JPWO2020004211A1 - Resin composition and its applications - Google Patents

Abstract

Resin compositions that are excellent in various performances such as heat resistance and excellent electrical characteristics, as well as cured products, prepregs, metal foil-clad laminates, resin sheets, printed wiring boards, resin composition manufacturing methods, dielectric constants, and / Or the provision of a dielectric loss tangent lowering agent. A resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the formula (1); in the formula (1), X represents an organic group having 1 to 12 carbon atoms, and R1 to R1. R3 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents an integer of 0 to 4.

Description

The present invention relates to resin compositions. Further, the present invention relates to a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, a method for producing a resin composition, and a dielectric constant and / or a dielectric loss tangent lowering agent using the resin composition.

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 Document 1 describes a specific polyphenylene as a composition having excellent varnish storage stability, improved electrical properties, peel strength, and heat resistance without lowering multi-layer moldability and heat resistance after moisture absorption. A bifunctional vinylbenzyl compound containing an ether skeleton, a specific maleimide compound, a specific cyanate ester resin, and a specific epoxy resin are disclosed as constituents in a predetermined ratio.

On the other hand, Patent Document 2 describes bismaleimide having a specific structure, (b) one or more liquid co-reactants which may optionally additionally contain other additives, and (c) structural fibers. There is a description about the prepreg consisting of. However, there is no description about electrical characteristics and the like.

Japanese Unexamined Patent Publication No. 2010-138364 Japanese Unexamined Patent Publication No. 05-25298

As described above, a resin composition containing a cyanate ester compound and a maleimide compound having excellent electrical properties is known. However, with the recent technological innovation, further improvement of electrical characteristics is required. Moreover, even if it is excellent in electrical characteristics, it lacks usefulness if other performances are inferior.
An object of the present invention is to solve such a problem, which is a resin composition containing a cyanate ester compound and a maleimide compound, which is excellent in various performances such as heat resistance and excellent in electrical characteristics. It is an object of the present invention to provide a resin composition and a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, a method for producing the resin composition, a dielectric constant and / or a dielectric loss tangent lowering agent.

式（１）中、Ｘは炭素数１〜１２の有機基を表し、Ｒ^１〜Ｒ^３は、各々独立に水素原子または炭素数１〜３のアルキル基を表し、ａは各々独立に０〜４の整数を表す。
＜２＞式（１）中、Ｘは炭素数１〜３のアルキレン基であり、Ｒ^１〜Ｒ^３は、各々独立に水素原子、メチル基またはエチル基を表し、ａは各々独立に０〜２の整数を表す、＜１＞に記載の樹脂組成物。
＜３＞前記ビスマレイミド化合物（Ｂ）が下記式（２）で表される、＜１＞に記載の樹脂組成物。

＜４＞さらに溶媒を含有する、＜１＞〜＜３＞のいずれか１つに記載の樹脂組成物。
＜５＞前記ビスマレイミド化合物（Ｂ）の含有量が、樹脂組成物の０．１〜３０質量％である＜４＞に記載の樹脂組成物。
＜６＞前記シアン酸エステル化合物（Ａ）および前記ビスマレイミド化合物（Ｂ）の含有割合が、前記ビスマレイミド化合物（Ｂ）の不飽和イミド基と前記シアン酸エステル化合物（Ａ）のシアネート基との当量比（不飽和イミド基の当量／シアネート基の当量）で表して、０．０１以上１．１未満である、＜１＞〜＜５＞のいずれか１つに記載の樹脂組成物。
＜７＞前記ビスマレイミド化合物（Ｂ）以外のマレイミド化合物、エポキシ樹脂、フェノール樹脂、オキセタン樹脂、ベンゾオキサジン化合物、重合可能な不飽和基を有する化合物、炭素−炭素不飽和二重結合（マレイミドを除く）を含有する置換基により末端変性された変性ポリフェニレンエーテル、エラストマーおよび活性エステル化合物よりなる群から選択される１種以上をさらに含有する、＜１＞〜＜６＞のいずれか１つに記載の樹脂組成物。
＜８＞さらに充填材（Ｃ）を含有する、＜１＞〜＜７＞のいずれか１つに記載の樹脂組成物。
＜９＞前記充填材（Ｃ）の含有量が、前記樹脂組成物中の樹脂成分の総量１００質量部に対して、５０〜１６００質量部である、＜８＞に記載の樹脂組成物。
＜１０＞低誘電率材料および／または低誘電正接材料である、＜１＞〜＜９＞のいずれか１つに記載の樹脂組成物。
＜１１＞＜１＞〜＜１０＞のいずれか１つに記載の樹脂組成物の硬化物。
＜１２＞基材と、＜１＞〜＜１０＞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。
＜１３＞少なくとも１枚の＜１２＞に記載のプリプレグから形成された層と、前記プリプレグから形成された層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。
＜１４＞支持体と、前記支持体の表面に配置された＜１＞〜＜１０＞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。
＜１５＞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＞〜＜１０＞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＜１２＞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。
＜１６＞シアン酸エステル化合物（Ａ）と、下記式（１）で表されるビスマレイミド化合物（Ｂ）を含有する樹脂組成物の製造方法であって、シアン酸エステル化合物（Ａ）とビスマレイミド化合物（Ｂ）と溶媒を混合することを含み、前記ビスマレイミド化合物（Ｂ）の含有量が、樹脂組成物の０．１〜３０質量％である樹脂組成物の製造方法；

式（１）中、Ｘは炭素数１〜１２の有機基を表し、Ｒ^１〜Ｒ^３は、各々独立に水素原子または炭素数１〜３のアルキル基を表し、ａは各々独立に０〜４の整数を表す。
＜１７＞さらに、前記ビスマレイミド化合物（Ｂ）以外のマレイミド化合物、エポキシ樹脂、フェノール樹脂、オキセタン樹脂、ベンゾオキサジン化合物、重合可能な不飽和基を有する化合物、炭素−炭素不飽和二重結合（マレイミドを除く）を含有する置換基により末端変性された変性ポリフェニレンエーテル、エラストマーおよび活性エステル化合物よりなる群から選択される１種以上を含有する、＜１６＞に記載の樹脂組成物の製造方法。
＜１８＞下記式（１）で表されるビスマレイミド化合物（Ｂ）を含む、誘電率および／または誘電正接の低下剤；

式（１）中、Ｘは炭素数１〜１２の有機基を表し、Ｒ^１〜Ｒ^３は、各々独立に水素原子または炭素数１〜３のアルキル基を表し、ａは各々独立に０〜４の整数を表す。As a result of studies by the present inventor based on the above problems, a resin composition having excellent various performances such as heat resistance and improved electrical properties can be obtained by using a bismaleimide compound having a specific structure. We have found that it can be obtained and have completed the present invention. Specifically, the above-mentioned problems were solved by the following means <1>, preferably by <2> to <18>.
<1> A resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1);

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents 0 to 0. Represents an integer of 4.
<2> In the formula (1), X is an alkylene group having 1 to 3 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom, a methyl group or an ethyl group, and a independently represents 0 to 0. The resin composition according to <1>, which represents an integer of 2.
<3> The resin composition according to <1>, wherein the bismaleimide compound (B) is represented by the following formula (2).

<4> The resin composition according to any one of <1> to <3>, which further contains a solvent.
<5> The resin composition according to <4>, wherein the content of the bismaleimide compound (B) is 0.1 to 30% by mass of the resin composition.
<6> The content ratio of the cyanate ester compound (A) and the bismaleimide compound (B) is the unsaturated imide group of the bismaleimide compound (B) and the cyanate group of the cyanate ester compound (A). The resin composition according to any one of <1> to <5>, which is expressed as an equivalent ratio (equivalent of unsaturated imide group / equivalent of cyanate group) and is 0.01 or more and less than 1.1.
<7> Maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, carbon-carbon unsaturated double bonds (excluding maleimides) ) Is further contained in one or more selected from the group consisting of a modified polyphenylene ether terminal-modified with a substituent containing (), an elastomer and an active ester compound, according to any one of <1> to <6>. Resin composition.
<8> The resin composition according to any one of <1> to <7>, which further contains a filler (C).
<9> The resin composition according to <8>, wherein the content of the filler (C) is 50 to 1600 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.
<10> The resin composition according to any one of <1> to <9>, which is a low dielectric constant material and / or a low dielectric loss tangent material.
<11> A cured product of the resin composition according to any one of <1> to <10>.
<12> A prepreg formed from a base material and the resin composition according to any one of <1> to <10>.
<13> A metal leaf-clad laminate comprising at least one layer formed from the prepreg according to <12> and metal foils arranged on one or both sides of the layer formed from the prepreg.
<14> A resin sheet containing a support and a layer formed from the resin composition according to any one of <1> to <10> arranged on the surface of the support.
<15> 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 <10>. A printed wiring board containing at least one of a layer formed from an object and a layer formed from the prepreg according to <12>.
<16> A method for producing a resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1), wherein the cyanate ester compound (A) and bismaleimide are produced. A method for producing a resin composition, which comprises mixing the compound (B) and a solvent, and the content of the bismaleimide compound (B) is 0.1 to 30% by mass of the resin composition;

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents 0 to 0. Represents an integer of 4.
<17> Further, a maleimide compound other than the bismaleimide compound (B), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, and a carbon-carbon unsaturated double bond (maleimide). The method for producing a resin composition according to <16>, which contains at least one selected from the group consisting of a modified polyphenylene ether terminal-modified with a substituent containing (excluding), an elastomer and an active ester compound.
<18> Dielectric constant and / or dielectric loss tangent lowering agent containing the bismaleimide compound (B) represented by the following formula (1);

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents 0 to 0. Represents an integer of 4.

