JP7298623B2 - Resin composition, cured product of resin composition, prepreg, laminate, resin film, multilayer printed wiring board, multilayer printed wiring board for millimeter wave radar, and polyphenylene ether derivative - Google Patents

Description

The present invention relates to a resin composition, a cured product of the resin composition, a prepreg, a laminate, a resin film, a multilayer printed wiring board, a multilayer printed wiring board for millimeter wave radar, and a polyphenylene ether derivative.

2. Description of the Related Art Mobile communication devices such as mobile phones, network infrastructure devices such as base station devices, servers and routers, large computers, and the like use signals of higher speed and capacity year by year. Along with this, the printed wiring boards mounted on these electronic devices need to be compatible with higher frequencies. There is a demand for a substrate material that is excellent in the characteristics. In recent years, as applications for handling such high-frequency signals, in addition to the above-mentioned electronic devices, new systems that handle high-frequency wireless signals have been put into practical use or are planned to be put into practical use in the ITS field (related to automobiles and transportation systems) and in the indoor short-distance communication field. In the future, it is expected that there will be further demand for low transmission loss substrate materials for printed wiring boards mounted in these devices.

Conventionally, polyphenylene ether (PPE) resins have been used as heat-resistant thermoplastic polymers with 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 been proposed. Specifically, a resin composition containing polyphenylene ether and an epoxy resin (for example, see Patent Document 1), a resin composition containing polyphenylene ether and a cyanate resin having a low dielectric constant among thermosetting resins (for example, see Patent Document 1) Reference 2) and the like are disclosed.
However, the resin compositions described in Patent Documents 1 and 2 are generally insufficient in high frequency characteristics in the GHz region, adhesion with conductors, low coefficient of thermal expansion, and flame retardancy, and polyphenylene ether and heat curing In some cases, the heat resistance is lowered due to the low compatibility with the heat resistant resin.

（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。）Under such circumstances, resins with particularly good compatibility, dielectric properties in high frequency bands, high adhesion to conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion, and high flame retardancy An object of the present invention is to provide a composition comprising a polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula in one molecule, an epoxy resin, a cyanate resin and a maleimide compound. A resin composition containing at least one thermosetting resin (B) selected from the group and a styrene-based thermoplastic elastomer (C) has been proposed (see, for example, Patent Document 3).

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

JP-A-58-069046 Japanese Patent Publication No. 61-018937 WO2016/175326

The resin composition described in Patent Document 3 certainly has excellent dielectric properties in a high frequency band, but in recent years, fifth generation mobile communication systems using radio waves in a frequency band exceeding 6 GHz ( 5G) The development of a resin composition with further improved dielectric properties in a high frequency band that can be used for antennas and millimeter wave radars that use radio waves in the frequency band of 30 to 300 GHz is eagerly awaited. There is an urgent need to develop materials.

In view of such a situation, the present invention provides a resin composition capable of exhibiting excellent dielectric properties in a high frequency band of 10 GHz or higher, a cured product of the resin composition, a prepreg, a resin film, a multilayer printed wiring board and a mill. An object of the present invention is to provide a multi-layer printed wiring board for wave radar, and a polyphenylene ether derivative from which such a resin composition can be obtained.

As a result of intensive studies to solve the above problems, the present inventors have found that polyphenylene ether derivatives having a specific molecular structure and at least one selected from the group consisting of specific maleimide compounds and derivatives thereof. The present inventors have found that a resin composition containing it exhibits excellent dielectric properties in a high frequency band of 10 GHz or higher, and have completed the present invention.
That is, the present invention relates to the following [1] to [20].

（式（ａ－１）中、Ｒ^ａ１は炭素数２～１０の不飽和脂肪族炭化水素基である。ｍ１は１又は２であり、ｎ１は０又は１である。＊は、他の構造への結合位置を示す。）
［３］前記（Ａ）成分が有する不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－２）で表される構造を有する、上記［１］又は［２］に記載の樹脂組成物。

（式（ａ－２）中、Ｒ^ａ２及びＲ^ａ３は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）
［４］前記（Ａ）成分が有する不飽和脂肪族炭化水素基の合計数が２つ以上である、上記［１］～［３］のいずれかに記載の樹脂組成物。
［５］前記（Ａ）成分が有する不飽和脂肪族炭化水素基の合計数が４つ以上である、上記［１］～［４］のいずれかに記載の樹脂組成物。
［６］前記（Ａ）成分において、前記不飽和脂肪族炭化水素基が、ビニル基、イソプロペニル基、アリル基、１－メチルアリル基又は３－ブテニル基である、上記［１］～［５］のいずれかに記載の樹脂組成物。
［７］前記（Ｂ）成分が、Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物（ｂ１）由来の構造単位とジアミン化合物（ｂ２）由来の構造単位とを有する、上記［１］～［６］のいずれかに記載の樹脂組成物。
［８］前記（Ｂ）成分が、下記一般式（Ｂ－１）で表されるポリアミノビスマレイミド化合物を含む、上記［１］～［７］のいずれかに記載の樹脂組成物。

（式（Ｂ－１）中、Ｘ^Ｂ１及びＸ^Ｂ２は、各々独立に、有機基である。）
［９］１０ＧＨｚにおける誘電率が２．９０以下であり、且つ１０ＧＨｚにおける誘電正接が０．００５５以下である、上記［１］～［８］のいずれかに記載の樹脂組成物の硬化物。
［１０］上記［１］～［８］のいずれかに記載の樹脂組成物を含有してなるプリプレグ。
［１１］上記［１０］に記載のプリプレグと金属箔とを含有してなる積層板。
［１２］上記［１］～［８］のいずれかに記載の樹脂組成物を含有してなる樹脂フィルム。
［１３］上記［１０］に記載のプリプレグ、上記［１１］に記載の積層板及び上記［１２］に記載の樹脂フィルムからなる群から選択される少なくとも１種類を含有してなる多層プリント配線板。
［１４］上記［１０］に記載のプリプレグ、上記［１１］に記載の積層板及び上記［１２］に記載の樹脂フィルムからなる群から選択される少なくとも１種類を含有してなるミリ波レーダー用多層プリント配線板。
［１５］不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体。
［１６］前記不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－１）で表される構造を有する、上記［１５］に記載のポリフェニレンエーテル誘導体。

（式（ａ－１）中、Ｒ^ａ１は炭素数２～１０の不飽和脂肪族炭化水素基である。ｍ１は１又は２であり、ｎ１は０又は１である。＊は、他の構造への結合位置を示す。）
［１７］前記不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－２）で表される構造を有する、上記［１５］又は［１６］に記載のポリフェニレンエーテル誘導体。

（式（ａ－２）中、Ｒ^ａ２及びＲ^ａ３は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）
［１８］前記不飽和脂肪族炭化水素基の合計数が２つ以上である、上記［１５］～［１７］のいずれかに記載のポリフェニレンエーテル誘導体。
［１９］前記不飽和脂肪族炭化水素基の合計数が４つ以上である、上記［１５］～［１８］のいずれかに記載のポリフェニレンエーテル誘導体。
［２０］前記不飽和脂肪族炭化水素基が、ビニル基、イソプロペニル基、アリル基、１－メチルアリル基又は３－ブテニル基である、上記［１５］～［１９］のいずれかに記載のポリフェニレンエーテル誘導体。[1] Selected from the group consisting of (A) a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group, and (B) a maleimide compound having at least two N-substituted maleimide groups and derivatives thereof at least one
A resin composition comprising
[2] The resin composition according to [1] above, wherein the organic group substituted by the unsaturated aliphatic hydrocarbon group of the component (A) has a structure represented by the following general formula (a-1).

(In formula (a-1), R ^a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms; m1 is 1 or 2; n1 is 0 or 1; * is another structure; indicates the binding position to
[3] The above [1] or [2], wherein the organic group substituted by the unsaturated aliphatic hydrocarbon group of the component (A) has a structure represented by the following general formula (a-2): Resin composition.

(In formula (a-2), R ^a2 and R ^a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * indicates the bonding position to another structure.)
[4] The resin composition according to any one of [1] to [3] above, wherein the total number of unsaturated aliphatic hydrocarbon groups contained in component (A) is two or more.
[5] The resin composition according to any one of [1] to [4] above, wherein the total number of unsaturated aliphatic hydrocarbon groups in component (A) is 4 or more.
[6] The above [1] to [5], wherein in the component (A), the unsaturated aliphatic hydrocarbon group is a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group, or a 3-butenyl group. The resin composition according to any one of.
[7] The above [1] to [6], wherein the component (B) has a structural unit derived from the maleimide compound (b1) having at least two N-substituted maleimide groups and a structural unit derived from the diamine compound (b2). ] The resin composition according to any one of the above.
[8] The resin composition according to any one of [1] to [7] above, wherein the component (B) contains a polyaminobismaleimide compound represented by the following general formula (B-1).

(In formula (B-1), X ^B1 and X ^B2 are each independently an organic group.)
[9] A cured product of the resin composition according to any one of [1] to [8], which has a dielectric constant at 10 GHz of 2.90 or less and a dielectric loss tangent at 10 GHz of 0.0055 or less.
[10] A prepreg containing the resin composition according to any one of [1] to [8] above.
[11] A laminate containing the prepreg described in [10] above and a metal foil.
[12] A resin film comprising the resin composition according to any one of [1] to [8] above.
[13] A multilayer printed wiring board containing at least one selected from the group consisting of the prepreg described in [10] above, the laminate described in [11] above, and the resin film described in [12] above. .
[14] For millimeter wave radar, containing at least one selected from the group consisting of the prepreg described in [10] above, the laminated plate described in [11] above, and the resin film described in [12] above. Multilayer printed wiring board.
[15] A polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group.
[16] The polyphenylene ether derivative according to [15] above, wherein the organic group substituted with the unsaturated aliphatic hydrocarbon group has a structure represented by the following general formula (a-1).

(In formula (a-1), R ^a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms; m1 is 1 or 2; n1 is 0 or 1; * is another structure; indicates the binding position to
[17] The polyphenylene ether derivative according to [15] or [16] above, wherein the organic group substituted with the unsaturated aliphatic hydrocarbon group has a structure represented by the following general formula (a-2).

(In formula (a-2), R ^a2 and R ^a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * indicates the bonding position to another structure.)
[18] The polyphenylene ether derivative according to any one of [15] to [17] above, wherein the total number of the unsaturated aliphatic hydrocarbon groups is two or more.
[19] The polyphenylene ether derivative according to any one of [15] to [18] above, wherein the total number of unsaturated aliphatic hydrocarbon groups is 4 or more.
[20] The polyphenylene according to any one of [15] to [19] above, wherein the unsaturated aliphatic hydrocarbon group is a vinyl group, isopropenyl group, allyl group, 1-methylallyl group or 3-butenyl group. ether derivative.

According to the present invention, a resin composition that can exhibit excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in a high frequency band of 10 GHz or higher, a cured product of the resin composition, a prepreg, a resin film, and a multilayer print. It is possible to provide a wiring board, a multilayer printed wiring board for millimeter wave radar, and a polyphenylene ether derivative that makes it possible to obtain such a resin composition.

