JP2022162795A - Resin composition, prepreg, laminate, resin film, multilayer printed wiring board, semiconductor package, method for producing resin composition and modified conjugated diene polymer - Google Patents

Abstract

To provide a resin composition having excellent dielectric properties in a high frequency band of 10 GHz or more, excellent compatibility and flame-retardancy and a method for producing the same, and provide a prepreg, a laminate, a resin film, a multilayer printed wiring board and a semiconductor package, as well as a modified conjugated diene polymer each of which includes the resin composition.SOLUTION: The present invention discloses a resin composition that contains (A) at least one selected from the group consisting of a maleimide compound having one or more N-substituted maleimide groups and a derivative thereof and (B) a modified conjugated diene polymer that results from a reaction between (b1) a conjugated diene polymer having a vinyl group in a side chain and (b2) a compound having a phosphorus atom and an ethylenically unsaturated bond, and a method for producing the same. There are also provided a prepreg, a laminate, a resin film, a multilayer printed wiring board and a semiconductor package, as well as a modified conjugated diene polymer each of which includes the resin composition.SELECTED DRAWING: None

Description

The present embodiment relates to a resin composition and its manufacturing method, a prepreg, a laminate, a resin film, a multilayer printed wiring board, a semiconductor package, and a modified conjugated diene polymer.

2. Description of the Related Art Mobile communication devices such as mobile phones, network infrastructure devices such as base stations, servers and routers, and electronic devices such as large computers use signals with higher speeds and larger capacities year by year. With the increasing speed and capacity of signals, substrate materials for printed wiring boards mounted on electronic devices have dielectric properties capable of reducing transmission loss of high-frequency signals (hereinafter sometimes referred to as "high-frequency properties"). ], that is, a low dielectric constant and a low dielectric loss tangent are required.
In recent years, in addition to the above-mentioned electronic devices, in the field of ITS (Intelligent Transport Systems) such as those related to automobiles and traffic systems, and in the field of indoor short-distance communication, new systems that handle high-frequency wireless signals have been put to practical use or planned for practical use. there is Therefore, it is expected that there will be an increasing need for substrate materials with excellent high-frequency characteristics for printed wiring boards used in these fields in the future.

In Patent Document 1, the object is to provide a thermosetting resin composition having a low dielectric loss tangent, a low thermal expansion, and excellent wiring embedding properties and flatness. A technique of blending a polybutadiene-based elastomer modified with an acid anhydride in a thermosetting resin composition containing a polyimide compound having two structural units derived from a maleimide compound and a structural unit derived from a diamine compound is disclosed. ing.

JP 2018-012747 A

By the way, in recent years, substrate materials are required to be applied to 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. It is For that purpose, it is necessary to develop a resin composition with further improved dielectric properties in the 10 GHz band or higher.
Maleimide compounds used as thermosetting resins are excellent in heat resistance and the like, but have room for improvement in dielectric properties due to the presence of highly polar groups. As a method for improving dielectric properties, it is effective to add a low-polarity component such as a polybutadiene-based elastomer to a resin composition containing a maleimide compound, as in the technique of Patent Document 1. However, components with low polarity, such as polybutadiene-based elastomers, may separate in the resin composition due to their low compatibility with maleimide compounds with high polarity. If such separation occurs, the effect of improving the dielectric characteristics cannot be sufficiently obtained, and various problems such as deterioration of quality stability and deterioration of handling due to bleeding out occur. In addition, since components with low polarity, such as polybutadiene-based elastomers, are easily combustible, there is also the problem that it is difficult to obtain sufficient flame retardancy.

In the technique of Patent Document 1, by introducing an acid anhydride as a polar group into a polybutadiene-based elastomer, compatibility with a maleimide compound is improved. However, the introduction of the acid anhydride increases the polarity of the polybutadiene-based elastomer, which inhibits the effect of improving the dielectric properties. Moreover, even by this method, it is difficult to solve the problem of deterioration of flame retardancy.
Therefore, with the technique disclosed in Patent Document 1, it is difficult to improve the dielectric properties while maintaining good compatibility and flame retardancy.

In view of such a current situation, the present embodiment provides a resin composition having excellent dielectric properties, compatibility and flame retardancy in a high frequency band of 10 GHz or higher, a method for producing the same, a prepreg using the resin composition, and a laminate An object of the present invention is to provide a board, a resin film, a multilayer printed wiring board, a semiconductor package, and a modified conjugated diene polymer.

The inventors of the present invention have studied to solve the above problems, and as a result, a modified conjugated diene polymer obtained by reacting a conjugated diene polymer having a vinyl group in a side chain with a compound having a phosphorus atom and an ethylenically unsaturated bond was added to the maleimide compound to solve the above problems.
That is, the present embodiment relates to the following [1] to [13].
[1] (A) one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof;
(B) a modified conjugated diene polymer obtained by reacting (b1) a conjugated diene polymer having a vinyl group in a side chain with a (b2) compound having a phosphorus atom and an ethylenically unsaturated bond;
A resin composition containing
[2] The resin composition according to [1] above, wherein the component (b2) is a compound having a phosphine oxide group and an ethylenically unsaturated bond.
[3] The resin composition according to [2] above, wherein the compound having a phosphine oxide group and an ethylenically unsaturated bond is a phosphine oxide group-containing (meth)acrylate compound.
[4] The resin composition according to any one of [1] to [3] above, wherein the component (b1) is polybutadiene having a 1,2-vinyl group.
[5] The resin composition according to any one of [1] to [4] above, further comprising a styrene elastomer.
[6] The component (A) is selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof, wherein the molecular structure contains a condensed ring of an aromatic ring and an aliphatic ring. The resin composition according to any one of [1] to [5] above, which is one or more.
[7] A prepreg containing the resin composition according to any one of [1] to [6] above.
[8] A laminate containing the prepreg according to [7] above and a metal foil.
[9] A resin film comprising the resin composition according to any one of [1] to [6] above.
[10] A multilayer printed wiring board containing one or more selected from the group consisting of the prepreg described in [7] above, the laminate described in [8] above, and the resin film described in [9] above. .
[11] A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to [10] above.
[12] A method for producing the resin composition according to any one of [1] to [6] above,
(A) one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof;
(B) a modified conjugated diene polymer obtained by reacting (b1) a conjugated diene polymer having a vinyl group in a side chain with a (b2) compound having a phosphorus atom and an ethylenically unsaturated bond;
A method for producing a resin composition by mixing
[13] A modified conjugated diene polymer obtained by reacting (b1) a conjugated diene polymer having a vinyl group in a side chain with (b2) a compound having a phosphorus atom and an ethylenically unsaturated bond.

According to the present embodiment, a resin composition having excellent dielectric properties, compatibility and flame retardancy in a high frequency band of 10 GHz or higher, a method for producing the same, a prepreg, a laminate, a resin film using the resin composition, Multilayer printed wiring boards and semiconductor packages and modified conjugated diene polymers can be provided.

In this specification, a numerical range indicated using "to" indicates a range including the numerical values before and after "to" as the minimum and maximum values, respectively.
For example, the notation of a numerical range “X to Y” (where X and Y are real numbers) means a numerical range that is greater than or equal to X and less than or equal to Y. In addition, the description of "X or more" in this specification means X and a numerical value exceeding X, and this also applies when the numerical values are different. In addition, the description “Y or less” in this specification means Y and a numerical value less than Y.
The lower and upper limits of any numerical range recited herein are optionally combined with the lower or upper limits of other numerical ranges, respectively.
In the numerical ranges described herein, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.

Each component and material exemplified in this specification may be used alone or in combination of two or more unless otherwise specified.
In the present specification, the content of each component in the resin composition refers to the content of the plurality of substances present in the resin composition when there are multiple substances corresponding to each component in the resin composition, unless otherwise specified. means the total amount of
As used herein, the term "resin composition" includes a mixture of each component described below and a product obtained by semi-curing the mixture.

As used herein, the term “solid content” refers to non-volatile content excluding volatile substances such as solvents. , starch syrup-like and wax-like ones are also included. Here, room temperature indicates 25° C. in this specification.

The term "compatible" as used herein means that the resins are miscible with each other on a nano-unit or micro-unit or in terms of appearance, even if they are not necessarily compatible on a molecular basis.
As used herein, "(meth)acrylate" means "acrylate" and its corresponding "methacrylate". Similarly, "(meth)acrylic" means "acrylic" and corresponding "methacrylic", and "(meth)acryloyl" means "acryloyl" and corresponding "methacryloyl".
A number average molecular weight in this specification means the value measured in terms of polystyrene by gel permeation chromatography (GPC; Gas Permeation Chromatography). Specifically, the number average molecular weight herein can be measured by the method described in Examples.

The mechanism of action described in this specification is an assumption, and does not limit the mechanism of the effects of the resin composition according to the present embodiment.
Aspects in which the items described in this specification are arbitrarily combined are also included in this embodiment.

[Resin composition]
The resin composition of this embodiment is
(A) one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof;
(B) a modified conjugated diene polymer obtained by reacting (b1) a conjugated diene polymer having a vinyl group in a side chain with a (b2) compound having a phosphorus atom and an ethylenically unsaturated bond;
It is a resin composition containing

In the following description, one or more selected from the group consisting of (A) a maleimide compound having one or more N-substituted maleimide groups and derivatives thereof is referred to as "maleimide resin (A)" or "(A) component ” may be called.
(B) A modified conjugated diene polymer obtained by reacting (b1) a conjugated diene polymer having a vinyl group in a side chain with a (b2) compound having a phosphorus atom and an ethylenically unsaturated bond is referred to as a "modified conjugated diene polymer ( B)” or “component (B)” in some cases.
In addition, the (b1) conjugated diene polymer having a vinyl group in the side chain may be referred to as "conjugated diene polymer (b1)" or "(b1) component".
In addition, (b2) a compound having a phosphorus atom and an ethylenically unsaturated bond may be referred to as "phosphorus-containing monomer (b2)" or "(b2) component".

The reason why the resin composition of the present embodiment is excellent in dielectric properties, compatibility and flame retardancy in a high frequency band of 10 GHz or higher is not clear, but is presumed as follows.
The resin composition of the present embodiment contains a maleimide-based resin (A) that is excellent in heat resistance and the like. It is incompatible.
On the other hand, the modified conjugated diene polymer (B) contained in the resin composition of the present embodiment is obtained by reacting the conjugated diene polymer (b1) with the phosphorus-containing monomer (b2) to form the conjugated diene polymer (b1). It is presumed that the compatibility with the maleimide-based resin (A) was improved due to the partial increase in polarity.
Furthermore, the phosphorus-containing monomer (b2) to be reacted with the conjugated diene polymer (b1) contains phosphorus atoms and thus contributes to improvement in flame retardancy. Therefore, for example, even if some or all of the conventionally used flame retardants are replaced with the modified conjugated diene polymer (B), flame retardancy equivalent to or greater than conventional flame retardants can be achieved. In other words, the modified conjugated diene polymer (B) can simultaneously improve both flame retardancy and dielectric properties while having excellent compatibility, so the modified conjugated diene polymer (B) is included. It is presumed that the resin composition of this embodiment has excellent dielectric properties, compatibility and flame retardancy.
Each component that can be contained in the resin composition of the present embodiment will be described below in order.

