KR20220011116A - A resin composition, a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, and a printed wiring board - Google Patents

Abstract

It contains an epoxy compound (A), a hardening|curing agent (B), black particle (C), and an inorganic filler (D), and content of the said black particle (C) is the said epoxy compound (A) and the said hardening|curing agent (B) ) with respect to 100 parts by mass of a total content of 1 to 25 parts by mass, and the content of the inorganic filler (D) is 100 to 100 parts by mass of the total content of the epoxy compound (A) and the curing agent (B). 200 parts by mass of the resin composition.

Description

A resin composition, a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, and a printed wiring board

The present invention relates to a resin composition and to a method for manufacturing a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, and a printed wiring board using the composition.

In recent years, performance improvement, high functionalization, and miniaturization of an electronic component are progressing rapidly, and with this, the request|requirement of high functionalization is increasing also about the electronic material used for an electronic component. For example, electronic materials used for light emitting devices such as displays and LEDs are required to have light-shielding properties so that unnecessary light leakage to the outside does not occur, and electronic materials used for light receiving elements such as optical sensors of cameras , a light-shielding property is required so that the intrusion of light from the outside does not occur. Thus, light-shielding property is calculated|required by the printed wiring board used for a light emitting element, a light receiving element, or another electro-optical component.

For example, patent document 1 discloses the black polyimide film which secured light-shielding property by containing aniline black etc. as a flexible printed wiring board.

Japanese Patent Laid-Open No. 2016-047863

In recent years, the improvement of light-shielding property is desired also about the rigid board|substrate which impregnated or apply|coated the resin composition to the base material. As described in Patent Literature 1, it is known that aniline black or the like is used for a flexible printed wiring board as a method of improving light-shielding properties. It turned out that the problem that surface hardness falls or a moldability falls may generate|occur|produce when added.

The present invention has been made in view of the above problems, and a resin composition capable of obtaining a rigid substrate having excellent light-shielding properties and surface hardness, and a prepreg, a resin sheet, a laminated board, a metal foil-clad laminate, a printed wiring board using the resin composition, and It aims at providing the manufacturing method of a printed wiring board.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject. As a result, by using the black particle (C) of a predetermined amount and the inorganic filler (D) of a predetermined amount, it discovered that the said subject could be solved, and came to complete this invention.

That is, the present invention is as follows.

〔One〕

an epoxy compound (A), and

a curing agent (B);

black particles (C) and

containing an inorganic filler (D),

Content of the said black particle (C) is 1-25 mass parts with respect to 100 mass parts of total content of the said epoxy compound (A) and the said hardening|curing agent (B),

Content of the said inorganic filler (D) is 100-200 mass parts with respect to 100 mass parts of total content of the said epoxy compound (A) and the said hardening|curing agent (B),

resin composition.

〔2〕

The resin composition according to [1], wherein the black particles (C) are particles having an average particle diameter of 1 µm or less, at least a part of which is coated with a thermosetting resin on the surface.

[3]

The resin composition according to [1] or [2], wherein the epoxy compound (A) contains a compound represented by the following formula (I).

[Formula 1]

(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 (E) and/or a cyanate compound (F).

[5]

The resin composition according to [4], wherein the phenol compound (E) contains a compound represented by the following formula (II) or (III).

[Formula 2]

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

[Formula 3]

(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]

[4] wherein the cyanate ester compound (F) 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 ].

[Formula 4]

(In the formula (VI), R ⁵ each independently represents a hydrogen atom or a methyl group, and n6 represents an integer of 1 or more.)

[Formula 5]

(In the formula (VII), R ⁶ each 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 (G).

〔8〕

Said maleimide compound (G) is bis(4-maleimidephenyl)methane, 2,2'-bisb4-(4-maleimidephenoxy)-phenylbpropane, bis(3-ethyl-5-methyl The resin according to [7], containing at least one selected from the group consisting of -4-maleimidephenyl)methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V). composition.

[Formula 6]

(In formula (IV), R ³ each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 or more.)

[Formula 7]

(In the formula (V), R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n5 is an average value, and 1 < n5 ≤ 5.)

[9]

The inorganic filler (D) according to any one of [1] to [8], wherein the inorganic filler (D) contains at least one selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, magnesium oxide, and magnesium hydroxide. resin composition.

[10]

description and

Having the resin composition according to any one of [1] to [9] impregnated or applied to the substrate;

prepreg.

[11]

support and

Having the resin composition according to any one of [1] to [9] laminated on one side or both sides of the support,

resin sheet.

[12]

A laminate in which at least one selected from the group consisting of the prepreg according to [10] and the resin sheet according to [11] is laminated.

[13]

At least one selected from the group consisting of the prepreg according to [10] and the resin sheet according to [11];

having a metal foil laminated on the prepreg and/or the resin sheet,

Metal foil clad laminate.

[14]

The Barcol hardness of the metal foil-clad laminate is 70 to 80, and

The metal foil-clad laminate according to [13], wherein the transmittance in a wavelength range of 400 to 2000 nm of the substrate from which the metal foil has been removed from the metal foil-clad laminate is 0.1% or less.

[15]

A printed wiring board produced by using, as a buildup material, at least one selected from the group consisting of the prepreg according to [10] and the resin sheet according to [11].

[16]

A printed wiring board produced by using the metal foil-clad laminate according to [13] or [14] as a build-up material.

[17]

an insulating layer,

a conductor layer formed on the surface of the insulating layer;

The insulating layer contains the resin composition according to any one of [1] to [9],

printed wiring board.

According to the present invention, a resin composition capable of obtaining a rigid substrate having excellent light-shielding properties and surface hardness, and a method for manufacturing a prepreg, a resin sheet, a laminated board, a metal foil-clad laminate, a printed wiring board, and a printed wiring board using the resin composition intended to provide

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof. do.

[First embodiment: resin composition]

The resin composition of 1st Embodiment is a resin composition used for the rigid board|substrate which uses a prepreg, especially glass cloth as a base material, and impregnated or apply|coated the resin composition to the base material, for example. The said resin composition contains an epoxy compound (A), a hardening|curing agent (B), black particle (C), and an inorganic filler (D), and contains a maleimide compound (G) and other components as needed. You can do it.

In the resin composition of 1st Embodiment, in the said predetermined resin composition, content of black particle (C) is 1-25 mass parts with respect to 100 mass parts of total content of an epoxy compound (A) and a hardening|curing agent (B). Let it be part and let content of an inorganic filler (D) be 100-200 mass parts with respect to 100 mass parts of total content of an epoxy compound (A) and a hardening|curing agent (B). Thereby, while the rigid substrate excellent in light-shielding property in a visible thru|or near-infrared region, for example, 400-2000 nm wavelength region is obtained, the surface hardness of the rigid substrate obtained improves more.

