JPWO2020017412A1 - Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board - Google Patents

Abstract

Resin compositions capable of achieving high peel strength and low melt viscosity while maintaining low dielectric constant (Dk) and low dielectric loss tangent (Df), as well as prepregs, metal foil-clad laminates, resin sheets and printed wiring boards. Provided. It has two or more aromatic ring structures in one molecule, a compound (A) having a group represented by −Si (OR01) m (R02) 3-m, a resin having an aromatic ring structure, and an aromatic ring structure. A resin composition containing at least one elastomer (B) and a filler (C), wherein R01 and R02 are each independently a hydrocarbon group, and m is an integer of 1 to 3.

Description

The present invention relates to resin compositions, prepregs, metal foil-clad laminates, resin sheets and printed wiring boards.

In recent years, the high integration and miniaturization of semiconductors used in electronic devices, communication devices, personal computers, etc. are accelerating. Along with this, various characteristics required for a laminated board for a semiconductor package (for example, a metal foil-covered laminated board) used for a printed wiring board are becoming more and more severe. Examples of the required characteristics include low dielectric constant, low dielectric loss tangent property, low thermal expansion property, and heat resistance. In particular, an insulator material having a large dielectric constant and a dielectric loss tangent requires a material having a small dielectric constant and a dielectric loss tangent because the electric signal is attenuated and the reliability is impaired.

In order to obtain a printed wiring board with improved various characteristics, a material used as a material for the printed wiring board is being studied. For example, Patent Documents 1 and 2 disclose vinyl compounds having a low dielectric constant and a low dielectric loss tangent.

（式中、Ｘは、ポリフェニレンエーテル構造を含むｎ価の有機基を表し、Ｒ^１は、互いに独立して、非置換もしくは置換の炭素原子数１〜１０のアルキル基、または非置換もしくは置換の炭素原子数６〜１０のアリール基を表し、Ｒ^２は、互いに独立して、非置換もしくは置換の炭素原子数１〜１０のアルキル基、または非置換もしくは置換の炭素原子数６〜１０のアリール基を表し、Ａ^１は、単結合、またはヘテロ原子を含む２価の連結基を表し、Ａ^２は、ヘテロ原子を含まない、非置換もしくは置換の炭素原子数１〜２０の２価炭化水素基を表し、ｍは、１〜３の数であり、ｎは、１〜１０の数である。）On the other hand, in Patent Document 3, an organosilicon compound (silane coupling agent) that gives a cured product capable of exhibiting good copper foil adhesion and dielectric properties such as dielectric constant and dielectric loss tangent is represented by the average structural formula (i). Organosilicon compounds are disclosed.

(In the formula, X represents an n-valent organic group containing a polyphenylene ether structure, and R ¹ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted alkyl group. Representing an aryl group having 6 to 10 carbon atoms, R ² is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms independently of each other. ^{A 1} represents a single bond or a divalent linking group containing ^{a heteroatom, and A 2} is a heteroatom-free, unsubstituted or substituted divalent hydrocarbon having 1 to 20 carbon atoms. Representing a group, m is a number from 1 to 3 and n is a number from 1 to 10.)

Japanese Unexamined Patent Publication No. 2004-59644 Japanese Unexamined Patent Publication No. 2006-83364 Japanese Unexamined Patent Publication No. 2018-16709

As described above, various materials suitable for electronic material applications such as printed wiring boards have been studied. However, with the recent technological development, there is a further demand for new materials. In particular, there is a demand for materials that can achieve high peel strength and excellent manufacturability, i.e. low melt viscosity, while maintaining low dielectric constant (Dk) and low dielectric loss tangent (Df).
An object of the present invention is to solve such a problem, and a resin composition capable of achieving high peel strength and low melt viscosity while maintaining low dielectric constant (Dk) and low dielectric loss tangent (Df). , And a prepreg, a metal foil-clad laminate, a resin sheet and a printed wiring board.

式（Ｘ）中、Ｘは、ポリフェニレンエーテル構造を含むｎ価の有機基を表し、Ｒ^１およびＲ^２は、それぞれ独立に、炭素原子数１〜１０のアルキル基、または、炭素原子数６〜１０のアリール基を表し、Ａ^１は、単結合またはヘテロ原子を含む２価の連結基を表し、Ａ^２は、単結合または２価の連結基を表し、ｍは１〜３の整数であり、ｎは１〜１０の数である。
＜５＞前記化合物（Ａ）が、式（Ｙ）で表される化合物を含む、＜１＞に記載の樹脂組成物；
式（Ｙ）

式（Ｙ）中、Ａ^２は、単結合または２価の連結基であり、Ｒ^１およびＲ^２は、それぞれ独立に、炭素原子数１〜１０のアルキル基、または、炭素原子数６〜１０のアリール基を表し、ｍは、１〜３の整数であり、ｎは１〜１０の数である。
＜６＞前記化合物（Ａ）の重量平均分子量が１０００以上である、＜１＞〜＜５＞のいずれか１つに記載の樹脂組成物。
＜７＞前記芳香環構造を有するエラストマーが、スチレン系エラストマーを含む、＜１＞〜＜６＞のいずれか１つに記載の樹脂組成物。
＜８＞前記芳香環構造を有する樹脂が、ポリフェニレンエーテル化合物を含む、＜１＞〜＜７＞のいずれか１つに記載の樹脂組成物。
＜９＞前記ポリフェニレンエーテル化合物が、下記式（１）で表されるポリフェニレンエーテル化合物を含む、＜８＞に記載の樹脂組成物；

式（１）において、Ｘは芳香族基を表し、−（Ｙ−О）−ｎ_２はポリフェニレンエーテル構造を表し、Ｒ^１、Ｒ^２、および、Ｒ^３は、それぞれ独立して、水素原子、アルキル基、アルケニル基またはアルキニル基を表し、ｎ_１は１〜６の整数を表し、ｎ_２は１〜１００の整数を表し、ｎ_３は１〜４の整数を表す。
＜１０＞前記ポリフェニレンエーテル化合物の数平均分子量が１０００以上７０００以下である、＜８＞または＜９＞に記載の樹脂組成物。
＜１１＞さらに、マレイミド化合物を含有する、＜１＞〜＜１０＞のいずれか１つに記載の樹脂組成物。
＜１２＞前記マレイミド化合物が、式（２Ｍ）で表される化合物、式（３Ｍ）で表される化合物、および式（４Ｍ）で表される化合物からなる群より選ばれる少なくとも１種を含む、＜１１＞に記載の樹脂組成物；

式（２Ｍ）中、Ｒ^４はそれぞれ独立に、水素原子またはメチル基を表し、ｎ_４は１以上の整数を表す；

式（３Ｍ）中、Ｒ^５はそれぞれ独立に、水素原子、炭素原子数１〜８のアルキル基またはフェニル基を表し、ｎ_５は１以上１０以下の整数を表す；

式（４Ｍ）中、Ｒ^６はそれぞれ独立に水素原子、メチル基またはエチル基を表し、Ｒ^７はそれぞれ独立に水素原子またはメチル基を表す。
＜１３＞前記マレイミド化合物が、式（３Ｍ）で表される化合物を含む、＜１２＞に記載の樹脂組成物。
＜１４＞さらに、シアン酸エステル化合物を含む、＜１＞〜＜１３＞のいずれか１つに記載の樹脂組成物。
＜１５＞さらに、難燃剤を含む、＜１＞〜＜１４＞のいずれか１つに記載の樹脂組成物。
＜１６＞前記化合物（Ａ）の含有量が、樹脂成分１００質量部に対し、１〜１０質量部である、＜１＞〜＜１５＞のいずれか１つに記載の樹脂組成物。
＜１７＞、前記芳香環構造を有する樹脂および芳香環構造を有するエラストマーの合計含有量が、樹脂成分１００質量部に対し、１〜５０質量部である、＜１＞〜＜１６＞のいずれか１つに記載の樹脂組成物。
＜１８＞前記充填材（Ｃ）の含有量が、樹脂成分１００質量部に対し、５０〜３００質量部である、＜１＞〜＜１７＞のいずれか１つに記載の樹脂組成物。
＜１９＞基材と、＜１＞〜＜１８＞のいずれか１つに記載の樹脂組成物から形成されたプリプレグ。
＜２０＞少なくとも１枚の＜１９＞に記載のプリプレグと、前記プリプレグの片面または両面に配置された金属箔とを含む、金属箔張積層板。
＜２１＞支持体と、前記支持体の表面に配置された＜１＞〜＜１８＞のいずれか１つに記載の樹脂組成物から形成された層を含む樹脂シート。
＜２２＞絶縁層と、前記絶縁層の表面に配置された導体層とを含むプリント配線板であって、前記絶縁層が、＜１＞〜＜１８＞のいずれか１つに記載の樹脂組成物から形成された層および＜１９＞に記載のプリプレグから形成された層の少なくとも一方を含むプリント配線板。As a result of studies by the present inventor based on the above problems, in a resin composition containing a resin or an elastomer and a filler, a resin or an elastomer having an aromatic ring structure is used, and further, within one molecule. It has been found that the above-mentioned problems can be solved by blending the compound (A) having two or more aromatic ring structures with the compound (A). Specifically, the above problems were solved by the following means <1>, preferably by <2> to <22>.
<1> A compound (A) having two or more aromatic ring structures in one molecule, ^{a group represented by −Si (OR 01} ) _m (R ⁰² ) _3-m , a resin having an aromatic ring structure, and a resin having an aromatic ring structure. It contains at least one elastomer (B) having an aromatic ring structure and a filler (C), and R ^{01 and R 02} are each independently a hydrocarbon group, and m is an integer of 1 to 3. There is a resin composition.
<2> The resin composition according to <1>, wherein the compound (A) contains a repeating unit containing an aromatic ring structure.
<3> The resin composition according to <2>, wherein the repeating unit containing the aromatic ring structure of the compound (A) is polyphenylene ether.
<4> The resin composition according to <1>, wherein the compound (A) contains a compound represented by the formula (X);
Equation (X)

In the formula (X), X represents an n-valent organic group containing a polyphenylene ether structure, and R ¹ and R ² are independently alkyl groups having 1 to 10 carbon atoms or 6 to 6 carbon atoms, respectively. Represents an aryl group of 10, A ¹ represents a divalent linking group containing a single bond or a heteroatom, A ² represents a single bond or a divalent linking group, and m is an integer of 1-3. , N is a number from 1 to 10.
<5> The resin composition according to <1>, wherein the compound (A) contains a compound represented by the formula (Y);
Equation (Y)

In the formula (Y), A ² is a single bond or a divalent linking group, and R ¹ and R ² are independently alkyl groups having 1 to 10 carbon atoms or 6 to 10 carbon atoms. Represents the aryl group of, m is an integer of 1 to 3, and n is a number of 1 to 10.
<6> The resin composition according to any one of <1> to <5>, wherein the weight average molecular weight of the compound (A) is 1000 or more.
<7> The resin composition according to any one of <1> to <6>, wherein the elastomer having an aromatic ring structure contains a styrene-based elastomer.
<8> The resin composition according to any one of <1> to <7>, wherein the resin having an aromatic ring structure contains a polyphenylene ether compound.
<9> The resin composition according to <8>, wherein the polyphenylene ether compound contains a polyphenylene ether compound represented by the following formula (1);

In formula (1), X represents an aromatic group, − (Y—О) −n ₂ represents a polyphenylene ether structure, and R ¹ , R ² , and R ³ are independent hydrogen atoms, respectively. It represents an alkyl group, an alkenyl group or an alkynyl group, n ₁ represents an integer of 1 to 6, n ₂ represents an integer of 1 to 100, and n ₃ represents an integer of 1 to 4.
<10> The resin composition according to <8> or <9>, wherein the polyphenylene ether compound has a number average molecular weight of 1000 or more and 7000 or less.
<11> The resin composition according to any one of <1> to <10>, which further contains a maleimide compound.
<12> The maleimide compound comprises at least one selected from the group consisting of a compound represented by the formula (2M), a compound represented by the formula (3M), and a compound represented by the formula (4M). The resin composition according to <11>;

In formula (2M), R ⁴ independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer greater than or equal to 1.

