JP6910590B2 - Resin composition for printed wiring board, prepreg, metal foil-clad laminate, laminated resin sheet, resin sheet, and printed wiring board - Google Patents

Description

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

In recent years, information terminal devices such as personal computers and servers, and communication devices such as Internet routers and optical communications have been required to process a large amount of information at high speed, and the speed and frequency of electric signals have been increasing. There is. Along with this, the laminated boards for printed wiring boards used for these are required to have a low dielectric constant and a dielectric loss tangent, particularly a low dielectric loss tangent, in order to meet the demand for high frequencies. In order to meet these demands, conventionally, cyanate ester resin (see, for example, Patent Document 1) and polyphenylene ether resin (see, for example, Patent Document 2) are known as laminates for high frequency applications. Further, as an epoxy resin used for high frequency applications, there are many reports that the biphenyl aralkyl type novolak epoxy resin has excellent dielectric properties (see, for example, Patent Documents 3, 4 and 5).

Japanese Unexamined Patent Publication No. 2005-120173 Japanese Unexamined Patent Publication No. 2005-112981 Japanese Unexamined Patent Publication No. 10-237162 Japanese Unexamined Patent Publication No. 2002-179761 JP-A-2007-224162

However, in the above-mentioned prior art, there is still room for consideration that the dielectric constant and the dielectric loss tangent are excellent, and further, the copper foil peel strength and the glass transition temperature are also excellent.

The present invention has been made in view of the above problems, and is a resin composition for a printed wiring board which is excellent in dielectric constant and dielectric loss tangent, and also excellent in copper foil peel strength and glass transition temperature, and the printed wiring. It is an object of the present invention to provide a prepreg using a resin composition for a board, a metal foil-clad laminate, a laminate resin sheet, a resin sheet, and a printed wiring board.

The present inventors have diligently studied to solve the above problems. As a result, they have found that the above problems can be solved by using a specific two kinds of cyanic acid ester compounds in combination with a specific vinyl compound, and have completed the present invention.

（式中、Ｒは、各々独立して、水素原子又はメチル基を表し、ｎは１以上の整数を表す。）

（式中、Ｘは、下記式（４）、又は下記式（５）で表される基を示し、Ｙは、各々独立して、下記式（６）で表される基を示し、ａ及びｂは、０〜１００の整数を示し、少なくともいずれか一方が１以上である。）

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₇、及びＲ₈は、各々独立して、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を示し、Ｒ₄、Ｒ₅、及びＲ₆は、各々独立して、水素原子、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を示す。）

（式中、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、及びＲ₁₆は、各々独立して、水素原子、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を示し、Ａは、炭素数２０以下である、直鎖状、分岐状、又は環状の２価の炭化水素基を示す。）

（式中、Ｒ₁₇及びＲ₁₈は、各々独立して、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を表す。Ｒ₁₉及びＲ₂₀は、各々独立して、水素原子、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を表す。）
〔２〕
前記シアン酸エステル化合物（Ａ２）の含有量が、樹脂固形分１００質量部に対して、１質量部以上である、
〔１〕に記載のプリント配線板用樹脂組成物。
〔３〕
前記ビニル化合物（Ｃ）が、Ｘが、下記式（７）で表される基、下記式（８）で表される基、又は下記式（９）で表される基を示し、Ｙが、下記式（１０）で表される基、下記式（１１）で表される基、又は、下記式（１０）で表される基と下記式（１１）で表される基とがランダムに配列した基を示すビニル化合物を含む、
〔１〕又は〔２〕に記載のプリント配線板用樹脂組成物。

（式中、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、及びＲ₁₆は、各々独立して、水素原子又はメチル基を示し、Ａは、炭素数２０以下である、直鎖状、分岐状、又は環状の２価の炭化水素基を示す。）

（式中、Ａは、炭素数２０以下である、直鎖状、分岐状又は環状の２価の炭化水素基を示す。）

〔４〕
エポキシ樹脂（Ｄ）、ビニル化合物（Ｃ）以外の不飽和二重結合含有化合物（Ｅ）、シアン酸エステル化合物（Ａ１）及びシアン酸エステル化合物（Ａ２）以外のシアン酸エステル化合物（Ｆ）、フェノール樹脂（Ｇ）、オキセタン樹脂（Ｈ）、及びベンゾオキサジン化合物（Ｉ）からなる群より選ばれる１種以上をさらに含有する、
〔１〕〜〔３〕のいずれか一項に記載のプリント配線板用樹脂組成物。
〔５〕
無機充填材（Ｋ）をさらに含有する、
〔１〕〜〔４〕に記載のプリント配線板用樹脂組成物。
〔６〕
前記無機充填材（Ｋ）の含有量が、樹脂固形分１００質量部に対して、５０〜１６００質量部である、
〔５〕に記載のプリント配線板用樹脂組成物。
〔７〕
基材と、
該基材に含浸又は塗布された、〔１〕〜〔６〕のいずれか一項に記載の樹脂組成物と、を有する、
プリプレグ。
〔８〕
少なくとも１枚以上積層された〔７〕に記載のプリプレグと、
該プリプレグ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。
〔９〕
支持体と、
該支持体上に配された、〔１〕〜〔６〕のいずれか一項に記載の樹脂組成物と、を有する、
積層樹脂シート。
〔１０〕
〔１〕〜〔６〕のいずれか一項に記載の樹脂組成物含む、
樹脂シート。
〔１１〕
絶縁層と、
該絶縁層の表面に形成された導体層と、を有し、
前記絶縁層が、〔１〕〜〔６〕のいずれか一項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]
The cyanic acid ester compound (A1) represented by the following formula (1) and
The cyanic acid ester compound (A2) represented by the following formula (2) and
Maleimide compound (B) and
Containing a vinyl compound (C) represented by the following formula (3),
The total amount of the cyanate ester compound (A1) and the cyanate ester compound (A2) is, with respect to resin solid content 100 parts by mass, Ri 30 to 75 parts by mass der,
The content of the cyanate ester compound (A1) is, relative to the resin solid content of 100 parts by weight, Ru 30-70 parts by der,
Resin composition for printed wiring boards.