According to the present invention, it has become possible to provide a resin composition containing a cyanate ester compound and a maleimide compound, which is excellent in various performances such as heat resistance and excellent in electrical characteristics. Further, it has become possible to provide an excellent cured product, a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, a method for producing a resin composition, a dielectric constant and / or a dielectric loss tangent lowering agent.

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.

式（１）中、Ｘは炭素数１〜１２の有機基を表し、Ｒ^１〜Ｒ^３は、各々独立に水素原子または炭素数１〜３のアルキル基を表し、ａは各々独立に０〜４の整数を表す。
シアン酸エステル化合物（Ａ）に、式（１）で表されるビスマレイミド化合物（Ｂ）を配合することにより、各種性能（低吸水率、低加熱減量、良好なワニスの外観）を維持しつつ、誘電率（Ｄｋ）および誘電正接（Ｄｆ）を低くすることが可能になる。さらに、プリプレグとしたときの外観や、金属箔張積層板としたときの、ピール強度、耐熱性、難燃性なども高いレベルを維持できる。
以下、本発明の実施形態（以下、「本実施形態」ともいう）を例に用いて、本発明について詳細に説明する。The resin composition according to the present invention is characterized by being a resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1).

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents 0 to 0. Represents an integer of 4.
By blending the cyanate ester compound (A) with the bismaleimide compound (B) represented by the formula (1), various performances (low water absorption rate, low heating weight loss, good appearance of varnish) are maintained. , Dielectric constant (Dk) and dielectric loss tangent (Df) can be lowered. Furthermore, it is possible to maintain a high level of appearance when used as a prepreg, and high levels of peel strength, heat resistance, flame retardancy, etc. when used as a metal leaf-clad laminate.
Hereinafter, the present invention will be described in detail using an embodiment of the present invention (hereinafter, also referred to as “the present embodiment”) as an example.

<Cyanic acid ester compound (A)>
The cyanate ester compound (A) in the present embodiment is not particularly specified as long as it is a compound having a cyanate structure.
Examples of the cyanate ester compound (A) include naphthol aralkyl type cyanate compound (naphthol aralkyl type cyanate), naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, and trisphenol methane type cyanate ester. At least one selected from the group consisting of compounds and adamantan skeleton-type cyanate ester compounds can be mentioned. Among these, from the viewpoint of further improving plating adhesion and low water absorption, it was selected from the group consisting of naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, and xylene resin type cyanate ester compounds. It is preferably at least one kind, and more preferably a naphthol aralkyl type cyanate ester compound. 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 equivalent of the cyanate group of the cyanate ester compound (A) is preferably 200 g / eq or more, and preferably 400 g / eq or less. When a plurality of types of cyanate ester compounds (A) are contained, the weighted average cyanate group equivalent is used in consideration of the mass of each cyanate ester compound contained in the resin composition.

The lower limit of the content of the cyanate ester compound (A) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. , 20 parts by mass or more, more preferably 30 parts by mass or more, and may be 40 parts by mass or more. When the content of the cyanate ester compound is 1 part by mass or more, more preferably 10 parts by mass or more, heat resistance, combustion resistance, chemical resistance, low dielectric constant, low dielectric loss tangent, and insulating property tend to be improved. It is in. 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, and 70 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. It is more preferably parts or less, and even more preferably 60 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.

式（１）中、Ｘは炭素数１〜１２の有機基を表し、Ｒ^１〜Ｒ^３は、各々独立に水素原子または炭素数１〜３のアルキル基を表し、ａは各々独立に０〜４の整数を表す。<Bismaleimide compound (B) represented by the formula (1)>
The resin composition in this embodiment contains a bismaleimide compound (B) represented by the following formula (1).

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents 0 to 0. Represents an integer of 4.

式（１−２）中、Ｘは炭素数１〜１２の有機基を表し、Ｒ^１〜Ｒ^３は、各々独立に水素原子または炭素数１〜３のアルキル基を表し、ａは各々独立に０〜４の整数を表す。
式（１−２）における、Ｘ、Ｒ^１〜Ｒ^３およびａは、各々、式（１）におけるＸ、Ｒ^１〜Ｒ^３およびａと同義であり、好ましい範囲も同様である。式（１−２）で表されるビスマレイミド化合物を用いることにより、樹脂組成物の電気特性および耐熱性（特に、加熱減量の抑制）がより向上する傾向にある。In the formula (1), X represents an organic group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an isopropylene group. The two Xs may be the same or different. It is preferably the same.
R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom, a methyl group or an ethyl group is preferable, and a hydrogen atom is more preferable.
It is preferable that a independently represents an integer of 0 to 2, 0 or 1 is more preferable, and 0 is further preferable.
The bismaleimide compound (B) is preferably represented by the formula (1-2).

In formula (1-2), X represents an organic group having 1 to 12 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents an alkyl group having 1 to 3 carbon atoms. Represents an integer from 0 to 4.
In formula (1-2), ^X, R 1 to R ³ and a are each the same meaning as ^X, R 1 to R ³ and a in the formula (1), and preferred ranges are also the same. By using the bismaleimide compound represented by the formula (1-2), the electrical characteristics and heat resistance (particularly, suppression of heat loss) of the resin composition tend to be further improved.

The bismaleimide compound (B) represented by the formula (1) is preferably represented by the following formula (2).

The bismaleimide compound (B) used in the present embodiment is more preferably any of the following.

The equivalent of the unsaturated imide group of the bismaleimide compound (B) is preferably 200 g / eq or more, and preferably 400 g / eq or less. When a plurality of types of bismaleimide compounds (B) are contained, the weighted average unsaturated imide group equivalent is used in consideration of the mass of each bismaleimide compound (B) contained in the resin composition.

The lower limit of the content of the bismaleimide compound (B) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. It is more preferably 5 parts by mass or more, and further, 8 parts by mass or more, 10 parts by mass or more, and 15 parts by mass or more may be used. When the content of the bismaleimide compound (B) is 1 part by mass or more, the flame resistance tends to be improved. Further, the upper limit of the content of the bismaleimide compound (B) is 90 parts by mass or less with respect to 100 parts by mass of the total amount of the resin components in the resin composition when the bismaleimide compound (B) is contained. It is preferably 75 parts by mass or less, more preferably 60 parts by mass or less, further preferably 45 parts by mass or less, further preferably 35 parts by mass or less, and 30 parts by mass. The following is even more preferable.

The content of the bismaleimide compound (B) is preferably 0.1 to 30% by mass of the resin composition.
In particular, the lower limit of the content of the bismaleimide compound (B) is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass, based on the solid content (components other than the solvent). It is more preferably mass% or more. The upper limit value is preferably 90% by mass or less, more preferably 70% by mass or less, and further preferably 50% by mass or less.
The content of the bismaleimide compound (B) is preferably 0.1 to 30% by mass in the resin composition after being diluted with the solvent (in the resin composition containing the solvent). The lower limit of the content of the bismaleimide compound (B) is preferably 1% by mass or more, more preferably 5% by mass or more. It is more preferably 10% by mass or more. The upper limit value is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 17.5% by mass or less.
Within such a range, the appearance of the varnish, the appearance of the prepreg, and the electrical characteristics of the laminated board can be further improved.
The resin composition according to the present embodiment may contain only one type of bismaleimide compound (B), or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
The resin composition according to the present embodiment may contain only one type of bismaleimide compound (B), or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

The content ratio of the cyanate ester compound (A) and the bismaleimide compound (B) in the resin composition according to the present embodiment is the unsaturated imide group of the bismaleimide compound (B) and the cyanate ester compound (A). It is preferably 0.01 or more and less than 1.1 in terms of the equivalent ratio with the cyanate group (equivalent of unsaturated imide group / equivalent of cyanate group). The lower limit of the equivalent ratio is more preferably 0.05 or more, further preferably 0.1 or more, and even more preferably 0.3 or more. The upper limit of the equivalent ratio is more preferably 0.9 or less, further preferably 0.7 or less, and even more preferably 0.5 or less. Within such a range, the effects of water absorption rate, electrical characteristics, and thermophysical characteristics are more effectively exhibited.