In formula (3M), R ⁵ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer of 1 or more and 10 or less;

In formula (4M), R ⁶ independently represents a hydrogen atom, a methyl group or an ethyl group, and R ⁷ independently represents a hydrogen atom or a methyl group.
<13> The resin composition according to <12>, wherein the maleimide compound contains a compound represented by the formula (3M).
<14> The resin composition according to any one of <1> to <13>, further comprising a cyanic acid ester compound.
<15> The resin composition according to any one of <1> to <14>, further containing a flame retardant.
<16> The resin composition according to any one of <1> to <15>, wherein the content of the compound (A) is 1 to 10 parts by mass with respect to 100 parts by mass of the resin component.
<17>, any one of <1> to <16>, wherein the total content of the resin having an aromatic ring structure and the elastomer having an aromatic ring structure is 1 to 50 parts by mass with respect to 100 parts by mass of the resin component. The resin composition according to one.
<18> The resin composition according to any one of <1> to <17>, wherein the content of the filler (C) is 50 to 300 parts by mass with respect to 100 parts by mass of the resin component.
<19> A prepreg formed from a base material and the resin composition according to any one of <1> to <18>.
<20> A metal leaf-clad laminate comprising at least one prepreg according to <19> and metal foils arranged on one or both sides of the prepreg.
<21> A resin sheet containing a support and a layer formed from the resin composition according to any one of <1> to <18> arranged on the surface of the support.
<22> A printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer, wherein the insulating layer has the resin composition according to any one of <1> to <18>. A printed wiring board containing at least one of a layer formed from an object and a layer formed from the prepreg according to <19>.

According to the present invention, a resin composition capable of achieving high peel strength and low melt viscosity while maintaining a low dielectric constant (Dk) and a low dielectric loss tangent (Df), as well as a prepreg, a metal foil-clad laminate, a resin sheet and the like. It has become possible to provide printed wiring boards.

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.

The resin composition of the present embodiment has a compound (A) having two or more aromatic ring structures in one molecule and ^{a group represented by −Si (OR 01} ) _m (R ⁰² ) _{3-m (hereinafter,} It contains "compound (A)"), at least one resin having an aromatic ring structure and an elastomer having an aromatic ring structure (B), and a filler (C), and contains the above-mentioned R ⁰¹ and R ^02. Are independently hydrocarbon groups, and m is an integer of 1 to 3. With such a configuration, high peel strength can be achieved while maintaining a low dielectric constant (Dk) and a low dielectric loss tangent (Df). Further, since a low melt viscosity can be achieved, a resin composition having excellent manufacturability can be obtained.
The reason for this is presumed to be as follows.
^{That is, the group represented by −Si (OR 01} ) _m (R ⁰² ) _3-m contained in the compound (A) is bonded to the filler (C). Further, two or more aromatic ring structures of the compound (A) interact with a resin having an aromatic ring structure and / or an elastomer having an aromatic ring structure in a π-π system. It is considered that these actions strengthen the bond between the resin and / or the elastomer and the filler (C), thereby enhancing the peel strength. Then, since the aromatic ring structure of the compound (A) is effectively compatible with the resin having the aromatic ring structure and / or the elastomer having the aromatic ring structure, the dispersibility of the filler (C) in the resin composition is increased. It is considered that the melt viscosity is improved and the melt viscosity is lowered.
Further, when the resin composition is in the state of varnish, it is possible to effectively suppress the agglomeration of the components. Further, when the resin composition is layered, it is possible to prevent layer separation within the layer from occurring. That is, it becomes possible to obtain a resin composition having excellent manufacturability.
Hereinafter, the present invention will be described in detail.

<(A) A compound having two or more aromatic ring structures in one molecule and a group represented by ^{−Si (OR 01} ) _m (R ⁰² ) _3-m>
The resin composition according to this embodiment is a compound having two or more aromatic ring structures in one molecule and ^{a group represented by −Si (OR 01} ) _m (R ⁰² ) _3-m (Compound (A)). )including. In compound (A), the ^{group represented by −Si (OR 01} ) _m (R ⁰² ) _3-m is bonded to the filler (C), and the aromatic ring structure of compound (A) has an aromatic ring structure. It is compatible with resins and / or elastomers with an aromatic ring structure. That is, compound (A) acts like a silane coupling agent. As a result, high peel strength and low melt viscosity can be achieved while maintaining low dielectric constant (Dk) and low dielectric loss tangent (Df).
The compound (A) preferably contains a repeating unit containing an aromatic ring structure, more preferably the repeating unit containing the aromatic ring structure is a polyphenylene ether, and further preferably the compound (A) contains a polyphenylene ether. .. When the compound (A) contains a repeating unit containing an aromatic ring structure, the compatibility with the resin having an aromatic ring structure and the elastomer having an aromatic ring structure is further improved. In particular, when the resin having an aromatic ring structure contains a polyphenylene ether compound, it is preferable that the compound (A) contains a polyphenylene ether.

-Si (OR ⁰¹ ) _m (R ⁰² ) In the group represented by _3-m ^{, R 01} and R ⁰² are each independently a hydrocarbon group, and m is an integer of 1 to 3. It is preferable that R ⁰¹ and R ⁰² are independently alkyl groups or aryl groups, respectively, and the same range as ^{R 1} and R ^{2 in the formula (X) described later is more preferable.} m is preferably 2 to 3, and more preferably 3.
Compound (A) ^{may have only one group represented by −Si (OR 01} ) _m (R ⁰² ) _3-m in one molecule, or may have two or more groups. It is preferable to have 1 to 10, it is more preferable to have 1 to 5, and it is further preferable to have 1 or 2. The compound (A) may contain only one type of group represented by ^{−Si (OR 01} ) _m (R ⁰² ) _{3-m in one molecule, or may contain two or more types.}

式（Ｘ）中、Ｘは、ポリフェニレンエーテル構造を含むｎ価の有機基を表し、Ｒ^１およびＲ^２は、それぞれ独立に、炭素原子数１〜１０のアルキル基、または、炭素原子数６〜１０のアリール基を表し、Ａ^１は、単結合またはヘテロ原子を含む２価の連結基を表し、Ａ^２は、単結合または２価の連結基を表し、ｍは１〜３の整数であり、ｎは１〜１０の数である。The compound (A) preferably contains a compound represented by the formula (X).
Equation (X)

In the formula (X), X represents an n-valent organic group containing a polyphenylene ether structure, and R ¹ and R ² are independently alkyl groups having 1 to 10 carbon atoms or 6 to 6 carbon atoms, respectively. Represents an aryl group of 10, A ¹ represents a divalent linking group containing a single bond or a heteroatom, A ² represents a single bond or a divalent linking group, and m is an integer of 1-3. , N is a number from 1 to 10.

In formula (X), X represents an n-valent organic group containing a polyphenylene ether structure, and may have a linear structure, a branched structure, or a crosslinked structure therein. In the present invention, a linear structure is preferable.
The X is not particularly limited as long as it is an n-valent organic group containing a polyphenylene ether structure, but in consideration of improving metal foil adhesion and low dielectric properties, the following is particularly limited in the present invention. The groups represented by the formulas (X1) to (X3) are suitable.

式（Ｘ１）〜（Ｘ３）中、Ｒ³およびＲ⁴は、それぞれ独立に、炭素原子数１〜１２のアルキル基、炭素原子数１〜１２のアルコキシ基、または、ハロゲン原子である。ａおよびｂは、それぞれ独立して１〜１００の数である。Ｚは、式（ＸＸ）で表される連結基を表す。

In formulas (X1) to (X3), R ³ and R ⁴ are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. a and b are independently numbers 1 to 100, respectively. Z represents a linking group represented by the formula (XX).

Wherein (XX), R ⁴ represents the same meaning as ^{R 4} in the formula (X1) ~ (X3), L represents a linking group selected from the following formulas.

R ⁵ independently represents an alkyl group having a hydrogen atom or 1 to 12 carbon atoms, R ⁶ independently represents an alkyl group having 1 to 12 carbon atoms, and k represents 1 to 1. It represents an integer of 12, and j represents a number from 1 to 1,000.

In the formulas (X1) to (X3), the alkyl groups having 1 to 12 carbon atoms as ^{R 3} and R ^{4 may be linear, branched or cyclic.} Specific examples of R ³ and R ⁴ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group and n-hexyl. Linear or branched alkyl groups such as groups, n-heptyl groups, n-octyl groups, n-nonyl groups, n-decyl groups, n-undecyl groups, n-dodecyl groups, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, Cyclic alkyl groups such as cyclohexyl group, cycloheptyl group and cyclooctyl group can be mentioned. These groups may be substituted with substituents.
In the formulas (X1) to (X3), the alkoxy group having 1 to 12 carbon atoms as ^{R 3} and R ^{4 may be linear, branched or cyclic.} Specific examples of R ³ and R ⁴ include methoxy group, ethoxy group, propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group and n-hexyloxy. A linear or branched alkoxy group such as a group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclopentyloxy group, cyclohexyl. Cyclic alkyloxy groups such as an oxy group, a cycloheptyloxy group and a cyclooctyloxy group can be mentioned. These groups may be substituted with substituents.
In formulas (X1) to (X3), ^{some or all of the hydrogen atoms of R 3} and R ⁴ may be substituted with halogen atoms such as F, Cl and Br, a mercapto group, a cyano group and the like. Specific examples of such a group include 3-chloropropyl, 3,3,3-trifluoropropyl, 3-mercaptopropyl, 2-cyanoethyl group and the like.
In the formulas (X1) to (X3), ^{examples of the halogen atom as R 3} and R ⁴ include F, Cl, Br and the like.
Among these, ^{as R 3} , from the viewpoint of ease of production, a methyl group and a methoxy group are preferable, and a methyl group is more preferable. Further, as R ⁴ , a hydrogen atom, a methyl group, and a methoxy group are preferable, and a hydrogen atom is more preferable.

