufactured, for example, by the following method. First, prepare the metal foil-clad laminate of the present embodiment. Etch the metal foil of the metal foil-clad laminate into a predetermined wiring pattern to form an inner substrate having a conductive layer (inner circuit). Then, a predetermined number of prepregs or resin sheets with a support, and metal foil for the outer circuit are sequentially stacked on the surface of the conductive layer (inner circuit) of the inner substrate, and heated and pressurized to form them into a whole (stack-forming) to obtain a stack. At this time, the prepreg or the resin sheet with a support laminated on the surface of the conductor layer (inner circuit) of the inner substrate is equivalent to the stacking material. In addition, the stacking forming method and its forming conditions are the same as the stacking forming method and its forming conditions in the above-mentioned laminate and metal foil-clad laminate. Then, the laminate is subjected to opening processing for through holes and guide holes, and a plated metal film is formed on the wall of the hole formed thereby to conduct the conductor layer (inner circuit) with the metal foil for the outer circuit. Then, the metal foil for the outer circuit is etched into a predetermined wiring pattern to produce an outer substrate with a conductor layer (outer circuit). In this way, a printed wiring board is manufactured.

Furthermore, when a metal foil-clad laminate is not used, a conductor layer to be a circuit can be formed on the above-mentioned prepreg to produce a printed wiring board. When this is done, the conductor layer can also be formed using an electroless plating method. [Example]

The present invention is further described below using embodiments and comparative examples, but the present invention is not limited to these embodiments.

[Physical property evaluation] Using the varnish or prepreg obtained in the examples and comparative examples, samples for physical property evaluation were prepared using the procedures shown in the following items, and physical property evaluations of formability, transmittance, and insulation resistance were performed.

(Formability) For the prepreg obtained in each embodiment and comparative example, electrolytic copper foils with a thickness of 12 μm (manufactured by Mitsui Metal & Mining Co., Ltd., "3EC-LPIII") were arranged above and below it, and laminated for 120 minutes at a pressure of 30 kgf/ ^cm2 and a temperature of 220°C to obtain a copper-clad laminate with an insulating layer thickness of 0.1 mm. After all the copper foil of the copper-clad laminate was removed by etching, it was visually determined whether there were voids. The results are shown in Tables 1 and 2. The symbols are as follows. ○: No voids. ×: Voids.

(Transmittance) For the prepreg obtained in each embodiment and comparative example, electrolytic copper foils with a thickness of 12μm (Mitsui Metal Mining Co., Ltd., 3EC-LPIII) were arranged on the top and bottom, and laminated for 120 minutes at a pressure of 30kgf/ ^cm2 and a temperature of 220°C to obtain a copper-clad laminate with an insulating layer thickness of 0.1mm. After all the copper foil of the copper-clad laminate was removed by etching, the sample was cut into a size of 50×50mm, and the transmittance at a wavelength of 400~2000nm was measured using a spectrophotometer U-4100 manufactured by Hitachi Advanced Technologies. The results are shown in Tables 1 and 2. The symbols are described as follows. ○: The transmittance at 400-2000nm is less than 0.1%. ×: The transmittance at 400-2000nm exceeds 0.1%.

(Insulation resistance value) 8 prepregs obtained in the embodiments and comparative examples were stacked, and electrolytic copper foils with a thickness of 12 μm (Mitsui Metal & Mining Co., Ltd., 3EC-LPIII) were arranged above and below them. Lamination molding was carried out at a pressure of 30 kgf/cm ² and a temperature of 220°C for 120 minutes to obtain a copper-clad laminate with an insulation layer thickness of 0.8 mm. After the copper foil of the copper-clad laminate was completely removed by etching, the sample was cut into 20×40mm size and treated at normal temperature (25℃, 1 atmosphere) and at 121℃, 2 atmospheres for 24 hours (moisture and heat resistance test) using a pressure cooker tester (made by Hirayama Manufacturing, PC-3 model), and then 500V DC was applied. After 60 seconds, the insulation resistance between the terminals was measured. The results are shown in Tables 1 and 2.

[Synthesis Example 1] Synthesis of α-naphthol aralkyl type cyanate compound (SN495VCN) 0.47 mol (in terms of OH group conversion) of α-naphthol aralkyl resin (manufactured by Nippon Steel Chemical Co., Ltd., "SN495V", OH group equivalent: 236 g/eq.: including naphthol aralkyl with a repeating unit number n of 1 to 5) was dissolved in 500 ml of chloroform, and 0.7 mol of triethylamine (solution 1) was added to the solution. While maintaining the temperature at -10°C, solution 1 was added dropwise to 300 g of chloroform solution in which 0.93 mol of cyanogen chloride was dissolved for 1.5 hours. After the addition was completed, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise to the reactor, and the reaction was stirred for 30 minutes to complete. After the by-product triethylamine hydrochloride was filtered out from the reaction solution, the filtrate was washed with 500 ml of 0.1N hydrochloric acid, and then washed with 500 ml of water for 4 times. After drying with sodium sulfate, it was evaporated at 75°C and then degassed under reduced pressure at 90°C to obtain a brown solid α-naphthol aralkyl type cyanate compound represented by the above formula (VI) (wherein R5 is all hydrogen atom, n=1~5). When the obtained α-naphthol aralkyl type cyanate compound was analyzed by infrared absorption spectrum, the absorption of cyanate group was confirmed near 2264 cm ^-1 .

