JP7552591B2 - Resin composition, prepreg, resin sheet with support, metal foil-clad laminate, and printed wiring board - Google Patents

Description

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

In recent years, there has been a demand for materials with excellent light-blocking properties from visible light to near-infrared light (wavelengths 400 to 2000 nm) for use in printed wiring boards for displays and sensor substrates.

JP 11-172114 A

Carbon particles are an example of black powder that has excellent light-shielding properties from visible light to near-infrared light. For example, Patent Document 1 discloses a thermosetting resin composition with excellent light-shielding properties, which contains a thermosetting resin, carbon particles, and a thermosetting catalyst as essential components. On the other hand, carbon particles have high electrical conductivity, so if used as is, they may cause a short circuit between the surrounding conductive devices. In response to this, Patent Document 1 discloses a method of improving insulation by coating the surface of carbon particles with a thermosetting resin, but this type of processing increases product costs. Patent Document 1 also discloses that if the surface of carbon particles is not coated and the prepreg is made, the light-shielding properties are poor.

Therefore, the present invention aims to provide a resin composition, a prepreg, a resin sheet with a support, a metal foil-clad laminate, and a printed wiring board that have excellent moldability, light shielding properties from visible light to near-infrared light, and insulation resistance.

As a result of extensive research into solving the above problems, the inventors discovered that a resin composition containing an epoxy compound (A), a curing agent (B), and a specific amount of zirconium nitride (C) can solve the above problems, and thus completed the present invention.

（式（Ｉ）中、ｎ１は１以上の整数を表す。）
［４］
前記硬化剤（Ｂ）が、フェノール化合物（Ｄ）及び／又はシアン酸エステル化合物（Ｅ）を含む、［１］～［３］のいずれかに記載の樹脂組成物。
［５］
前記フェノール化合物（Ｄ）が、下記式（ＩＩ）又は式（ＩＩＩ）で表される化合物を含む、［４］に記載の樹脂組成物。

（式（ＩＩ）中、ｎ２は１以上の整数を表す。）

（式（ＩＩＩ）中、Ｒ^１、Ｒ^２は、各々独立に、水素原子又はメチル基を表し、ｎ３は１以上の整数を表す。）
［６］
前記シアン酸エステル化合物（Ｅ）が、下記式（ＶＩ）で表されるナフトールアラルキル型シアン酸エステル化合物、及び／又は、下記式（ＶＩＩ）で表されるノボラック型シアン酸エステル化合物を含む、
［４］に記載の樹脂組成物。

（上記式（ＶＩ）中、Ｒ^５は、各々独立して、水素原子又はメチル基を表し、ｎ６は１以上の整数を示す。）

（上記式（ＶＩＩ）中、Ｒ^６は、各々独立して、水素原子又はメチル基を表し、ｎ７は１以上の整数を示す。）
［７］
マレイミド化合物（Ｆ）をさらに含む、［１］～［６］のいずれかに記載の樹脂組成物。
［８］
前記マレイミド化合物（Ｆ）が、ビス（４－マレイミドフェニル）メタン、２，２’－ビス｛４－（４－マレイミドフェノキシ）－フェニル｝プロパン、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン、下記式（ＩＶ）で表されるマレイミド化合物、及び下記式（Ｖ）で表されるマレイミド化合物からなる群より選択される１種以上を含む、［７］に記載の樹脂組成物。

（式（ＩＶ）中、Ｒ^３は、各々独立して、水素原子又はメチル基を表し、ｎ４は１以上の整数を表す。）

（式（Ｖ）中、Ｒ^４は、各々独立に、水素原子、炭素数１～５のアルキル基又はフェニル基を表し、ｎ５は、平均値であり、１＜ｎ５≦５を表す。）
［９］
無機充填材（Ｇ）を更に含む、［１］～［８］のいずれかに記載の樹脂組成物。
［１０］
前記無機充填材（Ｇ）が、シリカ、水酸化アルミニウム、アルミナ、ベーマイト、酸化マグネシウム、酸化モリブデン、モリブデン酸亜鉛、及び水酸化マグネシウムからなる群より選択される１種以上を含む、［９］に記載の樹脂組成物。
［１１］
プリント配線板用である、
［１］～［１０］のいずれか一項に記載の樹脂組成物。
［１２］
基材と、該基材に含浸又は塗布された［１］～［１１］のいずれかに記載の樹脂組成物とを有する、プリプレグ。
［１３］
支持体と、該支持体の片面または両面に積層された［１］～［１１］のいずれかに記載の樹脂組成物とを有する、支持体付きレジンシート。
［１４］
［１２］に記載のプリプレグ及び［１３］に記載の支持体付きレジンシートからなる群より選択される１種以上で形成された積層体と、該積層体の片面又は両面に配された金属箔とを有する、金属箔張積層板。
［１５］ 金属箔張積層板から金属箔が除去された基板の波長４００～２０００ｎｍの範囲における透過率が、０．１％以下である、［１４］に記載の金属箔張積層板。
［１６］
［１２］に記載のプリプレグをビルドアップ材料として用いて作製されたプリント配線板。
［１７］
［１３］に記載の支持体付きレジンシートをビルドアップ材料として用いて作製されたプリント配線板。
［１８］
［１４］又は［１５］に記載の金属箔張積層板をビルドアップ材料として用いて作製されたプリント配線板。
［１９］
絶縁層と、該絶縁層の表面に形成された導体層とを含むプリント配線板であって、該絶縁層が［１］～［１１］のいずれかに記載の樹脂組成物を含む、プリント配線板。 That is, the present invention is as follows.
[1]
A resin composition comprising an epoxy compound (A), a curing agent (B), and zirconium nitride (C), wherein the content of the zirconium nitride (C) is 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).
[2]
The resin composition according to [1], wherein the zirconium nitride (C) contains particles having a primary particle diameter of 20 to 50 nm.
[3]
The resin composition according to [1] or [2], wherein the epoxy compound (A) contains a compound represented by the following formula (I):