<Other resin components>
The resin composition according to the present embodiment may contain other resin components other than the cyanate ester compound (A) and the bismaleimide compound (B). Other resin components include maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, and carbon-carbon unsaturated double bonds ( One or more selected from the group consisting of modified polyphenylene ethers, elastomers and active ester compounds terminally modified with a substituent containing (excluding maleimide) is exemplified, and maleimide compounds other than the bismaleimide compound (B) and epoxy resins are exemplified. , Phenol resin, oxetane resin, benzoxazine compound, and preferably one or more selected from the group consisting of compounds having a polymerizable unsaturated group, and at least a maleimide compound other than the bismaleimide compound (B). It is more preferable to include it. By blending such other resin components, the appearance can be further improved and other properties can be made better.

<< Maleimide compounds other than bismaleimide compound (B) >>
The maleimide compound other than the bismaleimide compound (B) (hereinafter, also referred to as another maleimide compound) is a maleimide compound other than the bismaleimide compound (B) and may have two or more maleimide groups in the molecule. There is no particular limitation. In particular, by using a maleimide compound having high solubility in a solvent, the appearance of the varnish and the appearance of the prepreg obtained from the varnish can be improved while improving the electrical characteristics. The other maleimide compound used in the present embodiment has, for example, a solubility in methyl ethyl ketone at 25 ° C. of preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 20% by mass or more. More preferred. Since methyl ethyl ketone has a relatively low boiling point, the drying temperature can be lowered when the solvent is dried, and unnecessary curing of the resin component during drying can be effectively suppressed.
As an example of another maleimide compound, a maleimide compound represented by the formula (1-3) can be mentioned. By using the maleimide compound represented by the formula (1-3), when it is used as a material for a printed wiring board (for example, a laminated board, a metal foil-clad laminated board), excellent heat resistance can be imparted and peel strength can be imparted. , Low water absorption, desmear resistance, and flame resistance can be improved.

前記式（１−３）中、複数存在するＲは、それぞれ独立に、水素原子、炭素数１〜５のアルキル基またはフェニル基を表し、ｎは、平均値であり、１＜ｎ≦５を表す。
前記式（１−３）中、複数存在するＲは、それぞれ独立して、水素原子、炭素数１〜５のアルキル基（例えば、メチル基、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−ペンチル基等）、またはフェニル基を表す。これらの中でも、耐燃性およびピール強度をより一層向上する観点から、水素原子、メチル基、およびフェニル基からなる群より選択される基であることが好ましく、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。

In the above formula (1-3), a plurality of Rs independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, n is an average value, and 1 <n ≦ 5 show.
In the above formula (1-3), each of a plurality of Rs present independently has a hydrogen atom and an alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-). It represents a butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc.), or a phenyl group. Among these, from the viewpoint of further improving flame resistance and peel strength, it is preferable that the group is selected from the group consisting of a hydrogen atom, a methyl group, and a phenyl group, and it is one of the hydrogen atom and the methyl group. Is more preferable, and a hydrogen atom is further preferable.

In the above formula (1-3), n is an average value and represents 1 <n ≦ 5. From the viewpoint of further excellent solvent solubility, n is preferably 4 or less, more preferably 3 or less, and further preferably 2 or less. Two or more compounds having different n may be contained.

The maleimide compound represented by the above formula (1-3) may be prepared by a known method, or a commercially available product may be used. Examples of commercially available products include "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.

In addition to the above, other maleimide compounds include 4,lu-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, and 1,6-bismaleimide. -(2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulphon bismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis ( 4-Maleimidephenoxy) benzene, polyphenylmethane maleimide, and prepolymers thereof, prepolymers of these maleimides and amines, and the like can be mentioned.

The equivalent of unsaturated imide groups of other maleimide compounds is preferably 200 g / eq or more, and preferably 400 g / eq or less. When a plurality of other maleimide compounds are contained, the weighted average unsaturated imide group equivalent is used in consideration of the mass of each other maleimide compound contained in the resin composition.

When the other maleimide compound is contained, the lower limit of the content of the other maleimide compound is preferably 1 part by mass or more, preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. It is more preferable that the amount is 20 parts by mass or more. When the content of the other maleimide compound is 1 part by mass or more, the flame resistance of the resin composition tends to be improved. Further, the upper limit of the content of the other maleimide compound is preferably 90 parts by mass or less when the total amount of the resin components in the resin composition is 100 parts by mass when the other maleimide compound is contained. It is more preferably 85 parts by mass or less, further preferably 75 parts by mass or less, further preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and 55 parts by mass or less. It is even more preferable that the amount is 45 parts by mass or less. When the content of the other maleimide compound is 90 parts by mass or less, the peel strength and low water absorption tend to be improved.
In particular, the resin composition in the present embodiment preferably contains both the bismaleimide compound represented by the formula (1) and the maleimide compound represented by the formula (1-3). The mass ratio of the bismaleimide compound represented by the formula (1) to the maleimide compound represented by the formula (1-3) in the resin composition is preferably 1: 0.1 to 2.0. It is more preferably 1: 1.0 to 2.0, further preferably 1: 1.2 to 1.8, and even more preferably 1: 1.4 to 1.6. With such a ratio, the appearance of the obtained varnish and the electrical characteristics of the cured product can be compatible at a high level.
The resin composition in the present embodiment may contain only one type of other 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.

<< 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, the lower limit of the epoxy resin content is 0.1 parts by mass or more when the total amount of resin components in the resin composition is 100 parts by mass when the epoxy resin is contained. It is preferably 1 part by mass or more, and further preferably 2 parts by mass or more. When the content of the epoxy resin is 0.1 part by mass or more, the peel strength and toughness of the metal foil (copper foil) tend to be improved. When the epoxy resin is contained, the upper limit of the epoxy resin content is preferably 50 parts by mass or less, preferably 30 parts by mass or less, when the total amount of the resin components in the resin composition is 100 parts by mass. It is more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and further 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 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.

<< Phenol resin >>
The phenol resin is not particularly limited as long as it is a 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 the phenol resin is contained, the content of the phenol resin is preferably 0.1 part by mass or more and 50 parts by mass or less when the total amount of the resin components in the resin composition is 100 parts by mass. Is preferable.
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 total amount of the resin components 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-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, and the like. 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 (Products of Toa Synthetic Co., Ltd.) and the like.

The oxetane resin is preferably contained within a range that does not impair the effects of the present invention. When the oxetane resin is contained, the lower limit of the content of the oxetane resin is preferably 0.1 part by mass or more, preferably 1 part by mass or more, when the total amount of the resin components in the resin composition is 100 parts by mass. It is more preferable that the amount is 2 parts by mass or more. When the content of the oxetane resin is 0.1 parts by mass or more, the peel strength and toughness of the metal foil (copper foil) tend to be improved. When the oxetane resin is contained, the upper limit of the content of the oxetane resin is preferably 50 parts by mass or less, preferably 30 parts by mass or less, when the total amount of the resin components in the resin composition is 100 parts by mass. 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. When the content of the oxetane resin is 50 parts by mass or less, the electrical characteristics of the resin composition tend to be further 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 parts by mass with respect to 100 parts by mass of the total amount of the resin components 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 the benzoxazine compound is contained, the content of the benzoxazine compound is preferably 0.1 part by mass or more, preferably 50 parts by mass or less, when the total amount of the resin components in the resin composition is 100 parts by mass. It is preferable to have.
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 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.

<< Compound with polymerizable unsaturated group >>
The compound having a polymerizable unsaturated group is not particularly limited, and any compound having two or more polymerizable unsaturated groups may be used.
Compounds having polymerizable unsaturated groups include, for example, vinyl compounds (eg, ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl, etc.), acrylates (eg, methyl (meth) acrylate, etc.), mono- or polyalcolate. (Meta) acrylates (for example, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropandi (meth) acrylate, trimethylolpropantri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, etc.), epoxy (meth) acrylates (for example, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, etc.), benzocyclobetane resin and the like. ..

The compound having a polymerizable unsaturated group is preferably contained within a range that does not impair the effects of the present invention. The content of the compound having a polymerizable unsaturated group is preferably 0.1 part by mass or more when the total amount of the resin components in the resin composition is 100 parts by mass when the compound is contained. It is preferably 50 parts by mass or less.
The resin composition in the present embodiment may contain only one compound having a polymerizable unsaturated group, or may contain two or more compounds. 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 a compound having a polymerizable unsaturated group. The term "substantially free" means that the content of the compound having a polymerizable unsaturated group is less than 0.1 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.