In the numerical ranges described herein, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples. Also, the lower and upper limits of a numerical range can be arbitrarily combined with the lower and upper limits of other numerical ranges, respectively.
In addition, each component and material exemplified in this specification may be used alone or in combination of two or more unless otherwise specified. As used herein, the content of each component in the composition refers to the total amount of the multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means
Embodiments in which the items described in this specification are combined arbitrarily are also included in the present invention.

[Resin composition]
One aspect of the present invention is
(A) a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group [hereinafter sometimes simply referred to as polyphenylene ether derivative (A) or component (A)], and (B) N-substituted at least one selected from the group consisting of maleimide compounds having at least two maleimide groups and derivatives thereof [hereinafter sometimes simply referred to as maleimide compound (B) or component (B)];
It is a resin composition containing
Each component will be described in detail below.

<Polyphenylene ether derivative (A)>
The polyphenylene ether derivative (A) has an organic group substituted with an unsaturated aliphatic hydrocarbon group, preferably at least one end thereof has an organic group substituted with an unsaturated aliphatic hydrocarbon group. The present invention also provides the polyphenylene ether derivative (A) itself. By using such a polyphenylene ether derivative (A), an ene reaction with the carbon-carbon double bond site of the N-substituted maleimide group of the component (B), and in some cases, a Diels-Alder reaction can occur. Therefore, it is presumed that this is due to the improvement of dielectric properties in a high frequency band of 10 GHz or higher.
The organic group substituted with an unsaturated aliphatic hydrocarbon group may be present at one end of the component (A), may be present at both ends, or may be present at the central skeleton. . Component (A) includes a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at one end, a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at both ends, and It may be a mixture of two or more selected from the group consisting of polyphenylene ether derivatives having an organic group substituted with an unsaturated aliphatic hydrocarbon group in the central skeleton. Component (A) preferably contains a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at one end, and an organic group substituted with an unsaturated aliphatic hydrocarbon group at one end. It is more preferable that the polyphenylene ether derivative itself has.
When the component (A) contains a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at one end, the unsaturated aliphatic hydrocarbon group substituted at one end of the component (A) The content of the polyphenylene ether derivative having an organic group may be 30% by mass or more, 45% by mass or more, 55% by mass or more, or 70% by mass or more. It may be 90% by mass or more, or may be substantially 100% by mass.

Examples of the "unsaturated aliphatic hydrocarbon group" in the "organic group substituted with an unsaturated aliphatic hydrocarbon group" of component (A) include vinyl group, isopropenyl group, allyl group, and 1-methylallyl group. , 3-butenyl group and the like. Among these, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, unsaturated aliphatic hydrocarbon groups having 2 to 10 carbon atoms are preferable, and unsaturated aliphatic hydrocarbon groups having 2 to 5 carbon atoms are more preferable. , allyl groups are more preferred. In the present invention, a portion of the unsaturated aliphatic hydrocarbon group such as a maleimide group and a (meth)acryloyl group is present, but the group as a whole has an unsaturated aliphatic hydrocarbon group. A group that cannot be said to be a hydrogen group is not included in the "unsaturated aliphatic hydrocarbon group" in the above "organic group substituted with an unsaturated aliphatic hydrocarbon group".
The total number of unsaturated aliphatic hydrocarbon groups contained in the component (A) is preferably 2 or more, more preferably 4 or more, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. is not particularly limited, and may be eight or less, or may be six or less. Furthermore, the total number of unsaturated aliphatic hydrocarbon groups at one end of the component (A) is preferably 2 or more, more preferably 4, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. There are no particular restrictions on the upper limit value, and the number may be eight or less, or may be six or less.
The total number of unsaturated aliphatic hydrocarbon groups possessed by component (A) and the total number of unsaturated aliphatic hydrocarbon groups possessed at one end of component (A) are both most preferably four. .

（式（ａ－１）中、Ｒ^ａ１は炭素数２～１０の不飽和脂肪族炭化水素基である。ｍ１は１又は２であり、ｎ１は０又は１である。＊は、他の構造への結合位置を示す。）The "organic group substituted with an unsaturated aliphatic hydrocarbon group" preferably has a structure represented by the following general formula (a-1) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. .

(In formula (a-1), R ^a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms; m1 is 1 or 2; n1 is 0 or 1; * is another structure; indicates the binding position to

In the above general formula (a-1), the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R ^a1 includes, for example, a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group, and a 3-butenyl group. and the like. Among these, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is preferred, and an allyl group is more preferred.
m1 may be 1 or 2, but is preferably 1. n1 may be 0 or 1.
When the "organic group substituted with an unsaturated aliphatic hydrocarbon group" has a structure represented by the general formula (a-1), at least the "organic group substituted with an unsaturated aliphatic hydrocarbon group" It is sufficient if the structure represented by the above general formula (a-1) is contained in part.

（式（ａ－２）中、Ｒ^ａ２及びＲ^ａ３は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）Further, the "organic group substituted with an unsaturated aliphatic hydrocarbon group" is represented by the following general formula (a-2) from the viewpoint of dielectric properties and compatibility in a high frequency band of 10 GHz or higher Structured embodiments are also preferred.

(In formula (a-2), R ^a2 and R ^a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * indicates the bonding position to another structure.)

In the above general formula (a-2), the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R ^a2 and R ^a3 is the same as R ^a1 in the above general formula (a-1). , preferably the same.
When the "organic group substituted with an unsaturated aliphatic hydrocarbon group" has a structure represented by the general formula (a-2), at least the "organic group substituted with an unsaturated aliphatic hydrocarbon group" It is sufficient if the structure represented by the above general formula (a-2) is contained in part.

The "organic group substituted with an unsaturated aliphatic hydrocarbon group" is represented by any one of the following general formulas (a-3) to (a-5) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. The structure represented by the following general formula (a-5) is more preferable from the viewpoint of dielectric properties and compatibility in a high frequency band of 10 GHz or higher.

（式（ａ－３）中、Ｒ^ａ４は炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）

(In formula (a-3), R ^a4 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * indicates a bonding position to another structure.)

（式（ａ－４）中、Ｒ^ａ５及びＲ^ａ６は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。Ｘ^ａ１は、炭素数１～６の脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）

(In formula (a-4), R ^a5 and R ^a6 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms; X ^a1 is an aliphatic hydrocarbon group having 1 to 6 carbon atoms; group. * indicates the bonding position to other structures.)

（式（ａ－５）中、Ｒ^ａ７～Ｒ^ａ１０は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。Ｘ^ａ２は有機基である。＊は、他の構造への結合位置を示す。）

(In formula (a-5), R ^a7 to R ^a10 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. X ^a2 is an organic group. * is another structure indicates the binding position to

As the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R ^a4 to R ^a10 in general formulas (a-3) to (a-5), R ^a1 in general formula (a-1) The same ones as in the case of are mentioned, and preferable ones are also the same.
The aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by X ^a1 in the general formula (a-4) includes, for example, methylene group, ethylene group, alkylene group having 1 to 6 carbon atoms such as trimethylene group; An alkylidene group having 2 to 6 carbon atoms such as a ridene group can be mentioned. Among these, a methylene group and an isopropylidene group are preferred, and an isopropylidene group is more preferred.
The organic group represented by X ^a2 in the general formula (a-5) includes an aliphatic hydrocarbon group which may partially contain a heteroatom, an aliphatic hydrocarbon group which may partially contain a heteroatom, A cyclic hydrocarbon group, an aromatic hydrocarbon group which may partially contain a heteroatom, a group consisting of any combination thereof, and the like can be mentioned. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and the like. The organic group represented by X ^a2 is preferably a group containing no heteroatom from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, and an aliphatic hydrocarbon group containing no heteroatom, A heteroatom-free alicyclic hydrocarbon group is more preferred, and a group consisting of a combination of a heteroatom-free aliphatic hydrocarbon group and a heteroatom-free alicyclic hydrocarbon group. It is even more preferable to have

（上記式中、Ｘ^ａ２は前記一般式（ａ－５）中のＸ^ａ２と同じである。＊は、他の構造への結合位置を示す。）A more preferred embodiment of the structure represented by the general formula (a-3), (a-4) or (a-5) is the following formula ( a-3′), (a-4′) or (a-5′). Among these, from the viewpoint of dielectric properties and compatibility in a high frequency band of 10 GHz or higher, a structure represented by the following formula (a-4') or (a-5') is more preferable, and the following formula (a -5') is more preferred.

(In the above formula, X ^a2 is the same as X ^a2 in the general formula (a-5). * indicates a bonding position to another structure.)

（式中、Ｒ^ａ１１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。ｐ１は０～４の整数である。）Since component (A) is a polyphenylene ether derivative, it goes without saying that it also has a structural unit represented by the following general formula (I).

(In the formula, each R ^a11 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p1 is an integer of 0 to 4.)

Each R ^a11 in the general formula (I) is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group. Further, the halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among the above, R ^a11 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p1 is an integer of 0 to 4, may be an integer of 0 to 2, or may be 2; When p1 is 1 or 2, R ^a11 may be substituted at the ortho position (based on the substitution position of the oxygen atom) on the benzene ring. Further, when p1 is 2 or more, the plurality of R ^a11 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').

（上記式中、Ｘ^ａ２は前記一般式（ａ－５）中のＸ^ａ２と同じである。ｑ１～ｑ３は、各々独立に、１～２００の整数である。）The polyphenylene ether derivative (A) may contain a polyphenylene ether derivative represented by any one of the following general formulas (Ai) to (A-iii), especially the following general formula (A-ii) or It preferably contains a polyphenylene ether derivative represented by (A-iii), and more preferably contains a polyphenylene ether derivative represented by the following general formula (A-iii).

(In the above formula, X ^a2 is the same as X ^a2 in the general formula (a-5). q1 to q3 are each independently an integer of 1 to 200.)

In the general formulas (Ai) to (A-iii), q1 to q3 are each independently an integer of 1 to 200, and from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher and the phase of the resin composition From the viewpoint of capacity, it is preferably an integer of 1-150, more preferably an integer of 1-120, even more preferably an integer of 1-100. The lower limit of the numerical range of q1 to q3 may be 10 or more, 20 or more, or 25 or more.
Any of the general formulas (Ai) to (A-iii) may be a mixture of polyphenylene ether derivatives with different values of q1 to q3, and usually tends to be a mixture.

(Number average molecular weight (Mn))
The number average molecular weight of the polyphenylene ether derivative (A) is preferably 1,000 to 25,000. If the polyphenylene ether derivative (A) has a number average molecular weight of 1,000 or more, the dielectric properties in a high frequency band of 10 GHz or higher tend to be even better. Further, when the number average molecular weight of the polyphenylene ether derivative (A) is 25,000 or less, the compatibility of the resin composition is improved, and separation tends to be difficult even if left standing for a long period of time. From the same point of view, the number average molecular weight of the polyphenylene ether derivative (A) is more preferably 2,000 to 20,000, still more preferably 2,500 to 15,000, still more preferably 3,000 to 10,000. , particularly preferably 3,000 to 7,500, most preferably 3,000 to 6,000.
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, measurement of the number average molecular weight described in the Examples. It is the value obtained by the method.