(In formula (I), n1 represents an integer of 1 or more.)
[4]
The resin composition according to any one of [1] to [3], wherein the curing agent (B) contains a phenol compound (D) and/or a cyanate ester compound (E).
[5]
The resin composition according to [4], wherein the phenol compound (D) includes a compound represented by the following formula (II) or formula (III).

(In formula (II), n2 represents an integer of 1 or more.)

(In formula (III), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.)
[6]
The cyanate ester compound (E) contains 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):
The resin composition according to [4].

(In the above formula (VI), each ^R5 independently represents a hydrogen atom or a methyl group, and n6 represents an integer of 1 or more.)

(In the above formula (VII), each ^R6 independently represents a hydrogen atom or a methyl group, and n7 represents an integer of 1 or more.)
[7]
The resin composition according to any one of [1] to [6], further comprising a maleimide compound (F).
[8]
The resin composition according to [7], wherein the maleimide compound (F) comprises at least one 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), each ^R3 independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 or more.)

(In formula (V), each R ⁴ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n5 represents an average value and 1<n5≦5.)
[9]
The resin composition according to any one of [1] to [8], further comprising an inorganic filler (G).
[10]
The resin composition according to [9], wherein the inorganic filler (G) comprises at least one selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, magnesium oxide, molybdenum oxide, zinc molybdate, and magnesium hydroxide.
[11]
For printed wiring boards,
The resin composition according to any one of [1] to [10].
[12]
A prepreg comprising a substrate and the resin composition according to any one of [1] to [11] impregnated into or coated on the substrate.
[13]
A resin sheet with a support, comprising a support and the resin composition according to any one of [1] to [11] laminated on one or both sides of the support.
[14]
A metal foil-clad laminate having a laminate formed of one or more selected from the group consisting of the prepreg described in [12] and the resin sheet with a support described in [13], and a metal foil arranged on one or both sides of the laminate.
[15] The metal foil-clad laminate according to [14], wherein the transmittance of a substrate from which the metal foil has been removed in the wavelength range of 400 to 2000 nm is 0.1% or less.
[16]
A printed wiring board produced by using the prepreg according to [12] as a build-up material.
[17]
A printed wiring board produced by using the resin sheet with a support according to [13] as a build-up material.
[18]
A printed wiring board produced by using the metal foil-clad laminate according to [14] or [15] as a build-up material.
[19]
A printed wiring board comprising an insulating layer and a conductor layer formed on a surface of the insulating layer, the insulating layer comprising the resin composition according to any one of [1] to [11].

According to the present invention, it is possible to provide a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board that have excellent moldability, light shielding properties (transmittance) from visible light to near-infrared light, and insulation resistance (insulation resistance value).

Below, we will explain in detail the form for implementing the present invention (hereinafter referred to as the "present embodiment"); however, the present invention is not limited to this, and various modifications are possible without departing from the gist of the present invention.

[Resin composition]
The resin composition of this embodiment contains an epoxy compound (A), a curing agent (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 curing agent (B). By adopting such a configuration, the resin composition of this embodiment has excellent moldability, light shielding property (transmittance) from visible light to near infrared light, and insulation resistance (insulation resistance value). In addition, the resin composition of this embodiment is also excellent in insulation resistance after a moist heat resistance test. Hereinafter, each component constituting the resin composition of this embodiment will be described.

(Zirconium nitride (C))
The resin composition of the present embodiment contains zirconium nitride (C). The zirconium nitride (C) is not particularly limited, but preferably contains particles having a primary particle diameter of 20 to 50 nm. By containing particles having a primary particle diameter of 20 nm or more, the dispersibility of the zirconium nitride (C) particles tends to be excellent, and by containing particles having a primary particle diameter of 50 nm or less, the moldability tends to be excellent. The primary particle diameter can be measured by a method such as observation with an electron microscope.

Commercially available products such as zirconium nitride (C) can be used, for example, "NITRBLACK (registered trademark) UB-1" manufactured by Mitsubishi Materials Corporation.

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 curing agent (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, the light blocking properties tend to be excellent. When the content of zirconium nitride (C) is 30 parts by mass or less, the moldability tends to be excellent.

(Epoxy compound (A))
The resin composition of the present embodiment contains an epoxy compound (A). The epoxy compound (A) is not particularly limited, but is preferably an epoxy compound having two or more epoxy groups in one molecule. Examples of such epoxy compounds include bisphenol type epoxy resins (e.g., bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins), diallyl bisphenol type epoxy resins (e.g., diallyl bisphenol A type epoxy resins, diallyl bisphenol E type epoxy resins, diallyl bisphenol F type epoxy resins, diallyl bisphenol S type epoxy resins, etc.), phenol novolac type epoxy resins (e.g., phenol novolac type 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 skeletons, glycidyl ester type epoxy resins, polyol type epoxy resins, isocyanurate ring-containing epoxy resins, dicyclopentadiene type epoxy resins, epoxy resins consisting of bisphenol A type structural units and hydrocarbon-based structural units, and halogen compounds thereof. These epoxy compounds may be used alone or in combination of two or more.