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

(In the formula, X represents a group represented by the following formula (4) or the following formula (5), and Y independently represents a group represented by the following formula (6), and a and b represents an integer from 0 to 100, and at least one of them is 1 or more.)

(In the formula, R ₁ , R ₂ , R ₃ , R ₇ , and R ₈ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R ₄ , R ₅ , and R 8 and R ₆ independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

(In the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are each independently a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or an alkyl group having 6 or less carbon atoms. It represents a phenyl group, and A represents a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

(In the formula, R ₁₇ and R ₁₈ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ₁₉ and R ₂₀ independently represent a hydrogen atom and a halogen atom, respectively. , An alkyl group having 6 or less carbon atoms, or a phenyl group.)
[2]
The content of the cyanate ester compound (A2) is 1 part by mass or more with respect to 100 parts by mass of the resin solid content.
The resin composition for a printed wiring board according to [1].
[3]
In the vinyl compound (C), X represents a group represented by the following formula (7), a group represented by the following formula (8), or a group represented by the following formula (9), and Y represents a group represented by the following formula (9). A group represented by the following formula (10), a group represented by the following formula (11), or a group represented by the following formula (10) and a group represented by the following formula (11) are randomly arranged. Containing a vinyl compound showing a random group,
The resin composition for a printed wiring board according to [1] or [2].

(In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₆ each independently represent a hydrogen atom or a methyl group, and A is a linear or branched product having 20 or less carbon atoms. , Or a cyclic divalent hydrocarbon group.)

(In the formula, A represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

[4]
Unsaturated double bond-containing compound (E) other than epoxy resin (D) and vinyl compound (C), cyanate ester compound (F) other than cyanate ester compound (A1) and cyanate ester compound (A2), phenol Further containing one or more selected from the group consisting of the resin (G), the oxetane resin (H), and the benzoxazine compound (I).
The resin composition for a printed wiring board according to any one of [1] to [3].
[5]
Further containing an inorganic filler (K),
The resin composition for a printed wiring board according to [1] to [4].
[6]
The content of the inorganic filler (K) is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.
The resin composition for a printed wiring board according to [5].
[7]
With the base material
The resin composition according to any one of [1] to [6], which is impregnated or coated on the base material.
Prepreg.
[8]
The prepreg according to [7], in which at least one or more sheets are laminated,
The prepreg has metal foils arranged on one or both sides of the prepreg.
Metal leaf-clad laminate.
[9]
With the support
The resin composition according to any one of [1] to [6], which is arranged on the support.
Laminated resin sheet.
[10]
The resin composition according to any one of [1] to [6] is included.
Resin sheet.
[11]
Insulation layer and
It has a conductor layer formed on the surface of the insulating layer and
The insulating layer contains the resin composition according to any one of [1] to [6].
Printed wiring board.

According to the present invention, a resin composition for a printed wiring board, which is excellent in dielectric constant and dielectric tangent, and also excellent in copper foil peel strength and glass transition temperature, and a prepreg using the resin composition for a printed wiring board. A metal foil-clad laminate, a laminate resin sheet, a resin sheet, and a printed wiring board can be provided.

Hereinafter, embodiments 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. Is.

[Resin composition for printed wiring board]
The resin composition for a printed wiring board of the present embodiment (hereinafter, also simply referred to as “resin composition”) includes a cyanic acid ester compound (A1) represented by the formula (1) described later and a formula (2) described later. ), A maleimide compound (B), and a vinyl compound (C) represented by the formula (3) described later.

（式中、Ｒは、各々独立して、水素原子又はメチル基を表し、水素原子が好ましく、ｎは１以上の整数を表す。） [Cyanic acid ester compound (A1)]
The cyanate ester compound (A1) is a compound represented by the following formula (1). The cyanate ester compound (A1) is not particularly limited, and is, for example, naphthols such as α-naphthol or β-naphthol, p-xylene glycol, α, α'-dimethoxy-p-xylene, 1,4-. It can be obtained by reacting with di (2-hydroxy-2-propyl) benzene or the like to obtain a naphthol aralkyl resin, and condensing the obtained naphthol aralkyl resin with cyanic acid.

(In the formula, R independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom, and n represents an integer of 1 or more.)

The content of the cyanate ester compound (A1) is preferably 1 to 90 parts by mass, more preferably 30 to 70 parts by mass, and further preferably 40 to 60 parts by mass with respect to 100 parts by mass of the resin solid content. It is a department. When the content of the cyanate ester compound (A1) is 1 part by mass or more, the dielectric constant tends to be further lowered and the glass transition temperature tends to be improved. Further, when the content of the cyanate ester compound (A1) is 60 parts by mass or less, the dielectric loss tangent tends to be further lowered.