(Method for producing polyphenylene ether derivative (A))
One aspect of the method for producing the polyphenylene ether derivative (A) will be described below, but the method is not particularly limited to the description below.
For example, a phenol compound having a structure represented by any of the general formulas (a-1) to (a-5) [hereinafter referred to as unsaturated aliphatic hydrocarbon group-containing phenol compound (1)], A polyphenylene ether derivative with an average molecular weight of 10,000 to 30,000 [hereinafter sometimes referred to as a raw material polyphenylene ether] is subjected to a redistribution reaction in an organic solvent while reducing the molecular weight of the polyphenylene ether. (A) can be produced.

In the redistribution reaction, for example, the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is mixed with the raw material polyphenylene ether that has already been polymerized, and if necessary, the reaction catalyst described later is added. By doing so, the oxy radical of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) attacks the carbon atom to which the oxygen atom in the raw material polyphenylene ether is bonded, and the OC bond is cut there, resulting in a low molecular weight. It is a reaction that converts At that time, the attacked oxy radical of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is bonded to the carbon atom where the bond has been broken and incorporated into the structure of the polyphenylene ether. A known method can be used and applied for the redistribution reaction.

The molecular weight of the polyphenylene ether derivative (A) can be controlled by the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used, and the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used is The higher the amount, the lower the molecular weight of the polyphenylene ether derivative (A). That is, the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used may be appropriately adjusted so that the finally produced polyphenylene ether derivative (A) has a suitable number average molecular weight.
The amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used is not particularly limited, but for example, the raw material polyphenylene ether to be reacted with the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) When the number average molecular weight is 10,000 to 30,000, the hydroxyl group of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is used in an amount of 1 to 10 mol per 1 mol of the raw material polyphenylene ether. , a polyphenylene ether derivative (A) having a number average molecular weight within the above preferred range is obtained.

The organic solvent used in the production process of the polyphenylene ether derivative (A) is not particularly limited, but examples include alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate and ethyl acetate; N,N-dimethylformamide and N,N-dimethyl nitrogen-containing compounds such as acetamide and N-methyl-2-pyrrolidone; These may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of solubility, toluene, xylene, and mesitylene may be selected, and toluene is preferably selected.

Moreover, in the production process of the polyphenylene ether derivative (A), as described above, a reaction catalyst can be used as necessary. As this reaction catalyst, for example, from the viewpoint of obtaining a polyphenylene ether derivative (A) having a stable number average molecular weight with good reproducibility, organic peroxides such as t-butylperoxyisopropyl monocarbonate and carboxylic acids such as manganese naphthenate can be used. It is preferable to use together with a metal salt. Also, the amount of the reaction catalyst used is not particularly limited. From the viewpoint of reaction rate and gelation suppression when producing the polyphenylene ether derivative (A), for example, with respect to 100 parts by mass of the raw material polyphenylene ether to be reacted with the unsaturated aliphatic hydrocarbon group-containing phenol compound (1), organic Peroxide may be 0.5 to 5 parts by mass, and carboxylic acid metal salt may be 0.05 to 0.5 parts by mass.

A predetermined amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1), the raw material polyphenylene ether having a number average molecular weight of 10,000 to 30,000, an organic solvent and, if necessary, a reaction catalyst are charged into a reactor, heated, kept warm, A polyphenylene ether derivative (A) is obtained by reacting with stirring. For the reaction temperature and reaction time in this step, the reaction conditions for known redistribution reactions can be applied, and they may be adjusted as appropriate.
From the viewpoint of workability and gelation suppression, and from the viewpoint of obtaining the component (A) having the desired number average molecular weight, the reaction may be carried out at, for example, a reaction temperature of 70 to 110° C. and a reaction time of 1 to 8 hours.

The solid content concentration (hereinafter referred to as reaction concentration) during the reaction in the production process of the polyphenylene ether derivative (A) is not particularly limited, but may be, for example, 10 to 60% by mass. It may be up to 55% by mass. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow, which tends to be more advantageous in terms of production cost. Further, when the reaction temperature is 60% by mass or less, better solubility tends to be obtained, and furthermore, solution viscosity is low, stirring efficiency is good, and gelation tends to be difficult.

The solution of the polyphenylene ether derivative (A) produced as described above may be concentrated as described later to remove part of the organic solvent, or may be diluted by adding an organic solvent. may

The resin composition of the present invention tends to have better dielectric properties in a high frequency band of 10 GHz or higher than a resin composition containing the raw material polyphenylene ether instead of the component (A).

<Maleimide compound (B)>
The maleimide compound (B) is at least one selected from the group consisting of maleimide compounds having at least two N-substituted maleimide groups and derivatives thereof. The maleimide compound (B) does not include the polyphenylene ether derivative (A). Furthermore, it is preferable that the maleimide compound (B) does not contain the structural unit represented by the general formula (I), in other words, does not contain a polyphenylene ether skeleton.
Examples of the "derivatives thereof" include addition reaction products of the maleimide compound having at least two N-substituted maleimide groups and an amine compound such as the diamine compound (b2) described later.
The maleimide compound (B) has at least two N-substituted maleimide groups from the viewpoint of solubility in organic solvents, compatibility with conductors, adhesion to conductors, and dielectric properties in high frequency bands of 10 GHz or higher. Derivatives of the maleimide compound are preferred, and the maleimide compound (b1) having at least two N-substituted maleimide groups [hereinafter sometimes simply referred to as maleimide compound (b1) or component (b1). ] and a structural unit derived from the diamine compound (b2) (hereinafter sometimes referred to as a polyaminobismaleimide compound (B1)).
The structural unit derived from the component (b1) and the structural unit derived from the component (b2) may be of one type or a combination of two or more types.

Specific examples of component (b1) are not particularly limited as long as they are maleimide compounds having two or more N-substituted maleimide groups. maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m - Aromatic maleimide compounds such as phenylene bismaleimide and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane; 1,6-bismaleimide-(2,2,4-trimethyl)hexane, pyrrolonic acid binders and aliphatic maleimide compounds such as long-chain alkyl bismaleimide. Among these, aromatic maleimide compounds are preferred from the viewpoint of adhesion to conductors and mechanical properties, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5, More preferred is 5'-diethyl-4,4'-diphenylmethanebismaleimide.

（式中、Ｘ^Ｂ１は有機基を示し、＊は他の構造への結合位置を示す。）The structural unit derived from component (b1) includes at least one selected from the group consisting of a group represented by the following general formula (B-1) and a group represented by the following general formula (B-2). be done.

(In the formula, X ^B1 represents an organic group and * represents a bonding position to another structure.)

X ^B1 in the general formulas (B-1) and (B-2) is an organic group and corresponds to the residue of component (b1). The term “residue of component (b1)” refers to the structure of the portion of component (b1) excluding the functional group used for bonding, that is, the maleimide group.
Examples of the organic group represented by X ^B1 include groups represented by the following general formulas (II), (III), (IV) and (V).

（式中、Ｒ^ｂ１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^ｂ１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、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。
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^ｂ１同士は同一であっても異なっていてもよい。

(In the formula, each R ^b1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer of 0 to 4.)
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^b1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
p is an integer of 0 to 4, may be an integer of 0 to 2, may be 0 or 1, or may be 0 from the viewpoint of availability. When p is an integer of 2 or more, a plurality of R ^b1 may be the same or different.

（式中、Ｒ^ｂ２及びＲ^ｂ３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。Ｗ^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、カルボニルオキシ基、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^ｂ２及びＲ^ｂ３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^ｂ１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。
Ｗ^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（低誘電率、低誘電正接）、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。
Ｗ^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（低誘電率、低誘電正接）、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。
Ｗ^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^ｂ２同士又はＲ^ｂ３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、Ｗ^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。

(wherein R ^b2 and R ^b3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; W ² is an alkylene group having 1 to 5 carbon atoms; an alkylidene group having 2 to 5 carbon atoms; group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, single bond, or a group represented by the following general formula (III-1), q and r are each independently an integer of 0 to 4 is.)
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^b2 and R ^b3 are the same as in the case of R ^b1 . 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 W ² include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, and the like. are mentioned. The alkylene group is an alkylene group having 1 to 3 carbon atoms from the viewpoint of high frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion to conductors, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy. or a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by W ² include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like. Among these, from the viewpoint of high frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion to conductors, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy, an isopropylidene group may be used.
W ² may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options.
q and r are each independently an integer of 0 to 4, and both may be an integer of 0 to 2, or may be 0 or 2, from the viewpoint of availability. When q or r is an integer of 2 or more, a plurality of R ^b2 or R ^b3 may be the same or different.
The group represented by general formula (III-1) represented by W ² is as follows.

（式中、Ｒ^ｂ４及びＲ^ｂ５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。Ｗ^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、カルボニルオキシ基、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^ｂ４及びＲ^ｂ５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^ｂ１の場合と同様に説明される。
Ｗ^３が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基としては、Ｗ^２が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基と同じものが挙げられる。
Ｗ^３としては、上記選択肢の中から、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^ｂ４同士又はＲ^ｂ５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 ^b4 and R ^b5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; W ³ is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond, and s and t are each independently an integer of 0 to 4.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^b4 and R ^b5 are explained in the same manner as in the case of R ^b1 .
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by W ³ include the same alkylene group having 1 to 5 carbon atoms and alkylidene group having 2 to 5 carbon atoms represented by W ² . be done.
As ^W3 , an alkylidene group having 2 to 5 carbon atoms may be selected from the above options.
s and t are integers of 0 to 4, and from the viewpoint of availability, both may be integers of 0 to 2, may be 0 or 1, or may be 0. When s or t is an integer of 2 or more, a plurality of ^Rb4 's or ^Rb5 's may 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。

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

（式中、Ｒ^ｂ６及びＲ^ｂ７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^ｂ６及びＲ^ｂ７が表す炭素数１～５の脂肪族炭化水素基としては、Ｒ^ｂ１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 ^b6 and R ^b7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer of 1 to 8.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^b6 and R ^b7 is explained in the same manner as in the case of R ^b1 .
u is an integer of 1 to 8, may be an integer of 1 to 3, or may be 1;

（波線は、マレイミド基中の窒素原子との結合位置を示す。）X ^B1 in the general formulas (B-1) and (B-2) includes adhesion to conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, flame retardancy, and a high frequency band of 10 GHz or higher. From the viewpoint of dielectric properties in , it is preferably a group represented by any one of the following formulas (X ^B1 -1) to (X ^B1 -3), and a group represented by the following formula (X ^B1 -3) It is more preferable to have In addition, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, as X ^B1 , both a group represented by the following formula (X ^B1 -1) and a group represented by the following formula (X ^B1 -3) or X ^B1 may have both a group represented by the following formula (X ^B1 -2) and a group represented by the following formula (X ^B1 -3) .

(The wavy line indicates the bonding position with the nitrogen atom in the maleimide group.)

The total content of structural units derived from the component (b1) in the maleimide compound (B) is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, further preferably 60 to 90% by mass, further preferably 75 to 90% by mass. % by weight is particularly preferred. When the content of the structural unit derived from the component (b1) is within the above range, dielectric properties in a high frequency band of 10 GHz or higher tend to be better, and good film handling property can be obtained.

The component (b2) is not particularly limited as long as it is a compound having two amino groups.
Component (b2) includes, for example, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4 '-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 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′-diaminodiphenylmethane, 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-aminophenoxy)phenyl]sulfone, 9,9- bis(4-aminophenyl)fluorene and the like.

