JP2021075729A - Resin composition, prepreg, laminate and multilayer printed wiring board - Google Patents

Abstract

To provide a resin composition especially good in compatibility and having excellent high frequency property (low dielectric constant and low dielectric loss tangent), high adhesiveness with a conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy, and a prepreg, a laminate and a multilayer printed wiring board using the same.SOLUTION: There are provided a resin composition containing a polyphenylene ether derivative having at least one N-substituted maleimide group in a molecule (A) and a bromine-based flame retardant having 5% mass reduction temperature of 300°C or higher (B), and a prepreg, a laminate and a multilayer printed wiring board using the same.SELECTED DRAWING: None

Description

The present invention relates to resin compositions containing polyphenylene ether derivatives, prepregs, laminated boards and multilayer printed wiring boards.

The speed and capacity of signals used in mobile communication devices such as mobile phones, their base station devices, servers, network infrastructure devices such as routers, and large computers are increasing year by year. Along with this, the printed wiring boards mounted on these electronic devices need to be compatible with high frequencies, and the dielectric properties in the high frequency band that enable reduction of transmission loss (low dielectric constant and low dielectric loss tangent; hereinafter, There is a demand for a substrate material having excellent high frequency characteristics). In recent years, as applications that handle such high-frequency signals, in addition to the above-mentioned electronic devices, new systems that handle high-frequency radio signals in the ITS (Intelligent Transport Systems) field (automobiles, transportation systems) and indoor short-range communication fields have also been introduced. Practical use and practical plans are in progress, and it is expected that low transmission loss substrate materials will be further required for printed wiring boards mounted on these devices in the future.
In addition, due to recent environmental problems, mounting of electronic components with lead-free solder and flame retardancy with halogen-free have come to be required, so that materials for printed wiring boards have higher heat resistance and flame retardancy than before. Sex is needed.

Conventionally, polyphenylene ether (PPE) -based resin has been used as a heat-resistant thermoplastic polymer having excellent high-frequency characteristics for printed wiring boards that require low transmission loss. For example, a method of using polyphenylene ether and a thermosetting resin in combination has also been proposed. Specifically, a resin composition containing a polyphenylene ether and an epoxy resin (see, for example, Patent Document 1), a resin composition containing a polyphenylene ether, and a cyanate resin having a low dielectric constant among thermosetting resins (for example). , Patent Document 2) and the like are disclosed.

However, the resin compositions described in Patent Documents 1 and 2 are comprehensively inadequate in high-frequency characteristics in the GHz region, adhesiveness to conductors, low coefficient of thermal expansion, and flame retardancy, or polyphenylene ether and heat. The heat resistance may be lowered due to the low compatibility with the curable resin.

On the other hand, the present inventors also made a semi-IPN (semi-interpenetrating network) at the production stage (A stage stage) of the resin composition containing an organic solvent based on the polyphenylene ether resin and the polybutadiene resin. We have proposed a resin composition (see, for example, Patent Document 3) that can improve properties, heat resistance, low coefficient of thermal expansion, adhesiveness to a conductor, and the like. However, in recent years, substrate materials for printed wiring boards have high adhesiveness to conductors, low coefficient of thermal expansion, and high due to the demands for high density, high reliability, and compatibility with environmental friendliness, in addition to high frequency. Further improvement in glass transition temperature, high flame retardancy, etc. is required.

In addition, the substrate material for printed wiring boards used for network-related equipment such as servers and routers needs to have a high number of layers as the density increases, and high reflow heat resistance and through-hole reliability are required. Has been done. Further, as high frequency characteristics, excellent dielectric properties in a higher frequency band are required, and in general, the substrate material tends to have a higher dielectric loss tangent as the frequency increases, but the conventional 1 to 5 GHz There is an increasing need to exhibit excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in the 10 GHz band or higher, instead of the dielectric characteristic value in.

Further, since the resin composition using polyphenylene ether has insufficient flame retardancy as it is, a method of imparting flame retardancy by using a flame retardant in combination has been proposed (see Patent Document 4).
However, even in a resin composition using a flame retardant as shown in Patent Document 4, compatibility, dielectric properties (low dielectric constant and low dielectric loss tangent), high adhesion to a conductor, excellent heat resistance, and high heat resistance are high. It was difficult to satisfy all of the glass transition temperature, low coefficient of thermal expansion and high flame retardancy.

Japanese Unexamined Patent Publication No. 58-069046 Tokukousho 61-018937 Gazette Japanese Unexamined Patent Publication No. 2008-95061 Japanese Unexamined Patent Publication No. 3-275760

In view of this situation, the present invention has particularly good compatibility, excellent high frequency characteristics (low dielectric constant and low dielectric loss tangent), high adhesion to conductors, excellent heat resistance, and high glass transition. An object of the present invention is to provide a resin composition having a temperature, a low coefficient of thermal expansion and a high flame retardancy, and a prepreg, a laminated board and a multilayer printed wiring board using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a polyphenylene ether derivative having a specific molecular structure and a specific flame retardant has good compatibility. The present invention has been completed by finding that it exhibits excellent high-frequency characteristics, high adhesiveness to a conductor, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion and high flame retardancy.

（式中、Ｒ^１は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｘは０〜４の整数である。）
［３］前記Ｎ−置換マレイミド構造含有基が下記一般式（Ｚ）で表される基である、上記［２］に記載の樹脂組成物。

（式中、Ｒ^２は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｙは０〜４の整数である。Ａ^１は、下記一般式（II）、（III）、（IV）又は（V）で表される基である。）

（式中、Ｒ^３は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｐは０〜４の整数である。）

（式中、Ｒ^４及びＲ^５は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^２は炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基、単結合又は下記一般式（III−１）で表される基である。ｑ及びｒは各々独立に０〜４の整数である。）

（式中、Ｒ^６及びＲ^７は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^３は炭素数１〜５のアルキレン基、イソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｓ及びｔは各々独立に０〜４の整数である。）

（式中、ｎは０〜１０の整数である。）

（式中、Ｒ^８及びＲ^９は各々独立に、水素原子又は炭素数１〜５の脂肪族炭化水素基である。ｕは１〜８の整数である。）
［４］前記一般式（Ｚ）中のＡ^１が下記式のいずれかで表される基である、上記［３］に記載の樹脂組成物。

［５］前記一般式（Ｉ）で表される構造単位が、下記式（Ｉ’）で表される構造単位である、上記［２］〜［４］のいずれか１項に記載の樹脂組成物。

［６］ポリフェニレンエーテル誘導体（Ａ）の数平均分子量が３０００〜１２０００である、上記［１］〜［５］のいずれか１項に記載の樹脂組成物。
［７］臭素系難燃剤（Ｂ）が、臭素化ポリフェニレンエーテル、臭素化ポリスチレン、２，４，６−トリス（トリブロモフェノキシ）−１，３，５−トリアジン、エチレンビス（ペンタブロモフェニル）及びエチレンビステトラブロモフタルイミドから選ばれる少なくとも１種である、上記［１］〜［６］のいずれか１項に記載の樹脂組成物。
［８］エポキシ樹脂、シアネートエステル樹脂及びマレイミド化合物から選ばれる少なくとも１種の熱硬化性樹脂（Ｃ）をさらに含む、上記［１］〜［７］のいずれか１項に記載の樹脂組成物。
［９］熱硬化性樹脂（Ｃ）が、分子中に少なくとも２個のＮ−置換マレイミド基を有するポリマレイミド化合物（ａ）又は下記一般式（VI）で表されるポリアミノビスマレイミド化合物（ｃ）を含む、上記［８］に記載の樹脂組成物。

（式中、Ａ^４は前記一般式（Ｚ）中のＡ^１の定義と同じであり、Ａ^５は下記一般式（VII）で表される基である。）

（式中、Ｒ^１７及びＲ^１８は各々独立に、炭素数１〜５の脂肪族炭化水素基、炭素数１〜５のアルコキシ基、水酸基又はハロゲン原子である。Ａ^８は炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基、フルオレニレン基、単結合、又は下記一般式（VII-１）もしくは（VII-2）で表される基である。ｑ’及びｒ’は各々独立に０〜４の整数である。）

（式中、Ｒ^１９及びＲ^２０は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^９は炭素数１〜５のアルキレン基、イソプロピリデン基、ｍ−又はｐ−フェニレンジイソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｓ’及びｔ’は各々独立に０〜４の整数である。）

（式中、Ｒ^２１は炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^１０及びＡ^１１は各々独立に、炭素数１〜５のアルキレン基、イソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｗは０〜４の整数である。）
［１０］前記（Ａ）成分と（Ｃ）成分の含有割合［（Ａ）：（Ｃ）］が、質量比で、５：９５〜９０：１０であり、（Ｂ）成分の含有割合が、（Ａ）成分と（Ｃ）成分との合計量１００質量部に対して、１〜２００質量部の範囲である、上記［８］又は［９］に記載の樹脂組成物。
［１１］更に無機充填剤（Ｄ）を含有する、上記［１］〜［１０］のいずれか１項に記載の樹脂組成物。
［１２］２３０℃で１８０分加熱した後のガラス転移温度が１９０℃以上である、上記［１］〜［１１］のいずれか１項に記載の樹脂組成物。
［１３］上記［１］〜［１２］のいずれか１項に記載の樹脂組成物とシート状繊維補強基材とを有するプリプレグ。
［１４］上記［１］〜［１２］のいずれか１項に記載の樹脂組成物の硬化物と金属箔とを有する積層板。
［１５］上記［１］〜［１２］のいずれか１項に記載の樹脂組成物の硬化物又は上記［１４］に記載の積層板を有する多層プリント配線板。
［１６］上記［１３］に記載のプリプレグ又は上記［１４］に記載の積層板を用いる多層プリント配線板の製造方法。 That is, the present invention relates to the following [1] to [16].
[1] A resin composition containing a polyphenylene ether derivative (A) having at least one N-substituted maleimide group in the molecule and a brominated flame retardant (B) having a 5% mass reduction temperature of 300 ° C. or higher. Stuff.
[2] The above-mentioned [1], wherein the polyphenylene ether derivative (A) has at least one N-substituted maleimide structure-containing group in the molecule and a structural unit represented by the following general formula (I). Resin composition.

(In the formula, R ¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. X is an integer of 0 to 4.)
[3] The resin composition according to the above [2], wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (Z).

(In the formula, R ² is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. Y is an integer of 0 to 4. A ¹ is the following general formula (II), ( III), a group represented by (IV) or (V).

(In the formula, R ³ is independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. P is an integer of 0 to 4.)

(In the formula, R ⁴ and R ⁵ are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. A 2} is an alkylene group having 1 to 5 carbon atoms and alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (III-1). Q and r are independently integers of 0 to 4. .)

(Wherein, ^{R 6} and ^{R 7} each independently, .A ³ is an alkylene group having 1 to 5 carbon atoms is an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms, an isopropylidene group, an ether group, It is a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. S and t are independently integers of 0 to 4).

(In the formula, n is an integer from 0 to 10.)

(In the formula, R ⁸ and R ⁹ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 5 carbon atoms. U is an integer of 1 to 8.)
[4] the formula A ¹ in (Z) is a group represented by any one of the following formulas, the resin composition according to [3].

[5] The resin composition according to any one of the above [2] to [4], wherein the structural unit represented by the general formula (I) is a structural unit represented by the following formula (I'). Stuff.

