JP2018131519A - Resin composition, resin sheet and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition containing thermosetting modified polyphenylene ether as a base suitable for a multilayer printed wiring board for high frequency which is excellent in handleability in a process of bonding to another laminate to constitute a laminate, prevents warpage and cracking, and prevents lowering of electric characteristics and a peeling strength, and to provide a metal foil-clad laminate and a resin sheet using the same.SOLUTION: A resin composition contains a polyphenylene ether resin (A), an elastomer (B) which has an SP value of 9 (cal/cm)or less and a weight average molecular weight of 80,000 or more, and is a solid at 25°C, and an elastomer (C) which has an SP value of 9 (cal/cm)or less and a weight average molecular weight of 40,000 or less, and is a liquid at 25°C.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition excellent in peel strength, heat resistance after moisture absorption, and electrical characteristics, and a resin sheet and a printed wiring board using the same. The obtained resin composition is suitably used for a printed circuit board for lead-free solder reflow, high frequency and high multi-layer applications, for a mother board, and for a semiconductor plastic package on which a semiconductor chip is mounted.

  In recent years, information terminals such as personal computers and servers, and communication devices such as Internet routers and optical communications are required to process large amounts of information at high speed, and the speed and frequency of electrical signals are increasing. Yes. Accordingly, laminated boards for printed wiring boards used for these are required to have low dielectric constant and low dielectric loss tangent, particularly low dielectric loss tangent, in order to meet the demand for high frequency. In order to meet these demands, a thermosetting resin (for example, see Patent Document 1) containing polyphenylene ether as a main component has been conventionally used for high-frequency laminates. However, a sheet made of a resin composition containing polyphenylene ether as a main component has poor handleability during handling, and cracks easily enter the resin composition and fall off from the support. It is used in combination with polybutadiene rubber, styrene-butadiene rubber (for example, see Patent Documents 2 and 3), epoxy resin and low molecular weight bismaleimide resin (for example, see Patent Document 4).

  However, if these components are included with emphasis on crack resistance, warping will occur greatly when manufacturing a printed wiring board using a sheet made of a resin composition as a build-up material, and subsequent processes may be carried out. It becomes difficult.

Japanese Patent Laid-Open No. 62-129319 JP 2005-105061 A JP 2009-001787 A JP 2006-010964 A

  The present invention is a high-frequency multilayer printed wiring board that is excellent in handleability in the process of constituting a laminated board by being laminated with another laminated board, is less likely to warp and crack, and does not deteriorate electrical properties, peel strength, etc. A resin composition based on a suitable thermosetting modified polyphenylene ether, and a metal foil-clad laminate and a resin sheet using the same are provided.

  In order to solve this problem, the present inventors have intensively studied, and as a result, blended a solid and liquid elastomer at room temperature with a polyphenylene ether resin, and further used an inorganic filler as necessary. It has been found that warping and cracking are less likely to occur in the process of laminating a resin sheet made of the above to another laminated plate, and that the electrical characteristics, peel strength, etc. are not reduced, and the present invention has been achieved.

（式中、−（Ｏ−Ｘ−Ｏ）−は、一般式（２）又は一般式（３）で定義される構造からなる。−（Ｙ−Ｏ）−は、一般式（４）で定義され、１種類の構造又は２種類以上の構造がランダムに配列している。ａ，ｂは、少なくともいずれか一方が０でない、０〜１００の整数を示す。）

（Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_７，Ｒ_８は、同一又は異なってもよく、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である。Ｒ_４，Ｒ_５，Ｒ_６は、同一又は異なってもよく、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である。）

（Ｒ_９，Ｒ_１０，Ｒ_１１，Ｒ_１２，Ｒ_１３，Ｒ_１４，Ｒ_１５，Ｒ_１６は、同一又は異なってもよく、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である。−Ａ−は、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基である。）

（Ｒ_１７，Ｒ_１８は、同一又は異なってもよく、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である。Ｒ_１９，Ｒ_２０は、同一又は異なってもよく、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である。）
［４］
前記エラストマー（Ｂ）が、ポリイソプレン、ポリブタジエン、スチレンブタジエン、ブチルゴム、エチレンプロピレンゴム、フッ素ゴム、シリコーンゴム、それらの水添化合物、それらのアルキル化合物、及びそれらの共重合体からなる群より選択される少なくとも１種である、［１］〜［３］のいずれか一項に記載の樹脂組成物。
［５］
前記エラストマー（Ｃ）が、ポリイソプレン、ポリブタジエン、スチレンブタジエン、ブチルゴム、エチレンプロピレンゴム、フッ素ゴム及びシリコーンゴムからなる群より選択される少なくとも１種である、［１］〜［４］のいずれか一項に記載の樹脂組成物。
［６］
さらに、無機充填材（Ｄ）を含有する［１］〜［５］のいずれか一項に記載の樹脂組成物。
［７］
前記無機充填材（Ｄ）が、天然シリカ、溶融シリカ、合成シリカ、アモルファスシリカ、中空シリカ及びガラス短繊維からなる群より選択される少なくとも１種である、［６］に記載の樹脂組成物。
［８］
さらに、エポキシ樹脂、シアン酸エステル化合物、マレイミド化合物及びホスファゼン化合物からなる群より選択される少なくとも一種を含有する、［１］〜［７］のいずれか一項に記載の樹脂組成物。
［９］
前記ポリフェニレンエーテル樹脂（Ａ）の含有量が、樹脂固形分１００質量部に対し、５０〜８０質量部である、［１］〜［８］のいずれか一項に記載の樹脂組成物。
［１０］
前記エラストマー（Ｂ）の含有量が、樹脂固形分１００質量部に対し、０．５〜３０質量部である、［１］〜［９］のいずれか一項に記載の樹脂組成物。
［１１］
前記エラストマー（Ｃ）の含有量が、樹脂固形分１００質量部に対し、０．５〜３０質量部である、［１］〜［１０］のいずれか一項に記載の樹脂組成物。
［１２］
前記無機充填材（Ｄ）の含有量が、樹脂固形分１００質量部に対し、１０〜２５０質量部である、［６］〜［１１］のいずれか一項に記載の樹脂組成物。
［１３］
［１］〜［１２］のいずれか一項に記載の樹脂組成物を含む樹脂シート。
［１４］
［１３］に記載の樹脂シートからなるプリント配線板のビルドアップ材。
［１５］
絶縁層と、該絶縁層の表面に形成された導体層とを有し、該絶縁層が、［１］〜［１２］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]
Polyphenylene ether resin (A), SP value of 9 (cal / cm ³ ) ^½ or less, weight average molecular weight of 80000 or more, and elastomer (B) that is solid at 25 ° C. and SP value of 9 (cal / cm ³ ) A resin composition containing an elastomer (C) that is ^1/2 or less, a weight average molecular weight of 40000 or less, and is liquid at 25 ° C.
[2]
The resin composition according to [1], wherein the polyphenylene ether resin (A) has a weight average molecular weight of 1000 to 5000.
[3]
The resin composition according to [1] or [2], wherein the polyphenylene ether resin (A) is represented by the general formula (1).