<Maleimide resin (A)>
The maleimide resin (A) is one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof.
The maleimide-based resin (A) may be used alone or in combination of two or more.
In the following description, a maleimide compound having one or more N-substituted maleimide groups may be referred to as "maleimide compound (AX)" or "(AX) component".
A derivative of a maleimide compound having one or more N-substituted maleimide groups is sometimes referred to as a "maleimide compound derivative (AY)" or "(AY) component".

(Maleimide compound (AX))
The maleimide compound (AX) is not particularly limited as long as it is a maleimide compound having one or more N-substituted maleimide groups.
From the viewpoint of dielectric properties, conductor adhesion and heat resistance, the maleimide compound (AX) is a maleimide containing a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups. The compound [hereinafter sometimes referred to as "maleimide compound (A1)" or "(A1) component". ] is preferable.

[Maleimide compound (A1)]
From the viewpoint of dielectric properties, conductor adhesion and heat resistance, the maleimide compound (A1) is an aromatic compound containing a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups. Group maleimide compounds are preferred.
Further, as the maleimide compound (A1), an aromatic bismaleimide compound containing a condensed ring of an aromatic ring and an aliphatic ring in the molecular structure and having two N-substituted maleimide groups is more preferable.
As used herein, the term "aromatic maleimide compound" means a compound having an N-substituted maleimide group directly bonded to an aromatic ring, and the term "aromatic bismaleimide compound" refers to a compound directly bonded to an aromatic ring. It means a compound having two N-substituted maleimide groups.

The condensed ring contained in the maleimide compound (A1) preferably has a condensed bicyclic structure, more preferably an indane ring, from the viewpoint of dielectric properties, conductor adhesiveness and ease of production.
As the maleimide compound (A1) containing an indane ring, an aromatic bismaleimide compound containing an indane ring is preferable.
In the present specification, the indane ring means a condensed bicyclic structure of a 6-membered aromatic ring and a 5-membered saturated aliphatic ring. At least one carbon atom among the ring-forming carbon atoms forming the indane ring has a bonding group for bonding to another group constituting the maleimide compound (A1). The ring-forming carbon atom having the bonding group and other ring-forming carbon atoms may not have a bonding group, a substituent, etc. other than the above bonding group, but by having a bonding group other than the above, 2 preferably form a valence group.

In the maleimide compound (A1), the indane ring is preferably included as a divalent group represented by general formula (A1-1) below.

（式中、Ｒ^ａ１は、炭素数１～１０のアルキル基、炭素数１～１０のアルキルオキシ基、炭素数１～１０のアルキルチオ基、炭素数６～１０のアリール基、炭素数６～１０のアリールオキシ基、炭素数６～１０のアリールチオ基、炭素数３～１０のシクロアルキル基、ハロゲン原子、水酸基又はメルカプト基である。ｎ^ａ１は０～３の整数である。Ｒ^ａ２～Ｒ^ａ４は、各々独立に、炭素数１～１０のアルキル基である。＊は結合部位を表す。）

(wherein R ^a1 is an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, aryloxy group, arylthio group having 6 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, halogen atom, hydroxyl group or mercapto group, n ^a1 is an integer of 0 to 3. R ^a2 to R ^a4 each independently represents an alkyl group having 1 to 10 carbon atoms.* represents a bonding site.)

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^a1 in the above general formula (A1-1) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. These alkyl groups may be linear or branched.
Examples of the alkyl group included in the alkyloxy group having 1 to 10 carbon atoms and the alkylthio group having 1 to 10 carbon atoms represented by R ^a1 include the same alkyl groups having 1 to 10 carbon atoms as described above.
Examples of the aryl group having 6 to 10 carbon atoms represented by R ^a1 include a phenyl group and a naphthyl group.
Examples of the aryl group contained in the aryloxy group having 6 to 10 carbon atoms and the arylthio group having 6 to 10 carbon atoms represented by R ^a1 include the same aryl groups having 6 to 10 carbon atoms as described above.
Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ^a1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. .
When n ^a1 in the above general formula (A1-1) is an integer of 1 to 3, R ^a1 is an alkyl group having 1 to 4 carbon atoms and 3 to 6 carbon atoms from the viewpoint of solvent solubility and reactivity. and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

Examples of alkyl groups having 1 to 10 carbon atoms represented by R ^a2 to R ^a4 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. and the like. These alkyl groups may be linear or branched. Among these, R ^a2 to R ^a4 are preferably alkyl groups having 1 to 4 carbon atoms, more preferably methyl groups and ethyl groups, and still more preferably methyl groups.
n ^a1 in the general formula (A1-1) is an integer of 0 to 3, and when n ^a1 is 2 or 3, a plurality of R ^a1 may be the same or different; good too.

Among the above, the ^divalent group represented by the general ^formula ( ^A1-1 ) is represented by the following formula ( A divalent group represented by A1-1a) is preferred.

（式中、＊は結合部位を表す。）

(In the formula, * represents a binding site.)

As the maleimide compound (A1) containing a divalent group represented by the general formula (A1-1), the following general formula (A1-2 ) is preferred.

（式中、Ｒ^ａ１～Ｒ^ａ４及びｎ^ａ１は、上記一般式（Ａ１－１）中のものと同じである。Ｒ^ａ５は、各々独立に、炭素数１～１０のアルキル基、炭素数１～１０のアルキルオキシ基、炭素数１～１０のアルキルチオ基、炭素数６～１０のアリール基、炭素数６～１０のアリールオキシ基、炭素数６～１０のアリールチオ基、炭素数３～１０のシクロアルキル基、ハロゲン原子、ニトロ基、水酸基又はメルカプト基である。ｎ^ａ２は、各々独立に、０～４の整数である。ｎ^ａ３は、０．９５～１０．０の数である。）

(In the formula, R ^a1 to R ^a4 and n ^a1 are the same as in the general formula (A1-1) above. R ^a5 each independently represents an alkyl group having 1 to 10 carbon atoms, ~10 alkyloxy group, C1-10 alkylthio group, C6-10 aryl group, C6-10 aryloxy group, C6-10 arylthio group, C3-10 a cycloalkyl group, a halogen atom, a nitro group, a hydroxyl group or a mercapto group, each n ^a2 is independently an integer of 0 to 4, and n ^a3 is a number of 0.95 to 10.0.

In the above general formula (A1-2), the plurality of R ^a1s , the plurality of n ^a1s , the plurality of R ^a5s , and the plurality of n ^a2s may be the same or different. good.
When n ^a3 exceeds 1, each of the plurality of R ^a2s , the plurality of R ^a3s and the plurality of R ^a4s may be the same or different.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^a5 in the general formula (A1-2) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. , a nonyl group, a decyl group, and the like. These alkyl groups may be linear or branched.
Examples of the alkyl group included in the alkyloxy group having 1 to 10 carbon atoms and the alkylthio group having 1 to 10 carbon atoms represented by R ^a5 include the same alkyl groups having 1 to 10 carbon atoms as described above.
Examples of the aryl group having 6 to 10 carbon atoms represented by R ^a5 include a phenyl group and a naphthyl group.
Examples of the aryl group contained in the aryloxy group having 6 to 10 carbon atoms and the arylthio group having 6 to 10 carbon atoms represented by R ^a5 include the same aryl groups having 6 to 10 carbon atoms as described above.
Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ^a5 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group and a cyclodecyl group. .
Among these, R ^a5 is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, from the viewpoint of solvent solubility and ease of production. An alkyl group having numbers 1 to 3 is more preferred, and a methyl group is even more preferred.

n ^a2 in the general formula (A1-2) is an integer of 0 to 4, and is preferably 1 to 3 from the viewpoint of compatibility with other resins, dielectric properties, conductor adhesion and ease of manufacture. is an integer of, more preferably 2 or 3, more preferably 2.
When n ^a2 is 1 or more, the benzene ring and the N-substituted maleimide group have a twisted conformation, and intermolecular stacking is suppressed, thereby tending to further improve solvent solubility. From the viewpoint of suppressing intermolecular stacking, when n ^a2 is 1 or more, the substitution position of R ^a5 is preferably ortho to the N-substituted maleimide group.
n ^a3 in the general formula (A1-2) is preferably a number of 0.98 to 8.0, more preferably 1, from the viewpoint of dielectric properties, conductor adhesion, solvent solubility, handling properties and heat resistance. .0 to 7.0, more preferably 1.1 to 6.0. Note that n ^a3 represents the average number of structural units containing an indane ring.

The maleimide compound (A1) represented by the above general formula (A1-2) is represented by the following general formula (A1-3) from the viewpoint of dielectric properties, conductor adhesion, solvent solubility and ease of production. is more preferable.

（式中、Ｒ^ａ１～Ｒ^ａ５及びｎ^ａ１及びｎ^ａ３は、上記一般式（Ａ１－２）中のものと同じである。）

(Wherein, R ^a1 to R ^a5 and n ^a1 and n ^a3 are the same as those in general formula (A1-2) above.)

Examples of the maleimide compound (A1) represented by the above general formula (A1-3) include compounds represented by the following general formula (A1-3-1), and compounds represented by the following general formula (A1-3-2). and compounds represented by the following general formula (A1-3-3).

（式中、ｎ^ａ３は、上記一般式（Ａ１－２）中のものと同じである。）

(Wherein, n ^a3 is the same as in general formula (A1-2) above.)

The number average molecular weight of the maleimide compound (A1) is not particularly limited, but is preferably 600 to 3,000, more preferably 800 to 2, from the viewpoints of compatibility with other resins, conductor adhesion and heat resistance. 000, more preferably 1,000 to 1,500.

The maleimide compound (A1) is, for example, an intermediate amine compound containing a condensed ring of an aromatic ring and an aliphatic ring [hereinafter sometimes simply referred to as an "intermediate amine compound". ] and maleic anhydride [hereinafter sometimes referred to as “maleimidation reaction”. ] can be produced by a method of

A method for producing the maleimide compound (A1) will be described below, taking as an example a maleimide compound containing an indane ring as a condensed ring of an aromatic ring and an aliphatic ring.
An intermediate amine compound of a maleimide compound containing an indane ring is, for example, a compound represented by the following general formula (A1-4) [hereinafter sometimes referred to as "compound A". ] and a compound represented by the following general formula (A1-5) [hereinafter sometimes referred to as “compound B”. ] in the presence of an acid catalyst [hereinafter sometimes referred to as “cyclization reaction”. ] can be obtained as a compound represented by the following general formula (A1-6).