In the formulas (X1) to (X3), a and b are independently numbers 1 to 100, but 3 to 50 are preferable from the viewpoint of the metal foil adhesion and the dielectric property of the compound (A). 5 to 20 are more preferable. By setting a and b to 1 or more, the adhesion to the metal foil tends to be further improved, and the dielectric property tends to be improved. Further, by setting a and b to 100 or less, the compatibility of the compound (A) with the resin component tends to be further improved.

In the formula (X), R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. Is preferable.
In the formula (X), ^{the alkyl group having 1 to 10 carbon atoms of R 1} and R ² may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group and n-propyl. Group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl Examples thereof include linear or branched alkyl groups such as groups, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclic alkyl groups such as cyclooctyl groups.
^{Specific examples of the aryl group having 6 to 10 carbon atoms of R 1} and R ^{2 in} the formula (X) include a phenyl group, an α-naphthyl group, a β-naphthyl group and the like.
In formula (X), ^{some or all of the hydrogen atoms of R 1} and R ² may be substituted with halogen atoms such as F, Cl and Br, cyano groups and the like, and as a specific example of such groups. Can exemplify 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group, tolyl group, xsilyl group and the like.

In the formula (X), as R ¹ , from the viewpoint of hydrolyzability, a linear alkyl group having 1 to 5 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is even more preferable.
In the formula (X), as R ² , a linear alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is even more preferable.

In the formula (X), m is an integer of 1 to 3, preferably 2 to 3 from the viewpoint of reactivity, and more preferably 3.
In the formula (X), n is a number of 1 to 10, preferably 1 to 5, and more preferably 1 to 2. n is an average number. By setting n to 1 or more, the reactivity can be further improved, and by setting n to 10 or less, the storage stability can be improved and cracks can be less likely to occur when the resin composition is cured.

In formula (X), A ¹ represents a divalent linking group containing a single bond or a heteroatom.
^{Specific examples of the divalent linking group containing the heteroatom represented by A 1} in the formula (X) include an ether bond (-O-), a thioether bond (-S-), an amino bond (-NH-), and a sulfonyl. Bond (-S (= O) _2- ), phosphinyl bond (-P (= O) OH-), oxo bond (-C (= O)-), thiooxo bond (-C (= S)-), ester Bond (-C (= O) O-), thioester bond (-C (= O) S-), thionoester bond (-C (= S) O-), dithioester bond (-C (= S) S-) ), Carbonate ester bond (-OC (= O) O-), Thioester bond (-OC (= S) O-), Amid bond (-C (= O) NH-), Thiouamide bond (-C (= O) O-) = S) NH-), urethane bond (-OC (= O) NH-), thiourethane bond (-SC (= O) NH-), thionourethane bond (-OC (= S) NH-), dithiourethane bond (-SC (= S) NH-), urea bond (-NHC (= O) NH-), thiourea bond (-NHC (= S) NH-) and the like can be mentioned.
Among these, ^{as A 1} , an ether bond (-O-) or a urethane bond (-OC (= O) NH-) is preferable.

In formula (X), A ² represents a single bond or a divalent linking group.
On the other hand, the ^{divalent linking group indicated by A 2} is preferably a linking group containing no heteroatom.
In the formula (X), the ^{divalent linking group represented by A 2} is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and is preferably a methylene group, an ethylene group, a trimethylene group, a propylene group, an isopropylene group, or a tetramethylene group. Group, isobutylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group , Hexadecamethylene group, Heptadecamethylene group, Octadecamethylene group, Nonadecamethylene group, Eikosadesilene group and other alkylene groups; Cyclopentylene group, Cyclohexylene group and other cyclic alkylene groups; Phenylene, α-, β- Examples thereof include methylene groups such as naphthylene groups.
Among these, a trimethylene group and an octamethylene group are preferable, and a trimethylene group is more preferable.

In the formula (X), the −A ¹ −A ² − group is a trimethylene group having a urethane bond (−OC (= O) NH−) represented by the formula (12), and is represented by the formula (13). A trimethylene group having an ether bond (−O−) is suitable.

Therefore, the compound (A) preferably has an average structural formula represented by the formula (1A) or the formula (2A), and by using these compounds, better metal foil adhesion and dielectric properties are exhibited. Will be done.

Wherein (1A) and ^{(2A), R 1, R} 2, A 1, A 2 and m represent the same meaning as ^{R 1, R 2, A 1} , A 2 and m in the formula (X), R ³ is independently a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or a halogen having 1 to 12 carbon atoms. Representing an alkoxy group, R ⁴ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkylthio group having 1 to 12 carbon atoms. , Or a halogenated alkoxy group having 1 to 12 carbon atoms, a and b are independently numbers of 1 to 100, c is a number of 0 or more and less than 2, and Z is described later. Represents a linking group represented by the formula (3).

式（Ｙ）中、Ａ^２は、単結合または２価の連結基であり、Ｒ^１およびＲ^２は、それぞれ独立に、炭素原子数１〜１０のアルキル基、または、炭素原子数６〜１０のアリール基を表し、ｍは、１〜３の整数であり、ｎは１〜１０の数である。
式（Ｙ）中、Ａ^２、Ｒ^１、Ｒ^２、ｍ、ｎの好ましい範囲は、式（Ｘ）におけるそれらの範囲と同じである。In the present embodiment, the compound (A) more preferably contains the compound represented by the formula (Y).
Equation (Y)

In the formula (Y), A ² is a single bond or a divalent linking group, and R ¹ and R ² are independently alkyl groups having 1 to 10 carbon atoms or 6 to 10 carbon atoms. Represents the aryl group of, m is an integer of 1 to 3, and n is a number of 1 to 10.
In formula (Y), ^{the preferred ranges of A 2} , R ¹ , R ² , m, n are the same as those ranges in formula (X).

The weight average molecular weight of compound (A) is not particularly limited, but is preferably 1000 or more, and more preferably 4000 or more. The upper limit of the weight average molecular weight is, for example, 20000 or less, and further 10,000 or less. The weight average molecular weight in this embodiment is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC).
In addition, the details of compound (A) can be referred to in JP-A-2018-016709, and these contents are incorporated in the present specification.

The lower limit of the content of the compound (A) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 2 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. It is more preferable that the amount is more than one part. The upper limit of the content of the compound (A) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. Is more preferable.
The lower limit of the content of the compound (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more in the resin composition. Is even more preferable. The upper limit of the content of the compound (A) is preferably 10% by mass or less, and may be 8% by mass or less in the resin composition.
The resin composition in the present embodiment may contain only one kind of the compound (A), or may contain two or more kinds of the compound (A). When two or more kinds are included, the total amount is preferably in the above range.

<< Other silane coupling agents >>
The resin composition according to the present embodiment may or may not contain a silane coupling agent other than the above compound (A).
When a silane coupling agent other than the compound (A) is contained, those generally used for surface treatment of fillers for electronic materials can be preferably used, and the types thereof are not particularly limited. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4) -Epoxycyclohexyl) Epoxysilanes such as ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxipropyltrimethoxysilane, vinyl-tri (β-methoxyethoxy) silane, N-β- (N-vinylbenzylaminoethyl)- Examples thereof include a cationic silane type such as γ-aminopropyltrimethoxysilane hydrochloride and a phenylsilane type.
When the resin composition according to the present embodiment contains a silane coupling agent other than the compound (A), the content thereof is about 1 to 5 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. There may be.
Further, the resin composition according to the present embodiment may have a structure that does not substantially contain a silane coupling agent other than the compound (A). The term "substantially free" means that the content of the compound (A) is 10% by mass or less, preferably 5% by mass or less, and more preferably 1% by mass or less.

<(B) Resin having an aromatic ring structure and elastomer having an aromatic ring structure>
The resin composition according to the present embodiment contains at least one of a resin having an aromatic ring structure and an elastomer having an aromatic ring structure, and preferably contains both a resin having an aromatic ring structure and an elastomer having an aromatic ring structure. ..
The resin composition according to the present embodiment preferably occupies 10% by mass or more, and more preferably 20% by mass or more of the resin component in total of the resin having an aromatic ring structure and the elastomer having an aromatic ring structure. , 30% by mass or more is more preferable. The upper limit value is preferably 90% by mass or less, more preferably 60% by mass or less, and may be 50% by mass or less of the resin component.

The total content of the resin component (meaning a resin having an aromatic ring structure, an elastomer having an aromatic ring structure, and other resin components) in the resin composition is 10 mass by mass of the resin composition. % Or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. The upper limit of the content of the resin component is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less in total. preferable.
Hereinafter, the details of the resin having an aromatic ring structure, the elastomer having an aromatic ring structure, and other resin components will be described.

<< Resin with aromatic ring structure >>
The resin having an aromatic ring structure is a resin containing one or more aromatic ring structures in one molecule, preferably two or more in one molecule, and a polymer containing two or more repeating units containing an aromatic ring structure (a polymer having an aromatic ring structure. For example, a compound having a weight average molecular weight of 1000 or more) is more preferable.
Examples of the resin having an aromatic ring structure include a polyphenylene ether compound, a phenol resin, and a benzoxazine compound, preferably containing at least a polyphenylene ether compound, and a substitution containing at least a carbon-carbon unsaturated double bond (excluding maleimide). More preferably, it contains a modified polyphenylene ether compound terminally modified by a group.

<<< Polyphenylene ether compound >>>
As the polyphenylene ether compound, as long as it has a polyphenylene ether structure, it is not particularly specified, and a known compound can be used. For example, a compound having a phenylene ether skeleton represented by the following formula (X1) is exemplified.

（式（Ｘ１）中、Ｒ^２４、Ｒ^２５、Ｒ^２６、およびＲ^２７は、同一または異なってもよく、炭素原子数６以下のアルキル基、アリール基、ハロゲン、または水素を表す。）

(In formula (X1), R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different and represent an alkyl group, an aryl group, a halogen, or a hydrogen having 6 or less carbon atoms.)

（式（Ｘ２）中、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３４、Ｒ^３５は、同一または異なってもよく、炭素原子数６以下のアルキル基またはフェニル基である。Ｒ^３１、Ｒ^３２、Ｒ^３３は、同一または異なってもよく、水素原子、炭素原子数６以下のアルキル基またはフェニル基である。）
で表される繰り返し単位、および／または、式（Ｘ３）：

（式（Ｘ３）中、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９、Ｒ^４０、Ｒ^４１、Ｒ^４２、Ｒ^４３は、同一または異なってもよく、水素原子、炭素原子数６以下のアルキル基またはフェニル基である。−Ａ−は、炭素原子数２０以下の直鎖、分岐または環状の２価の炭化水素である）で表される繰り返し単位をさらに含んでもよい。The polyphenylene ether compound has the formula (X2) :.

(In formula (X2), R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , R ³⁵ may be the same or different and are alkyl or phenyl groups having 6 or less carbon atoms. R ³¹ , R ³² , R ³³ may be the same or different, and is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)
Repeat unit represented by and / or formula (X3):

(In the formula (X3), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ may be the same or different, and are hydrogen atoms and alkyl groups having 6 or less carbon atoms. Alternatively, it is a phenyl group. -A- may further contain a repeating unit represented by (a linear, branched or cyclic divalent hydrocarbon having 20 or less carbon atoms).

