JPWO2020096036A1 - Resin composition, prepreg, laminated board, resin film, multi-layer printed wiring board and multi-layer printed wiring board for millimeter-wave radar - Google Patents

Abstract

(A) A polyphenylene ether derivative having an ethylenically unsaturated bond-containing group, (B) one or more selected from the group consisting of a maleimide compound having two or more N-substituted maleimide groups and a derivative thereof, and (C) A resin composition containing a cross-linking agent having two or more ethylenically unsaturated bonds, a prepreg using the resin composition, a laminate, a resin film, a multilayer print wiring plate, and a multilayer print for millimeter-wave radar. Regarding the wiring board.

Description

The present invention relates to a resin composition, a prepreg, a laminated board, a resin film, a multilayer printed wiring board, and a multilayer printed wiring board for millimeter wave radar.

In mobile communication devices such as mobile phones, their base station devices, servers, network infrastructure devices such as routers, and large computers, the speed and capacity of signals used are increasing year by year. Along with this, the printed wiring boards mounted on these electronic devices need to be compatible with high frequencies, and the dielectric characteristics in the high frequency band (low dielectric constant and low dielectric loss tangent; hereinafter, high frequency) that enable reduction of transmission loss. There is a demand for a substrate material having excellent properties). In recent years, as applications that handle such high-frequency signals, in addition to the above-mentioned electronic devices, practical application or practical planning of new systems that handle high-frequency wireless signals in the ITS field (automobiles, transportation system-related) and indoor short-range communication fields. Is progressing, and it is expected that low transmission loss substrate materials will be further required for printed wiring boards mounted on these devices in the future.

Conventionally, polyphenylene ether (PPE) -based resin has been used as a heat-resistant thermoplastic polymer having excellent high-frequency characteristics for printed wiring boards that require low transmission loss. For example, a method of using polyphenylene ether and a thermosetting resin in combination has been proposed. Specifically, a resin composition containing a polyphenylene ether and an epoxy resin (see, for example, Patent Document 1), and a resin composition containing a cyanate resin having a low dielectric constant among the polyphenylene ether and a thermosetting resin (for example, a patent). (See Document 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, adhesiveness to conductors, low coefficient of thermal expansion, flame retardancy, or thermosetting with polyphenylene ether. Due to the low compatibility with the resin, the heat resistance may decrease.

（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, a resin having particularly good compatibility, dielectric properties in a high frequency band, high adhesion to a conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient, and high flame retardancy. It is an object of the present invention to provide a composition, which comprises 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 one or more thermosetting resins (B) selected from the group and a styrene-based thermoplastic elastomer (C) has been proposed (see, for example, Patent Document 3).

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

Japanese Unexamined Patent Publication No. 58-069046 Tokukousho 61-018937 Gazette International Publication No. 2016/175326

The resin composition described in Patent Document 3 is certainly excellent in dielectric properties in the high frequency band, but there is room for further improvement in heat resistance. Furthermore, in recent years, the 10 GHz band can also be used for fifth-generation mobile communication system (5G) antennas that use radio waves in the frequency band exceeding 6 GHz and millimeter-wave radars that use radio waves in the frequency band of 30 to 300 GHz. The development of a resin composition having further improved dielectric properties is desired.

In view of the current situation, the present invention relates to a resin composition having excellent heat resistance and capable of exhibiting excellent dielectric properties in a high frequency band of 10 GHz or higher, a prepreg using the resin composition, a laminated board, and a resin film. It is an object of the present invention to provide a multilayer printed wiring board and a multilayer printed wiring board for millimeter wave radar.

As a result of intensive research to solve the above problems, the present inventors have found that polyphenylene ether derivatives containing a specific molecular structure, one or more selected from the group consisting of a specific maleimide compound and its derivatives, and one or more. We have found that a resin composition containing a specific cross-linking agent has excellent heat resistance and exhibits excellent dielectric properties in a high frequency band of 10 GHz or higher, and has completed the present invention.
That is, the present invention relates to the following [1] to [15].

（式中、Ｒ^ａ１は炭素数２〜１０のエチレン性不飽和結合含有基である。ｎ１は１又は２であり、ｎ２は０又は１である。＊は、他の構造への結合位置を示す。）
［８］前記（Ａ）成分が、記一般式（ａ１−２）で表される構造を含む、上記［１］〜［７］のいずれかに記載の樹脂組成物。

（式中、Ｒ^ａ２及びＲ^ａ３は、各々独立に、炭素数２〜１０のエチレン性不飽和結合含有基である。＊は、他の構造への結合位置を示す。）
［９］前記（Ａ）成分において、エチレン性不飽和結合含有基の数が、２個以上である、上記［１］〜［８］のいずれかに記載の樹脂組成物。
［１０］前記（Ｂ）成分が、Ｎ−置換マレイミド基を２個以上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］〜［９］のいずれかに記載の樹脂組成物。
［１１］上記［１］〜［１０］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。
［１２］上記［１１］に記載のプリプレグと金属箔とを含有してなる積層板。
［１３］上記［１］〜［１０］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。
［１４］上記［１１］に記載のプリプレグ、上記［１２］に記載の積層板及び上記［１３］に記載の樹脂フィルムからなる群から選択される１種以上を含有してなる多層プリント配線板。
［１５］上記［１１］に記載のプリプレグ、上記［１２］に記載の積層板及び上記［１３］に記載の樹脂フィルムからなる群から選択される１種以上を含有してなるミリ波レーダー用多層プリント配線板。[1] (A) A polyphenylene ether derivative having an ethylenically unsaturated bond-containing group and
(B) One or more selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof, and
(C) A cross-linking agent having two or more ethylenically unsaturated bonds,
A resin composition comprising.
[2] The resin composition according to the above [1], wherein the component (C) has the two or more ethylenically unsaturated bonds as a vinyl group.
[3] The resin composition according to the above [2], wherein the component (C) is polybutadiene having the two or more ethylenically unsaturated bonds as a 1,2-vinyl group.
[4] The resin composition according to the above [3], wherein the content of the structural unit having a 1,2-vinyl structure is 50 mol% or more with respect to all the structural units derived from butadiene constituting the polybutadiene. ..
[5] The resin composition according to the above [3] or [4], wherein the polybutadiene has a number average molecular weight of 500 to 10,000.
[6] The above-mentioned [1] to [5], wherein the content of the component (C) is 5 to 60 parts by mass with respect to 100 parts by mass of the total resin components in the resin composition. Resin composition.
[7] The resin composition according to any one of the above [1] to [6], wherein the component (A) contains a structure represented by the following general formula (a1-1).

^{(Wherein, R a1} is .n1 an ethylenically unsaturated bond-containing group having 2 to 10 carbon atoms is 1 or 2, n2 is 0 or 1. * Is the point of attachment to other structures show.)
[8] The resin composition according to any one of the above [1] to [7], wherein the component (A) contains a structure represented by the general formula (a1-2).

(In the formula, ^Ra2 and ^Ra3 are independently ethylenically unsaturated bond-containing groups having 2 to 10 carbon atoms. * Indicates a bond position to another structure.)
[9] The resin composition according to any one of [1] to [8] above, wherein the number of ethylenically unsaturated bond-containing groups in the component (A) is two or more.
[10] The above-mentioned [1] to [9], wherein the component (B) has a structural unit derived from a maleimide compound (b1) having two or more N-substituted maleimide groups and a structural unit derived from a diamine compound (b2). ] The resin composition according to any one of.
[11] A prepreg containing the resin composition according to any one of the above [1] to [10].
[12] A laminated board containing the prepreg and the metal foil according to the above [11].
[13] A resin film containing the resin composition according to any one of the above [1] to [10].
[14] A multilayer printed wiring board containing at least one selected from the group consisting of the prepreg according to the above [11], the laminated board according to the above [12], and the resin film according to the above [13]. ..
[15] For millimeter-wave radar containing one or more selected from the group consisting of the prepreg according to the above [11], the laminate according to the above [12], and the resin film according to the above [13]. Multi-layer printed wiring board.

According to the present invention, a resin composition having excellent heat resistance and capable of exhibiting excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in a high frequency band of 10 GHz band or higher, a prepreg using the resin composition, and a resin. A film, a laminated board, a multilayer printed wiring board, and a multilayer printed wiring board for a millimeter wave radar can be provided.

In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Further, the lower limit value and the upper limit value of the numerical range are arbitrarily combined with the lower limit value or the upper limit value of the other numerical range, respectively.
Further, as for each component and material exemplified in this specification, one kind may be used alone or two or more kinds may be used in combination unless otherwise specified. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means.
The present invention also includes aspects in which the items described in the present specification are arbitrarily combined.

[Resin composition]
The resin composition of this embodiment is
(A) Polyphenylene ether derivative having an ethylenically unsaturated bond-containing group [Hereinafter, it may be simply abbreviated as the polyphenylene ether derivative (A) or the component (A). ]When,
(B) One or more selected from the group consisting of a maleimide compound having two or more N-substituted maleimide groups and a derivative thereof [hereinafter, may be simply abbreviated as a maleimide compound (B) or a component (B). ]When,
(C) A cross-linking agent having two or more ethylenically unsaturated bonds [hereinafter, may be simply abbreviated as a cross-linking agent (C) or a component (C). ]When,
It is a resin composition containing.
Hereinafter, each component will be described in detail in order.

<Polyphenylene ether derivative (A)>
The polyphenylene ether derivative (A) has an ethylenically unsaturated bond-containing group.
In the present specification, the "ethylenically unsaturated bond-containing group" means a substituent containing a carbon-carbon double bond capable of an addition reaction, and does not include a double bond of an aromatic ring. do.

The position of the ethylenically unsaturated bond-containing group is not particularly limited, and for example, it may be present at one end of the component (A) or at both ends. The component (A) may be a mixture of a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end and a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at both ends, but at least It is preferable to contain a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end, and more preferably the polyphenylene ether derivative itself having an ethylenically unsaturated bond-containing group at one end.
When the component (A) contains a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end, the content of the polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end in the component (A). May be 30% by mass or more, 45% by mass or more, 55% by mass or more, 70% by mass or more, 90% by mass or more. It may be substantially 100% by mass.

Examples of the ethylenically unsaturated bond-containing group contained in the component (A) include unsaturated aliphatic hydrocarbon groups such as vinyl group, isopropenyl group, allyl group, 1-methylallyl group and 3-butenyl group; maleimide group, Examples thereof include a substituent containing a hetero atom such as a (meth) acryloyl group. Among these, an unsaturated aliphatic hydrocarbon group or a maleimide group is preferable, an allyl group or a maleimide group is more preferable, and an allyl group is further preferable, from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or more.
In the present specification, although a part of the group has an unsaturated aliphatic hydrocarbon group such as a maleimide group and a (meth) acryloyl group, the unsaturated aliphatic hydrocarbon is viewed as a whole. A group that cannot be said to be a hydrogen group shall not be included in the above-mentioned "unsaturated aliphatic hydrocarbon group".

Next, a polyphenylene ether derivative having an unsaturated aliphatic hydrocarbon group as an ethylenically unsaturated bond-containing group [hereinafter, may be abbreviated as simply a polyphenylene ether derivative (A1) or a component (A1). ], And a polyphenylene ether derivative having a maleimide group as an ethylenically unsaturated bond-containing group [hereinafter, may be abbreviated as simply a polyphenylene ether derivative (A2) or (A2) component. ] Will be described in more detail.