式（Ｉ）中、ｎ１は１以上の整数を表す。ｎ１の上限値は、好ましくは１０であり、より好ましくは７である。 Among these, the epoxy compound (A) preferably contains a biphenylaralkyl type epoxy resin from the viewpoint of achieving excellent linear thermal expansion coefficient (CTE), glass transition temperature (Tg), copper foil peel strength, and heat resistance in addition to moldability. The biphenylaralkyl type epoxy resin is preferably a compound represented by the following formula (I).

In formula (I), n1 represents an integer of 1 or more. The upper limit of n1 is preferably 10, and more preferably 7.

The content of the epoxy compound (A) in the resin composition of this embodiment is not particularly limited, but from the viewpoint of achieving superior glass transition temperature (Tg), heat resistance, and linear thermal expansion coefficient (CTE) in addition to moldability, it 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, per 100 parts by mass of the total amount of the epoxy compound (A) and the curing agent (B). When two or more types of epoxy compounds (A) are used in combination, it is preferable that their total amount satisfies the above value.

(Curing Agent (B))
The curing agent (B) in this embodiment is not particularly limited as long as it is a compound generally used as a curing agent for epoxy compounds, but for example, one or more selected from the group consisting of a phenol compound (D), a cyanate ester compound (E), an acid anhydride, and an amine compound can be suitably used. Among these, it is more preferable that the curing agent (B) contains a phenol compound (D) and/or a cyanate ester compound (E).

(Phenol Compound (D))
The phenolic compound (D) is not particularly limited, but is preferably a phenolic compound having two or more phenolic groups in one molecule.Such phenolic compounds include, for example, 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-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenolic novolac resins (e.g., phenol novolac resin, naphthol novolac resin, cresol novolac resin, 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 formaldehyde resins, etc.These phenolic compounds can be used alone or in combination of two or more.

Among these, it is preferable that the phenolic compound (D) contains a biphenyl aralkyl type phenolic resin and/or a naphthalene type phenolic resin, from the viewpoint of being superior in linear thermal expansion coefficient (CTE), glass transition temperature (Tg), heat resistance, and low water absorption in addition to moldability.

式（ＩＩ）中、ｎ２は１以上の整数を表す。ｎ２の上限値は、好ましくは１０、より好ましくは７であり、さらに好ましくは６である。

式（ＩＩＩ）中、Ｒ^１、Ｒ^２は、各々独立に、水素原子又はメチル基を表し、ｎ３は１以上の整数を表す。ｎ３の上限値は、好ましくは１０、より好ましくは７であり、さらに好ましくは６である。 The biphenylaralkyl type phenolic resin or the naphthalene type phenolic resin preferably contains a compound represented by the following formula (II) or formula (III).

In formula (II), n2 represents an integer of 1 or more. The upper limit of n2 is preferably 10, more preferably 7, and further 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 of 1 or greater. 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 this embodiment is not particularly limited, but from the viewpoint of achieving excellent linear thermal expansion coefficient (CTE), glass transition temperature (Tg), heat resistance, and low water absorption in addition to moldability, it 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 per 100 parts by mass of the total amount of the epoxy compound (A) and the curing agent (B). When two or more types of phenol compounds (D) are used in combination, it is preferable that their total amount satisfies the above value.

(Cyanate Ester Compound (E))
The cyanate ester compound (E) is not particularly limited as long as it is a compound in which a cyanate ester group (cyanato group) is directly bonded to an aromatic ring, and examples thereof include naphthol aralkyl cyanate ester compounds (naphthol aralkyl cyanates), naphthylene ether cyanate ester compounds, xylene resin type cyanate ester compounds, trisphenolmethane type cyanate ester compounds, and adamantane skeleton type cyanate ester compounds. Among these, from the viewpoint of further improving plating adhesion and low water absorption, the cyanate ester compound (E) preferably contains one or more selected from the group consisting of naphthol aralkyl cyanate ester compounds, naphthylene ether cyanate ester compounds, novolac type cyanate ester compounds, and xylene resin type cyanate ester compounds, and is more preferably a naphthol aralkyl cyanate ester compound or a novolac type cyanate ester compound. These cyanate ester compounds can be used alone or in combination of two or more. These cyanate ester compounds may be prepared by a known method, or commercially available products may be used.

式（ＶＩ）中、Ｒ^５は、各々独立して、水素原子又はメチル基を表し、水素原子が好ましい。また、式（ＶＩ）中、ｎは１以上の整数を示す。ｎ６の上限値は、好ましくは１０であり、より好ましくは６である。 The naphthol aralkyl cyanate compound is not particularly limited, but for example, a compound represented by the following formula (VI) is preferable.

In formula (VI), ^R5 each independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In formula (VI), n represents an integer of 1 or more. The upper limit of n6 is preferably 10, and more preferably 6.

（上記式（ＶＩＩ）中、Ｒ６は、各々独立して、水素原子又はメチル基を表し、この中でも水素原子が好ましい。また、上記式（ＶＩＩ）中、ｎ７は１以上の整数を示す。ｎ７の上限値は、好ましくは１０であり、より好ましくは７である。） The novolac-type cyanate ester compound is not particularly limited, but is preferably, for example, a compound represented by the following formula (VII).