<< Modified polyphenylene ether terminal-modified with a substituent containing a carbon-carbon unsaturated double bond (excluding maleimide) >>
A modified polyphenylene ether terminally modified with a substituent containing a carbon-carbon unsaturated double bond (excluding maleimide), for example, all or part of the terminal of the polyphenylene ether has a carbon-carbon unsaturated double bond. It is a modified product terminally modified by the substituent having. The substituent having a carbon-carbon unsaturated double bond is not particularly limited as long as it is not a maleimide group, and examples thereof include an ethylenically unsaturated group. 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 cycloalkenyl 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 term "polyphenylene ether" as used herein refers to a compound having a phenylene ether skeleton represented by the following formula (X1).

（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、炭素数６以下のアルキル基、アリール基、ハロゲン原子、または水素原子を表す。）

(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 atom, or a hydrogen atom having 6 or less carbon atoms.)

（式（Ｘ２）中、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３４、Ｒ^３５は、同一であっても、異なってもよく、炭素数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、同一であっても、異なってもよく、水素原子、炭素数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、同一であっても、異なってもよく、水素原子、炭素数６以下のアルキル基またはフェニル基である。−Ａ−は、炭素数２０以下の直鎖状、分岐状または環状の２価の炭化水素基である）で表される繰り返し単位をさらに含んでもよい。The modified polyphenylene ether has the formula (X2) :.

(In formula (X2), R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , and R ³⁵ may be the same or different, and are alkyl or phenyl groups having 6 or less carbon atoms. R ³¹ , R ³² and R ³³ may be the same or different, and are 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 have a hydrogen atom and 6 or less carbon atoms. -A- may further contain a repeating unit represented by a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

As the modified polyphenylene ether, a modified polyphenylene ether in which a part of the terminal is functionalized with an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxy group, a silyl group or the like can also be used. These may be used alone or in combination of two or more.

The method for producing the modified polyphenylene ether is not particularly limited as long as the effects of the present invention can be obtained. For example, in the case of being functionalized with a vinylbenzyl group, a bifunctional phenylene ether oligomer and vinylbenzyl chloride are dissolved in a solvent, a base is added under heating and stirring to react, and then the resin is solidified. Can be manufactured. A carboxy group functionalized product is produced, for example, by melt-kneading an unsaturated carboxylic acid or a functionalized derivative thereof with a polyphenylene ether in the presence or absence of a radical initiator and reacting them. NS. Alternatively, it is produced by dissolving a polyphenylene ether 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 preferably contains a modified polyphenylene ether having ethylenically unsaturated groups at both ends (hereinafter, may be referred to as "modified polyphenylene ether (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 cycloalkenyl 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.

（式（Ｇ１）中、Ｘは芳香族基を示し、（Ｙ）ｍはポリフェニレンエーテル部分を示し、Ｒ^Ｇ１、Ｒ^Ｇ２、Ｒ^Ｇ３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示し、ｍは１〜１００の整数を示し、ｎは１〜６の整数を示し、ｑは１〜４の整数を示す。好ましくは、Ｒ^Ｇ１、Ｒ^Ｇ２、Ｒ^Ｇ３は水素原子である。）
好ましくは、ｎは１以上４以下の整数であり、さらに好ましくは、ｎは１または２であり、一層好ましくは、ｎは１である。また、好ましくは、ｑは１以上３以下の整数であり、さらに好ましくは、ｑは１または２であり、一層好ましくはｑは２である。Examples of the modified polyphenylene ether (g) having an ethylenically unsaturated group at the terminal (hereinafter, may be simply referred to as modified polyphenylene ether (g)) include a structure represented by the formula (G1).

(In the formula (G1), X represents an aromatic group, (Y) m represents a polyphenylene ether moiety, and ^RG1 , ^RG2 , and ^RG3 are independently hydrogen atoms, alkyl groups, alkenyl groups, or alkynyl groups, respectively. , M represents an integer of 1 to 100, n represents an integer of 1 to 6, q represents an integer of 1 to 4. Preferred, ^RG1 , ^RG2 , and ^RG3 are hydrogen atoms. )
Preferably n is an integer greater than or equal to 1 and less than or equal to 4, more preferably n is 1 or 2, and even more preferably n is 1. Further, q is preferably an integer of 1 or more and 3 or less, more preferably q is 1 or 2, and even more preferably q is 2.

ここで、−（Ｏ−Ｘ−Ｏ）−は、式（Ｇ３）：

（式（Ｇ３）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（Ｇ４）：

（式（Ｇ４）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、炭素数２０以下の直鎖状、分岐状または環状の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 (g) in the present embodiment is preferably represented by the formula (G2).

Here, − (OX—O) − is the equation (G3) :.

(In formula (G3), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , 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 formula (G4):

(In formula (G4), 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 may be a hydrogen atom, an alkyl group having 6 or less carbon atoms, or an alkyl group having 6 or less carbon atoms. It is a phenyl group. -A- is preferably a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms).

（式（Ｇ５）中、Ｒ^２２およびＲ^２３は、同一または異なってもよく、炭素数６以下のアルキル基またはフェニル基である。Ｒ^２０およびＲ^２１は、同一または異なってもよく、水素原子、炭素数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。
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、ｂが２以上の整数の場合、−（Ｙ−Ｏ）−ａまたは−（Ｙ−Ｏ）−ｂは、１種の式（Ｇ５）で表される構造が配列していてもよく、２種以上の式（Ｇ５）で表される構造がランダムに配列していてもよい。Further,-(YO)-is the formula (G5) :.

(In formula (G5), R ²² and R ²³ may be the same or different and are alkyl or phenyl groups having 6 or less carbon atoms. R ²⁰ and R ²¹ may be the same or different and are hydrogen atoms. , It is preferably an alkyl group or a phenyl group having 6 or less carbon atoms.
a and b represent integers from 0 to 100 in which at least one of them is not 0. When a and b are integers of 2 or more,-(YO) -a or-(YO) -b may be arranged with a structure represented by one kind of formula (G5). The structures represented by two or more kinds of formulas (G5) may be randomly arranged.

Examples of -A- in the formula (G4) include methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 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.

Said modified poly Among the polyphenylene ether (g) ^is a ^{R 4, R 5, R 6} , R 10, R 11, R 20, R 21 is an alkyl group having 3 or less carbon ^{atoms, R 7, R 8, R} 9 , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² and R ²³ are preferably hydrogen atoms or polyphenylene ethers having an alkyl group having 3 or less carbon atoms, particularly the formula. -(O-X-O)-represented by (G3) or the formula (G4) is the formula (9), the formula (10), and / or the formula (11), and is represented by the formula (G5). -(YO)-preferably is the formula (12) or the formula (13). When a and b are integers of 2 or more,-(YO) -a or-(YO) -b is a structure in which equation (12) or equation (13) is arranged, or equation (12). It is preferable that the structure (13) is randomly arranged.

（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、炭素数２０以下の直鎖状、分岐状または環状の２価の炭化水素基である。）
−Ｂ−は、式（Ｇ４）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、炭素数２０以下の直鎖状、分岐状または環状の２価の炭化水素基である。）
−Ｂ−は、式（Ｇ４）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 product having 20 or less carbon atoms. It is a divalent hydrocarbon group in the form or cyclic.)
As the specific example of −B−, the same specific example as that of −A− in the formula (G4) can be mentioned.

(In the 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 (G4) can be mentioned.

The polystyrene-equivalent number average molecular weight of the modified polyphenylene ether 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 according to the present embodiment is used as 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 modified polyphenylene ether 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, the carbon-carbon unsaturated double bond equivalent at the terminal of the modified polyphenylene ether is preferably 400 to 5000 g, more preferably 400 g to 2500 g per carbon-carbon unsaturated double bond. 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 upper limit or less, the solubility in a solvent, low viscosity and moldability tend to be further improved.

The method (production method) for preparing the modified polyphenylene ether represented by the formula (2) in the present embodiment is not particularly limited, and for example, a bifunctional phenol compound and a monofunctional phenol compound are oxidatively coupled to 2 It can be produced by a step of obtaining a functional 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). Further, as such a modified polyphenylene ether, for example, Mitsubishi Gas Chemical Company, Inc. (OPE-2St1200, etc.) 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, a base is added under heating and stirring to react, 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.

The lower limit of the content of the modified polyphenylene ether is preferably 1 part by mass or more, preferably 5 parts by mass or more, when the total amount of the resin components in the resin composition is 100 parts by mass when the modified polyphenylene ether is contained. It is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, further preferably 20 parts by mass or more, and further preferably 25 parts by mass or more. More preferred. When the modified polyphenylene ether is contained, the upper limit of the content of the modified polyphenylene ether is preferably 90 parts by mass or less, preferably 85 parts by mass or less, when the total amount of the resin components in the resin composition is 100 parts by mass. It is more preferably 70 parts by mass or less, and further preferably 60 parts by mass or less. When the content of the modified polyphenylene ether 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 modified polyphenylene ether, or may contain two or more types of modified polyphenylene ether. When two or more kinds are included, the total amount is preferably in the above range.