Among these, as the component (b2), 4,4'-diaminodiphenylmethane, 4,4'-diamino -3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4′-[1, 3-phenylenebis(1-methylethylidene)]bisaniline and 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred. In addition, the component (b2) is 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption in a high frequency band of 10 GHz or higher. preferable. Further, the component (b2) is preferably 2,2-bis[4-(4-aminophenoxy)phenyl]propane from the viewpoint of excellent mechanical properties such as high adhesion to conductors, elongation and breaking strength. Furthermore, in addition to the above-mentioned solubility in organic solvents, reactivity during synthesis, heat resistance, and high adhesion to conductors, it is said to have excellent dielectric properties and low hygroscopicity in high frequency bands of 10 GHz and above. From the viewpoint, the component (b2) is 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline is preferred.

The structural unit derived from the component (b2) is, for example, at least one type selected from the group consisting of a group represented by the following general formula (B-3) and a group represented by the following general formula (B-4). is mentioned.

（式中、Ｘ^Ｂ２は有機基を示し、＊は他の構造への結合位置を示す。）

(In the formula, X ^B2 represents an organic group, and * represents a bonding position to another structure.)

X ^B2 in the general formulas (B-3) and (B-4) is an organic group and corresponds to the residue of component (b2). The residue of the component (b2) refers to the structure of the portion of the component (b2) excluding the functional group used for bonding, that is, the amino group.

（式中、Ｒ^ｂ１１及びＲ^ｂ１２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。Ｗ^４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、カルボニルオキシ基、ケト基、フルオレニレン基、単結合、又は下記一般式（VI-1）もしくは（VI-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。）X ^B2 in the general formulas (B-3) and (B-4) is preferably a group represented by the following general formula (VI).

(wherein R ^b11 and R ^b12 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom; W ⁴ is a 5 alkylene group, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or the following general formula (VI-1) or (VI-2 ), q′ and r′ are each independently an integer of 0 to 4.)

（式中、Ｒ^ｂ１３及びＲ^ｂ１４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。Ｗ^５は炭素数１～５のアルキレン基、イソプロピリデン基、ｍ－フェニレンジイソプロピリデン基、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、カルボニルオキシ基、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。）

(wherein R ^b13 and R ^b14 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; W ⁵ is an alkylene group having 1 to 5 carbon atoms, isopropylidene group, m-phenyl diisopropylidene group, p-phenylenediisopropylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group or single bond, s' and t' each independently being an integer of 0 to 4; .)

（式中、Ｒ^ｂ１５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。Ｗ^６及びＷ^７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、カルボニルオキシ基、ケト基又は単結合である。ｗは０～４の整数である。）

(Wherein, R ^b15 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; W ⁶ and W ⁷ are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond, and w is an integer of 0 to 4.)

Aliphatic hydrocarbon groups having 1 to 5 carbon atoms or halogen atoms represented by R ^b11 , R ^b12 , R ^b13 , R ^b14 and R ^b15 in general formula (VI), (VI-1) or (VI-2) above The same as ^Rb1 in the general formula (II) 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.
As an alkylene group having 1 to 5 carbon atoms represented by W ⁴ and W ⁵ in the general formula (VII), (VII-1) or (VII-2) and an alkylidene group having 2 to 5 carbon atoms represented by W ⁴ is explained in the same manner as for ^W2 in the general formula (III). The alkylene group having 1 to 5 carbon atoms represented by W ⁶ and W ⁷ in general formula (VII-2) is explained in the same manner as W ² in general formula (III).
q' and r' are integers of 0 to 4, and both may be integers of 0 to 2, or may be 0 or 2 from the viewpoint of availability. s' and t' are integers of 0 to 4, and from the viewpoint of availability, both may be integers of 0 to 2, may be 0 or 1, or 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 total content of structural units derived from the component (b2) in the maleimide compound (B) is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, even more preferably 10 to 40% by mass, further preferably 10 to 25% by mass. % by weight is particularly preferred. When the content of the structural unit derived from the component (b2) is within the above range, excellent dielectric properties in a high frequency band of 10 GHz or higher, and a tendency to obtain better heat resistance, flame retardancy and glass transition temperature. It is in.

The content ratio of the structural unit derived from the component (b1) to the structural unit derived from the component (b2) in the maleimide compound (B) is the ratio of the _-NH2 group derived from the component (b2) in the maleimide compound (B). The equivalent ratio (Ta2/Ta1) between the total equivalent weight (Ta2) of the group (including _—NH2 ) and the total equivalent weight (Ta1) of the maleimide group-derived group (including the maleimide group) derived from the component (b1) is , preferably 0.05 to 10, more preferably 1.0 to 5. When the equivalent ratio (Ta2/Ta1) is within the above range, there is a tendency to obtain excellent dielectric properties in a high frequency band of 10 GHz or higher, as well as better heat resistance, flame retardancy and glass transition temperature.

The maleimide compound (B) is selected from the following general formula (B- It is preferable that the polyaminobismaleimide compound represented by 5) is included.

（式中、Ｘ^Ｂ１及びＸ^Ｂ２は、上記で説明したとおりである。）

(Wherein, X ^B1 and X ^B2 are as described above.)

(Method for producing polyaminobismaleimide compound (B1))
The polyaminobismaleimide compound (B1) having a structural unit derived from the maleimide compound (b1) and a structural unit derived from the diamine compound (b2) can be prepared, for example, by combining the components (b1) and (b2) in an organic solvent. It can be produced by reacting.
When the (b1) component and the (b2) component are reacted to produce the polyaminobismaleimide compound (B1), a reaction catalyst can be used as necessary. Examples of the reaction catalyst include, but are not limited to, acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; triphenylphosphine and the like. and phosphorus-based catalysts. These may be used individually by 1 type, and may use 2 or more types together. The amount of the reaction catalyst to be added is not particularly limited, but may be, for example, 0.01 to 5 parts by mass per 100 parts by mass of the total amount of components (b1) and (b2).

The above polyaminobismaleimide compound is obtained by charging predetermined amounts of components (b1), (b2) and, if necessary, other components into a synthesis vessel, and subjecting components (b1) and (b2) to a Michael addition reaction. The reaction conditions in this step are not particularly limited, but, for example, from the viewpoint of workability such as reaction rate and suppression of gelation, the reaction temperature is preferably 50 to 160° C., and the reaction time is preferably 1 to 10 hours. .
Further, in this step, an organic solvent can be added or concentrated to adjust the solid content concentration and solution viscosity of the reaction raw materials. The solid content concentration of the reaction raw material is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass. When the solid content concentration of the reaction raw material is 10% by mass or more, the reaction rate does not become too slow, which tends to be advantageous in terms of production cost. Further, when the solid content concentration of the reaction raw material is 90% by mass or less, better solubility is obtained, stirring efficiency is improved, and gelation tends to be difficult.

The number average molecular weight of the polyaminobismaleimide compound (B1) thus obtained is not particularly limited, but is preferably from 400 to 10,000, more preferably from 500 to 5,000, still more preferably from 500 to 2,000. , 300 are particularly preferred. The number average molecular weight of the polyaminobismaleimide compound (B1) can be determined by the method described in Examples.

(Contents of (A) component and (B) component, and their content ratios)
In the resin composition of the present invention, the content of component (A) is not particularly limited, but from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, It is preferably 1 part by mass or more, more preferably 1 to 20 parts by mass, even more preferably 3 to 10 parts by mass, and particularly preferably 3 to 7 parts by mass. As used herein, the term "resin component" refers to the components (A) and (B), and optionally the components (C) and (G). That is, when the resin composition does not contain the (C) component and the (G) component, the "resin component" refers to the (A) component and the (B) component, and the resin composition contains the (C) component and the (G) component. ) component, the “resin component” includes the components (A) and (B) as well as those components further included.
The content of the component (B) is not particularly limited, but from the viewpoint of dielectric properties and moldability in a high frequency band of 10 GHz or higher, 10 to 10 parts by mass of the total resin components in the resin composition. It is preferably 90 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 30 to 70 parts by mass, and particularly preferably 35 to 60 parts by mass.
The content ratio [(A)/(B)] of the component (A) and the component (B) is not particularly limited, but the mass ratio may be 1/99 to 80/20, or 3/97. ~75/25, 5/95 to 70/30, 5/95 to 50/50, 5/95 to 20/80, 5 /95 to 15/85. If the content of component (A) with respect to the total amount of component (A) and component (B) is 1% by mass or more, excellent dielectric properties tend to be obtained in a high frequency band of 10 GHz or higher. Moreover, if it is 80% by mass or less, the heat resistance, moldability and workability tend to be excellent.

<Other ingredients>
The resin composition of one embodiment of the present invention may further contain other components. Other components include, for example, a styrene-based thermoplastic elastomer (C) [hereinafter sometimes referred to as component (C). ], an inorganic filler (D) [hereinafter sometimes referred to as component (D). ], curing accelerator (E) [hereinafter sometimes referred to as component (E). ], Flame Retardant (F) [hereinafter sometimes referred to as component (F). ] and at least one selected from the cross-linking agent (G). By containing these, it is possible to further improve various properties of the laminate.
These components are described in detail below.

（上記式中、Ｒ^ｃ１は水素原子又は炭素数１～５のアルキル基であり、Ｒ^ｃ２は、炭素数１～５のアルキル基である。ｋは、０～５の整数である。）
Ｒ^ｃ１及びＲ^ｃ２が表す炭素数１～５のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基等が挙げられ、炭素数１～３のアルキル基であってもよく、メチル基であってもよい。
Ｒ^ｃ１は、水素原子であってもよい。
ｋは、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。(Styrene-based thermoplastic elastomer (C))
By including the styrene-based thermoplastic elastomer (C) in the resin composition of the present invention, dielectric properties, moldability, adhesion to conductors, solder heat resistance, glass transition temperature, heat The coefficient of expansion and flame retardancy are improved, and the balance between these tends to be improved.
The styrene-based thermoplastic elastomer (C) is not particularly limited as long as it is a thermoplastic elastomer having ^a structural unit derived from a styrene-based compound represented by the following general formula (see below). =hydrogen atom, k=0).

(In the above formula, R ^c1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ^c2 is an alkyl group having 1 to 5 carbon atoms, and k is an integer of 0 to 5.)
The alkyl group having 1 to 5 carbon atoms represented by R ^c1 and R ^c2 includes, for example, a methyl group, an ethyl group, an n-propyl group and the like, and may be an alkyl group having 1 to 3 carbon atoms. may be a base.
R ^c1 may be a hydrogen atom.
k may be an integer from 0 to 2, may be 0 or 1, or may be 0;

Structural units other than the styrene-based compound-derived structural units possessed by the styrene-based thermoplastic elastomer (C) include butadiene-derived structural units, isoprene-derived structural units, maleic acid-derived structural units, and maleic anhydride-derived structural units. etc. The styrene-based thermoplastic elastomer (C) may be used alone or in combination of two or more.
The butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. When hydrogenated, structural units derived from butadiene become structural units in which ethylene units and butylene units are mixed, and structural units derived from isoprene become structural units in which ethylene units and propylene units are mixed.