In the present embodiment, the "resin solid content" refers to a component of the resin composition excluding the solvent and the inorganic filler (K), unless otherwise specified, and is "100 parts by mass of the resin solid content". Means that the total of the components excluding the solvent and the inorganic filler (K) in the resin composition is 100 parts by mass.

[Cyanic acid ester compound (A2)]
The cyanate ester compound (A2) is a compound represented by the following formula (2).

The content of the cyanate ester compound (A2) is preferably 1 to 90 parts by mass, more preferably 3 to 40 parts by mass, and further preferably 5 to 25 parts by mass with respect to 100 parts by mass of the resin solid content. It is a department. When the content of the cyanate ester compound (A2) is 1 part by mass or more, the copper foil peel strength tends to be further improved and the dielectric constant tends to be further lowered. Further, when the content of the cyanate ester compound (A2) is 90 parts by mass or less, the dielectric loss tangent tends to be further lowered.

The content of the cyanate ester compound (A2) is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and further, with respect to 100 parts by mass of the cyanate ester compound (A1). It is preferably 15 to 70 parts by mass. When the contents of the cyanate ester compound (A1) and the cyanate ester compound (A2) have the above relationship, the copper foil peel strength tends to be further improved, and the dielectric constant and the dielectric loss tangent tend to be further lowered.

Further, the total content of the cyanate ester compound (A1) and the cyanate ester compound (A2) is preferably 30 to 75 parts by mass, more preferably 35 to 70 parts by mass with respect to 100 parts by mass of the resin solid content. Parts, more preferably 40 to 65 parts by mass. When the total content of the cyanate ester compound (A1) and the cyanate ester compound (A2) is within the above range, the copper foil peel strength tends to be further improved, and the dielectric constant and the dielectric loss tangent tend to be further lowered.

（式中、Ｒ¹⁷は各々独立に、水素原子又はメチル基を表す。ｎ２は平均値として１〜１０の範囲である。） [Maleimide compound (B)]
The maleimide compound (B) is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, and is not particularly limited, and is 4,4-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, 2, 2-Bis (4- (4-maleimidephenoxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1 , 6-Bismaleimide- (2,2,4-trimethyl) hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulphon bismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3 Examples thereof include −bis (4-maleimidephenoxy) benzene, a maleimide compound represented by the following formula (12), a prepolymer of these maleimide compounds, or a prepolymer of a maleimide compound and an amine compound. These maleimide compounds can be used alone or in admixture of two or more. Among these, the maleimide compound represented by the formula (2) is preferable from the viewpoint of moisture absorption heat resistance and flame resistance. Commercially available products can be used for the compound, and examples thereof include BMI-2300 manufactured by KI Kasei Co., Ltd.

(In the formula, R ¹⁷ independently represents a hydrogen atom or a methyl group. N2 is in the range of 1 to 10 as an average value.)

Among these, the maleimide compound represented by the above formula (12) is preferable. By using such a maleimide compound (B), the glass transition temperature, flame retardancy, and hygroscopic heat resistance tend to be further improved.

The content of the maleimide compound (B) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and further preferably 15 to 30 parts by mass with respect to 100 parts by mass of the resin solid content. be. When the content of the maleimide compound (B) is 5 parts by mass or more, the dielectric loss tangent tends to be further lowered. Further, when the content of the maleimide compound (B) is 50 parts by mass or less, the copper foil peel strength tends to be further improved and the dielectric constant tends to be further lowered.

（式中、Ｘは、下記式（４）、又は下記式（５）で表される基を示し、Ｙは、各々独立して、下記式（６）で表される基を示し、ａ及びｂは、０〜１００の整数を示し、少なくともいずれか一方が１以上である。）

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₇、及びＲ₈は、各々独立して、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を示し、Ｒ₄、Ｒ₅、及びＲ₆は、各々独立して、水素原子、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を示す。）

（式中、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、及びＲ₁₆は、各々独立して、水素原子、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を示し、Ａは、炭素数２０以下である、直鎖状、分岐状、又は環状の２価の炭化水素基を示す。）

（式中、Ｒ₁₇及びＲ₁₈は、各々独立して、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を表す。Ｒ₁₉及びＲ₂₀は、各々独立して、水素原子、ハロゲン原子、炭素数６以下のアルキル基、又はフェニル基を表す。） [Vinyl compound (C)]
The vinyl compound (C) is a compound represented by the following formula (3).

(In the formula, X represents a group represented by the following formula (4) or the following formula (5), and Y independently represents a group represented by the following formula (6), and a and b represents an integer from 0 to 100, and at least one of them is 1 or more.)

(In the formula, R ₁ , R ₂ , R ₃ , R ₇ , and R ₈ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R ₄ , R ₅ , and R 8 and R ₆ independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

(In the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are each independently a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or an alkyl group having 6 or less carbon atoms. It represents a phenyl group, and A represents a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

(In the formula, R ₁₇ and R ₁₈ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ₁₉ and R ₂₀ independently represent a hydrogen atom and a halogen atom, respectively. , An alkyl group having 6 or less carbon atoms, or a phenyl group.)

（式中、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、及びＲ₁₆は、各々独立して、水素原子又はメチル基を示し、Ａは、炭素数２０以下である、直鎖状、分岐状、又は環状の２価の炭化水素基を示す。）

（式中、Ａは、炭素数２０以下である、直鎖状、分岐状又は環状の２価の炭化水素基を示す。） X represents a group represented by the formula (4) or the formula (5), preferably a group represented by the following formula (7), a group represented by the following formula (8), or a group represented by the following formula (9). ) Indicates a group. By using such a vinyl compound (C), the dielectric constant and the dielectric loss tangent tend to be further lowered.