[6] The resin composition according to any one of [1] to [5] above, wherein the polyphenylene ether derivative (A) has a number average molecular weight of 3000 to 12000.
[7] The brominated flame retardant (B) includes brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, ethylenebis (pentabromophenyl) and The resin composition according to any one of the above [1] to [6], which is at least one selected from ethylene bistetrabromophthalimide.
[8] The resin composition according to any one of [1] to [7] above, further comprising at least one thermosetting resin (C) selected from an epoxy resin, a cyanate ester resin and a maleimide compound.
[9] The thermosetting resin (C) has a polymaleimide compound (a) having at least two N-substituted maleimide groups in the molecule, or a polyaminobismaleimide compound (c) represented by the following general formula (VI). The resin composition according to the above [8].

(In the formula, A ⁴ is the same as the definition ^{of A 1 in} the general formula (Z) ^{, and A 5} is a group represented by the following general formula (VII).)

(In the formula, R ¹⁷ and R ¹⁸ are independently aliphatic hydrocarbon groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, hydroxyl groups or halogen atoms. A ⁸ has 1 to 5 carbon atoms. Alkoxy group, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carooxy group, keto group, fluorenylene group, single bond, or the following general formula (VII-1) or (VII-2) The groups represented. Q'and r'are independently integers 0-4.)

(In the formula, R ¹⁹ and R ²⁰ are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. A 9} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or an atom. It is a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. S'and t'are independently integers of 0 to 4).

(In the formula, R ²¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. A ¹⁰ and A ¹¹ are independently alkylene groups, isopropylidene groups and ether groups having 1 to 5 carbon atoms, respectively. It is a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. W is an integer of 0 to 4.)
[10] The content ratios of the component (A) and the component (C) [(A): (C)] are 5:95 to 90:10 in terms of mass ratio, and the content ratio of the component (B) is The resin composition according to the above [8] or [9], which is in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (C).
[11] The resin composition according to any one of the above [1] to [10], which further contains an inorganic filler (D).
[12] The resin composition according to any one of [1] to [11] above, wherein the glass transition temperature after heating at 230 ° C. for 180 minutes is 190 ° C. or higher.
[13] A prepreg having the resin composition according to any one of the above [1] to [12] and a sheet-shaped fiber reinforced base material.
[14] A laminated board having a cured product of the resin composition according to any one of the above [1] to [12] and a metal foil.
[15] A multilayer printed wiring board having a cured product of the resin composition according to any one of the above [1] to [12] or the laminated board according to the above [14].
[16] A method for manufacturing a multilayer printed wiring board using the prepreg according to the above [13] or the laminate according to the above [14].

The resin composition of the present invention has particularly good compatibility and excellent high frequency characteristics (low dielectric constant, low dielectric loss tangent), high adhesiveness to a conductor, excellent heat resistance, high glass transition temperature, and low heat. It has an expansion coefficient and high flame retardancy. Therefore, the prepreg and the laminated board obtained by using the resin composition can be suitably used for electronic component applications such as a multilayer printed wiring board.

Hereinafter, embodiments of the present invention will be described in detail.

[Resin composition]
One aspect of the present invention is a polyphenylene ether derivative (A) having at least one N-substituted maleimide group in the molecule [hereinafter, may be simply abbreviated as a polyphenylene ether derivative (A) or a component (A)]. A resin composition containing a brominated flame retardant (B) having a 5% mass reduction temperature of 300 ° C. or higher [hereinafter, may be simply abbreviated as the component (B)].

(Polyphenylene ether derivative (A))
The polyphenylene ether derivative (A) can be used without particular limitation as long as it is a polyphenylene ether derivative having at least one N-substituted maleimide group in the molecule.
In particular, since the polyphenylene ether derivative (A) has at least one N-substituted maleimide group in the molecule, it has excellent high frequency characteristics (low dielectric constant, low dielectric loss tangent), high adhesion to a conductor, and excellent heat resistance. It is a resin composition having properties, high glass transition temperature, low thermal expansion coefficient and high flame retardancy. Here, the coefficient of thermal expansion referred to in the present invention is a value also called a coefficient of linear expansion.

From the same viewpoint as above, the polyphenylene ether derivative (A) may have at least one N-substituted maleimide structure-containing group in the molecule and a structural unit represented by the following general formula (I). ..

（式中、Ｒ^１は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｘは０〜４の整数である。）
前記一般式（Ｉ）中のＲ^１が表す脂肪族炭化水素基としては、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−ペンチル基等が挙げられる。該脂肪族炭化水素基としては、炭素数１〜３の脂肪族炭化水素基であってもよく、メチル基であってもよい。また、ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。ハロゲン原子としては、ハロゲンフリーとする観点から、フッ素原子であってもよい。
以上の中でも、Ｒ^１としては炭素数１〜５の脂肪族炭化水素基であってもよい。
ｘは０〜４の整数であり、０〜２の整数であってもよく、２であってもよい。なお、ｘが１又は２である場合、Ｒ^１はベンゼン環上のオルト位（但し、酸素原子の置換位置を基準とする。）に置換していてもよい。また、ｘが２以上である場合、複数のＲ^１同士は同一であっても異なっていてもよい。
前記一般式（Ｉ）で表される構造単位としては、具体的には、下記一般式（Ｉ'）で表される構造単位であってもよい。

(In the formula, R ¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. X is an integer of 0 to 4.)
^{Examples of the aliphatic hydrocarbon group represented by R 1} in the general formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and n. -Pentyl group and the like can be mentioned. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or a methyl group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. The halogen atom may be a fluorine atom from the viewpoint of making it halogen-free.
Among the above, R ¹ may be an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
x is an integer of 0 to 4, and may be an integer of 0 to 2, or may be 2. When x is 1 or 2, R ¹ may be substituted at the ortho position on the benzene ring (however, based on the substitution position of the oxygen atom). Further, when x is 2 or more, plural R ¹ each other may be the same or different.
Specifically, the structural unit represented by the general formula (I) may be a structural unit represented by the following general formula (I').

The N-substituted maleimide structure-containing group of the polyphenylene ether derivative (A) includes two maleimide groups from the viewpoints of high frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy. It may be a group containing a bismaleimide structure in which nitrogen atoms are bonded to each other via an organic group, or a group represented by the following general formula (Z).

（式中、Ｒ^２は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｙは０〜４の整数である。Ａ^１は、下記一般式（II）、（III）、（IV）又は（Ｖ）で表される基である。）

(In the formula, R ² is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. Y is an integer of 0 to 4. A ¹ is the following general formula (II), ( III), a group represented by (IV) or (V).

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ² will be described in the same manner as in the case of ^{R 1.}
y is an integer of 0 to 4, may be an integer of 0 to 2, or may be 0. If y is an integer of 2 or more, plural R ² together may be different even in the same.
The groups represented by the general formulas (II), (III), (IV) or (V) represented by ^{A 1 are as follows.}

（式中、Ｒ^３は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｐは０〜４の整数である。）
Ｒ^３が表す炭素数１〜５の脂肪族炭化水素基、ハロゲン原子としては、Ｒ^１の場合と同様に説明される。
ｐは０〜４の整数であり、入手容易性の観点から、０〜２の整数であってもよく、０又は１であってもよく、０であってもよい。ｐが２以上の整数である場合、複数のＲ^３同士は同一であっても異なっていてもよい。

(In the formula, R ³ is independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. P is an integer of 0 to 4.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ³ will be described in the same manner as in the case of ^{R 1.}
p is an integer of 0 to 4, and may be an integer of 0 to 2, 0 or 1, or 0 from the viewpoint of availability. If p is an integer of 2 or more, plural R ³ together may be different even in the same.

（式中、Ｒ^４及びＲ^５は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^２は炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基、単結合又は下記一般式（III−１）で表される基である。ｑ及びｒは各々独立に０〜４の整数である。）
Ｒ^４及びＲ^５が表す炭素数１〜５の脂肪族炭化水素基、ハロゲン原子としては、Ｒ^１の場合と同じものが挙げられる。該脂肪族炭化水素基としては、炭素数１〜３の脂肪族炭化水素基であってもよく、メチル基、エチル基であってもよく、エチル基であってもよい。
Ａ^２が表す炭素数１〜５のアルキレン基としては、例えば、メチレン基、１，２−ジメチレン基、１，３−トリメチレン基、１，４−テトラメチレン基、１，５−ペンタメチレン基等が挙げられる。該アルキレン基としては、高周波特性、導体との接着性、耐熱性、ガラス転移温度、熱膨張係数及び難燃性の観点から、炭素数１〜３のアルキレン基であってもよく、メチレン基であってもよい。
Ａ^２が表す炭素数２〜５のアルキリデン基としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。これらの中でも、高周波特性、導体との接着性、耐熱性、ガラス転移温度、熱膨張係数及び難燃性の観点から、イソプロピリデン基であってもよい。
Ａ^２としては、上記選択肢の中でも、炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基であってもよい。
ｑ及びｒは各々独立に０〜４の整数であり、入手容易性の観点から、いずれも、０〜２の整数であってもよく、０又は２であってもよい。ｑ又はｒが２以上の整数である場合、複数のＲ^４同士又はＲ^５同士は、それぞれ同一であっても異なっていてもよい。
なお、Ａ^２が表す一般式（III−１）で表される基は以下のとおりである。

(In the formula, R ⁴ and R ⁵ are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. A 2} is an alkylene group having 1 to 5 carbon atoms and alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (III-1). Q and r are independently integers of 0 to 4. .)
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁴ and R ⁵ are the same as those in the case of ^{R 1.} The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a methyl group, an ethyl group, or an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Can be mentioned. The alkylene group may be an alkylene group having 1 to 3 carbon atoms from the viewpoint of high frequency characteristics, adhesiveness to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy, and may be a methylene group. There may be.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ² include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. Among these, an isopropylidene group may be used from the viewpoints of high frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy.
Among the above options, A ² may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.
q and r are each independently an integer of 0 to 4, and from the viewpoint of availability, both may be an integer of 0 to 2, and may be 0 or 2. If q or r is an integer of 2 or more, plural R ⁴ s or R ⁵ together may each be the same or different.
The groups represented by the general formula (III-1) represented by ^{A 2 are as follows.}

（式中、Ｒ^６及びＲ^７は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^３は炭素数１〜５のアルキレン基、イソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｓ及びｔは各々独立に０〜４の整数である。）
Ｒ^６及びＲ^７が表す炭素数１〜５の脂肪族炭化水素基、ハロゲン原子としては、Ｒ^４及びＲ^５の場合と同様に説明される。
Ａ^３が表す炭素数１〜５のアルキレン基としては、Ａ^２が表す炭素数１〜５のアルキレン基と同じものが挙げられる。
Ａ^３としては、上記選択肢の中でも、炭素数２〜５のアルキリデン基を選択してもよい。
ｓ及びｔは０〜４の整数であり、入手容易性の観点から、いずれも、０〜２の整数であってもよく、０又は１であってもよく、０であってもよい。ｓ又はｔが２以上の整数である場合、複数のＲ^６同士又はＲ^７同士は、それぞれ同一であっても異なっていてもよい。

(Wherein, ^{R 6} and ^{R 7} each independently, .A ³ is an alkylene group having 1 to 5 carbon atoms is an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms, an isopropylidene group, an ether group, It is a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. S and t are independently integers of 0 to 4).
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁶ and R ⁷ will be described in the same manner as in the case of ^{R 4} and R ^5.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ³ include the same alkylene group having 1 to 5 carbon atoms represented ^{by A 2.}
The A ^3, among the above-mentioned alternatives may select an alkylidene group having 2 to 5 carbon atoms.
s and t are integers from 0 to 4, and from the viewpoint of availability, both may be integers from 0 to 2, 0 or 1, and may be 0. When s or t is an integer of 2 or more, plural R ⁶ s or R ⁷ together may each be the same or different.