(In the formula, — (O—X—O) — has a structure defined by General Formula (2) or General Formula (3). — (Y—O) — is defined by General Formula (4). And one type of structure or two or more types of structures are arranged at random. A and b are integers of 0 to 100, at least one of which is not 0.)

(R ₁ , R ₂ , R ₃ , R ₇ and R ₈ may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. R ₄ , R ₅ and R ₆ are They may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

(R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

(R ₁₇ and R ₁₈ may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ₁₉ and R ₂₀ may be the same or different, and are a hydrogen atom or a halogen atom. And an alkyl group having 6 or less carbon atoms or a phenyl group.)
[4]
The elastomer (B) is selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, fluorine rubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof. The resin composition according to any one of [1] to [3], which is at least one kind.
[5]
Any one of [1] to [4], wherein the elastomer (C) is at least one selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, fluorine rubber, and silicone rubber. The resin composition according to item.
[6]
Furthermore, the resin composition as described in any one of [1]-[5] containing an inorganic filler (D).
[7]
The resin composition according to [6], wherein the inorganic filler (D) is at least one selected from the group consisting of natural silica, fused silica, synthetic silica, amorphous silica, hollow silica, and short glass fibers.
[8]
Furthermore, the resin composition as described in any one of [1]-[7] containing at least 1 type selected from the group which consists of an epoxy resin, a cyanate ester compound, a maleimide compound, and a phosphazene compound.
[9]
Resin composition as described in any one of [1]-[8] whose content of the said polyphenylene ether resin (A) is 50-80 mass parts with respect to 100 mass parts of resin solid content.
[10]
Resin composition as described in any one of [1]-[9] whose content of the said elastomer (B) is 0.5-30 mass parts with respect to 100 mass parts of resin solid content.
[11]
Resin composition as described in any one of [1]-[10] whose content of the said elastomer (C) is 0.5-30 mass parts with respect to 100 mass parts of resin solid content.
[12]
Resin composition as described in any one of [6]-[11] whose content of the said inorganic filler (D) is 10-250 mass parts with respect to 100 mass parts of resin solid content.
[13]
A resin sheet comprising the resin composition according to any one of [1] to [12].
[14]
A build-up material for a printed wiring board comprising the resin sheet according to [13].
[15]
The printed wiring board which has an insulating layer and the conductor layer formed in the surface of this insulating layer, and this insulating layer contains the resin composition as described in any one of [1]-[12].

  A solution comprising the resin composition of the present invention and an organic solvent, that is, a resin sheet obtained by coating a varnish on a metal foil or film is less likely to warp or crack even when pasted to another laminate, and therefore the process is delayed. The printed wiring board obtained from the resin composition has a high multi-layer / high-frequency-compatible printed wiring board material, such as heat resistance after moisture absorption, peel strength, electrical characteristics, dimensional stability, and moldability. It is suitable and has very high industrial practicality.

（Ｒ_２１，Ｒ_２２，Ｒ_２３，Ｒ_２４はそれぞれ水素原子、ハロゲン原子、アルキル基、アルケニル基、アルキニル基又はアルケニルカルボニル基を示す。ｍは１〜１００の整数を示す。） The polyphenylene ether resin (A) used in the present invention has a structure represented by the general formula (5).

(R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkenylcarbonyl group. M represents an integer of 1 to 100.)

  In the general formula (5), the value of m is adjusted so that the number average molecular weight of the polyphenylene ether of the general formula (5) is 1000 or more and 5000 or less. That is, m is not a fixed value but may be a variable within a certain range such that the number average molecular weight of the whole polyphenylene ether contained in the polyphenylene ether resin composition is 1000 or more and 5000 or less. When the number average molecular weight is within this range, fluidity, heat resistance, and electrical characteristics can be obtained.

  In addition, the polyphenylene ether having the number average molecular weight is more compatible with the mixture as the number average molecular weight is smaller. Therefore, viscosity increase due to phase separation hardly occurs, and volatilization of the low molecular weight cross-linking curing agent is suppressed. As a result, the embedding property of the polyphenylene ether resin composition into a via hole or the like can be improved.

  As the alkyl group, alkenyl group, and alkynyl group in the general formula (5), those described below can be used. As the alkenylcarbonyl group, a carbonyl group substituted with the above alkenyl group can be used. Specifically, an acryloyl group or a methacryloyl group can be used.

Here, the general formula (5) is a vinyl group, 2-propylene group (allyl group), methacryloyl group, acryloyl group, 2-propyne group (propargyl group) as the substituents R ₂₁ , R ₂₂ , R ₂₃ , R _24. It may have an unsaturated hydrocarbon-containing group such as By providing the unsaturated hydrocarbon-containing group in the substituents R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ , a more remarkable effect of the cross-linking curing agent can be obtained.

  The polyphenylene ether having the above-mentioned group at the terminal has good interaction with the cross-linking curing agent. Therefore, the heat resistance can be improved only by adding a relatively small amount of the cross-linking curing agent, and a low dielectric constant can be realized.

(Alkyl group)
A saturated hydrocarbon group can be used as the alkyl group in the general formula (5). As said alkyl group, it is good to use a C1-C10 alkyl group. Preferably, an alkyl group having 1 to 6 carbon atoms is used as the alkyl group. More preferably, an alkyl group having 1 to 4 carbon atoms may be used as the alkyl group. More preferably, an alkyl group having 1 or 2 carbon atoms is used as the alkyl group. Specifically, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group can be used as the alkyl group.

(Alkenyl group)
As the alkenyl group in the general formula (5), an unsaturated hydrocarbon group having at least one carbon-carbon double bond in the structure can be used. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms may be used. Preferably, an alkenyl group having 2 to 6 carbon atoms is used as the alkenyl group. More preferably, an alkenyl group having 2 to 4 carbon atoms may be used as the alkenyl group. Specifically, an ethylene group, a 1-propylene group, a 2-propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, or a hexylene group can be used as the alkenyl group.