As the polyphenylene ether compound, a modified polyphenylene ether compound in which a part or all of the terminals are functionalized with an ethylenically unsaturated group, an epoxy group, an amino group, a mercapto group, a carboxyl group, a silyl group or the like can also be used. .. In particular, a modified polyphenylene ether compound functionalized with an ethylenically unsaturated group is preferable. By adopting such a modified polyphenylene ether compound, it becomes possible to further reduce the Df and increase the peel strength. These may be used alone or in combination of two or more.

The method for producing the modified polyphenylene ether compound is not particularly limited as long as the effects of the present invention can be obtained. For example, for those functionalized with an ethylenically unsaturated group (specifically, a vinylbenzyl group or the like), a bifunctional phenylene ether oligomer and vinylbenzyl chloride are dissolved in a solvent, and a base is added under heating and stirring. It can be produced by solidifying the resin after the reaction. Those functionalized with a carboxyl group are produced, for example, by melt-kneading an unsaturated carboxylic acid or a functionalized derivative thereof with a polyphenylene ether compound in the presence or absence of a radical initiator and reacting them. Will be done. Alternatively, it is produced by dissolving a polyphenylene ether compound and an unsaturated carboxylic acid or a functional derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting them in a solution.

The modified polyphenylene ether compound preferably contains a modified polyphenylene ether compound having ethylenically unsaturated groups at both ends (hereinafter, may be referred to as "modified polyphenylene ether compound (g)"). Examples of the ethylenically unsaturated group include an alkenyl group such as an ethenyl group, an allyl group, an acrylic group, a methacrylic group, a propenyl group, a butenyl group, a hexenyl group and an octenyl group, a cyclic alkenyl group such as a cyclopentenyl group and a cyclohexenyl group, and vinyl. Examples thereof include an alkenylaryl group such as a benzyl group and a vinylnaphthyl group, and a vinylbenzyl group is preferable. The two ethylenically unsaturated groups at both ends may be the same functional group or different functional groups. By adopting such a modified polyphenylene ether compound, it becomes possible to further reduce the Df and increase the peel strength.

式（１）において、Ｘは芳香族基を表し、−（Ｙ−О）ｎ_２−はポリフェニレンエーテル構造を表し、Ｒ^１、Ｒ^２、および、Ｒ^３は、それぞれ独立して、水素原子、アルキル基、アルケニル基またはアルキニル基を表し、ｎ_１は１〜６の整数を表し、ｎ_２は１〜１００の整数を表し、ｎ_３は１〜４の整数を表す。Examples of the modified polyphenylene ether compound (g) include a compound represented by the formula (1).

In formula (1), X represents an aromatic group, − (Y−О) n ₂₋ represents a polyphenylene ether structure, and R ¹ , R ² and R ³ are independent hydrogen atoms, respectively. It represents an alkyl group, an alkenyl group or an alkynyl group, n ₁ represents an integer of 1 to 6, n ₂ represents an integer of 1 to 100, and n ₃ represents an integer of 1 to 4.

ここで、−（Ｏ−Ｘ−Ｏ）−は、式（３）：

（式（３）中、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^１０、Ｒ^１１は、同一または異なってもよく、炭素原子数６以下のアルキル基またはフェニル基である。Ｒ^７、Ｒ^８、Ｒ^９は、同一または異なってもよく、水素原子、炭素原子数６以下のアルキル基またはフェニル基である。）
および／または式（４）：

（式（４）中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９は、同一または異なってもよく、水素原子、炭素原子数６以下のアルキル基またはフェニル基である。−Ａ−は、炭素原子数２０以下の直鎖、分岐または環状の２価の炭化水素基である。）で表されることが好ましい。The modified polyphenylene ether compound (g) in the present embodiment is preferably represented by the formula (2).

Here, − (OX—O) − is the equation (3) :.

(In formula (3), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , and R ¹¹ may be the same or different, and are alkyl or phenyl groups having 6 or less carbon atoms. R ⁷ , R ⁸ , R ⁹ may be the same or different, and is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)
And / or equation (4):

(In formula (4), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and may be the same or different, and are hydrogen atoms and alkyl groups having 6 or less carbon atoms. Alternatively, it is a phenyl group. -A- is preferably a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms).

（式（５）中、Ｒ^２２、Ｒ^２３は、同一または異なってもよく、炭素原子数６以下のアルキル基またはフェニル基である。Ｒ^２０、Ｒ^２１は、同一または異なってもよく、水素原子、炭素原子数６以下のアルキル基またはフェニル基である。）で表されることが好ましい。
式（２）において、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。ａおよび／またはｂが２以上の整数の場合、２以上の−（Ｙ−Ｏ）ａ−および／または２以上の−（Ｙ−Ｏ）ｂ−は、それぞれ独立に、１種の構造がめ配列したものであってよく、２種以上の構造がブロックまたはランダムに配列していてもよい。Further, − (YO) − is the equation (5) :.

(In the formula (5), R ²² and R ²³ may be the same or different, and may be an alkyl group or a phenyl group having 6 or less carbon atoms. R ²⁰ and R ²¹ may be the same or different, and hydrogen. It is preferably represented by an atom, an alkyl group having 6 or less carbon atoms, or a phenyl group).
In the formula (2), a and b represent integers from 0 to 100 in which at least one of them is not 0. When a and / or b are integers of 2 or more, 2 or more- (YO) a- and / or 2 or more- (YO) b- are independently one type of structural array. Two or more types of structures may be arranged in blocks or randomly.

Examples of −A− in the formula (4) include methylene, ethylidene, 1-methylethylidene, 1,1-propyridene, 1,4-phenylenebis (1-methylethylidene), and 1,3-phenylenebis (1-). Divalent organic groups such as methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene can be mentioned, but are not limited thereto.

Among the modified polyphenylene ether compounds (g), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ²⁰ , and R ²¹ are alkyl groups having 3 or less carbon atoms, and R ⁷ , R ⁸ , Polyphenylene ether compounds in which R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² , and R ²³ are hydrogen atoms or alkyl groups with 3 or less carbon atoms. Preferably, in particular, − (OX—O) − represented by formula (3) or formula (4) is formula (9), formula (10), and / or formula (11), and formula (5). ) Is preferably the formula (12) or the formula (13). When a and / or are integers greater than or equal to 2, two or more-(YO) a- and / or two or more-(YO) b- are independent of equation (12) and / or The structure may be such that the formula (13) is arranged in two or more, or the formula (12) and the formula (13) are arranged in blocks or randomly.

（式（１０）中、Ｒ^４４、Ｒ^４５、Ｒ^４６、Ｒ^４７は、同一でも異なってもよく、水素原子またはメチル基である。−Ｂ−は、炭素原子数２０以下の直鎖、分岐または環状の２価の炭化水素基である。）
−Ｂ−は、式（４）における−Ａ−の具体例と同じものが具体例として挙げられる。

（式（１１）中、−Ｂ−は、炭素原子数２０以下の直鎖、分岐または環状の２価の炭化水素基である）
−Ｂ−は、式（４）における−Ａ−の具体例と同じものが具体例として挙げられる。

(In formula (10), R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ may be the same or different, and are hydrogen atoms or methyl groups. -B- is a linear or branched group having 20 or less carbon atoms. Or a cyclic divalent hydrocarbon group.)
As the specific example of −B−, the same specific example as that of −A− in the formula (4) can be mentioned.

(In formula (11), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms).
As the specific example of −B−, the same specific example as that of −A− in the formula (4) can be mentioned.

The method (production method) for preparing the modified polyphenylene ether compound (g) represented by the formula (2) of the present embodiment is not particularly limited, and for example, a bifunctional phenol compound and a monofunctional phenol compound are oxidized cups. Produced by a step of ringing to obtain a bifunctional phenylene ether oligomer (oxidation coupling step) and a step of converting the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer into vinylbenzyl ether (vinylbenzyl etherification step). can. Further, as such a modified polyphenylene ether compound, for example, Mitsubishi Gas Chemical Company (OPE-2St1200 or the like) can be used.

In the oxidation coupling step, for example, a bifunctional phenol compound, a monofunctional phenol compound, and a catalyst are dissolved in a solvent, and oxygen is blown under heating and stirring to obtain a bifunctional phenylene ether oligomer. The bifunctional phenol compound is not particularly limited, and is, for example, 2,2', 3,3', 5,5'-hexamethyl- (1,1'-biphenol) -4,4'-diol, 4, At least one selected from the group consisting of 4'-methylenebis (2,6-dimethylphenol), 4,4'-dihydroxyphenylmethane, and 4,4'-dihydroxy-2,2'-diphenylpropane can be mentioned. .. The monofunctional phenol compound is not particularly limited, and examples thereof include 2,6-dimethylphenol and / or 2,3,6-trimethylphenol. The catalyst is not particularly limited, and is, for example, copper salts (for example, CuCl, CuBr, CuI, CuCl ₂ , CuBr _2, etc.), amines (for example, di-n-butylamine, n-butyldimethylamine, N, N). '-Di-t-butylethylenediamine, pyridine, N, N, N', N'-tetramethylethylenediamine, piperidine, imidazole, etc.) and the like. The solvent is not particularly limited, and examples thereof include at least one selected from the group consisting of toluene, methanol, methyl ethyl ketone, and xylene.

In the vinylbenzyl etherification step, for example, the bifunctional phenylene ether oligomer obtained by the oxidation coupling step and vinylbenzyl chloride are dissolved in a solvent, postponed under heating and stirring to cause a reaction, and then the resin is solidified. Can be manufactured by The vinylbenzyl chloride is not particularly limited, and examples thereof include at least one selected from the group consisting of o-vinylbenzyl chloride, m-vinylbenzyl chloride, and p-vinylbenzyl chloride. The base is not particularly limited, and examples thereof include at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide. In the vinylbenzyl etherification step, an acid may be used to neutralize the base remaining after the reaction, and the acid is not particularly limited and consists of, for example, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and nitric acid. At least one selected from the group is mentioned. The solvent is not particularly limited, and examples thereof include at least one selected from the group consisting of toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, methylene chloride, and chloroform. Examples of the method of solidifying the resin include a method of evaporating a solvent to dry it, a method of mixing a reaction solution with a poor solvent, and a method of reprecipitation.

In addition to the above, the polyphenylene ether compound used in the present embodiment may be an unmodified polyphenylene ether compound having a hydroxyl group at the end. As the unmodified polyphenylene ether compound, for example, the description in paragraphs 0011 to 0016 of JP2017-197739A can be adopted, and these contents are incorporated in the present specification.

The polystyrene-equivalent number average molecular weight of the polyphenylene ether compound (preferably a modified polyphenylene ether compound) by the GPC method is preferably 500 or more and 3000 or less. When the number average molecular weight is 500 or more, stickiness tends to be further suppressed when the resin composition of the present embodiment is formed into a coating film. When the number average molecular weight is 3000 or less, the solubility in a solvent tends to be further improved.
The polystyrene-equivalent weight average molecular weight of the polyphenylene ether compound by GPC is preferably 800 or more and 10000 or less, and more preferably 800 or more and 5000 or less. When it is set to the lower limit value or more, the dielectric constant and the dielectric loss tangent tend to be lower, and when it is set to the upper limit value or less, the solubility in a solvent, low viscosity and moldability tend to be further improved.
Further, in the case of a modified polyphenylene ether compound, the carbon-carbon unsaturated double bond equivalent at the terminal is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, and is preferably 400 g to 2500 g. Is more preferable. By setting the value to the lower limit or higher, the permittivity and the dielectric loss tangent tend to be lower. By setting the value to the above upper limit or less, the solubility in a solvent, low viscosity and moldability tend to be further improved.