[Example 1] 50 parts by mass of biphenyl aralkyl type epoxy resin ("NC-3000FH" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 320 eq.) as epoxy compound (A), 20 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane ("BMI-70" manufactured by K.I Chemical Co., Ltd.), 50 parts by mass of biphenyl aralkyl type phenolic resin ("GPH-103" manufactured by Nippon Kayaku Co., Ltd.) as curing agent (B), 1 part by mass of wetting dispersant ("DISPERBYK-161" manufactured by BYK Co., Ltd.), and talc coated with zinc molybdate as inorganic filler (Sherwin-Williams Co., Ltd.) were mixed (mixed). Chemicals, "KEMGARD 911C", zinc molybdate supporting amount: 10 mass %, 10 mass parts, fused silica as an inorganic filler (G) (Admatechs Co., Ltd., "SC4500SQ", average particle size 1.5 μm) 120 mass parts, zirconium nitride (Mitsubishi Materials Co., Ltd., "NITRBLACK (registered trademark) UB-1", primary particle size 20-50 nm) 10 mass parts, and 2,4,5-triphenylimidazole (Tokyo Chemical Industries, Ltd., "TPIZ") 0.3 mass parts, then diluted with methyl ethyl ketone to obtain a varnish (resin composition). The varnish (resin composition) was impregnated onto E-glass fabric with a thickness of 0.1 mm and dried at 165°C for 3 minutes to obtain a prepreg with a resin content of 50% by mass. The evaluation results of formability, transmittance, and insulation resistance are shown in Table 1.

[Example 2] The same procedure as in Example 1 was followed except that 10 parts by mass of zirconium nitride ("NITRBLACK (registered trademark) UB-1" manufactured by Mitsubishi Materials Corporation, primary particle size 20-50 nm) was used instead of 5 parts by mass of the same zirconium nitride to obtain a prepreg having a resin content of 50% by mass. The evaluation results of formability, transmittance, and insulation resistance are shown in Table 1.

[Example 3] The same procedure as in Example 1 was followed except that 10 parts by mass of zirconium nitride ("NITRBLACK (registered trademark) UB-1" manufactured by Mitsubishi Materials Corporation, primary particle size 20-50 nm) was used instead of 20 parts by mass of the same zirconium nitride to obtain a prepreg having a resin content of 50% by mass. The evaluation results of formability, transmittance, and insulation resistance are shown in Table 1.

[Example 4] Example 1 was prepared by replacing 50 parts by mass of the biphenyl aralkyl phenolic resin (manufactured by Nippon Kayaku Co., Ltd., "GPH-103") with 50 parts by mass of the α-naphthol aralkyl cyanate compound ("SN495VCN", cyanate equivalent: 261 g/eq.) obtained in the form of a curing agent (B) in Synthesis Example 1, and obtaining a prepreg having a resin content of 50% by mass. The evaluation results of the formability, transmittance, and insulation resistance are shown in Table 1.

[Example 5] Except that 20 parts by weight of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (manufactured by K.I Chemical Industry Co., Ltd., "BMI-70") in Example 4 was not used, the same process as in Example 4 was performed to obtain a prepreg having a resin content of 50% by weight. The evaluation results of formability, transmittance, and insulation resistance are shown in Table 1.

[Comparative Example 1] Except that 10 parts by weight of zirconium nitride (manufactured by Mitsubishi Materials Corporation, "NITRBLACK (registered trademark) UB-1") was not used in Example 1, the same process as in Example 1 was performed to obtain a prepreg having a resin content of 50% by weight. The evaluation results of formability, transmittance, and insulation resistance are shown in Table 2.

[Comparative Example 2] Example 1 was performed in the same manner as Example 1 except that 10 parts by mass of zirconium nitride ("NITRBLACK (registered trademark) UB-1" manufactured by Mitsubishi Materials Corporation) was replaced with 10 parts by mass of carbon particles ("MHI BLACK #273" manufactured by Mikoku Color Co., Ltd.) to obtain a prepreg having a resin content of 50% by mass. The evaluation results of formability, transmittance, and insulation resistance are shown in Table 2.

[Comparative Example 3] Except that 10 parts by mass of carbon particles (MHI BLACK#273, manufactured by Mitsubishi Materials Corporation) was used instead of 10 parts by mass of zirconium nitride (manufactured by Mitsubishi Materials Corporation, "NITRBLACK (registered trademark) UB-1") in Example 4, the same procedure as in Example 4 was followed to obtain a prepreg having a resin content of 50% by mass. The evaluation results of formability, transmittance, and insulation resistance are shown in Table 2.

[Comparative Example 4] A prepreg having a resin content of 50% by mass was obtained in the same manner as in Example 5 except that 10 parts by mass of carbon particles (MHI BLACK#273, manufactured by Mitsubishi Materials Corporation) was used instead of 10 parts by mass of zirconium nitride (manufactured by Mitsubishi Materials Corporation, "NITRBLACK (registered trademark) UB-1") in Example 5. The evaluation results of formability, transmittance, and insulation resistance are shown in Table 2.