(Alkynyl group)
As the alkynyl group in the general formula (5), an unsaturated hydrocarbon group having at least one carbon-carbon triple bond in the structure can be used. As said alkynyl group, it is good to use a C2-C10 alkynyl group. Preferably, an alkynyl group having 2 to 6 carbon atoms is used as the alkynyl group. More preferably, an alkynyl group having 2 to 4 carbon atoms may be used as the alkynyl group. Specifically, an ethyn group, a 1-propyne group, a 2-propyne group, an isopropyne group, a butyne group, an isobutyne group, a pentyne group, and a hexyne group can be used as the alkynyl group.

（式中、−（Ｏ−Ｘ−Ｏ）−は、一般式（２）又は一般式（３）で定義される構造からなる。−（Ｙ−Ｏ）−は、一般式（４）
で定義され、１種類の構造又は２種類以上の構造がランダムに配列している。ａ，ｂは、少なくともいずれか一方が０でない、０〜１００の整数を示す。）

（Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_７，Ｒ_８は、同一又は異なってもよく、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であり、Ｒ_４，Ｒ_５，Ｒ_６は、同一又は異なってもよく、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である。）

（Ｒ_９，Ｒ_１０，Ｒ_１１，Ｒ_１２，Ｒ_１３，Ｒ_１４，Ｒ_１５，Ｒ_１６は、同一又は異なってもよく、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であり、−Ａ−は、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基である。）

（Ｒ_１７，Ｒ_１８は、同一又は異なってもよく、炭素数６以下のアルキル基又はフェニル基であり、Ｒ_１９，Ｒ_２０は、同一又は異なってもよく、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である。）
また、本発明の樹脂組成物には、構造の異なる２種類以上のポリフェニレンエーテル樹脂（Ａ）が混合されていてもよい。 A preferred form of the polyphenylene ether resin (A) used in the present invention is represented by the general formula (1).

(In the formula, — (O—X—O) — has a structure defined by General Formula (2) or General Formula (3). — (YO) — represents General Formula (4).
One type of structure or two or more types of structures are randomly arranged. a and b each represents an integer of 0 to 100, at least one of which is not 0. )

(R ₁ , R ₂ , R ₃ , R ₇ , R ₈ may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R ₄ , R ₅ , R ₆ are They may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

(R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

(R ₁₇ and R ₁₈ may be the same or different, and are an alkyl group or a phenyl group having 6 or less carbon atoms, and R ₁₉ and R ₂₀ may be the same or different, and are a hydrogen atom, a halogen atom, or a carbon number. 6 or less alkyl group or phenyl group.)
Moreover, two or more types of polyphenylene ether resins (A) having different structures may be mixed in the resin composition of the present invention.

  Examples of -A- in formula (3) include methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis (1-methylethylidene), 1,3-phenylenebis (1 -Methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, 1-phenylethylidene, and other divalent organic groups are exemplified, but not limited thereto.

（式中、Ｒ_２５，Ｒ_２６，Ｒ_２７，Ｒ_２８は、水素原子又はメチル基である。−Ａ−は、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基である。）

（−Ａ−は、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基である。）

Among the polyphenylene ether resins (A) in the present invention, R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₁₇ , R ₁₈ are alkyl groups having 3 or less carbon atoms, and R ₄ , R ₅ , Compounds in which R ₆ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₉ , R ₂₀ are a hydrogen atom or an alkyl group having 3 or less carbon atoms are particularly preferred. -(OXO)-represented by the general formula (2) or the general formula (3) is the formula (6), the general formula (7), or the general formula (8), and the general formula (4). -(YO)-represented by general formula (9) or general formula (10) or a compound having a structure in which general formula (9) and general formula (10) are randomly arranged is more preferable. .

(In the formula, R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are a hydrogen atom or a methyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. .)

(-A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

  As for the number average molecular weight of polystyrene conversion by GPC method of polyphenylene ether resin (A), the range of 1000-5000 is preferable. When the number average molecular weight is within this range, stickiness is less likely to occur when the film is formed, and the solubility in a solvent is improved.

  The production method of these vinyl compounds is not particularly limited. For example, the terminal phenolic hydroxyl group of a bifunctional phenylene ether oligomer obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound is vinylbenzyl ether. Can be manufactured.

The bifunctional phenylene ether oligomer can be produced, for example, by dissolving a bifunctional phenol compound, a monofunctional phenol compound, and a catalyst in a solvent and then blowing oxygen under heating and stirring. Examples of the bifunctional phenol compound include 2,2 ′, 3,3 ′, 5,5′-hexamethyl- (1,1′-biphenol) -4,4′-diol, 4,4′-methylenebis (2 , 6-dimethylphenol), 4,4′-dihydroxyphenylmethane, 4,4′-dihydroxy-2,2′-diphenylpropane and the like, but are not limited thereto. Examples of the monofunctional phenol include 2,6-dimethylphenol and 2,3,6-trimethylphenol, but are not limited thereto. Examples of the catalyst include copper salts such as CuCl, CuBr, CuI, CuCl ₂ and CuBr ₂ and di-n-butylamine, n-butyldimethylamine, N, N′-di-t-butylethylenediamine, pyridine, N, N, A combination of amines such as N ′, N′-tetramethylethylenediamine, pyridine, piperidine and imidazole can be used, but is not limited thereto. As the solvent, for example, toluene, methanol, methyl ethyl ketone, xylene and the like can be used, but the solvent is not limited thereto.

  As a method for converting the terminal phenolic hydroxyl group of the bifunctional phenylene ether oligomer to vinyl benzyl ether, for example, the bifunctional phenylene ether oligomer and vinyl benzyl chloride are dissolved in a solvent, and after adding and reacting with heating and stirring, It can be produced by solidifying the resin. Vinyl benzyl chlorides include, but are not limited to, o-vinyl benzyl chloride, m-vinyl benzyl chloride, p-vinyl benzyl chloride, and mixtures thereof.

  Examples of the base include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, and the like. An acid can also be used to neutralize excess base after the reaction.

  Examples of the acid used for neutralization include, but are not limited to, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, nitric acid, and the like.

  Examples of the reaction solvent for vinylbenzyl etherification include, but are not limited to, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, methylene chloride, chloroform, and the like. Examples of the solidification method include a method of evaporating a solvent to dryness, a method of reprecipitation by mixing a reaction solution with a poor solvent, and the like, but are not limited thereto.

The content of the polyphenylene ether resin (A) in the resin composition is preferably 30 to 95 parts by mass, particularly preferably 50 to 80 parts by mass with respect to 100 parts by mass of the resin solid content. When it is within this range, the electrical properties and reactivity of the resin composition are improved.
Here, resin solid content shall mean the total mass of each component except the inorganic filler and solvent in a resin composition.