(In the above formula (VII), R6 each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. In addition, in the above formula (VII), n7 represents an integer of 1 or more. The upper limit of n7 is preferably 10, and more preferably 7.)

The content of the cyanate ester compound (E) in the resin composition of this embodiment is not particularly limited, but from the viewpoint of achieving excellent plating adhesion and low water absorption in addition to moldability, it 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, per 100 parts by mass of the total amount of the epoxy compound (A) and the curing agent (B). When two or more types of cyanate ester compounds (E) are used in combination, it is preferable that their total amount satisfies the above value.

The resin composition of this embodiment may contain both the phenol compound (D) and the cyanate ester compound (E) as the curing agent (B). In this case, the total content of the phenol compound (D) and the cyanate ester 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, per 100 parts by mass of the total amount of the epoxy compound (A) and the curing agent (B). When the total content of the phenol compound (D) and the cyanate ester compound (E) is within the above range, moldability tends to be improved.

(Maleimide Compound (F))
The resin composition of the present 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-hydrophenylmaleimide, 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 described above may be in the form of a monomer or a prepolymer, or may be in the form of a prepolymer of a maleimide compound and an amine compound. These maleimide compounds (F) may be used alone or in appropriate combination of two or more.

式（ＩＶ）中、Ｒ^３は、各々独立して、水素原子又はメチル基を表し、ともにメチル基であることが好ましい。ｎ４は１以上の整数を表す。ｎ４の上限値は、好ましくは１０であり、より好ましくは７であり、更に好ましくは６である。

式（Ｖ）中、Ｒ^４は、各々独立に水素原子、炭素数１～５のアルキル基又はフェニル基を表し、水素原子、メチル基又はフェニル基であることが好ましい。ｎ５は、平均値であり、１＜ｎ５≦５を表す。 Among these, from the viewpoint of heat resistance, the maleimide compound (F) is preferably at least one 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 preferably both are methyl groups. n4 represents an integer of 1 or more. The upper limit of n4 is preferably 10, more preferably 7, and even more preferably 6.

In formula (V), ^R4 's each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and are 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 curing agent (B). When two or more types of maleimide compounds (F) are used in combination, it is preferable that their total amount satisfies the above value.

(Other resins)
The resin composition of the present embodiment may contain other resins as shown below, so long as they do not impair the effects of the present invention. Examples of other resins include compounds having a polymerizable unsaturated group other than the above-mentioned epoxy compound (A), curing agent (B), and maleimide compound (F), oxetane resins, and benzoxazine compounds. Examples of compounds having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; (meth)acrylates of monohydric or polyhydric alcohols such as methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and benzocyclobutene resins. Examples of the oxetane resin include alkyl oxetanes such as oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, and 3,3-dimethyl oxetane, 3-methyl-3-methoxymethyl oxetane, 3,3'-di(trifluoromethyl)perfluoro oxetane, 2-chloromethyl oxetane, 3,3-bis(chloromethyl) oxetane, biphenyl-type oxetane, and "OXT-101" and "OXT-121" manufactured by Toa Gosei Co., Ltd. Examples of the benzoxazine compound include compounds having two or more dihydrobenzoxazine rings in one molecule, and examples of the benzoxazine compound include "bisphenol F-type benzoxazine BF-BXZ" and "bisphenol S-type benzoxazine BS-BXZ" manufactured by Konishi Chemical Co., Ltd.

(Inorganic filler (G))
The resin composition of the present embodiment may further contain an inorganic filler (G) other than the zirconium nitride (C). Examples of such an inorganic filler (G) include silicas, silicon compounds (e.g. , white carbon, etc.), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides other than zirconium nitride (C) (e.g., boron nitride, aggregated boron nitride, silicon nitride , aluminum nitride, etc.), metal sulfates (e.g., barium sulfate, etc.), metal hydroxides (e.g., aluminum hydroxide, aluminum hydroxide heat-treated products (e.g., aluminum hydroxide is heat-treated to remove some of the water of crystallization) (reduced), boehmite, magnesium hydroxide Zn, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), zinc molybdate supported on talc, zinc oxide or calcium carbonate, zinc compounds (e.g., 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, Examples of the inorganic filler include short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, and spherical glass. or a combination of two or more of them can be used.

Among these, from the viewpoint of achieving even better coefficient of linear thermal expansion (CTE), flexural modulus, and flame retardancy, it is preferable that the inorganic filler (G) contains one or more types selected from the group consisting of silica, metal hydroxides, and metal oxides, more preferably contains one or more types selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, magnesium oxide, molybdenum oxide, zinc molybdate, and magnesium hydroxide, even more preferably contains one or more types selected from the group consisting of silica, boehmite, zinc molybdate, and alumina, and silica is particularly preferable.

Examples of silica include natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica, etc. Of these, fused silica is preferred.

The content of the inorganic filler (G) is not particularly limited, but 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 curing agent (B). When the content of the inorganic filler (G) is 100 parts by mass or more, the linear thermal expansion coefficient (CTE), flexural 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 tend to be excellent and the moldability tends to be good, making it suitable for use as a printed wiring board. From the same viewpoint, the content of the inorganic filler (G) is more preferably 110 to 200 parts by mass, and even more preferably 110 to 150 parts by mass. When two or more types of inorganic fillers (G) are used in combination, it is preferable that the total amount of these satisfies the above value.