（式中、Ｒ^ａ１及びｎ^ａ１は、上記一般式（Ａ１－１）中のものと同じである。Ｒ^ａ６は、各々独立に、上記式（Ａ１－４－１）又は上記式（Ａ１－４－２）で表される基であり、２つのＲ^ａ６の少なくとも一方のＲ^ａ６のオルト位が水素原子である。）

(Wherein, R ^a1 and n ^a1 are the same as those in the above general formula (A1-1). R ^a6 each independently represents the above formula (A1-4-1) or the above formula (A1- 4-2), wherein the ortho position of at least one R ^a6 of two R ^a6 is a hydrogen atom.)

（式中、Ｒ^ａ５及びｎ^ａ２は、上記一般式（Ａ１－２）中のものと同じである。但し、アミノ基のオルト位及びパラ位のうち、少なくとも１つは水素原子である。）

(In the formula, R ^a5 and n ^a2 are the same as in the above general formula (A1-2), provided that at least one of the ortho and para positions of the amino group is a hydrogen atom.)

（式中、Ｒ^ａ１、Ｒ^ａ５及びｎ^ａ１～ｎ^ａ３は、上記一般式（Ａ１－２）中のものと同じである。）

(Wherein, R ^a1 , R ^a5 and n ^a1 to n ^a3 are the same as in general formula (A1-2) above.)

Compound A includes, for example, p- or m-diisopropenylbenzene, p- or m-bis(α-hydroxyisopropyl)benzene, 1-(α-hydroxyisopropyl)-3-isopropenylbenzene, 1-(α -hydroxyisopropyl)-4-isopropenylbenzene, mixtures thereof, nuclear alkyl group-substituted products of these compounds, and nuclear halogen-substituted products of these compounds.
Examples of the nucleus alkyl group-substituted product include diisopropenyltoluene and bis(α-hydroxyisopropyl)toluene.
Examples of the nucleus halogen-substituted compounds include chlorodiisopropenylbenzene, chlorobis(α-hydroxyisopropyl)benzene and the like.
These compounds A may be used individually by 1 type, and may be used in combination of 2 or more type.

Compound B includes, for example, aniline, dimethylaniline, diethylaniline, diisopropylaniline, ethylmethylaniline, cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, chloroaniline, dichloroaniline, toluidine, xylidine, phenylaniline, nitroaniline, aminophenol , methoxyaniline, ethoxyaniline, phenoxyaniline, naphthoxyaniline, aminothiol, methylthioaniline, ethylthioaniline, phenylthioaniline and the like. These compounds B may be used individually by 1 type, and may be used in combination of 2 or more type.

In the cyclization reaction, for example, compound A and compound B are combined at a molar ratio (compound B/compound A) of preferably 0.1 to 2.0, more preferably 0.15 to 1.5, and still more preferably is charged at a ratio of 0.2 to 1.0, and the first stage reaction is performed.
Next, the compound B to be further added is preferably 0.5 to 20, more preferably 0.6 to 10, still more preferably 0 in a molar ratio to the previously added compound A (additional compound B/compound A). It is preferable to add at a ratio of 0.7 to 5 and carry out the second reaction.

Examples of acid catalysts used in the cyclization reaction include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; Solid acids such as acidic clay, silica alumina, zeolite, and strongly acidic ion exchange resins; heteropolyhydrochloric acid; These may be used individually by 1 type, and may be used in combination of 2 or more type.
From the viewpoint of reaction rate and reaction uniformity, the amount of the acid catalyst is preferably 5 to 40 parts by mass, more preferably 5 to 35 parts by mass, with respect to 100 parts by mass of the total amount of compound A and compound B charged first. , more preferably 5 to 30 parts by mass.

The reaction temperature for the cyclization reaction is preferably 100 to 300°C, more preferably 130 to 250°C, still more preferably 150 to 230°C, from the viewpoint of reaction rate and reaction uniformity.
The reaction time for the cyclization reaction is preferably 2 to 24 hours, more preferably 4 to 16 hours, still more preferably 8 to 12 hours, from the viewpoint of productivity and sufficient progress of the reaction.
However, these reaction conditions are not particularly limited and can be appropriately adjusted depending on the type of raw material used.
In the cyclization reaction, a solvent such as toluene, xylene, chlorobenzene, or the like may be used as necessary. Moreover, when water is produced as a by-product during the cyclization reaction, the dehydration reaction may be promoted by using a solvent capable of azeotropic dehydration.

Next, the intermediate amine compound obtained above is reacted with maleic anhydride in an organic solvent to perform a maleimidation reaction in which the primary amino group of the intermediate amine compound is a maleimide group. A maleimide compound (A1) can be obtained by performing this maleimidation reaction.
The equivalent ratio of maleic anhydride to the primary amino group equivalents of the intermediate amine compound in the maleimidation reaction (maleic anhydride/primary amino group) is not particularly limited, but the amount of unreacted primary amino groups And from the viewpoint of reducing the amount of unreacted maleic anhydride, it is preferably 1.0 to 1.5, more preferably 1.05 to 1.3, still more preferably 1.1 to 1.2.
The amount of the organic solvent used in the maleimidation reaction is not particularly limited, but from the viewpoint of reaction rate and reaction uniformity, it is preferably 50 to 5,000 parts per 100 parts by mass of the total amount of the intermediate amine compound and maleic anhydride. parts by mass, more preferably 70 to 2,000 parts by mass, and even more preferably 100 to 500 parts by mass.

In the maleimidation reaction, it is preferable to react the intermediate amine compound and maleic anhydride in two stages.
The reaction temperature in the first stage reaction is preferably 10 to 100°C, more preferably 20 to 70°C, still more preferably 30 to 50°C.
The reaction time in the first stage reaction is preferably 0.5 to 12 hours, more preferably 0.7 to 8 hours, still more preferably 1 to 4 hours.
The reaction in the second stage is preferably carried out after the reaction in the first stage is completed and a catalyst such as toluenesulfonic acid is added.
The reaction temperature in the second stage reaction is preferably 90 to 130°C, more preferably 100 to 125°C, still more preferably 105 to 120°C.
The reaction time in the second stage reaction is preferably 2 to 24 hours, more preferably 4 to 15 hours, still more preferably 6 to 10 hours.
However, the above reaction conditions are not particularly limited and can be appropriately adjusted depending on the type of raw material used.
After the reaction, unreacted raw materials, other impurities, etc. may be removed by performing purification such as washing with water, if necessary.

The maleimide compound (A1) obtained by the above method may contain a maleimide compound containing no indane ring as a by-product. Maleimide compounds containing no indane ring include, for example, compounds in which n ^a3 is 0 in the general formula (A1-2).
The content of the maleimide compound not containing the by-product indane ring in the reaction product can be measured, for example, by measuring the GPC of the reaction product. Specifically, for example, a calibration curve of the elution time versus the number of n ^a3 is prepared using each compound having n ^a3 of 0 to 4 in the above general formula (A1-2), and then the reaction product From the elution time of the peak seen in the GPC chart, the number of ^na3 of the compounds contained in the reaction product and its average value can be grasped. Moreover, the content ratio of the compound having the number of ^na3 represented by the peak can be grasped from the area ratio of each peak.
The maleimide compound (A1) preferably has a small content of a maleimide compound that does not contain an indane ring as a by-product. Therefore, in the GPC chart of the reaction product, the area ratio of the maleimide compound containing no indane ring as a by-product to the peak area of the entire reaction product is preferably 40% or less, more preferably 30% or less, More preferably 20% or less, particularly preferably 10% or less.

The maleimide compound (AX) is a maleimide compound (A2) other than the maleimide compound (A1) [hereinafter sometimes referred to as "maleimide compound (A2)" or "component (A2)". ] may be.

[Maleimide compound (A2)]
As the maleimide compound (A2), a maleimide compound represented by the following general formula (A2-1) is preferable.

（式中、Ｘ^ａ１１は、芳香族環と脂肪族環との縮合環を含まない２価の有機基である。）

(In the formula, ^Xa11 is a divalent organic group that does not contain a condensed ring of an aromatic ring and an aliphatic ring.)

X ^a11 in general formula (A2-1) above is a divalent organic group that does not contain a condensed ring of an aromatic ring and an aliphatic ring.
Examples of the divalent organic group represented by X ^a11 in general formula (A2-1) include a divalent group represented by general formula (A2-2) below, and general formula (A2-3) below. a divalent group represented by the following general formula (A2-4), a divalent group represented by the following general formula (A2-5), and the following general formula (A2-6) A divalent group represented by is mentioned.

（式中、Ｒ^ａ１１は、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｎ^ａ１１は０～４の整数である。＊は結合部位を表す。）

(In the formula, R ^a11 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. n ^a11 is an integer of 0 to 4. * represents a bonding site.)

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^a11 in the general formula (A2-2) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl t-butyl group, n-pentyl group and other alkyl groups having 1 to 5 carbon atoms; alkenyl groups having 1 to 5 carbon atoms and alkynyl groups having 1 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
n ^a11 in the general formula (A2-2) is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, still more preferably 0, from the viewpoint of availability.
When n ^a11 is an integer of 2 or more, the plurality of R ^a11 may be the same or different.

（式中、Ｒ^ａ１２及び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。Ｘ^ａ１２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。ｎ^ａ１２及びｎ^ａ１３は、各々独立に、０～４の整数である。＊は結合部位を表す。）

(In the formula, R ^a12 and R ^a13 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X ^a12 is an alkylene group having 1 to 5 carbon atoms; n ^a12 and n ^a13 are an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (A2-3-1). , each independently an integer from 0 to 4. * represents a binding site.)

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^a12 and R ^a13 in the general formula (A2-3) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl alkyl groups having 1 to 5 carbon atoms such as isobutyl group, t-butyl group and n-pentyl group; alkenyl groups having 1 to 5 carbon atoms and alkynyl groups having 1 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms from the viewpoint of compatibility with other resins and suppression of gelation of the product during the reaction. , more preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^a12 in the general formula (A2-3) include methylene group, 1,2-dimethylene group, 1,3-trimethylene group and 1,4-tetramethylene group, 1,5-pentamethylene group, and the like. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.

The alkylidene group having 2 to 5 carbon atoms represented by X ^a12 in the general formula (A2-3) includes, for example, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. etc. Among these, an alkylidene group having 2 to 4 carbon atoms is preferred, an alkylidene group having 2 or 3 carbon atoms is more preferred, and an isopropylidene group is even more preferred.

n ^a12 and n ^a13 in the general formula (A2-3) are each independently an integer of 0 to 4, and both are readily available, compatible with other resins, and products during the reaction From the viewpoint of suppressing gelation, it is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 2.
n ^a12 +n ^a13 is preferably an integer of 1 to 8, more preferably an integer of 2 to 6, from the viewpoint of availability, compatibility with other resins, and suppression of gelation of the product during the reaction. Four is preferred.
When n ^a12 or n ^a13 is an integer of 2 or more, the plurality of R ^a12s or the plurality of R ^a13s may be the same or different.

The divalent group represented by general formula (A2-3-1) represented by X ^a12 in general formula (A2-3) is as follows.