<< Elastomer >>
The elastomer is not particularly limited, and known elastomers can be widely used.
Examples of the elastomer include polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluororubber, and silicone. Included is at least one selected from the group consisting of rubbers, their hydrogenated compounds, their alkyl compounds, and their copolymers. Among these, from the viewpoint of excellent electrical characteristics, styrene butadiene, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, their hydrogenated compounds, and their alkyl compounds. , And at least one selected from the group consisting of copolymers thereof, and from the viewpoint of being more excellent in compatibility with modified polyphenylene ether, from the group consisting of styrene-butadiene rubber, butadiene rubber, and isoprene rubber. More preferably, it is at least one selected.

The elastomer in the present embodiment preferably has an SP value of 9 (cal / cm ³ ) ^1/2 or less from the viewpoint of excellent electrical characteristics. The SP value is called a dissolution parameter and is calculated from the square root (cal / cm ³ ) ^{1/2 of the heat generation required for the liquid of 1 cm 3 to evaporate.} Generally, the smaller this value is, the lower the polarity is, and the closer this value is, the higher the affinity between the two components is. When the SP value of the elastomer is 9 (cal / cm ³ ) ^1/2 or less, it is used for high frequency applications. More suitable electrical properties can be obtained with the resin composition used for the printed wiring board.

If the elastomer in the present embodiment has a polystyrene-equivalent weight average molecular weight of 80,000 or more by the GPC method and is solid at 25 ° C., it can be used as a material for a printed wiring board (for example, a laminated board, a metal foil-clad laminated board) or the like. When used, it is preferable because the crack resistance is further improved. On the other hand, if the polystyrene-equivalent weight average molecular weight by the GPC method is 40,000 or less and the liquid is liquid at 25 ° C., the warp when the film is applied to the substrate is reduced, so that the printed wiring board is built up. It is particularly suitable as a material.

The elastomer is preferably contained within a range that does not impair the effects of the present invention. When the elastomer is contained, the lower limit of the elastomer content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. It is more preferably 5 parts by mass or more. When the content of the elastomer is 5 parts by mass or more, the electrical characteristics tend to be further improved. When the elastomer is contained, the upper limit of the elastomer content is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, based on 100 parts by mass of the total amount of the resin components in the resin composition. , 70 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. When the content of the elastomer is 20 parts by mass or less, the combustion resistance tends to be improved.
The resin composition in the present embodiment may contain only one type of elastomer, 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.
Further, the resin composition in the present embodiment may have a structure that does not substantially contain an elastomer. The term "substantially free" means that the content of the elastomer is less than 1 part by mass with respect to 100 parts by mass of the total amount of the resin components 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, 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 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 and having two or more active ester groups in one molecule is particularly preferable. Examples of the 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 thiocarboxylic acid compound include one or more selected from the group consisting of thioacetic acid and thiobenzoic acid. Examples of the 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, and 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 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 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 improvement, the 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 Corporation), etc.), and acetylated phenol novolac (for example, products of DIC Corporation). , DC808 (a product of Mitsubishi Chemical Corporation)), and a benzoyl compound of phenol novolac (for example, YLH1026, YLH1030, YLH1048 (all products of Mitsubishi Chemical Corporation)). EXB9460S is preferable from the viewpoint of further improving the storage stability of the varnish and the low coefficient of thermal expansion of the cured product.

The method for preparing the active ester compound can be prepared by a known method, and can be obtained, for example, by a condensation reaction between 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 1 mol of the carboxy group or acid halide group of (a) (b). Examples thereof include a method of reacting with 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 the active ester compound is contained, the content of the active ester compound is preferably 1 part by mass or more, and preferably 90 parts by mass or less, based on 100 parts by mass of the total amount of the resin components 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 total amount of the resin components in the resin composition.

When the resin composition in the present embodiment does not contain or substantially does not contain the filler (C) described later, the total amount of the resin components is 70% by mass or more of the components excluding the solvent of the resin composition. It is preferably 80% by mass or more, and more preferably 90% by mass or more.
When the resin composition in the present embodiment contains the filler (C) described later, the total amount of the resin components is preferably 30% by mass or more, preferably 35% by mass or more, of the components excluding the solvent of the resin composition. It is preferably 40% by mass or more, and more preferably 40% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, and further preferably 60% by mass or less.
In any of the above cases, 90% by mass or more of the resin component is composed of the cyanate ester compound (A), the bismaleimide compound (B) represented by the formula (1), and other maleimide compounds. Is preferable.

<Filler (C)>
The resin composition according to 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, and silica is more preferable. The silica is preferably spherical silica. The spherical silica may also be hollow silica.
By using these fillers (C), characteristics 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 according to the present embodiment can be appropriately set according to the desired properties, and is not particularly limited, but the total amount of the resin components in the resin composition is 100 parts by mass. , 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and 75 parts by mass. The above is even more preferable. The upper limit is preferably 1600 parts by mass or less, more preferably 1200 parts by mass or less, further preferably 1000 parts by mass or less, further preferably 750 parts by mass or less, and 500 parts by mass. It is even more preferably parts or less, 300 parts by mass or less, even more preferably 250 parts by mass or less, and may be 200 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.
On the other hand, in the present embodiment, the resin composition may have a structure that does not substantially contain the filler (C). The term "substantially free" means that the content of the filler (C) is less than 1% by mass of the content of the resin component, and is preferably 0.1% by mass or less.

Here, when using the filler (C), it is preferable to use a silane coupling agent and / or a wet dispersant in combination. As the silane coupling agent, those generally used for surface treatment of inorganic substances can be preferably used, and the type thereof is 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. The silane coupling agent may be used alone or in combination of two or more. Further, as the wet dispersant, those generally used for paints can be preferably used, and the type thereof is not particularly limited. Preferably, a copolymer-based wet dispersant is used, and specific examples thereof include Disperbyk-110, 111, 161, 180, 2009, 2152, BYK-W996, BYK-W9010 manufactured by Big Chemie Japan Co., Ltd. , BYK-W903, BYK-W940 and the like. The wet dispersant may be used alone or in combination of two or more.

The content of the silane coupling agent is not particularly limited, and may be about 1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. The content of the dispersant (particularly the wet dispersant) is not particularly limited, and may be, for example, about 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.

<Curing accelerator>
The resin composition according to this 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. Examples thereof include those dissolved in a hydroxyl group-containing compound such as; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; and organic tin compounds such as dioctyl tin oxide and other alkyl tin and alkyl tin oxide.
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 of the content of the curing accelerator is preferably 0.005 parts by mass or more with respect to 100 parts by mass of the total amount of the resin components in the resin composition. It is more preferably 01 parts by mass or more, and further 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, based on 100 parts by mass of the total amount of the resin components in the resin composition. It is more preferably 2 parts by mass or less.
The curing accelerator may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

<Solvent>
The resin composition according to the present embodiment may contain a solvent, and preferably contains an organic solvent. In this case, the resin composition according to 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.). ).
When the resin composition according to the present embodiment contains a solvent, the content thereof is not particularly specified, but can be, for example, 1% by mass or more of the resin composition, even if it is 10% by mass or more. It may be 30% by mass or more and 40% by mass or more. The upper limit value can be 99% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less.
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 falls within the above range.
The resin composition according to the present embodiment preferably has a solid content of 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. It is more preferably 30% by mass or more, and may be 40% by mass or more and 50% by mass or more. The upper limit of the amount of the lone shadow is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and may be 60% by mass or less. ..
The solid content refers to a component of the resin composition excluding the solvent.

<Other ingredients>
In addition to the above-mentioned components, the resin composition according to the present embodiment may contain various polymer compounds such as a thermoplastic resin and an oligomer thereof, and various additives as long as the effects of the present invention are not impaired. .. Additives include flame retardants, UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, defoamers, and dispersions. Examples include agents, leveling agents, brighteners, polymerization inhibitors and the like. These additives may be used alone or in combination of two or more.
Further, the resin composition according to the present embodiment may have a structure that does not substantially contain a flame retardant. The term "substantially free" means that the content of the flame retardant is less than 0.01 parts by mass with respect to 100 parts by mass of the total amount of the resin composition, and is preferably 0 parts by mass. The resin composition in the present embodiment is valuable in that it can maintain high flame retardancy even if it has a structure that does not substantially contain a flame retardant. Specifically, the resin composition in the present embodiment is a flame-retardant material (printed wiring board, etc.) formed to a thickness of 0.8 mm (further 0.4 mm) according to the UL (Underwriters Laboratories Inc.) standard. The sex can be V-0. Flame retardancy is measured according to the description of Examples described below.