[Table 1] Embodiment 1 2 3 4 5 Reviews Formability ○ ○ ○ ○ ○ Transmittance ○ ○ ○ ○ ○ Insulation resistance(Ω) Normal 3.0×10 ¹⁵ 1.2×10 ¹⁵ 3.0×10 ¹⁵ 5.0×10 ¹⁵ 1.0×10 ¹⁵ After treatment at 121℃ and 2 atmospheres for 24 hours 3.0×10 ¹⁴ 1.0×10 ¹⁵ 2.0×10 ¹⁵ 1.0×10 ¹⁵ 1.0×10 ¹⁴

[Table 2] Comparison Example 1 2 3 4 Reviews Formability ○ × × × Transmittance × ○ ○ ○ Insulation resistance(Ω) Normal 6.0×10 ¹⁵ ＜1.0×10 ⁸ ＜1.0×10 ⁸ ＜1.0×10 ⁸ After treatment at 121℃ and 2 atmospheres for 24 hours 1.2×10 ¹⁴ ＜1.0×10 ⁸ ＜1.0×10 ⁸ ＜1.0×10 ⁸

As can be seen from Table 1 and Table 2, the copper-clad foil laminates obtained using the resin compositions of Examples 1 to 5 all have excellent formability, light shielding properties (transmittance) from visible light to near-infrared light, and insulation resistance (insulation resistance value). In addition, the insulation resistance is still good after the moisture and heat resistance test. In contrast, the resin composition of Comparative Example 1 does not contain zirconium nitride, so the light shielding property is poor. The resin compositions of Comparative Examples 2 to 4 replace zirconium nitride with carbon particles, so the formability and insulation resistance are poor. [Industrial Utilization]

The resin composition of the present invention has industrial applicability as a material used in the manufacture of printed wiring boards, etc.

Claims (17)

A resin composition is used for printed wiring boards, the resin composition contains: an epoxy compound (A), a hardener (B), zirconium nitride (C), and a maleimide compound (F); the content of the zirconium nitride (C) is 1 to 30 parts by mass relative to 100 parts by mass of the total amount of the epoxy compound (A) and the hardener (B). The resin composition of claim 1, wherein the zirconium nitride (C) comprises particles having a primary particle size of 20 to 50 nm. The resin composition of claim 1 or 2, wherein the epoxy compound (A) comprises a compound represented by the following formula (I);

In formula (I), n1 represents an integer greater than or equal to 1. The resin composition of claim 1 or 2, wherein the hardener (B) contains a phenol compound (D) and/or a cyanate compound (E). The resin composition of claim 4, wherein the phenol compound (D) comprises a compound represented by the following formula (II) or formula (III);

In formula (II), n2 represents an integer greater than 1;

In formula (III), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n3 represents an integer greater than 1. The resin composition of claim 4, wherein the cyanate compound (E) comprises a naphthol aralkyl type cyanate compound represented by the following formula (VI) and/or a novolac type cyanate compound represented by the following formula (VII);

In the formula (VI), R ⁵ each independently represents a hydrogen atom or a methyl group, and n6 represents an integer greater than 1;

In the formula (VII), R ⁶ each independently represents a hydrogen atom or a methyl group, and n7 represents an integer greater than 1. The resin composition of claim 1, wherein the maleimide compound (F) comprises one or more selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2'-bis{4-(4-maleimidophenoxy)phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V);

In formula (IV), R ³ each independently represents a hydrogen atom or a methyl group, and n4 represents an integer greater than 1;

In formula (V), R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n5 is an average value and represents 1<n5≦5. The resin composition of claim 1 or 2 further contains an inorganic filler (G). The resin composition of claim 8, wherein the inorganic filler (G) comprises at least one selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum oxide, alumina, magnesium oxide, molybdenum oxide, zinc molybdate, and magnesium hydroxide. A prepreg having: a substrate, and a resin composition as described in any one of claims 1 to 9 impregnated or coated on the substrate. A resin sheet with a support, comprising: a support, and a resin composition as described in any one of claims 1 to 9 laminated on one or both sides of the support. A metal foil-clad laminate having: a laminate formed of one or more selected from the group consisting of a prepreg as in claim 10 and a resin sheet with a support as in claim 11, and metal foil disposed on one or both sides of the laminate. The metal foil-clad laminate of claim 12, wherein the transmittance of the substrate obtained by removing the metal foil from the metal foil-clad laminate is less than 0.1% in the wavelength range of 400 to 2000 nm. A printed wiring board is manufactured using the prepreg as claimed in claim 10 as a stacking material. A printed wiring board is produced by using a resin sheet with a support as claimed in claim 11 as a stacking material. A printed wiring board is manufactured using the metal-clad laminate of claim 12 or 13 as a stacking material. A printed wiring board comprising: an insulating layer, and a conductive layer formed on the surface of the insulating layer; the insulating layer contains a resin composition as described in any one of claims 1 to 9.