(In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₆ each independently represent a hydrogen atom or a methyl group, and A is a linear or branched product having 20 or less carbon atoms. , Or a cyclic divalent hydrocarbon group.)

(In the formula, A represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

Each of Y independently represents a group represented by the formula (6), preferably a group represented by the following formula (10), a group represented by the following formula (11), or a group represented by the following formula (10). ) And the group represented by the following formula (11) are randomly arranged. By using such a vinyl compound (C), the dielectric constant and the dielectric loss tangent tend to be further lowered.

The number average molecular weight of the vinyl compound (C) is preferably 500 to 5000, more preferably 700 to 3500, and even more preferably 900 to 2500 in terms of polystyrene by the GPC method. Since the number average molecular weight of the vinyl compound (C) is 500 or more, it tends to be less sticky when formed into a coating film. Further, when the number average molecular weight of the vinyl compound (C) is 5000 or less, it tends to be possible to prevent a decrease in solubility in a solvent.

The vinyl group equivalent (g / eq.) Of the vinyl compound (C) is preferably 250 to 2000 g / eq. More preferably, 350 to 1500 g / eq. And more preferably 450 to 1300 g / eq. Is. When the vinyl group equivalent (g / eq.) Of the vinyl compound (C) is within the above range, heat resistance and low water absorption tend to be further improved.

The content of the vinyl compound (C) is preferably 1 to 75 parts by mass, more preferably 3 to 50 parts by mass, and further preferably 5 to 30 parts by mass with respect to 100 parts by mass of the resin solid content. be. When the content of the vinyl compound (C) is 1 part by mass or more, the dielectric constant and the dielectric loss tangent tend to be further lowered. Further, when the content of the vinyl compound (C) is 75 parts by mass or less, the copper foil peel strength tends to be further improved.

[Inorganic filler (K)]
The resin composition of the present embodiment preferably further contains an inorganic filler (K). The inorganic filler (K) is not particularly limited, but for example, silicas such as natural silica, molten silica, synthetic silica, amorphous silica, aerodyl, and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, and the like. Metal oxides such as magnesium oxide and zirconium oxide; metal nitrides such as boron nitride, coagulated boron nitride, silicon nitride and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide and aluminum hydroxide heat-treated products (hydroxide) Aluminum is heat-treated to reduce a part of crystalline water), metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdenum; zinc borate and zinc tintate. Compounds: Alumina, 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, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass and Q glass), hollow glass, spherical glass and the like can be mentioned.

Of these, silica is preferable. By using such an inorganic filler (K), the coefficient of thermal expansion tends to be further lowered.

The content of the inorganic filler (K) is preferably 50 to 1600 parts by mass, more preferably 50 to 750 parts by mass, and further preferably 50 to 400 parts by mass with respect to 100 parts by mass of the resin solid content. It is particularly preferably 50 to 300 parts by mass. When the content of the inorganic filler (K) is 50 parts by mass or more, the coefficient of thermal expansion tends to be further improved.

[Silane coupling agent and wet dispersant]
The resin composition of the present embodiment may further contain a silane coupling agent and a wet dispersant.

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, but for example, γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ. Aminosilane compounds such as −aminopropyltrimethoxysilane; epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; acrylicsilane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N-) Examples thereof include cationic silane compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds. The silane coupling agent may be used alone or in combination of two or more.

The wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints, but for example, DISPER-110, 111, 118, 180, 161 and BYK-W996 manufactured by Big Chemie Japan Co., Ltd. , W9010, W903 and the like.

[Other ingredients]
The resin composition of the present embodiment may contain other components in addition to the above components, if necessary. The other components are not particularly limited, but are, for example, unsaturated double bond-containing compounds (E) other than epoxy resin (D) and vinyl compound (C), cyanate ester compounds (A1), and cyanate ester compounds ( It is selected from the group consisting of a cyanate ester compound (F) other than A2), a phenol resin (G), an oxetane resin (H), a benzoxazine compound (I), and a compound (J) having a polymerizable unsaturated group. One or more types can be mentioned.

(Epoxy resin (D))
As the epoxy resin, as long as it is a compound having two or more epoxy groups in one molecule, generally known ones can be used, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, and cresol novolac. Type epoxy resin, xylene novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional Phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, phenol aralkyl novolac type epoxy resin, Double naphthol aralkylnovolac type epoxy resin, aralkylnovolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, butadiene, etc. Examples thereof include a compound having an epoxy bond, a compound obtained by reacting a hydroxyl group-containing silicone resin with epichlorohydrin, and a halide thereof. These epoxy resins may be used alone or in combination of two or more.

Among these, it is preferable that the epoxy resin is at least one selected from the group consisting of a biphenyl aralkyl type epoxy resin, a naphthylene ether type epoxy resin, a polyfunctional phenol type epoxy resin, and a naphthalene type epoxy resin. By including such an epoxy resin, the flame retardancy and heat resistance of the obtained cured product tend to be further improved.

(Unsaturated double bond-containing compound (E))
The unsaturated double bond-containing compound (E) other than the vinyl compound (C) is not particularly limited, and is, for example, allyl chloride, allyl acetate, allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, and phthalic acid. Examples thereof include diallyl, diallyl isophthalate, and diallyl maleate. The "unsaturated double bond" is not particularly limited, and examples thereof include a vinyl group and an aryl group.