The elastomer (B) used in the present invention is not particularly limited as long as it has an SP value of 9 (cal / cm ³ ) ^1/2 or less, a weight average molecular weight of 80000 or more, and is solid at 25 ° C. Things can be used. The SP value is called a solubility parameter, and is calculated from the square root of heat of vaporization (cal / cm ³ ) ^1/2 required for evaporating 1 cm ³ of liquid. In general, the smaller the value, the lower the polarity, and the closer this value, the higher the affinity between the two components. When the SP value of the elastomer (B) is 9 (cal / cm ³ ) ^1/2 or less, Electrical characteristics suitable for a resin composition used for a printed wiring board for high frequency applications can be obtained.

Examples of the structure of the elastomer (B) include polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, fluorine rubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof. .
Of these, styrene butadiene, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof are preferable from the viewpoint of electrical characteristics.
Examples thereof include styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, and the like. Among these, styrene butadiene styrene is preferable from the viewpoints of compatibility with the polyphenylene ether resin (A) and the solvent and electrical characteristics.
These elastomer components may be used alone or in combination of two or more.

  The weight average molecular weight in terms of polystyrene by the GPC method of the elastomer (B) is 80000 or more. When the weight average molecular weight is in this range, it becomes a solid at 25 ° C. and crack resistance is improved.

  The content of the elastomer (B) in the resin composition is a total of 100 resin solids in the resin composition from the viewpoint of occurrence of cracks, the amount of warpage when pasted to another laminate, heat resistance, and elastic modulus. The range of 0.5-30 mass parts is preferable with respect to mass parts. By being in such a range, a cured product having good properties such as crack resistance, heat resistance, elastic modulus, appearance, and moldability can be obtained. Among these, 1 to 15 parts by mass is particularly preferable.

The elastomer (C) used in the present invention is not particularly limited as long as it has an SP value of 9 (cal / cm ³ ) ^1/2 or less, a weight average molecular weight of 40000 or less, and is liquid at 25 ° C. Can be used. When the SP value is 9 (cal / cm ³ ) ^1/2 or less, electrical characteristics suitable for a resin composition used for a printed wiring board for high frequency applications can be obtained.

Examples of the structure of the elastomer (C) include styrene butadiene rubber, isoprene rubber, butadiene rubber, silicone rubber, ethylene propylene rubber, and fluorine rubber.
Among these, styrene butadiene rubber, butadiene rubber, and isoprene rubber can be suitably used from the viewpoints of compatibility between the polyphenylene ether resin (A) and the elastomer (B) and electrical characteristics. These elastomer components may be used alone or in combination of two or more.

  The weight average molecular weight in terms of polystyrene by the GPC method of the elastomer (C) is 40000 or less. When the weight average molecular weight is in this range, it becomes a liquid at 25 ° C., and the warpage when a film coated on a substrate is bonded to a substrate is small. Therefore, it is suitable as a build-up material for a printed wiring board.

  The content of the elastomer (C) used in the present invention in the resin composition is such that cracks are generated in the resin composition from the viewpoint of generation of cracks, warpage when laminated to other laminates, heat resistance, and elastic modulus. The range of 0.5-30 mass parts is preferable with respect to a total of 100 mass parts of resin solids. By being in such a range, a cured product having good properties such as crack resistance, heat resistance, elastic modulus, appearance, and moldability can be obtained. Among these, 1 to 15 parts by mass is particularly preferable.

  The inorganic filler (D) used in the present invention is applicable as long as it is generally used in laminate applications. Specifically, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, hollow silica, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc , Calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (glass fine powders such as E glass and D glass), hollow glass and the like, and one kind or two or more kinds may be used in appropriate combination. Is possible.

The average particle diameter (D50) of the inorganic filler (D) to be used is not particularly limited, but considering dispersibility, mesoporous silica, spherical fused silica, spherical synthetic silica having an average particle diameter (D50) of 0.1 to 3 μm, A hollow spherical silica etc. are mentioned as a preferable thing.
When the average particle diameter is in the range of 0.1 to 3 μm, the flow characteristics at the time of molding are good, and problems such as breakage at the time of using a small diameter drill bit do not occur.

  Although content in the resin composition of the inorganic filler (D) used for this invention does not have limitation in particular, The range of 10-250 mass parts is preferable with respect to 100 mass parts of resin solid content in a resin composition. A range of 20 to 200 parts by weight is particularly suitable. Since a moldability improves, 150 mass parts or less are especially preferable.

  With respect to the inorganic filler, it is possible to use a silane coupling agent or a wetting and dispersing agent in combination. These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for inorganic surface treatment. Specific examples include γ-aminopropyltriethoxysilane, aminosilanes such as N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ Vinyl silanes such as -methacryloxypropyltrimethoxysilane, cationic silanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, phenylsilanes, etc. It is also possible to use one kind or a combination of two or more kinds as appropriate.

  In the resin composition of the present invention, a phosphazene compound can be used as an epoxy resin, a cyanate ester compound, a maleimide compound, and a flame retardant compound.

As the epoxy resin, generally known epoxy resins having two or more glycidyl groups in one molecule can be used. Bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, xylene novolak type epoxy resin, Bisphenol A novolac type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, biphenyl Type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, alicyclic ester Xy-resin, dicyclopentadiene-type epoxy resin, aralkyl novolac-type epoxy resin, polyol-type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, butadiene epoxidized compound, hydroxyl group-containing silicon resins and Examples include compounds obtained by reaction with epichlorohydrin.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, brominated bisphenol A type epoxy resin Brominated phenol novolac type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin maintain heat resistance and have excellent properties such as water absorption and moisture absorption heat resistance In particular, the biphenyl aralkyl type novolac type epoxy resin is excellent in dielectric properties. These epoxy resins may be used alone or in combination of two or more.

As the cyanate ester compound, generally known cyanate ester compounds having two or more cyanato groups in the molecule can be used. For example, naphthol aralkyl cyanate ester compound, novolak cyanate ester compound, bisphenol A type cyanate ester compound, diallyl bisphenol A type cyanate ester compound, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1 , 3,5-tricyanatobenzene, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2'-bis (4-cyanatophenyl) ethane, 1,3-dicyanatonaphthalene, 1, 4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4, 4'-dicyanatobiphenyl, 2,2'-bis (4-cyanatophenyl) methane, 2,2 ' -Bis (4-cyanatophenyl) propane, 2,2'-bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone and the like.
Among these, naphthol aralkyl type cyanate compound, novolak type cyanate ester compound, bisphenol A type cyanate ester compound and diallyl bisphenol A type cyanate ester compound are excellent in flame retardancy, high curability, and heat of cured product. It is preferable because of its low expansion coefficient.