Hereinafter, each component is demonstrated in detail.

[Epoxy compound (A)]

As an epoxy compound (A), if it is a compound which has one or more epoxy groups in 1 molecule, a well-known thing can be used suitably, The kind in particular is not limited. The number of epoxy groups per molecule of an epoxy compound (A) is 1 or more, Preferably it is 2 or more.

It does not specifically limit as an epoxy compound (A), A conventionally well-known epoxy resin can be used, For example, a biphenyl aralkyl type epoxy compound, a naphthalene type epoxy compound, a bisnaphthalene type epoxy compound, a polyfunctional phenol type epoxy Resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, xylene novolak type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, dicyclopenta Diene novolak type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, aromatic hydrocarbon formaldehyde type epoxy compound, anthra Quinone type epoxy compound, anthracene type epoxy resin, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy resin, xylok type epoxy compound, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S Type epoxy resin, bisphenol A novolak type epoxy resin, phenol type epoxy compound, biphenyl type epoxy resin, aralkyl novolak type epoxy resin, triazine skeleton epoxy compound, triglycidyl isocyanurate, alicyclic epoxy resin, A compound obtained by epoxidizing a double bond of a compound containing double bonds such as polyol type epoxy resin, glycidylamine, glycidyl type ester resin, butadiene, and a compound obtained by reaction of hydroxyl group containing silicone resin with epichlorhydrin and the like. An epoxy compound (A) may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

In addition, as described in the above example, in this specification, an epoxy compound having a structure obtained by epoxidizing a certain resin or compound may be described as "-type epoxy compound" in the name of the resin or compound. .

Among them, the epoxy compound (A) is a biphenyl aralkyl type epoxy compound, a naphthalene type epoxy compound, a bisnaphthalene type epoxy compound, an aromatic hydrocarbon formaldehyde type, from the viewpoint of improving the adhesion between the insulating layer and the conductor layer, the flame retardancy, and the like. It is preferable that it is 1 type, or 2 or more types chosen from the group which consists of an epoxy compound, an anthraquinone type epoxy compound, and a naphthol aralkyl type epoxy compound.

In addition, from the viewpoint of further lowering the coefficient of thermal expansion of the resin composition, the epoxy compound (A) is selected from the group consisting of a biphenyl aralkyl type epoxy resin, a naphthalene type epoxy compound, a bisnaphthalene type epoxy compound, and an anthraquinone type epoxy compound It is preferable that it is used 1 type, or 2 or more types, and a biphenyl aralkyl type epoxy resin is more preferable.

Although it does not specifically limit as a biphenyl aralkyl type epoxy compound, For example, the compound represented by following formula (I) is preferable. By using such a biphenyl aralkyl type epoxy resin, there exists a tendency for a moldability and surface hardness to improve more other than the above.

[Formula 8]

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

The content of the epoxy compound (A) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, with respect to 100 parts by mass of the total content of the epoxy compound (A) and the curing agent (B), further Preferably it is 40-60 mass parts. When content of an epoxy compound (A) exists in the said range, there exists a tendency for a moldability and surface hardness to improve more. Moreover, when using together 2 or more types of epoxy compounds (A), it is preferable that these total content satisfy|fills the said value.

[curing agent (B)]

A hardening|curing agent (B) is a compound which has a functional group which reacts with an epoxy compound (A). Although it does not restrict|limit especially as such a hardening|curing agent (B), For example, a phenol compound (E), a cyanate ester compound (F), an acid anhydride, an amine compound, etc. are mentioned. A hardening|curing agent (B) may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Among these, a phenol compound (E) and/or a cyanate ester compound (F) is preferable. By using such a hardening|curing agent (B), there exists a tendency for a moldability and surface hardness to improve more.

(Phenolic compound (E))

A well-known thing can be used suitably as long as a phenolic compound (E) is a compound which has two or more phenolic hydroxyl groups in 1 molecule, The kind in particular is not limited.

Although it does not restrict|limit especially as a phenol compound (E), For example, cresol novolak-type phenol resin, the biphenyl aralkyl type phenol resin represented by the following formula (II), and a naphthol aralkyl type phenol represented by the following formula (III) Resin, aminotriazine novolak type phenol resin, naphthalene type phenol resin, phenol novolak resin, alkylphenol novolak resin, bisphenol A type novolac resin, dicyclopentadiene type phenol resin, xylok type phenol resin, terpene modified phenol Resin, polyvinyl phenols, etc. are mentioned. A phenol compound (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

Among these, from the viewpoint of moldability and surface hardness, cresol novolak-type phenol resin, biphenyl aralkyl-type phenol resin represented by the following formula (II), naphthol aralkyl-type phenol resin represented by the following formula (III), aminotri An azine novolak-type phenol resin and a naphthalene-type phenol resin are preferable, and the biphenyl aralkyl-type phenol resin represented by the following formula (II) and a naphthol aralkyl-type phenol resin represented by the following formula (III) are more preferable.

[Formula 9]

(In formula (II), n2 represents an integer greater than or equal to 1. The upper limit of n2 is preferably 10, more preferably 7, still more preferably 6.)

[Formula 10]

(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 upper limit of n3 is preferably 10, more preferably 7, More preferably, it is 6.)

To [ content of a phenol compound (E) / 100 mass parts of total content of an epoxy compound (A) and a hardening|curing agent (B)), Preferably it is 30-70 mass parts, More preferably, it is 35-65 mass parts, More Preferably it is 40-60 mass parts. When content of a phenol compound (E) is in the said range, there exists a tendency for a moldability and surface hardness to improve more. Moreover, when using together 2 or more types of phenolic compounds (E), it is preferable that these total content satisfy|fills the said value.

(Cyanic acid ester compound (F))

As the cyanate ester compound (F), a known compound can be appropriately used as long as it is a compound having two or more cyanate ester groups directly bonded to an aromatic ring in one molecule, and the type thereof is not particularly limited.

Although it does not restrict|limit especially as a cyanate ester compound (F), For example, a naphthol aralkyl type cyanate ester compound, a novolak type cyanate ester compound, an aromatic hydrocarbon formaldehyde type cyanate ester compound, and a biphenyl aralkyl A type cyanate ester compound is mentioned. A cyanate ester compound (F) may be used individually by 1 type, and may be used in combination of 2 or more type.

Among these, a naphthol aralkyl type cyanate ester compound or a novolak type cyanate ester compound is preferable from a viewpoint of a moldability and surface hardness.