(Silane coupling agent)
The resin composition of the present embodiment may further contain a silane coupling agent. By containing a silane coupling agent, the resin composition of the present embodiment tends to have better dispersibility of the zirconium nitride (C) and the inorganic filler (G) and to have better adhesive strength between each component of the resin composition of the present embodiment and a substrate described later.

Examples of silane coupling agents include silane coupling agents generally used for surface treatment of inorganic substances, such as aminosilane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), acrylicsilane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), phenylsilane compounds, etc. These silane coupling agents can be used alone or in combination of two or more. Among these, the silane coupling agent is preferably an epoxysilane compound. Examples of epoxysilane compounds include Shin-Etsu Chemical Co., Ltd. products such as "KBM-403", "KBM-303", "KBM-402", and "KBE-403".

The content of the silane coupling agent is not particularly limited, but may be approximately 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, per 100 parts by mass of the total amount of the epoxy compound (A) and the curing agent (B).

(Wetting and dispersing agent)
The resin composition of the present embodiment may further contain a wetting dispersant. By containing the wetting dispersant, the resin composition of the present embodiment tends to have even better dispersibility of the zirconium nitride (C) and the inorganic filler (G).

The wetting dispersant may be any known dispersant (dispersion stabilizer) used to disperse the inorganic filler (G), such as BYK Japan KK products such as "DISPERBYK-110", "DISPERBYK-111", "DISPERBYK-118", "DISPERBYK-180", "DISPERBYK-161", "BYK-W996", "BYK-W9010", and "BYK-W903".

The content of the wetting and dispersing agent is not particularly limited, but from the viewpoint of achieving even better dispersibility of the zirconium nitride (C) and inorganic filler (G), it 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, per 100 parts by mass of the total amount of the epoxy compound (A) and the curing agent (B).

(Cure Accelerator)
The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, but examples thereof include imidazole compounds described later; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-di-perphthalate; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, tertiary amines such as N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, and catechol; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and iron acetylacetonate; these organic metal salts dissolved in hydroxyl group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; and organic tin compounds such as dioctyltin oxide, other alkyl tins, and alkyl tin oxides.

The resin composition of the present embodiment preferably contains an imidazole compound as a curing accelerator. From the viewpoint of excellent curing properties, examples of the imidazole compound include 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, and 2-phenyl-4-methylimidazole. Among these, 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, but may be about 0.1 to 10 parts by mass per 100 parts by mass of the total amount of the epoxy compound (A) and the curing agent (B). From the viewpoint of more effectively and reliably achieving 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 part by mass.

(solvent)
The resin composition of the present embodiment may contain a solvent. By containing a solvent, the resin composition of the present embodiment tends to have a lower viscosity during preparation of the resin composition, and to have better handleability 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, but examples include ketones (acetone, methyl ethyl ketone, methyl cellosolve, etc.), aromatic hydrocarbons (for example, toluene, xylene, etc.), amides (for example, dimethylformaldehyde, etc.), propylene glycol monomethyl ether and its acetate, etc. These solvents can be used alone or in combination of two or more.

(Transmittance)
The resin composition of the present embodiment preferably has a transmittance of 0.1% or less in the wavelength range of 400 to 2000 nm of a substrate obtained by removing the metal foil from a metal foil-clad laminate obtained by using the resin composition. The lower limit of the transmittance is not particularly limited, but it is preferably below the detection limit. By having a transmittance of 0.1% or less, sufficient light-shielding properties are obtained. The transmittance can be adjusted by the content of zirconium nitride (C) and the particle size of zirconium nitride (C), etc. The transmittance can be measured by the measurement method described in the examples.

(Method for producing resin composition)
The method for producing the resin composition of the present embodiment is not particularly limited, and may be, for example, a method in which each component is mixed in a solvent all at once or successively and stirred. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, kneading, etc. are used.

[Application]
The resin composition of the present embodiment can be suitably used for a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, or a printed wiring board. Hereinafter, the prepreg, the resin sheet, the laminate, the metal foil-clad laminate, and the printed wiring board will be described.

[Prepreg]
The prepreg of the present embodiment includes a substrate and the resin composition of the present embodiment impregnated or applied to the substrate. The prepreg of the present embodiment may be a prepreg obtained by a known method using the resin composition of the present embodiment, and specifically, the prepreg can be obtained by impregnating or applying the resin composition of the present embodiment to a substrate, and then semi-curing (B-stage) by heating and drying at a temperature of 100 to 200°C.

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

The content of the resin composition of this embodiment in the prepreg of this embodiment is preferably 30 to 90 mass %, more preferably 35 to 85 mass %, and even more preferably 40 to 80 mass %, calculated as solid content relative to the total amount of the prepreg. When the content of the resin composition is within the above range, moldability tends to be further improved. The solid content of the prepreg refers to the components remaining after removing the solvent from the prepreg. For example, the filler is included in the solid content of the prepreg.

(Substrate)
The substrate is not particularly limited, and examples thereof include known substrates used as materials for various printed wiring boards. Specific examples of the substrate include glass substrates, inorganic substrates other than glass (e.g., inorganic substrates composed of inorganic fibers other than glass such as quartz), organic substrates (e.g., organic substrates composed of organic fibers such as wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, and polyimide), and the like. These substrates are used alone or in combination of two or more. Among these, glass substrates are preferred from the viewpoint of further improving rigidity and further improving heating dimensional stability.

Examples of fibers constituting the glass substrate include E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among these, from the viewpoint of being superior in strength and low water absorption, it is preferable that the fibers constituting the glass substrate are one or more types of fibers selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass.