<Specific form of resin composition>
A more specific embodiment of the present embodiment will be described below. Needless to say, the present embodiment is not limited to these.
The first specific example of the resin composition according to the present embodiment is a form in which the solid content in the resin composition contains a resin component of 90% by mass or more (preferably 95% by mass or more). In the present embodiment, the resin component preferably contains a cyanate ester compound (A), a bismaleimide compound (B) represented by the formula (1), and another maleimide compound.
In the resin composition of the first specific example, the dielectric constant (Dk) of the test piece formed to a thickness of 0.8 mm at 10 GHz can be 3.0 or less, and can also be 2.8 or less. Ideally, the lower limit of the dielectric constant is 0, but 2.0 or more is practical. Further, in the resin composition of the first specific example, the dielectric loss tangent (Df) of the test piece formed to a thickness of 0.8 mm at 10 GHz can be 0.0050 or less, and can be less than 0.0045. , 0.0044 or less. Ideally, the lower limit of the dielectric constant is 0, but 0.0020 or more is practical. The permittivity and the dielectric loss tangent are measured by the methods described in Examples described later.
In the resin composition of the first specific example, the 1% mass reduction temperature of the test piece formed to a thickness of 0.8 mm can be 370 ° C. or higher, and can also be 380 ° C. or higher. The upper limit of the 1% mass reduction temperature is not particularly determined, but is practically 420 ° C. or lower.
In the resin composition of the first specific example, the mass reduction rate of the test piece formed to a thickness of 0.8 mm at 450 ° C. can be 19.0% or less, and can also be 18.0% or less. The lower limit of the mass reduction rate at 450 ° C. is ideally 0%, but practically 10% or more.

In the second specific example of the resin composition according to the present embodiment, the solid content in the resin composition is 5 to 70% by mass (preferably 20 to 60% by mass) and 95 to 30% by mass (preferably 20 to 60% by mass). It is preferably in the form of containing a filler (80 to 40% by mass). In the present embodiment, the resin component preferably contains a cyanate ester compound (A), a bismaleimide compound (B) represented by the formula (1), and another maleimide compound. The filler is preferably spherical silica.

<Manufacturing method of resin composition>
The method for producing a resin composition according to the present embodiment is a method for producing a resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the formula (1). The content of the bismaleimide compound (B) is 0.1 to 30% by mass (preferably 0) of the resin composition, which comprises mixing the acid ester compound (A), the bismaleimide compound (B) and the solvent. 1 to 20% by mass).
By setting the content of the bismaleimide compound (B) in the above range as described above, it is possible to appropriately dissolve the varnish in a solvent, and further improve the appearance of the varnish and the appearance of the prepreg. Becomes possible. In particular, by using the bismaleimide compound represented by the above formula (1-2) as the bismaleimide compound represented by the formula (1), the appearance can be further improved.
Further, the method for producing the resin composition according to the present embodiment includes a maleimide compound other than the bismaleimide compound (B), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, and carbon. -It is preferable to further contain at least one selected from the group consisting of modified polyphenylene ethers, elastomers and active ester compounds terminally modified with a substituent containing a carbon unsaturated double bond (excluding maleimide), preferably a resin. It may further contain one or more selected from the group consisting of maleimide compounds other than the maleimide compound (B), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group. preferable. By blending such other resin components, the appearance can be further improved and other properties can be made better.

<Use>
The resin composition according to this embodiment is used as a cured product. Specifically, the resin composition according to 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, and as a material for a semiconductor package. The resin composition according to 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 according to the present embodiment is used as a material for a layered (meaning including a film-like, sheet-like, etc.) molded product such as an insulating layer of a printed wiring board, a prepreg, and a resin sheet. When it is a molded product, its thickness is preferably 5 μm or more, and more preferably 10 μm or more. The upper limit of the thickness of the molded product is preferably 200 μm or less, and more preferably 180 μm or less. The thickness of the layered molded product means, for example, the thickness including the base material when the resin composition according to the present embodiment is impregnated with a base material such as glass cloth.
The material formed from the resin composition according to 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 a resin composition according to the present embodiment. The prepreg of the present embodiment is, for example, a method in which the resin composition according to the present embodiment is applied (for example, impregnated or coated) to a base material and then heated (for example, dried at 120 to 220 ° C. for 2 to 15 minutes). ) To be semi-cured. In this case, the amount of the resin composition (including the cured product of the resin composition) adhered to the substrate, that is, the amount of the resin composition (including the filler) with respect to the total amount of prepreg after semi-curing is in the range of 20 to 99% by mass. Is preferable.

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, inorganic fibers other than glass fiber (for example, E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, etc.) glass (for example, spherical glass, etc.) Examples thereof include organic fibers (eg, polyimide, polyamide, polyester, liquid crystal polyester, etc.). The form of the base material is not particularly limited, and examples thereof include a base material composed of layered fibers such as a woven fabric, a non-woven fabric, a roving, a chopped strand mat, and a surfaced mat. In particular, a base material composed of long fibers such as glass cloth is preferable. Here, the long fiber means, for example, a fiber having a number average fiber length of 6 mm or more. These base materials may be used alone or in combination of two or more. Among these base materials, woven fabrics that have undergone super-opening treatment and filling treatment are preferable from the viewpoint of dimensional stability, and from the viewpoint of moisture absorption and heat resistance, silane coupling agents such as epoxy silane treatment and amino silane treatment are used. A glass woven fabric surface-treated with is preferable, and from the viewpoint of electrical characteristics, a low-dielectric glass cloth made of glass fibers exhibiting low dielectric constant and low dielectric adjacency such as L-glass, NE-glass, and Q-glass is used. preferable. The thickness of the base material is not particularly limited, and may be, for example, about 0.01 to 0.19 mm.

<< Metal leaf-clad laminate >>
The metal leaf-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 is produced by, for example, a method in which at least one prepreg of the present embodiment is arranged (preferably two or more are laminated), and metal foils are arranged on one or both sides of the prepreg and laminated. can. 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 (copper foil) is not particularly limited, and may be 1.5 μm or more, and further may be about 2 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 wiring board for the inner layer (also referred to as the inner layer circuit board) separately produced to form a multilayer board. As a method for manufacturing a multilayer plate, for example, a metal foil (copper foil) of about 35 μm is arranged on both sides of one prepreg of the present embodiment, laminated and formed by the above-mentioned molding method, and then an inner layer circuit is formed. An inner layer circuit board is formed by blackening this circuit, and then the inner layer circuit board and the prepreg of the present embodiment are alternately arranged one by one, and a metal foil (copper foil) is further formed on the outermost layer. A multilayer plate can be produced by arranging the above-mentioned materials and laminating and molding them under the above conditions, preferably 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 according to 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 copper 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 thermosetting resin composition is formed between an inner layer circuit and a metal foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in this multilayer laminated plate, 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 according to the present embodiment described above. .. That is, in the above-mentioned prepreg of the present embodiment (for example, a prepreg formed from a base material and a resin composition according to the present embodiment impregnated or applied thereto), and the above-mentioned metal leaf-clad laminate according to the present embodiment. , The layer formed from the resin composition 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 according to 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 resin sheet is obtained by applying (coating) a solution of the resin composition according to the present embodiment in a solvent to a support and drying the resin sheet. The method 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 an organic film base material such as a film, a conductor foil such as a copper foil and an aluminum foil, and a plate-like material such as a glass plate, a SUS plate, and an FRP, but the present invention is not particularly limited.

As a coating method (coating method), for example, a method in which a solution obtained by dissolving the resin composition according to the present embodiment in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Can be mentioned. 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 according to 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 single layer of the present embodiment or the resin layer of the resin sheet can be adjusted by the concentration of the solution of the resin composition according to 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.

<Dielectric constant and / or dielectric loss tangent lowering agent>
The dielectric constant and / or dielectric loss tangent lowering agent of the present embodiment contains a bismaleimide compound (B) represented by the formula (1). By blending the bismaleimide compound represented by the formula (1) with a maleimide compound other than the cyanate ester compound (A) and the bismaleimide compound (B), and other resin components, the dielectric constant of the resin composition and / Alternatively, it becomes possible to reduce the dielectric loss tangent. In particular, the dielectric constant and / or dielectric loss tangent lowering agent of the present embodiment is effective as a dielectric loss tangent lowering agent. The preferred range of the bismaleimide compound represented by the formula (1) is the same as described above.

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 mass 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. The equivalent of the cyanate group of the obtained SNCN was 256 g / eq.