(Polyphenylene ether derivative (A1))
The component (A1) is a polyphenylene ether derivative having an unsaturated aliphatic hydrocarbon group as an ethylenically unsaturated bond-containing group.
The number of unsaturated aliphatic hydrocarbon groups in one molecule of the component (A1) is preferably 2 or more, more preferably 4 or more, from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or more. The upper limit value is not particularly limited, and may be 8 or less, or 6 or less. Furthermore, the number of unsaturated aliphatic hydrocarbon groups at one end of the component (A1) is preferably 2 or more, more preferably 4 or more, from the viewpoint of dielectric properties in the high frequency band of 10 GHz band or more. There is no particular limitation on the upper limit value, and the number may be 8 or less, or 6 or less.
It is most preferable that the number of unsaturated aliphatic hydrocarbon groups contained in the component (A1) and the number of unsaturated aliphatic hydrocarbon groups contained in the component (A1) at one end are both four.

（式（ａ１−１）中、Ｒ^ａ１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。ｎ１は１又は２であり、ｎ２は０又は１である。＊は、他の構造への結合位置を示す。）The component (A1) preferably contains a structure represented by the following general formula (a1-1) from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher.

(In the formula (a1-1), R ^a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms, respectively. N1 is 1 or 2, and n2 is 0 or 1. * Indicates the position of connection to other structures.)

In the general formula ^(a1-1), examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms ^{which R a1} represents, for example, vinyl group, isopropenyl group, allyl group, 1-methylallyl group, 3-butenyl The group etc. can be mentioned. Among these, an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is preferable, and an allyl group is more preferable, from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or more.

（式（ａ１−２）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, from the viewpoint of the dielectric property in the high frequency band of 10 GHz band or higher, the component (A1) preferably includes a structure represented by the following general formula (a1-2).

(In the formula (a1-2), ^Ra2 and ^Ra3 are independently unsaturated aliphatic hydrocarbon groups having 2 to 10 carbon atoms. * Indicates the bonding position to another structure.)

In the general formula (a1-2), the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented ^{by Ra 2} and Ra ³ is the same ^{as Ra 1 in the general formula (a1-1).} , The same is preferable.

The component (A1) more preferably contains a structure represented by any of the following general formulas (a1-3) to (a1-5) from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, and is described below. It is more preferable to include a structure represented by the general formula (a1-5).

（式（ａ１−３）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 the formula (a1-3), ^Ra4 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Indicates a bond position to another structure.)

（式（ａ１−４）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２価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 the formula (a1-4), R ^a5 and R ^a6 are each independently unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. X ^a1 is a divalent fat having 1 to 6 carbon atoms. It is a group hydrocarbon group. * Indicates the bond position to other structures.)

（式（ａ１−５）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２価の有機基である。＊は、他の構造への結合位置を示す。）

(In the formula (a1-5), R ^{a7 to} R ^a10 are independently unsaturated aliphatic hydrocarbon groups having 2 to 10 carbon atoms. X ^a2 is a divalent organic group. * Is a divalent organic group. Indicates the position of connection to other structures.)

The unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by ^{R a4 to} R ^a10 in the general formulas (a1-3) to (a1-5) ^{is R a1 in the general formula (a1-1).} The same as in the case of, and the preferable one is also the same.
^{Examples of the divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by X a1} in the general formula (a1-4) include alkylene groups having 1 to 6 carbon atoms such as a methylene group, an ethylene group and a trimethylene group. Group: An alkylidene group having 2 to 6 carbon atoms such as an isopropylidene group can be mentioned. Among these, a methylene group and an isopropylidene group are preferable, and an isopropylidene group is more preferable.
The divalent organic group X ^a2 in the general formula (a1-5) represents, partially aliphatic optionally containing heteroatoms hydrocarbon group, contain some heteroatom Examples thereof include an alicyclic hydrocarbon group, an aromatic hydrocarbon group which may contain a heteroatom in part, and a group composed of any combination thereof. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like. The ^{divalent organic group represented by X a2} is preferably a group that does not contain a hetero atom, an aliphatic hydrocarbon group that does not contain a hetero atom, and an alicyclic hydrocarbon that does not contain a hetero atom. A hydrogen group is more preferable, and a group composed of a combination of an aliphatic hydrocarbon group containing no hetero atom and an alicyclic hydrocarbon group containing no hetero atom is further preferable.

（式中、Ｘ^ａ２は上記一般式（ａ１−５）中のＸ^ａ２と同じである。＊は、他の構造への結合位置を示す。）With respect to the structures represented by the general formulas (a1-3), (a1-4) or (a1-5), more preferable embodiments are described in the following formulas from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher. It is a structure represented by a1-3'), (a1-4') or (a1-5'). Among these, from the viewpoint of the dielectric property in the high frequency band of 10 GHz band or higher, the structure represented by the following formula (a1-4') or (a1-5') is more preferable, and the following formula (a1-5') is used. The structure represented by is more preferable.

^{(Wherein, X a2} is the same as ^{X a2} in the above general formula (a1-5). * Indicates the point of attachment to other structures.)

（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。ｎ３は０〜４の整数である。）Since the component (A1) is a polyphenylene ether derivative, it goes without saying that it also has a phenylene ether bond, and it is preferable to have a structural unit represented by the following general formula (a-1).

^{(Wherein, R a11} are each independently, .N3 an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms is an integer of 0-4.)

^{R a11} in the general formula (a-1) is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and the like. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among the above, the R ^a11, it is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
n3 is an integer of 0 to 4, and may be an integer of 1 or 2, or may be 2. In the case n3 is 1 or 2, R ^a11 ortho-position on the benzene ring (provided that the basis of the substitution position of an oxygen atom.) May be substituted on. Further, when n3 is 2 or more, the plurality of Ra ^11s may be the same or different from each other.
Specifically, the structural unit represented by the general formula (a-1) may be a structural unit represented by the following general formula (a-1').

（式中、Ｘ^ａ２は上記一般式（ａ１−５）中のＸ^ａ２と同じである。ｎ４〜ｎ６は、各々独立に、１〜２００の整数である。）The component (A1) may contain a polyphenylene ether derivative represented by any of the following general formulas (a1-6) to (a1-8), and in particular, the following general formula (a1-7) or (a1). It preferably contains the polyphenylene ether derivative represented by −8), and more preferably contains the polyphenylene ether derivative represented by the following general formula (a1-8).

^{(Wherein, .n4~n6 X a2} is the same as ^{X a2} in the above general formula (a1-5) are each independently an integer of 1 to 200.)

In the above general formulas (a1-6) to (a1-8), n4 to n6 are independently integers of 1 to 200, and the viewpoint of dielectric properties in the high frequency band of 10 GHz band or higher and the phase of the resin composition. From the viewpoint of compatibility, it may be an integer of 1 or more, an integer of 10 or more, an integer of 20 or more, or an integer of 25 or more. From the same viewpoint, n4 to n6 may be independently an integer of 150 or less, an integer of 120 or less, or an integer of 100 or less.
In any of the above general formulas (a1-6) to (a1-8), a mixture of polyphenylene ether derivatives having different values of n4 to n6 may be used, and usually tends to be a mixture.

[Number average molecular weight (Mn) of component (A1)]
The number average molecular weight of the polyphenylene ether derivative (A1) is preferably 1,000 to 25,000. When the number average molecular weight of the polyphenylene ether derivative (A1) is 1,000 or more, the dielectric properties in the high frequency band of 10 GHz band or more tend to be further improved, and when it is 25,000 or less, the resin composition The compatibility with the above becomes good, and it tends to be difficult to separate even if it is left for a long period of time. From the same viewpoint, the number average molecular weight of the polyphenylene ether derivative (A1) is more preferably 2,000 to 20,000, further preferably 3,000 to 10,000, and particularly preferably 4,000 to 6,000. be.
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 is more specifically obtained by the measurement method described in Examples. The value.

[Method for manufacturing component (A1)]
Hereinafter, one aspect of the method for producing the component (A1) will be described, but the description is not particularly limited to the following description.
For example, a phenol compound containing a structure represented by any of the above general formulas (a1-1) to (a1-5) [hereinafter, may be abbreviated as an unsaturated aliphatic hydrocarbon group-containing phenol compound (1). .. ], And a polyphenylene ether having a number average molecular weight of 3,000 to 30,000 [hereinafter, may be abbreviated as a raw material polyphenylene ether. ] Is redistributed in an organic solvent to produce a polyphenylene ether derivative (A1) while reducing the molecular weight of the polyphenylene ether.

In the redistribution reaction, for example, an unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is mixed with the raw material polyphenylene ether already produced by polymerization, and a reaction catalyst described later is added as necessary. 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 broken there to reduce the molecular weight. It is a reaction that turns into a compound. At that time, the oxyradical of the attacked unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is bonded to the broken carbon atom and incorporated into the structure of the polyphenylene ether. As the redistribution reaction, known methods can be used and applied.

The molecular weight of the polyphenylene ether derivative (A1) can be controlled by the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used, and the larger the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used (1). A1) The component is reduced in molecular weight. That is, the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used may be appropriately adjusted so that the number average molecular weight of the component (A1) finally produced is in a suitable range.
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 3,000 to 30,000, the hydroxyl group of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is 1 to 10 mol, preferably 2 to 6 mol, with respect to 1 mol of the raw material polyphenylene ether. When used in such an amount, the component (A1) having a number average molecular weight within the above-mentioned preferable range can be obtained.

The organic solvent used in the production process of the polyphenylene ether derivative (A1) is not particularly limited, and for example, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone, methyl ethyl ketone and 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, N, N-dimethyl Examples thereof include nitrogen-containing compounds such as acetamide and N-methyl-2-pyrrolidone. One of these may be used alone, or two or more thereof may be used in combination.

Further, in the production process of the polyphenylene ether derivative (A1), as described above, a reaction catalyst can be used if necessary. Examples of this reaction catalyst include organic peroxides such as t-butylperoxyisopropylmonocarbonate and manganese naphthenate, manganese octylate, etc. from the viewpoint of obtaining a component (A1) having a stable number average molecular weight with good reproducibility. It is preferable to use it in combination with a carboxylic acid metal salt. The amount of the reaction catalyst used is not particularly limited. From the viewpoint of reaction rate and suppression of gelation when producing the component (A1), for example, 100 parts by mass of the raw material polyphenylene ether to be reacted with the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is organically peroxidized. The compound may be 0.5 to 5 parts by mass and the carboxylic acid metal salt may be 0.05 to 0.5 parts by mass.

The unsaturated aliphatic hydrocarbon group-containing phenol compound (1), the raw material polyphenylene ether having a number average molecular weight of 3,000 to 30,000, an organic solvent and, if necessary, a reaction catalyst are charged in a predetermined amount in a reactor, and heated and kept warm. The polyphenylene ether derivative (A1) is obtained by reacting with stirring.
The reaction temperature and reaction time in this step can be appropriately adjusted by applying the known reaction conditions at the time of the redistribution reaction, but from the viewpoint of workability and suppression of gelation, and the above-mentioned desired number average molecular weight (A1). ) From the viewpoint of obtaining the components, the conditions may be, for example, a reaction temperature of 70 to 110 ° C. and a reaction time of 1 to 8 hours.

Solid content concentration during reaction in the production process of the component (A1) [hereinafter, also referred to as reaction concentration. ] Is not particularly limited, but may be, for example, 10 to 60% by mass or 20 to 50% by mass. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow and tends to be more advantageous in terms of production cost, and when it is 60% by mass or less, better solubility tends to be obtained. Furthermore, the solution viscosity is low, the stirring efficiency is good, and gelation tends to be difficult.

The solution of the polyphenylene ether derivative (A1) produced as described above may be concentrated as necessary to remove a part of the organic solvent, or may be diluted by adding an organic solvent.