（式中、ｎは０〜１０の整数である。）
ｎは、入手容易性の観点から、０〜５の整数であってもよく、０〜３の整数であってもよい。

(In the formula, n is an integer from 0 to 10.)
From the viewpoint of availability, n may be an integer of 0 to 5 or an integer of 0 to 3.

（式中、Ｒ^８及びＲ^９は各々独立に、水素原子又は炭素数１〜５の脂肪族炭化水素基である。ｕは１〜８の整数である。）
Ｒ^８及びＲ^９が表す炭素数１〜５の脂肪族炭化水素基、ハロゲン原子としては、Ｒ^１の場合と同様に説明される。
ｕは１〜８の整数であり、１〜３の整数であってもよく、１であってもよい。

(In the formula, R ⁸ and R ⁹ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 5 carbon atoms. U is an integer of 1 to 8.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁸ and R ⁹ will be described in the same manner as in the case of ^{R 1.}
u is an integer of 1 to 8, may be an integer of 1 to 3, or may be 1.

The A ¹ in the group represented by the general formula (Z), the high frequency characteristics, adhesion to the conductor, heat resistance, glass transition temperature, in view of thermal expansion coefficient and flame retardancy, any one of the following formulas It may be a group represented by.

The polyphenylene ether derivative (A) may be a polyphenylene ether derivative represented by the following general formula (A').

（式中、Ａ^１、Ｒ^１、Ｒ^２、ｘ及びｙは前記定義のとおりである。ｍは１以上の整数である。）
ｍは、１〜３００の整数であってもよく、１０〜３００の整数であってもよく、３０〜２００の整数であってもよく、５０〜１５０の整数であってもよい。

(In the formula, A ¹ , R ¹ , R ² , x and y are as defined above. M is an integer of 1 or more.)
m may be an integer of 1 to 300, an integer of 10 to 300, an integer of 30 to 200, or an integer of 50 to 150.

The polyphenylene ether derivative (A) may be a polyphenylene ether derivative represented by any of the following formulas.

（式中、ｍは前記一般式（Ａ’）中のｍと同じである。）

(In the formula, m is the same as m in the general formula (A').)

From the viewpoint that the raw material is inexpensive, the polyphenylene ether derivative of the above formula (A'-1) may be used, and from the viewpoint of excellent dielectric properties and low water absorption, the above formula (A'-2) It may be a polyphenylene ether derivative, or may be a polyphenylene ether derivative of the above formula (A'-3) from the viewpoint of excellent adhesion to a conductor and mechanical properties (elongation, breaking strength, etc.). Therefore, one of the polyphenylene ether derivatives represented by any of the above formulas (A'-1) to (A'-3) may be used alone or in combination of two or more according to the desired properties. Can be done.

The number average molecular weight of the polyphenylene ether derivative (A) of the present invention may be 3000 to 12000, 5000 to 12000, 700 to 12000, or 700 to 10000. Good. When the number average molecular weight is 3000 or more, a better glass transition temperature tends to be obtained in the resin composition of the present invention, the prepreg using the resin composition, and the laminated board. Further, when the number average molecular weight is 12000 or less, better moldability tends to be obtained when the resin composition of the present invention is used for a laminated board.
In the present specification, the number average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, the measurement of the number average molecular weight described in Examples. It is a value obtained by the method.

(Method for producing polyphenylene ether derivative (A))
The polyphenylene ether derivative (A) can be obtained, for example, by the following production method.
First, an aminophenol compound represented by the following general formula (VIII) [hereinafter referred to as an aminophenol compound (VIII)] and, for example, a polyphenylene ether having a number average molecular weight of 1500 to 25000 are known redistributed in an organic solvent. By reacting, the polyphenylene ether compound (A ″) having a primary amino group in the molecule is accompanied by a reduction in the molecular weight of the polyphenylene ether (hereinafter, also simply referred to as a polyphenylene ether compound (A ″)). Then, the polyphenylene ether compound (A ″) and the bismaleimide compound represented by the general formula (IX) [hereinafter referred to as bismaleimide compound (IX). ] Is subjected to a Michael addition reaction to produce a polyphenylene ether derivative (A).

（式中、Ｒ^２及びｙは、前記一般式（Ｚ）中のものと同じである。）

(In the formula, R ² and y are the same as those in the general formula (Z).)

（式中、Ａ^１は、前記一般式（Ｚ）中のものと同じである。）

(In the formula, A ¹ is the same as that in the general formula (Z).)

Examples of the aminophenol compound (VIII) include o-aminophenol, m-aminophenol, p-aminophenol and the like. Among these, m-aminophenol and p-aminophenol are used from the viewpoint of the reaction yield when producing the polyphenylene ether compound (A ″) and the heat resistance when the resin composition, prepreg and laminated plate are prepared. It may be present, or it may be p-aminophenol.

The molecular weight of the polyphenylene ether compound (A ″) can be controlled by the amount of the aminophenol compound (VIII) used, and the larger the amount of the aminophenol compound (VIII) used, the lower the obtained polyphenylene ether compound (A ″). It is molecularized. That is, the amount of the aminophenol compound (VIII) used may be appropriately adjusted so that the number average molecular weight of the finally produced polyphenylene ether derivative (A) is in a suitable range.
The blending amount of the aminophenol compound (VIII) is not particularly limited, but for example, if the number average molecular weight of the polyphenylene ether to be reacted with the aminophenol compound (VIII) is 1500 to 25,000, the polyphenylene ether By using it in the range of 0.5 to 6 parts by mass with respect to 100 parts by mass, a polyphenylene ether derivative (A) having a number average molecular weight of 5000 to 12000 can be obtained.

The organic solvent used in the production process of the polyphenylene ether compound (A ″) is not particularly limited, and for example, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone and methyl ethyl ketone. , Methylisobutylketone, ketones such as cyclohexanone; aromatic hydrocarbons such as toluene, xylene, mesityrene; esters such as methoxyethyl acetate, ethoxyethylacetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N Examples thereof include nitrogen-containing compounds such as −dimethylacetamide and N-methyl-2-pyrrolidone. One of these may be used alone, or two or more thereof may be used in combination. Among these, toluene, xylene, and mesitylene may be used from the viewpoint of solubility.

Further, in the production process of the polyphenylene ether compound (A ″), a reaction catalyst can be used if necessary. As this reaction catalyst, a known reaction catalyst at the time of redistribution reaction can be applied. For example, from the viewpoint of obtaining a polyphenylene ether compound (A ″) having a stable number average molecular weight with good reproducibility, an organic peroxide such as t-butylperoxyisopropyl monocarbonate and a carboxylic acid metal salt such as manganese naphthenate can be used. May be used together. The amount of the reaction catalyst used is not particularly limited. For example, from the viewpoint of reaction rate and suppression of gelation when producing the polyphenylene ether compound (A ″), 0 organic peroxide is added to 100 parts by mass of the polyphenylene ether to be reacted with the aminophenol compound (VIII). .5 to 5 parts by mass and the carboxylic acid metal salt may be 0.05 to 0.5 parts by mass.

The aminophenol compound (VIII), the polyphenylene ether having a number average molecular weight of 15,000 to 25,000, an organic solvent and, if necessary, a reaction catalyst are charged in a predetermined amount into a reactor, and the reaction is carried out with heating, heat retention and stirring to cause the polyphenylene ether compound (A). '') Is obtained. As the reaction temperature and reaction time in this step, known reaction conditions at the time of redistribution reaction can be applied.
From the viewpoint of workability and suppression of gelation, and from the viewpoint of being able to control the molecular weight of the polyphenylene ether compound (A ″) for obtaining the component (A) having a desired number average molecular weight, for example, the reaction temperature is 70 to 110. The reaction may be carried out at ° C. and a reaction time of 1 to 8 hours.

The solution of the polyphenylene ether compound (A ″) produced as described above may be continuously supplied as it is to the production step of the polyphenylene ether derivative (A) in the next step. At this time, the solution of the polyphenylene ether compound (A ″) may be cooled or adjusted to the reaction temperature of the next step. Further, this solution may be concentrated as necessary to remove a part of the organic solvent as described later, or may be diluted by adding an organic solvent.

Examples of the bismaleimide compound (IX) used in producing the polyphenylene ether derivative (A) include bis (4-maleimidephenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidephenyl) ether, and bis ( 4-maleimidephenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2, 2-Bis (4- (4-maleimide phenoxy) phenyl) propane, bis (4-maleimide phenyl) sulfone, bis (4-maleimide phenyl) sulfide, bis (4-maleimide phenyl) ketone, 2,2-bis (4) -(4-Maleimide phenoxy) phenyl) propane, bis (4- (4-maleimide phenoxy) phenyl) sulfone, 4,4'-bis (3-maleimide phenoxy) biphenyl, 1,6-bismaleimide- (2,2) , 4-trimethyl) hexane and the like. One of these may be used alone, or two or more thereof may be used in combination.
Among these, bis (4-maleimidephenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 2,2-bis (4- (4-maleimide phenoxy)) Phenyl) propane may be selected.
Bis (4-maleimidephenyl) methane may be used from the viewpoint that a polyphenylene ether derivative containing the polyphenylene ether derivative represented by the formula (A'-1) can be obtained and is inexpensive.
A polyphenylene ether derivative containing the polyphenylene ether derivative represented by the above formula (A'-2) can be obtained, and from the viewpoint of excellent dielectric properties and low water absorption, 3,3'-dimethyl-5,5'- Dielectric-4,4'-diphenylmethane bismaleimide may be used.
A polyphenylene ether derivative containing the polyphenylene ether derivative represented by the above formula (A'-3) can be obtained, and from the viewpoint of excellent adhesion to the conductor and mechanical properties (elongation, breaking strength, etc.), 2,2- Bis (4- (4-maleimide phenoxy) phenyl) propane may be used.

The amount of bismaleimide compound (IX) used is determined by the amount of aminophenol compound (VIII) used. _{That is, even if the equivalent ratio (Tb1 / Ta1) of the −NH 2} group equivalent (Ta1) of the aminophenol compound (VIII) to the maleimide group equivalent (Tb1) of the bismaleimide compound (IX) is in the range of 2 to 6. It may be blended in the range of 2 to 4. By using the bismaleimide compound (IX) within the above equivalent ratio range, better heat resistance, high glass transition temperature and high flame retardancy can be obtained in the resin composition, prepreg and laminated board of the present invention. Tend to be.

If necessary, a reaction catalyst can be used for the Michael addition reaction in producing the polyphenylene ether derivative (A). The reaction catalyst that can be used is not particularly limited, and for example, an acidic catalyst such as p-toluenesulfonic acid; an amine such as triethylamine, pyridine, or tributylamine; an imidazole compound such as methylimidazole or phenylimidazole; or triphenylphosphine or the like. Examples include phosphorus-based catalysts. These may be used alone or in combination of two or more. The amount of the reaction catalyst to be blended is not particularly limited, but may be 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether compound (A ″).

The polyphenylene ether derivative (A) is obtained by charging a predetermined amount of the bismaleimide compound (IX) and, if necessary, a reaction catalyst or the like in a solution of the polyphenylene ether compound (A ″), and causing a Michael addition reaction while heating, keeping warm, and stirring. can get. The reaction conditions in this step may be, for example, a reaction temperature of 50 to 160 ° C. and a reaction time of 1 to 10 hours from the viewpoint of workability and suppression of gelation. Further, in this step, the reaction concentration (solid content concentration) and the solution viscosity can be adjusted by adding or concentrating the organic solvent as described above. As the organic solvent additionally used, the organic solvent exemplified in the production process of the polyphenylene ether compound (A ″) can be applied, and one of these may be used alone or two or more of them may be used in combination. Good. Among these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide may be selected from the viewpoint of solubility.