  The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. For example, 1,1 ′-(methylenedi-4,1-phenylene) bismaleimide, phenylmethanemaleimide, N , N'-m-phenylenebismaleimide, 2,2'-bis- [4- (4-maleimidophenoxy) phenyl] propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane Bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3 -Bis (4-maleimidophenoxy) benzene, N, N'-4,4'-diphenyl ether bismaleimi N, N'-4,4-dicyclohexylmethane bismaleimide, N, N'-ethylene bismaleimide, N, N'-butylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-diphenylcyclohexane Bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 1,6-bismaleimide hexane, 1,11-bismaleimide diethylene glycol, 1,4-bis (4-maleimidophenoxy) ethane, 1,4-bis (4-maleimidophenoxy) propane, 1,4-bis (4-maleimidophenoxy) butane, 1,4-bis (4-maleimidophenoxy) hexane, tris (4-maleimidophenyl) amine, bis ( 4-maleimidophenyl) methylamine, bis (4-maleimidophenyl) Eniruamin, N, N'-4,4'-diphenyl sulfone bismaleimide, N, N'-4,4'-diphenyl sulfide bismaleimides, aniline, polycondensation products of formaldehyde and maleic anhydride. These maleimide compounds can be used alone or in admixture of two or more, but bismaleimide is preferred from the viewpoint of reactivity with polyphenylene ether resin and moisture absorption heat resistance.

（式中、ｎは３〜１５の整数を示し、Ｒ_２９及びＲ_３０は（ａ）炭素数１〜６のアルキル基、アルケニル基、アルコキシ基、アリール基、シアノ基及びヒドロキシル基から選ばれる少なくとも１種の基が置換されていてもよい炭素数６〜２０のアリール基、又は、（ｂ）炭素数１〜６のアルキル基、アルケニル基及びアリール基から選ばれる少なくとも１種の基を示し、同一であっても異なっていてもよいが、少なくとも１つは（ａ）である。これら置換基は、単一でなく混合されて置換しても良い。）
ホスファゼン化合物として具体的には、トリフェノキシトリス（４−メチルフェノキシ）シクロトリホスファゼン、トリフェノキシトリス（４−ヒドロキシフェノキシ）シクロトリホスファゼン、トリフェノキシトリス（４−シアノフェノキシ）シクロトリホスファゼン、フェノキシ基と４−メチルフェノキシ基が混合置換した環状ホスホニトリルの混合物、フェノキシ基と４−ヒドロキシフェノキシ基が混合置換した環状ホスホニトリルの混合物、フェノキシ基と４−シアノフェノキシ基が混合置換した環状ホスホニトリルの混合物が挙げられ、その中でもトリフェノキシトリス（４−メチルフェノキシ）シクロトリホスファゼン、トリフェノキシトリス（４−ヒドロキシフェノキシ）シクロトリホスファゼン、トリフェノキシトリス（４−シアノフェノキシ）シクロトリホスファゼンが好ましく、難燃効果と電気特性の観点から特にトリフェノキシトリス（４−シアノフェノキシ）シクロトリホスファゼンが好ましい。 The phosphazene compound has a cyclic structure represented by the general formula (11).

(In the formula, n represents an integer of 3 to 15, and R ₂₉ and R ₃₀ are (a) at least selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkoxy group, an aryl group, a cyano group, and a hydroxyl group. An aryl group having 6 to 20 carbon atoms which may be substituted by one group, or (b) at least one group selected from an alkyl group, alkenyl group and aryl group having 1 to 6 carbon atoms; (It may be the same or different, but at least one is (a). These substituents may be substituted instead of single.)
Specific examples of the phosphazene compound include triphenoxytris (4-methylphenoxy) cyclotriphosphazene, triphenoxytris (4-hydroxyphenoxy) cyclotriphosphazene, triphenoxytris (4-cyanophenoxy) cyclotriphosphazene, phenoxy group and A mixture of cyclic phosphonitriles substituted with 4-methylphenoxy groups, a mixture of cyclic phosphonitriles mixed with phenoxy groups and 4-hydroxyphenoxy groups, and a mixture of cyclic phosphonitriles substituted with phenoxy groups and 4-cyanophenoxy groups Among them, triphenoxytris (4-methylphenoxy) cyclotriphosphazene, triphenoxytris (4-hydroxyphenoxy) cyclotriphosphazene, triphenoxytris (4 Cyanophenoxy) cyclotriphosphazene are preferred, triphenoxy tris terms of flame retardant effect and the electrical characteristics (4-cyanophenoxy) cyclotriphosphazene are preferred.

A crosslinking type curing agent can be added to the resin composition of the present invention as necessary. The resin composition has the effects of improving the fluidity of the resin composition and improving the peel strength of the copper foil. As the cross-linking type curing agent, those having particularly good compatibility with the polyphenylene ether resin (A) are used.
Specifically, polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl, vinylbenzyl ether compounds synthesized from the reaction of phenol and vinylbenzyl chloride, styrene monomer, synthesized from the reaction of phenol and allyl chloride Examples include allyl ether compounds. Further, trialkenyl isocyanurate is preferable. Particularly, trialkenyl isocyanurate having good compatibility is good. Specifically, triallyl isocyanurate (TAIC) and triallyl cyanurate (TAC) are particularly preferable. This is because a printed wiring board having excellent formability and excellent copper foil peeling strength can be obtained.

  A polymerization inhibitor can also be added to the resin composition of the present invention in order to increase storage stability. Generally known polymerization inhibitors can be used, and examples thereof include quinones such as hydroquinone, methylhydroquinone, p-benzoquinone, chloranil and trimethylquinone, aromatic diols, and di-t-butylhydroxytoluene.

  The resin composition of the present invention includes various polymer compounds such as other thermosetting resins, thermoplastic resins and oligomers thereof, other flame retardant compounds, and additives as long as desired characteristics are not impaired. Combinations such as these are also possible. These are not particularly limited as long as they are generally used. Examples of flame retardant compounds include bromine compounds such as 4,4-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, silicon compounds Etc. Additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, brighteners Etc., and can be used in appropriate combinations as desired.

  The resin composition of the present invention may contain a curing accelerator for adjusting the curing rate of the thermosetting resin as necessary. These are not particularly limited as long as they are generally used as curing accelerators for polyphenylene ether resins (A), epoxy resins, cyanate ester compounds, and maleimide compounds. Specific examples thereof include organic metal salts such as copper, zinc, cobalt and nickel, imidazoles and derivatives thereof, tertiary amines, radical polymerization initiators and the like.