The resin composition of the present embodiment tends to have better dielectric properties in the high frequency band of 10 GHz band or higher than the resin composition containing the raw material polyphenylene ether instead of the component (A1).

(Polyphenylene ether derivative (A2))
The component (A2) is a polyphenylene ether derivative having a maleimide group as an ethylenically unsaturated bond-containing group, and the number of maleimide groups in one molecule is preferably from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher. It may be 1 or more, 5 or less, 3 or less, or 2 or less.

（式中、Ｒ^ａ１２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。ｍ１は０〜４の整数である。Ｘ^ａ３は、下記一般式（ａ２−２）、（ａ２−３）、（ａ２−４）又は（ａ２−５）で表される２価の基である。）The component (A2) is a nitrogen atom of two maleimide groups from the viewpoints 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. Those containing a structure derived from bismaleimide in which they are bonded to each other via an organic group are preferable, and those having a group represented by the following general formula (a2-1) are more preferable.

(In the formula, R ^a12 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. M1 is an integer of 0 to 4. X ^a3 is the following general formula (a2-2). ), (A2-3), (a2-4) or (a2-5) is a divalent group.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^a12 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group. Group etc. can be mentioned. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or a methyl group. Further, examples of the halogen atom represented by Ra ¹² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Among the above, Ra ¹² may be an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
m1 is an integer of 0 to 4, and may be an integer of 0 to 2 or 0. When m1 is an integer of 2 or more, the plurality of Ra ^12s may be the same or different.
The divalent groups represented by the general formulas (a2-2), (a2-3), (a2-4) or (a2-5) represented by ^{X a3 are as follows.}

（式中、Ｒ^ａ１３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。ｍ２は０〜４の整数である。）
Ｒ^ａ１３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^ａ１２の場合と同様に説明される。
ｍ２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。ｍ２が２以上の整数である場合、複数のＲ^ａ１３同士は同一であっても異なっていてもよい。

^{(Wherein, R a13} are each independently, .m2 an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms is an integer of 0-4.)
Aliphatic hydrocarbon group having 1 to 5 carbon atoms R ^a13 represents, as the halogen ^atom, is described as in the case of ^{R a12.}
m2 is an integer of 0 to 4, and may be an integer of 0 to 2, 0 or 1, or 0 from the viewpoint of availability. When m2 is an integer of 2 or more, the plurality of Ra ^13s may be the same or different.

（式中、Ｒ^ａ１４及びＲ^ａ１５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^ａ４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（ａ２−３−１）で表される２価の基である。ｍ３及びｍ４は各々独立に０〜４の整数である。）
Ｒ^ａ１４及びＲ^ａ１５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^ａ１２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。
Ｘ^ａ４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。
Ｘ^ａ４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。
Ｘ^ａ４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。
ｍ３及びｍ４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。ｍ３又はｍ４が２以上の整数である場合、複数のＲ^ａ１４同士又はＲ^ａ１５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、Ｘ^ａ４が表す一般式（ａ２−３−１）で表される２価の基は以下のとおりである。

(In the formula, R ^a14 and R ^a15 are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. X a4} is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. Alkylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, single bond, or divalent group represented by the following general formula (a2-3-1). M3 and m4 are independent of each other. Is an integer from 0 to 4.)
Aliphatic hydrocarbon group having 1 to 5 carbon atoms R ^a14 and ^{R a15} are represented, as the halogen atom ^include the same ones as for ^{R a12.} 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.
As the alkylene group having 1 to 5 carbon atoms which X ^a4 represents, for example, methylene, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group Can be mentioned. The alkylene group is an alkylene group having 1 to 3 carbon atoms from the viewpoints of high frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy. It may be a methylene group.
The alkylidene group having 2 to 5 carbon atoms which X ^a4 represents, for example, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. Among these, an isopropylidene group may be used from the viewpoints of high frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy.
Among the above options, X ^a4 may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.
m3 and m4 are independently integers of 0 to 4, and from the viewpoint of availability, both may be integers of 0 to 2 and may be 0 or 2. When m3 or m4 is an integer of 2 or more, the plurality of Ra ^14s or Ra ^15s may be the same or different from each other.
The divalent group represented by the general formula (a2-3-1) represented by X ^{a4 is as follows.}

（式中、Ｒ^ａ１６及びＲ^ａ１７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^ａ５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。ｍ５及びｍ６は各々独立に０〜４の整数である。）
Ｒ^ａ１６及びＲ^ａ１７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^ａ１４及びＲ^ａ１５の場合と同様に説明される。
Ｘ^ａ５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、Ｘ^ａ４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。
Ｘ^ａ５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。
ｍ５及びｍ６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。ｍ５又はｍ６が２以上の整数である場合、複数のＲ^ａ１６同士又はＲ^ａ１７同士は、それぞれ同一であっても異なっていてもよい。

(In the formula, R ^a16 and R ^a17 are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. X a5} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, and an ether group. , A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. M5 and m6 are independently integers of 0 to 4).
Aliphatic hydrocarbon group having 1 to 5 carbon atoms R ^a16 and ^{R a17} are represented, as the halogen ^atom, is described as in the case of ^{R a14} and ^{R a15.
Examples} of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X a5 include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented ^{by X a4.} Be done.
As X ^a5 , an alkylidene group having 2 to 5 carbon atoms may be selected from the above options.
m5 and m6 are integers of 0 to 4, and from the viewpoint of availability, they may be integers of 0 to 2, 0 or 1, and may be 0. When m5 or m6 is an integer of 2 or more, among the plurality of ^{R a16} each other or ^{R a17} may each be the same or different.

（式中、ｍ７は０〜１０の整数である。）
ｍ７は、入手容易性の観点から、０〜５の整数であってもよく、０〜３の整数であってもよい。

(In the formula, m7 is an integer from 0 to 10.)
From the viewpoint of availability, m7 may be an integer of 0 to 5 or an integer of 0 to 3.

（式中、Ｒ^ａ１８及びＲ^ａ１９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。ｍ８は１〜８の整数である。）
Ｒ^ａ１８及びＲ^ａ１９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^ａ１２の場合と同様に説明される。
ｍ８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 ^a18 and R ^a19 are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 5 carbon atoms. M8 is an integer of 1 to 8.)
Aliphatic hydrocarbon group having 1 to 5 carbon atoms R ^a18 and ^{R a19} are represented, as the halogen ^atom, is described as in the case of ^{R a12.}
m8 is an integer of 1 to 8, and may be an integer of 1 to 3 or 1.

Among the groups represented by the general formula (a2-1), X ^a3 includes high frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion to a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, and From the viewpoint of flame retardancy, it is preferable that the group is represented by any of the following formulas.

（式中、Ｘ^ａ３、Ｒ^ａ１１、Ｒ^ａ１２、ｎ３及びｍ１は上記定義のとおりである。ｍ９は１以上の整数である。）
ｍ９は、１〜３００の整数であってもよく、１０〜２５０の整数であってもよく、３０〜２００の整数であってもよく、５０〜１５０の整数であってもよい。The component (A2) is preferably a polyphenylene ether derivative represented by the following general formula (a2-6).

(In the equation, X ^a3 , R ^a11 , R ^a12 , n3 and m1 are as defined above. M9 is an integer of 1 or more.)
m9 may be an integer of 1 to 300, an integer of 10 to 250, an integer of 30 to 200, or an integer of 50 to 150.

（式中、ｍ９は上記一般式（ａ２−６）中のｍ９と同じである。）The component (A2) is more preferably a polyphenylene ether derivative represented by any of the following general formulas.

(In the formula, m9 is the same as m9 in the above general formula (a2-6).)

As the component (A2), the polyphenylene ether derivative represented by the general formula (a2-7) is preferable from the viewpoint that the raw material is inexpensive, and the general formula is described from the viewpoint of excellent dielectric properties and low water absorption. The polyphenylene ether derivative represented by (a2-8) is preferable, and the polyphenylene ether represented by the above general formula (a2-9) is excellent from the viewpoint of excellent adhesion to the conductor and mechanical properties (elongation, breaking strength, etc.). Derivatives are preferred. Therefore, one of the polyphenylene ether derivatives represented by any of the above general formulas (a2-7) to (a2-9) can be used alone or in combination of two or more according to the desired characteristics. ..

[Number average molecular weight (Mn) of component (A2)]
The number average molecular weight of the component (A2) is preferably 4,000 to 12,000, more preferably 5,000 to 10,000, and even more preferably 6,000 to 8,000. When the number average molecular weight of the component (A2) is 4,000 or more, a better glass transition temperature tends to be obtained, and when it is 12,000 or less, better moldability tends to be obtained.

[Method for manufacturing component (A2)]
The component (A2) can be obtained, for example, by the following production method.
First, an aminophenol compound represented by the following general formula (a2-10) [hereinafter, may be abbreviated as an aminophenol compound (AP). ], For example, by subjecting a polyphenylene ether having a number average molecular weight of 15,000 to 25,000 to a known redistribution reaction in an organic solvent, the first in one molecule is accompanied by a reduction in the molecular weight of the polyphenylene ether. Polyphenylene ether compound (A ″) having a secondary amino group [Hereinafter, it may be simply abbreviated as polyphenylene ether compound (A ″). ], Then, the polyphenylene ether compound (A ″) and the bismaleimide compound represented by the following general formula (a2-11) [hereinafter, may be abbreviated as the bismaleimide compound (BM). ] By the Michael addition reaction, the component (A2) can be produced.

（式中、Ｒ^ａ１２及びｍ１は、上記一般式（ａ２−１）中のものと同じである。）

(In the formula, ^Ra12 and m1 are the same as those in the above general formula (a2-1).)

（式中、Ｘ^ａ３は、上記一般式（ａ２−１）中のものと同じである。）

(In the formula, X ^a3 is the same as that in the above general formula (a2-1).)

Examples of the aminophenol compound (AP) include o-aminophenol, m-aminophenol, p-aminophenol and the like. Among these, m-aminophenol and p-aminophenol are selected from the viewpoints of the reaction yield when producing the polyphenylene ether compound (A ″) and the heat resistance when the resin composition, prepreg and laminated plate are used. Preferably, p-aminophenol is more preferable.

The molecular weight of the polyphenylene ether compound (A ″) can be controlled by the amount of the aminophenol compound (AP) used, and the larger the amount of the aminophenol compound (AP) used, the lower the molecular weight of the polyphenylene ether compound (A ″). NS. That is, the amount of the aminophenol compound (AP) used may be appropriately adjusted so that the number average molecular weight of the component (A2) finally produced is in a suitable range.
The blending amount of the aminophenol compound (AP) is not particularly limited, but for example, if the number average molecular weight of the polyphenylene ether to be reacted with the aminophenol compound (AP) is 15,000 to 25,000. By using the polyphenylene ether in the range of 0.5 to 6 parts by mass with respect to 100 parts by mass, the component (A2) having a number average molecular weight of 4,000 to 12,000 can be obtained.

Aminophenol compound (AP), the above-mentioned polyphenylene ether having a number average molecular weight of 15,000 to 25,000, an organic solvent and, if necessary, a reaction catalyst are charged in a predetermined amount into a reactor, and the reaction is carried out while heating, keeping warm and stirring. Compound (A ″) is obtained. The reaction temperature and reaction time in this step can be applied to the known reaction conditions at the time of the redistribution reaction, and are the same as in the above-mentioned method for producing the component (A1). Moreover, the preferred embodiment of the organic solvent, the reaction catalyst, and the amount used thereof used in the above-mentioned production step is the same as in the case of the method for producing the component (A1).