The form of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc. The weaving method of the woven fabric is not particularly limited, but examples of known weaving methods include plain weave, sash weave, twill weave, etc., and an appropriate selection can be made from these known methods depending on the intended use and performance. In addition, glass woven fabrics that have been subjected to fiber opening treatment or surface treatment with a silane coupling agent or the like are preferably used. The thickness and mass of the substrate are not particularly limited, but typically those of about 0.01 to 0.3 mm are preferably used.

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

The resin sheet of this embodiment may also have a support and the resin composition of this embodiment laminated on one or both sides of the support. Such a resin sheet is also called a resin sheet with a support. A resin sheet with a support is used as one means of thinning, and can be produced, for example, by applying and drying a resin composition (including a filler) used in prepregs, etc., directly to a support such as a metal foil or film.

The support is not particularly limited, but may be any known material used in various printed wiring board materials. Examples include 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, and SUS plate. Among these, electrolytic copper foil and PET film are preferred.

Examples of methods for applying the resin composition include a method in which the resin composition of this embodiment, which has been soaked in a solvent and put into a solution state, is applied onto a support using a bar coater, die coater, doctor blade, baker applicator, etc.

The resin sheet with a support is preferably one in which the resin composition of this embodiment is applied to a support and then semi-cured (B-staged). Specifically, for example, the resin composition of this embodiment is applied to a support such as copper foil, and then semi-cured by, for example, heating in a dryer at 20 to 200°C for 1 to 90 minutes to produce a resin sheet with a support. The amount of the composition attached to the support is preferably in the range of 0.1 to 500 μm in terms of the thickness of the resin layer.

[Laminate]
The laminate of this embodiment has the prepreg or the resin sheet with a support of this embodiment. The laminate of this embodiment includes one or more prepregs or resin sheets with a support, and when including more than one, the laminate has a form in which the prepregs and/or the resin sheets with a support are laminated. The laminate of this embodiment has excellent heat resistance, chemical resistance, low water absorption, and electrical properties by having the prepreg or the resin sheet with a support of this embodiment. The method for manufacturing the laminate can be appropriately applied by a generally known method, and is not particularly limited. For example, the laminate can be obtained by laminating the above-mentioned prepregs with each other or the prepreg and another layer, and molding them under heat and pressure. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, and more preferably 120 to 270 ° C. The pressure to be applied is also not particularly limited, but is preferably 2 to 5 MPa, and more preferably 2.5 to 4 MPa. The laminate of this embodiment can be suitably used as a metal foil-clad laminate described later by further comprising a layer made of metal foil.

[Metal foil laminate]
The metal foil-clad laminate of this embodiment has a laminate formed of one or more selected from the group consisting of the prepreg and the resin sheet of this embodiment, and a metal foil arranged on one or both sides of the laminate. The metal foil-clad laminate of this embodiment includes one or more selected from the group consisting of the prepreg and the resin sheet with a support. When the number of members 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 a metal foil is arranged on one or both sides of the prepreg or the resin sheet with a support. When the number of members selected from the group consisting of the prepreg and the resin sheet with a support is plural, the metal foil-clad laminate has a form in which a metal foil is arranged on one or both sides of a laminate (for example, a laminate of prepregs, a laminate of prepregs and a resin sheet with a support) formed of one or more members selected from the group consisting of laminated prepregs and the resin sheet with a support. The metal foil-clad laminate of this embodiment has excellent heat resistance, chemical resistance, low water absorbency, and electrical properties by containing one or more selected from the group consisting of the prepreg of this embodiment and the resin sheet with a support.

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

The molding method and molding conditions of the metal foil-clad laminate are not particularly limited, and general methods and conditions for laminates and multilayer boards for printed wiring boards can be applied. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used when molding the metal foil-clad laminate. In addition, in molding (lamination molding) the metal foil-clad laminate, the temperature is generally 100 to 300°C, the pressure is 2 to 100 kgf/cm ² , and the heating time is generally in the range of 0.05 to 5 hours. Furthermore, post-curing can be performed at a temperature of 150 to 300°C as necessary. In particular, when a multi-stage press is used, from the viewpoint of sufficiently promoting the curing of the prepreg or supported resin sheet, a temperature of 200°C to 250°C, a pressure of 10 to 40 kgf/ ^cm2 , and a heating time of 80 to 130 minutes are preferred, and a temperature of 215°C to 235°C, a pressure of 25 to 35 kgf/ ^cm2 , and a heating time of 90 to 120 minutes are more preferred. It is also possible to form a multilayer board by combining the above-mentioned prepreg or supported resin sheet with a separately prepared wiring board for an inner layer and laminating and molding it.

In the metal foil-clad laminate of this embodiment, the transmittance of the substrate from which the metal foil has been removed in the wavelength range of 400 to 2000 nm is preferably 0.1% or less. The lower limit of the transmittance is not particularly limited, but it is preferably below the detection limit. A transmittance of 0.1% or less provides sufficient light blocking properties. The transmittance can be adjusted by the content of zirconium nitride (C) and the particle size of zirconium nitride (C), etc. The transmittance can be measured by the measurement method described in the examples. Note that the transmittance in the examples was measured using a metal foil-clad laminate using E-glass woven fabric from the viewpoint of specifying the measurement conditions, but the substrate used to form the prepreg using the resin composition of this embodiment is not particularly limited, and the various substrates described above can be used.