When contained, the lower limit of the content of the polyphenylene ether compound is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and 10 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. It is more preferably parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more. When contained, the upper limit of the content of the polyphenylene ether compound is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and 40 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. It is more preferably parts by mass or less. In particular, when the content of the modified polyphenylene ether compound is in the above range, the low dielectric loss tangent property and the reactivity tend to be further improved.
The resin composition in the present embodiment may contain only one type of polyphenylene ether compound, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

<<< Phenol formaldehyde >>
The phenol resin is not particularly limited as long as it is a phenol compound or resin having two or more phenolic hydroxy groups in one molecule.
Examples of the phenol resin 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 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, Examples thereof include naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, and hydroxyl group-containing silicone resin. Among these, at least one selected from the group consisting of biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, phosphorus-containing phenol resin, and hydroxyl group-containing silicone resin from the viewpoint of further improving flame resistance. preferable.

The phenol resin is preferably contained within a range that does not impair the effects of the present invention. When it is contained, it is preferably 0.1 part by mass or more, and preferably 50 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition.
The resin composition in the present embodiment may contain only one type of phenol resin, or may contain two or more types of phenol resin. When two or more kinds are included, the total amount is preferably in the above range.
Further, the resin composition in the present embodiment may have a structure that does not substantially contain a phenol resin. The term "substantially free" means that the content of the phenol resin is less than 0.1 parts by mass with respect to 100 parts by mass of the resin component in the resin composition.

<<< Benzoxazine compound >>>
The benzoxazine compound is not particularly limited as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule.
Examples of the benzoxazine compound include bisphenol A type benzoxazine BA-BXZ (product of Konishi Chemical Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (product of Konishi Chemical Co., Ltd.), and bisphenol S type benzoxazine BS-BXZ. (Products of Konishi Chemical Co., Ltd.) and the like.

The benzoxazine compound is preferably contained within a range that does not impair the effects of the present invention. When it is contained, it is preferably 0.1 part by mass or more, and preferably 50 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition.
The resin composition in the present embodiment may contain only one type of benzoxazine compound, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
Further, the resin composition in the present embodiment may be configured to be substantially free of the benzoxazine compound. The term "substantially free" means that the content of the benzoxazine compound is less than 0.1 part by mass with respect to 100 parts by mass of the resin component in the resin composition.

In addition to the above, a resin having an aromatic ring structure, which is another resin component described later, is also exemplified as a preferable example.
In the resin composition according to the present embodiment, the content of the resin having an aromatic ring structure is preferably 1 part by mass or more, more preferably 5 parts by mass, based on 100 parts by mass of the resin component. It is more preferable to occupy 10 parts by mass or more. The upper limit may be 100 parts by mass with respect to 100 parts by mass of the resin component, but is preferably 90 parts by mass or less, more preferably 60 parts by mass or less, and 50 parts by mass or less. It is more preferably 45 parts by mass or less, and it may be 40 parts by mass or less.
The resin composition in the present embodiment may contain only one type of resin having an aromatic ring structure, or may contain two or more types of resin. When two or more kinds are included, the total amount is preferably in the above range.

<< Elastomer with aromatic ring structure >>
The elastomer having an aromatic ring structure is an elastomer containing one or more aromatic ring structures in one molecule, preferably two or more in one molecule, and an elastomer containing two or more repeating units containing an aromatic ring structure (an elastomer having an aromatic ring structure. For example, a compound having a weight average molecular weight of 1000 or more) is more preferable.
The elastomer having an aromatic ring structure is preferably a styrene-based elastomer.
Examples of styrene elastomers include styrene-butadiene-styrene elastomer (SBS), styrene-isoprene-styrene elastomer (SIS), polystyrene-poly (ethylene-propylene) elastomer (SEP), and polystyrene-poly (ethylene-propylene) -polystyrene elastomer. It is preferably at least one selected from the group consisting of (SEPS), polystyrene-poly (ethylene-butylene) -polystyrene elastomer (SEBS), and polystyrene-poly (ethylene / ethylene-propylene) -polystyrene elastomer (SEEPS). ..

The proportion of the repeating unit derived from styrene in the styrene-based elastomer is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more. Within such a range, solvent solubility and low dielectric properties can be improved.

The resin composition according to the present embodiment preferably has an elastomer having an aromatic ring structure in an amount of 1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the resin component. More preferably, it is 8 parts by mass or more. The upper limit is preferably 60 parts by mass or less, and more preferably 40 parts by mass or less with respect to 100 parts by mass of the resin component.
The resin composition in the present embodiment may contain only one type of elastomer having an aromatic ring structure, or may contain two or more types of elastomer. When two or more kinds are included, the total amount is preferably in the above range.

<Other resin components>
The resin composition in the present embodiment may contain other resin components in addition to the above. The other resin component is selected from the group consisting of maleimide compounds, cyanate ester compounds, epoxy resins, oxetane resins, elastomers other than elastomers having an aromatic ring structure, active ester compounds and compounds having polymerizable unsaturated groups. At least one of these can be exemplified, and it is preferable that the maleimide compound and the cyanate ester compound are contained at least.

式（２Ｍ）中、Ｒ^４はそれぞれ独立に、水素原子またはメチル基を表し、ｎ_４は１以上の整数を表す。ｎ_４は１〜１０の整数が好ましく、１〜５の整数がより好ましく、１〜３の整数がさらに好ましく、１または２であることが一層好ましい。

式（３Ｍ）中、Ｒ^５はそれぞれ独立に、水素原子、炭素原子数１〜８のアルキル基またはフェニル基を表し、ｎ_５は１以上１０以下の整数を表す。
Ｒ^５は、水素原子、エチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基、フェニル基が好ましく、水素原子およびメチル基の一方であることがより好ましく、水素原子であることがさらに好ましい。
ｎ_５は１以上５以下の整数であることが好ましく、１〜３の整数がさらに好ましく、１または２であることが一層好ましい。

式（４Ｍ）中、Ｒ^６はそれぞれ独立に水素原子、メチル基またはエチル基を表し、Ｒ^７はそれぞれ独立に水素原子またはメチル基を表す。<< Maleimide compound >>
The maleimide compound is not particularly limited as long as it is a compound having two or more maleimide groups in the molecule.
Examples of maleimide compounds include maleimide compounds represented by formulas (2M) to (4M). By using these maleimide compounds, when used as a material for printed wiring boards (for example, laminated boards, metal foil-clad laminated boards), excellent heat resistance can be imparted, and peel strength, low water absorption, and desmear resistance can be imparted. , And flame resistance can be improved.

In formula (2M), R ⁴ independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more. n ₄ is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, and even more preferably 1 or 2.

In formula (3M), R ⁵ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer of 1 or more and 10 or less.
R ⁵ is a hydrogen atom, an ethyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, n- pentyl group, preferably a phenyl group, a hydrogen atom and a methyl group On the other hand, it is more preferable, and it is more preferable that it is a hydrogen atom.
n ₅ is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and even more preferably 1 or 2.

In formula (4M), R ⁶ independently represents a hydrogen atom, a methyl group or an ethyl group, and R ⁷ independently represents a hydrogen atom or a methyl group.

The maleimide compound represented by the formulas (2M) to (4M) is more preferably a maleimide compound represented by the formula (3M).
The maleimide compound may be prepared by a known method, or a commercially available product may be used. Examples of commercially available products include the product "MIR-3000" of Nippon Kayaku Co., Ltd.

Examples of maleimide compounds other than the above include 4,4-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, 2,2-bis (4- (4-maleimidephenoxy) -phenyl) propane, and 3 , 3-Dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 4 , 4-diphenyl ether bismaleimide, 4,4-diphenylsulphon bismaleimide, 1,3-bis (3-maleimide phenoxy) benzene, 1,3-bis (4-maleimide phenoxy) benzene, polyphenylmethane maleimide, and theirs. Examples include prepolymers, prepolymers of these maleimides and amines, and the like.

When contained, the lower limit of the content of the maleimide compound is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and 15 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. It may be more than one part. When the content of the maleimide compound is 1 part by mass or more, the flame resistance tends to be improved. When the maleimide compound is contained, the upper limit of the content is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the resin component in the resin composition. It is more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less. When the content of the maleimide compound is 70 parts by mass or less, the peel strength and low water absorption tend to be improved.
The resin composition in the present embodiment may contain only one type of maleimide compound, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

<< Cyanic acid ester compound >>
The cyanate ester compound is not particularly specified as long as it is a compound having a cyanate structure.
Examples of the cyanate ester compound include a phenol novolac type cyanate ester compound, a naphthol aralkyl type cyanate compound (naphthol aralkyl type cyanate), a naphthylene ether type cyanate ester compound, a biphenyl aralkyl type cyanate ester compound, and a xylene resin. Consists of type cyanate ester compound, trisphenol methane type cyanate ester compound, adamantan skeleton type cyanate ester compound, bisphenol M type cyanate ester compound, bisphenol A type cyanate ester compound, and diallyl bisphenol A type cyanate ester compound. At least one selected from the group is mentioned. Among these, from the viewpoint of further improving low water absorption, phenol novolac type cyanate ester compound, naphthol aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, bisphenol M It is preferably at least one selected from the group consisting of the type cyanate ester compound, the bisphenol A type cyanate ester compound, and the diallyl bisphenol A type cyanate ester compound, and the naphthol aralkyl type cyanate ester compound is preferable. More preferred. These cyanate ester compounds may be prepared by a known method, or commercially available products may be used. The cyanate ester compound having a naphthol aralkyl skeleton, a naphthylene ether skeleton, a xylene skeleton, a trisphenolmethane skeleton, or an adamantan skeleton has a relatively large functional group equivalent number and a small number of unreacted cyanate ester groups. Therefore, the water absorption tends to be further reduced. Further, the plating adhesion tends to be further improved mainly due to having an aromatic skeleton or an adamantane skeleton.

The cyanate ester compound is preferably contained within a range that does not impair the effects of the present invention. When it is contained, the lower limit of the content is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and 20 parts by mass or more with respect to 100 parts by mass of the resin component in the resin composition. Is more preferable. When the content of the cyanate ester compound is 1 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, heat resistance, combustion resistance, chemical resistance, low dielectric constant, and low dielectric constant There is a tendency for normal contact and insulation to improve. When contained, the upper limit of the content of the cyanate ester compound is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, based on 100 parts by mass of the resin component in the resin composition. It is more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less.
The resin composition in the present embodiment may contain only one type of cyanate ester compound, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

<< Epoxy resin >>
The epoxy resin is not particularly limited as long as it is a compound or resin having two or more epoxy groups in one molecule.
The epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl. Novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol Double aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, 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 the like. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin, and naphthalene type epoxy resin are preferable, and biphenyl aralkyl type. More preferably, it is a type epoxy resin.