The resin composition of the present invention may contain an organic solvent as necessary. The organic solvent is not particularly limited as long as it dissolves a mixture of polyphenylene ether resin (A), elastomer (B), elastomer (C) and the like. Specific examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; polar solvents such as dimethylacetamide and dimethylformamide; and aromatic hydrocarbon solvents such as toluene and xylene. Used.
The dissolution procedure of each component when preparing a resin composition using an organic solvent is not particularly limited. Each component can be used after being dissolved in the solvent, or can be used after being mixed in the solvent after all the components are mixed. The resin solid content concentration is preferably 50 to 80% by mass, particularly preferably 60 to 70% by mass, from the viewpoint of viscosity at the time of compounding the varnish or coating on the substrate.

  The resin sheet of the present invention is obtained by peeling or etching the substrate after applying the varnish to the substrate and drying it. Examples of the base material include polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, release films obtained by applying a release agent to the surfaces of these films, and organic films such as polyimide films. Film base materials, conductive foils such as copper foil and aluminum foil, and plate-like base materials such as glass plates, SUS plates, and FRP. Examples of the application method include a method in which a solution of a resin composition is applied onto a substrate with a bar coater, a die coater, a doctor blade, a baker applicator, and the like, and the solvent is dried to be in a semi-cured state.

  There are no particular restrictions on the conditions for drying the solvent, but if the temperature is low, the solvent tends to remain in the resin composition, and if the temperature is high, curing of the resin composition proceeds. It is preferable to dry for 1 to 10 minutes. Although the thickness of a resin layer can be adjusted with the density | concentration and application | coating thickness of a resin composition solution, since a solvent will remain easily at the time of application | coating thickening, 1-150 micrometers is preferable.

  The resin composition of the present invention can be used as an insulating layer of a printed wiring board and a semiconductor package material. For example, by using a copper foil as a base material and applying a solution obtained by dissolving the curable resin composition of the present invention in a solvent and drying, a copper foil with a resin is obtained, or a peelable plastic film is used as a base material By using a film with a resin, it can be used as a build-up film, a dry film solder resist, or a die attach film.

The printed wiring board of the present invention is obtained by laminating a prepreg obtained by impregnating a glass woven fabric with another metal foil-clad laminate or a resin composition using the above-described resin sheet and making it semi-cured. . Specifically, a predetermined number of the resin-coated copper foil and copper-clad laminate or prepreg of the present invention are stacked, or the substrate is peeled off by stacking a predetermined number of the resin-coated film and the copper-clad laminate or prepreg. A copper foil is disposed on the substrate, and is laminated and formed at a temperature of 180 to 220 ° C., a heating time of 100 to 300 minutes, a surface pressure of 20 to 40 kg / cm ² , and a copper foil-clad laminate is obtained. Although the thickness of the copper foil to be used is not particularly limited, an electrolytic copper foil of 1 to 35 μm is preferably used. The electrolytic copper foil is not particularly limited as long as it is generally used for laminated board applications, but an electrolytic copper foil having a small mat surface roughness is preferable in consideration of conductor loss in a high frequency region.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Synthesis example 1
(Synthesis of bifunctional phenylene ether oligomer)
CuBr ₂ 3.88 g (17.4 mmol), N, N′-di-t-butylethylenediamine 0.75 g (4.4 mmol) in a 12 L vertical reactor equipped with a stirrer, thermometer, air introduction tube and baffle plate ), 28.04 g (277.6 mmol) of n-butyldimethylamine and 2,600 g of toluene, stirred at a reaction temperature of 40 ° C., and dissolved in 2,300 g of methanol in advance. 3 ', 5,5'-hexamethyl- (1,1'-biphenol) -4,4'-diol 129.3 g (0.48 mol), 2,6-dimethylphenol 233.7 g (1.92 mol), 2 , 3,6-trimethylphenol 64.9 g (0.48 mol), N, N′-di-t-butylethylenediamine 0.51 g (2.9 mmol), n-butyldimethyl A mixed gas of 10.90 g (108.0 mmol) of min was added dropwise over 230 minutes while bubbling at a flow rate of 5.2 L / min with a mixed gas adjusted to an oxygen concentration of 8% by mixing nitrogen and air. Stirring was performed. After completion of the dropwise addition, 1,500 g of water in which 19.89 g (52.3 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated to 50 wt% with an evaporator to obtain 836.5 g of a toluene solution of a bifunctional phenylene ether oligomer. The number average molecular weight of this oligomer was 986, the weight average molecular weight was 1,530, and the hydroxyl group equivalent was 471.
(Synthesis of polyphenylene ether resin)
In a reactor equipped with a stirrer, a thermometer, and a reflux tube, 836.5 g of the toluene solution of the oligomer, 162.6 g of vinylbenzyl chloride (trade name CMS-P; manufactured by Seimi Chemical Co., Ltd.), 1600 g of methylene chloride, benzyl 12.95 g of dimethylamine, 420 g of pure water, and 178.0 g of a 30.5 wt% NaOH aqueous solution were charged, and the mixture was stirred at a reaction temperature of 40 ° C. After stirring for 24 hours, the organic layer was washed with a 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated with an evaporator, dropped into methanol for solidification, and the solid was collected by filtration and vacuum dried to obtain 503.5 g of a polyphenylene ether resin (A). In the polyphenylene ether resin (A), in the general formula (1),-(OXO)-is the general formula (6), and-(YO)-is the general formula (9).
The number average molecular weight was 1187, the weight average molecular weight was 1675, and the vinyl group equivalent was 590 g / vinyl group.

Example 1
70 parts by mass of polyphenylene ether resin (A) (number average molecular weight 1187, vinyl group equivalent is 590 g / vinyl group) obtained in Synthesis Example 1, styrene butadiene styrene (TR2003, manufactured by JSR Corporation, SP value) as elastomer (B) 8.6, 5 parts by weight of weight average molecular weight 100,000, butadiene rubber (LBR-307, SP value 8.3, weight average molecular weight 8000, manufactured by Kuraray Co., Ltd.) as elastomer (C), 5 parts by weight, α-naphthol aralkyl Type cyanate ester resin (SN495CN, manufactured by Mitsubishi Gas Chemical Co., Inc., cyanate equivalent: 244 g / eq.) 3 parts by mass, bismaleimide (BMI-70, manufactured by KAI Kasei Co., Ltd.) 1 part by mass, naphthalene Skeletal modified novolac type epoxy resin (HP-9900, manufactured by DIC Corporation) 3 parts by mass, cyano group Cyclophosphazene (FP-300B, manufactured by Fushimi Pharmaceutical Co., Ltd.) 13 parts by mass, spherical silica (SC2050, average particle size 0.5 μm, manufactured by Admatex) 60 parts by mass, zinc octylate 0.01 parts by mass A varnish was obtained by mixing 0.05 part of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemicals Co., Ltd.). This varnish was applied onto the mat surface of an electrolytic copper foil (3EC-VLP: manufactured by Mitsui Kinzoku Co., Ltd.) having a thickness of 12 μm and dried by heating at 110 ° C. for 3 minutes to obtain a copper foil with resin. Next, the two resin sheets with copper foil were placed so that the resin layers faced each other, and vacuum-pressed for 105 minutes at a pressure of 30 kg / cm ² and a temperature of 210 ° C. to obtain a copper-clad laminate. Table 1 shows the physical properties of the obtained copper-clad laminate. Moreover, this varnish was applied to a polyethylene terephthalate film (Lumirror 25S10, manufactured by Toray Industries, Inc.) having a thickness of 23 μm and dried by heating at 110 ° C. for 3 minutes to obtain a resin-coated film having a resin layer thickness of about 20 μm.