（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^ａ１３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、ケト基又は単結合である。ｎ^ａ１４及びｎ^ａ１５は、各々独立に、０～４の整数である。＊は結合部位を表す。）

(wherein R ^a14 and R ^a15 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X ^a13 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, n ^a14 and n ^a15 are each independently an integer of 0 to 4. * represents a bonding site. )

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^a14 and R ^a15 in the general formula (A2-3-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n C1-5 alkyl groups such as -butyl group, isobutyl group, t-butyl group and n-pentyl group; C1-5 alkenyl groups and C1-5 alkynyl groups; The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^a13 in the general formula (A2-3-1) include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4- A tetramethylene group, a 1,5-pentamethylene group and the like can be mentioned. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.

Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^a13 in the general formula (A2-3-1) include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentyl A lidene group and the like can be mentioned. Among these, an alkylidene group having 2 to 4 carbon atoms is preferred, an alkylidene group having 2 or 3 carbon atoms is more preferred, and an isopropylidene group is even more preferred.

Among the above options, X ^a13 in the general formula (A2-3-1) is preferably an alkylidene group having 2 to 5 carbon atoms, more preferably an alkylidene group having 2 to 4 carbon atoms, and further an isopropylidene group. preferable.

n ^a14 and n ^a15 in the general formula (A2-3-1) are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, and more It is preferably 0 or 1, more preferably 0.
When n ^a14 or n ^a15 is an integer of 2 or more, the plurality of R ^a14s or the plurality of R ^a15s may be the same or different.

As X ^a12 in the general formula (A2-3), among the above options, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, and the above general formula (A2-3-1) is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is even more preferred.

（式中、ｎ^ａ１６は０～１０の整数である。＊は結合部位を表す。）

(Wherein, n ^a16 is an integer of 0 to 10. * represents a binding site.)

n ^a16 in general formula (A2-4) is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and still more preferably an integer of 0 to 3, from the viewpoint of availability.

（式中、ｎ^ａ１７は０～５の数である。＊は結合部位を表す。）

(Wherein, n ^a17 is a number from 0 to 5. * represents a binding site.)

（式中、Ｒ^ａ１６及びＲ^ａ１７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。ｎ^ａ１８は１～８の整数である。＊は結合部位を表す。）

(In the formula, R ^a16 and R ^a17 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. n ^a18 is an integer of 1 to 8. * represents a bonding site. )

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^a16 and R ^a17 in the general formula (A2-6) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. alkyl groups having 1 to 5 carbon atoms such as isobutyl group, t-butyl group and n-pentyl group; alkenyl groups having 1 to 5 carbon atoms and alkynyl groups having 1 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
n ^a18 in general formula (A2-6) above is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1. When n ^a18 is an integer of 2 or more, the plurality of R ^a16 or the plurality of R ^a17 may be the same or different.

Examples of the maleimide compound (A2) include aromatic maleimide compounds having two N-substituted maleimide groups, aromatic polymaleimide compounds, and aliphatic maleimide compounds.
Specific examples of the maleimide compound (A2) include N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'- [1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, Bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis(4-maleimide phenyl)ether, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl) ) cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene , bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1 -bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane , 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy) ) phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3, 3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidophenoxy) Biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl ] ketone, bis(4-maleimidophenyl) disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy) phenyl]sulfoxide, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4- (3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1, 3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3- bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl -α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethanemaleimide and the like.

(Maleimide compound derivative (AY))
As the maleimide compound derivative (AY), an aminomaleimide compound having a structural unit derived from the maleimide compound (AX) and a structural unit derived from the diamine compound [hereinafter referred to as "aminomaleimide compound (A3)" or "(A3) component ” may be called. ] is preferable.

[Aminomaleimide compound (A3)]
The aminomaleimide compound (A3) is a structural unit derived from the maleimide compound (AX) and a diamine compound [hereinafter sometimes referred to as "diamine compound (a)" or "component (a)". ] and a structural unit derived from.

<<Structural Unit Derived from Maleimide Compound (AX)>>
As the structural unit derived from the maleimide compound (AX), for example, among the N-substituted maleimide groups possessed by the maleimide compound (AX), at least one N-substituted maleimide group undergoes a Michael addition reaction with an amino group possessed by the diamine compound. A structural unit consisting of
Structural units derived from the maleimide compound (AX) contained in the aminomaleimide compound (A3) may be one type alone or two or more types.

The content of structural units derived from the maleimide compound (AX) in the aminomaleimide compound (A3) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and still more preferably 60 to 90%. % by mass. When the content of structural units derived from the maleimide compound (AX) in the aminomaleimide compound (A3) is within the above range, dielectric properties and film handling properties tend to be better.

<<Structural Unit Derived from Diamine Compound (a)>>
As the structural unit derived from the diamine compound (a), for example, one or both of the two amino groups possessed by the diamine compound (a) is an N-substituted maleimide group possessed by the maleimide compound (AX). Structural units obtained by Michael addition reaction can be mentioned.
The structural unit derived from the diamine compound (a) contained in the aminomaleimide compound (A3) may be one type alone, or two or more types.

The amino group of the diamine compound (a) is preferably a primary amino group.
Examples of the structural unit derived from the diamine compound (a) having two primary amino groups include a group represented by the following general formula (a-1) and a group represented by the following general formula (a-2). etc.

（式中、Ｘ^ａ２１は２価の有機基であり、＊は結合部位を表す。）

(In the formula, X ^a21 is a divalent organic group, and * represents a binding site.)

X ^a21 in the above general formulas (a-1) and (a-2) is a divalent organic group and corresponds to a divalent group obtained by removing two amino groups from the diamine compound (a). do.

X ^a21 in general formulas (a-1) and (a-2) above is preferably a divalent group represented by general formula (a-3) below.

（式中、Ｒ^ａ２１及びＲ^ａ２２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^ａ２２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（ａ－３－１）若しくは下記一般式（ａ－３－２）で表される２価の基である。ｎ^ａ２１及びｎ^ａ２２は、各々独立に、０～４の整数である。＊は結合部位を表す。）

(In the formula, R ^a21 and R ^a22 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom ^. -5 alkylene group, C2-5 alkylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, fluorenylene group, single bond, or general formula (a-3-1) below or below It is a divalent group represented by the general formula (a-3-2), n ^a21 and n ^a22 are each independently an integer of 0 to 4. * represents a binding site.)

（式中、Ｒ^ａ２３及びＲ^ａ２４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^ａ２３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、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。ｎ^ａ２３及びｎ^ａ２４は、各々独立に、０～４の整数である。＊は結合部位を表す。）

(In the formula, R ^a23 and R ^a24 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X ^a23 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, a m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, n ^a23 and n ^a24 are each independently , an integer from 0 to 4. * represents a binding site.)

（式中、Ｒ^ａ２５は、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘ^ａ２４及びＸ^ａ２５は、各々独立に、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、ケト基又は単結合である。ｎ^ａ２５は０～４の整数である。＊は結合部位を表す。）

(In the formula, R ^a25 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X ^a24 and X ^a25 each independently represent an alkylene group having 1 to 5 carbon atoms; is an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, ^na25 is an integer of 0 to 4. * represents a bonding site.)

Number of carbon atoms represented by R ^a21 , R ^a22 , R ^a23 , R ^a24 and R ^a25 in general formula (a-3), general formula (a-3-1) and general formula (a-3-2) Examples of 1 to 5 aliphatic hydrocarbon groups include 1 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl group. to 5 alkyl groups; alkenyl groups having 1 to 5 carbon atoms; and alkynyl groups having 1 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.

The number of carbon atoms represented by X ^a22 in the general formula (a-3), X ^a23 in the general formula (a-3-1), and X ^a24 and X ^a25 in the general formula (a-3-2) is 1 Examples of the alkylene group of 1 to 5 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.

Number of carbon atoms represented by X ^a22 in general formula (a-3), X ^a23 in general formula (a-3-1), and X ^a24 and X ^a25 in general formula (a-3-2) Examples of alkylidene groups of 2 to 5 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like. The alkylidene group having 2 to 5 carbon atoms is preferably an alkylidene group having 2 to 4 carbon atoms, more preferably an alkylidene group having 2 or 3 carbon atoms, and still more preferably an isopropylidene group.

n ^a21 and n ^a22 in the general formula (a-3) are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 3, more preferably It is an integer from 0 to 2, more preferably 0 or 2.
When n ^a21 or n ^a22 is an integer of 2 or more, the plurality of R ^a21s or the plurality of R ^a22s may be the same or different.

n ^a23 and n ^a24 in the general formula (a-3-1) are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, and more It is preferably 0 or 1, more preferably 0.
When n ^a23 or n ^a24 is an integer of 2 or more, the plurality of R ^a23s or the plurality of R ^a24s may be the same or different.

n ^a25 in the general formula (a-3-2) is an integer of 0 to 4, and from the viewpoint of availability, preferably an integer of 0 to 2, more preferably 0 or 1, more preferably 0 is.
When n ^a25 is an integer of 2 or more, a plurality of R ^a25 may be the same or different.

The content of the structural unit derived from the diamine compound (a) in the aminomaleimide compound (A3) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and still more preferably 10 to 40%. % by mass. When the content of the structural unit derived from the diamine compound (a) in the aminomaleimide compound (A3) is within the above range, dielectric properties, heat resistance, flame retardancy and glass transition temperature tend to be better.

Examples of the diamine compound (a) 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'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3' -dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1 , 3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy) Biphenyl, 1,3-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1 -methylethyl]benzene, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3, 3′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 9,9 -Bis(4-aminophenyl)fluorene and the like.

Among these, as the diamine compound (a), 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'- Dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1 -methylethylidene)]bisaniline and 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred. Further, the diamine compound (a) is preferably 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption. Further, the diamine compound (a) is preferably 2,2-bis[4-(4-aminophenoxy)phenyl]propane from the viewpoint of excellent mechanical properties such as high adhesion to conductors, elongation and breaking strength. . Furthermore, the diamine compound (a) is excellent in solubility in organic solvents, reactivity during synthesis, heat resistance, and high adhesion to conductors, as well as excellent dielectric properties and low hygroscopicity. , 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline and 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred.

In the aminomaleimide compound (A3), the total equivalent weight (Ta2) of the groups (including _-NH2 ) derived from the _-NH2 group of the diamine compound (a) and the N-substituted maleimide group derived from the maleimide compound (AX) The equivalent ratio (Ta2/Ta1) to the total equivalent weight (Ta1) of the group is not particularly limited, but is preferably 0.05 to 10, more preferably 0.05 to 10, from the viewpoint of dielectric properties, heat resistance, flame retardancy and glass transition temperature. is 0.5-7, more preferably 1-5. The group derived from the —NH ₂ group of the diamine compound (a) includes —NH ₂ itself. Further, the group derived from the N-substituted maleimide group of the maleimide compound (AX) includes the N-substituted maleimide group itself.

Although the number average molecular weight of the aminomaleimide compound (A3) is not particularly limited, it is preferably 400 to 10,000, more preferably 500 to 5,000, still more preferably 600 to 2,000 from the viewpoint of handleability and moldability. 000.