<Synthesis Example 2 Synthesis of Bismaleimide Compound (BMI-Bisanilin-M)>
17.23 g (50.0 mmol) of 1,3-bis [2- (4-aminophenyl)) manufactured by Tokyo Kasei Kogyo Co., Ltd. in a flask equipped with a stirrer, nitrogen introduction tube, Dean Stark, cooler and thermometer. -2-propyl] benzene and 120.0 g of N, N-dimethylformamide as a solvent were charged and dissolved by stirring while passing through nitrogen gas. 10.8 g (110 mmol) of maleic anhydride was added to this solution, and the mixture was stirred overnight at room temperature. Then, 0.951 g (5.00 mmol) of p-toluenesulfonic acid monohydrate as a catalyst and 60 g of toluene as a dehydration azeotropic solvent were charged, and azeotropic stirring was carried out for 6 hours. At this time, evaporation of toluene and water occurred, and some of them were condensed in the cooler. After separating the water trapped in Dean-Stark and toluene, only toluene was refluxed into the system, and a part of it was distilled off from the upper part of the cooling pipe by the flow of nitrogen gas.
After cooling the reaction mixture, toluene was distilled off with an evaporator. Then, the obtained solution was put into 1 mass% aqueous sodium hydrogen carbonate to remove excess maleic anhydride and p-toluenesulfonic acid. The obtained crude product was dissolved in N, N-dimethylformamide, methanol was added to reprecipitate, and the precipitate was collected by filtration and dried. This operation was repeated 3 times to obtain 4,4'-bismaleimide diphenyl ether (yield 70%).
The equivalent of the maleimide group of the obtained BMI-Bisanilin-M was 252.3 g / eq.

<Synthesis Example 3 Synthesis of Bismaleimide Compound (BMI-Bisanilin-P)>
17.23 g (50.0 mmol) of 1,4-bis [2- (4-aminophenyl)) manufactured by Tokyo Kasei Kogyo Co., Ltd. in a flask equipped with a stirrer, a nitrogen introduction tube, a Dean Stark apparatus, a cooler and a thermometer. -2-propyl] benzene and 120.0 g of N, N-dimethylformamide as a solvent were charged and dissolved by stirring while passing through nitrogen gas. 10.8 g (110 mmol) of maleic anhydride was added to this solution, and the mixture was stirred overnight at room temperature. Then, 0.951 g (5.00 mmol) of p-toluenesulfonic acid monohydrate as a catalyst and 60 g of toluene as a dehydration azeotropic solvent were charged, and azeotropic stirring was carried out for 6 hours. At this time, evaporation of toluene and water occurred, and some of them were condensed in the cooler. After separating the water trapped in Dean-Stark and toluene, only toluene was refluxed into the system, and a part of it was distilled off from the upper part of the cooling pipe by the flow of nitrogen gas.
After cooling the reaction mixture, toluene was distilled off with an evaporator. Then, the obtained solution was put into 1 mass% aqueous sodium hydrogen carbonate to remove excess maleic anhydride and p-toluenesulfonic acid. The obtained crude product was dissolved in N, N-dimethylformamide, methanol was added to reprecipitate, and the precipitate was collected by filtration and dried. This operation was repeated 3 times to obtain 4,4'-bismaleimide diphenyl ether (yield 70%).
The functional group equivalent of the obtained BMI-Bisanilin-P was 252.3 g / eq.

<Example 1>
50 parts by mass of SNCN obtained in Synthesis Example 1, 20 parts by mass of BMI-Bisanilin-M obtained in Synthesis Example 2, biphenyl aralkyl type polymaleimide compound ("MIR-3000", manufactured by Nippon Kayakusha, equivalent of maleimide group) 275 g / eq) 30 parts by mass, TPIZ (2,4,5-triphenylimidazole, curing accelerator) 0.5 parts by mass, zinc octylate ("Oct-Zn", manufactured by Nippon Kagaku Sangyo Co., Ltd., curing accelerator) 0.10 parts by mass was dissolved and mixed using methylethyl ketone as a solvent so as to have a solid content concentration of 50% by mass to obtain a varnish. The content of each of the above components indicates the amount of solid content. The appearance of the obtained varnish was evaluated according to the method described later.

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 ^{side of 100 mm and a thickness of 0.8 mm, and vacuum pressed at a pressure of 40 kg / cm 2} and a temperature of 230 ° C. for 120 minutes to test a cured product having a side of 100 mm and a thickness of 0.8 mm. I got a piece.
The water absorption rate, electrical characteristics (Dk and Df), and heat loss were measured for the obtained 0.8 mm thick test piece according to the following method.

<< Appearance of varnish >>
The appearance of the obtained varnish was visually evaluated as follows. Evaluations A to C are practical levels.
A: It was uniform and no precipitate was observed.
B: It was uniform and almost no precipitate was observed.
C: It was slightly non-uniform, and some precipitates were observed.
D: It was non-uniform and many precipitates were observed.

<< Water absorption rate >>
Using the obtained 0.8 mm thick test piece, according to JIS C6481, using a pressure cooker (PCT) tester, the water absorption rate was determined by the weight change after steam treatment at 120 ° C., 0.1 MPa, 5 hours. Was calculated. However, in JIS C6481, the sample size was changed from a 0.8 mm thick test piece to 30 mm × 30 mm.
As the pressure cooker tester, a PC-3 type manufactured by Hirayama Seisakusho Co., Ltd. was used.
The results are shown in Table 1 below.

<< Electrical characteristics (Dk and Df) >>
For the obtained 0.8 mm thick test piece, the permittivity (Dk) and the dielectric loss tangent (Df) at 10 GHz were measured using a perturbation cavity resonator.
As the perturbation cavity resonator, Agilent 8722ES, a product of Agilent Technologies, Inc. was used.
The results are shown in Table 1 below.

<< Heating weight loss >>
A thermogravimetric analysis of the cured product was performed under a nitrogen atmosphere and a heating rate of 10 ° C./min using a thermogravimetric measuring device.
As the thermogravimetric measuring device, "TGA5200" manufactured by SII Nanotechnology Co., Ltd. was used.
The results are shown in Table 1 below.

<Example 2>
In Example 1, BMI-Bisanilin-M was changed to BMI-Bisanilin-P obtained in the same amount of Synthesis Example 3, and the others were carried out in the same manner. The results are shown in Table 1 below.

<Comparative example 1>
In Example 1, BMI-Bisanilin-M was not used, and the same procedure was carried out except that the content of MIR-3000 was 50 parts by mass. The results are shown in Table 1 below.

<Comparative example 2>
In Example 1, SNCN and MIR-3000 were not used, and the same procedure was carried out except that the content of BMI-Bisanilin-M was 100 parts by mass. The results are shown in Table 1 below.

<Comparative example 3>
In Example 1, SNCN, MIR-3000 and BMI-Bisanilin-M were not used, and the same procedure was carried out except that the content of BMI-Bisanilin-P was 100 parts by mass. The results are shown in Table 1 below.

As is clear from the above results, the resin compositions of Examples 1 and 2 maintain the same good varnish appearance and low water absorption as that of Comparative Example 1, and further reduce the amount of heat by heating as compared with Comparative Example 1. Was reduced, and the electrical characteristics were improved. In particular, Df was significantly reduced. In Comparative Example 2 and Comparative Example 3, the appearance of the varnish was D, and the result was that it could not be used practically.

<Example 3>
50 parts by mass of SNCN obtained in Synthesis Example 1, 20 parts by mass of BMI-Bisanilin-M obtained in Synthesis Example 2, 30 parts by mass of biphenyl aralkyl type polymaleimide compound ("MIR-3000", manufactured by Nippon Kayaku Co., Ltd.), spherical Silica (SC2050-MB, manufactured by Admatex Co., Ltd., average particle size 0.5 μm) 100 parts by mass, TPIZ (2,4,5-triphenylimidazole, curing accelerator) 0.5 parts by mass, zinc octylate ( 0.10 parts by mass of "Oct-Zn" (manufactured by Nippon Kagaku Sangyo Co., Ltd., curing accelerator) was dissolved and mixed using methyl ethyl ketone as a solvent so as to have a solid content concentration of 50% by mass to obtain a varnish. In addition, each content mentioned above shows the solid content amount. The appearance of the obtained varnish was evaluated according to the method described later.

The obtained varnish is impregnated and coated on an E glass cloth having a thickness of 0.1 mm, and dried by heating at 165 ° C. for 5 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). , 50% by mass of the resin composition and 50% by mass of the glass cloth were obtained. The appearance of the obtained prepreg was evaluated according to the method described below.
With 4 or 8 of the obtained prepregs stacked, 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) was placed on both sides, and the pressure was 40 kg / cm ² , and the temperature was 220 ° C. Vacuum pressing was performed for 1 minute to obtain copper foil-clad laminates having a thickness of 0.4 mm and 0.8 mm.
With respect to the obtained copper foil-clad laminate, peel strength, bending physical properties, water absorption rate, electrical properties (Dk and Df), glass transition temperature, flame retardancy, thermal expansion rate, heat loss and thermal conductivity were measured.

<< Appearance of varnish >>
The appearance of the obtained varnish was visually evaluated as follows. Evaluations A to C are practical levels.
A: It was uniform and no precipitate was observed.
B: It was uniform and almost no precipitate was observed.
C: It was slightly non-uniform, and some precipitates were observed.
D: It was non-uniform and many precipitates were observed.