The styrene-based thermoplastic elastomer (C) is a styrene-butadiene-styrene block copolymer from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, adhesion to conductors, heat resistance, glass transition temperature and coefficient of thermal expansion. At least one selected from the group consisting of hydrogenated coalescing (SEBS, SBBS), hydrogenated styrene-isoprene-styrene block copolymers (SEPS) and styrene-maleic anhydride copolymer (SMA) It is preferably at least one selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymer (SEBS) and hydrogenated styrene-isoprene-styrene block copolymer (SEPS) is more preferable.

As the hydrogenated product of the styrene-butadiene-styrene block copolymer, SEBS having a carbon-carbon double bond hydrogenation rate of usually 90% or more (may be 95% or more), SBBS in which the carbon-carbon double bonds (see left below) at the 1,2-bonded sites in the butadiene block are partially hydrogenated (the hydrogenation rate for the entire carbon-carbon double bonds is approximately 60-85% ). In other words, SBBS may have crosslinkability, and in that case, it may be included in the crosslinker (G) described later, but in the present invention, even if it has crosslinkability, the styrene thermoplastic elastomer is classified as (C) component. The component (C) may be one that does not have crosslinkability, that is, it may be a hydrogenated styrenic thermoplastic elastomer, and its hydrogen conversion rate is preferably 70% or more, more preferably. is 80% or more, more preferably 90% or more, particularly preferably 95% or more, and most preferably 99% or more.

In the SEBS, the content of structural units derived from styrene (hereinafter sometimes abbreviated as styrene content) is determined by dielectric properties, adhesion to conductors, heat resistance, glass transition in high frequency bands of 10 GHz or higher. From the viewpoint of temperature and thermal expansion coefficient, it may be 5 to 80% by mass, 5 to 70% by mass, 10 to 70% by mass, or 10 to 50% by mass. good too. The melt flow rate (MFR) of SEBS is not particularly limited, but may be 0.1 to 20 g / 10 min under the measurement conditions of 230 ° C. and a load of 2.16 kgf (21.2 N), and may be 0.5 to It may be 15 g/10 min.
Commercially available products of SEBS include, for example, Tuftec (registered trademark) H series and M series manufactured by Asahi Kasei Chemicals Corporation, Septon (registered trademark) series manufactured by Kuraray Co., Ltd., and Kraton (registered trademark) manufactured by Clayton Polymer Japan Co., Ltd. G polymer series and the like.

In the SBBS, the styrene content may be 40 to 80% by mass from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, adhesiveness with conductors, heat resistance, glass transition temperature and thermal expansion coefficient. , 50 to 75% by mass, or 55 to 75% by mass. The melt flow rate (MFR) of SBBS is not particularly limited, but may be 0.1 to 10 g / 10 min under the measurement conditions of 190 ° C. and a load of 2.16 kgf (21.2 N). It may be 10 g/10 min, or 1 to 6 g/10 min.
Examples of commercial products of SBBS include Tuftec (registered trademark) P series manufactured by Asahi Kasei Chemicals Corporation.

The hydrogenation rate of the hydrogenated styrene-isoprene-styrene block copolymer (SEPS) may be 90% or more, or 95% or more. In SEPS, the styrene content is 5 to 60% by mass from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, adhesiveness with conductors, heat resistance, glass transition temperature and thermal expansion coefficient. It may be 5 to 50% by mass, or 10 to 40% by mass. The melt flow rate (MFR) of SEPS is not particularly limited, but may be 0.1 to 130 g/10 min, 10 to 100 g/ It may be 10 min, or it may be 50 to 90 g/10 min.
Commercially available products of SEPS include, for example, Septon (registered trademark) series manufactured by Kuraray Co., Ltd., and Kraton G Polymer series manufactured by Kraton Polymer Japan.

In the styrene-maleic anhydride copolymer (SMA), the styrene content is 20 from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, adhesion to conductors, heat resistance, glass transition temperature and coefficient of thermal expansion. It may be up to 90% by mass, 40 to 90% by mass, 50 to 90% by mass, or 55 to 85% by mass.
In the styrene-maleic anhydride copolymer (SMA), structural units derived from maleic anhydride may be esterified.
Commercially available SMA products include SMA (registered trademark) resin manufactured by Clay Valley Technologies USA.
As the styrene-based thermoplastic elastomer (C), commercial products may be used. The above styrene content and melt flow rate (MFR) are the values described in the manufacturer's catalog or website.

When the resin composition of the present invention contains the component (C), the content of the component (C) is determined by the dielectric properties, adhesion to conductors, heat resistance, glass transition temperature and heat resistance in a high frequency band of 10 GHz or higher. From the viewpoint of expansion coefficient, it is preferably 5 to 60 parts by mass, more preferably 10 to 60 parts by mass, more preferably 15 to 60 parts by mass with respect to 100 parts by mass of the total of components (A) to (C). parts, particularly preferably 15 to 50 parts by mass, and most preferably 15 to 40 parts by mass. If the content of component (C) is 5 parts by mass or more with respect to the total of 100 parts by mass of components (A) to (C), dielectric properties and moisture absorption resistance in a high frequency band of 10 GHz or higher are expected to be better. If the content is 60 parts by mass or less, heat resistance, moldability, processability and flame retardancy tend to be better.

(Inorganic filler (D))
By including the inorganic filler (D) in the resin composition of the present invention, there is a tendency that the low coefficient of thermal expansion, high elastic modulus, heat resistance and flame retardancy can be improved.
Component (D) is not particularly limited, but examples include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, hydroxide magnesium, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay, etc.), talc, aluminum borate, silicon carbide, and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance and flame retardancy, silica, alumina, mica, talc, silica, alumina, or silica may be used. Silica includes, for example, precipitated silica that is produced by a wet method and has a high water content, and dry-process silica that is produced by a dry method and contains almost no bound water. Crushed silica, fumed silica, fused silica (fused spherical silica).
Also, the shape and particle size of the inorganic filler (D) are not particularly limited. For example, the particle size may be 0.01-20 μm, or 0.1-10 μm. Here, the particle diameter refers to the average particle diameter, and is the particle diameter at the point corresponding to 50% volume when the cumulative frequency distribution curve of the particle diameter is obtained with the total volume of the particles being 100%. It can be measured with a particle size distribution measuring device or the like using a laser diffraction scattering method.

When the resin composition of the present invention contains component (D), the content of component (D) in the resin composition is not particularly limited. From the viewpoint of the properties, it is preferably 5 to 70 parts by mass, more preferably 15 to 70 parts by mass, still more preferably 20 to 60 parts by mass, and particularly preferably 35 to 60 parts by mass, based on 100 parts by mass of the total resin components. , and most preferably 40 to 55 parts by weight.

Further, when component (D) is used, a coupling agent is optionally used in combination for the purpose of improving the dispersibility of component (D) and the adhesion between component (D) and the organic component in the resin composition. 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. Also, 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 component (D). . Within this range, there is little deterioration in various properties, and there is a tendency that the features of using the component (D) can be effectively exhibited.
When a coupling agent is used, the coupling agent is added to the inorganic filler in advance instead of the so-called integral blending method, in which the coupling agent is added after the component (D) is blended into the resin composition. A method using a wet surface-treated inorganic filler can be adopted. By adopting this method, the features of the component (D) can be exhibited more effectively.

When component (D) is used in the present invention, for the purpose of improving the dispersibility of component (D) in the resin composition, if necessary, component (D) may be used as a slurry in which component (D) is previously dispersed in an organic solvent. can be done. The organic solvent used for slurrying the component (D) is not particularly limited, but for example, the organic solvents exemplified in the process for producing the polyphenylene ether derivative (A) described above can be applied. These may be used individually by 1 type, and may use 2 or more types together. Among these, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be selected from the viewpoint of dispersibility. In addition, the solid content (non-volatile content) concentration of the slurry is not particularly limited. % by mass.

(Curing accelerator (E))
By including the curing accelerator (E) in the resin composition of the present invention, the curability of the resin composition is improved, and the dielectric properties, heat resistance, adhesion to conductors, and elasticity in a high frequency band of 10 GHz or higher It tends to be able to improve the modulus and glass transition temperature.
Component (E) includes, for example, acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine and tributylamine; tertiary amine compounds; quaternary ammonium compounds; phosphorous compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2, 5-bis(t-butylperoxy)-3-hexyne, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, α,α'-bis organic peroxides such as (t-butylperoxy)diisopropylbenzene; carboxylates such as manganese, cobalt and zinc; These may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of heat resistance, glass transition temperature and storage stability, imidazole compounds, organic peroxides and carboxylates may be used. Therefore, an imidazole compound and an organic peroxide or carboxylate may be used in combination. Also, among the organic peroxides, α,α'-bis(t-butylperoxy)diisopropylbenzene may be selected, and among the carboxylates, manganese naphthenate may be selected.

When the resin composition of the present invention contains the component (E), the content of the component (E) is not particularly limited. .01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.1 to 5 parts by mass, or 0.5 to 5 parts by mass . When the component (E) is used within such a range, better heat resistance and storage stability tend to be obtained.

(Flame retardant (F))
By incorporating the flame retardant (F) and, if necessary, the auxiliary flame retardant into the resin composition of the present invention, there is a tendency that the flame retardancy of the resin composition can be improved.
Component (F) includes phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, and the like. From the viewpoint of environmental problems, phosphorus-based flame retardants and metal hydrates may be used. One type of the flame retardant (F) may be used alone, or two or more types may be used in combination.

-Phosphorus Flame Retardant-
The phosphorus-based flame retardant is not particularly limited as long as it contains a phosphorus atom among those commonly used as flame retardants, and may be an inorganic phosphorus-based flame retardant or an organic flame retardant. It may be a phosphorus-based flame retardant. From the viewpoint of environmental problems, one that does not contain a halogen atom can be selected. From the viewpoint of dielectric properties, adhesion to conductors, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy in a high frequency band of 10 GHz or higher, an organic phosphorus-based flame retardant may be used.
Examples of inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as amide phosphoric acid. ; phosphoric acid; phosphine oxide;
Examples of organic phosphorus-based flame retardants include aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, and the like. is mentioned. Among these, aromatic phosphoric acid ester compounds and metal salts of disubstituted phosphinic acids can be selected. Here, the metal salt may be lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, zinc salt, or aluminum salt. Further, among organic phosphorus-based flame retardants, aromatic phosphate esters can be selected.