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

The printed wiring board of this embodiment can be produced using the prepreg of this embodiment as a build-up material. The printed wiring board of this embodiment can be produced using the resin sheet of this embodiment as a build-up material. The printed wiring board of this embodiment can be produced using the metal foil-clad laminate of this embodiment as a build-up material. That is, the printed wiring board of this embodiment may have one or more selected from the group consisting of the prepreg of this embodiment and the 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 this embodiment and the resin sheet with a support.

Specifically, the printed wiring board of this embodiment can be manufactured, for example, by the following method. First, the metal foil-clad laminate of this embodiment is prepared. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to create an inner layer substrate having a conductor layer (inner layer circuit). Next, a predetermined number of prepregs or resin sheets with supports and metal foil for the outer layer circuit are laminated in this order on the surface of the conductor layer (interior circuit) of the inner layer substrate, and the laminate is integrally molded (lamination molding) by heating and pressing to obtain a laminate. In this case, the prepregs or resin sheets with supports laminated on the surface of the conductor layer (interior circuit) of the inner layer substrate correspond to the build-up material. The method and molding conditions for the laminate molding are the same as those for the laminate and metal foil-clad laminate described above. Next, the laminate is subjected to a hole punching process for through holes and via holes, and a plated metal film is formed on the wall surface of the hole formed thereby to conduct the conductor layer (interior circuit) and the metal foil for the outer layer circuit. Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to produce an outer layer substrate having a conductor layer (outer layer circuit), thus completing the manufacture of a printed wiring board.

In addition, when a metal foil-clad laminate is not used, a conductor layer that will become a circuit may be formed on the prepreg to produce a printed wiring board. In this case, an electroless plating technique may be used to form the conductor layer.

The present invention will be further explained below using examples and comparative examples, but the present invention is not limited to these examples in any way.

[Physical property evaluation]
Using the varnishes or prepregs obtained in the Examples and Comparative Examples, samples for evaluating physical properties were prepared according to the procedures shown in the following items, and the physical properties of moldability, transmittance, and insulation resistance were evaluated.

(Moldability)
A 12 μm thick electrolytic copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., "3EC-LPIII") was placed on top and bottom of the prepreg obtained in each Example and Comparative Example, and laminate molding was performed at a pressure of 30 kgf/cm2 and a temperature of 220°C for 120 minutes to obtain a copper foil-clad laminate with an insulating layer thickness of 0.1 mm. After removing all the copper foil from the copper foil-clad laminate by etching, the presence or absence of voids was visually determined. The results are shown in Tables 1 and 2. The respective symbols are as follows:
○: No voids.
×: Voids present.

(Transmittance)
A 12 μm thick electrolytic copper foil (3EC-LPIII, manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed on top and bottom of the prepreg obtained in each Example and Comparative Example, and laminate molding was performed for 120 minutes at a pressure of 30 kgf/cm2 and a temperature of 220°C to obtain a copper foil-clad laminate with an insulating layer thickness of 0.1 mm. After removing all the copper foil from the copper foil-clad laminate by etching, a sample cut to a size of 50 x 50 mm was measured for transmittance at wavelengths of 400 to 2000 nm using a spectrophotometer U-4100 manufactured by Hitachi High-Technologies. The results are shown in Tables 1 and 2. The symbols are as follows:
◯: The transmittance from 400 to 2000 nm was 0.1% or less.
×: The transmittance from 400 to 2000 nm exceeded 0.1%.

(Insulation resistance value)
Eight prepregs obtained in each Example and Comparative Example were stacked, and 12 μm thick electrolytic copper foil (Mitsui Mining & Smelting Co., Ltd., 3EC-LPIII) was placed on top and bottom, and laminate molding was performed for 120 minutes at a pressure of 30 kgf/cm2 and a temperature of 220°C to obtain a copper foil-clad laminate with an insulating layer thickness of 0.8 mm. After removing all the copper foil from the copper foil-clad laminate by etching, a sample cut to a size of 20 x 40 mm was treated in normal state (25°C, 1 atmosphere) and at 121°C, 2 atmospheres in a pressure cooker tester (Hirayama Seisakusho, PC-3 type) for 24 hours (humid heat resistance test), and then a DC of 500 V was applied, and the insulation resistance value between the terminals was measured after 60 seconds. The results are shown in Tables 1 and 2.

[Synthesis Example 1]
Synthesis of α-naphthol aralkyl cyanate ester compound (SN495VCN) 0.47 mol (OH group equivalent) of α-naphthol aralkyl resin (manufactured by Nippon Steel Chemical Co., Ltd., "SN495V", OH group equivalent: 236 g/eq.: the number of repeating units n of naphthol aralkyl is included from 1 to 5) was dissolved in 500 ml of chloroform, and 0.7 mol of triethylamine was added to this solution (solution 1). While keeping the temperature at -10°C, solution 1 was added dropwise over 1.5 hours to 300 g of chloroform solution in which 0.93 mol of cyanogen chloride was dissolved, and after the dropwise addition, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was further added dropwise to the reactor, and the mixture was stirred for 30 minutes to complete the reaction. The by-produced triethylamine hydrochloride was filtered off from the reaction solution, and the filtrate was washed with 500 ml of 0.1N hydrochloric acid, and then washed four times with 500 ml of water. The filtrate was dried over sodium sulfate, evaporated at 75°C, and degassed under reduced pressure at 90°C to obtain a brown solid α-naphthol aralkyl cyanate compound represented by the above formula (VI) (wherein R5's are all hydrogen atoms, n=1 to 5). When the obtained α-naphthol aralkyl cyanate compound was analyzed by infrared absorption spectroscopy, the absorption of the cyanate ester group was confirmed at around 2264 cm-1.