(Method for producing aminomaleimide compound (A3))
The aminomaleimide compound (A3) can be produced, for example, by reacting the maleimide compound (AX) with the diamine compound (a) in an organic solvent.
By reacting the maleimide compound (AX) with the diamine compound (a), an aminomaleimide compound (A3) is obtained through Michael addition reaction between the maleimide compound (AX) and the diamine compound (a).

When reacting the maleimide compound (AX) and the diamine compound (a), a reaction catalyst may be used as necessary.
Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus catalysts such as triphenylphosphine. . These may be used individually by 1 type, or may be used in combination of 2 or more type.
The amount of the reaction catalyst is not particularly limited, but from the viewpoint of reaction rate and reaction uniformity, it is preferably 0.01 to 5 parts per 100 parts by mass of the total amount of the maleimide compound (AX) and the diamine compound (a). parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 2 parts by mass.

The reaction temperature of the Michael addition reaction is preferably 50 to 160° C., more preferably 60 to 150° C., and still more preferably 70 to 140° C., from the viewpoint of workability such as reaction rate and suppression of gelation of the product during the reaction. °C.
The reaction time of the Michael addition reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, still more preferably 2 to 6 hours, from the viewpoint of productivity and sufficient progress of the reaction.
However, these reaction conditions are not particularly limited and can be appropriately adjusted depending on the type of raw material used.

In the Michael addition reaction, the solid content concentration and solution viscosity of the reaction solution may be adjusted by adding or concentrating the organic solvent. The solid content concentration of the reaction solution is not particularly limited, but is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, still more preferably 20 to 80% by mass. When the solid content concentration of the reaction raw material is equal to or higher than the above lower limit, a good reaction rate is obtained, and productivity tends to be better. Further, when the solid content concentration of the reaction raw material is equal to or less than the above upper limit value, better solubility is obtained, stirring efficiency is improved, and gelling of the product during the reaction tends to be more suppressed.

Among the component (A) described above, from the viewpoint of dielectric properties, conductor adhesion and heat resistance, the component (A) contains a condensed ring of an aromatic ring and an aliphatic ring in the molecular structure, N- It is preferably one or more selected from the group consisting of maleimide compounds having two or more substituted maleimide groups and derivatives thereof.

<Modified conjugated diene polymer (B)>
The resin composition of the present embodiment contains a modified conjugated diene polymer obtained by reacting (b1) a conjugated diene polymer having a vinyl group in a side chain with (b2) a compound having a phosphorus atom and an ethylenically unsaturated bond. .
The modified conjugated diene polymer (B) may be used alone or in combination of two or more.

(Conjugated diene polymer (b1))
As used herein, "conjugated diene polymer" means a polymer of a conjugated diene compound.
Examples of conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. is mentioned.
The conjugated diene polymer (b1) may be a polymer of one conjugated diene compound or a polymer of two or more conjugated diene compounds.
Moreover, the conjugated diene polymer (b1) may be obtained by copolymerizing one or more conjugated diene compounds with a monomer other than one or more conjugated diene compounds.
When the conjugated diene polymer (b1) is a copolymer, the polymerization mode is not particularly limited, and may be random polymerization, block polymerization or graft polymerization.
The conjugated diene polymer (b1) may be used alone or in combination of two or more.

As the conjugated diene polymer (b1), a conjugated diene polymer having a plurality of vinyl groups in side chains is preferable from the viewpoint of compatibility with other resins and dielectric properties.
The number of vinyl groups in one molecule of the conjugated diene polymer (b1) is not particularly limited, but from the viewpoint of compatibility with other resins and dielectric properties, it is preferably 3 or more, more preferably 5 or more. , more preferably 10 or more.
The upper limit of the number of vinyl groups in one molecule of the conjugated diene polymer (b1) is not particularly limited, but may be 100 or less, 80 or less, or 60 or less. .

Examples of the conjugated diene polymer (b1) include polybutadiene having a 1,2-vinyl group, butadiene-styrene copolymer having a 1,2-vinyl group, and polyisoprene having a 1,2-vinyl group. . Among these, polybutadiene having a 1,2-vinyl group and a butadiene-styrene copolymer having a 1,2-vinyl group are preferable from the viewpoint of dielectric properties and heat resistance, and polybutadiene having a 1,2-vinyl group is preferable. more preferred. As the polybutadiene having a 1,2-vinyl group, a polybutadiene homopolymer having a 1,2-vinyl group is preferable.
The butadiene-derived 1,2-vinyl group of the conjugated diene polymer (b1) is a vinyl group contained in a butadiene-derived structural unit represented by the following formula (b1-1).

When the conjugated diene polymer (b1) is a polybutadiene having a 1,2-vinyl group, the content of structural units having a 1,2-vinyl group with respect to all butadiene-derived structural units constituting the polybutadiene [hereinafter, Sometimes referred to as "vinyl group content". ] is not particularly limited, but is preferably 50 mol % or more, more preferably 70 mol % or more, and still more preferably 85 mol % or more from the viewpoint of compatibility with other resins, dielectric properties and heat resistance. . The upper limit of the vinyl group content is not particularly limited, and may be 100 mol % or less, 95 mol % or less, or 90 mol % or less. As the structural unit having a 1,2-vinyl group, a butadiene-derived structural unit represented by the above formula (b1-1) is preferable.
From the same point of view, the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.

The number average molecular weight of the conjugated diene polymer (b1) is not particularly limited, but is preferably 400 to 3,000, more preferably 600 to 2, from the viewpoints of compatibility with other resins, dielectric properties and heat resistance. 000, more preferably 800 to 1,500.

(Phosphorus-containing monomer (b2))
The phosphorus-containing monomer (b2) is not particularly limited as long as it is a compound having a phosphorus atom and an ethylenically unsaturated bond.
One of the phosphorus-containing monomers (b2) may be used alone, or two or more thereof may be used in combination.

As used herein, the term "ethylenically unsaturated bond" means a carbon-carbon double bond capable of an addition reaction, and does not include a double bond of an aromatic ring.
Further, in this specification, a substituent containing an "ethylenically unsaturated bond" may be referred to as an "ethylenically unsaturated bond-containing group".
Examples of ethylenically unsaturated bond-containing groups possessed by the phosphorus-containing monomer (b2) include heteroatom-free unsaturated aliphatic groups such as vinyl groups, isopropenyl groups, allyl groups, 1-methylallyl groups, and 3-butenyl groups. hydrocarbon groups; substituents containing heteroatoms such as maleimide groups and (meth)acryloyl groups; Among these, a vinyl group and a (meth)acryloyl group are preferred, and a (meth)acryloyl group is more preferred, from the viewpoint of dielectric properties and reactivity.
Incidentally, the (meth)acryloyl group may be a (meth)acryloyloxy group, in which case the phosphorus-containing monomer (b2) is an ethylenically unsaturated bond-containing group, (meth)acryloyl Suppose that it has an oxy group.
The number of ethylenically unsaturated bond-containing groups that the phosphorus-containing monomer (b2) has in one molecule is not particularly limited, but from the viewpoint of suppressing gelation of the product during the reaction, preferably 1 to 3. , more preferably one or two, and still more preferably one.

The phosphorus-containing monomer (b2) preferably contains a P=O bond in its molecule. The number of P═O bonds contained in one molecule of the phosphorus-containing monomer (b2) is preferably 1 to 3, more preferably 1 or 2, still more preferably 1.

The phosphorus-containing monomer (b2) is preferably a compound represented by the following general formula (b2-1) from the viewpoint of reactivity and flame retardancy.

（式中、Ｒ^ｂ１及びＲ^ｂ２は、各々独立に、炭素数１～１０のアルキル基、炭素数６～２０のアリール基又は水素原子である。Ｒ^ｂ１及びＲ^ｂ２は、互いに結合して環を形成してもよい。ｎ^ｂ１及びｎ^ｂ２は、各々独立に、０又は１である。Ｚ^ｂ１は、エチレン性不飽和結合を含む有機基である。）

(In the formula, R ^b1 and R ^b2 are each independently an alkyl group having ¹ to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydrogen atom ^. n ^b1 and n ^b2 are each independently 0 or 1. Z ^b1 is an organic group containing an ethylenically unsaturated bond.)

The number of carbon atoms in the alkyl group having 1 to 10 carbon atoms represented by R ^b1 and R ^b2 in general formula (b2-1) is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 or 2. be.
Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. Among these, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.
The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic.
The alkyl group having 1 to 10 carbon atoms may or may not have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, a cyano group, an aryl group, an alkoxy group, and groups in which these substituents are linked. When the alkyl group having 1 to 10 carbon atoms has a substituent, the carbon number of the alkyl group also includes the carbon number of the substituent.

The number of carbon atoms in the aryl group having 6 to 20 carbon atoms represented by R ^b1 and R ^b2 in general formula (b2-1) is preferably 6 to 18, more preferably 6 to 12, still more preferably 6 to 10. be.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, naphthyl group, biphenyl group and anthranyl group. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. A phenyl group is preferably an unsubstituted phenyl group.
The aryl group having 6 to 20 carbon atoms may or may not have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, a cyano group, an alkyl group, an alkoxy group, and groups in which these substituents are linked. When the aryl group having 6 to 20 carbon atoms has a substituent, the number of carbon atoms in the aryl group also includes the number of carbon atoms in the substituent.

Among the above options, R ^b1 and R ^b2 in general formula (b2-1) are preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group.

n ^b1 and n ^b2 in the general formula (b2-1) are 0 or 1, preferably 0. Note that ^nb1 or ^nb2 being 0 means that ^Rb1 or ^Rb2 is directly bonded to a phosphorus atom.

Z ^b1 in general formula (b2-1) above is an organic group containing an ethylenically unsaturated bond, and examples thereof include groups represented by general formula (b2-2) below.

（式中、Ｘ^ｂ１は、炭素数１～１２の２価の炭化水素基である。Ｙ^ｂ１は、ビニル基又は（メタ）アクリロイルオキシ基である、ｎ^ｂ３は０又は１である。＊は上記一般式（ｂ２－１）中のリン原子に結合する部位を表す。）

(In the formula, X ^b1 is a divalent hydrocarbon group having 1 to 12 carbon atoms. Y ^b1 is a vinyl group or a (meth)acryloyloxy group. n ^b3 is 0 or 1. * is It represents the site that binds to the phosphorus atom in general formula (b2-1) above.)

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by X ^b1 in the general formula (b2-2) include an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, and the like. mentioned.
Examples of the alkylene group having 1 to 12 carbon atoms include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. The alkylene group having 1 to 12 carbon atoms is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.
Examples of the arylene group having 6 to 12 carbon atoms include phenylene group, naphthylene group, biphenylene group and the like. The arylene group having 6 to 12 carbon atoms is preferably an arylene group having 6 to 10 carbon atoms, more preferably an arylene group having 6 to 8 carbon atoms, and still more preferably a phenylene group.