The reaction concentration (solid content concentration) in the production steps of the polyphenylene ether derivative (A) and the polyphenylene ether compound (A ″) is not particularly limited, but for example, in any of the production steps, 10 to 60% by mass. It may be 20 to 50% by mass. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow, and it tends to be more advantageous in terms of production cost. Further, when the reaction concentration is 60% by mass or less, better solubility tends to be obtained. In addition, the solution viscosity is low, the stirring efficiency is good, and gelation tends to be less.
After the polyphenylene ether derivative (A) is produced, various thermocurable resins and the like are added to the polyphenylene ether derivative (A) from the viewpoint of workability when taken out from the reactor to obtain the resin composition of the present invention. From the viewpoint of setting the solution viscosity and solution concentration suitable for the usage situation (for example, solution viscosity suitable for producing prepreg, solution concentration, etc.), a part or all of the organic solvent in the solution is appropriately removed and concentrated. Alternatively, it may be diluted by adding an organic solvent. The organic solvent to be added is not particularly limited, and one or more of the above-mentioned organic solvents can be applied.

The formation of the polyphenylene ether compound (A ″) and the polyphenylene ether derivative (A) obtained in the above production steps can be confirmed by taking out a small amount of sample after each step and measuring by GPC and IR.
First, the polyphenylene ether compound (A ″) has a lower molecular weight than the raw material polyphenylene ether from the GPC measurement, and the peak of the raw material aminophenol compound (VIII) has disappeared, and from the IR measurement 3300 to 3 It can be confirmed that the desired polyphenylene ether compound (A ″) is produced by the appearance of the primary amino group of 3500 cm ^-1. In the polyphenylene ether derivative (A), after purification by reprecipitation, the peak derived from the primary amino group of ^{3300 to 3500 cm -1} disappeared from the IR measurement, and the peak derived from the carbonyl group of maleimide of ^{1700 to 1730 cm -1 appeared.} It can be confirmed that the desired polyphenylene ether derivative (A) is produced by confirming.

The resin composition of the present invention has more adhesiveness to a conductor, heat resistance, coefficient of thermal expansion, and flame retardancy than a resin composition containing a polyphenylene ether compound (A ″) and a component (C) described later. , Tends to be superior in workability (drilling, cutting).

(Brominated flame retardant (B))
The component (B) used in the resin composition of the present invention is a brominated flame retardant having a 5% mass reduction temperature at the time of thermal decomposition of 300 ° C. or higher.
The component (B) has a 5% mass reduction temperature at the time of thermal decomposition of 300 ° C. or higher from the viewpoint of achieving heat resistance under high temperature conditions corresponding to lead-free solder while maintaining good dielectric properties. The 5% mass reduction temperature referred to here is a temperature obtained by thermogravimetric analysis (TGA) in a nitrogen atmosphere under the condition of a temperature rising rate of 10 ° C./min, and the temperature is reduced by 5% by mass from the initial mass. ..
From the above viewpoint, the 5% mass reduction temperature of the component (B) may be 300 ° C. or higher, 320 ° C. or higher, 340 ° C. or higher, or 360 ° C. or higher. The higher the upper limit of the 5% mass reduction temperature, the better, but for example, it may be 600 ° C. or lower, or 500 ° C. or lower.

The component (B) is not particularly limited as long as it is a bromine-based flame retardant having a 5% mass reduction temperature at the time of thermal decomposition of 300 ° C. or higher, but it affects the curability of the resin and the dielectric properties of the cured product. In consideration of the above, the molecule may not have reactivity with the component (A), and it is desirable that the molecule does not contain a polar group such as an epoxy group, a hydroxyl group, a (meth) acrylic group, or a carbonyl group. ..
Specific examples of the component (B) preferably used in the present invention include brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, and ethylene bis ( Pentabromophenyl), ethylene bistetrabromophthalimide, etc. can be mentioned, but from the viewpoint of balance of dielectric properties, adhesiveness (strength of peeling metal foil, adhesiveness to substrate such as glass, etc.), glass transition temperature, etc. , Bromineed polystyrene and ethylene bis (pentabromophenyl).
These components (B) may be used alone or in combination of two or more, or if they contain at least one of these flame retardants, the blending amount is within a range that does not impair the effects of the present invention. One or more other flame retardants may be used in combination.

The blending ratio of the component (B) in the resin composition of the present invention is not particularly limited, but the total amount of the component (A) and the component (C) described later is 100 parts by mass (however, when the component (C) is not used). (A) component (100 parts by mass) may be 1 to 200 parts by mass, 10 to 150 parts by mass, 20 to 100 parts by mass, and 30 to 80 parts by mass. It may be. When the compounding ratio of the flame retardant is 1 part by mass or more, the flame retardancy tends to be further improved, and when it is 200 parts by mass or less, the heat resistance and the metal foil peeling strength when used as a printed wiring board tend to be further improved. It is in.

(Thermosetting resin (C))
The resin composition of the present invention may further contain at least one thermosetting resin selected from an epoxy resin, a cyanate resin and a maleimide compound as the component (C). The maleimide compound does not include the polyphenylene ether derivative (A).

The epoxy resin may be an epoxy resin having two or more epoxy groups in one molecule. Here, the epoxy resin is classified into a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and the like. Among these, a glycidyl ether type epoxy resin may be selected.
Epoxy resins are classified into various epoxy resins according to the difference in the main skeleton. In each of the above types of epoxy resins, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin are further classified. Epoxy resin; alicyclic epoxy resin; aliphatic chain epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, etc. Type epoxy resin; Stilben type epoxy resin; Dicyclopentadiene type epoxy resin; Naftor novolac type epoxy resin, Naftor aralkyl type epoxy resin and other naphthalene skeleton-containing epoxy resin; Biphenyl type epoxy resin; Biphenyl aralkyl type epoxy resin; Xylylene type epoxy Resins; dihydroanthracene type epoxy resins; dicyclopentadiene type epoxy resins and the like.
One type of epoxy resin may be used alone, or two or more types may be used in combination. Among these, a naphthalene skeleton-containing epoxy resin and a biphenyl aralkyl type epoxy resin may be used from the viewpoints of high frequency characteristics, heat resistance, glass transfer temperature, coefficient of thermal expansion, flame retardancy and the like.

When an epoxy resin is used as the component (C), a curing agent, a curing aid, or the like of the epoxy resin can be used in combination, if necessary. These are not particularly limited, but are, for example, polyamine compounds such as diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, m-phenylenediamine, and dicyandiamide; bisphenol A, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, phenol. Examples thereof include polyphenol compounds such as aralkyl resins; acid anhydrides such as phthalic anhydride and pyromellitic anhydride; carboxylic acid compounds; and active ester compounds. One of these may be used alone, or two or more thereof may be used in combination. The amount used is not particularly limited and can be appropriately adjusted according to the purpose. Among these, polyphenol compounds and active ester compounds may be used from the viewpoints of heat resistance, glass transition temperature, coefficient of thermal expansion, storage stability and insulation reliability.

The cyanate resin is not particularly limited, and is, for example, 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, and bis (3,5-dimethyl-4-cyanato). Phenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α'-bis (4-cyanatophenyl) -m-diisopropyl Examples thereof include benzene, a cyanate ester compound of a phenol-added dicyclopentadiene polymer, a phenol novolac type cyanate ester compound, and a cresol novolac type cyanate ester compound. One type of cyanate resin may be used alone, or two or more types may be used in combination. Among these, 2,2-bis (4-cyanatophenyl) propane may be used from the viewpoint of manufacturing cost and the total balance of high frequency characteristics and other characteristics.

When a cyanate resin is used as the component (C), a curing agent, a curing aid, or the like of the cyanate resin can be used in combination, if necessary. These are not particularly limited, and examples thereof include monophenol compounds, polyphenol compounds, amine compounds, alcohol compounds, acid anhydrides, and carboxylic acid compounds. One of these may be used alone, or two or more thereof may be used in combination. The amount of the curing agent and the curing aid used is not particularly limited, and can be appropriately adjusted according to the purpose. Among these, a monophenol compound may be used from the viewpoint of high frequency characteristics, heat resistance, hygroscopicity and storage stability.
When a monophenol compound is used in combination with the cyanate resin, a method of prereacting and using it as a phenol-modified cyanate prepolymer can be adopted from the viewpoint of solubility in an organic solvent. The monophenol compound to be used in combination may be blended in the specified amount at the time of prepolymerization, or may be blended in separate amounts before and after prepolymerization, but from the viewpoint of storage stability, they may be blended separately. Can be adopted.

The maleimide compound is not particularly limited, but for example, it may be referred to as a polymaleimide compound (a) [hereinafter, referred to as a component (a)) having at least two N-substituted maleimide groups in the molecule. ], And the polyaminobismaleimide compound (c) represented by the following general formula (VI) [hereinafter, may be referred to as a component (c). ], At least one of them can be contained. Further, the maleimide compound may be a polyaminobismaleimide compound (c) from the viewpoint of solubility in an organic solvent, high frequency characteristics, adhesiveness to a conductor, and moldability of a prepreg.
The polyaminobismaleimide compound (c) is, for example, an aromatic diamine compound (b) having a component (a) and two primary amino groups in the molecule [hereinafter, may be referred to as a component (b). ] And by a Michael addition reaction in an organic solvent.

（式中、Ａ^４は前記一般式（Ｚ）中のＡ^１の定義と同じであり、Ａ^５は下記一般式（VII）で表される基である。）

(In the formula, A ⁴ is the same as the definition ^{of A 1 in} the general formula (Z) ^{, and A 5} is a group represented by the following general formula (VII).)

（式中、Ｒ^１７及びＲ^１８は各々独立に、炭素数１〜５の脂肪族炭化水素基、炭素数１〜５のアルコキシ基、水酸基又はハロゲン原子である。式中、Ａ^８は炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基、フルオレニレン基、単結合、又は下記一般式（VII-1）もしくは（VII-2）で表される基である。ｑ’及びｒ’は各々独立に０〜４の整数である。）

(In the formula, R ¹⁷ and R ¹⁸ are independently aliphatic hydrocarbon groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, hydroxyl groups or halogen atoms. In the formula, A ⁸ has carbon atoms. An alkylene group of 1 to 5, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a fluorenylene group, a single bond, or the following general formula (VII-1) or (VII-). It is a group represented by 2). Q'and r'are independently integers of 0 to 4.)

（式中、Ｒ^１９及びＲ^２０は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^９は炭素数１〜５のアルキレン基、イソプロピリデン基、ｍ−又はｐ−フェニレンジイソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｓ’及びｔ’は各々独立に０〜４の整数である。）

(In the formula, R ¹⁹ and R ²⁰ are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. A 9} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or a halogen atom. It is a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. S'and t'are independently integers of 0 to 4).

（式中、Ｒ^２１は炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^１０及びＡ^１１は各々独立に、炭素数１〜５のアルキレン基、イソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｗは０〜４の整数である。）

(In the formula, R ²¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. A ¹⁰ and A ¹¹ are independently alkylene groups, isopropylidene groups and ether groups having 1 to 5 carbon atoms, respectively. It is a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. W is an integer of 0 to 4.)

Aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms represented ^{by R 17} , R ¹⁸ , R ¹⁹ , R ²⁰ and R ^{21 in the} general formula (VII), (VII-1) or (VII-2). ^{As, the same as R 1} in the general formula (I) can be mentioned. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or may be a methyl group or an ethyl group.
Formula (VII) or (VII-1) an alkylene group and an alkylidene group having 2 to 5 carbon atoms of 1 to 5 carbon atoms which A ⁸ and A ⁹ represents in, and the general formula (VII-2) in the The alkylene group having 1 to 5 carbon atoms represented by A ¹⁰ and A ¹¹ will be described in the same manner as in the case ^{of A 2 in the general formula (III).}
q'and r'are integers from 0 to 4, and from the viewpoint of availability, both may be integers from 0 to 2, and may be 0 or 2. s'and t'are integers from 0 to 4, and from the viewpoint of availability, both may be integers from 0 to 2, 0 or 1, and may be 0. w is an integer of 0 to 4, and may be an integer of 0 to 2 or 0 from the viewpoint of availability.