Although it does not specifically limit as said naphthol aralkyl type cyanate ester compound, For example, the compound represented by following formula (VI) is preferable.

[Formula 11]

(In the formula (VI), R ⁵ each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. In the formula (VI), n6 represents an integer of 1 or more. Upper limit of n6 is preferably 10, more preferably 6).

Moreover, although it does not specifically limit as a novolak-type cyanate ester compound, For example, the compound represented by following formula (VII) is preferable.

[Formula 12]

(In the formula (VII), R ⁶ each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. In the formula (VII), n7 represents an integer of 1 or more. Upper limit of n7 is preferably 10, more preferably 7).

To [ content of cyanate ester compound (F) / 100 mass parts of total content of an epoxy compound (A) and a hardening|curing agent (B)), Preferably it is 30-70 mass parts, More preferably, it is 35-65 mass parts, , More preferably, it is 40-60 mass parts. When content of a cyanate ester compound (F) exists in the said range, there exists a tendency for a moldability and surface hardness to improve more. Moreover, when using together 2 or more types of cyanate ester compounds (F), it is preferable that these total content satisfy|fills the said value.

Since both a cyanate ester compound (F) and a phenol compound (E) have the function in a resin composition as a hardening|curing agent (B), the content adds up and calculates. The total content of the cyanate ester compound (F) and the phenol compound (E) is preferably 30 to 70 parts by mass with respect to 100 parts by mass of the total content of the epoxy compound (A) and the curing agent (B), more preferably is 35 to 65 parts by mass, more preferably 40 to 60 parts by mass. When total content of a cyanate ester compound (F) and a phenol compound (E) exists in the said range, there exists a tendency for a moldability and surface hardness to improve more.

[Black Particles (C)]

The black particles (C) are not particularly limited, and include, for example, carbon black, graphite powder, activated carbon powder, flaky graphite powder, acetylene black, Ketjen black, fullerene, single-walled carbon nanotube, double-walled carbon nanotube, carbon nano carbon-based particles (carbon particles) such as cones; Titanium-type particle|grains, such as titanium black, are mentioned. Among these, carbon particles are preferable, and carbon black is more preferable. A black particle (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

The black particle (C) may use what coat|covered at least one part of the surface with the thermosetting resin. By using such a black particle (C), there exists a tendency for a moldability and insulation reliability to improve more. Although it does not restrict|limit especially as a thermosetting resin which coat|covers the surface of black particle (C), For example, an epoxy resin, a polyurethane resin, an acrylic resin, a polyethylene resin, a polycarbonate resin, and a polyamide resin are mentioned.

The average particle diameter of black particle (C) becomes like this. Preferably it is 1 micrometer or less, More preferably, it is 0.5 micrometer or less. When an average particle diameter is 1 micrometer or less, there exists a tendency for light-shielding property, a moldability, and surface hardness to improve more. In addition, the average particle diameter of black particle (C) refers to the average particle diameter after coating when black particle (C) is coated with a thermosetting resin, When black particle (C) is not coated with a thermosetting resin, , refers to the average particle diameter of the uncoated state. In addition, an average particle diameter is a volume-based average particle diameter (mode diameter), and can measure with a well-known method.

Content of black particle (C) is 1-25 mass parts with respect to 100 mass parts of total content of an epoxy compound (A) and a hardening|curing agent (B), Preferably it is 1-20 mass parts, More preferably, it is 3 - 17 mass parts, More preferably, it is 5-15 mass parts. When content of a black particle (C) exists in the said range, there exists a tendency for light-shielding property and a moldability to improve more.

Content of a black particle (C) is 1-20 mass parts with respect to content 100 mass parts of an inorganic filler (D), Preferably it is 2-17 mass parts, More preferably, it is 3-10 mass parts. When content of the black particle (C) with respect to an inorganic filler (D) exists in the said range, there exists a tendency for light-shielding property and a moldability to improve more.

[Inorganic filler (D)]

The inorganic filler (D) is not particularly limited, but for example, kaolin, calcined kaolin, calcined clay, uncalcined clay, silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, wet silica, synthetic Silica, aerosil, etc.), aluminum compounds (eg boehmite, aluminum hydroxide, alumina, hydrotalcite, aluminum borate, aluminum nitride, etc.), magnesium compounds (eg magnesium carbonate, magnesium oxide, magnesium hydroxide, etc.) ), calcium compounds (eg, calcium carbonate, calcium hydroxide, calcium sulfate, calcium sulfite, calcium borate, etc.), molybdenum compounds (eg, molybdenum oxide, zinc molybdate, etc.), talc (eg natural talc, calcined talc, etc.) ), mica (mica), glass (for example, A glass, NE glass, C glass, L glass, S glass, M glass G20, E glass, T glass, D glass, S glass, Q glass, etc., short fibers glass, spherical glass, fine powder glass, hollow glass, etc.), titanium oxide, zinc oxide, zirconium oxide, barium sulfate, zinc borate, barium borate, sodium borate, boron nitride, boron agglomeration, boron nitride, silicon nitride, carbon nitride, strontium titanate, titanic acid Tartrates, such as barium and zinc stannate, etc. are mentioned. An inorganic filler (D) may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Among these, as an inorganic filler (D), the 1 type(s) or 2 or more types chosen from the group which consists of silica, aluminum hydroxide, alumina, a boehmite, magnesium oxide, and magnesium hydroxide is preferable. By using such an inorganic filler (D), there exists a tendency for a moldability and surface hardness to improve more.

Content of an inorganic filler (D) is 100-200 mass parts with respect to 100 mass parts of total content of an epoxy compound (A) and a hardening|curing agent (B), Preferably it is 105-180 mass parts, More preferably, it is 110 -160 mass parts, More preferably, it is 110-155 mass parts. When content of an inorganic filler (D) exists in the said range, there exists a tendency for a moldability and surface hardness to improve more.

Total content of an inorganic filler (D) and black particle (C) is 101-180 mass parts with respect to 100 mass parts of total content of an epoxy compound (A) and a hardening|curing agent (B), Preferably it is 105-160 mass parts. and More preferably, it is 110-150 mass parts. When total content of an inorganic filler (D) and a black particle (C) exists in the said range, there exists a tendency for a moldability and surface hardness to improve more.

[Maleimide Compound (G)]

A well-known thing can be used suitably as long as a maleimide compound (G) is a compound which has one or more maleimide groups in 1 molecule, The kind in particular is not limited. The number of maleimide groups per molecule of a maleimide compound (G) is 1 or more, Preferably it is 2 or more.