(Cyanic acid ester compound (F))
The cyanate ester compound (F) other than the cyanate ester compound (A1) and the cyanate ester compound (A2) is not particularly limited, and is, for example, a novolac type cyanate ester, a biphenyl aralkyl type cyanate ester, and a bis (3). , 5-Dimethyl 4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-disyanatobenzene, 1,4-disyanatobenzene, 1,3,5-trisianatobenzene, 1, 3-Disianatonaphthalene, 1,4-Disyanatnaphthalene, 1,6-Disyanatnaphthalene, 1,8-Disianatnaphthalene, 2,6-Disianatnaphthalene, 2,7-Disianatnaphthalene, 1,3 6-Trisianatonaphthalene, 4,4'-disianatobiphenyl, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and 2,2' -Bis (4-cyanatophenyl) propane; prepolymers of these cyanate esters and the like can be mentioned. The cyanate ester compound may be used alone or in combination of two or more.

(Phenol resin (G))
As the phenol resin, generally known phenol resins can be used as long as they have two or more hydroxy groups in one molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, and aralkyl novolac type. Phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin , Naftor aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, hydroxyl-containing silicone resin, etc., but are particularly limited. It's not a thing. These phenol resins can be used alone or in combination of two or more.

(Oxetane resin (H))
As the oxetane resin, generally known ones can be used, and the type thereof is not particularly limited. Specific examples thereof include alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3'. -Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toa Synthetic), OXT-121 (manufactured by Toa Synthetic) Product name) and the like. These oxetane resins can be used alone or in combination of two or more.

(Benzooxazine compound (I))
As the benzoxazine compound, a generally known compound can be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type benzoxazine BA-BXZ (trade name manufactured by Konishi Chemical Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (trade name manufactured by Konishi Chemical Co., Ltd.), and bisphenol S type benzoxazine BS-BXZ (trade name manufactured by Konishi Chemical Co., Ltd.). First name) and so on. These benzoxazine compounds can be used alone or in admixture of two or more.

(Compound with polymerizable unsaturated group)
As the compound having a polymerizable unsaturated group, generally known compounds can be used, and the type thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polypropylene glycol di (). (Meta) of monovalent or polyhydric alcohols such as trimethylolpropane di (meth) acrylate, trimethylol propanedi (meth) acrylate, trimethylol propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Examples thereof include acrylates; epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; benzocyclobutene resin; (bis) maleimide resin and the like. These compounds having unsaturated groups can be used alone or in admixture of two or more.

[Curing accelerator]
The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, but for example, imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate and the like. Organic peroxides; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine Tertiary amines such as pyridine, quinoline, N-methylmorpholin, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidin; phenols such as phenol, xylenol, cresol, resorcin, catechol; naphthenic acid Organic metal salts such as lead, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts contain hydroxyl groups such as phenol and bisphenol. Those dissolved in a compound; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyl tin oxide and other organic tin compounds such as alkyl tin and alkyl tin oxide can be mentioned. Among these, triphenylimidazole is particularly preferable because it promotes the curing reaction and tends to have excellent glass transition temperature and coefficient of thermal expansion.

〔solvent〕
The resin composition of the present embodiment may further contain a solvent. By containing the solvent, the viscosity of the resin composition at the time of preparation is lowered, the handleability is further improved, and the impregnation property into the substrate, which will be described later, tends to be further improved.

The solvent is not particularly limited as long as it can dissolve a part or all of the resin components in the resin composition, but for example, ketones such as acetone, methyl ethyl ketone and methyl cell solve; aromatics such as toluene and xylene. Group hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and acetates thereof and the like. As the solvent, one type may be used alone, or two or more types may be used in combination.

[Manufacturing method of resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, and examples thereof include a method in which each component is sequentially mixed with a solvent and sufficiently stirred. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the inorganic filler (K) in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirring machine having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading treatment can be appropriately performed using, for example, an apparatus for mixing such as a ball mill or a bead mill, or a known apparatus such as a revolving or rotating type mixing apparatus.

Further, when preparing the resin composition of the present embodiment, an organic solvent can be used if necessary. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples thereof are as described above.

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

[Prepreg]
The prepreg of the present embodiment has a base material and the above-mentioned resin composition impregnated or coated on the base material. The method for producing the prepreg can be carried out according to a conventional method, and is not particularly limited. For example, after impregnating or coating the base material with the resin component of the present embodiment, it is semi-cured (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. The prepreg of the present embodiment can be produced.

The content of the resin composition (including the inorganic filler (K)) is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and preferably 40, based on the total amount of the prepreg. ~ 80% by mass. When the content of the resin composition is within the above range, the moldability tends to be further improved.

The base material is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. Specific examples of the fibers constituting the base material are not particularly limited, but for example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; quartz and the like. Inorganic fibers other than glass; polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technora (registered trademark), Teijin Techno Products Limited) Total aromatic polyamide such as 2,6-hydroxynaphthoic acid / parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Klaray Co., Ltd.), polyester such as Zexion (registered trademark, manufactured by KB Salen); polyparaphenylene Examples thereof include organic fibers such as benzoxazole (Zylon (registered trademark), manufactured by Toyo Spinning Co., Ltd.) and polyimide. 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 fibers is preferable from the viewpoint of low coefficient of thermal expansion. These base materials may be used alone or in combination of two or more.