(Example 2)
Example 1 except that 5 parts by mass of isoprene rubber (LIR-30, SP value 8.1, weight average molecular weight 30000, manufactured by Kuraray Co., Ltd.) was used instead of butadiene rubber (LBR-307) as the elastomer (C). In the same manner as above, a copper-clad laminate and a resin-coated film were obtained.

(Example 3)
Example 1 except that 5 parts by mass of butadiene rubber (LBR-305, SP value 8.3, weight average molecular weight 28000, manufactured by Kuraray Co., Ltd.) was used as the elastomer (C) instead of butadiene rubber (LBR-307). In the same manner as above, a copper-clad laminate and a resin-coated film were obtained.

Example 4
Except for using 5 parts by mass of styrene butadiene rubber (L-SBR-820, SP value 8.6, weight average molecular weight 8000, manufactured by Kuraray Co., Ltd.) instead of butadiene rubber (LBR-307) as elastomer (C). In the same manner as in Example 1, a copper-clad laminate and a resin-coated film were obtained.

(Example 5)
72 parts by mass of polyphenylene ether resin (A) (number average molecular weight 1187, vinyl group equivalent is 590 g / vinyl group) obtained in Synthesis Example 1, styrene butadiene styrene (TR2003, manufactured by JSR Corporation, SP value) as elastomer (B) 8.6, 3 parts by weight of weight average molecular weight 100,000), 3 parts by weight of butadiene rubber (LBR-305, SP value 8.3, weight average molecular weight 8000, Kuraray Co., Ltd.) as elastomer (C), α-naphthol aralkyl Type cyanate ester resin (SN495CN, manufactured by Mitsubishi Gas Chemical Co., Inc., cyanate equivalent: 244 g / eq.) 3 parts by mass, bismaleimide (BMI-70, manufactured by KAI Kasei Co., Ltd.) 1 part by mass, naphthalene Skeletal modified novolac type epoxy resin (HP-9900, manufactured by DIC Corporation) 3 parts by mass, cyano group Cyclophosphazene (FP-300B, manufactured by Fushimi Pharmaceutical Co., Ltd.) 15 parts by mass, spherical silica (SC2050, average particle size 0.5 μm, manufactured by Admatechs Co., Ltd.) 60 parts by mass, zinc octylate 0.01 parts by mass A varnish was obtained by mixing 0.05 part of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemicals Co., Ltd.). Otherwise in the same manner as in Example 1, a copper-clad laminate and a resin-coated film were obtained.

(Comparative Example 1)
76 parts by mass of the polyphenylene ether resin (A) obtained in Synthesis Example 1, 3 parts by mass of an α-naphthol aralkyl cyanate ester resin (SN495CN, cyanate equivalent: 244 g / eq.), 1 part by mass of bismaleimide (BMI-70) Parts, 3 parts by mass of a novolak-type epoxy resin (HP-9900) modified with a naphthalene skeleton, 17 parts by mass of cyclophosphazene (FP-300B) having a cyano group, 70 parts by mass of spherical silica (SC2050, average particle size 0.5 μm) Then, 0.01 parts by mass of zinc octylate and 0.05 part of 2-ethyl-4-methylimidazole (2E4MZ) were mixed to obtain a varnish. Otherwise in the same manner as in Example 1, a copper-clad laminate and a resin-coated film were obtained.

(Comparative Example 2)
70 parts by mass of the polyphenylene ether resin (A) obtained in Synthesis Example 1, acrylonitrile butadiene rubber (N220S, SP value 10.4, weight average molecular weight 300000, manufactured by JSR Corporation) as an elastomer (B), 10 parts by mass, α- 3 parts by mass of naphthol aralkyl-type cyanate ester resin (SN495CN), 1 part by mass of bismaleimide (BMI-70), 3 parts by mass of novolak type epoxy resin (HP-9900) modified with naphthalene skeleton, cyclophosphazene having a cyano group (FP-300B) 13 parts by mass, spherical silica (SC2050, average particle size 0.5 μm) 60 parts by mass, zinc octylate 0.01 parts by mass, 2-ethyl-4-methylimidazole 0.05 parts (2E4MZ) The varnish was obtained by mixing. Otherwise in the same manner as in Example 1, a copper-clad laminate and a resin-coated film were obtained.

(Comparative Example 3)
70 parts by mass of polyphenylene ether resin (A) obtained in Synthesis Example 1, 10 parts by mass of styrene butadiene styrene (TR2003) as elastomer (B), 3 parts by mass of α-naphthol aralkyl type cyanate ester resin (SN495CN), bismaleimide (BMI-70) 1 part by mass, naphthalene skeleton-modified novolak epoxy resin (HP-9900) 3 parts by mass, cyclophosphazene (FP-300B) having a cyano group 13 parts by mass, spherical silica (SC2050, average particle size) 0.5 μm) 60 parts by mass, 0.01 parts by mass of zinc octylate, and 0.05 parts of 2-ethyl-4-methylimidazole (2E4MZ) were mixed to obtain a varnish. Otherwise in the same manner as in Example 1, a copper-clad laminate and a resin-coated film were obtained.

(Comparative Example 4)
70 parts by mass of the polyphenylene ether resin (A) obtained in Synthesis Example 1, 10 parts by mass of butadiene rubber (LBR-307) as the elastomer (C), an α-naphthol aralkyl type cyanate ester resin (SN495CN, cyanate equivalent: 244 g / eq.) 3 parts by mass, bismaleimide (BMI-70) 1 part by mass, naphthalene skeleton-modified novolac type epoxy resin (HP-9900) 3 parts by mass, cyclophosphazene having a cyano group (FP-300B) 13 parts by mass Then, 60 parts by mass of spherical silica (SC2050, average particle size 0.5 μm), 0.01 parts by mass of zinc octylate, 0.05 parts of 2-ethyl-4-methylimidazole (2E4MZ) were mixed to obtain a varnish. Otherwise in the same manner as in Example 1, a copper-clad laminate and a resin-coated film were obtained.