Although it does not restrict|limit especially as a maleimide compound (G), For example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 2,2-biss4-( 4-maleimidephenoxy)-phenyl｝propane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3, 5-diethyl-4-maleimidephenyl)methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V), a prepolymer of these maleimide compounds, and the maleimide compound and the prepolymer of an amine compound, etc. are mentioned. A maleimide compound (G) may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Among these, bis(4-maleimidephenyl)methane, 2,2'-bisb4-(4-maleimidephenoxy)-phenylbpropane, and bis(3-ethyl-5-methyl-4-maleimidephenyl) ) At least one selected from the group consisting of methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V) is preferable.

[Formula 13]

(In formula (IV) ^{, each R 3} independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 or more. The upper limit of n4 is preferably 10, more preferably 7, and more preferably It is usually 6.)

[Formula 14]

(In the formula (V), R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n5 is an average value, and 1 < n5 ≤ 5.)

The content of the maleimide compound (G) is preferably 5 to 35 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the total content of the epoxy compound (A) and the curing agent (B), More preferably, it is 15-20 mass parts. When content of a maleimide compound (G) is in the said range, there exists a tendency for a moldability and surface hardness to improve more. Moreover, when using together 2 or more types of maleimide compounds (G), it is preferable that these total content satisfy|fills the said value.

[Silane coupling agent and wetting and dispersing agent]

The resin composition of 1st Embodiment may contain a silane coupling agent and a wet dispersing agent further. By containing a silane coupling agent or a wetting and dispersing agent, there exists a tendency for the dispersibility of the said filler, a resin component, a filler, and the adhesive strength of the base material mentioned later to improve more.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances. For example, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-amino aminosilane-based compounds such as propyltrimethoxysilane; Epoxysilane-type compounds, such as (gamma)-glycidoxy propyl trimethoxysilane; acrylsilane-type compounds, such as (gamma)-acryloxypropyl trimethoxysilane; cationic silane compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; A phenylsilane type compound etc. are mentioned. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

Although it will not specifically limit if it is a dispersion stabilizer used for paints as a wetting and dispersing agent, For example, DISPERBYK-110, 111, 118, 180, 161, BYK-W996, W9010 manufactured by Bick Chemie Japan Co., Ltd., W903 etc. are mentioned.

[curing accelerator]

The resin composition of 1st Embodiment may contain a hardening accelerator further. Although it does not specifically limit as a hardening accelerator, For example, Imidazole, such as 2-ethyl- 4-methylimidazole and 2,4,5- triphenylimidazole; 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 , tertiary amines such as triethylenediamine, tetramethylbutanediamine and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; What is formed by dissolving these organometallic salts in hydroxyl-containing compounds, such as a phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; Organotin compounds, such as a dioctyl tin oxide, other alkyl tin, and an alkyl tin oxide, etc. are mentioned.

[Second embodiment: resin composition]

The resin composition of 2nd Embodiment is a resin composition containing an epoxy compound (A), a hardening|curing agent (B), black particle (C), and an inorganic filler (D), Comprising: Metal foil coating obtained using this resin composition. Barcol hardness of a laminated board is 60-90, and the transmittance|permeability in the range of 400-2000 nm wavelength of the board|substrate from which the metal foil was removed from this metal-foil-clad laminated board is 0.1 % or less.

The Barcol hardness of the metal foil clad laminated board obtained using the resin composition of 2nd Embodiment is 60-90, Preferably it is 65-75, More preferably, it is 70-80. When Barcol's hardness is in the said range, it has sufficient surface hardness. Barcol hardness can be adjusted with content of an inorganic filler (D), content ratio of a black particle (C) and an inorganic filler (D), the kind of inorganic filler (D), etc. Barcol hardness can be measured by the measuring method as described in an Example.

In addition, the transmittance in a wavelength range of 400 to 2000 nm of the substrate from which the metal foil is removed from the metal foil-clad laminate obtained using the resin composition of the second embodiment is 0.1% or less, and the lower limit of the transmittance is not particularly limited, It is preferably below the detection limit. When the transmittance is 0.1% or less, it has sufficient light-shielding properties. The transmittance|permeability can be adjusted with content of a black particle (C), content ratio of a black particle (C) and an inorganic filler (D), the kind of black particle (C), etc. Transmittance can be measured by the measuring method described in an Example.

In addition, about the kind, content, etc. of an epoxy compound (A), a hardening|curing agent (B), a black particle (C), and an inorganic filler (D), the thing similar to 1st Embodiment can be illustrated.

[Method for Producing Resin Composition]

Although the manufacturing method of the resin composition (resin composition of 1st Embodiment and 2nd embodiment) of this embodiment mentioned above is not specifically limited, For example, each component mentioned above is mix|blended with a solvent sequentially, and sufficient A method of stirring is mentioned. At this time, in order to melt|dissolve or disperse|distribute each component uniformly, well-known processes, such as stirring, mixing, a kneading|mixing process, can be performed. The dispersibility of the filler with respect to a resin composition can be improved by performing a stirring dispersion process using the stirring tank which specifically, attached the stirrer which has suitable stirring ability. The above-described stirring, mixing, and kneading treatment can be appropriately performed using, for example, an apparatus for the purpose of mixing such as a ball mill or a bead mill, or a known apparatus such as a revolving or autorotating mixing apparatus.

Moreover, at the time of preparation of a resin composition, an organic solvent can be used as needed. The kind of organic solvent will not be specifically limited, if resin in a composition can be dissolved.

〔Usage〕

The resin composition of this embodiment mentioned above can be used suitably as a prepreg, a resin sheet, a laminated board, a metal foil clad laminated board, or a printed wiring board. Hereinafter, a prepreg, a resin sheet, a laminated board, a metal foil clad laminated board, or a printed wiring board is demonstrated.

[Prepreg]

The prepreg of this embodiment has a base material and the resin composition of this embodiment impregnated or apply|coated to the base material. The manufacturing method of a prepreg can be performed according to a conventional method, and is not specifically limited. For example, after impregnating or applying the resin composition of this embodiment to a substrate, semi-hardening (B-staging), such as heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes, to produce the prepreg of this embodiment can

The content of the resin composition (including filler) of the present embodiment in the prepreg is preferably 30 to 90 mass%, more preferably 35 to 85 mass%, with respect to the total amount of the prepreg, Preferably it is 40-80 mass %. When content of a resin composition exists in the said range, there exists a tendency for a moldability to improve more.