The component (a) is not particularly limited, and for example, the same component as the bismaleimide compound (IX) may be applied. Examples of the component (a) include bis (4-maleimidephenyl) methane, polyphenylmethane maleimide, bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, 3,3'-dimethyl-5, 5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, Bis (4-maleimidephenyl) sulfone, bis (4-maleimidephenyl) sulfide, bis (4-maleimidephenyl) ketone, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, bis (4- (4-(4-maleimidephenyl) phenyl) Examples thereof include 4-maleimidephenoxy) phenyl) sulfone, 4,4'-bis (3-maleimidephenoxy) biphenyl, and 1,6-bismaleimide- (2,2,4-trimethyl) hexane. As the component (a), one type may be used alone or two or more types may be used in combination according to the purpose, application and the like. Further, the component (a) may be a bismaleimide compound, or may be bis (4-maleimidephenyl) methane from the viewpoint of low cost, and has excellent dielectric properties and low water absorption. From the viewpoint of being present, it may be 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, and has high adhesiveness to a conductor and mechanical properties (elongation, breaking strength, etc.). From the viewpoint of excellence, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane may be used.

As described above, in the polyaminobismaleimide compound (c), the component (a) and the aromatic diamine compound (b) having two primary amino groups in the molecule are subjected to a Michael addition reaction in an organic solvent. Can be obtained by

The component (b) is not particularly limited, but is, for example, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-. 3,3'-diethyl-diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylketone, 4,4'-diamino Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-) 4-Hydroxyphenyl) propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-) (4-Aminophenoxy) Phenyl) Propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4 , 4'-bis (4-aminophenoxy) biphenyl, 1,3-bis (1-4- (4-aminophenoxy) phenyl) -1-methylethyl) benzene, 1,4-bis (1-4-( 4-Aminophenoxy) Phenyl) -1-Methylethyl) benzene, 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1,4-phenylenebis (1) -Methylethylidene)] bisaniline, 3,3'-[1,3-phenylenebis (1-methylethylidene)] bisaniline, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-amino) Examples thereof include phenoxy) phenyl) sulfone and 9,9-bis (4-aminophenyl) fluorene. One of these may be used alone, or two or more thereof may be used in combination.
Among these, 4,4'-diaminodiphenylmethane and 4,4'-diamino-3,3 are highly soluble in organic solvents, have a high reaction rate during synthesis, and can have high heat resistance. '-Dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 4,4'-[1,3- You may choose from phenylene bis (1-methylethylidene)] bisaniline and 4,4'-[1,4-phenylene bis (1-methylethylidene)] bisaniline. 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'from the viewpoint of low cost in addition to excellent solubility, reaction rate and heat resistance. It may be −diamino-3,3′-diethyl-diphenylmethane. Further, from the viewpoint of being able to exhibit high adhesiveness to a conductor in addition to being excellent in solubility, reaction rate and heat resistance, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 4, It may be 4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline or 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline. Furthermore, in addition to being excellent in solubility, reaction rate, heat resistance, and adhesion to conductors, from the viewpoint of high frequency characteristics and moisture absorption resistance, 4,4'-[1,3-phenylene bis (1-) Methylethylidene)] bisaniline and 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline may be selected. One type of these may be used alone or two or more types may be used in combination according to the purpose, application and the like.

The organic solvent used in producing the polyaminobismaleimide compound (c) is not particularly limited, and for example, the organic solvent exemplified in the production step of the polyphenylene ether compound (A ″) described above can be applied. One of these may be used alone, or two or more thereof may be mixed and used. Among these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, and N, N-dimethylacetamide may be used from the viewpoint of solubility.

The amounts of the components (a) and (b) used in producing the component (c) are the -NH ₂ equivalent (Ta2) of the component (b) and the maleimide group equivalent (Tb2) of the component (a). The equivalent ratio (Tb2 / Ta2) with and may be in the range of 1 to 10, or may be in the range of 2 to 10. By using the components (a) and (b) within the above range, the resin composition, prepreg and laminated board of the present invention have excellent high frequency characteristics, high adhesiveness to a conductor, excellent heat resistance, and high heat resistance. Glass transition temperature and high flame retardancy can be obtained.

The reaction catalyst does not have to be used for the Michael addition reaction in producing the polyaminobismaleimide compound (c), but it can also be used if necessary. The reaction catalyst is not particularly limited, but a reaction catalyst that can be used for the Michael addition reaction during the production of the above-mentioned polyphenylene ether derivative (A) can be applied. As described above, the blending amount of the reaction catalyst is not particularly limited.

When a maleimide compound is used as the component (C), a curing agent, a cross-linking agent, a curing aid, or the like of the maleimide compound can be used in combination. These are not particularly limited, but for example, vinyl compounds such as styrene monomer, divinylbenzene and divinylbiphenyl; (meth) acrylate compounds; allyl compounds such as triallyl cyanurate and triallyl isocyanurate; diaminodiphenylmethane and the like. Polyamine compounds and the like. These may be used alone or in combination of two or more. The amount of these used is not particularly limited, and can be appropriately adjusted according to the purpose. Among these, vinyl compounds and polyamine compounds may be used from the viewpoint of high frequency characteristics and heat resistance.

The polyaminobismaleimide compound (c) is prepared by charging a predetermined amount of the above component (a), component (b), organic solvent and, if necessary, a reaction catalyst, etc. into the reactor, and carrying out a Michael addition reaction while heating, keeping warm, and stirring as necessary. ) Is obtained. As the reaction conditions such as the reaction temperature and the reaction time in this step, for example, the reaction conditions at the time of the Michael addition reaction at the time of producing the polyphenylene ether derivative (A) described above can be applied.
The reaction concentration (solid content concentration) is not particularly limited, but may be 10 to 90% by mass or 20 to 80% by mass. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow, and it tends to be more advantageous in terms of production cost. When it is 90% by mass or less, better solubility tends to be obtained. In addition, since the solution viscosity is low, the stirring efficiency is good and gelation is less likely to occur. After the production of the polyaminobismaleimide compound (c), a part or all of the organic solvent may be removed (concentrated) or an organic solvent may be added according to the purpose, as in the production of the polyphenylene ether derivative (A). Can be diluted.

(Content ratio of component (A) and component (C))
The content ratio [(A): (C)] of the component (A) to the component (C) is not particularly limited, but may be 5:95 to 90:10 in terms of mass ratio, 5:95. It may be ~ 80:20, 5:95 ~ 75:25, 5:95 ~ 70:30, 20:80 ~ 70:30, 40. : 60 to 70:30 may be used. When the content ratio of the component (A) to the total amount of the component (A) and the component (C) is 5% by mass or more, better high frequency characteristics and low hygroscopicity tend to be obtained. Further, when it is 90% by mass or less, more excellent heat resistance, better moldability and better processability tend to be obtained.

<Other ingredients>
The resin composition of the present invention may be optionally referred to as an inorganic filler (D) [hereinafter, a component (D)), if necessary. ], Curing accelerator (E) [Hereinafter, it may be referred to as a component (E). ], At least one selected from the above may be contained. By containing these, various characteristics when the laminated board is formed can be further improved.
For example, by arbitrarily containing an appropriate inorganic filler (D) in the resin composition of the present invention, low thermal expansion coefficient, high elastic modulus, heat resistance and flame retardancy can be improved. Further, by containing an appropriate curing accelerator (E), the curability of the resin composition can be improved, and the high frequency characteristics, heat resistance, adhesiveness to a conductor, elastic modulus and glass transition temperature can be improved.

(Inorganic filler (D))
The component (D) is not particularly limited, but is, for example, silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, and hydroxide. Examples thereof include magnesium, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (baked clay, etc.), talc, aluminum borate, aluminum borate, silicon carbide and the like. .. One of these may be used alone, or two or more thereof may be used in combination. Among these, silica, alumina, mica, talc, silica, alumina, or silica may be used from the viewpoints of coefficient of thermal expansion, elastic modulus, heat resistance, and flame retardancy. Examples of silica include precipitated silica manufactured by a wet method and having a high water content, and dry silica manufactured by a dry method and containing almost no bound water or the like. Further, as dry method silica, there is a difference in manufacturing method. Examples thereof include crushed silica, fumed silica, and fused silica (molten spherical silica).
Further, the shape and particle size of the inorganic filler (D) are not particularly limited. For example, the particle size may be 0.01 to 20 μm, or 0.1 to 10 μm. Here, the particle size refers to the volume average particle size, and is the particle size of a point corresponding to a volume of 50% when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of particles as 100%. The volume average particle size can be measured by a particle size distribution measuring device or the like using a laser diffraction / scattering method.

When the component (D) is used, the content ratio of the component (D) in the resin composition is not particularly limited, but from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance and flame retardancy, the resin composition The content ratio of the component (D) in the component may be 3 to 65% by volume, 5 to 60% by volume, or 15 to 55% by volume. When the content ratio of the component (D) in the resin composition is within the above range, better curability, moldability and chemical resistance tend to be obtained.
When the component (D) is used, a coupling agent is used in combination as necessary for the purpose of improving the dispersibility of the component (D) and the adhesion between the component (D) and the organic component in the resin composition. You may. The coupling agent is not particularly limited, and for example, a silane coupling agent or a titanate coupling agent can be appropriately selected and used. One type of coupling agent may be used alone, or two or more types may be used in combination. Further, the amount of the coupling agent used is not particularly limited, and may be, for example, 0.1 to 5 parts by mass or 0.5 to 3 parts by mass with respect to 100 parts by mass of the component (D). .. Within this range, there is little deterioration of various characteristics, and there is a tendency that the features of the use of the above component (D) can be effectively exhibited.
When a coupling agent is used, it is not a so-called integral blend treatment method in which the coupling agent is added after the component (D) is blended in the resin composition, but the coupling agent is dried or dried in advance in the inorganic filler. A method using a wet surface-treated inorganic filler can be adopted. By adopting this method, the features of the above component (D) can be expressed more effectively.

When the component (D) is used in the present invention, the component (D) is used as a slurry in which the component (D) is previously dispersed in an organic solvent, if necessary, for the purpose of improving the dispersibility of the component (D) in the resin composition. Can be done. The organic solvent used for slurrying the component (D) is not particularly limited, and for example, the organic solvent exemplified in the above-mentioned production step of the polyphenylene ether compound (A ″) can be applied. One of these may be used alone, or two or more thereof may be used in combination. Among these, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be selected from the viewpoint of dispersibility. The solid content (nonvolatile content) concentration of the slurry is not particularly limited, but may be 50 to 80% by mass, and may be 60 to 80, for example, from the viewpoint of sedimentation and dispersibility of the inorganic filler (D). It may be% by mass.

(Curing accelerator (E))
When the resin composition of the present invention contains the component (E), a suitable component (E) can be used according to the type of the component (C) used.
Examples of the component (E) when an epoxy resin is used as the component (C) include an imidazole compound and a derivative thereof; a tertiary amine compound; a quaternary ammonium compound; and a phosphorus compound such as triphenylphosphine. .. One of these may be used alone, or two or more thereof may be used in combination. Among these, an imidazole compound and a derivative thereof or a phosphorus compound may be used from the viewpoint of heat resistance, glass transition temperature and storage stability. Examples of the imidazole compound include methylimidazole, phenylimidazole, isocyanate masked imidazole (for example, an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole, etc.), and isocyanate masked imidazole is selected. You may.