The epoxy resin is preferably contained within a range that does not impair the effects of the present invention. From the viewpoint of moldability and adhesion, when it is contained, it is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the resin component in the resin composition. It is more preferably parts by mass or more. When the content of the epoxy resin is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved. When contained, the upper limit of the content of the epoxy resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and 20 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. It is more preferably parts or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. When the content of the epoxy resin is 50 parts by mass or less, the electrical characteristics tend to be improved.
The resin composition in the present embodiment may contain only one type of epoxy resin, or may contain two or more types of epoxy resin. When two or more kinds are included, the total amount is preferably in the above range.
Further, the resin composition in the present embodiment may have a structure that does not substantially contain an epoxy resin. The term "substantially free" means that the content of the epoxy resin is less than 0.1 part by mass with respect to 100 parts by mass of the resin component in the resin composition.

<< Oxetane resin >>
The oxetane resin is not particularly limited as long as it is a compound having two or more oxetanyl groups.
Examples of the oxetane resin include oxetane, alkyl oxetane (for example, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxatan, etc.) and 3-methyl-3-methoxymethyloxetane. , 3,3-di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (a product of Toa Synthetic Co., Ltd.), OXT- 121 (product of Toa Synthetic Co., Ltd.) and the like can be mentioned.

The oxetane resin is preferably contained within a range that does not impair the effects of the present invention. When it is contained, it is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more with respect to 100 parts by mass of the resin component in the resin composition. .. When the content of the oxetane resin is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved. When contained, the upper limit of the content of the oxetane resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and 20 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. It is more preferably parts or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. When the content of the oxetane resin is 50 parts by mass or less, the electrical characteristics tend to be improved.
The resin composition in the present embodiment may contain only one type of oxetane resin, or may contain two or more types of oxetane resin. When two or more kinds are included, the total amount is preferably in the above range.
Further, the resin composition in the present embodiment may have a structure that does not substantially contain an oxetane resin. The term "substantially free" means that the content of the oxetane resin is less than 0.1 part by mass with respect to 100 parts by mass of the resin component in the resin composition.

<< Elastomers other than elastomers with an aromatic ring structure >>
Elastomers other than elastomers having an aromatic ring structure include polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, polyacrylic elastomers, silicone-based elastomers, and polyimide-based elastomers, and do not contain aromatic rings. Things are illustrated.
Elastomers other than the elastomer having an aromatic ring structure are preferably contained as long as the effects of the present invention are not impaired. When it is contained, it is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more with respect to 100 parts by mass of the resin component in the resin composition. .. When contained, the upper limit of the content of the elastomer other than the elastomer having an aromatic ring structure is preferably 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the resin component in the resin composition. More preferably, it is more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less.
The resin composition in the present embodiment may contain only one kind of elastomer other than the elastomer having an aromatic ring structure, or may contain two or more kinds of elastomers. When two or more kinds are included, the total amount is preferably in the above range.
Further, the resin composition in the present embodiment may be configured to substantially contain no elastomer other than the elastomer having an aromatic ring structure. The term "substantially free" means that the content of the elastomer other than the elastomer having an aromatic ring structure is less than 0.1 part by mass with respect to 100 parts by mass of the resin component in the resin composition.

<< Active ester compound >>
The active ester compound is not particularly limited, and examples thereof include compounds having two or more active ester groups in one molecule.
The active ester compound may be a linear or branched or cyclic compound. Among these, an active ester compound obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound is preferable from the viewpoint of further improving heat resistance. An active ester compound obtained by reacting one or more compounds selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferable, and a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group are used. An aromatic compound obtained by reaction and having two or more active ester groups in one molecule is more preferable, and a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group are more preferable. An aromatic compound obtained by reacting with a compound and having two or more active ester groups in one molecule is particularly preferable. Examples of the above-mentioned carboxylic acid compound include one or more selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, from the viewpoint of further improving heat resistance, one or more selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid is preferable, and the group consisting of isophthalic acid and terephthalic acid is preferable. One or more selected from the above is more preferable. Examples of the above-mentioned thiocarboxylic acid compound include one or more selected from the group consisting of thioacetic acid and thiobenzoic acid. Examples of the above-mentioned phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, One or more selected from the group consisting of benzenetriol, dicyclopentadienyldiphenol, and phenol novolac can be mentioned. From the viewpoint of further improving heat resistance and solvent solubility, bisphenol A, bisphenol F, bisphenol S, Methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri Hydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, benzenetriol, dicyclopentadienyldiphenol, phenol novolac are preferred, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone. , Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac, one or more selected from the group is more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxy. One or more selected from the group consisting of naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolac is more preferable, and dihydroxybenzophenone and trihydroxybenzophenone are more preferable. , Tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolac. Above (preferably one or more selected from the group consisting of dicyclopentadienyl diphenol and phenol novolac, more preferably dicyclopentadienyl diphenol) is particularly preferable. Examples of the above-mentioned thiol compound include one or more selected from the group consisting of benzenedithiol and triazinedithiol. Further, the active ester compound is preferably a compound having at least two or more carboxylic acids in one molecule and containing an aliphatic chain from the viewpoint of further improving the compatibility with the epoxy resin, and has heat resistance. From the viewpoint of further improving the above, a compound having an aromatic ring is preferable. More specific active ester compounds include the active ester compounds described in JP-A-2004-277460.

The active ester compound may be a commercially available product or may be prepared by a known method. Commercially available products include compounds containing a dicyclopentadienyldiphenol structure (for example, EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all products of DIC Co., Ltd.), etc.), and acetylated phenol novolac (for example, products of DIC Co., Ltd.). , DC808 (a product of Mitsubishi Chemical Co., Ltd.), and a benzoylated product of phenol novolac (for example, YLH1026, YLH1030, YLH1048 (all products of Mitsubishi Chemical Co., Ltd.)), and storage stability of varnish, resin composition. EXB9460S is preferable from the viewpoint of further improving the low thermal expansion rate when (cured product) is cured.

The active ester compound can be prepared by a known method, and can be obtained, for example, by a condensation reaction of a carboxylic acid compound and a hydroxy compound. Specific examples include (a) a carboxylic acid compound or a halide thereof, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound with respect to (b) 1 mol of the carboxyl group or the acid halide group of (a). Examples thereof include a method of reacting at a ratio of 0.05 to 0.75 mol of the phenolic hydroxyl group and 0.25 to 0.95 mol of (c).

The active ester compound is preferably contained within a range that does not impair the effects of the present invention. When it is contained, it is preferably 1 part by mass or more and preferably 90 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition.
The resin composition in the present embodiment may contain only one type of active ester compound, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
Further, the resin composition in the present embodiment may have a structure that does not substantially contain an active ester compound. The term "substantially free" means that the content of the active ester compound is less than 1 part by mass with respect to 100 parts by mass of the resin component in the resin composition.

<(C) Filler>
The resin composition of the present embodiment preferably contains a filler (C) in order to improve low dielectric constant, low dielectric loss tangent property, flame resistance and low thermal expansion property. As the filler (C) used in the present embodiment, a known filler (C) can be appropriately used, and the type thereof is not particularly limited, and a filler generally used in the art can be preferably used. .. Specifically, natural silica, molten silica, synthetic silica, amorphous silica, aerodil, silica such as hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, coagulated boron nitride, silicon nitride. , Aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated product (aluminum hydroxide is heat-treated and a part of crystalline water is reduced), metal hydrate such as boehmite and magnesium hydroxide, oxidation Molybdenum compounds such as molybdenum and zinc molybdenate, zinc borate, zinc nitrate, 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, glass short fiber (including fine glass powders such as E glass, T glass, D glass, S glass, Q glass), hollow In addition to inorganic fillers such as glass and spherical glass, organic fillers such as styrene type, butadiene type, acrylic type rubber powder, core shell type rubber powder, silicone resin powder, silicone rubber powder, and silicone composite powder, etc. Can be mentioned.
Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide is preferable. By using these fillers, the properties such as thermal expansion characteristics, dimensional stability, and flame retardancy of the resin composition are improved.

The content of the filler (C) in the resin composition of the present embodiment can be appropriately set according to the desired properties, and is not particularly limited, but is 50 with respect to 100 parts by mass of the resin component in the resin composition. It is preferably parts by mass or more, and more preferably 75 parts by mass or more. Further, it is preferably 1600 parts by mass or less, more preferably 1200 parts by mass or less, further preferably 1000 parts by mass or less, and further preferably 750 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. Yes, it is even more preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less.
The resin composition in the present embodiment may contain only one type of filler (C), or may contain two or more types of filler (C). When two or more kinds are included, the total amount is preferably in the above range.

<Flame retardant>
The resin composition of the present embodiment may contain a flame retardant.
Known flame retardants can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth) acrylate, pentabromo. Halogen flame retardants such as toluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenyl ethane, chlorinated polystyrene, chlorinated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate. , Cresyldiphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris (chloroethyl) phosphate, phosphazene, 1,3-phenylenebis (2,6-dixylenyl phosphate), 10- (2,5-) Dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, etc., phosphorus-based flame retardants, aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, antimony trioxide, etc. Examples thereof include silicone flame retardants such as flame retardants, polystyrene rubbers and polystyrene resins. These flame retardants may be used alone or in combination of two or more. Among these, 1,3-phenylenebis (2,6-dixylenyl phosphate) is preferable because it does not impair the low dielectric property.

When contained, the content of the flame retardant is preferably 0.1 to 20% by mass of the resin composition.
The flame retardant may be used alone or in combination of two or more. When two or more types are used, the total amount is within the above range.

<Dispersant>
The resin composition of the present embodiment may contain a dispersant. As the dispersant, those generally used for paints can be preferably used, and the type thereof is not particularly limited. In this embodiment, a urethane-based dispersant is exemplified. As the dispersant, a copolymer-based wet dispersant is preferably used, and specific examples thereof include Disperbyk-110, 111, 161 and 180, 2009, 2152, 2155 manufactured by Big Chemie Japan Co., Ltd. , BYK-W996, BYK-W9010, BYK-W903, BYK-W940 and the like.

When the dispersant is contained, the lower limit thereof is preferably 0.01 part by mass or more and 0.1 part by mass or more with respect to 100 parts by mass of the resin component in the resin composition. Is more preferable, and may be 0.3 parts by mass or more. The upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. Is more preferable.
The dispersant may be used alone or in combination of two or more. When two or more types are used, the total amount is within the above range.

<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, manganese octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts are phenols and bisphenols. Those dissolved in a hydroxyl group-containing compound such as; 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.
Preferred curing accelerators are imidazoles and organometallic salts, and it is more preferable to use both imidazoles and organometallic salts in combination.

When the curing accelerator is contained, the lower limit thereof is preferably 0.005 parts by mass or more, and 0.01 parts by mass or more, based on 100 parts by mass of the resin component in the resin composition. More preferably, it is more preferably 0.1 parts by mass or more. The upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 2 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. The following is more preferable.
The curing accelerator may be used alone or in combination of two or more. When two or more types are used, the total amount is within the above range.