(write)

It does not specifically limit as a base material, According to the target use and performance, the well-known thing used for various printed wiring board materials can be selected and used suitably. Although it does not specifically limit as a specific example of the fiber which comprises a base material, For example, Glass fibers, such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, T glass; Inorganic fibers other than glass, such as quartz; Polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene-3,4'-oxydiphenylene terephthalamide (Technora (registered trademark), manufactured by Teijin Techno Products Co., Ltd.) wholly aromatic polyamides, such as; polyesters such as 2,6-hydroxynaphthoic acid-parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.) and Xexion (registered trademark, manufactured by KB Siren); Organic fibers, such as polyparaphenylene benzoxazole (Xylon (trademark), Toyo Spinning Co., Ltd. make) and polyimide, are mentioned. Among these, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fiber is preferable from the viewpoint of a low coefficient of thermal expansion. These base materials may be used individually by 1 type, and may use 2 or more types together.

Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat, a surfacing mat, etc. are mentioned. The method of weaving the woven fabric is not particularly limited, and for example, plain weave, lion weave, twill weave, etc. are known, and from these known ones, they can be appropriately selected and used according to the intended use and performance. Moreover, the thing which carried out the fiber opening treatment of these, the glass woven fabric surface-treated with the silane coupling agent etc. are used preferably. Although the thickness and mass of a base material are not specifically limited, Usually, the thing of about 0.01-0.3 mm is used preferably. In particular, from the viewpoint of strength and water absorption, the substrate is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g/m 2 or less, and more preferably a woven glass fabric made of glass fibers of E glass, S glass, and T glass. .

[resin sheet]

The resin sheet of this embodiment has a support body and the said resin composition arrange|positioned on the support body. A resin sheet is used as one means of thin-leaf paper, For example, it can apply|coat and dry a resin composition directly to supports, such as copper foil and a resin film, and can manufacture it. A resin sheet can be used in order to form insulating layers, such as a metal foil clad laminated board and a printed wiring board.

Although it does not specifically limit as a support body, The well-known thing used for various printed wiring board materials can be used. For example, polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polycarbonate film , ethylene tetrafluoroethylene copolymer films, organic film substrates such as release films coated with a release agent on the surface of these films, conductor foils such as copper foil, glass plates, SUS plates, and plate-shaped inorganic films such as FPR. have. Among them, an electrolytic copper foil and a PET film are preferable.

As a coating method, the method of apply|coating the solution which melt|dissolved the resin composition of this embodiment in the solvent on a support body with a bar coater, a die coater, a doctor blade, a baker applicator etc. is mentioned, for example.

It is preferable that the resin sheet apply|coats the said resin composition to a support body, and what made it semi-hardened (B-staging). Specifically, for example, after the resin composition is applied to a support such as copper foil, semi-cured by a method of heating for 1 to 60 minutes in a dryer at 100 to 200° C., a method for producing a resin sheet, etc. can be heard As for the adhesion amount of the resin composition with respect to a support body, the range of 1-300 micrometers is preferable in resin thickness of a resin sheet.

As another aspect of the resin sheet of this embodiment, a single-layered resin sheet is mentioned. A single-layered resin sheet contains the resin composition of this embodiment. A single-layered resin sheet is formed by shape|molding the said resin composition into a sheet form. The manufacturing method of a single-layer resin sheet can be performed according to a conventional method, and is not specifically limited. For example, it can obtain by peeling or etching a support body from the said resin sheet. Alternatively, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to form a sheet, thereby obtaining a single-layered resin sheet without using a sheet substrate.

[Laminate]

The laminated board of this embodiment laminates|stacks the said prepreg. A laminate will not be specifically limited if it is provided with one or more layers of prepreg, You may have any other layer. As a manufacturing method of a laminated board, a generally well-known method can be applied suitably, It does not specifically limit. For example, a laminated board can be obtained by laminating|stacking said prepreg or a prepreg and another layer, and heat-pressing-molding. Although the temperature to heat is not specifically limited at this time, 65-300 degreeC is preferable and 120-270 degreeC is more preferable. Moreover, the pressure to press is although it does not specifically limit, 2-5 Mpa is preferable and 2.5-4 Mpa is more preferable. The laminated board of this embodiment can be used suitably as a metal foil clad laminated board mentioned later by further providing the layer which consists of metal foil.

[Metal foil clad laminate]

The metal foil-clad laminate of this embodiment has the said prepreg and/or the said resin sheet, and the metal foil laminated|stacked on the said prepreg and/or the said resin sheet. In the metal foil-clad laminate of this embodiment, the prepreg and the resin sheet form an insulating layer, but the insulating layer may consist of one prepreg and/or a resin sheet, and the prepreg and/or the resin Two or more layers of sheets may be laminated.

As metal foil, copper, aluminum, etc. can be used. Although the metal foil used here will not be specifically limited if used for a printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable. Moreover, although the thickness of metal foil (conductor layer) is not specifically limited, 1-70 micrometers is preferable, More preferably, it is 1.5-35 micrometers.

The forming method of the metal foil-clad laminate and the forming conditions thereof are not particularly limited, and the methods and conditions of general laminates for printed wiring boards and multilayer boards are applicable. For example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of shaping|molding of a metal foil clad laminated board. Moreover, in shaping|molding of a metal foil clad laminated board, temperature is 100-300 degreeC, a pressure is 2-100 kgf/cm<2> of surface pressure, and the range of 0.05 to 5 hours is common for a heating time. Moreover, you can also post-cure at the temperature of 150-300 degreeC as needed. Moreover, it can also be set as a multilayer board by combining the above-mentioned prepreg or resin sheet, and the wiring board for inner layers produced separately and lamination|stacking.

The Barcol's hardness of the metal foil clad laminated board of this embodiment becomes like this. Preferably it is 60-90, More preferably, it is 65-75, More preferably, it is 70-80. When Barcol's hardness is in the said range, it has sufficient surface hardness. Barcol hardness can be adjusted with content of an inorganic filler (D), content ratio of a black particle (C) and an inorganic filler (D), the kind of inorganic filler (D), etc. Barcol hardness can be measured by the measuring method as described in an Example.

Moreover, the transmittance|permeability in the range of 400-2000 nm wavelength of the board|substrate from which the metal foil (for example, electrolytic copper foil) was removed from the said metal foil clad laminated board becomes like this. Preferably it is 0.1 % or less. Although the lower limit in particular of the transmittance|permeability is not restrict|limited, It is preferable that it is below a detection limit. When the transmittance is 0.1% or less, it has sufficient light-shielding properties. The transmittance|permeability can be adjusted with content of a black particle (C), content ratio of a black particle (C) and an inorganic filler (D), the kind of black particle (C), etc. Transmittance can be measured by the measuring method described in an Example.