When the cyanate resin is used as the component (C), the component (E) includes, for example, an imidazole compound and a derivative thereof; a carboxylate such as manganese, cobalt, and zinc; an acetylacetone complex of a transition metal such as manganese, cobalt, and zinc. Organic metal compounds and the like. One of these may be used alone, or two or more thereof may be used in combination. Among these, an organometallic compound may be used from the viewpoint of heat resistance, glass transition temperature and storage stability.

When a maleimide compound is used as the component (C), the component (E) includes, for example, an acidic catalyst such as p-toluenesulfonic acid; an amine compound such as triethylamine, pyridine and tributylamine; methylimidazole, phenylimidazole and isocyanate masked imidazole. Imidazole compounds such as (for example, addition reaction products of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl Peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxy Organic peroxides such as isopropyl monocarbonate and α, α'-bis (t-butylperoxy) diisopropylbenzene; carboxylates such as manganese, cobalt and zinc can be mentioned. One of these may be used alone, or two or more thereof may be used in combination. Among these, imidazole compounds, organic peroxides, and carboxylates may be used from the viewpoints of heat resistance, glass transition temperature, and storage stability, and from the viewpoints of heat resistance, glass transition temperature, elastic modulus, and coefficient of thermal expansion. Therefore, the imidazole compound and the organic peroxide may be used in combination. Further, among the organic peroxides, α, α'-bis (t-butylperoxy) diisopropylbenzene may be selected.

When the resin composition of the present invention contains the component (E), the content ratio of the component (E) is not particularly limited, but for example, the total of the components (A) and (C) of the present invention is 100. It may be 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass with respect to parts by mass (however, when the component (C) is not used, 100 parts by mass of the component (A)). .. When the component (E) is used in such a range, better heat resistance and storage stability tend to be obtained.

The resin composition of the present invention contains, if necessary, a known thermoplastic resin, a resin material such as an elastomer, a coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, and a pigment. , Coloring agent, lubricant and the like can be appropriately selected and contained. One of these may be used alone, or two or more thereof may be used in combination. Moreover, the amount of these used is not particularly limited.

(Organic solvent)
The resin composition of the present invention may contain an organic solvent from the viewpoint of facilitating handling by diluting and facilitating the production of a prepreg described later.
The organic solvent is not particularly limited, and is, for example, an alcohol solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran. Ether-based solvents such as; Aromatic solvents such as toluene, xylene, mesityrene; Nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Sulfur atom-containing solvents such as dimethylsulfoxide; Esters such as γ-butyrolactone Examples include system solvents.
Among these, from the viewpoint of solubility, an alcohol solvent, a ketone solvent, a nitrogen atom-containing solvent may be used, a ketone solvent may be used, or acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone may be used. It may be methyl ethyl ketone.
One type of organic solvent may be used alone, or two or more types may be used in combination.
The content of the organic solvent in the resin composition of the present invention is not particularly limited, but the solid content concentration may be 30 to 90% by mass, 40 to 80% by mass, or 40 to 70% by mass. It may be%, and it may be 40 to 60% by mass. By using a resin composition having a solid content concentration within the above range, the handleability is facilitated, the impregnation property into the base material and the appearance of the produced prepreg are good, and the solid resin in the prepreg described later is used. There is a tendency that the component concentration can be easily adjusted and the prepreg having a desired thickness can be easily produced.

The resin composition of the present invention is obtained by mixing the above-mentioned components (A) and (B), as well as the component (C) used as necessary, other components, an organic solvent, and the like by a known method. Can be done. At this time, it may be dissolved or dispersed while stirring. Conditions such as the mixing order, the temperature at the time of mixing and stirring, and the time are not particularly limited and can be set arbitrarily.

The glass transition temperature of the cured product of the resin composition when the laminated plate is produced from the resin composition of the present invention is not particularly limited, but good heat resistance, through-hole connection reliability, and when manufacturing electronic parts and the like. From the viewpoint of excellent processability, the glass transition temperature after heating at 230 ° C. for 180 minutes may be 190 ° C. or higher, 200 ° C. or higher, or 210 ° C. or higher. The upper limit of the glass transition temperature is not particularly limited, but for example, it may be 1000 ° C. or lower, 500 ° C. or lower, or 300 ° C. or lower. When the glass transition temperature is 190 ° C. or higher, good solder heat resistance, through-hole connection reliability, and excellent workability in manufacturing electronic parts and the like can be obtained.
Further, the coefficient of thermal expansion (Z direction, Tg or less) of the cured product of the resin composition when the laminated board is produced from the resin composition of the present invention is not particularly limited, but from the viewpoint of suppressing the warp of the laminated board, from the viewpoint of suppressing the warp of the laminated board. It may be 45 ppm / ° C. or lower, or 40 ppm / ° C. or lower. The lower limit of the coefficient of thermal expansion is not limited, but is usually 30 ppm / ° C. or higher, and further 35 ppm / ° C. or higher.
The glass transition temperature and the coefficient of thermal expansion are values measured according to the IPC standard as described in the examples.

The dielectric constant and the dielectric loss tangent of the cured product of the resin composition when the laminated board is produced from the resin composition of the present invention are not particularly limited, but the dielectric constant at 10 Ghz is small from the viewpoint of suitable use in the high frequency band. Is preferable, it may be 3.8 or less, 3.75 or less, or 3.65 or less. The lower limit of the dielectric constant is not particularly limited, but may be, for example, 0.5 or more, 1 or more, 3 or more, or 3.5 or more.
Further, the dielectric loss tangent is preferably small, and the dielectric loss tangent at 10 GHz may be 0.007 or less, or 0.006 or less. The lower limit of the dielectric loss tangent is not particularly limited, and the smaller it is, the better. For example, it may be 0.0001 or more, 0.002 or more, 0.004 or more, and 0. It may be 005 or more.
The dielectric constant and the dielectric loss tangent are values measured in accordance with JPCA-TM001 (Triplate Resonator Method) as in the examples.

[Prepreg]
The present invention also provides a prepreg having the resin composition of the present invention and a sheet-like fiber reinforced base material. The prepreg can be obtained by impregnating or coating a sheet-shaped fiber reinforced base material with the resin composition of the present invention and drying it. More specifically, for example, the prepreg of the present invention can be produced by heating and drying in a drying oven at a temperature of 80 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage). .. The amount of the resin composition used can be determined so that the solid content concentration derived from the resin composition in the prepreg after drying is 30 to 90% by mass. When the solid content concentration is in the above range to form a laminated plate, better moldability tends to be obtained.

As the sheet-shaped fiber reinforced base material of the prepreg, known materials used for various laminated plates for electrical insulating materials are used. Examples of the material of the sheet-shaped reinforcing base material include inorganic fibers such as E glass, D glass, S glass and Q glass; organic fibers such as polyimide, polyester and tetrafluoroethylene; and a mixture thereof. These sheet-shaped reinforcing base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats. Further, the thickness of the sheet-shaped fiber reinforced base material is not particularly limited, and for example, one having a thickness of 0.02 to 0.5 mm can be used. Further, those surface-treated with a coupling agent or the like and those subjected to mechanical opening treatment are suitable from the viewpoints of impregnation property of the resin composition, heat resistance when formed into a laminated board, moisture absorption resistance and processability. Can be used for.

As a method of impregnating or coating the sheet-shaped reinforcing base material with the resin composition, for example, the following hot melt method or solvent method can be adopted.
The hot melt method is a method in which the resin composition does not contain an organic solvent, (1) is once coated on coated paper having good peelability from the composition, and the resin composition is laminated on a sheet-like reinforcing base material or (2). ) This is a method of directly coating the sheet-shaped reinforcing base material with a die coater.
On the other hand, in the solvent method, the resin composition is impregnated with an organic solvent, the sheet-shaped reinforcing base material is immersed in the obtained resin composition, the resin composition is impregnated into the sheet-shaped reinforcing base material, and then dried. The method.

[Laminated board and multi-layer printed wiring board]
The laminated board of the present invention has a cured product of the resin composition of the present invention and a metal foil. The cured product of the resin composition of the present invention used for the laminated board of the present invention may be contained in a heated and pressurized prepreg. In this case, in the laminated plate of the present invention, a metal plate is arranged on one side or both sides of one prepreg of the present invention, or a metal foil is arranged on one side or both sides of a stack of two or more prepregs of the present invention. It can then be obtained by heat and pressure molding.
The metal of the metal leaf is not particularly limited as long as it is used for electrical insulating material, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium. , Chromium or an alloy containing at least one of these metallic elements, copper, aluminum, or copper.
The conditions for heat and pressure molding are not particularly limited, but for example, the temperature may be 100 to 300 ° C., the pressure may be 0.2 to 10.0 MPa, and the time may be 0.1 to 5 hours. it can. Further, for heat and pressure molding, a method of holding the vacuum state for 0.5 to 5 hours using a vacuum press or the like can be adopted.
Further, the multilayer printed wiring board of the present invention has a cured product or a laminated board of the resin composition of the present invention. The cured product of the resin composition of the present invention used for the multilayer printed wiring board of the present invention may be contained in a heated and pressurized prepreg.
The multilayer printed wiring board of the present invention uses, for example, the prepreg or the laminate of the present invention, and is subjected to drilling, metal plating, circuit formation (etching of metal foil, etc.) and multi-layer bonding by a known method. It can be manufactured by performing.

In the laminated board of the present invention, the adhesiveness between the cured product of the resin composition and the conductor may be 0.6 kN / m or more in terms of the copper foil peeling strength. The copper foil peeling strength was measured in accordance with JIS C 6481. For the above values, for example, by using the resin composition of the present invention and a low profile copper foil (Rz: 1 to 2 μm) having a very small surface roughness on the adhesive surface side with the resin composition. Can be achieved.

The resin composition, prepreg, laminated board and multilayer printed wiring board of the present invention can be suitably used for manufacturing an electronic device that handles a high frequency signal of 1 GHz or higher, and particularly for manufacturing an electronic device that handles a high frequency signal of 10 GHz or higher. It can be preferably used.

Although preferred embodiments of the present invention have been described above, these are examples for explaining the present invention, and the scope of the present invention is not limited to these embodiments.
The present invention can be carried out in various aspects different from the above-described embodiment without departing from the gist thereof.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.

[Manufacturing of polyphenylene ether derivative (A)]
The polyphenylene ether derivative (A) was produced according to the following procedure and the blending amount shown in Table 1.