Examples of aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3 -phenylene bis(di-2,6-xylenyl phosphate), bisphenol A-bis(diphenyl phosphate), 1,3-phenylene bis(diphenyl phosphate) and the like.
The monosubstituted phosphonic acid diesters include, for example, divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate and the like.
Disubstituted phosphinate esters include, for example, phenyl diphenylphosphinate and methyl diphenylphosphinate.
The metal salts of disubstituted phosphinic acids include metal salts of dialkylphosphinic acid, metal salts of diallylphosphinic acid, metal salts of divinylphosphinic acid, and metal salts of diarylphosphinic acid. These metal salts may be lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts or zinc salts, and aluminum salts may be selected.
Examples of organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.
Cyclic organic phosphorus compounds include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10- and phosphaphenanthrene-10-oxide.
Among these, at least one selected from aromatic phosphate esters, metal salts of disubstituted phosphinic acids and cyclic organic phosphorus compounds may be used, and may be selected from metal salts of disubstituted phosphinic acids and cyclic organic phosphorus compounds. or a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound may be used in combination. In particular, the metal salt of a disubstituted phosphinic acid may be a metal salt of a dialkylphosphinic acid or an aluminum salt of a dialkylphosphinic acid. The cyclic organic phosphorus compound may be 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Further, the aromatic phosphate may be an aromatic phosphate represented by the following general formula (F-1), and the metal salt of the disubstituted phosphinic acid may be represented by the following general formula (F-2 ) may be a metal salt of a disubstituted phosphinic acid represented by

(Wherein, R ^F1 to R ^F3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. f1 and f2 are each independently an integer of 0 to 5, and f3 is 0 to 4 integers.
R ^F4 and R ^F5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. M is a lithium atom, sodium atom, potassium atom, calcium atom, magnesium atom, aluminum atom, titanium atom, zinc atom. y is an integer from 1 to 4; )

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^F1 to R ^F3 are the same as those for R ^a11 in the general formula (I).
Both f1 and f2 may be integers from 0 to 2, or may be 2. f3 may be an integer from 0 to 2, may be 0 or 1, or may be 0.
The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^F4 and R ^F5 includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. , isobutyl group, t-butyl group, n-pentyl group and the like. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or an ethyl group.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ^{1 F4} and R ^{2 F5} include phenyl group, naphthyl group, biphenylyl group and anthryl group. The aromatic hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms.
y represents the valence of the metal ion, ie, varies from 1 to 4 depending on the type of M.
M may be an aluminum atom. In addition, y is 3 when M is an aluminum atom.

-metal hydrate-
Examples of metal hydrates include aluminum hydroxide hydrates and magnesium hydroxide hydrates. These may be used individually by 1 type, and may use 2 or more types together. Although the metal hydroxide can also correspond to an inorganic filler, it is classified as a flame retardant in the case of a material capable of imparting flame retardancy.

- Halogen Flame Retardant -
Halogen-based flame retardants include chlorine-based flame retardants, brominated flame-retardants, and the like. Examples of chlorine-based flame retardants include chlorinated paraffins. Examples of brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resins and brominated phenol novolac type epoxy resins; Bromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2, Brominated additive flame retardants such as 4,6-tris(tribromophenoxy)-1,3,5-triazine (here, "additive" refers to flame retardants in which bromine is not chemically bound to the polymer. unsaturated dimethacrylates such as tribromophenylmaleimide, tribromophenylacrylate, tribromophenylmethacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromobenzylacrylate, and brominated styrene. A brominated reactive flame retardant containing a heavy bond group (here, "reactive type" refers to one in which bromine is introduced into a polymer in a chemically bonded form), and the like. These may be used individually by 1 type, and may use 2 or more types together.

(Content of component (F))
When the resin composition of the present invention contains component (F), and when a phosphorus-based flame retardant is used as component (F), the content of the phosphorus-based flame retardant in the resin composition is not particularly limited. However, for example, it is preferably 0.2 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, in terms of phosphorus atoms with respect to 100 parts by mass of the total resin component, and 0.5 More preferably, it is up to 3 parts by mass. When the phosphorus atom content is 0.2 parts by mass or more, better flame retardancy tends to be obtained. Further, when the content of phosphorus atoms is 5 parts by mass or less, there is a tendency to obtain better moldability, high adhesion to conductors, excellent heat resistance, and a high glass transition temperature.
On the other hand, when the resin composition of the present invention contains a halogen-based flame retardant, from the viewpoint of environmental problems and chemical resistance, it is preferably 20 parts by mass or less with respect to the total of 100 parts by mass of the resin components. It is more preferably not more than 5 parts by mass, even more preferably not more than 5 parts by mass, and particularly preferably not more than 3 parts by mass. An aspect in which no halogen flame retardant is used as the component (F) is also preferred.
Further, when the resin composition of the present invention contains a flame retardant other than a phosphorus-based flame retardant, it is not particularly limited, but 0.5 to 20 parts by mass with respect to 100 parts by mass of the total resin components. 1 to 15 parts by mass, 1 to 10 parts by mass, or 2 to 8 parts by mass.

(flame retardant aid)
The resin composition of the present invention may contain an auxiliary flame retardant such as antimony trioxide and zinc molybdate.
When the resin composition of the present invention contains a flame retardant aid, the content is not particularly limited, but for example, 0.1 to 20 parts by mass with respect to 100 parts by mass of the total resin components. It may be 0.1 to 10 parts by mass. Using a flame retardant aid within such a range tends to result in better chemical resistance.

(Crosslinking agent (G))
By including the cross-linking agent (G) in the resin composition of the present invention, there is a tendency that the reaction between the components (A) and (B) can be promoted.
The cross-linking agent (G) is not particularly limited as long as it can cross-link with components (A) and (B). is preferably a compound having Among these, the cross-linking agent (G) is preferably a cross-linking agent having two or more ethylenically unsaturated bonds. Examples of the ethylenically unsaturated bond include unsaturated aliphatic hydrocarbon groups such as vinyl group, isopropenyl group, allyl group, 1-methylallyl group and 3-butenyl group; Unsaturated bonds included in substituents containing heteroatoms are included. The cross-linking agent (G) preferably has an ethylenically unsaturated bond as the unsaturated aliphatic hydrocarbon group, more preferably a vinyl group, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. . The number of ethylenically unsaturated bonds that the cross-linking agent (G) has in one molecule is preferably 3 or more, more preferably 5 or more, and still more preferably 10 or more, from the viewpoint of obtaining excellent heat resistance. .

Specific examples of the cross-linking agent (G) include unsaturated polyesters; polybutadiene having a carbon-carbon double bond in the side chain; polyisoprene having a carbon-carbon double bond in the side chain; Polyalkadiene having a carbon double bond; Polyvinyl compounds such as divinylbenzene and divinylbiphenyl; Poly(meth)acrylate compounds; Polyallyl compounds such as triallyl cyanurate and triallyl isocyanurate; Polyamine compounds such as diaminodiphenylmethane; mentioned. Among these, polyalkadiene having a carbon-carbon double bond in the side chain is preferred, and polybutadiene having a carbon-carbon double bond in the side chain is more preferred. One type of crosslinking agent may be used alone, or two or more types may be used in combination.

The resin composition of the present invention may further contain, if necessary, resin materials such as thermoplastic resins and elastomers (excluding the above component (C)), coupling agents, antioxidants, heat stabilizers, and antistatic agents. Agents, UV absorbers, pigments, coloring agents, lubricants, etc. can be appropriately selected and contained. These may be used individually by 1 type, and may use 2 or more types together. Moreover, the amount of these to be used is not particularly limited, and may be used within a range that does not impair the effects of the present invention.

(Organic solvent)
The resin composition of the present invention may contain an organic solvent from the viewpoint of facilitating handling by dilution and from the viewpoint of facilitating the production of a prepreg to be described later. A resin composition containing an organic solvent is generally called a resin varnish or varnish.
Examples of the organic solvent include, but are not limited to, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and tetrahydrofuran. aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide; esters such as γ-butyrolactone system solvents and the like.
Among these, alcohol-based solvents, ketone-based solvents, nitrogen atom-containing solvents, ketone-based solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone may be used from the viewpoint of solubility. well, it may be methyl ethyl ketone.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.

The content of the organic solvent in the resin composition of the present invention is not particularly limited. % by mass, or 40 to 60% by mass. By using a resin composition having a solid content concentration within the above range, it is easy to handle, and the impregnation of the substrate and the appearance of the produced prepreg are good, and the solid content of the resin in the prepreg, which will be described later, is improved. There is a tendency that it becomes easier to adjust the concentration, and it becomes easier to manufacture a prepreg having a desired thickness.

The resin composition of the present invention can be obtained by mixing the components (A) and (B), other components used in combination as needed, and an organic solvent as needed by a known method. At this time, it may be dissolved or dispersed while stirring. Conditions such as mixing order, temperature and time are not particularly limited and can be arbitrarily set.

The resin composition of the present invention has good compatibility and tends not to form precipitates even after being left for one day. In addition, in an embodiment with more excellent compatibility, there is a tendency that no precipitates are formed even after standing for one week (although phase separation may occur). In an embodiment with more excellent compatibility, Even if it is left for one week, it tends not to even phase-separate.
Cured products of the resin composition of the present invention (laminates and resin films containing no fiber base material such as glass cloth) tend to have a dielectric constant (Dk) of 2.90 or less at 10 GHz, which is more preferable. It tends to be 2.80 or less, more preferably 2.75 or less. Also, the dielectric loss tangent (Df) at 10 GHz tends to be 0.0055 or less.
Although there is no particular lower limit for the dielectric constant (Dk) at 10 GHz, it tends to be 2.4 or higher, and may be 2.6 or higher.
The lower limit of the dielectric loss tangent (Df) at 10 GHz is not particularly limited, but tends to be 0.0015 or more, may be 0.0020 or more, or may be 0.0023 or more.
In a more preferred embodiment, the dielectric loss tangent (Df) at 10 GHz is 0.0050 or less, 0.0045 or less, 0.0035 or less, 0.0030 or less, and 0.0029 or less. In recent years, there has been a strict demand for improvement of the dielectric loss tangent (Df) at 10 GHz, and a level of 0.0030 or less is extremely desirable and extremely difficult to achieve.
The dielectric constant and dielectric loss tangent are values measured by the cavity resonator method, more specifically, values measured by the method described in Examples. In addition, when simply referred to as a permittivity, it means a relative permittivity.

[Prepreg]
The present invention also provides a prepreg containing the resin composition of the present invention. More specifically, the prepreg contains the resin composition of the present invention and a sheet-like fiber-reinforced base material, and the sheet-like fiber-reinforced base material is impregnated or coated with the resin composition of the present invention. , and then dried. More specifically, for example, the prepreg of the present invention can be produced by heat-drying in a drying furnace usually at a temperature of 80 to 200° C. for 1 to 30 minutes to semi-harden (B-stage). . The amount of the resin composition used is such that the solid content concentration derived from the resin composition in the prepreg after drying is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and still more preferably 65 to 80% by mass. can be determined as By setting the solid content concentration within the above range, there is a tendency that better moldability can be obtained when a laminate is formed.

As the sheet-like fiber-reinforced base material of the prepreg, known materials used for various laminates for electrical insulating materials are used. Examples of materials for the sheet-like reinforcing substrate include inorganic fibers such as E-glass, D-glass, S-glass and Q-glass; organic fibers such as polyimide, polyester and tetrafluoroethylene; and mixtures thereof. These sheet-like reinforcing substrates have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, surfacing mats, and the like. Moreover, the thickness of the sheet-shaped fiber-reinforced base material is not particularly limited, and for example, a thickness of 0.02 to 0.5 mm can be used. In addition, from the viewpoint of the impregnability of the resin composition, the heat resistance, moisture absorption resistance, and workability when laminated, the resin composition is surface-treated with a coupling agent or the like, and mechanically fiber-opened. can be used.