The phosphorus-containing monomer (b2) containing a structure formed by combining R ^b1 and R ^b2 in general formula (b2-1) with each other is represented by, for example, general formula (b2-3) below. Phosphorus-containing monomers having the structure

（式中、Ｚ^ｂ１は、上記一般式（ｂ２－１）における説明の通りである。）

(Wherein, Z ^b1 is as described in general formula (b2-1) above.)

As the compound represented by the above general formula (b2-1), a compound represented by the following general formula (b2-4) is more preferable.

（上記一般式（ｂ２－４）中のＲ^ｂ３及びＲ^ｂ４は、各々独立に、炭素数１～５の脂肪族炭化水素基、ハロゲン原子又は水酸基である。ｎ^ｂ１及びｎ^ｂ２は、各々独立に、１又は０である。ｎ^ｂ４及びｎ^ｂ５は、各々独立に、０～５の整数である。Ｙ^ｂ２は、上記一般式（ｂ２－４－１）で表される基、又は、上記式（ｂ２－４－２）で表される基である。上記一般式（ｂ２－４－１）中のＲ^ｂ５は、水素原子又はメチル基である。上記一般式（ｂ２－４－１）及び上記式（ｂ２－４－２）中の＊は、上記一般式（ｂ２－４）中のリン原子に結合する部位を表す。）

(R ^b3 and R ^b4 in the general formula (b2-4) are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group. n ^b1 and n ^b2 are each independently is 1 or 0. n ^b4 and n ^b5 are each independently an integer of 0 to 5. Y ^b2 is a group represented by the general formula (b2-4-1), or A group represented by the formula (b2-4-2), wherein R ^b5 in the above general formula (b2-4-1) is a hydrogen atom or a methyl group, the above general formula (b2-4-1) and * in the above formula (b2-4-2) represents a site that binds to the phosphorus atom in the above general formula (b2-4).)

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^b3 and R ^b4 in the general formula (b2-4) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.
Halogen atoms represented by R ^b3 and R ^b4 include, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
n ^b1 and n ^b2 in the general formula (b2-4) are 0 or 1, preferably 0.
n ^b4 and n ^b5 in the general formula (b2-4) are each independently an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, still more preferably 0 .
When ^nb4 or ^nb5 is an integer of 2 or more, the plurality of ^Rb3 's or the plurality of ^Rb4 's may be the same or different.
R ^b5 in general formula (b2-4-1) above is a hydrogen atom or a methyl group, preferably a methyl group.

Examples of the phosphorus-containing monomer (b2) include a compound having a phosphate ester group and an ethylenically unsaturated bond, a compound having a phosphonate ester group and an ethylenically unsaturated bond, a phosphinate ester group and an ethylenically unsaturated bond, and compounds having a phosphine oxide group and an ethylenically unsaturated bond.
Examples of the compound having a phosphate group and an ethylenically unsaturated bond include 2-(meth)acryloyloxyethyl phosphate, dimethyl-(2-(meth)acryloyloxyethyl)phosphate, diethyl-(2-(meth) ) Phosphate ester group-containing (meth)acrylate compounds such as acryloyloxyethyl) phosphate and diphenyl-(2-(meth)acryloyloxyethyl) phosphate; phosphate ester group-containing vinyl compounds; phosphate ester group-containing styryl compounds, etc. mentioned.
Examples of the compound having a phosphonate group and an ethylenically unsaturated bond include diphenyl-((meth)acryloyloxymethyl)phosphonate, diphenyl-(2-((meth)acryloyloxy)ethyl)phosphonate, diphenyl-( 3-((meth)acryloyloxy)propyl)phosphonate, diphenyl-(4-((meth)acryloyloxy)butyl)phosphonate, dimethyl-((meth)acryloyloxymethyl)phosphonate, dimethyl-(2-((meth) Acryloyloxy)ethyl)phosphonate, Dimethyl-(3-((meth)acryloyloxy)propyl)phosphonate, Dimethyl-(4-((meth)acryloyloxy)butyl)phosphonate, Diethyl-((meth)acryloyloxymethyl)phosphonate , diethyl-(2-((meth)acryloyloxy)ethyl)phosphonate, diethyl-(3-((meth)acryloyloxy)propyl)phosphonate, diethyl-(4-((meth)acryloyloxy)butyl)phosphonate, etc. Phosphonate ester group-containing (meth)acrylate compounds; vinyl phosphonates such as diphenyl vinyl phosphonate, dimethyl vinyl phosphonate, diethyl vinyl phosphonate, dipropyl vinyl phosphonate, dibutyl vinyl phosphonate, dipentyl vinyl phosphonate, dihexyl vinyl phosphonate nate compound; diphenyl styrylphosphonate, dimethyl styrylphosphonate, diethyl styrylphosphonate, diphenyl styrylmethylphosphonate, dimethyl styrylmethylphosphonate, diethyl styrylmethylphosphonate, diphenyl styrylethylphosphonate, dimethyl styrylethylphosphonate, diethyl styrylethylphosphonate , diphenyl styrylpropylphosphonate, dimethyl styrylpropylphosphonate, and diethyl styrylpropylphosphonate.
Examples of the compound having a phosphinate ester group and an ethylenically unsaturated bond include diphenyl-((meth)acryloyloxymethyl)phosphinate, diphenyl-(2-((meth)acryloyloxy)ethyl)phosphinate, diphenyl-( 3-((meth)acryloyloxy)propyl)phosphinate, diphenyl-(4-((meth)acryloyloxy)butyl)phosphinate, dimethyl-((meth)acryloyloxymethyl)phosphinate, dimethyl-(2-((meth) Acryloyloxy)ethyl)phosphinate, dimethyl-(3-((meth)acryloyloxy)propyl)phosphinate, dimethyl-(4-((meth)acryloyloxy)butyl)phosphinate, diethyl-((meth)acryloyloxymethyl)phosphinate , diethyl-(2-((meth)acryloyloxy)ethyl)phosphinate, diethyl-(3-((meth)acryloyloxy)propyl)phosphinate, diethyl-(4-((meth)acryloyloxy)butyl)phosphinate, etc. phosphinate group-containing (meth)acrylate compounds; phosphinate group-containing vinyl compounds; and phosphinate group-containing styrene compounds.
Examples of the compound having a phosphine oxide group and an ethylenically unsaturated bond include diphenyl-((meth)acryloyloxymethyl)phosphine oxide, diphenyl-(2-((meth)acryloyloxy)ethyl)phosphine oxide, diphenyl- (3-((meth)acryloyloxy)propyl)phosphine oxide, diphenyl-(4-((meth)acryloyloxy)butyl)phosphine oxide, dimethyl-((meth)acryloyloxymethyl)phosphine oxide, dimethyl-(2- ((meth)acryloyloxy)ethyl)phosphine oxide, dimethyl-(3-((meth)acryloyloxy)propyl)phosphine oxide, dimethyl-(4-((meth)acryloyloxy)butyl)phosphine oxide, diethyl-(( meth)acryloyloxymethyl)phosphine oxide, diethyl-(2-((meth)acryloyloxy)ethyl)phosphine oxide, diethyl-(3-((meth)acryloyloxy)propyl)phosphine oxide, diethyl-(4-(( Phosphine oxide group-containing (meth)acrylate compounds such as meth)acryloyloxy)butyl)phosphine oxide; styryldiphenylphosphine oxide, styryldimethylphosphine oxide, styryldiethylphosphine oxide, (styrylmethyl)diphenylphosphine oxide, (styrylmethyl)dimethylphosphine oxide, (styrylmethyl)diethylphosphine oxide, (styrylethyl)diphenylphosphine oxide, (styrylethyl)dimethylphosphine oxide, (styrylethyl)diethylphosphine oxide, (styrylpropyl)diphenylphosphine oxide, (styrylpropyl)dimethylphosphine oxide, phosphine oxide group-containing styrene compounds such as (styrylpropyl)diethylphosphine oxide; and vinylphosphine oxide compounds.
Among these, the compound having a phosphine oxide group and an ethylenically unsaturated bond is preferably a phosphine oxide group-containing (meth)acrylate compound.

The modified conjugated diene polymer (B) has a substituent group [ Hereinafter, it may be referred to as "substituent (x)". ] is preferred.
Substituent (x) is preferably a group containing a structure represented by general formula (B-1) below.

（式中、Ｒ^ｂ１、Ｒ^ｂ２、ｎ^ｂ１及びｎ^ｂ２は、上記一般式（ｂ２－１）における説明の通りである。＊は結合部位を表す。）

(Wherein, R ^b1 , R ^b2 , n ^b1 and n ^b2 are as described in the general formula (b2-1) above. * represents a binding site.)

The number average molecular weight of the modified conjugated diene polymer (B) is not particularly limited, but is preferably 1,000 to 6,000, more preferably 1 , 500 to 5,000, more preferably 2,000 to 3,000.

The modified conjugated diene polymer (B) can be produced by reacting the conjugated diene polymer (b1) with the phosphorus-containing monomer (b2).
The method for reacting the conjugated diene polymer (b1) and the phosphorus-containing monomer (b2) is not particularly limited. For example, a conjugated diene polymer (b1), a phosphorus-containing monomer (b2), a reaction catalyst, and an organic solvent are charged into a reaction vessel, and if necessary, the reaction is carried out while heating, keeping warm, stirring, etc., thereby modifying the conjugated diene polymer (B). ) can be obtained.

The reaction temperature for the above reaction is preferably 70 to 120°C, more preferably 80 to 110°C, still more preferably 85 to 105°C, from the viewpoint of workability and suppression of gelling of the product during the reaction.
The reaction time for the above reaction is preferably 0.5 to 15 hours, more preferably 1 to 10 hours, and even more preferably 3 to 7 hours, from the viewpoint of productivity and sufficient progress of the reaction.
However, these reaction conditions are not particularly limited and can be appropriately adjusted depending on the type of raw material used.

Examples of the organic solvent used in the above reaction include alcohol solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. aromatic hydrocarbon solvents such as toluene, xylene and mesitylene; ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate and ethyl acetate; N,N-dimethylformamide, N,N-dimethylacetamide, N nitrogen atom-containing solvents such as -methyl-2-pyrrolidone.
An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, toluene is preferable from the viewpoint of resin solubility.

When the above reaction is carried out in an organic solvent, the total content of the conjugated diene polymer (b1) and the phosphorus-containing monomer (b2) in the reaction solution is not particularly limited, but is preferably 10 to 70% by mass, more preferably 15% by mass. to 60% by mass, more preferably 20 to 50% by mass. When the total content of the conjugated diene polymer (b1) and the phosphorus-containing monomer (b2) is at least the above lower limit, a good reaction rate can be obtained, and productivity tends to be better. In addition, when the total content of the conjugated diene polymer (b1) and the phosphorus-containing monomer (b2) is equal to or less than the above upper limit, better solubility is obtained, stirring efficiency is improved, and the product gels during the reaction. It tends to be possible to further suppress erosion.