<< Appearance of prepreg >>
The appearance of the obtained prepreg was visually evaluated as follows. Evaluations A to C are practical levels.
A: It was uniform and no precipitate was observed.
B: It was uniform and almost no precipitate was observed.
C: It was slightly non-uniform, and some precipitates were observed.
D: It was non-uniform and many precipitates were observed.

<< Peel strength >>
A test method for a copper-clad laminate for a printed wiring board of JIS C6481 using a test piece (30 mm × 150 mm × thickness 0.8 mm) obtained by cutting a 0.8 mm-thick copper foil-clad laminate obtained above (5. 7 The peeling strength of the copper foil was measured three times according to the peeling strength), and the average value of the lower limit values was taken as the measured value. The results are shown in Table 2.

<< Bending physical properties >>
The copper foil on the surface layer of the 0.8 mm thick copper foil-clad laminate obtained above is removed by etching, and both ends of the test piece are supported by fulcrums using an autograph tester according to JIS K6911. The bending strength was obtained by measuring the maximum bending stress when a concentrated load was applied from above to the center of the fulcrum supporting both ends.
In addition, using a test piece from which the copper foil of the copper foil-clad laminate has been removed, using an autograph tester according to JIS K6911, deformation of the test piece with respect to bending stress in the straight part of the load deflection curve within the elastic limit. The resistance was measured by the bending stress per unit strain, and the flexural modulus was obtained.
As the autograph tester, AG-Xplus manufactured by Shimadzu Corporation was used.
The results are shown in Table 2.

<< Water absorption rate >>
A sample obtained by cutting a 0.8 mm thick copper foil-clad laminate into a size of 30 mm × 30 mm was prepared at 120 ° C., 0.1 MPa, 5 hours using a pressure cooker (PCT) tester in accordance with JIS C6481. The water absorption rate was calculated from the change in weight after the treatment.
As the pressure cooker tester, a PC-3 type manufactured by Hirayama Seisakusho Co., Ltd. was used.
The results are shown in Table 2.

<< Electrical characteristics >>
Using the samples obtained by removing the copper foil of the obtained copper foil-clad laminates having a thickness of 0.4 mm and 0.8 mm by etching, the permittivity (Dk) and the dielectric loss tangent (Df) at 2 GHz and 10 GHz were obtained, respectively. It was measured.
As the perturbation cavity resonator, Agilent 8722ES, a product of Agilent Technologies, Inc. was used.
The results are shown in Table 2.

<< Glass transition temperature >>
The glass transition temperature (Tg) is determined by DMA (Dynamic Mechanical) with a dynamic viscoelastic analyzer in accordance with JIS C6481 after removing the copper foils on both sides of the obtained 0.8 mm thick copper foil-clad laminate by etching. It was measured by the Analysis) method. In Table 2 below, E'' indicates the loss elastic modulus, and tan δ indicates the loss tangent.
As the dynamic viscoelastic analyzer, one manufactured by TA Instruments was used.
The results are shown in Table 2.

<< Flame Retardant >>
The copper foils on both sides of the metal foil-clad laminates obtained in each Example and Comparative Example were removed by etching. Next, a flame retardancy test was carried out in accordance with the UL94 vertical combustion test method using a sample from which the copper foils on both sides were removed.
The results are shown in Table 2.

<< Thermal expansion rate >>
Using a sample obtained by removing the copper foil of the obtained copper foil-clad laminate having a thickness of 0.8 mm by etching, the insulating layer of the laminate was made of glass by the TMA method (Thermo-mechanical analysis) specified in JlSC 6481. The coefficient of thermal expansion of the cloth (x direction, y direction and z direction) was measured, and the value was obtained. Specifically, after removing the copper foils on both sides of the copper foil-clad laminate obtained above by etching, an evaluation substrate of 4.5 mm × 16 mm was prepared, and a thermomechanical analyzer (manufactured by TA Instruments) was produced. The temperature was raised from 40 ° C. to 340 ° C. at 10 ° C. per minute, and the coefficient of thermal expansion (ppm / K) in the x-direction, y-direction and z-direction from 60 ° C. to 120 ° C. was measured.
The results are shown in Table 2.

<< Heating weight loss >>
Thermogravimetric analysis of a sample obtained by etching the copper foil of a 0.8 mm thick copper foil-clad laminate obtained under a nitrogen atmosphere and a heating rate of 10 ° C./min using a thermogravimetric measuring device. Was done.
As the thermogravimetric measuring device, "TGA5200" manufactured by SII Nanotechnology Co., Ltd. was used.
The results are shown in Table 2.

<< Thermal conductivity >>
The density and specific heat of the copper foil-clad laminates obtained in each Example and Comparative Example were measured.
The specific heat was measured by a TA instrument product Q100 type DSC.
In addition, the thermal diffusivity of the copper foil-clad laminate in the thickness direction of the copper foil-clad laminate was measured.
The thermal diffusivity was measured by a xenon flash analyzer (Bruker: LFA447Nanoflash). The thermal conductivity was calculated by the following formula.
Thermal conductivity (W / m ・ K)
= Density (kg / m ³ ) x Specific heat (kJ / kg · K) x Thermal diffusivity (m ² / S) x 1000
The results are shown in Table 2.

<Example 4>
In Example 3, BMI-Bisanilin-M was changed to BMI-Bisanilin-P obtained in the same amount of Synthesis Example 3, and the others were carried out in the same manner. The results are shown in Table 2 below.

<Comparative example 4>
In Example 3, BMI-Bisanilin-M was not used, and the same procedure was carried out except that the content of MIR-3000 was 50 parts by mass. The results are shown in Table 2 below.

As is clear from the above results, the copper foil-clad laminates of Examples 3 and 4 have the same good varnish appearance, good prepreg appearance, high peel strength, high bending properties, low water absorption, and low thermal expansion as in Comparative Example 4. While maintaining the coefficient and thermal conductivity, higher Tg and less heat loss were achieved as compared with Comparative Example 4, and the electrical characteristics (lower Dk and lower Df) were also improved.

Claims (18)

Cyanic acid ester compound (A) and bismaleimide compound (B) represented by the following formula (1)
Resin composition containing

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents 0. Represents an integer of ~ 4. In the formula (1), X is an alkylene group having 1 to 3 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom, a methyl group or an ethyl group, and a is an integer of 0 to 2 independently. The resin composition according to claim 1. The resin composition according to claim 1, wherein the bismaleimide compound (B) is represented by the following formula (2).

The resin composition according to any one of claims 1 to 3, further containing a solvent. The resin composition according to claim 4, wherein the content of the bismaleimide compound (B) is 0.1 to 30% by mass of the resin composition. The content ratio of the cyanate ester compound (A) and the bismaleimide compound (B) is the equivalent ratio of the unsaturated imide group of the bismaleimide compound (B) to the cyanate group of the cyanate ester compound (A). The resin composition according to any one of claims 1 to 5, which is 0.01 or more and less than 1.1 in terms of (equivalent of unsaturated imide group / equivalent of cyanate group). Contains a maleimide compound other than the bismaleimide compound (B), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, and a carbon-carbon unsaturated double bond (excluding maleimide). The resin composition according to any one of claims 1 to 6, further containing one or more selected from the group consisting of a modified polyphenylene ether, an elastomer and an active ester compound terminally modified with a substituent. The resin composition according to any one of claims 1 to 7, further containing a filler (C). The resin composition according to claim 8, wherein the content of the filler (C) is 50 to 1600 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. The resin composition according to any one of claims 1 to 9, which is a low dielectric constant material and / or a low dielectric loss tangent material. The cured product of the resin composition according to any one of claims 1 to 10. A prepreg formed from a base material and the resin composition according to any one of claims 1 to 10. A metal leaf-clad laminate comprising at least one layer formed from the prepreg according to claim 12 and metal foils arranged on one or both sides of the layer formed from the prepreg. A resin sheet containing a support and a layer formed from the resin composition according to any one of claims 1 to 10 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 10 and a layer formed from a prepreg according to claim 12. A method for producing a resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1).
A resin composition comprising mixing a cyanate ester compound (A), a bismaleimide compound (B) and a solvent, and the content of the bismaleimide compound (B) being 0.1 to 30% by mass of the resin composition. Manufacturing method of things;

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents 0 to 0. Represents an integer of 4. Further, a maleimide compound other than the bismaleimide compound (B), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, and a carbon-carbon unsaturated double bond (excluding maleimide). The method for producing a resin composition according to claim 16, which comprises at least one selected from the group consisting of a modified polyphenylene ether terminal-modified with a substituent containing the above, an elastomer and an active ester compound. Dielectric constant and / or dielectric loss tangent lowering agent containing the bismaleimide compound (B) represented by the following formula (1);

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a independently represents 0 to 0. Represents an integer of 4.