The shape of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfaced mats. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones according to the intended use and performance. .. Further, a glass woven fabric obtained by opening the fibers or surface-treating with a silane coupling agent or the like is preferably used. The thickness and mass of the base material are not particularly limited, but usually those having a thickness and mass of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorption, the base material is ^{preferably a glass woven cloth having a thickness of 200 μm or less and a mass of 250 g / m 2} or less, and a glass woven cloth made of glass fibers of E glass, S glass, and T glass is preferable. More preferred.

[Laminated resin sheet]
The laminated resin sheet of the present embodiment has a support and the resin composition arranged on the support. The laminated resin sheet is used as one means for thinning leaves, and can be produced, for example, by directly coating and drying the resin composition on a support such as a metal foil or a film.

The support is not particularly limited, but known materials 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, aluminum foil, copper foil, gold foil and the like can be mentioned. Among them, electrolytic copper foil and PET film are preferable.

Examples of the coating method include a method in which a solution of the resin composition of the present embodiment dissolved in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

The laminated resin sheet is preferably one in which the above resin composition is applied to a support and then semi-cured (B-staged). Specifically, for example, the resin composition is applied to a support such as a copper foil and then semi-cured by heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes to obtain a laminated resin sheet. Examples include the manufacturing method. The amount of the resin composition adhered to the support is preferably in the range of 1 to 300 μm in terms of the resin thickness of the laminated resin sheet.

[Resin sheet]
The resin sheet of this embodiment contains a resin composition. The resin sheet is formed by molding a resin composition into a sheet shape. The method for producing the resin sheet can be carried out according to a conventional method, and is not particularly limited. For example, it can be obtained by peeling or etching the support from the laminated resin sheet. By supplying a solution of the resin composition of the present embodiment in a solvent into a mold having a sheet-like cavity and drying the solution to form a sheet, the sheet base material is not used. A resin sheet (single layer resin sheet) can also be obtained.

[Metal leaf-clad laminate]
The metal foil-clad laminate of the present embodiment has the above-mentioned prepreg in which at least one or more sheets are laminated, and metal foil arranged on one side or both sides of the prepreg. That is, the metal foil-clad laminate of the present embodiment is obtained by laminating and curing the prepreg and the metal foil.

The conductor layer can be a metal foil such as copper or aluminum. The metal foil used here is not particularly limited as long as it is used as a material for a printed wiring board, but a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. The thickness of the conductor layer is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm.

The molding method of the metal foil-covered laminated board and the molding conditions thereof are not particularly limited, and general methods and conditions for the laminated board for printed wiring boards and the multilayer board can be applied. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when forming a metal foil-clad laminate. Further, in molding a metal leaf-clad laminate, the temperature is ^{generally in the range of 100 to 300 ° C., the pressure is generally in the range of 2 to} 100 kgf / cm 2, and the heating time is in the range of 0.05 to 5 hours. Further, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C. Further, it is also possible to form a multilayer plate by laminating and molding the above-mentioned prepreg in combination with a separately prepared wiring plate for an inner layer.

[Printed circuit board]
The printed wiring board of the present embodiment is a printed wiring board including an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition. The metal foil-clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal leaf-clad laminate has a low coefficient of thermal expansion, good moldability and chemical resistance, and is particularly effectively used as a printed wiring board for a semiconductor package in which such performance is required. Can be done.

Specifically, the printed wiring board of the present embodiment can be manufactured by, for example, the following method. First, the above-mentioned metal foil-clad laminate (copper-clad laminate, etc.) is prepared. The surface of the metal foil-clad laminate is etched to form an inner layer circuit to create an inner layer substrate. The inner layer circuit surface of this inner layer substrate is subjected to surface treatment to increase the adhesive strength as necessary, then the required number of the above-mentioned prepregs are laminated on the inner layer circuit surface, and the metal foil for the outer layer circuit is laminated on the outer side thereof. Then, heat and pressurize to integrally mold. In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a thermosetting resin composition is formed between an inner layer circuit and a metal foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in this multilayer laminated plate, desmear treatment is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer. .. After that, a plated metal film that conducts the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of this hole, and the metal foil for the outer layer circuit is further etched to form the outer layer circuit, and the printed wiring board is manufactured. Will be done.

For example, the above-mentioned prepreg (the base material and the above-mentioned resin composition attached thereto) and the resin composition layer of the metal leaf-clad laminate (the above-mentioned layer composed of the above-mentioned resin composition) include the above-mentioned resin composition. It will form an insulating layer.

When the metal foil-clad laminate is not used, a conductor layer to be a circuit may be formed on the prepreg, the laminate resin sheet, or the resin composition to produce a printed wiring board. At this time, an electroless plating method can also be used to form the conductor layer.