As the reaction catalyst, from the viewpoint of obtaining sufficient reactivity while suppressing gelation of the product during the reaction, an organic peroxide is preferable, and α,α'-bis(t-butylperoxy)diisopropyl. Benzene is more preferred.
One of the reaction catalysts may be used alone, or two or more thereof may be used in combination.
The amount of the reaction catalyst used is not particularly limited, but from the viewpoint of reaction rate and reaction uniformity, it is preferably 0.01 to 0.01 parts per 100 parts by mass of the total amount of the conjugated diene polymer (b1) and the phosphorus-containing monomer (b2). 1 part by mass, more preferably 0.03 to 0.5 parts by mass, still more preferably 0.05 to 0.2 parts by mass.

The ratio of the number of moles (M _m ) of ethylenically unsaturated bonds possessed _{by the} phosphorus-containing monomer (b2) to the number of moles (M _v ) of the side chain vinyl groups possessed by the conjugated diene polymer (b1) when performing the above reaction (M _m /M _v ) is not particularly limited, but from the viewpoint of compatibility with other resins of the resulting modified conjugated diene polymer (B) and suppression of gelation of the product during the reaction, it is preferably 0.5. 001 to 0.5, more preferably 0.003 to 0.1, still more preferably 0.005 to 0.05.

The amount of the phosphorus-containing monomer (b2) blended in the above reaction is not particularly limited, but the compatibility of the resulting modified conjugated diene polymer (B) with other resins and the gelation of the product during the reaction From the viewpoint of suppression, it is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the conjugated diene polymer (b1).

<Contents of maleimide-based resin (A) and modified conjugated diene polymer (B), and their content ratios>
In the resin composition of the present embodiment, the content of the maleimide-based resin (A) is not particularly limited, but is preferably 5 to 70 parts by mass with respect to 100 parts by mass of the total resin components in the resin composition of the present embodiment. parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 20 to 40 parts by mass. When the content of the maleimide resin (A) is at least the above lower limit, heat resistance, moldability, workability and conductor adhesion tend to be better. Further, when the content of the maleimide resin (A) is equal to or less than the above upper limit, the dielectric properties tend to be better.

As used herein, the term "resin component" means a resin and a compound that forms a resin through a curing reaction.
For example, in the resin composition of this embodiment, the maleimide resin (A) and the modified conjugated diene polymer (B) correspond to the resin component.
When the resin composition of the present embodiment contains, as optional components, a resin or a compound that forms a resin by a curing reaction in addition to the above components, these optional components are also included in the resin component.
On the other hand, inorganic fillers and flame retardants are not included in the resin component.

In the resin composition of the present embodiment, the content of the modified conjugated diene polymer (B) is not particularly limited. 70 parts by mass, more preferably 10 to 50 parts by mass, still more preferably 20 to 40 parts by mass. When the content of the modified conjugated diene polymer (B) is at least the above lower limit, dielectric properties and flame retardancy tend to be better. Moreover, when the content of the modified conjugated diene polymer (B) is equal to or less than the above upper limit, heat resistance, moldability, processability and conductor adhesion tend to be better.

In the resin composition of the present embodiment, the content ratio [(A)/(B)] of the maleimide resin (A) and the modified conjugated diene polymer (B) is not particularly limited, but is preferably 0.1 to 9, more preferably 0.25 to 4, still more preferably 0.3 to 3. When the content ratio [(A)/(B)] of the maleimide resin (A) and the modified conjugated diene polymer (B) is at least the above lower limit, heat resistance, moldability, workability and conductor adhesion tend to be better. Further, when the content ratio [(A)/(B)] of the maleimide-based resin (A) and the modified conjugated diene polymer (B) is equal to or less than the above upper limit value, dielectric properties and flame retardancy are further improved. There is a tendency.

The content of the resin component in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of low thermal expansion, heat resistance, flame retardancy and conductor adhesion, preferably 10 to 70% by mass, more preferably 20 to 65% by mass, more preferably 30 to 60% by mass.

<Other ingredients>
The resin composition of the present embodiment may further contain other components in addition to the components described above, depending on the desired performance.
Other components include, for example, one or more selected from the group consisting of styrene elastomer (C), inorganic filler (D), flame retardant (E) and curing accelerator (F).
However, the resin composition of the present embodiment is selected from the group consisting of a styrene elastomer (C), an inorganic filler (D), a flame retardant (E) and a curing accelerator (F) depending on desired performance. It is not necessary to contain one or more of the
These components are described in detail below.

<Styrene-based elastomer (C)>
Styrene-based elastomer (C) [hereinafter sometimes referred to as "component (C)". ] is not particularly limited as long as it is an elastomer having a structural unit derived from a styrene compound.
The styrene elastomer (C) may be used alone or in combination of two or more.
As used herein, the term “elastomer” means a polymer having a glass transition temperature of 25° C. or lower as measured by differential scanning calorimetry according to JIS K 6240:2011.

As the styrene-based elastomer (C), one having a styrene-derived structural unit represented by the following general formula (C-1) is preferable.

（式中、Ｒ^ｃ１は水素原子又は炭素数１～５のアルキル基であり、Ｒ^ｃ２は、炭素数１～５のアルキル基である。ｎ^ｃ１は、０～５の整数である。）

(In the formula, R ^c1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ^c2 is an alkyl group having 1 to 5 carbon atoms, and n ^c1 is an integer of 0 to 5.)

Examples of alkyl groups having 1 to 5 carbon atoms represented by R ^c1 and R ^c2 in general formula (C-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group, t-butyl group, n-pentyl group and the like. Alkyl groups having 1 to 5 carbon atoms may be linear or branched. Among these, an alkyl group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 or 2 carbon atoms is more preferred, and a methyl group is even more preferred.
n ^c1 in the general formula (C-1) is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, still more preferably 0.

The styrene-based elastomer (C) may contain structural units other than structural units derived from styrene-based compounds.
Structural units other than the styrene-based compound-derived structural units possessed by the styrene-based elastomer (C) include, for example, butadiene-derived structural units, isoprene-derived structural units, maleic acid-derived structural units, and maleic anhydride-derived structural units. etc.
The butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. When hydrogenated, structural units derived from butadiene become structural units in which ethylene units and butylene units are mixed, and structural units derived from isoprene become structural units in which ethylene units and propylene units are mixed.

Examples of the styrene elastomer (C) include hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, styrene-maleic anhydride copolymers, and the like. be done.
Hydrogenated products of styrene-butadiene-styrene block copolymers are SEBS obtained by completely hydrogenating the carbon-carbon double bonds in the butadiene block, and SBBS obtained by partially hydrogenating a heavy bond can be mentioned. In addition, the complete hydrogenation in SEBS is usually 90% or more of the entire carbon-carbon double bond, may be 95% or more, may be 99% or more, or may be 100%. There may be. Also, the partial hydrogenation rate in SBBS is, for example, 60 to 85% with respect to the entire carbon-carbon double bond. A hydrogenated styrene-isoprene-styrene block copolymer is obtained as SEPS by hydrogenating the polyisoprene portion.
Among these, SEBS and SEPS are preferred, and SEBS is more preferred, from the viewpoint of dielectric properties, conductor adhesion, heat resistance, glass transition temperature and low thermal expansion.

In the above SEBS, the content of structural units derived from styrene [hereinafter sometimes referred to as "styrene content". ] is not particularly limited, but is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, and still more preferably 10 to 20% by mass.

The melt flow rate (MFR) of SEBS is not particularly limited, but is preferably 0.1 to 20 g/10 min, more preferably 1 to 10 g/10 min under the measurement conditions of 230°C and a load of 2.16 kgf (21.2 N). , more preferably 3 to 7 g/10 min.

Commercially available products of SEBS include, for example, Tuftec (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. polymer series and the like.

Although the number average molecular weight of the styrene elastomer (C) is not particularly limited, it is preferably 10,000 to 500,000, more preferably 50,000 to 350,000, still more preferably 100,000 to 200,000. .

When the resin composition of the present embodiment contains the styrene-based elastomer (C), the content thereof is not particularly limited, but is preferably is 10 to 80 parts by mass, more preferably 20 to 60 parts by mass, and still more preferably 30 to 50 parts by mass.
When the content of the styrene-based elastomer (C) is at least the above lower limit, dielectric properties and moisture absorption resistance tend to be better. Moreover, when the content of the styrene-based elastomer (C) is equal to or less than the above upper limit, heat resistance, moldability, processability and flame retardancy tend to be better.

When the resin composition of the present embodiment contains the styrene elastomer (C), the content ratio [(B)/(C)] of the modified conjugated diene polymer (B) and the styrene elastomer (C) is Although not limited, it is preferably from 0.1 to 10, more preferably from 0.2 to 5, and even more preferably from 0.5 to 1, from the viewpoint of compatibility, dielectric properties and flame retardancy.

(Inorganic filler (D))
The resin composition of the present embodiment may be referred to as an inorganic filler (D) [hereinafter, "component (D)". ], low thermal expansion, heat resistance and flame retardancy tend to be further improved.
An inorganic filler (D) may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of the inorganic filler (D) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, silicon aluminum oxide, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide and the like. Among these, silica, alumina, mica, and talc are preferable, silica and alumina are more preferable, and silica is still more preferable, from the viewpoint of low thermal expansion, heat resistance, and flame retardancy.
Silica includes, for example, precipitated silica produced by a wet method and having a high moisture content, and dry-process silica produced by a dry method and containing almost no bound water. Examples of dry process silica include crushed silica, fumed silica, fused silica, etc., depending on the production method.

Although the average particle size of the inorganic filler (D) is not particularly limited, it is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 0.1 to 10 μm, from the viewpoint of dispersibility and fine wiring properties of the inorganic filler. is 0.2 to 1 μm, particularly preferably 0.3 to 0.8 μm.
In this specification, the average particle size of the inorganic filler (D) is the particle size at the point corresponding to 50% volume when the cumulative frequency distribution curve by particle size is obtained with the total volume of the particles being 100%. be. The average particle size of the inorganic filler (D) can be measured, for example, with a particle size distribution analyzer using a laser diffraction scattering method.
Examples of the shape of the inorganic filler (D) include a spherical shape and a pulverized shape, with a spherical shape being preferred.

When the resin composition of the present embodiment contains an inorganic filler (D), the content of the inorganic filler (D) in the resin composition is not particularly limited. , preferably 10 to 70% by mass, more preferably 20 to 65% by mass, still more preferably 30 to 60% by mass. When the content of the inorganic filler (D) is at least the above lower limit, low thermal expansion, heat resistance and flame retardancy tend to be better. Moreover, when the content of the inorganic filler (D) is equal to or less than the above upper limit, moldability and conductor adhesiveness tend to be better.

When the resin composition of the present embodiment contains the inorganic filler (D), a coupling agent may be used for the purpose of improving the dispersibility of the inorganic filler (D) and the adhesion to the organic component. . Examples of coupling agents include silane coupling agents and titanate coupling agents. Among these, silane coupling agents are preferred. Silane coupling agents include, for example, aminosilane coupling agents, vinylsilane coupling agents, and epoxysilane coupling agents.