(Comparative Example 5)
70 parts by mass of the polyphenylene ether resin (A) obtained in Synthesis Example 1, 10 parts by mass of butadiene rubber (LBR-305) as the elastomer (C), α-naphthol aralkyl type cyanate ester resin (SN495CN, cyanate equivalent: 244 g / eq.) 3 parts by mass, bismaleimide (BMI-70) 1 part by mass, naphthalene skeleton-modified novolac type epoxy resin (HP-9900) 3 parts by mass, cyclophosphazene having a cyano group (FP-300B) 13 parts by mass Then, 60 parts by mass of spherical silica (SC2050, average particle size 0.5 μm), 0.01 parts by mass of zinc octylate, 0.05 parts of 2-ethyl-4-methylimidazole (2E4MZ) were mixed to obtain a varnish. Otherwise in the same manner as in Example 1, a copper-clad laminate and a resin-coated film were obtained.

(Measuring method)
1) The number average molecular weight and the weight average molecular weight were determined by a gel permeation chromatography (GPC) method. Data processing was performed from the GPC curve and molecular weight calibration curve of the sample. The molecular weight calibration curve was obtained by approximating the relationship between the molecular weight of standard polystyrene and the elution time to the following equation. Log M = A ₀ X ³ + A ₁ X ² + A ₂ X + A ₃ + A ₄ / X ² (where M: molecular weight, X: elution time −19 (min), A: coefficient)
2) The vinyl group equivalent was determined from the absorption intensity at 910 cm ⁻¹ by conducting IR analysis (liquid cell method: cell length = 1 mm) using 1-octene as a standard substance and carbon disulfide as a solvent.
3) The cyanate equivalent is the infrared absorption spectrum, after confirming the absorption of the cyanate ester group in the vicinity of 2264 cm ⁻¹ , the structure is identified by 13C-NMR and 1H-NMR, and the conversion rate from the OH group to the OCN group Measure. Calculated from the OH equivalent of the naphthol aralkyl resin used for evaluation based on the conversion rate.
4) Copper foil peel strength Using the obtained copper-clad laminate, the peel strength of the copper foil was measured according to JIS C6481.
5) Dielectric constant, dielectric loss tangent Using the test piece from which the copper foil of the obtained copper-clad laminate was removed, the dielectric constant and dielectric loss tangent of 2 GHz were measured by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). .
6) Crack resistance The obtained resin-coated film was coated with a copper-clad laminate (CCL-HL832NS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) from which a copper foil of 345 mm × 260 mm × thickness 0.1 mm was removed. After evacuating for 30 seconds using Morton, lamination was performed at a pressure of 10 kgf / cm 2 and a temperature of 90 ° C. for 30 seconds, and further at a pressure of 20 kgf / cm 2 and a temperature of 90 ° C. for 60 seconds. Thereafter, the substrate was peeled off and wound around a circular tube having a specific diameter, and the presence or absence of cracks entering the resin was observed with an optical microscope. Table 1 shows the diameters of the cracked circular tubes. A value of less than 40 mm was evaluated as ◯ and a value of 40 mm or more was evaluated as ×.
7) Warpage amount The obtained resin-coated film was laminated in the same manner as described above, and immediately after that, the average value of the lifted amount at the four corners of the test piece was measured and listed in Table 1. Less than 10 mm was marked with ◯, and 10 mm or more was marked with ×.

Claims (15)

Polyphenylene ether resin (A), SP value of 9 (cal / cm ³ ) ^½ or less, weight average molecular weight of 80000 or more, and elastomer (B) that is solid at 25 ° C. and SP value of 9 (cal / cm ³ ) A resin composition containing an elastomer (C) that is ^1/2 or less, a weight average molecular weight of 40000 or less, and is liquid at 25 ° C.   The resin composition according to claim 1, wherein the polyphenylene ether resin (A) has a weight average molecular weight of 1,000 to 5,000. The resin composition according to claim 1 or 2, wherein the polyphenylene ether resin (A) is represented by the general formula (1).

(In the formula, — (O—X—O) — has a structure defined by General Formula (2) or General Formula (3). — (YO) — represents General Formula (4).
One type of structure or two or more types of structures are randomly arranged. a and b each represents an integer of 0 to 100, at least one of which is not 0. )

(R ₁ , R ₂ , R ₃ , R ₇ and R ₈ may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. R ₄ , R ₅ and R ₆ are They may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

(R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

(R ₁₇ and R ₁₈ may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ₁₉ and R ₂₀ may be the same or different, and are a hydrogen atom or a halogen atom. And an alkyl group having 6 or less carbon atoms or a phenyl group.)   The elastomer (B) is selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, fluorine rubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof. The resin composition according to any one of claims 1 to 3, wherein the resin composition is at least one kind.   The elastomer (C) is at least one selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, fluorine rubber, and silicone rubber. The resin composition as described.   Furthermore, the resin composition as described in any one of Claims 1-5 containing an inorganic filler (D).   The resin composition according to claim 6, wherein the inorganic filler (D) is at least one selected from the group consisting of natural silica, fused silica, synthetic silica, amorphous silica, hollow silica, and short glass fibers.   Furthermore, the resin composition as described in any one of Claims 1-7 containing at least 1 type selected from the group which consists of an epoxy resin, a cyanate ester compound, a maleimide compound, and a phosphazene compound.   The resin composition according to any one of claims 1 to 8, wherein the content of the polyphenylene ether resin (A) is 30 to 95 parts by mass with respect to 100 parts by mass of the resin solid content.   The resin composition as described in any one of Claims 1-9 whose content of the said elastomer (B) is 0.5-30 mass parts with respect to 100 mass parts of resin solid content.   The resin composition according to any one of claims 1 to 10, wherein the content of the elastomer (C) is 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin solid content.   The resin composition according to any one of claims 6 to 11, wherein the content of the inorganic filler (D) is 10 to 250 parts by mass with respect to 100 parts by mass of the resin solid content.   The resin sheet containing the resin composition as described in any one of Claims 1-12.   A build-up material for a printed wiring board comprising the resin sheet according to claim 13.   The printed wiring board which has an insulating layer and the conductor layer formed in the surface of this insulating layer, and this insulating layer contains the resin composition as described in any one of Claims 1-12.