The printed wiring board of the present embodiment is used for semiconductor packages because the above-mentioned insulating layer maintains an excellent elastic modulus even under the reflow temperature at the time of semiconductor mounting, thereby effectively suppressing the warp of the semiconductor plastic package. It can be particularly effectively used as a printed wiring board.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

[Synthesis Example 1] Synthesis of α-naphthol aralkyl type cyanate ester resin (SN495VCN) In a reactor, α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd .: The number of repeating units n of naphthol aralkyl includes 1 to 5.) 0.47 mol (in terms of OH group) was dissolved in 500 ml of chloroform, and 0.7 mol of triethylamine was added to this solution. While maintaining the temperature at −10 ° C., 300 g of a 0.93 mol cyanogen chloride chloroform solution was added dropwise over 1.5 hours, and the mixture was stirred for 30 minutes after the addition was completed. After that, 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 obtained filtrate was washed with 500 ml of 0.1N hydrochloric acid, and then washed with 500 ml of water was repeated 4 times. This is dried over sodium sulfate, evaporated at 75 ° C., and degassed under reduced pressure at 90 ° C. to obtain a brown solid α-naphthol aralkyl type cyanate ester compound represented by the above formula (1) (in the formula). All R's are hydrogen atoms.) When the obtained α-naphthol aralkyl type cyanate ester compound was analyzed by an infrared absorption spectrum, absorption of a cyanate ester group was confirmed in the vicinity of ^{2264 cm -1.}

[Synthesis Example 2] Synthesis of cyanide ester compound (DABPA-CN) of diallyl bisphenol A 700 g of diallyl bisphenol A (hydroxyl group equivalent 154.2 g / eq.) (OH group equivalent 4.54 mol) (DABPA, Daiwa Kasei Kogyo Co., Ltd.) ) And 459.4 g (4.54 mol) of triethylamine (1.0 mol with respect to 1 mol of hydroxyl group) were dissolved in 2100 g of dichloromethane, and this was used as solution 1.

474.4 g (7.72 mol) of cyanide chloride (1.7 mol per 1 mol of hydroxyl group), 1106.9 g of dichloromethane, 735.6 g (7.26 mol) of 36% hydrochloric acid (1. 6 mol), 4560.7 g of water was poured over 90 minutes with stirring while maintaining the liquid temperature at −2 to −0.5 ° C. After pouring 1 solution, the mixture was stirred at the same temperature for 30 minutes, and then 459.4 g (4.54 mol) of triethylamine (1.0 mol with respect to 1 mol of hydroxyl group) was dissolved in 459.4 g of dichloromethane (a solution). Solution 2) was poured over 25 minutes. After 2 pouring of the solution was completed, the reaction was completed by stirring at the same temperature for 30 minutes.

After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed with 2 L of 0.1N hydrochloric acid and then washed 6 times with 2000 g of water. The electrical conductivity of the wastewater after the sixth washing with water was 20 μS / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.

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 805 g of the desired cyanate ester compound DABPA-CN (light yellow liquid). The IR spectrum of the obtained cyanide ester compound DABPA-CN ^{showed absorption of 2264 cm -1} (cyanic acid ester group) and no absorption of hydroxyl groups.

(Example 1)
Vinyl benzyl-modified polyphenylene ether (OPE-2St 1200, manufactured by Mitsubishi Gas Chemical Company, Inc., number average molecular weight 1187, vinyl group equivalent: 590 g / eq.) 20 parts by mass, α-naphthol aralkyl type cyan obtained by Synthesis Example 1. 50 parts by mass of acid ester resin (SN495VCN), 10 parts by mass of cyanate ester compound (DABPA-CN) obtained in Synthesis Example 2, 20 parts by mass of novolak type bismaleimide compound (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300), A vinyl silane-treated molten silica (SC2050MNU, manufactured by Admatex) was mixed with 100 parts by mass and zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd.) with 0.1 parts by mass to obtain a varnish.

(Example 2)
By the same operation as in Example 1 except that the amount of α-naphthol aralkyl type cyanate ester resin (SN495VCN) used was 40 parts by mass and the amount of cyanate ester compound (DABPA-CN) used was 20 parts by mass. , Got a varnish.

(Comparative Example 1)
60 parts by mass of vinylbenzyl-modified polyphenylene ether (OPE-2St 1200), 30 parts by mass of α-naphthol aralkyl type cyanate ester resin (SN495VCN) obtained in Synthesis Example 1, novolak type bismaleimide compound (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300) 10 parts by mass, vinylsilane-treated molten silica (SC2050MNU, manufactured by Admatex) 100 parts by mass, and zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.1 parts by mass were mixed to obtain a varnish. ..

(Comparative Example 2)
50 parts by mass of vinylbenzyl-modified polyphenylene ether (OPE-2St 1200), 37.5 parts by mass of α-naphthol aralkyl type cyanate resin (SN495VCN), novolac type bismaleimide compound (BMI-2300) ) Was used in an amount of 12.5 parts by mass, and a varnish was obtained by the same operation as in Comparative Example 1.

(Comparative Example 3)
20 parts by mass of vinylbenzyl-modified polyphenylene ether (OPE-2St 1200), 60 parts by mass of α-naphthol aralkyl type cyanate resin (SN495VCN), novolak type bismaleimide compound (BMI-2300) A varnish was obtained by the same operation as in Comparative Example 1 except that the amount used was 20 parts by mass.

(Comparative Example 4)
20 parts by mass of vinylbenzyl-modified polyphenylene ether (OPE-2St 1200), 50 parts by mass of α-naphthol aralkyl type cyanate resin (SN495VCN), novolak type bismaleimide compound (BMI-2300) A varnish was obtained by the same operation as in Comparative Example 1 except that the amount used was 30 parts by mass.

(Comparative Example 5)
20 parts by mass of vinylbenzyl-modified polyphenylene ether (OPE-2St 1200), 40 parts by mass of α-naphthol aralkyl type cyanate resin (SN495VCN), and 40 parts by mass of novolak type bismaleimide compound (BMI-2300). A varnish was obtained by the same operation as in Comparative Example 1 except that the amount used was 40 parts by mass.