In addition, the measurement of the Barcol hardness and transmittance in an Example was performed using the metal foil clad laminated board using the E glass woven fabric which has the following structure from a viewpoint of specifying measurement conditions, but using the resin composition of this embodiment The glass woven fabric at the time of forming a prepreg is not limited to the E glass woven fabric which has the following structure, The various base materials mentioned above can be used.

IPC applicable varieties: 2116

Density (pieces/25 mm) Length: 62

Density (pieces/25 mm) Width: 58

Thickness (mm): 0.100

Mass (g/m2): 108.5

Although it does not restrict|limit as a commercial item in particular of the E glass woven fabric which has the said structure, For example, the Arisa Corporation make, 1031NT-1270-S640 is mentioned.

[Metal foil clad laminate (another embodiment)]

In another embodiment, a metal foil-clad laminate having a prepreg and/or a resin sheet and a metal foil laminated on the prepreg and/or a resin sheet, wherein the prepreg is a substrate and a resin composition impregnated or coated on the substrate The resin sheet has a support and a resin composition laminated on one or both surfaces of the support, the Barcol hardness is 60 to 90, and the wavelength of the substrate from which the metal foil is removed from the metal foil clad laminate is in the range of 400 to 2000 nm. It is also possible to provide a metal foil-clad laminate having a transmittance of 0.1% or less.

The metal foil-clad laminate of another embodiment is not particularly limited as long as it satisfies the above configuration. For example, as a resin composition constituting a prepreg or a resin sheet, the resin composition of the first or second embodiment is not used. do. Among these, it is preferable to use the resin composition of 1st or 2nd Embodiment. In addition, about the kind, content, etc. of the resin component in the resin composition in that case, a filler, etc., the thing similar to 1st Embodiment can be illustrated. Moreover, also about Barcol hardness and transmittance|permeability, the range similar to what was mentioned above can be illustrated.

[printed wiring board]

The printed wiring board of this embodiment has an insulating layer and the conductor layer formed in the surface of the said insulating layer, The said insulating layer contains the resin composition of this embodiment. As such a printed wiring board, what was produced using 1 or more types chosen from the group which consists of a prepreg, a resin sheet, and a metal foil clad laminated board as a buildup material is mentioned. Among these, the printed wiring board produced using 1 or more types chosen from the group which consists of a prepreg and a resin sheet as a buildup material is preferable. The above-described metal foil-clad laminate can be preferably used as a printed wiring board by forming a predetermined wiring pattern. And said metal foil clad laminated board has a low coefficient of thermal expansion, favorable moldability, and chemical-resistance, and can be used especially effectively as a material of the printed wiring board for semiconductor packages which such performance is calculated|required.

Moreover, as a printed wiring board which has a multilayer structure, it has several laminated|stacked insulating layer, and the some conductor layer arrange|positioned between the several insulating layers and on the outermost layer surface, The said insulating layer is the resin composition of this embodiment and those containing Such a multilayer printed wiring board can have a well-known structure as a multilayer printed wiring board, such as a plating through-hole which penetrates several insulating layers as another structure.

Moreover, the multilayer printed wiring board of this embodiment does not have a core board|substrate as an insulating layer, but the coreless printed wiring board which laminated|stacked only the buildup layer as an insulating layer may be sufficient as it. As such a coreless printed wiring board, what has at least one insulating layer and the some conductor layer arrange|positioned on the outermost layer surface of this insulating layer is mentioned. When there are two or more insulating layers, you may have a conductor layer further between several insulating layers. In this case, one or more insulating layers contain the resin composition of the present embodiment.

A conventional build-up substrate has a structure in which an insulating layer and a conductor layer are stacked on top and bottom of a core substrate serving as a support substrate. The insulating layer and the conductor layer stacked on top and bottom of the core substrate are also called a build-up layer. From the viewpoint of forming wirings with high density, the build-up layer is constituted by lamination of thin layers. On the other hand, the core substrate also has a role as a support substrate having a certain level of strength or the like in the step of laminating the insulating layer and the conductor layer. Therefore, in general, the core substrate is thicker than the insulating layer in the buildup layer. The coreless printed wiring board in this embodiment means a printed wiring board which does not have this core board.

The manufacturing method in particular of a multilayer printed wiring board is not restrict|limited, Conventionally well-known methods, such as the method of laminating|stacking a printed wiring board, can be used.

[Method for manufacturing a printed wiring board]

The printed wiring board of this embodiment can be manufactured with the following method specifically, for example. First, the above-mentioned metal foil-clad laminated board (copper-clad laminated board etc.) is prepared. The surface of the metal foil-clad laminate is etched to form an inner-layer circuit to prepare an inner-layer substrate. The inner circuit surface of this inner layer substrate is subjected to surface treatment to increase adhesive strength as necessary, and then the above-mentioned prepreg is superimposed on the inner circuit surface for the required number of sheets, and further on the outer side of the inner circuit surface Metal foils are laminated, heated and pressed, and integrally molded. In this way, the multilayer laminated board in which the insulating layer which consists of a base material and the hardened|cured material of the resin composition of this embodiment was formed between the metal foil for inner-layer circuits and outer-layer circuits is manufactured. Next, after drilling for through-holes or via-holes is performed on this multilayer laminate, desmear processing is performed in order to remove the smear which is a residue of the resin derived from the resin component contained in the hardened|cured material layer. Thereafter, a conductor layer for conducting the inner circuit and the metal foil for the outer circuit is formed on the wall surface of the hole, and the metal foil for the outer circuit is further etched to form an outer circuit, and a printed wiring board is manufactured.

For example, the above-mentioned prepreg (base material and the above-mentioned resin composition affixed thereto), the resin composition layer (layer consisting of the above-mentioned resin composition) in the metal foil-clad laminate contains the resin composition of this embodiment to constitute an insulating layer that

Moreover, when not using a metal foil clad laminated board, you may form the conductor layer used as a circuit on the said prepreg, and may produce a printed wiring board. At this time, the method of electroless plating can also be used for formation of a conductor layer.

Moreover, you may perform the process of forming the insulating film which apply|coats a soldering resist and protects a circuit pattern with respect to the printed wiring board obtained by making it above. More specifically, the step of preparing the printed wiring board as described above, the step of forming a photosensitive composition layer cured with light having a wavelength of 350 to 420 nm on both sides of the printed wiring board, and disposing a mask pattern on the surface of the photosensitive composition layer and the method of having the process of exposing with the light of wavelength 350-420 nm through the mask pattern is mentioned. After exposure, the non-hardened part of the photosensitive composition layer can be developed, and the printed wiring board in which the circuit pattern was protected can be obtained. Moreover, as a photosensitive composition layer, a soldering resist layer is mentioned, for example.