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

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

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

[Example 4]
A prepreg with a resin amount of 50 mass% was obtained in the same manner as in Example 1, except that 50 parts by mass of the α-naphthol aralkyl cyanate ester compound ("SN495VCN", cyanate ester equivalent: 261 g/eq.) obtained in Synthesis Example 1 was used as the curing agent (B) instead of 50 parts by mass of the biphenyl aralkyl phenol resin (manufactured by Nippon Kayaku Co., Ltd., "GPH-103") in Example 1. The evaluation results of the moldability, transmittance, and insulation resistance are shown in Table 1.

[Example 5]
A prepreg having a resin amount of 50% by mass was obtained in the same manner as in Example 4, except that 20 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (manufactured by K.I. Kasei Co., Ltd., "BMI-70") was not used in Example 4. The evaluation results of moldability, transmittance, and insulation resistance are shown in Table 1.

[Comparative Example 1]
A prepreg having a resin amount of 50% by mass was obtained in the same manner as in Example 1, except that 10 parts by mass of zirconium nitride (manufactured by Mitsubishi Materials Corporation, "NITRBLACK (registered trademark) UB-1") was not used. The evaluation results of moldability, transmittance, and insulation resistance are shown in Table 2.

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

[Comparative Example 3]
A prepreg having a resin amount of 50% by mass was obtained in the same manner as in Example 4, except that 10 parts by mass of carbon particles (Mitsubishi Materials Corporation, "NITRBLACK (registered trademark) UB-1") were used instead of 10 parts by mass of zirconium nitride (Mitsubishi Materials Corporation, "NITRBLACK #273") in Example 4. The evaluation results of moldability, transmittance, and insulation resistance are shown in Table 2.

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

As is clear from Tables 1 and 2, the copper foil-clad laminates obtained using the resin compositions of Examples 1 to 5 all have excellent moldability, light shielding properties (transmittance) from visible light to near-infrared light, and insulation resistance (insulation resistance value). Furthermore, the insulation resistance was good even after the moist heat resistance test. In contrast, the resin composition of Comparative Example 1 does not contain zirconium nitride and therefore has poor light shielding properties. The resin compositions of Comparative Examples 2 to 4 use carbon particles instead of zirconium nitride and therefore have poor moldability and insulation resistance.

The resin composition of the present invention has industrial applicability as a material used in the production of printed wiring boards and the like.

Claims (17)

An epoxy compound (A),
A curing agent (B);
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 curing agent (B);
The zirconium nitride (C) contains particles having a primary particle size of 20 to 50 nm,
For printed wiring boards ,
Resin composition. The epoxy compound (A) contains a compound represented by the following formula (I):
The resin composition according to claim 1.

(In formula (I), n1 represents an integer of 1 or more.) The curing agent (B) contains a phenol compound (D) and/or a cyanate ester compound (E);
The resin composition according to claim 1 or 2. The phenol compound (D) includes a compound represented by the following formula (II) or formula (III):
The resin composition according to claim 3.

(In formula (II), n2 represents an integer of 1 or more.)

(In formula (III), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.) The cyanate ester compound (E) contains 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):
The resin composition according to claim 3.

(In the above formula (VI), each ^R5 independently represents a hydrogen atom or a methyl group, and n6 represents an integer of 1 or more.)

(In the above formula (VII), each ^R6 independently represents a hydrogen atom or a methyl group, and n7 represents an integer of 1 or more.) Further comprising a maleimide compound (F),
The resin composition according to any one of claims 1 to 5. The maleimide compound (F) includes at least one 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):
The resin composition according to claim 6.

(In formula (IV), each ^R3 independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 or more.)

(In formula (V), each ^R4 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n5 represents an average value and 1<n5≦5.) Further comprising an inorganic filler (G);
The resin composition according to any one of claims 1 to 7. The inorganic filler (G) contains one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, magnesium oxide, molybdenum oxide, zinc molybdate, and magnesium hydroxide.
The resin composition according to claim 8. A substrate;
The resin composition according to any one of claims 1 to 9, which is impregnated or applied to the substrate ;
For printed wiring boards ,
Prepreg. A support;
and the resin composition according to any one of claims 1 to 9 laminated on one or both sides of the support,
For printed wiring boards ,
Resin sheet with support. A laminate formed of at least one selected from the group consisting of the prepreg according to claim 10 and the resin sheet with a support according to claim 11 , and a metal foil disposed on one or both sides of the laminate ,
For printed wiring boards ,
Metal foil laminate. The transmittance of the substrate from which the metal foil has been removed from the metal foil-clad laminate in the wavelength range of 400 to 2000 nm is 0.1% or less;
The metal foil-clad laminate according to claim 12 . A laminate produced by using the prepreg according to claim 10 as a build-up material.
Printed wiring board. A resin sheet with a support according to claim 11 is used as a build-up material.
Printed wiring board. A laminate produced by using the metal foil clad laminate according to claim 12 or 13 as a build-up material.
Printed wiring board. A printed wiring board comprising an insulating layer and a conductor layer formed on a surface of the insulating layer, the insulating layer comprising the resin composition according to any one of claims 1 to 9 .
Printed wiring board.