The solution of the polyphenylene ether compound (A ″) produced as described above may be continuously supplied as it is to the production step of the polyphenylene ether derivative (A2) in the next step. At this time, the solution of the polyphenylene ether compound (A ″) may be cooled, or the reaction temperature may be adjusted to the reaction temperature in the next step. In addition, this solution may be concentrated to remove a part of the organic solvent, or may be diluted by adding an organic solvent, if necessary.

Examples of the bismaleimide compound (BM) used in producing the component (A2) include bis (4-maleimidephenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidephenyl) ether, and bis (4-maleimide). Phenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis [4- (4-Maleimidephenoxy) phenyl] Propane, bis (4-maleimidephenyl) sulfone, bis (4-maleimidephenyl) sulfide, bis (4-maleimidephenyl) ketone, 2,2-bis [4- (4) -Maleimidephenoxy) phenyl] propane, bis [4- (4-maleimidephenoxy) phenyl] sulfone, 4,4'-bis (3-maleimidephenoxy) biphenyl, 1,6-bismaleimide- (2,2,4- Trimethyl) hexane and the like can be mentioned. One of these may be used alone, or two or more thereof may be used in combination.
Among these, bis (4-maleimidephenyl) methane is preferable from the viewpoint that a polyphenylene ether derivative containing the above general formula (a2-7) can be obtained and is inexpensive, and the above general formula (a2-8) is included. From the viewpoint that a polyphenylene ether derivative can be obtained, excellent in dielectric properties, and low water absorption, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide is preferable, and the above general formula is used. A polyphenylene ether derivative containing (a2-9) can be obtained, and from the viewpoint of high adhesion to the conductor and excellent mechanical properties (elongation, breaking strength, etc.), 2,2-bis [4- (4-maleimidephenoxy) ) Phenyl] Propane is preferred.

The amount of the bismaleimide compound (BM) used is determined by the amount of the aminophenol compound (AP) used. _{The equivalent ratio (Tb1 / Ta1) of the -NH 2} equivalent (Ta1) of the aminophenol compound (AP) to the maleimide group equivalent (Tb1) of the bismaleimide compound (BM) is preferably 2 to 6, preferably 2 to 4. More preferred. By using the bismaleimide compound within the above equivalent ratio range, the resin composition, prepreg and laminated plate of the present embodiment tend to have better heat resistance, high glass transition temperature and high flame retardancy. It is in.

If necessary, a reaction catalyst can be used for the Michael addition reaction in producing the component (A2). The reaction catalyst is not particularly limited, but for example, an acidic catalyst such as p-toluenesulfonic acid; an amine such as triethylamine, pyridine or tributylamine; an imidazole compound such as methylimidazole or phenylimidazole; a phosphorus catalyst such as triphenylphosphine. And so on. These may be used alone or in combination of two or more. The amount of the reaction catalyst to be blended is not particularly limited, but is, for example, 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether compound (A ″).

The component (A2) is obtained by adding a predetermined amount of the bismaleimide compound (BM) and, if necessary, a reaction catalyst or the like to a polyphenylene ether compound (A ″) solution, and causing a Michael addition reaction while heating, keeping warm, and stirring. Be done. The reaction conditions in this step may be, for example, a reaction temperature of 50 to 160 ° C. and a reaction time of 1 to 10 hours from the viewpoint of workability and suppression of gelation. Further, in this step, the reaction concentration (solid content concentration) and the solution viscosity can be adjusted by adding or concentrating the organic solvent as described above. As the organic solvent additionally used, the organic solvent exemplified in the production process of the polyphenylene ether compound (A ″) can be applied, and one of these may be used alone or two or more thereof may be used in combination. good. Among these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, and N, N-dimethylacetamide may be selected from the viewpoint of solubility.

The reaction concentration (solid content concentration) in the production process of the component (A2) and the polyphenylene ether compound (A ″) is not particularly limited, but for example, any of the above production processes may be 10 to 60% by mass. It may be 20 to 50% by mass. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow, 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. In addition, the solution viscosity is low, the stirring efficiency is good, and gelation tends to be less.
After the component (A2) is produced, the workability when taking it out from the reactor and the usage situation when various thermosetting resins are added to the component (A2) to prepare the resin composition of the present embodiment (for example). , A part or all of the organic solvent in the solution may be removed and concentrated according to the solution viscosity, solution concentration, etc. suitable for the production of the prepreg, or the organic solvent may be added and diluted. good. The organic solvent for addition is not particularly limited, and one or more of the above-mentioned organic solvents can be applied.

The formation of the polyphenylene ether compound (A ″) and the component (A2) obtained by the above production steps can be confirmed by taking out a small amount of sample after the completion of each step and measuring by GPC and IR.
First, the polyphenylene ether compound (A ″) has a lower molecular weight than the polyphenylene ether having a number average molecular weight of 15,000 to 25,000 as measured by GPC, and the peak of the raw material aminophenol compound (AP) disappears. It can be confirmed from the IR measurement that the desired polyphenylene ether compound (A ″) is produced by the appearance of the primary amino group of ^{3300 to 3500 cm -1.} Then the component (A2), after purification by reprecipitation, confirming a primary disappearance of the peak of the amino group of 3300～3500Cm ^-1 from the IR measurement, the appearance of the peak of the carbonyl group of the maleimide 1700～1730Cm ^-1 This makes it possible to confirm that the desired component (A2) is produced.

<Maleimide compound (B)>
The maleimide compound (B) is one or more selected from the group consisting of a maleimide compound having two or more N-substituted maleimide groups and a derivative thereof. The maleimide compound (B) does not include the polyphenylene ether derivative (A). Further, the maleimide compound (B) does not contain the structural unit represented by the above general formula (a-1), and does not contain a polyphenylene ether skeleton.
In addition, examples of the above-mentioned "derivative" include an addition reaction product of the above-mentioned maleimide compound having two or more N-substituted maleimide groups and an amine compound such as a diamine compound (b2) described later.
The maleimide compound (B) has two or more N-substituted maleimide groups from the viewpoints of solubility in an organic solvent, compatibility, adhesion to a conductor, and dielectric properties in a high frequency band of 10 GHz band or higher. A derivative of the maleimide compound is preferable, and the maleimide compound (b1) having two or more N-substituted maleimide groups [hereinafter, may be simply abbreviated as the maleimide compound (b1) or (b1) component. ] -Derived structural unit and a polyaminobismaleimide compound having a diamine compound (b2) -derived structural unit [hereinafter, may be abbreviated as a polyaminobismaleimide compound (B1) or (B1) component. ] Is more preferable.
The structural unit derived from the component (b1) and the structural unit derived from the component (b2) may be one kind or a combination of two or more kinds for each.

Specific examples of the component (b1) are not particularly limited as long as it is a maleimide compound having two or more N-substituted maleimide groups, and for example, bis (4-maleimidephenyl) methane, polyphenylmethane maleimide, and bis (4-). Maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m Aromatic maleimide compounds such as −phenylene bismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane; 1,6-bismaleimide- (2,2,4-trimethyl) hexane, pyrolylic acid binder Examples thereof include aliphatic maleimide compounds such as long-chain alkylbismaleimide. Among these, aromatic maleimide compounds are preferable from the viewpoint of adhesiveness to conductors and mechanical properties, and 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, 3,3'-dimethyl-5, and so on. 5'-diethyl-4,4'-diphenylmethanebismaleimide is more preferred.

（式中、Ｘ^ｂ１は２価の有機基を示し、＊は他の構造への結合位置を示す。）Examples of the structural unit derived from the component (b1) include one or more selected from the group consisting of a group represented by the following general formula (b1-1) and a group represented by the following general formula (b1-2). Be done.

(In the formula, X ^b1 indicates a divalent organic group, and * indicates a bond position to another structure.)

^{X b1} in the above general formulas (b1-1) and (b1-2) is a divalent organic group and corresponds to the residue of the component (b1). The residue of the component (b1) refers to the structure of the portion of the component (b1) excluding the functional group provided for binding, that is, the maleimide group.
Examples of the divalent organic group represented by X ^b1 include groups represented by the following general formulas (b1-3), (b1-4), (b1-5) or (b1-6).

（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。ｐ１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としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基等が挙げられる。該脂肪族炭化水素基としては、炭素数１〜３の脂肪族炭化水素基であってもよく、メチル基であってもよい。
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。
ｐ１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。ｐ１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, R ^b1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. P1 is an integer of 0 to 4.)
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^b1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group. Group etc. can be mentioned. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or a methyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
p1 is an integer of 0 to 4, and may be an integer of 0 to 2, 0 or 1, or 0 from the viewpoint of availability. When p1 is an integer of 2 or more, the plurality of R ^b1s 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。Ｘ^ｂ２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（ｂ１−４−１）で表される２価の基である。ｐ２及びｐ３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。
Ｘ^ｂ２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。
Ｘ^ｂ２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。
Ｘ^ｂ２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。
ｐ２及びｐ３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。ｐ２又はｐ３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、Ｘ^ｂ２が表す一般式（ｂ１−４−１）で表される２価の基は以下のとおりである。

(In the formula, R ^b2 and R ^b3 are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. X b2} is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. Alkylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, single bond, or divalent group represented by the following general formula (b1-4-1). P2 and p3 are independent of each other. Is an integer from 0 to 4.)
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 those 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 X ^b2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Can be mentioned. The alkylene group is an alkylene group having 1 to 3 carbon atoms from the viewpoints of high frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy. It may be a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^b2 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. Among these, an isopropylidene group may be used from the viewpoints of high frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy.
Among the above options, X ^b2 may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.
p2 and p3 are independently integers of 0 to 4, and from the viewpoint of availability, both may be integers of 0 to 2 and may be 0 or 2. When p2 or p3 is an integer of 2 or more, the plurality of R ^b2s or R ^b3s may be the same or different from each other.
The divalent group represented by the general formula (b1-4-1) represented by X ^{b2 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。Ｘ^ｂ３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。ｐ４及びｐ５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。
Ｘ^ｂ３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、Ｘ^ｂ２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。
Ｘ^ｂ３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。
ｐ４及びｐ５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。ｐ４又はｐ５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。

(In the formula, R ^b4 and R ^b5 are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. X b3} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, and an ether group. , A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. P4 and p5 are independently integers 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 will be described 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 X ^b3 include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented ^{by X b2.} Be done.
As X ^b3 , an alkylidene group having 2 to 5 carbon atoms may be selected from the above options.
p4 and p5 are integers of 0 to 4, and from the viewpoint of availability, they may be integers of 0 to 2, 0 or 1, and may be 0. When p4 or p5 is an integer of 2 or more, the plurality of R ^b4s or R ^b5s may be the same or different from each other.

（式中、ｐ６は０〜１０の整数である。）
ｐ６は、入手容易性の観点から、０〜５の整数であってもよく、０〜３の整数であってもよい。

(In the formula, p6 is an integer from 0 to 10.)
From the viewpoint of availability, p6 may be an integer of 0 to 5 or an integer of 0 to 3.

（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。ｐ７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、ハロゲン原子としては、Ｒ^ｂ１の場合と同様に説明される。
ｐ７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 independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 5 carbon atoms. P7 is an integer of 1 to 8.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^b6 and R ^b7 will be described in the same manner as in the case of ^{R b1.}
p7 is an integer of 1 to 8, and may be an integer of 1 to 3 or 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 above general formulas (b1-1) and (b1-2) includes adhesion to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion, flame retardancy, and a high frequency band of 10 GHz band or higher. in terms of dielectric properties, is preferably a divalent group represented by any one of the following formulas ^{(X b1 -1) ~ (X} b1 -3), represented by the following formula ^(X b1 -3) It is more preferable that it is a divalent group. Further, both in terms of dielectric properties at high frequencies above 10GHz ^band, as ^{X b1,} a group represented by the group and the following formula represented by the following formula ^{(X b1 -1) (X b1} -3) may have a, as X ^b1, may have both a group represented by the group and the following formula represented by the following formula ^{(X b1 -2) (X b1} -3) ..