(Production Example A-1: Production of polyphenylene ether derivative (A-1))
Toluene, polyphenylene ether having a number average molecular weight of about 16000, and p-aminophenol are placed in a glass flask container having a volume of 2 L that can be heated and cooled and equipped with a thermometer, a reflux condenser, and a stirrer, and stirred at 90 ° C. Dissolved while.
After visually confirming that it was dissolved, t-butylperoxyisopropyl monocarbonate and manganese naphthenate were added, and the mixture was reacted at a solution temperature of 90 ° C. for 4 hours and then cooled to 70 ° C. to have a primary amino group at the molecular terminal. A polyphenylene ether compound (A ″) was obtained.
When a small amount of this reaction solution was taken out and measured by gel permeation chromatography (GPC), the peak derived from p-aminophenol disappeared and the number average molecular weight of the polyphenylene ether compound (A ″) was about. It was 9200. The reaction solution taken out a small amount of methanol / benzene mixed solvent (weight ratio: 1: 1) was added dropwise, was subjected to FT-IR measurement of solids were purified by reprecipitation (reaction product), 3400 cm ^- The appearance of a peak derived from a primary amino group near ^{1 was confirmed.}

Here, the number average molecular weight was converted from the calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, Product name] was used to approximate with a cubic equation. The measurement conditions of GPC are shown below.
apparatus:
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Column: Guard column; TSK Guardcolum HHR-L + column; TSKgel G4000HHR + TSKgel G2000HHR [All manufactured by Tosoh Corporation, product name]
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL / min Measurement temperature: 40 ° C

Next, bis (4-maleimidephenyl) methane and propylene glycol monomethyl ether are added to the above reaction solution, the temperature of the liquid is raised with stirring, the reaction is carried out at 120 ° C. for 4 hours, and then the solution is cooled. Then, the polyphenylene ether derivative (A-1) was produced by filtering through a 200 mesh filter.
Taking out a small amount of the reaction solution in the same manner as described above and re-precipitation, carried out an FT-IR measurements of the purified solid, and disappearance of the primary amino groups from peak near 3400 cm ^-1, carbonyl maleimide 1700～1730Cm ^-1 The appearance of a group-derived peak was confirmed. Moreover, when GPC (the same conditions as above) of this solid substance was measured, the number average molecular weight was about 9400.

(Production Examples A-2 to A-9: Production of Polyphenylene Ether Derivatives (A-2) to (A-9))
Polyphenylene ether derivatives (A-2) to (A-9) were produced in the same manner as in Production Example A-1 except that the raw materials and the blending amounts were changed as shown in Table 1 in Production Example A-1. did. The number average molecular weights of the polyphenylene ether derivatives (A-2) to (A-9) are shown in Table 1.

[Manufacturing of comparative polymer]
Comparative polymers (R-1) to (R-3), which are comparative materials, were produced according to the following procedure and the blending amounts shown in Table 1.

(Comparative Production Example R-1: Production of Polyphenylene Ether (R-1))
Toluene, polyphenylene ether having a number average molecular weight of about 16000, and bisphenol A are placed in a glass flask container having a volume of 2 L that can be heated and cooled and equipped with a thermometer, a reflux condenser, and a stirrer, and the mixture is stirred at 80 ° C. Dissolved.
After visually confirming that it was dissolved, t-butylperoxyisopropyl monocarbonate and cobalt naphthenate were blended and reacted for 1 hour to obtain polyphenylene ether (R-1). The number average molecular weight of this polyphenylene ether (R-1) was about 8000.

(Comparative Production Example R-2: Production of Polyphenylene Ether (R-2))
In Comparative Production Example R-1, a polyphenylene ether solution was obtained in the same manner as in Comparative Production Example R-1 except that the blending amount of each raw material was changed to the blending amount shown in Table 1. A large amount of methanol was added to this solution to reprecipitate the polyphenylene ether, which was then dried under reduced pressure at 80 ° C. for 3 hours to remove the organic solvent to obtain a solid polyphenylene ether (R-2'). ..
The resulting polyphenylene ether (R-2'), chloromethylstyrene, tetra-n-butylammonium bromide, and toluene can then be heated and cooled with a thermometer, reflux condenser, stirrer and dropping funnel. It was placed in a 2 L glass flask container and dissolved with stirring at 75 ° C.
After visually confirming that the solution was dissolved, an aqueous sodium hydroxide solution was added dropwise to this solution in 20 minutes, and the mixture was further stirred at 75 ° C. for 4 hours to react. Next, the contents of the flask were neutralized with a 10 mass% hydrochloric acid aqueous solution, a large amount of methanol was added to reprecipitate, and then the flask was filtered. The filtrate was washed 3 times with a mixed solution of methanol and water (methanol: water = 80:20 (volume ratio)), dried under reduced pressure at 80 ° C. for 3 hours, and the terminal was ethenylbenzylized polyphenylene ether. (R-2) was obtained. The number average molecular weight of this polyphenylene ether (R-2) was about 3000.

(Comparative Production Example R-3: Production of Polyphenylene Ether-Modified Butadiene Prepolymer (R-3))
To a glass flask container having a volume of 2 L that can be heated and cooled equipped with a thermometer, a reflux condenser, a vacuum concentrator, and a stirrer, toluene and polyphenylene ether having a number average molecular weight of about 16000 are put into the flask to adjust the temperature inside the flask. The temperature was set to 90 ° C. and the mixture was stirred and dissolved. Next, a polybutadiene resin and bis (4-maleimidephenyl) methane were added, and the mixture was stirred and dissolved. After the liquid temperature is adjusted to 110 ° C., 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane is added as a reaction initiator, and the mixture is reacted for 1 hour with stirring to obtain polyphenylene ether. The butadiene resin and bismaleimide were pre-reacted in the presence of. Further, after setting the liquid temperature to 80 ° C., the solution was concentrated under reduced pressure so that the solid content concentration of the solution was 45% by mass with stirring, and then cooled to obtain a polyphenylene ether-modified butadiene prepolymer (R-3) solution. Conversion rate of bis (4-maleimidephenyl) methane in this polyphenylene ether-modified butadiene prepolymer (R-3) solution (value obtained by subtracting the unconverted portion (measured value) of bis (4-maleimidephenyl) methane from 100) Was measured by GPC (polystyrene equivalent, eluent: tetrahydrofuran) and found to be 30%.

The abbreviations of each material in Table 1 are as follows.
(1) Polyphenylene ether / PPO640: Polyphenylene ether (manufactured by SABIC Innovative Plastics), number average molecular weight = about 16000, trade name (2) Aminophenol compound (VIII)
・ P-Aminophenol: manufactured by Ihara Chemical Industry Co., Ltd. ・ m-Aminophenol: manufactured by Kanto Chemical Co., Inc. (3) Phenol compound ・ Bisphenol A: manufactured by Tokyo Kasei Kogyo Co., Ltd. (4) Bismaleimide compound (IX)
-BMI-1000: Bis (4-maleimidephenyl) methane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
BMI-5100: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
-BMI-4000: 2,2-bis (4- (4-maleimide phenoxy) phenyl) propane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
-BMI-2300: Polyphenylmethane maleimide, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
-BMI-TMH: 1,6-bismaleimide- (2,2,4-trimethyl) hexane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
(5) Polybutadiene resin B-3000: Butadiene homopolymer, trade name (number average molecular weight: about 3000, manufactured by Nippon Soda Corporation)
(6) Reaction catalyst, perbutyl (registered trademark) I: t-butylperoxyisopropyl monocarbonate, trade name (manufactured by NOF CORPORATION)
-PerhexaTMH: 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, trade name (manufactured by NOF CORPORATION)
・ Manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)
・ Cobalt naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)
(7) Reaction solvent, toluene (manufactured by Kanto Chemical Co., Inc.)
・ Propylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Inc.)

[Production of Polyaminobismaleimide Compounds (B-1) to (B-3) and Phenol-Modified Cyanate Prepolymer (B-4)]
Polyaminobismaleimide compounds (B-1) to (B-3) and phenol-modified cyanate prepolymer (B-4) were produced according to the following procedure and the blending amounts shown in Table 2.

(Production Example B-1: Production of Polyaminobismaleimide Compound (B-1))
2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane in a 1 L volume glass flask container equipped with a thermometer, a reflux condenser, and a stirrer. 4- (4-Aminophenoxy) phenyl) propane and propylene glycol monomethyl ether are added, and the mixture is reacted for 3 hours with stirring while keeping the liquid temperature at 120 ° C., cooled, and then filtered through a 200 mesh filter. As a result, a polyaminobismaleimide compound (B-1) was produced.

(Production Examples B-2 to B-3: Production of Polyaminobismaleimide Compounds (B-2) to (B-3))
Polyaminobismaleimide compounds (B-2) to (B-3) in the same manner as in Production Example B-1 except that the raw materials and their blending amounts were changed as shown in Table 2 in Production Example B-1. Manufactured.

(Production Example B-4: Production of Phenol-Modified Cyanate Prepolymer (B-4))
Toluene, 2,2-bis (4-cyanatophenyl) propane, p- (α-cumyl) phenol in a 1 L volume glass flask container equipped with a thermometer, a reflux condenser, and a stirrer. After adding and visually confirming that it was dissolved, zinc naphthenate was added as a reaction catalyst while stirring while keeping the liquid temperature at 110 ° C., and the mixture was reacted for 3 hours, cooled, and then 200 mesh was added. A phenol-modified cyanate prepolymer (B-4) was produced by filtering through a filter.

The abbreviations of each material in Table 2 are as follows.
(1) Polymaleimide compound (a)
-BMI-4000: 2,2-bis (4- (4-maleimide phenoxy) phenyl) propane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
BMI-5100: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
(2) Aromatic diamine compound (b)
・ BAPP: 2,2-bis (4- (4-aminophenoxy) phenyl) propane, trade name (manufactured by Wakayama Seika Kogyo Co., Ltd.)
-Bisaniline-P: 4,4'-[1,4-phenylene bis (1-methylethylidene)] bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
-Bisaniline-M: 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
(3) Cyanate resin / BADCy: Primaset (registered trademark) BADCy, 2,2-bis (4-cyanatophenyl) propane, trade name (manufactured by Lonza)
(4) Monophenol compound ・ p- (α-cumyl) phenol (manufactured by Mitsui Kagaku Fine Co., Ltd.)
(5) Reaction catalyst, zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)
(6) Organic solvent, toluene (manufactured by Kanto Chemical Co., Inc.)
・ Propylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Inc.)

[Examples 1 to 13, Comparative Examples 1 to 8; Preparation of resin composition]
Each component shown in Tables 3 and 4 is stirred and mixed while heating at room temperature or 50 to 80 ° C. according to the blending amount (unit: parts by mass) shown in Tables 3 and 4, and the solid content (nonvolatile content). A resin composition having a concentration of 40 to 60% by mass was prepared.
Here, as for the blending amount of the inorganic filler, the density of the resin composition (excluding the inorganic filler) is usually 1.20 to 1.25 g / cm ³ , and the density of the inorganic filler used is 2. Since it is 2 to 3.01 g / cm ³ , when the inorganic filler is blended in an amount of 80 parts by mass with respect to 100 parts by mass of the resin composition, it is about 24 to 31% by volume.

[Evaluation and measurement method]
Using the resin compositions obtained in the above Examples and Comparative Examples, each measurement and evaluation was carried out according to the following methods. The results are shown in Tables 3 and 4.

(1. Evaluation of compatibility of resin composition)
The resin composition obtained in each example and the appearance after drying the resin composition at 160 ° C. for 10 minutes to volatilize the organic solvent are visually observed, and the compatibility (macroscopic phase separation or macroscopic phase separation) of each is observed. The presence or absence of unevenness) was evaluated according to the following criteria.
◯: There is no macroscopic phase separation and unevenness.
X: There is macroscopic phase separation or unevenness.

(2. Preparation of prepreg and copper-clad laminate)
The resin composition obtained in each example was applied to a glass cloth (E glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and then heated and dried at 160 ° C. for 7 minutes to obtain a resin content (resin content). ) Approximately 54% by mass of prepreg was prepared. Six of these prepregs were stacked, and a low profile copper foil (FV-WS, M surface Rz: 1.5 μm, manufactured by Furukawa Electric Co., Ltd.) with a thickness of 18 μm was placed above and below the prepreg so that the M surface was in contact with each other. A double-sided copper-clad laminate (thickness: 0.8 mm) was produced by heat-press molding under the conditions of a temperature of 230 ° C. (however, 200 ° C. in Example 12), a pressure of 3.9 MPa, and a time of 180 minutes.
(2-1. Appearance evaluation of prepreg)
The appearance of the prepreg obtained above was observed. The appearance was visually evaluated, and those having some unevenness, streaks, foaming, and phase separation on the surface of the prepreg and lacking surface smoothness were marked with x, and those without the above-mentioned abnormalities in appearance were marked with ○. ..
(2-2. Evaluation of characteristics of copper-clad laminate)
The copper-clad laminates obtained above were evaluated for moldability, dielectric properties, copper foil peeling strength, glass transition temperature, coefficient of thermal expansion, solder heat resistance and flame retardancy. The method for evaluating the characteristics of the copper-clad laminate is as follows.