<Solvent>
The resin composition of the present embodiment may contain a solvent, and preferably contains an organic solvent. In this case, the resin composition of the present embodiment is in the form (solution or varnish) in which at least a part, preferably all of the above-mentioned various resin components are dissolved or compatible with a solvent. The solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent capable of dissolving or compatible with at least a part, preferably all of the above-mentioned various resin components, and the polar organic solvent includes, for example, ketones. (For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (for example, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, etc.) , Ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (eg, dimethoxyacetamide, dimethylformamide, etc.), and examples of the non-polar organic solvent include aromatic hydrocarbons (eg, toluene, xylene). Etc.).
As the solvent, one type can be used alone, or two or more types can be used in combination. When two or more types are used, the total amount is within the above range.

<Other ingredients>
In addition to the above components, the resin composition of the present embodiment may contain various polymer compounds such as a thermoplastic resin and an oligomer thereof, and various additives. Additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, defoamers, leveling agents, gloss. Examples include agents and polymerization inhibitors. These additives may be used alone or in combination of two or more.

<Use>
The resin composition of this embodiment is used as a cured product. Specifically, the resin composition of the present embodiment can be suitably used as a low dielectric constant material and / or a low dielectric loss tangent material, as an insulating layer of a printed wiring board, or as a material for a semiconductor package. The resin composition of the present embodiment can be suitably used as a material for constituting a prepreg, a metal foil-clad laminate using a prepreg, a resin sheet, and a printed wiring board.
The resin composition of the present embodiment is used as a layered material (meaning including a film form, a sheet form, etc.) such as an insulating layer, a prepreg, and a resin sheet of a printed wiring board. The thickness thereof is preferably 5 μm or more, and more preferably 10 μm or more. The upper limit value is preferably 200 μm or less, and more preferably 180 μm or less. The thickness of the layered material means, for example, the thickness including the glass cloth when the resin composition of the present embodiment is impregnated with the glass cloth or the like.
The material formed from the resin composition of the present embodiment may be used for the purpose of forming a pattern by exposure development, or may be used for the purpose of not exposure development. In particular, it is suitable for applications that do not undergo exposure development.

<< Prepreg >>
The prepreg of the present embodiment is formed from a base material (prepreg base material) and the resin composition of the present embodiment. The prepreg of the present embodiment is, for example, a method of applying the resin composition of the present embodiment to a substrate (for example, impregnation or coating) and then heating (for example, a method of drying at 120 to 220 ° C. for 2 to 15 minutes). Obtained by semi-curing with. In this case, the amount of the resin composition adhered to the substrate, that is, the amount of the resin composition (including the filler (C)) with respect to the total amount of prepreg after semi-curing is preferably in the range of 20 to 99% by mass.

The base material is not particularly limited as long as it is a base material used for various printed wiring board materials. As the material of the base material, for example, glass fiber (for example, E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.) , Inorganic fibers other than glass (for example, quartz, etc.), organic fibers (for example, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfaced mats. These base materials may be used alone or in combination of two or more. Among these base materials, woven fabrics that have undergone super-spreading treatment and filling treatment are preferable from the viewpoint of dimensional stability, and the base material has a thickness of 200 μm or less and a mass of 250 g / m from the viewpoint of strength and water absorption. ^{A glass woven fabric of 2} or less is preferable, and from the viewpoint of moisture absorption and heat resistance, a glass woven fabric whose surface is treated with a silane coupling agent such as epoxy silane treatment or amino silane treatment is preferable. From the viewpoint of electrical characteristics, a low-dielectric glass cloth made of glass fibers exhibiting low dielectric constant and low dielectric loss tangent properties such as L-glass, NE-glass, and Q-glass is more preferable.

<< Metal leaf-clad laminate >>
The metal foil-clad laminate of the present embodiment includes a layer formed from at least one prepreg of the present embodiment and a metal foil arranged on one or both sides of the layer formed from the prepreg. The metal foil-clad laminate of the present embodiment includes, for example, a method of arranging at least one prepreg of the present embodiment (preferably two or more prepregs) and arranging metal foils on one side or both sides of the prepreg and laminating. Be done. More specifically, it can be produced by arranging a metal foil such as copper or aluminum on one side or both sides of the prepreg and laminating and molding it. The number of prepregs is preferably 1 to 10, more preferably 2 to 10, and even more preferably 2 to 7. The metal foil is not particularly limited as long as it is used as a material for a printed wiring board, and examples thereof include copper foils such as rolled copper foils and electrolytic copper foils. The thickness of the metal foil (preferably copper foil) is not particularly limited and may be about 1.5 to 70 μm. Examples of the molding method include a method usually used when molding a laminated board for a printed wiring board and a multi-layer board, and more specifically, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine and the like are used. Then, a method of laminating molding at a temperature of about 180 to 350 ° C., a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg / cm ^{2 can be mentioned.} Further, the prepreg of the present embodiment can be laminated and molded by combining the separately produced wiring board for the inner layer to form a multilayer board. As a method for manufacturing a multilayer plate, for example, copper foil of about 35 μm is arranged on both sides of one prepreg of the present embodiment, laminated and formed by the above molding method, and then an inner layer circuit is formed, and black is formed on this circuit. The inner layer circuit board is formed by carrying out the chemical treatment, and then the inner layer circuit board and the prepreg of the present embodiment are alternately arranged one by one, and further, a copper foil is arranged on the outermost layer to meet the above conditions. A multilayer plate can be produced by laminating and molding under vacuum. The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board.

<< Printed circuit board >>
The printed wiring board of the present embodiment is a printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer, and the insulating layer is formed from the resin composition of the present embodiment. It includes at least one of a layer and a layer formed from the prepreg of the present embodiment. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. The following is an example of a method for manufacturing a printed wiring board. First, a metal foil-clad laminate such as the metal foil-clad laminate described above is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, and an inner layer substrate is produced. 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 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, a plated metal film for conducting the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the holes, and further, the outer layer circuit is formed. A printed wiring board is manufactured by forming an outer layer circuit by etching a metal foil for use.

The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment described above. That is, the resin composition of the above-mentioned prepreg of the present embodiment (for example, a prepreg formed from the base material and the resin composition of the present embodiment impregnated or coated thereto), and the above-mentioned metal foil-clad laminate of the present embodiment described above. The layer formed from the object becomes the insulating layer of the present embodiment.

<< Resin sheet >>
The resin sheet of the present embodiment includes a support and a layer formed from the resin composition of the present embodiment arranged on the surface of the support. The resin sheet can be used as a build-up film or a dry film solder resist. The method for producing the resin sheet is not particularly limited, but for example, a method for obtaining a resin sheet by applying (coating) a solution prepared by dissolving the resin composition of the present embodiment in a solvent to a support and drying the resin sheet. Can be mentioned.

Examples of the support used here include a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, a release film in which a release agent is applied to the surface of these films, and a polyimide. Examples thereof include organic film base materials such as films, conductor foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, and plate-shaped materials such as FRP (Fiber-Reinforced Plastics). It is not limited.

Examples of the coating method (coating method) include a method of applying a solution of the resin composition of the present embodiment in a solvent onto a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Be done. Further, after drying, the support can be peeled off or etched from the resin sheet on which the support and the resin composition are laminated to obtain a single-layer sheet. A support is used 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. It is also possible to obtain a single-layer sheet without using it.

In the production of the single-layer sheet or the resin sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but the solvent tends to remain in the resin composition at a low temperature, and the resin is at a high temperature. Since the composition is cured, it is preferably at a temperature of 20 ° C. to 200 ° C. for 1 to 90 minutes. Further, in the single-layer sheet or the resin sheet, the resin composition can be used in an uncured state in which the solvent is simply dried, or if necessary, used in a semi-cured state (B-staged). You can also. Further, the thickness of the resin layer in the single-layer sheet or the resin sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited, but is generally coated. The thicker the thickness, the easier it is for the solvent to remain during drying, so 0.1 to 500 μm is preferable.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Synthesis Example 1 Synthesis of naphthol aralkyl type cyanate ester compound (SNCN)>
1-Naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 300 g (1.28 mol in terms of OH group) and 194.6 g (1.92 mol) of triethylamine (1.5 mol with respect to 1 mol of hydroxy group) were dissolved in 1800 g of dichloromethane. This was designated as solution 1.
Cyanogen chloride 125.9 g (2.05 mol) (1.6 mol with respect to 1 mol of hydroxy group), dichloromethane 293.8 g, 36% hydrochloric acid 194.5 g (1.92 mol) (1.5 mol with respect to 1 mol of hydroxy group) ), 1205.9 g of water was poured over 30 minutes while maintaining the liquid temperature at -2 to -0.5 ° C. with stirring. After pouring 1 solution, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane was added for 10 minutes. I poured it over. 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 5 times with 1300 g of water. The electrical conductivity of the wastewater after the fifth washing with water was 5 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 331 g of the target naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance). The weight average molecular weight of the obtained SNCN was 600. In addition, the IR spectrum of SNCN ^{showed absorption of 2250 cm -1} (cyanic acid ester group) and no absorption of hydroxy group.

<Synthesis Example 2 Synthesis of Modified Polyphenylene Ether Compound>
<< Synthesis of bifunctional phenylene ether oligomer >>
_{CuBr 2} 9.36 g (42.1 mmol), N, N'-di-t-butylethylenediamine 1.81 g (10) in a 12 L longitudinal reactor with stirrer, thermometer, air inlet tube and baffle plate. .5 mmol), 67.77 g (671.0 mmol) of n-butyldimethylamine, and 2,600 g of toluene were charged, stirred at a reaction temperature of 40 ° C., and 2,2', previously dissolved in 2,300 g of methanol. 3,3', 5,5'-hexamethyl- (1,1'-biphenol) -4,4'-diol 129.32 g (0.48 mol), 2,6-dimethylphenol 878.4 g (7.2 mol) , N, N'-di-t-butylethylenediamine 1.22 g (7.2 mmol), n-butyldimethylamine 26.35 g (260.9 mmol) mixed solution of nitrogen and air mixed with oxygen concentration 8 The mixed gas adjusted to% by volume was added dropwise over 230 minutes while bubbling at a flow rate of 5.2 L / min, and stirring was performed. After completion of the dropping, 1,500 g of water in which 48.06 g (126.4 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added, and the reaction was stopped. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N aqueous hydrochloric acid solution and then pure water. The obtained solution was concentrated to 50% by mass with an evaporator to obtain 1981 g of a toluene solution of a bifunctional phenylene ether oligomer (resin "A"). The polystyrene-equivalent number average molecular weight of the resin "A" by the GPC method was 1975, the polystyrene-equivalent weight average molecular weight by the GPC method was 3514, and the hydroxyl group equivalent was 990.