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

The total content of the 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, still more preferably 60 to 90% by mass, and particularly preferably. It is 75 to 90% by mass. When the content of the structural unit derived from the component (b1) is within the above range, the dielectric property in the high frequency band of 10 GHz band or higher tends to be better, and good film handling property tends to be obtained.

The component (b2) is not particularly limited as long as it is a compound having two amino groups.
Examples of the component (b2) include 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'-dihydroxybenzene, 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- Examples thereof include bis (4-aminophenyl) fluorene.

Among these, as the component (b2), 4,4'-diaminodiphenylmethane and 4,4'-diamino are excellent from the viewpoint of solubility in an organic solvent, reactivity with the component (b1), and heat resistance. -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. Further, the component (b2) is excellent in dielectric properties and low water absorption in a high frequency band of 10 GHz or higher, and is 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane. Is preferable. The component (b2) is preferably 2,2-bis [4- (4-aminophenoxy) phenyl] propane from the viewpoint of excellent mechanical properties such as high adhesiveness to a conductor, elongation, and breaking strength. Further, in addition to being excellent in solubility in the above-mentioned organic solvent, reactivity at the time of synthesis, heat resistance, and high adhesion to a conductor, it is said to be excellent in dielectric properties and low hygroscopicity in a high frequency band of 10 GHz band or higher. 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.

As the structural unit derived from the component (b2), for example, one or more selected from the group consisting of a group represented by the following general formula (b2-1) and a group represented by the following general formula (b2-2). Can be mentioned.

（式中、Ｘ^ｂ４は２価の有機基を示し、＊は他の構造への結合位置を示す。）

(In the formula, X ^b4 indicates a divalent organic group, and * indicates a bond position to another structure.)

^{X b4} in the above general formulas (b2-1) and (b2-2) is a divalent organic group and corresponds to the residue of the component (b2). The residue of the component (b2) refers to the structure of the portion of the component (b2) excluding the functional group provided for binding, 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。Ｘ^ｂ５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（ｂ２−３−１）もしくは（ｂ２−３−２）で表される２価の基である。ｐ８及びｐ９は各々独立に０〜４の整数である。） ^{It is preferable that X b4} in the general formula (b2-1) and the general formula (b2-2) is a divalent group represented by the following general formula (b2-3).

(In the formula, R ^b11 and R ^b12 are independently aliphatic hydrocarbon groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, hydroxyl groups or halogen atoms. X ^b5 has 1 carbon atom. An alkylene group of ~ 5, 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 (b2-3-1) or ( It is a divalent group represented by b2-3-2). P8 and p9 are independently integers 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。Ｘ^ｂ６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。ｐ１０及びｐ１１は各々独立に０〜４の整数である。）

(In the formula, R ^b13 and R ^b14 are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. X b6} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m-. A phenylenediisopropylidene group, a p-phenylenediisopropyridene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. P10 and p11 are independently integers of 0 to 4, respectively. )

（式中、Ｒ^ｂ１５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^ｂ７及びＸ^ｂ８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。ｐ１２は０〜４の整数である。）

(In the formula, R ^b15 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms independently. X b7} and X ^b8 are independently alkylene groups having 1 to 5 carbon atoms, isopropylidene. Group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group or single bond. P12 is an integer from 0 to 4.)

The general formula (b2-3), (b2-3-1) or ^{(b2-3-2) R b11, R b12} , R b13, R b14 and aliphatic C1-5 represented by ^{R b15} in Examples of the hydrocarbon group or halogen atom include those same ^{as R b1 in the above general formula (b1-3).} 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.
The alkylene group having 1 to 5 carbon atoms represented by ^{X b5} and X ^{b6 in the} general formula (b2-3), (b2-3-1) or (b2-3-2), and the carbon number 2 represented by ^{X b5.} The alkylidene group of ~ 5 will be described in the same manner as in the case ^{of X b2 in the above general formula (b1-4).} Further, the alkylene groups having 1 to 5 carbon atoms represented by ^{X b7} and X ^{b8 in the} general formula (b2-3-2) are described in the same manner as in the case ^{of X b2 in the general formula (b1-4).} NS.
p8 and p9 are integers of 0 to 4, and from the viewpoint of availability, both may be integers of 0 to 2 and may be 0 or 2. p10 and p11 are integers of 0 to 4, and from the viewpoint of availability, they may be integers of 0 to 2, 0 or 1, and may be 0. p12 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 the 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, still more preferably 10 to 40% by mass, and particularly preferably. It is 10 to 25% by mass. (B2) When the total content of the structural units derived from the components is within the above range, excellent dielectric properties in the high frequency band of 10 GHz band or higher, and better heat resistance, flame retardancy and glass transition temperature can be obtained. There is a tendency.

The content ratio of the structural unit derived from the component (b1) in the maleimide compound (B) to the structural unit derived from the component (b2) is derived from the _{-NH 2 group of the component (b2) in the maleimide compound (B).} The equivalent ratio (Ta2 / Ta1) between the total equivalent (Ta2) of the group ( _{including -NH 2} ) and the total equivalent (Ta1) of the maleimide group-derived group (including the maleimide group) derived from the component (b1) is The content ratio is preferably 0.05 to 10, more preferably 1 to 5. When the equivalent ratio (Ta2 / Ta1) is within the above range, the dielectric properties in the high frequency band of 10 GHz band or higher are excellent, and better heat resistance, flame retardancy and glass transition temperature tend to be obtained.

The maleimide compound (B) has the following general formula (b2) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, solubility in an organic solvent, high adhesiveness to a conductor, moldability of a resin film, and the like. It is preferable to contain the polyaminobismaleimide compound represented by -4).

（式中、Ｘ^ｂ１及びＸ^ｂ４は、上記で説明したとおりである。）

(In the equation, X ^b1 and X ^b4 are as described above.)

(Method for producing polyaminobismaleimide compound (B1))
The component (B1) can be produced, for example, by reacting the component (b1) and the component (b2) in an organic solvent.
When the component (b1) and the component (b2) are reacted to produce the polyaminobismaleimide compound (B1), a reaction catalyst can be used if necessary. The reaction catalyst is not limited, for example, an acidic catalyst such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; triphenylphosphine and the like. Phosphorus catalyst and the like. One of these may be used alone, or two or more thereof may be used in combination. The amount of the reaction catalyst to be blended is not particularly limited, but for example, 0.01 to 5 parts by mass may be used with respect to 100 parts by mass of the total amount of the component (b1) and the component (b2).

The above polyaminobismaleimide compound is obtained by charging a predetermined amount of the component (b1), the component (b2), and if necessary other components into a synthetic kettle, and carrying out a Michael addition reaction between the component (b1) and the component (b2). The reaction conditions in this step are not particularly limited, but for example, the reaction temperature is preferably 50 to 160 ° C., and the reaction time is preferably 1 to 10 hours from the viewpoint of workability such as reaction rate and suppression of gelation. ..
Further, in this step, the solid content concentration and the solution viscosity of the reaction raw material can be adjusted by adding or concentrating the organic solvent. 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, for example. 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 400 to 10,000, more preferably 500 to 5,000, still more preferably 600 to 2,000, and particularly preferably. It is 700 to 1,500. The weight average molecular weight of the polyaminobismaleimide compound (B1) is measured by gel permeation chromatography (GPC) in terms of polystyrene.

(Contents of component (A) and component (B), and their content ratio)
In the resin composition of the present embodiment, the content of the component (A) is not particularly limited, but from the viewpoint of the dielectric property in the high frequency band of 10 GHz band or higher, the total of the resin components in the resin composition is 100 parts by mass. On the other hand, it is preferably 1 part by mass or more, more preferably 1 to 20 parts by mass, further preferably 2 to 10 parts by mass, and particularly preferably 3 to 7 parts by mass.
Here, in the present specification, the "resin component" refers to the component (A), the component (B), the component (C), and the component (D) arbitrarily used. That is, when the resin composition does not contain the component (D), the "resin component" refers to the component (A), the component (B) and the component (C), and the resin composition contains the component (D). In the case, the "resin component" includes (A) component, (B) component, (C) component and (D) component.
The content of the component (B) is not particularly limited, but is preferably 10 with respect to 100 parts by mass of the total resin component in the resin composition from the viewpoint of dielectric properties and moldability in a high frequency band of 10 GHz band or higher. It is ~ 90 parts by mass, more preferably 20 to 80 parts by mass, further preferably 30 to 70 parts by mass, and particularly preferably 35 to 60 parts by mass.
The content ratio of the component (A) to the component (B) [(A) / (B)] is not particularly limited, but is preferably 1/99 to 80/20, more preferably 3/97 to 75 in terms of mass ratio. / 25, more preferably 5/95 to 70/30, even more preferably 5/95 to 50/50, particularly preferably 5/95 to 20/80, and most preferably 5/95 to 15/85. When the content ratio [(A) / (B)] is 1/99 or more, excellent dielectric properties tend to be obtained in the high frequency band of 10 GHz band or more, and when it is 80/20 or less, heat resistance, It tends to be excellent in moldability and processability.

<Crosslinking agent (C)>
The cross-linking agent (C) is a cross-linking agent having two or more ethylenically unsaturated bonds.
By containing the cross-linking agent (C), the resin composition of the present embodiment is particularly excellent in heat resistance and dielectric properties. The cause is not clear, but it is expected as follows.
The polyphenylene ether derivative (A) contained in the resin composition of the present embodiment has an ethylenically unsaturated bond as a reactive group and reacts with the components (A) or with the component (B) to form a cured product. What you get. However, since the component (A) is a polymer, miscibility with other components cannot be sufficiently obtained, and the ethylenically unsaturated bond serving as a reaction point is partly located at the end of the molecular chain or the like. Due to its presence, it may not be sufficiently reactive with other reactive groups. In the resin composition of the present embodiment, by applying the cross-linking agent (C), the ethylenically unsaturated bond (derived from the cross-linking agent (C)) is placed in the vicinity of the ethylenically unsaturated bond of the component (A). It is expected that the probability of existence of the (A) component will increase, and an environment in which the ethylenically unsaturated bond of the component (A) will easily react will be created. As a result, it is presumed that the reactivity of the component (A) was improved as compared with the conventional case, and excellent heat resistance and dielectric properties were obtained. Furthermore, it is presumed that the application of the cross-linking agent (C) made it possible to further refine the three-dimensional cross-linked structure of the formed cured product, and further excellent heat resistance and dielectric properties were obtained. Will be done.

The ethylenically unsaturated bond contained in the component (C) is, for example, an unsaturated aliphatic hydrocarbon group such as a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group; a maleimide group, (meth). It is an unsaturated bond contained in a substituent containing a hetero atom such as an acryloyl group. Among these, the component (C) preferably has an ethylenically unsaturated bond as the unsaturated aliphatic hydrocarbon group, preferably as a vinyl group, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. More preferred.

The number of ethylenically unsaturated bonds contained in one molecule of the component (C) is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, from the viewpoint of obtaining excellent heat resistance.