As a method for impregnating or coating the sheet-like reinforcing substrate with the resin composition, the following hot-melt method or solvent method can be employed.
In the hot melt method, the resin composition does not contain an organic solvent, and (1) a coated paper having good releasability from the resin composition is once coated and then laminated to a sheet-shaped reinforcing substrate, or (2) A method of directly coating a sheet-shaped reinforcing substrate with a die coater.
On the other hand, in the solvent method, a resin composition is made to contain an organic solvent, a sheet-shaped reinforcing substrate is immersed in the obtained resin composition, the sheet-shaped reinforcing substrate is impregnated with the resin composition, and then dried. The method.

[Resin film]
The present invention also provides a resin film containing the resin composition of the present invention. For example, the resin film can be produced by applying a resin composition containing an organic solvent, ie, a resin varnish, to a support and drying by heating. Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter also referred to as "PET") and polyethylene naphthalate; various plastics such as polycarbonate films and polyimide films. film and the like. As the support, metal foil such as copper foil or aluminum foil, release paper, or the like may be used. The support may be subjected to surface treatment such as matte treatment and corona treatment. Further, the support may be subjected to release treatment with a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, or the like.
The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

The method of applying the resin varnish to the support is not particularly limited, and coating devices known to those skilled in the art such as a comma coater, bar coater, kiss coater, roll coater, gravure coater and die coater can be used. These coating apparatuses may be appropriately selected depending on the film thickness.
The drying temperature and drying time may be appropriately determined according to the amount of organic solvent used and the boiling point of the organic solvent used. A resin film can be preferably formed by drying at ~150°C for about 3 to 10 minutes.

[Laminate]
A laminate containing the prepreg of the present invention and a metal foil can also be produced. Specifically, a metal foil is placed on one or both sides of one prepreg of the present invention, or a metal foil is placed on one or both sides of a prepreg obtained by stacking two or more prepregs of the present invention, and then heated. A laminate can be obtained by pressure molding. A laminate on which metal foil is arranged is sometimes called a metal-clad laminate.
The metal of the metal foil is not particularly limited as long as it is used as an 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 metal elements, and may be copper or aluminum, preferably copper.
The conditions for the heat and pressure molding are not particularly limited, but for example, the temperature is 100° C. to 300° C., the pressure is 0.2 to 10 MPa, and the time is 0.1 to 5 hours. . In addition, for the heating and pressure molding, a method of maintaining a vacuum state using a vacuum press or the like for 0.5 to 5 hours can be adopted.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present invention contains at least one selected from the group consisting of the prepreg of the present invention, the resin film of the present invention and the laminate of the present invention. The multilayer printed wiring board of the present invention uses at least one selected from the group consisting of the prepreg of the present invention, the resin film of the present invention, and the laminate of the present invention, and is subjected to drilling and metal plating by a known method. A multilayer printed wiring board can be manufactured by performing processing, circuit forming processing such as etching of metal foil, and multilayer bonding processing.

The resin composition, prepreg, laminate, resin film, and multilayer printed wiring board of the present invention can be suitably used in electronic devices that handle high frequency signals of 10 GHz or higher. In particular, the multilayer printed wiring board is useful as a multilayer printed wiring board for millimeter wave radar.

Although preferred embodiments of the present invention have been described above, these are examples for explaining the present invention, and are not intended to limit the scope of the present invention only to these embodiments. The present invention can be implemented in various aspects different from the above embodiments without departing from the scope of the invention.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples.
In each example, the number average molecular weight was measured as follows.
(Method for measuring number average molecular weight)
Conversion was performed from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). Calibration curve, 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] and approximated by a cubic equation. GPC measurement conditions are shown below.
Device:
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 Guardcolumn HHR-L + column; TSKgel G4000HHR + TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade 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

[Production Example A-1: Production of polyphenylene ether derivative (A-1)]
Toluene and raw polyphenylene ether "Zylon (registered trademark) S202A" (product number average molecular weight of about 16,000) were placed in a 2 L glass flask equipped with a thermometer, a reflux condenser, and a stirrer and capable of being heated and cooled. Asahi Kasei Co., Ltd.) 1 mol and 2-allylphenol in an amount equivalent to 4 mol in terms of hydroxyl group were added and dissolved with stirring at 90 to 100°C.
After visually confirming the dissolution, t-butylperoxyisopropyl monocarbonate and manganese octylate were added, and the solution was allowed to undergo a redistribution reaction at a temperature of 90 to 100°C for 6 hours. A polyphenylene ether derivative (A-1) having an organic group substituted with an allyl group was obtained. A small amount of this reaction solution was taken out and subjected to GPC measurement (converted to polystyrene, eluent: tetrahydrofuran). As a result, the double peak derived from 2-allylphenol became a single peak, and the number average molecular weight of the polyphenylene ether compound was 5,100. there were.
Table 1 shows the amount of each component used.

[Production Example A-2: Production of polyphenylene ether derivative (A-2)]
Polyphenylene having an organic group substituted with one allyl group at one end of the molecule by performing the same operation as in Production Example A-1, except that the charged amount of 2-allylphenol was changed as shown in Table 1. An ether derivative (A-2) was obtained. The number average molecular weight of the polyphenylene ether compound was 3,300.

[Production Example A-3: Production of polyphenylene ether derivative (A-3)]
In Production Example A-1, diallyl bisphenol A (DABPA) was used instead of 2-allylphenol, and the amount of each component used was as shown in Table 1. A polyphenylene ether derivative (A-3) having an organic group substituted with two allyl groups at one end of the molecule was obtained. The number average molecular weight of the polyphenylene ether compound was 4,300.

[Production Example A-4: Production of polyphenylene ether derivative (A-4)]
A polyphenylene ether derivative having an organic group substituted with two allyl groups at one end of the molecule ( A-4) was obtained. The number average molecular weight of the polyphenylene ether compound was 3,500.

（式中、Ｘ^ａ２は有機基であり、前記一般式（ａ－５）中のＸ^ａ２と同様に説明される。）[Production Example A-5: Production of polyphenylene ether derivative (A-5)]
In Production Example A-1, instead of 2-allylphenol, an allyl group-containing compound represented by the following general formula (1) (hereinafter sometimes referred to as tetraallylbisphenols) is used, and each component is A polyphenylene ether derivative (A-5) having an organic group substituted with four allyl groups at one end of the molecule was obtained by performing the same operation except that the amount used was as shown in Table 1. The number average molecular weight of the polyphenylene ether compound was 5,400.

(In the formula, X ^a2 is an organic group and is explained in the same manner as X ^a2 in the general formula (a-5).)

[Production Example A-6: Production of polyphenylene ether derivative (A-6)]
By performing the same operation as in Production Example A-5, except that the charged amount of the allyl group-containing compound represented by the following general formula (1) was changed as shown in Table 1, an allyl was added to one end of the molecule. A polyphenylene ether derivative (A-6) having four substituted organic groups was obtained. The number average molecular weight of the polyphenylene ether compound was 4,500.

[Production Example A-7: Production of polyphenylene ether derivative (A-7)]
Same as in Production Example A-5, except that "Zylon (registered trademark) S202A" (trade name, manufactured by Asahi Kasei Corporation) was changed to "Zylon (registered trademark) S203A" (trade name, manufactured by Asahi Kasei Corporation). By carrying out the operation, a polyphenylene ether derivative (A-7) having an organic group substituted with four allyl groups at one end of the molecule was obtained. The number average molecular weight of the polyphenylene ether compound was 4,200.

[Production Example A-8: Production of polyphenylene ether derivative (A-8)]
By performing the same operation as in Production Example A-7, except that the charged amount of the allyl group-containing compound represented by the following general formula (1) was changed as shown in Table 1, an allyl was added to one end of the molecule. A polyphenylene ether derivative (A-8) having an organic group substituted with four groups was obtained. The number average molecular weight of the polyphenylene ether compound was 3,800.

[Comparative Production Example A'-9: Production of polyphenylene ether derivative (A'-9)]
Toluene and raw polyphenylene ether "Zylon (registered trademark) S202A" (product number average molecular weight of about 16,000) were placed in a 2 L glass flask equipped with a thermometer, a reflux condenser, and a stirrer and capable of being heated and cooled. Asahi Kasei Co., Ltd.) and p-aminophenol were added and dissolved with stirring at 90 to 100°C.
After visually confirming the dissolution, t-butylperoxyisopropyl monocarbonate and manganese naphthenate were added and the solution was allowed to undergo a redistribution reaction at a temperature of 90 to 100°C for 6 hours. A polyphenylene ether derivative with primary amino groups was obtained. Here, when a small amount of this reaction solution was taken out and subjected to GPC measurement (in terms of polystyrene, eluent: tetrahydrofuran), the peak derived from p-aminophenol disappeared, and the polyphenylene ether compound had a number average molecular weight of 000. In addition, a small amount of the reaction solution ^taken out was added dropwise to a mixed solvent of methanol / benzene (mixing mass ratio = 1:1), and FT-IR measurement of the solid content purified by reprecipitation was performed. The appearance of peaks derived from primary amino groups was confirmed.

Next, BMI-4000 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and propylene glycol monomethyl ether are added to the above reaction solution, the liquid temperature is raised while stirring, and the reaction is performed for 4 hours while maintaining the temperature at 100°C. After cooling and filtering through a 200 mesh filter, a polyphenylene ether derivative (A'-9) was produced.
A small amount of this reaction solution is taken out, reprecipitated in the same manner as above, FT-IR measurement of the purified solid is performed, and the disappearance of the primary amino group-derived peak near 3,500 cm ^-1 and 1,700 to 1,730 cm The appearance of the carbonyl group of ^-1 was confirmed. The number average molecular weight of this solid was about 6,500.
Table 1 shows the amount of each component used.

（式（１）中、Ｘ^ａ２は有機基であり、前記一般式（ａ－５）中のＸ^ａ２と同様に説明される。）
・ｐ－アミノフェノール：イハラケミカル工業株式会社製
（３）変性用化合物
・ＢＭＩ－４０００：２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン、商品名（大和化成工業株式会社製）
（４）反応触媒
・パーブチル（登録商標）Ｉ：ｔ－ブチルペルオキシイソプロピルモノカーボネート（日油株式会社製）
・ナフテン酸マンガン（和光純薬工業株式会社製）Each material in Table 1 is as follows.
(1) Polyphenylene ether Zylon (registered trademark) S202A: Polyphenylene ether (manufactured by Asahi Kasei Chemicals Corporation), number average molecular weight = 16,000, trade name Zylon (registered trademark) S203A: Polyphenylene ether (manufactured by Asahi Kasei Chemicals Corporation) , number average molecular weight = 12,000, trade name (2) compound for redistribution reaction 2-allylphenol: manufactured by Tokyo Chemical Industry Co., Ltd. diallyl bisphenol A: 2,2-bis(3-allyl-4-hydroxyphenyl ) Propane, manufactured by Daiwa Kasei Kogyo Co., Ltd. Tetraallyl bisphenols: compounds represented by the following general formula (1), manufactured by Gunei Chemical Industry Co., Ltd.