Moreover, in the manufacturing method of a coreless printed wiring board, for example, instead of the process of preparing the said printed wiring board as mentioned above, instead of the process of preparing a core board, on a core board|substrate, containing the resin composition of this embodiment , a step of obtaining a laminate in which at least one insulating layer and a plurality of conductor layers disposed on the surface of the outermost layer of the insulating layer are laminated. That is, by laminating|stacking 1 or some insulating layer and 1 or some conductor layer on a core board|substrate, the laminated body in which the buildup layer was formed on the core board|substrate can be obtained. Then, by removing (peeling) a core board|substrate, a coreless printed wiring board (it is also mentioned a coreless board|substrate) is formed.

And by performing the process of forming a photosensitive composition layer, and the process of exposing with respect to this coreless board|substrate, the coreless printed wiring board with a circuit pattern can be obtained.

Example

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. The present invention is not limited at all by the following examples.

[Synthesis Example 1] Synthesis of 1-naphthol aralkyl type cyanate ester resin (SNCN)

300 g of α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g/eq., manufactured by Shin-Nitetsu Chemical Co., Ltd.) (1,28 mol in terms of OH groups) and 194.6 g (1.92 mol) of triethylamine (hydroxyl group) 1.5 mol) with respect to 1 mol) was dissolved in 1800 g of dichloromethane, and this was made into the solution 1.

125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per 1 mol of hydroxyl group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of hydroxyl), 1205.9 g of water Under stirring, the solution 1 was dripped over 30 minutes, maintaining liquid temperature -2 - -0.5 degreeC. After completion of dripping of solution 1, after stirring at the same temperature for 30 minutes, the solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxyl groups) was dissolved in 65 g of dichloromethane It was dripped over 10 minutes. After completion of the dropwise addition of the solution 2, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

After that, the reaction solution was allowed to stand to separate an organic phase and an aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water, and the electrical conductivity of the wastewater at the 5th time of washing with water was 5 µS/cm, and it was confirmed that the ionic compound that can be removed by washing with water was sufficiently removed.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90°C for 1 hour to obtain 331 g of the target naphthol aralkyl cyanate ester compound (SNCN) (orange viscous material). The mass average molecular weight Mw of the obtained SNCN was 600. Moreover, the infrared absorption spectrum of SNCN showed absorption of 2250 cm<^-1> (cyanate ester group), and absorption of a hydroxyl group was not shown.

[Example 1]

50 parts by mass of a biphenyl aralkyl type epoxy resin (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.) and a biphenyl aralkyl type phenol resin (KAYAHARD GPH-103, hydroxyl equivalent: 231 g/eq., manufactured by Nippon Kayaku Co., Ltd.) ) 50 parts by mass, insulating coating carbon black (product name #B503, manufactured by Mikuni Dyes Co., Ltd., average particle diameter of 0.1 µm) 10 parts by mass, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane (BMI-70, manufactured by Daiwa Chemical Industry Co., Ltd.) 20 parts by mass, silica (SC4500-SQ, manufactured by Admatex Co., Ltd., average particle diameter of 1.5 µm) 120 parts by mass, wetting and dispersing agent (Disperbyk-161, Bick) 1 part by mass of Chemi Japan Co., Ltd.), 10 parts by mass of talc coated with zinc molybdate (Chem Guard 911C, zinc molybdate supported: 10% by mass, Sherwin Williams Chemicals), and a curing accelerator (2 ,4,5-triphenylimidazole, Tokyo Chemical Industry Co., Ltd.) 0.3 mass part was mixed, and the varnish was obtained by diluting with methyl ethyl ketone.

This varnish was impregnated and coated on a 0.1 mm-thick E glass woven fabric (1031NT-1270-S640, manufactured by Arisawa Seisakusho), and heat-dried at 165°C for 3 minutes to obtain a prepreg having a resin content of 46% by mass. In addition, the characteristics of the E glass woven fabric used are as follows.

IPC applicable varieties: 2116

Density (pieces/25 mm) Length: 62

Density (pieces/25 mm) Width: 58

Thickness (mm): 0.100

Mass (g/m2): 108.5

[Example 2]

A prepreg was obtained in the same manner as in Example 1 except that the amount of the insulating coating carbon black used was 5 parts by mass.

[Example 3]

A prepreg was obtained in the same manner as in Example 1 except that the amount of the insulating coating carbon black used was 20 parts by mass.

[Example 4]

Except having made the usage-amount of silica into 100 mass parts, it carried out similarly to Example 1, and obtained the prepreg.

[Example 5]

Except having made the usage-amount of silica into 150 mass parts, it carried out similarly to Example 1, and obtained the prepreg.

[Example 6]

A prepreg was obtained in the same manner as in Example 1 except that 50 parts by mass of SNCN was used instead of the biphenyl aralkyl-type phenol resin.

[Example 7]

A prepreg was prepared in the same manner as in Example 1 except that 50 parts by mass of SNCN was used instead of the biphenylaralkyl type phenol resin and bis(3-ethyl-5-methyl-4-maleimidephenyl)methane was not used. got

[Example 8]

A prepreg was obtained in the same manner as in Example 1 except that titanium black (product name: 13M-T, manufactured by Mitsubishi Materials Co., Ltd.) was used instead of the insulating coating carbon black.

[Comparative Example 1]

Except not using the insulating coating carbon black, it carried out similarly to Example 1, and obtained the prepreg.

[Comparative Example 2]

Except having made the usage-amount of silica into 50 mass parts, it carried out similarly to Example 1, and obtained the prepreg.

[Comparative Example 3]

Except having made the usage-amount of silica into 70 mass parts, it carried out similarly to Example 1, and obtained the prepreg.

[Comparative Example 4]

Except having made the usage-amount of silica into 250 mass parts, it carried out similarly to Example 1, and obtained the prepreg.

[Comparative Example 5]

A prepreg was obtained in the same manner as in Example 1 except that the amount of the insulating coating carbon black used was 30 parts by mass.

[Reference Example 1]

Mixed resin powder was obtained by evaporating and distilling the methyl ethyl ketone of the varnish obtained by Example 1. The obtained mixed resin powder was filled into a mold having a side of 100 mm, a thickness of 0.1 mm and 0.8 mm, and lamination molding was performed at a pressure of 30 kgf/cm 2 and a temperature of 220° C. for 120 minutes, and a side of 100 mm and a thickness of 0.1 mm and A 0.8 mm cured product was obtained. The said hardened|cured material does not use a glass woven fabric.