(2-2-1) Moldability The moldability was evaluated by observing the appearance of the laminated plate obtained by etching the copper foils on both sides. The moldability was visually evaluated, and those having some unevenness, streaks, cassoulet, and voids and lacking surface smoothness were marked with x, and those without the above-mentioned abnormalities in appearance were marked with ◯.
(2-2-2) Dielectric properties 2 mm x 85 mm from the evaluation substrate from which the copper foil was removed by immersing the copper-clad laminate in a 10 mass% solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Company, Inc.), which is a copper etching solution. The evaluation substrate of was prepared.
The evaluation substrate was measured in the 10 GHz band in accordance with JPCA-TM001 (Triplate resonator method).

(2-2-3) Copper Foil Peeling Strength The copper foil peeling strength was measured in accordance with JIS C 6481, and the adhesiveness with the conductor was measured.
(2-2-4) Solder heat resistance The solder heat resistance was evaluated using a 50 mm square test piece in which copper foils on both sides were etched. After the test piece was treated in a normal and pressure cooker test (PCT) device (condition: 121 ° C., 2.2 atm) for a predetermined time (1 hour, 3 hours and 5 hours), it was melted at 288 ° C. The appearance of the test piece after being immersed in the solder obtained by immersing it in the solder for 20 seconds was visually observed. The numbers in the table mean the number of the three test pieces after the solder immersion, in which no abnormality such as swelling in the laminated plate and occurrence of measling was observed.
(2-2-5) Glass transition temperature (Tg) and coefficient of thermal expansion The glass transition temperature (Tg) and coefficient of thermal expansion (plate thickness direction, temperature range: 30 to 150 ° C.) are 5 mm obtained by etching copper foil on both sides. Compliant with IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard by thermomechanical measuring device (TMA) [manufactured by TA Instruments Japan Co., Ltd., Q400 (model number)] using a corner test piece. And measured.
(2-2-6) Length from the evaluation substrate from which the copper foil was removed by immersing the flame-retardant copper-clad laminate in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemicals, Inc.), which is a copper etching solution. A test piece having a width of 127 mm and a width of 12.7 mm was cut out, and the test piece was used to test and evaluate the flame retardancy according to the UL94 test method (V method).
That is, the lower end of the test piece held vertically was contacted twice with a 20 mm flame for 10 seconds. The evaluation was performed according to the UL94 V method standard.

The abbreviations and the like of each material in Tables 3 and 4 are as follows.
(1) Polyphenylene ether / PPO640: Polyphenylene ether (manufactured by SABIC Innovative Plastics), number average molecular weight = about 16000, trade name (2) brominated flame retardant / PBS64HW: brominated polystyrene, trade name (5% mass reduction temperature) : 370 ° C, manufactured by Great Lakes)
-BT-93W: Ethylene bistetrabromophthalimide, trade name (5% mass reduction temperature: 410 ° C, manufactured by Albemarle Corporation)
SR-245: 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, trade name (5% mass reduction temperature: 385 ° C, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
-PO-64P: Brominated polyphenylene ether, trade name (5% mass reduction temperature: 363 ° C, manufactured by Great Lakes)
-SAYTEX8010: Ethylene bis (pentabromophenyl), trade name (5% mass reduction temperature: 344 ° C, manufactured by Albemarle Corporation)
-HBB: Hexabromobenzene, trade name (5% mass reduction temperature: 270 ° C, manufactured by Manac)
-CD-75: Hexabromocyclododecane, trade name (5% mass reduction temperature: 228 ° C, manufactured by Great Lakes)
-FF-680: Bis (tribromophenoxy) ethane, trade name (5% mass reduction temperature: 276 ° C, manufactured by Great Lakes)
BE-51: Dialyl ether of brominated bisphenol A, manufactured by Great Lakes, trade name (3) thermosetting resin (C)
-BMI-4000: 2,2-bis (4- (4-maleimide phenoxy) phenyl) propane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
-NC-3000H: Biphenyl aralkyl type epoxy resin, trade name (manufactured by Nippon Kayaku Co., Ltd.)
-NC-7000L: Naftor novolac type epoxy resin, trade name (manufactured by Nippon Kayaku Co., Ltd.)
-BA230S: Prepolymer of 2,2-bis (4-cyanatophenyl) propane, trade name (solid content concentration 75% by mass, manufactured by Lonza)
・ TAIC: Triallyl isocyanurate (manufactured by Nihon Kasei Corporation)
(4) Inorganic filler (D)
SC-2050-KNG: Spherical molten silica (average particle size: 0.5 μm, surface treatment: vinylsilane coupling agent (1% by mass / solid content), dispersion medium: methyl isobutyl ketone (MIBK), solid content concentration 70 mass) %, Density 2.2 g / cm ³ , manufactured by Admatex Co., Ltd.)
-AlOOH: Boehmite type aluminum hydroxide, manufactured by Kawai Coal Industry Co., Ltd. (5) Reaction accelerator (E)
-Perbutyl (registered trademark) P: α, α'-bis (t-butylperoxy) diisopropylbenzene, trade name (manufactured by NOF CORPORATION)
G-8009L: Isocyanate mask imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole), trade name (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
-Zinc naphthenate: manufactured by Wako Pure Chemical Industries, Ltd. (6) Compatibility agent-Tufprene A: Styrene-butadiene block copolymer, trade name (manufactured by Asahi Kasei Chemicals, Inc.)
(7) Organic solvent, toluene (manufactured by Kanto Chemical Co., Inc.)
・ Methyl ethyl ketone (manufactured by Kanto Chemical Co., Inc.)
・ Cyclohexane (manufactured by Kanto Chemical Co., Inc.)

As is clear from the results shown in Tables 3 and 4, in the examples of the present invention, the compatibility of the resin varnish and the resin composition and the appearance (uniformity) of the prepreg are excellent. In addition, the copper-clad laminates produced using these are good in all of formability, high-frequency characteristics, adhesiveness to conductors, solder heat resistance, glass transition temperature, thermal expansion characteristics and flame retardancy, and are well-balanced. Are better.

As shown in Table 4, those using unreacted polyphenylene ether (Comparative Example 1) are inferior in compatibility between the resin varnish and the resin composition and the appearance (uniformity) of the prepreg.
In Comparative Examples, those using a polyphenylene ether derivative that cannot be applied to the present invention (Comparative Examples 2 to 4) have moldability, dielectric properties, adhesiveness to a conductor, solder heat resistance, glass transition temperature, thermal expansion characteristics and difficulty. Not all of the flammability is satisfactory and one of the properties is inferior.
In the comparative example, the one to which a flame retardant having a 5% mass reduction temperature of less than 300 ° C., which cannot be applied to the present invention, is added (Comparative Examples 5 to 8) is inferior in solder heat resistance.

The resin composition of the present invention has good compatibility, has a high flame retardancy of V-0 or higher, excellent high frequency characteristics, high adhesion to a conductor, excellent heat resistance, a low coefficient of thermal expansion and a high glass transition temperature. Have. Further, the resin composition of the present invention can keep the raw material cost and the manufacturing cost of the substrate material low, and the prepreg and the laminated board provided by using this resin composition are suitable for electronic component applications such as a multilayer printed wiring board. Can be used for.

Claims (16)

A resin composition containing a polyphenylene ether derivative (A) having at least one N-substituted maleimide group in the molecule and a brominated flame retardant (B) having a 5% mass reduction temperature of 300 ° C. or higher. The resin composition according to claim 1, wherein the polyphenylene ether derivative (A) has at least one N-substituted maleimide structure-containing group in the molecule and a structural unit represented by the following general formula (I). ..

(In the formula, R ¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. X is an integer of 0 to 4.) The resin composition according to claim 2, wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (Z).

(In the formula, R ² is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. Y is an integer of 0 to 4. A ¹ is the following general formula (II), ( III), a group represented by (IV) or (V).

(In the formula, R ³ is independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. P is an integer of 0 to 4.)

(In the formula, R ⁴ and R ⁵ are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. A 2} is an alkylene group having 1 to 5 carbon atoms and alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (III-1). Q and r are independently integers of 0 to 4. .)

(Wherein, ^{R 6} and ^{R 7} each independently, .A ³ is an alkylene group having 1 to 5 carbon atoms is an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms, an isopropylidene group, an ether group, It is a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. S and t are independently integers of 0 to 4).

(In the formula, n is an integer from 0 to 10.)

(In the formula, R ⁸ and R ⁹ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 5 carbon atoms. U is an integer of 1 to 8.) Wherein A ¹ in the general formula (Z) is a group represented by any one of the following formulas, the resin composition according to claim 3.

The resin composition according to any one of claims 2 to 4, wherein the structural unit represented by the general formula (I) is a structural unit represented by the following formula (I').

The resin composition according to any one of claims 1 to 5, wherein the polyphenylene ether derivative (A) has a number average molecular weight of 3000 to 12000. The brominated flame retardant (B) is brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, ethylenebis (pentabromophenyl) and ethylenebistetra. The resin composition according to any one of claims 1 to 6, which is at least one selected from bromophthalimide. The resin composition according to any one of claims 1 to 7, further comprising at least one thermosetting resin (C) selected from an epoxy resin, a cyanate ester resin, and a maleimide compound. The thermosetting resin (C) contains a polymaleimide compound (a) having at least two N-substituted maleimide groups in the molecule or a polyaminobismaleimide compound (c) represented by the following general formula (VI). The resin composition according to claim 8.

(In the formula, A ⁴ is the same as the definition ^{of A 1 in} the general formula (Z) ^{, and A 5} is a group represented by the following general formula (VII).)

(In the formula, R ¹⁷ and R ¹⁸ are independently aliphatic hydrocarbon groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, hydroxyl groups or halogen atoms. A ⁸ has 1 to 5 carbon atoms. Alkoxy group, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carooxy group, keto group, fluorenylene group, single bond, or the following general formula (VII-1) or (VII-2). The groups represented. Q'and r'are independently integers 0-4.)

(In the formula, R ¹⁹ and R ²⁰ are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. A 9} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or a halogen atom. It is a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. S'and t'are independently integers of 0 to 4).

(In the formula, R ²¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. A ¹⁰ and A ¹¹ are independently alkylene groups, isopropylidene groups and ether groups having 1 to 5 carbon atoms, respectively. It is a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. W is an integer of 0 to 4.) The content ratio of the component (A) and the component (C) [(A): (C)] is 5:95 to 90:10 in terms of mass ratio, and the content ratio of the component (B) is (A). The resin composition according to claim 8 or 9, which is in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of the component and the component (C). The resin composition according to any one of claims 1 to 10, further containing an inorganic filler (D). The resin composition according to any one of claims 1 to 11, wherein the glass transition temperature after heating at 230 ° C. for 180 minutes is 190 ° C. or higher. A prepreg having the resin composition according to any one of claims 1 to 12 and a sheet-like fiber reinforced base material. A laminated board having a cured product of the resin composition according to any one of claims 1 to 12 and a metal foil. A multilayer printed wiring board having a cured product of the resin composition according to any one of claims 1 to 12 or a laminated board according to claim 14. A method for manufacturing a multilayer printed wiring board using the prepreg according to claim 13 or the laminate according to claim 14.