(In formula (1), X ^a2 is an organic group and is described in the same manner as X ^a2 in general formula (a-5).)
・p-Aminophenol: (3) modification compound manufactured by Ihara Chemical Industry Co., Ltd. ・BMI-4000: 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd. )
(4) Reaction catalyst Perbutyl (registered trademark) I: t-butylperoxyisopropyl monocarbonate (manufactured by NOF Corporation)
・Manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)

[Production Example B-1: Production of polyaminobismaleimide compound (B1-1)]
2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (maleimide compound (b1)) was placed in a heatable and coolable 1 L glass flask equipped with a thermometer, a reflux condenser and a stirrer. , 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide (maleimide compound (b1)), 4,4′-[1,3-phenylenebis(1-methylethylidene)] Bisaniline (diamine compound (b2)) and propylene glycol monomethyl ether were added, the liquid temperature was kept at 120°C, and the mixture was reacted for 3 hours while stirring. to produce a polyaminobismaleimide compound (B1-1).
Table 2 shows the amount of each component used.

Each material in Table 2 is as follows.
(1) maleimide compound (b1)
・BMI-5100: 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name ・BMI-4000: 2,2-bis[4- (4-maleimidophenoxy)phenyl]propane, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name (2) diamine compound (b2)
Bisaniline-M: 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, manufactured by Mitsui Chemicals, Inc., trade name

[Examples 1-8, Comparative Examples 1-2]
Each component shown in Table 3 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 Table 3, and the solid content (nonvolatile content) concentration is about 50% by mass. A resin composition was prepared.
After applying the resin composition obtained in each example to a glass cloth (NE glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.07 mm, it is dried by heating at 105 ° C. for 5 minutes, and the resin content (resin component Amount) A prepreg of about 73% by mass was produced. Six sheets of these prepregs were stacked, and 18 μm-thick low-profile copper foils (BF-ANP18, M surface Rz: 1.5 μm, manufactured by Furukawa Electric Co., Ltd.) were placed on the top and bottom so that the M surface was in contact. , a temperature of 230° C., a pressure of 4 MPa, and a time of 180 minutes to fabricate a double-sided copper-clad laminate (thickness: 0.8 mm).

<Evaluation/measurement method>
Using the resin compositions or double-sided copper-clad laminates obtained in the above Examples and Comparative Examples, measurements and evaluations were carried out according to the following methods. Table 3 shows the results.

(1. Evaluation of compatibility of resin composition)
The resin composition obtained in each example was visually observed to evaluate compatibility (presence or absence of macroscopic (macro) phase separation and precipitates) according to the following criteria. The evaluations A to C are preferred, A or B is more preferred, and A is even more preferred.
A: There was no macroscopic (macro) phase separation and precipitates even after standing for 1 week or more.
B: There was no change even after standing for 1 day, but after standing for 1 week or longer, there was no precipitate but slight macroscopic phase separation occurred.
C: When left for 1 day, there was no precipitate, but macroscopic (macro) phase separation occurred.
D: Precipitates were observed after standing for 1 day.

(2. Evaluation of dielectric properties of double-sided copper-clad laminate)
Each component shown in Table 3 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 Table 3, and the solid content (nonvolatile content) concentration is 40 to 60% by mass. was prepared.
The resin composition obtained in each example was applied to a PET film (G2-38, manufactured by Teijin Limited) having a thickness of 38 μm, and then dried by heating at 170° C. for 5 minutes to prepare a B-stage resin film. . After peeling the resin film from the PET film, the resin was pulverized and put into a Teflon (registered trademark) sheet punched into a size of 1 mm thick and 50 mm × 35 mm. A foil (BF-ANP18, manufactured by Furukawa Electric Co., Ltd.) is placed so that the M surface is in contact, and heat and pressure molding is performed under the conditions of a temperature of 230 ° C., a pressure of 2.0 MPa, and a time of 120 minutes to form a double-sided copper-clad laminate. (thickness: 1 mm).
The double-sided copper-clad laminate thus obtained was immersed in a 10% by mass solution of ammonium persulfate (Mitsubishi Gas Chemical Co., Ltd.), which is a copper etchant, to remove the copper foil from the evaluation board. made.
Using the evaluation substrate, the dielectric constant (Dk) and dielectric loss tangent (Df) in the 10 GHz band were calculated from the resonance frequency and unloaded Q value obtained by the cavity resonator method. For the measuring instruments, Agilent Technologies Inc.'s vector-type network analyzer E8364B, Kanto Denshi Applied Development Co., Ltd.'s CP531 (10 GHz resonator) and CPMA-V2 (program) are used, respectively, at an ambient temperature of 25 ° C. gone.
The dielectric constant (Dk) is preferably 2.90 or less, more preferably 2.75 or less. The dielectric loss tangent (Df) is preferably 0.0055 or less, more preferably 0.0050 or less, even more preferably 0.0045 or less.

（式（２）中、ｘ１及びｘ２は、各々独立に、０～２０である。ｘ１及びｘ２の合計は１～３０であることが好ましい。）In addition, each material in Table 3 is as follows.
(1) Polyphenylene ether derivative (A)
- Polyphenylene ether derivatives (A-1) to (A-8): The polyphenylene ether derivatives (A-1) to (A-8) produced in Production Examples A-1 to A-8 above were used.
• Polyphenylene ether derivative (A'-9): The polyphenylene ether derivative (A'-9) produced in Production Example A'-9 was used.
- SA9000: Both-terminal methacryl-modified polyphenylene ether derivative represented by the following formula (2), weight average molecular weight 1,700 (manufactured by SABIC Innovative Plastics, trade name)

(In formula (2), x1 and x2 are each independently 0 to 20. The sum of x1 and x2 is preferably 1 to 30.)

(2) maleimide compound (B)
· Polyaminobismaleimide compound (B-1): The polyaminobismaleimide compound (B1-1) produced in Production Example B-1 was used.
(3) Styrene-based thermoplastic elastomer (C)
・ Kraton (registered trademark) G1652: Hydrogenated styrene thermoplastic elastomer (SEBS), melt flow rate 5.0 g / 10 minutes, styrene content 30%, hydrogenation rate 100% (manufactured by Kraton Polymer Japan Co., Ltd., trade name )
(4) Inorganic filler (D)
・Silica: spherical fused silica, average particle size = 0.5 μm
(5) Curing accelerator (E)
・ Perbutyl (registered trademark) P: α, α'-bis (t-butylperoxy) diisopropylbenzene (manufactured by NOF Corporation, trade name)
・G-8009L: isocyanate mask imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole) (Daiichi Kogyo Seiyaku Co., Ltd., trade name)
(6) Flame retardant (F)
・PQ-60: paraxylylene bisdiphenylphosphine oxide, manufactured by Shinichi Kako Co., Ltd. ・OP935: dialkylphosphinic acid aluminum salt, metal salt of disubstituted phosphinic acid, phosphorus content: 23.5% by mass (Clariant company, product name)
(7) Crosslinking agent (G)
・B-1000: 1,2-polybutadiene homopolymer, number average molecular weight 1,200 (manufactured by Nippon Soda Co., Ltd., trade name)

As is clear from the results shown in Table 3, in the examples of the present invention, the compatibility of the resin composition is good or excellent, and the copper-clad laminates produced using these are 10 GHz band or higher. Excellent dielectric properties in the high frequency band of
On the other hand, in Comparative Example 1, the compatibility of the resin composition is poor, and the dielectric properties in a high frequency band of 10 GHz or higher are also insufficient. In Comparative Example 2, although the compatibility of the resin composition was good, the copper-clad laminate had poor dielectric properties in a high frequency band of 10 GHz or higher.

The resin composition of the present invention has good compatibility, and the laminate produced from the resin composition is particularly excellent in dielectric properties in a high frequency band of 10 GHz or higher, so radio waves in a frequency band exceeding 6 GHz can be used. It is useful for multilayer printed wiring boards used for fifth-generation mobile communication system (5G) antennas and millimeter wave radars that use radio waves in the frequency band of 30 to 300 GHz.

Claims (18)

(A) a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group; and (B) at least one type selected from the group consisting of a maleimide compound having at least two N-substituted maleimide groups and derivatives thereof. ,
A resin composition comprising
In the component (A), the unsaturated aliphatic hydrocarbon group is an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group,
A resin composition wherein, in the component (A), the organic group substituted with the unsaturated aliphatic hydrocarbon group is represented by the following general formula (a-5).

(In formula (a-5), R ^a7 to R ^a10 are each independently an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group . X ^a2 is an organic group. * is Indicate the point of attachment to other structures.) In the general formula (a-5), the organic group represented by X ^a2 is an aliphatic hydrocarbon group which may partially contain a heteroatom, and an alicyclic ring which may partially contain a heteroatom. 2. The resin composition according to claim 1 , which is a group consisting of a hydrocarbon group of the formula, an aromatic hydrocarbon group which may partially contain a heteroatom, or any combination thereof. 3. The resin composition according to claim 1 , wherein the component (A) has a number average molecular weight of 1,000 to 25,000. 4. The resin composition according to any one of claims 1 to 3, wherein in component (A) , the unsaturated aliphatic hydrocarbon group is an allyl group or a 1-methylallyl group . 5. Any one of claims 1 to 4 , wherein the component (B) has a structural unit derived from the maleimide compound (b1) having at least two N-substituted maleimide groups and a structural unit derived from the diamine compound (b2). The resin composition according to . The resin composition according to any one of claims 1 to 5 , wherein the component (B) contains a polyaminobismaleimide compound represented by the following general formula (B-1).

(In formula (B-1), X ^B1 and X ^B2 are each independently an organic group.) 7. Any one of claims 1 to 6 , wherein the content ratio [(A)/(B)] of the component (A) and the component (B) is 1/99 to 80/20 in mass ratio. A cured product of the described resin composition. The cured product of the resin composition according to any one of claims 1 to 7 , which has a dielectric constant at 10 GHz of 2.90 or less and a dielectric loss tangent at 10 GHz of 0.0055 or less. A prepreg containing the resin composition according to any one of claims 1 to 7 . A laminate comprising the prepreg according to claim 9 and a metal foil. A resin film comprising the resin composition according to any one of claims 1 to 7 . A multilayer printed wiring board comprising at least one selected from the group consisting of the prepreg according to claim 9 , the laminate according to claim 10 , and the resin film according to claim 11 . A multilayer printed wiring board for millimeter wave radar, comprising at least one selected from the group consisting of the prepreg according to claim 9 , the laminate according to claim 10 , and the resin film according to claim 11 . A polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group, wherein the unsaturated aliphatic hydrocarbon group is an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group, A polyphenylene ether derivative, wherein the organic group substituted with the unsaturated aliphatic hydrocarbon group is represented by the following general formula (a-5).

(In formula (a-5), R ^a7 to R ^a10 are each independently an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group . X ^a2 is an organic group. * is Indicate the point of attachment to other structures.) In the general formula (a-5), the organic group represented by X ^a2 is an aliphatic hydrocarbon group which may partially contain a heteroatom, and an alicyclic ring which may partially contain a heteroatom. 15. The polyphenylene ether derivative according to claim 14 , which is a group consisting of a hydrocarbon group of the formula, an aromatic hydrocarbon group which may partially contain heteroatoms, or any combination thereof. The polyphenylene ether derivative according to claim 14 or 15 , having a number average molecular weight of 1,000 to 25,000. The polyphenylene ether derivative according to any one of claims 14-16 , having a number average molecular weight of 2,000-6,000. The polyphenylene ether derivative according to any one of claims 14-17 , wherein said unsaturated aliphatic hydrocarbon group is an allyl group or a 1-methylallyl group .