Examples of the component (C) include 1,2,4-trivinylcyclohexane, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and triethylene glycol divinyl ether. , Trimethylolpropantrivinyl ether, pentaerythritol tetravinyl ether, divinylbenzene, divinylbiphenyl, 1,3-bis (vinyloxy) adamantan, 1,3,5-tris (vinyloxy) adamantan, vinylcyclohexene, 1,2-vinyl group A monomer or polymer having two or more ethylenically unsaturated bonds as a vinyl group, such as polybutadiene having two or more, butadiene-styrene copolymer having two or more 1,2-vinyl groups; diallyl phthalate, triallyl triyl. Meritate, Diethylene Glycolbisallyl Carbonate, Trimethylol Propane Diallyl Ether, Trimethylol Propanetriallyl Ether, Pentaerythritol Triallyl Ether, Pentaerythritol Tetraallyl Ether, Triallyl Cyanurate, Triallyl Isocyanurate, Dialyl Monobenzyl Isocyanurate, Bisphenol S diallyl ether, 1,3-bis (allyloxy) adamantan, 1,3,5-tris (allyloxy) adamantan, diallyl ether, bisphenol A diallyl ether, 2,5-diallylphenol allyl ether, novolakphenol allyl ether, A monomer or polymer having two or more ethylenically unsaturated bonds as an allylic group, such as allylated polyphenylene oxide; Compounds having a saturated bond as a diisopropenyl group; examples thereof include diene compounds having two or more ethylenically unsaturated bonds such as 1,5-hexadiene, 1,9-decadien, and dicyclopentadiene.
Among these, a polymer having two or more ethylenically unsaturated bonds as a vinyl group is preferable from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, and 1,2-vinyl groups are preferable. Polybutadiene having two or more, butadiene-styrene copolymer having two or more 1,2-vinyl groups is more preferable, and polybutadiene having two or more 1,2-vinyl groups is further preferable.
In addition, in this specification, when it simply describes as "polybutadiene", it means a butadiene homopolymer. That is, as the component (C), a butadiene homopolymer having two or more 1,2-vinyl groups is preferable.
As the component (C), one type may be used alone, or two or more types may be used in combination.

When the component (C) is polybutadiene having two or more 1,2-vinyl groups, the content of the structural unit having a 1,2-vinyl structure with respect to all the structural units derived from butadiene constituting the polybutadiene [hereinafter. , Vinyl group content may be abbreviated. ] Is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 85 mol% or more. From the same viewpoint, the polybutadiene having two or more 1,2-vinyl groups is preferably a 1,2-polybutadiene homopolymer.

The number average molecular weight of a polymer having two or more ethylenically unsaturated bonds, preferably polybutadiene having two or more 1,2-vinyl groups, has compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. From this point of view, it is preferably 500 to 10,000, more preferably 800 to 5,000, and even more preferably 1,000 to 3,500. Further, from the viewpoint of compatibility, it may be 3,000 or less, or 2,500 or less. The number average molecular weight of a polymer having two or more ethylenically unsaturated bonds can be measured by the method described in Examples.

In the resin composition of the present embodiment, the content of the component (C) is not particularly limited, but from the viewpoint of obtaining excellent heat resistance and the dielectric property in the high frequency band of 10 GHz band or higher, the resin composition is contained. It is preferably 5 to 60 parts by mass, more preferably 7 to 40 parts by mass, still more preferably 10 to 30 parts by mass, and particularly preferably 13 to 20 parts by mass with respect to 100 parts by mass of the total resin components of.

<Other ingredients>
The resin composition of the present embodiment may further contain other components. As other components, for example, the styrene-based thermoplastic elastomer (D) [hereinafter, may be abbreviated as the component (D). ], Inorganic filler (E) [Hereinafter, it may be abbreviated as the component (E). ], Curing Accelerator (F) [Hereinafter, it may be abbreviated as the component (F). ] And the flame retardant (G) [hereinafter, may be abbreviated as the component (G). ], One or more selected from. By containing these, various characteristics when the laminated board is formed can be further improved. However, the resin composition of the present embodiment does not contain one or more selected from the component (D), the component (E), the component (F) and the component (G) according to the desired performance. You may.
Hereinafter, these components will be described in detail.

（式中、Ｒ^ｄ１は水素原子又は炭素数１〜５のアルキル基であり、Ｒ^ｄ２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。）(Styrene-based thermoplastic elastomer (D))
By containing the styrene-based thermoplastic elastomer (D) in the resin composition of the present embodiment, the dielectric properties, moldability, adhesion to the conductor, solder heat resistance, glass transition temperature, etc. in the high frequency band of 10 GHz band or higher can be determined. The coefficient of thermal expansion and flame retardancy are good, and the balance between them tends to be good.
The component (D) is not particularly limited as long as it is a thermoplastic elastomer having a structural unit (see below) derived from a styrene compound represented by the following general formula (d-1), and the structural unit (R) derived from styrene. ^It may be a thermoplastic elastomer having d1 = hydrogen atom, k = 0).

(In the formula, R ^d1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ^d2 is an alkyl group having 1 to 5 carbon atoms. K is an integer of 0 to 5.)

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^d1 and R ^d2 include a methyl group, an ethyl group, an n-propyl group and the like, and an alkyl group having 1 to 3 carbon atoms may be used. It may be a group.
k may be an integer of 0 to 2, 0 or 1, or 0.

Examples of the structural unit other than the structural unit derived from the styrene compound (D) include a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, a structural unit derived from maleic anhydride, and the like. ..
As the component (D), one type may be used alone, or two or more types may be used in combination.
The structural unit derived from butadiene and the structural unit derived from isoprene may be hydrogenated. When hydrogenated, the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed, and the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed.

As the component (D), hydrogenation of a styrene-butadiene-styrene block copolymer is performed from the viewpoints of dielectric properties in a high frequency band of 10 GHz or higher, adhesion to a conductor, heat resistance, glass transition temperature and thermal expansion coefficient. One or more selected from the group consisting of (SEBS, SBBS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS) and styrene-maleic anhydride copolymer (SMA) is preferable, and styrene-. One or more selected from the group consisting of the hydrogenated product of the butadiene-styrene block copolymer (SEBS) and the hydrogenated product of the styrene-isoprene-styrene block copolymer (SEPS) is more preferable, and styrene-butadiene-styrene is more preferable. A block copolymer hydrogenated product (SEBS) is more preferred.

In the above SEBS, the content of structural units derived from styrene [hereinafter, may be abbreviated as styrene content. ] Is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, from the viewpoints of dielectric properties in a high frequency band of 10 GHz band or higher, adhesion to a conductor, heat resistance, glass transition temperature and coefficient of thermal expansion. , More preferably 15 to 70% by mass, and particularly preferably 20 to 50% by mass. 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 is 0.5 to 20 g / 10 min. It may be 15 g / 10 min.
As commercial products of SEBS, for example, Tough Tech (registered trademark) H series and M series manufactured by Asahi Kasei Corporation, Septon (registered trademark) series manufactured by Kuraray Co., Ltd., and Kraton (registered trademark) G manufactured by Kraton Polymer Japan Co., Ltd. Examples include the polymer series.

The weight average molecular weight (Mw) of the component (D) is not particularly limited, but is preferably 12,000 to 1,000,000, more preferably 30,000 to 500,000, still more preferably 50,000 to 120, 000, particularly preferably 70,000 to 100,000. The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) in terms of polystyrene.

When the resin composition of the present embodiment contains the component (D), the content of the component (D) is not particularly limited, but the dielectric property in the high frequency band of 10 GHz band or more and the adhesiveness to the conductor. From the viewpoint of heat resistance, glass transition temperature and coefficient of thermal expansion, preferably 5 to 60 parts by mass, more preferably 10 to 55 parts by mass, based on 100 parts by mass of the total components (A) to (D). It is preferably 15 to 50 parts by mass, particularly preferably 20 to 45 parts by mass, and most preferably 25 to 40 parts by mass. When the content of the component (D) is 5 parts by mass or more, the dielectric properties and moisture absorption resistance in the high frequency band of 10 GHz band or more tend to be better, and when it is 60 parts by mass or less, the heat resistance tends to be better. , Moldability, processability and flame retardancy tend to be better.

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

When the resin composition of the present embodiment contains the component (E), the content of the component (E) in the resin composition is not particularly limited, but the thermal expansion coefficient, elasticity, heat resistance and difficulty. From the viewpoint of flammability, it is preferably 5 to 70 parts by mass, more preferably 15 to 65 parts by mass, still more preferably 20 to 60 parts by mass, particularly preferably 20 to 60 parts by mass, based on 100 parts by mass of the total resin components in the resin composition. Is 30 to 55 parts by mass, most preferably 40 to 50 parts by mass.

When the component (E) is used, a coupling agent is used in combination as necessary for the purpose of improving the dispersibility of the component (E) and the adhesion between the component (E) and the organic component in the resin composition. You may. The coupling agent is not particularly limited, and for example, a silane coupling agent or a titanate coupling agent can be appropriately selected and used. One type of coupling agent may be used alone, or two or more types may be used in combination. Further, the amount of the coupling agent used is not particularly limited, and may be, for example, 0.1 to 5 parts by mass or 0.5 to 3 parts by mass with respect to 100 parts by mass of the component (E). .. Within this range, there is little deterioration in various characteristics, and there is a tendency that the features of the use of the above component (E) can be effectively exhibited.
When a coupling agent is used, a so-called integral blend treatment method may be used in which the component (E) is blended in the resin composition and then the coupling agent is added, but the coupling agent is coupled to the inorganic filler in advance. A method using an inorganic filler in which the agent is surface-treated by a dry method or a wet method is preferable. By adopting this method, the features of the component (E) can be expressed more effectively.

When the component (E) is used in the present embodiment, the component (E) is used as a slurry in which the component (E) is previously dispersed in an organic solvent, if necessary, for the purpose of improving the dispersibility of the component (E) in the resin composition. be able to. The organic solvent used for slurrying the component (E) is not particularly limited, and for example, the organic solvent exemplified in the above-mentioned production step of the component (A1) can be applied. One of these may be used alone, or two or more thereof may be used in combination. Among these, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable from the viewpoint of dispersibility. The solid content (nonvolatile content) concentration of the slurry is not particularly limited, but is, for example, 50 to 80% by mass and 60 to 80% by mass from the viewpoint of sedimentation and dispersibility of the inorganic filler (E). There may be.

(Curing accelerator (F))
By containing the curing accelerator (F) in the resin composition of the present embodiment, the curability of the resin composition is improved, and the dielectric properties, heat resistance, adhesion to the conductor in the high frequency band of 10 GHz band or higher, There is a tendency that the elastic modulus and the glass transition temperature can be improved.
The component (F) includes, for example, an acidic catalyst such as p-toluenesulfonic acid; an amine compound such as triethylamine, pyridine, and tributylamine; methylimidazole, phenylimidazole, isocyanate masked imidazole (for example, hexamethylenediisocyanate resin and 2-ethyl). Imidazole compounds such as -4-methylimidazole addition reaction products); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexin-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, α, α'-bis ( Organic peroxides such as t-butylperoxy) diisopropylbenzene; carboxylates such as manganese, cobalt and zinc can be mentioned. One of these may be used alone, or two or more thereof may be used in combination. Among these, imidazole compounds, organic peroxides, and carboxylates may be used from the viewpoints of heat resistance, glass transition temperature, and storage stability, and from the viewpoints of heat resistance, glass transition temperature, elasticity, and thermal expansion coefficient. Therefore, the imidazole compound may be used in combination with an organic peroxide or a carboxylate. Further, α, α'-bis (t-butylperoxy) diisopropylbenzene may be selected among the organic peroxides, and manganese naphthenate may be selected among the carboxylates.