[Manufacturing method of copper-clad laminate]
The varnish obtained as described above is impregnated and coated on an E glass cloth having a thickness of 0.08 mm (IPC No. # 3313) and dried (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). Was dried by heating at 170 ° C. for 5 minutes to obtain a prepreg having a resin composition of 55% by mass. Eight of these prepregs were stacked, 18 μm copper foil (3EC-III, manufactured by Mitsui Metal Mining Co., Ltd.) was placed on both sides, and ^{vacuum press was performed at a pressure of 30 kg / cm 2} and a temperature of 210 ° C. for 150 minutes to obtain a thickness of 0. An 8 mm 18 μm copper-clad laminate was obtained. The following evaluation was performed using the obtained copper-clad laminate.

[Copper foil peel strength]
According to the JIS C6481 copper-clad laminate test method for printed wiring boards (see 5.7 Peeling strength), a copper-clad laminate test piece (30 mm x 150 mm x thickness approx. 0.8 mm) was used to measure the peeling strength of the copper foil.

[Dielectric constant (Dk)]
Using a test piece (n = 1) from which the copper foil of the copper-clad laminate was removed, the dielectric loss tangent of 10 GHz was measured by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies), and the average value of 5 times was measured. I asked. Based on the obtained values, the dielectric loss tangent was evaluated based on the following evaluation criteria.
A: less than 3.5 B: 3.5 or more

[Dissipation factor (Df)]
Using a test piece (n = 1) from which the copper foil of the copper-clad laminate was removed, the dielectric loss tangent of 10 GHz was measured by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies), and the average value of 5 times was measured. I asked. Based on the obtained values, the dielectric loss tangent was evaluated based on the following evaluation criteria.
A: less than 0.0045 B: 0.0045 or more

[Glass transition temperature (Tg)]
Using a test piece (n = 1) from which the copper foil of the copper-clad laminate was removed, the glass transition temperature was measured by the DMA method with a dynamic viscoelastic analyzer (manufactured by TA Instruments) in accordance with JIS C6481. ..

The resin composition for a printed wiring board of the present invention has industrial applicability as a material for a prepreg, a metal foil-clad laminate, a laminated resin sheet, a resin sheet, a printed wiring board, and the like.

Claims (11)

The cyanic acid ester compound (A1) represented by the following formula (1) and
The cyanic acid ester compound (A2) represented by the following formula (2) and
Maleimide compound (B) and
Containing a vinyl compound (C) represented by the following formula (3),
The total amount of the cyanate ester compound (A1) and the cyanate ester compound (A2) is, with respect to resin solid content 100 parts by mass, Ri 30 to 75 parts by mass der,
The content of the cyanate ester compound (A1) is, relative to the resin solid content of 100 parts by weight, Ru 30-70 parts by der,
Resin composition for printed wiring boards.

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

(In the formula, X represents a group represented by the following formula (4) or the following formula (5), and Y independently represents a group represented by the following formula (6), and a and b represents an integer from 0 to 100, and at least one of them is 1 or more.)

(In the formula, R ₁ , R ₂ , R ₃ , R ₇ , and R ₈ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R ₄ , R ₅ , and R 8 and R ₆ independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

(In the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are each independently a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or an alkyl group having 6 or less carbon atoms. It represents a phenyl group, and A represents a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

(In the formula, R ₁₇ and R ₁₈ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ₁₉ and R ₂₀ independently represent a hydrogen atom and a halogen atom, respectively. , An alkyl group having 6 or less carbon atoms, or a phenyl group.) The content of the cyanate ester compound (A2) is 1 part by mass or more with respect to 100 parts by mass of the resin solid content.
The resin composition for a printed wiring board according to claim 1. In the vinyl compound (C), X represents a group represented by the following formula (7), a group represented by the following formula (8), or a group represented by the following formula (9), and Y represents a group represented by the following formula (9). A group represented by the following formula (10), a group represented by the following formula (11), or a group represented by the following formula (10) and a group represented by the following formula (11) are randomly arranged. Containing a vinyl compound showing a random group,
The resin composition for a printed wiring board according to claim 1 or 2.

(In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₆ each independently represent a hydrogen atom or a methyl group, and A is a linear or branched product having 20 or less carbon atoms. , Or a cyclic divalent hydrocarbon group.)

(In the formula, A represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

An epoxy resin (D), an unsaturated double bond-containing compound (E) other than the vinyl compound (C), a cyanate ester compound (F) other than the cyanate ester compound (A1) and the cyanate ester compound (A2), Further containing one or more selected from the group consisting of the phenol resin (G), the oxetane resin (H), and the benzoxazine compound (I).
The resin composition for a printed wiring board according to any one of claims 1 to 3. Further containing an inorganic filler (K),
The resin composition for a printed wiring board according to any one of claims 1 to 4. The content of the inorganic filler (K) is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.
The resin composition for a printed wiring board according to claim 5. With the base material
The resin composition according to any one of claims 1 to 6, which is impregnated or coated on the base material.
Prepreg. The prepreg according to claim 7, wherein at least one of the prepregs is laminated.
The prepreg has metal foils arranged on one or both sides of the prepreg.
Metal leaf-clad laminate. With the support
The resin composition according to any one of claims 1 to 6, which is arranged on the support.
Laminated resin sheet. The resin composition according to any one of claims 1 to 6 is included.
Resin sheet. Insulation layer and
It has a conductor layer formed on the surface of the insulating layer and
The insulating layer contains the resin composition according to any one of claims 1 to 6.
Printed wiring board.