<< Synthesis of modified polyphenylene ether compound >>
A reactor equipped with a stirrer, a thermometer, and a reflux tube contains 833.4 g of a toluene solution of resin "A", 76.7 g of vinylbenzyl chloride (manufactured by Seimi Chemical Co., Ltd., "CMS-P"), and 1 methylene chloride. , 600 g, 6.2 g of benzyldimethylamine, 199.5 g of pure water, and 83.6 g of a 30.5 mass% 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 1N aqueous hydrochloric acid solution and then pure water. The obtained solution was concentrated with an evaporator, dropped into methanol to solidify, and the solid was recovered by filtration and vacuum dried to obtain 450.1 g of a modified polyphenylene ether compound. The polystyrene-equivalent number average molecular weight of the modified polyphenylene ether compound by the GPC method was 2250, the polystyrene-equivalent weight average molecular weight by the GPC method was 3920, and the vinyl group equivalent was 1189 g / vinyl group.

<Evaluation of manufacturability>
The states of the varnish and copper foil-clad laminates obtained in Examples and Comparative Examples described later were visually evaluated as follows.
A: At the time of varnish, no aggregation of components was observed, and no phase separation was observed even after the copper foil-clad laminate was formed.
B: In the case of varnish, agglomeration of components was observed to some extent, but a copper foil-clad laminate could be produced, and phase separation was not observed even after the copper foil-clad laminate was formed.
C: Separation of the components was observed and the varnish could not be adjusted, or the varnish could be adjusted, but a large amount of agglutination of the components was observed.

<Electrical characteristics (Dk and Df)>
A test piece obtained by etching a 0.8 mm thick copper foil-clad laminate obtained in Examples and Comparative Examples to be described later and removing the copper foil was subjected to a dielectric constant (Dk) at 10 GHz using a perturbation cavity resonator. And the dielectric loss tangent (Df) was measured.
As the perturbation cavity resonator, Agilent 8722ES, a product of Agilent Technologies, Inc. was used.

<Peel strength>
The 0.8 mm thick copper foil-clad laminates obtained in Examples and Comparative Examples described later were subjected to an autograph device (AG-IS manufactured by Shimadzu Corporation) at a temperature of 25 ° C. according to JIS C6481. The bending strength was measured with the number of tests 5, and the average value of the maximum values was used as the measured value. The unit is kN / m.

<Minimum melt viscosity>
Using 1 g of the mixed resin powder obtained in Examples and Comparative Examples described later as a sample, the minimum melt viscosity was measured with a rheometer. Here, a disposable plate having a plate diameter of 25 mm is used, and the mixed resin powder is used under the conditions of a heating rate of 2 ° C./min, a frequency of 10.0 rad / sec, and a strain of 0.1% in the range of 40 ° C. to 200 ° C. The minimum melt viscosity of was measured. The unit is indicated by poise.
As the rheometer, ARES-G2 manufactured by TA Instruments Co., Ltd. was used.

<Example 1>
Biphenyl aralkyl type polymaleimide compound ("MIR-3000", manufactured by Nippon Kayaku Co., Ltd.) 15 parts by mass, SNCN 35 parts by mass obtained in Synthesis Example 1, styrene-isoprene-styrene elastomer ("SEPTON2104", manufactured by Kuraray Co., Ltd.) 10 20 parts by mass, phosphorus-based flame retardant (“PX200”, manufactured by Daihachi Chemical Industry Co., Ltd.), 20 parts by mass of the modified polyphenylene ether compound obtained in Synthesis Example 2, PPE-based coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd.) , X-12-1288) 2.5 parts by mass, spherical silica (SC2500SQ, manufactured by Admatex, average particle diameter 0.5 μm) 100 parts by mass, urethane dispersant (BYK161, manufactured by Big Chemie) 1 part by mass, octyl acid Dissolve 0.05 parts by mass of manganese (“Oct-Mn”, manufactured by Nippon Kagaku Sangyo Co., Ltd., curing accelerator) and 0.3 parts by mass of TPIZ (2,4,5-triphenylimidazole, curing accelerator) with methyl ethyl ketone. And mixed to obtain a varnish. In addition, each of the above-mentioned compounding amounts indicates the solid content amount. The varnish obtained was evaluated for its manufacturability. The results are shown in Table 1 together with the manufacturability of the copper foil-clad laminate.

Further, a mixed resin powder was obtained by evaporating and distilling methyl ethyl ketone from the obtained varnish. The mixed resin powder is filled in a mold having a length of 40 mm × 80 mm and a depth of 0.8 mm, and 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) is placed on both sides, and the pressure is 40 kg / cm ² Vacuum pressing was performed at a temperature of 210 ° C. for 120 minutes to obtain a cured product having a length of 40 mm × 80 mm and a thickness of 0.8 mm. The electrical characteristics (Dk and Df) and peel strength were measured using the obtained cured product. Moreover, the minimum melt viscosity was measured using the mixed resin powder. These results are shown in Table 1.

<Example 2>
In Example 1, the same procedure as in Example 1 was carried out except that the blending amount of the PPE-based coupling agent was changed to 5 parts by mass. The results are shown in Table 1.

<Comparative example 1>
In Example 1, the composition was the same as that of Example 1 except that the PPE-based coupling agent was not blended. Aggregation of the filler was observed, and a uniform varnish could not be prepared. Therefore, no further evaluation was conducted. The results are shown in Table 1.

<Comparative example 2>
The same applies except that in Example 1, the PPE-based coupling agent was changed to an equal amount of epoxy-based coupling agent (manufactured by Shinetsu Silicone Co., Ltd., KBM403, 3-glycidoxypropyltrimethoxysilane, 2.5 parts by mass). The composition was set to. Various evaluations and measurements were performed in the same manner as in Example 1. The results are shown in Table 1.

<Comparative example 3>
In Example 2, the composition is the same except that the PPE-based coupling agent is changed to an equal amount of epoxy-based coupling agent (manufactured by Shinetsu Silicone Co., Ltd., KBM403, 3-glycidoxypropyltrimethoxysilane, 5 parts by mass). And said. Various evaluations and measurements were performed in the same manner as in Example 2. The results are shown in Table 1.

<Comparative example 4>
In Example 1, the modified polyphenylene ether compound and the styrene-isoprene-styrene elastomer obtained in the above Synthesis Example 2 were not blended, and instead, 10 parts by mass of nitrile rubber (N220S, manufactured by JSR Corporation) was blended. It had the same composition. Separation of the components was observed, and it was not possible to prepare a uniform varnish. Therefore, no further evaluation was conducted. The results are shown in Table 1.

As is clear from the above results, the resin composition of the present embodiment was able to achieve high peel strength and low melt viscosity while maintaining low dielectric constant (Dk) and low dielectric loss tangent (Df) (Example 1, 2). It was also excellent in manufacturability. On the other hand, when the compound (A) is not blended, the varnish cannot be produced, or even if it can be produced, the dielectric loss tangent (Df) becomes high, the peel strength becomes small, and the minimum melt viscosity becomes high. (Comparative Examples 1 to 3). Further, even if the compound (A) was blended, the varnish could not be produced unless neither the resin having the aromatic ring structure nor the elastomer having the aromatic ring structure was blended.

Claims (22)

A compound (A) having two or more aromatic ring structures in one molecule and ^{a group represented by −Si (OR 01} ) _m (R ⁰² ) _3-m,
At least one type (B) of a resin having an aromatic ring structure and an elastomer having an aromatic ring structure,
Contains filler (C),
The ^{resin compositions in which R 01} and R ⁰² are each independently a hydrocarbon group and m is an integer of 1 to 3. The resin composition according to claim 1, wherein the compound (A) contains a repeating unit containing an aromatic ring structure. The resin composition according to claim 2, wherein the repeating unit containing the aromatic ring structure of the compound (A) is polyphenylene ether. The resin composition according to claim 1, wherein the compound (A) contains a compound represented by the formula (X);
Equation (X)

In the formula (X), X represents an n-valent organic group containing a polyphenylene ether structure, and R ¹ and R ² are independently alkyl groups having 1 to 10 carbon atoms or 6 to 6 carbon atoms, respectively. Represents an aryl group of 10, A ¹ represents a divalent linking group containing a single bond or a heteroatom, A ² represents a single bond or a divalent linking group, and m is an integer of 1-3. , N is a number from 1 to 10. The resin composition according to claim 1, wherein the compound (A) contains a compound represented by the formula (Y);
Equation (Y)

In the formula (Y), A ² is a single bond or a divalent linking group, and R ¹ and R ² are independently alkyl groups having 1 to 10 carbon atoms or 6 to 10 carbon atoms. Represents the aryl group of, m is an integer of 1 to 3, and n is a number of 1 to 10. The resin composition according to any one of claims 1 to 5, wherein the compound (A) has a weight average molecular weight of 1000 or more. The resin composition according to any one of claims 1 to 6, wherein the elastomer having an aromatic ring structure contains a styrene-based elastomer. The resin composition according to any one of claims 1 to 7, wherein the resin having an aromatic ring structure contains a polyphenylene ether compound. The resin composition according to claim 8, wherein the polyphenylene ether compound contains a polyphenylene ether compound represented by the following formula (1);

In formula (1), X represents an aromatic group, − (Y−О) n ₂₋ represents a polyphenylene ether structure, and R ¹ , R ² and R ³ are independent hydrogen atoms, respectively. It represents an alkyl group, an alkenyl group or an alkynyl group, n ₁ represents an integer of 1 to 6, n ₂ represents an integer of 1 to 100, and n ₃ represents an integer of 1 to 4. The resin composition according to claim 8 or 9, wherein the polyphenylene ether compound has a number average molecular weight of 1000 or more and 7000 or less. The resin composition according to any one of claims 1 to 10, further comprising a maleimide compound. 11. The maleimide compound comprises at least one selected from the group consisting of a compound represented by the formula (2M), a compound represented by the formula (3M), and a compound represented by the formula (4M). The resin composition according to

In formula (2M), R ⁴ independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer greater than or equal to 1.

In formula (3M), R ⁵ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer of 1 or more and 10 or less;

In formula (4M), R ⁶ independently represents a hydrogen atom, a methyl group or an ethyl group, and R ⁷ independently represents a hydrogen atom or a methyl group. The resin composition according to claim 12, wherein the maleimide compound contains a compound represented by the formula (3M). The resin composition according to any one of claims 1 to 13, further comprising a cyanic acid ester compound. The resin composition according to any one of claims 1 to 14, further comprising a flame retardant. The resin composition according to any one of claims 1 to 15, wherein the content of the compound (A) is 1 to 10 parts by mass with respect to 100 parts by mass of the resin component. The resin according to any one of claims 1 to 16, wherein the total content of the resin having an aromatic ring structure and the elastomer having an aromatic ring structure is 1 to 50 parts by mass with respect to 100 parts by mass of the resin component. Composition. The resin composition according to any one of claims 1 to 17, wherein the content of the filler (C) is 50 to 300 parts by mass with respect to 100 parts by mass of the resin component. A prepreg formed from a base material and the resin composition according to any one of claims 1 to 18. A metal foil-clad laminate comprising at least one prepreg according to claim 19 and metal foils arranged on one or both sides of the prepreg. A resin sheet containing a support and a layer formed from the resin composition according to any one of claims 1 to 18 arranged on the surface of the support. A printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer.
A printed wiring board in which the insulating layer includes at least one of a layer formed from the resin composition according to any one of claims 1 to 18 and a layer formed from the prepreg according to claim 19.