[Formability]

Electrolytic copper foil (3EC-LPIII, manufactured by Mitsui Metal Mining Co., Ltd.) having a thickness of 12 µm was placed vertically on the prepreg obtained in the Example or Comparative Example, and the pressure was 30 kgf/cm 2 and the temperature was 220°C for 120 minutes. Lamination molding was performed to obtain a copper-clad laminate with an insulating layer thickness of 0.1 mm as a metal foil-clad laminate. After the copper foil of a copper clad laminated board was removed by etching, the surface was observed, the presence or absence of a void was confirmed, and the following evaluation criteria evaluated moldability. Moreover, in Reference Example 1, the surface of the hardened|cured material of thickness 0.1mm and 0.8mm was observed, and the presence or absence of a void was confirmed.

○: When the occurrence of voids is not confirmed

×: When the occurrence of voids is confirmed

[Light-shielding properties]

Electrolytic copper foil (3EC-LPIII, manufactured by Mitsui Metal Mining Co., Ltd.) having a thickness of 12 µm was placed vertically on the prepreg obtained in the Example or Comparative Example, and the pressure was 30 kgf/cm 2 and the temperature was 220°C for 120 minutes. Lamination molding was performed to obtain a copper-clad laminate with an insulating layer thickness of 0.1 mm as a metal foil-clad laminate. The board|substrate obtained by removing the copper foil of a copper clad laminated board by etching was made into the sample, and the transmittance|permeability of wavelength 400-2000 nm was measured. The Hitachi High-Technology make, spectrophotometer U-4100 was used for the measurement. Based on the obtained transmittance|permeability, the following evaluation criteria evaluated light-shielding property. Moreover, in the reference example 1, the transmittance|permeability with a wavelength of 400-2000 nm was measured using the hardened|cured material of thickness 0.1mm as a sample.

(circle): The transmittance|permeability in the range of wavelength 400-2000 nm is 0.1 % or less

x: The transmittance|permeability in the range of wavelength 400-2000 nm exceeds 0.1 %

[Surface hardness]

Eight prepregs obtained in Examples or Comparative Examples were stacked on top of each other, and 12 μm thick electrolytic copper foil (3EC-LPIII, manufactured by Mitsui Metals Mining Co., Ltd.) was placed up and down, pressure 30 kgf/cm 2 , temperature 220° C. was laminated for 120 minutes to obtain a copper clad laminate having an insulating layer thickness of 0.8 mm as a metal foil clad laminate. The obtained copper clad laminate was used as a sample, and according to JISK7060, Barcol hardness was measured using GYZJ935 by COLMAN. In Reference Example 1, a cured product having a thickness of 0.8 mm was used as a sample, and Barcol hardness was measured according to JISK7060. It is excellent in wire bonding property, so that surface hardness (Barcol hardness) is high.

In addition to the above, a prepreg was produced in the same manner as in Example 1 using carbon black not coated with resin. As a result, since the resin coating was not carried out, the dispersibility was inferior, and when compared with the other Example, the moldability was slightly inferior.

Industrial Applicability

The resin composition of this invention has industrial applicability as a material used for manufacture of a rigid board|substrate.

Claims (17)

an epoxy compound (A), and
a curing agent (B);
black particles (C) and
containing an inorganic filler (D),
Content of the said black particle (C) is 1-25 mass parts with respect to 100 mass parts of total content of the said epoxy compound (A) and the said hardening|curing agent (B),
Content of the said inorganic filler (D) is 100-200 mass parts with respect to 100 mass parts of total content of the said epoxy compound (A) and the said hardening|curing agent (B),
resin composition. The method of claim 1,
The resin composition wherein the black particles (C) are particles having an average particle diameter of 1 μm or less, at least a part of which is coated with a thermosetting resin on the surface. 3. The method according to claim 1 or 2,
The resin composition in which the said epoxy compound (A) contains the compound represented by following formula (I).

(In formula (I), n1 represents an integer of 1 or more.) 4. The method according to any one of claims 1 to 3,
The resin composition containing a phenol compound (E) and/or a cyanate ester compound (F) as said hardening|curing agent (B). 5. The method of claim 4,
The resin composition in which the said phenol compound (E) contains the compound represented by 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.) 5. The method of claim 4,
A resin composition in which the cyanate ester compound (F) 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) .

(In the formula (VI), R ⁵ each independently represents a hydrogen atom or a methyl group, and n6 represents an integer of 1 or more.)

(In the formula (VII), R ⁶ each independently represents a hydrogen atom or a methyl group, and n7 represents an integer of 1 or more.) 7. The method according to any one of claims 1 to 6,
The resin composition which further contains a maleimide compound (G). 8. The method of claim 7,
Said maleimide compound (G) is bis(4-maleimidephenyl)methane, 2,2'-bisb4-(4-maleimidephenoxy)-phenylbpropane, bis(3-ethyl-5-methyl A resin composition comprising at least one selected from the group consisting of -4-maleimidephenyl)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 of 1 or more.)

(In the formula (V), R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n5 is an average value, and 1 < n5 ≤ 5.) 9. The method according to any one of claims 1 to 8,
The resin composition in which the said inorganic filler (D) contains 1 or more types chosen from the group which consists of silica, aluminum hydroxide, alumina, boehmite, magnesium oxide, and magnesium hydroxide. description and
Having the resin composition according to any one of claims 1 to 9 impregnated or applied to the base material,
prepreg. support and
Having the resin composition according to any one of claims 1 to 9 laminated on one side or both sides of the support,
resin sheet. A laminate in which at least one selected from the group consisting of the prepreg according to claim 10 and the resin sheet according to claim 11 is laminated. At least one selected from the group consisting of the prepreg according to claim 10 and the resin sheet according to claim 11;
having a metal foil laminated on the prepreg and/or the resin sheet,
Metal foil clad laminate. 14. The method of claim 13,
The Barcol hardness of the metal foil-clad laminate is 70 to 80, and
The metal foil-clad laminated board whose transmittance|permeability in the range of 400-2000 nm wavelength of the board|substrate from which the metal foil was removed from the said metal foil-clad laminated board is 0.1 % or less. The printed wiring board produced using 1 or more types chosen from the group which consists of the prepreg of Claim 10 and the resin sheet of Claim 11 as a buildup material. The printed wiring board produced using the metal foil clad laminated board of Claim 13 or 14 as a buildup material. an insulating layer,
a conductor layer formed on the surface of the insulating layer;
The said insulating layer contains the resin composition in any one of Claims 1-9,
printed wiring board.