When the resin composition of the present embodiment contains the component (F), the content of the component (F) is not particularly limited, but for example, with respect to a total of 100 parts by mass of the resin components in the resin composition. It is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, still more preferably 0.1 to 6 parts by mass, and particularly preferably 0.5 to 5 parts by mass. When the content of the component (F) is in the above range, better heat resistance and storage stability tend to be obtained.

(Flame retardant (G))
By containing the flame retardant (G) in the resin composition of the present embodiment, the flame retardancy of the resin composition tends to be improved.
Examples of the component (G) include 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. As the flame retardant (G), one type may be used alone, or two or more types may be used in combination. Further, a flame retardant aid may be contained if necessary.

-Phosphorus flame retardant-
The phosphorus-based flame retardant is not particularly limited as long as it contains a phosphorus atom among those generally used as a flame retardant, and may be an inorganic phosphorus-based flame retardant or an organic-based flame retardant. It may be a phosphorus flame retardant. From the viewpoint of environmental problems, those containing no halogen atom are preferable. From the viewpoints of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy, an organic phosphorus flame retardant may be used.
Examples of the inorganic phosphorus-based flame retardant include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. ; Phosphoric acid; phosphine oxide and the like.
Examples of the organic phosphorus-based flame retardant include aromatic phosphoric acid ester, mono-substituted phosphonic acid diester, 2-substituted phosphinic acid ester, metal salt of 2-substituted phosphinic acid, organic nitrogen-containing phosphorus compound, and cyclic organic phosphorus compound. Can be mentioned. Among these, aromatic phosphoric acid ester compounds and metal salts of disubstituted phosphinic acid are preferable. Here, the metal salt may be any of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt, and a zinc salt, and may be an aluminum salt. Among the organic phosphorus-based flame retardants, aromatic phosphoric acid esters are preferable.

Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresildiphenyl phosphate, cresildi-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 can be mentioned.
Examples of the mono-substituted phosphonic acid diester include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
Examples of the disubstituted phosphinic acid ester include phenyl diphenylphosphinate and methyl diphenylphosphinate.
Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, and a metal salt of diarylphosphinic acid. These metal salts may be any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt, and aluminum salt may be selected.
Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicredylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.
As the cyclic organic phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- Examples thereof include phosphaphenanthrene-10-oxide.
Among these, aromatic phosphate ester and disubstituted phosphine are preferable, and aluminum salts of 1,3-phenylenebis (di-2,6-xylenyl phosphate) and dialkylphosphinic acid are preferable.

-Metal hydrate-
Examples of the metal hydrate include aluminum hydroxide hydrate and magnesium hydroxide hydrate. One of these may be used alone, or two or more thereof may be used in combination. The metal hydroxide may also correspond to an inorganic filler, but if it is a material that can impart flame retardancy, it is classified as a flame retardant.
-Halogen flame retardant-
Examples of the halogen-based flame retardant include chlorine-based flame retardants and brominated flame retardants. Examples of the chlorine-based flame retardant include chlorinated paraffin and the like.

When the resin composition of the present embodiment contains the component (G), when a phosphorus-based flame retardant is used as the component (G), the content of the phosphorus-based flame retardant in the resin composition is not particularly limited. However, for example, with respect to 100 parts by mass of the total resin components in the resin composition, in terms of phosphorus atoms, it is preferably 0.2 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably. It is 0.5 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, and when it is 5 parts by mass or less, better moldability and high adhesion to the conductor are obtained. Excellent heat resistance and high glass transition temperature tend to be obtained.

If necessary, the resin composition of the present embodiment includes a thermoplastic resin other than the above components, a resin material such as an elastomer, a coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, and ultraviolet rays. Absorbents, pigments, colorants, flame retardant aids, lubricants and the like can be appropriately selected and contained. One of these may be used alone, or two or more thereof may be used in combination. The amount of these 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 embodiment may contain an organic solvent from the viewpoint of facilitating handling by diluting and from the viewpoint of facilitating the production of a prepreg described later. The resin composition containing an organic solvent may be generally referred to as a resin varnish or a varnish.
The organic solvent is not particularly limited, and is, for example, an alcohol solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran. Etc. Ether-based solvent; Aromatic solvent such as toluene, xylene, mesityrene; Nitrogen atom-containing solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Sulfur atom-containing solvent such as dimethylsulfooxide; Examples include system solvents.
Among these, from the viewpoint of solubility, an alcohol solvent, a ketone solvent, and a nitrogen atom-containing solvent are preferable, a ketone solvent is more preferable, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are further preferable, and methyl ethyl ketone is particularly preferable.
As the organic solvent, one type may be used alone, or two or more types may be used in combination.

When the resin composition of the present embodiment contains an organic solvent, the solid content concentration thereof is, for example, 30 to 90% by mass, 35 to 80% by mass, or 40 to 60% by mass. May be good. By using a resin composition having a solid content concentration within the above range, the handleability is facilitated, the impregnation property into the base material and the appearance of the produced prepreg are good, and the solid resin in the prepreg described later is used. The component concentration tends to be easily adjusted, and the production of a prepreg having a desired thickness tends to be easier.

In the resin composition of the present embodiment, the component (A), the component (B), the component (C), and other components used in combination as necessary are mixed by a known method to obtain the resin composition of the present embodiment. Obtainable. At this time, each component may be dissolved or dispersed while stirring. Conditions such as mixing order, temperature, and time are not particularly limited and can be set arbitrarily.

The resin composition of the present embodiment has good compatibility and tends not to form a precipitate even if left for one day. Further, in a mode having better compatibility, there is a tendency that no precipitate is formed even if left for one week (however, phase separation may occur), and in a mode having further excellent compatibility, there is a tendency that no precipitate is formed. Even if left for a week, there is a tendency that even phase separation does not occur.

The dielectric constant (Dk) of the cured product of the resin composition of the present embodiment (a cured product of a laminate and a resin film that does not contain a fiber base material such as glass cloth) at 10 GHz is preferably 3.0 or less, more preferably. It is 2.8 or less. The smaller the dielectric constant (Dk) is, the more preferable it is, and the lower limit thereof is not particularly limited. However, in consideration of the balance with other physical properties, for example, it may be 2.4 or more, or 2.6 or more. You may.
The dielectric positive contact (Df) of the cured product of the resin composition of the present embodiment (a laminated body not containing a fiber base material such as glass cloth and a cured product of a resin film) at 10 GHz is preferably 0.0055 or less, more preferably 0.0055 or less. It is 0.0050 or less, more preferably 0.0045 or less, particularly preferably 0.0035 or less, and most preferably 0.0030 or less. The smaller the dielectric loss tangent (Df) is, the more preferable it is, and the lower limit value thereof is not particularly limited. However, in consideration of the balance with other physical properties, for example, it may be 0.0015 or more, and 0.0020 or more. It may be 0.0023 or more.
The dielectric constant (Dk) and the dielectric loss tangent (Df) are values based on the cavity resonator perturbation method, and more specifically, they are values measured by the method described in Examples. Further, in the present specification, the term "dielectric constant" means the relative permittivity.

[Prepreg]
The present invention also provides a prepreg containing the resin composition of the present embodiment and a sheet-like fiber reinforced base material. The prepreg is formed by using the resin composition of the present embodiment and the sheet-shaped fiber reinforced base material. For example, the resin composition of the present embodiment is impregnated or coated on the sheet-shaped fiber reinforced base material and dried. It can be obtained by letting it. More specifically, for example, the prepreg of the present embodiment can be produced by heating and drying in a drying oven at a temperature of 80 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage). can. The amount of the resin composition used can be determined so that the solid content concentration derived from the resin composition in the prepreg after drying is 30 to 90% by mass. By setting the solid content concentration in the above range, better moldability tends to be obtained when the laminated board is formed.

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

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

[Resin film]
The present invention also provides a resin film containing the resin composition of the present embodiment. For example, the resin film can be produced by applying a resin composition containing an organic solvent, that is, a resin varnish, to a support and heat-drying the support. Examples of the support include a polyolefin film such as polyethylene, polypropylene, and polyvinyl chloride; a polyester film such as polyethylene terephthalate (hereinafter, also referred to as “PET”) and polyethylene naphthalate; and various plastics such as a polycarbonate film and a polyimide film. Examples include film. Further, as the support, a metal foil such as a copper foil or an aluminum foil, a paper pattern, or the like may be used. The support may be subjected to surface treatment such as matte treatment or corona treatment. Further, the support may be subjected to a mold release treatment with a silicone resin-based mold release agent, an alkyd resin-based mold release agent, a fluororesin-based mold 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 for example, a coating device known to those skilled in the art such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater can be used. These coating devices may be appropriately selected depending on the film thickness.
The drying temperature and drying time may be appropriately determined according to the amount of the organic solvent used, the boiling point of the organic solvent used, and the like. For example, in the case of a resin varnish containing an organic solvent of about 40 to 60% by mass, the drying temperature and the drying time may be determined. A resin film can be suitably formed by drying at 50 to 150 ° C. for about 3 to 10 minutes.

[Laminated board]
It is also possible to manufacture a laminated board containing the prepreg and the metal foil of the present embodiment. Specifically, the metal foil is arranged on one side or both sides of one prepreg of the present embodiment, or the metal foil is arranged on one side or both sides of the prepreg obtained by stacking two or more prepregs of the present embodiment. Next, a laminated plate can be obtained by heat and pressure molding. A laminated board having a metal foil is sometimes referred to as a metal-clad laminated board.
The metal of the metal foil is not particularly limited as long as it is used for electrical insulating material, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium. , Chromium, or an alloy containing one or more of these metal elements, preferably copper and aluminum, and more preferably copper.
The conditions for heat and pressure molding are not particularly limited, but for example, the temperature can be 100 to 300 ° C., the pressure can be 0.2 to 10 MPa, and the time can be 0.1 to 5 hours. Further, for the heat and pressure molding, a method of holding the vacuum state for 0.5 to 5 hours using a vacuum press or the like can be adopted.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present embodiment contains one or more selected from the group consisting of the prepreg of the present embodiment, the resin film of the present embodiment, and the laminated board of the present embodiment. The multilayer printed wiring board of the present embodiment is drilled by a known method using one or more selected from the group consisting of the prepreg of the present embodiment, the resin film of the present embodiment, and the laminated board of the present embodiment. It can be manufactured by performing circuit forming processing such as processing, metal plating processing, etching of metal foil, and multi-layer bonding processing.

The resin composition, prepreg, laminated board, resin film and multilayer printed wiring board of the present embodiment can be suitably used for 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 the scope of the present invention is not limited to these embodiments. The present invention can be carried out in various aspects different from the above-described embodiment without departing from the gist thereof.

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

In each example, the number average molecular weight was measured by the following procedure.
(Measurement method of number average molecular weight)
The number average molecular weight was converted from the calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, Product name] was used for approximation by a cubic equation. The measurement conditions of GPC 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 Guardcolum 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

（式中、Ｘ^ａ２は２価の有機基であり、上記一般式（ａ１−５）中のＸ^ａ２と同様に説明される。）[Production Example A-1: Production of Polyphenylene Ether Derivative (A-1)]
Toluene, polyphenylene ether "Zylon (registered trademark) S203A" (trade name, manufactured by Asahi Kasei Co., Ltd., number average molecular weight) in a glass flask container with a volume of 2 L that can be heated and cooled equipped with a thermometer, a reflux condenser, and a stirrer. = 12,000), and an allyl group-containing compound represented by the following general formula (1) [hereinafter, may be abbreviated as tetraallyl bisphenols. ] Was added and dissolved with stirring at 90 to 100 ° C. The amount of toluene used was such that the reaction concentration was 35% by mass.

(In the formula, X ^a2 is a divalent organic group and is described in the same manner as ^{X a2} in the above general formula (a1-5).)

After visually confirming that the allyl group-containing compound was dissolved, t-butylperoxyisopropyl monocarbonate and manganese octylate were added, and the solution was redistributed at a solution temperature of 90 to 100 ° C. for 6 hours, and then brought to 40 ° C. After cooling, a polyphenylene ether derivative (A-1) having an allyl group at the molecular terminal was obtained. When a small amount of this reaction solution was taken out and GPC measurement (polystyrene conversion, eluent: tetrahydrofuran) was performed, the double peak derived from tetraallyl bisphenols became a single peak, and the number average molecular weight of the polyphenylene ether compound was 4,200. there were.
The amount of each component used is shown in Table 1.

[Production Example A-2: Production of Polyphenylene Ether Derivative (A-2)]
Toluene, polyphenylene ether "Zylon (registered trademark) S202A" (trade name, manufactured by Asahi Kasei Co., Ltd., number average molecular weight) in a glass flask container with a volume of 2 L that can be heated and cooled equipped with a thermometer, a reflux condenser, and a stirrer. = 16,000) and p-aminophenol were added and dissolved with stirring at 90 ° C. The amount of toluene used was such that the reaction concentration was 35% by mass.
After visually confirming that it was dissolved, t-butylperoxyisopropyl monocarbonate and manganese naphthenate were added, and the solution was redistributed at a solution temperature of 90 ° C. for 4 hours, then cooled to 70 ° C. and first at the molecular terminal. A polyphenylene ether derivative having a secondary amino group was obtained. Here, when a small amount of this reaction solution was taken out and GPC measurement (polystyrene conversion, eluent: tetrahydrofuran) was performed, the peak derived from p-aminophenol disappeared, and the number average molecular weight of the polyphenylene ether compound was about 6, It was 200. The reaction solution taken out a small amount of methanol / benzene mixed solvent (weight ratio = 1: 1) was added dropwise, was subjected to FT-IR measurement of solids were purified by reprecipitation, 3,400 cm ^-1 vicinity of The appearance of a peak derived from the primary amino group was confirmed.

Next, 2,2'-bis [4- (4-maleimide phenoxy) phenyl] propane and propylene glycol monomethyl ether (amount at which the reaction concentration becomes 30% by mass) are added to the above reaction solution, and the solution is stirred with stirring. The polyphenylene ether derivative (A-2) was produced by raising the temperature, reacting at 120 ° C. for 4 hours, cooling and filtering through a 200 mesh filter.
Taking out a small amount of the reaction solution, and the same re-precipitation, it carried out an FT-IR measurements of the purified solids, loss of primary amino groups from a peak in the vicinity of 3,500cm ^-1, 1,700~1,730cm ^{The appearance of a -1} carbonyl group was confirmed. Moreover, when GPC (the same conditions as above) of this solid substance was measured, the number average molecular weight was about 6,500.
The amount of each component used is shown in Table 1.

[Production Example B-1: Production of Polyaminobismaleimide Compound (B-1)]
2,2-Bis [4- (4-maleimidephenoxy) phenyl] propane as the maleimide compound (b1) in a 1 L volume glass flask container equipped with a thermometer, a reflux cooling tube, and a stirrer and capable of heating and cooling. , 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, as diamine compound (b2), 4,4'-[1,3-phenylenebis (1-methylethylidene)] A polyaminobismaleimide compound (B) having a number average molecular weight of 800 was added by adding bisaniline and propylene glycol monomethyl ether, keeping the liquid temperature at 120 ° C., reacting for 3 hours with stirring, and then cooling and filtering through a 200 mesh filter. -1) was manufactured.
The amount of each component used is shown in Table 2.

[Preparation of resin composition]
Examples 1-5, Comparative Example 1
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.
The resin composition obtained in each example was applied to a PET film having a thickness of 38 μm (manufactured by Teijin Limited, trade name: G2-38), and then heated and dried at 170 ° C. for 5 minutes to obtain a resin in a B stage state. A film was made. This resin film was peeled off from the PET film and then pulverized to obtain a resin powder. Next, the above resin powder was put into a Teflon (registered trademark) sheet stamped to a size of 1 mm in thickness × 50 mm in length × 35 mm in width, and a low profile copper foil (Furukawa Denki Kogyo Co., Ltd.) having a thickness of 18 μm was placed above and below the sheet. A company-made product, trade name: BF-ANP18) is placed so that the M surface is in contact with the charged resin powder, and is heat-press molded under the conditions of a temperature of 230 ° C., a pressure of 2.0 MPa, and a time of 120 minutes to form a resin composition. The object was cured to prepare a resin plate with double-sided copper foil (resin plate thickness: 1 mm).

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

(1. Evaluation of compatibility of resin composition)
The resin compositions obtained in each example were visually observed, and the compatibility (macroscopic phase separation and the presence or absence of precipitates) was evaluated according to the following criteria.
A: There was no macroscopic phase separation and no precipitate even after being left for 1 week or longer.
B: There was no change even when left for 1 day, but when left for 3 days or more, there was no precipitate, but macroscopic (macro) phase separation occurred slightly.
C: When left for 1 day, there was no precipitate, but macroscopic phase separation occurred.
D: After leaving for 1 day, precipitates were confirmed.

(2. Evaluation of the dielectric properties (dielectric constant and dielectric loss tangent) of the resin plate)
Evaluation of 2 mm x 50 mm from the evaluation substrate from which the copper foil was removed by immersing the resin plate with double-sided copper foil obtained in each example in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Company, Inc.), which is a copper etching solution. A substrate was prepared.
The evaluation substrate was measured for dielectric constant (Dk) and dielectric loss tangent (Df) in the 10 GHz band according to the cavity resonator perturbation method.

(3. Method for measuring thermal expansion rate and glass transition temperature)
The coefficient of thermal expansion (plate thickness direction, temperature range: 30 to 120 ° C.) and glass transition temperature (Tg) are determined by using a 5 mm square test piece obtained by etching the copper foil on both sides of a resin plate with double-sided copper foil. It was measured by a measuring device (TMA) [manufactured by TA Instruments Japan Co., Ltd., Q400 (model number)] in accordance with the IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard.

The materials in Table 3 are as follows.
[(A) component]
-Polyphenylene ether derivatives (A-1) and (A-2): The polyphenylene ether derivatives (A-1) and (A-2) produced in Production Examples A-1 and A-2 were used.

[(B) component]
-Polyaminobismaleimide compound (B-1): The polyaminobismaleimide compound (B-1) produced in Production Example B-1 was used.

[(C) component]
-Ricon257: butadiene-styrene copolymer (manufactured by CRAY VALLEY, trade name, mass ratio (butadiene / styrene): 65/35)
B-1000: 1,2-polybutadiene homopolymer, number average molecular weight = 1,200, vinyl group content = 85% or more (manufactured by Nippon Soda Co., Ltd., trade name)
B-2000: 1,2-polybutadiene homopolymer, number average molecular weight = 2,100, vinyl group content = 90% or more (manufactured by Nippon Soda Co., Ltd., trade name)
B-3000: 1,2-polybutadiene homopolymer, number average molecular weight = 3,200, vinyl group content = 90% or more (manufactured by Nippon Soda Co., Ltd., trade name)

[(D) component]
-Clayton (registered trademark) G1652: Hydrogenated styrene-based thermoplastic elastomer (SEBS), melt flow rate 5.0 g / 10 min, styrene content 30%, hydrogenation rate 100% (manufactured by Kraton Polymer Japan Co., Ltd., trade name)

[(E) component]
-Silica: Spherical fused silica, average particle size = 0.5 μm

[(F) component]
-Α, α'-bis (t-butylperoxy) diisopropylbenzene-G-8009L: Isocyanate mask imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole) (Daiichi Kogyo Seiyaku Co., Ltd.) Made, product name)

[(G) component]
OP-935: Aluminum salt of dialkylphosphinic acid, metal salt of disubstituted phosphinic acid, phosphorus content: 23.5% by mass (manufactured by Clariant, trade name)
-1,3-Phenylenebis (di2,6-xylenyl phosphate), phosphorus content: 9.0% by mass

As is clear from the results shown in Table 3, in Examples 1 to 5 of this embodiment, the compatibility of the resin composition is good, and the cured product prepared by using these has good heat resistance. Excellent in dielectric properties in the high frequency band of 10 GHz band.
On the other hand, in Comparative Example 1, the glass transition temperature is low and the dielectric characteristics in the high frequency band of 10 GHz band are also insufficient.

The resin composition of the present invention has good compatibility, and the laminated board produced from the resin composition is particularly excellent in heat resistance and dielectric properties in a high frequency band of 10 GHz or higher, so that the frequency exceeds 6 GHz. It is useful for 5th generation mobile communication system (5G) antennas in which radio waves in the band are used and multi-layer printed wiring boards used in millimeter-wave radars in which radio waves in the frequency band of 30 to 300 GHz are used.

Claims (15)

(A) A polyphenylene ether derivative having an ethylenically unsaturated bond-containing group and
(B) One or more selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof, and
(C) A cross-linking agent having two or more ethylenically unsaturated bonds,
A resin composition comprising. The resin composition according to claim 1, wherein the component (C) has the two or more ethylenically unsaturated bonds as a vinyl group. The resin composition according to claim 2, wherein the component (C) is polybutadiene having the two or more ethylenically unsaturated bonds as a 1,2-vinyl group. The resin composition according to claim 3, wherein the content of the structural unit having a 1,2-vinyl structure is 50 mol% or more with respect to all the structural units derived from butadiene constituting the polybutadiene. The resin composition according to claim 3 or 4, wherein the polybutadiene has a number average molecular weight of 500 to 10,000. The resin composition according to any one of claims 1 to 5, wherein the content of the component (C) is 5 to 60 parts by mass with respect to 100 parts by mass of the total of the resin components in the resin composition. .. The resin composition according to any one of claims 1 to 6, wherein the component (A) contains a structure represented by the following general formula (a1-1).

^{(Wherein, R a1} is .n1 an ethylenically unsaturated bond-containing group having 2 to 10 carbon atoms is 1 or 2, n2 is 0 or 1. * Is the point of attachment to other structures show.) The resin composition according to any one of claims 1 to 7, wherein the component (A) contains a structure represented by the following general formula (a1-2).

(In the formula, ^Ra2 and ^Ra3 are independently ethylenically unsaturated bond-containing groups having 2 to 10 carbon atoms. * Indicates a bond position to another structure.) The resin composition according to any one of claims 1 to 8, wherein the number of ethylenically unsaturated bond-containing groups in the component (A) is two or more. Any one of claims 1 to 9, wherein the component (B) has a structural unit derived from a maleimide compound (b1) having two or more N-substituted maleimide groups and a structural unit derived from a diamine compound (b2). The resin composition according to. A prepreg containing the resin composition according to any one of claims 1 to 10. A laminated board containing the prepreg according to claim 11 and a metal foil. A resin film containing the resin composition according to any one of claims 1 to 10. A multilayer printed wiring board containing at least one selected from the group consisting of the prepreg according to claim 11, the laminated board according to claim 12, and the resin film according to claim 13. A multilayer printed wiring board for a millimeter-wave radar, comprising one or more selected from the group consisting of the prepreg according to claim 11, the laminated board according to claim 12, and the resin film according to claim 13.