When a coupling agent is used in the resin composition of the present embodiment, the surface treatment method of the inorganic filler (D) is to add the coupling agent after the inorganic filler (D) is blended into the resin composition. An integral blend treatment method may be used, or a method in which the inorganic filler (D) is surface-treated in advance with a coupling agent in a dry or wet manner. Among these, the method of surface-treating the inorganic filler (D) with a coupling agent in advance in a dry or wet manner is preferable from the viewpoint of more effectively expressing the features of the inorganic filler (D).
For the purpose of improving the dispersibility in the resin composition, the inorganic filler (D) may be previously dispersed in an organic solvent to form a slurry, and then mixed with other components.

(Flame retardant (E))
The resin composition of the present embodiment may be referred to as a flame retardant (E) [hereinafter, "component (E)". ], the flame retardancy tends to be further improved.
However, since the resin composition of the present embodiment contains the modified conjugated diene polymer (B) having a flame retardant effect, it may not contain the flame retardant (E).
A flame retardant (E) may be used individually by 1 type, and may be used in combination of 2 or more type.
Moreover, the resin composition of the present embodiment may contain a flame retardant aid as necessary.

Examples of the flame retardant (E) include phosphorus-based flame retardants, metal hydrates, and halogen-based flame retardants. From the viewpoint of environmental problems, phosphorus-based flame retardants and metal hydrates are preferred.

-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 flame retardants.
The phosphorus-based flame retardant may be an inorganic phosphorus-based flame retardant or an organic phosphorus-based flame retardant. From the viewpoint of environmental problems, the phosphorus-based flame retardant preferably does not contain a halogen atom.

Examples of inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as amide phosphoric acid. ; phosphoric acid; phosphine oxide;

Examples of organic phosphorus-based flame retardants include aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, and the like. is mentioned. Among these, aromatic phosphate compounds and metal salts of disubstituted phosphinic acids are preferred. Here, examples of metal salts include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, zinc salts and the like. Among these, aluminum salts are preferred. Among organic phosphorus-based flame retardants, aromatic phosphate esters are preferred.

Examples of aromatic phosphates include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3 -phenylene bis(di-2,6-xylenyl phosphate), bisphenol A-bis(diphenyl phosphate), 1,3-phenylene bis(diphenyl phosphate) and the like.

The monosubstituted phosphonic acid diesters include, for example, divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate and the like.
Disubstituted phosphinate esters include, for example, phenyl diphenylphosphinate and methyl diphenylphosphinate.

Examples of metal salts of disubstituted phosphinic acids include metal salts of dialkylphosphinic acid, metal salts of diallylphosphinic acid, metal salts of divinylphosphinic acid, and metal salts of diarylphosphinic acid. Aluminum salts are preferred as these metal salts.

Examples of organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.

Examples of cyclic organic phosphorus compounds include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- and 10-phosphaphenanthrene-10-oxide.

Among the above organic phosphorus-based flame retardants, aromatic phosphoric acid esters and metal salts of disubstituted phosphinic acids are preferable, and 1,3-phenylene bis(di-2,6-xylenyl phosphate) and dialkylphosphinic acid is more preferred, and aluminum trisdiethylphosphinate is even more preferred.

-metal hydrate-
Examples of metal hydrates include aluminum hydroxide hydrates and magnesium hydroxide hydrates.

- Halogen Flame Retardant -
Examples of halogen-based flame retardants include chlorine-based flame retardants and bromine-based flame retardants. Examples of chlorine-based flame retardants include chlorinated paraffins.

When the resin composition of the present embodiment contains the flame retardant (E), the content of the flame retardant (E) is not particularly limited. On the other hand, it is preferably 1 to 15 parts by mass, more preferably 4 to 12 parts by mass, still more preferably 6 to 10 parts by mass. When the content of the flame retardant (E) is at least the above lower limit, flame retardancy tends to be better. Moreover, when the content of the flame retardant (E) is equal to or less than the above upper limit, dielectric properties, moldability, and conductor adhesion tend to be better.

Examples of flame retardant aids include inorganic flame retardant aids such as antimony trioxide and zinc molybdate.
When the resin composition of the present embodiment contains a flame retardant aid, the content is not particularly limited, but is preferably 0 per 100 parts by mass of the total resin components in the resin composition of the present embodiment. 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, still more preferably 0.1 to 5 parts by mass. When the content of the flame retardant aid is within the above range, better chemical resistance tends to be obtained.

(Curing accelerator (F))
By containing the curing accelerator (F), the resin composition of the present embodiment tends to be improved in curability and have better dielectric properties, heat resistance, conductor adhesion, and the like.
The curing accelerator (F) may be used alone or in combination of two or more.

Examples of the curing accelerator (F) include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; hexamethylene diisocyanate resin and 2-ethyl - isocyanate mask imidazole compounds such as adducts of 4-methylimidazole; tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2, 5-bis(t-butylperoxy)hexyne-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;
Among these, from the viewpoint of heat resistance and storage stability, imidazole compounds, isocyanate-masked imidazole compounds, organic peroxides, and carboxylates are preferred, organic peroxides are more preferred, and dicumyl peroxide is even more preferred.

When the resin composition of the present embodiment contains the curing accelerator (F), the content of the curing accelerator (F) is not particularly limited, but the total sum of the resin components in the resin composition of the present embodiment is 100 mass. parts, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass. When the content of the curing accelerator (F) is at least the above lower limit, dielectric properties, heat resistance and conductor adhesion tend to be better. Moreover, when the content of the curing accelerator (F) is equal to or less than the above upper limit, the storage stability tends to be better.

The resin composition of the present embodiment further contains resin materials other than the above components, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and other additives. It may contain one or more optional ingredients selected from the group consisting of agents.
Each of the above optional components may be used alone or in combination of two or more.
The content of the above optional components in the resin composition of the present embodiment is not particularly limited, and may be used as necessary within a range that does not impair the effects of the present embodiment.
Moreover, the resin composition of the present embodiment may not contain any of the above optional components depending on the desired performance.

(organic solvent)
The resin composition of the present embodiment may contain an organic solvent from the viewpoint of facilitating handling and facilitating production of resin films and prepregs.
An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
In addition, the resin composition containing an organic solvent may be called a resin varnish in this specification.

Examples of organic solvents include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide; ester solvents such as γ-butyrolactone, etc. mentioned.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, nitrogen atom-containing solvents, and aromatic hydrocarbon solvents are preferred, aromatic hydrocarbon solvents are more preferred, and toluene is even more preferred.

When the resin composition of the present embodiment contains an organic solvent, the solid content concentration of the resin composition is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and still more preferably 40% by mass. ~60% by mass. When the solid content concentration is within the above range, the resin composition tends to be easy to handle, and tends to have good applicability to a support, impregnation to a substrate, and the like. In addition, it becomes easier to adjust the solid content concentration of the resin in the prepreg, and there is a tendency to make it easier to manufacture a prepreg having a desired thickness.

The relative dielectric constant (Dk) at 10 GHz of the cured product of the resin composition of the present embodiment is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 3.0 or less, more preferably 2.9 or less, and further It is preferably 2.8 or less. The dielectric constant (Dk) of the cured product is preferably as small as possible, and the lower limit thereof is not particularly limited. It may be 4 or more, or 2.5 or more.
The conditions for obtaining a cured product from the resin composition of the present embodiment can be the conditions described in Examples.
The dielectric constant (Dk) above is a value based on the cavity resonator perturbation method, more specifically, a value measured by the method described in the Examples.

The dielectric loss tangent (Df) at 10 GHz of the cured product of the resin composition of the present embodiment is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 0.0040 or less, more preferably 0.0030 or less, and still more preferably is 0.0020 or less. The dielectric loss tangent (Df) of the cured product is preferably as small as possible, and the lower limit thereof is not particularly limited. or more, or 0.0014 or more.
The conditions for obtaining a cured product from the resin composition of the present embodiment can be the conditions described in Examples.
The above dielectric loss tangent (Df) is a value based on the cavity resonator perturbation method, more specifically, a value measured by the method described in Examples.

[Prepreg]
The prepreg of this embodiment is a prepreg containing the resin composition of this embodiment.
The prepreg of the present embodiment is preferably obtained by impregnating or applying the resin composition of the present embodiment to a sheet-like fiber-reinforced base material, followed by B-stage. In this specification, the B-staging refers to making the state of B-stage defined in JIS K6900 (1994), and is also called semi-curing.

As the sheet-like fiber-reinforced base material contained in the prepreg of the present embodiment, known sheet-like fiber-reinforced base materials used for various laminates for electrical insulating materials can be used.
Examples of materials for the sheet-like fiber-reinforced 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 mixtures thereof. These sheet-like fiber-reinforced substrates have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, surfacing mats, and the like.
The thickness of the sheet-like fiber-reinforced base material is not particularly limited, but is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and even more preferably 0.02 to 0.3 mm, from the viewpoint of mechanical strength and thinning of the prepreg. is 0.03 to 0.1 mm.
The sheet-like fiber reinforced substrate may be surface-treated with a coupling agent or the like from the viewpoint of impregnation of the resin composition, heat resistance, moisture absorption resistance and workability when laminated. It may also be one that has undergone a fiber opening treatment.

The prepreg of the present embodiment can be produced, for example, by impregnating or applying the resin composition of the present embodiment to a sheet-like fiber-reinforced base material, and then drying it as necessary.
As a method for impregnating or applying the resin composition of the present embodiment to the sheet-like fiber-reinforced base material, for example, a hot-melt method, a solvent method, or the like can be employed.

The hot-melt method is a method of impregnating or coating a sheet-like fiber-reinforced base material with a resin composition that does not contain an organic solvent.
As one aspect of the hot-melt method, the resin composition of the present embodiment that does not contain an organic solvent is once coated on coated paper with good releasability, and then the coated resin composition is applied to a sheet-shaped fiber-reinforced base material. A method of laminating to
Another aspect of the hot-melt method is a method in which the resin composition of the present embodiment containing no organic solvent is directly applied to the sheet-like fiber-reinforced base material using a die coater or the like.

The solvent method is a method of impregnating or coating a sheet-like fiber-reinforced base material with a resin composition containing an organic solvent. Specifically, for example, a method of immersing a sheet-like fiber-reinforced base material in the resin composition of the present embodiment containing an organic solvent and then drying the base material may be used. By drying, the organic solvent in the resin composition can be removed and the resin composition can be B-staged.
Although the drying temperature is not particularly limited, it is preferably 50 to 200° C., more preferably 100 to 190° C., still more preferably 150 to 150° C., from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment. 180°C.
The drying time is not particularly limited, but from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment, it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and still more preferably 3 to 30 minutes. 10 minutes.

The solid content concentration derived from the resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 20 to 90% by mass, more It is preferably 25 to 80% by mass, more preferably 30 to 75% by mass.

The thickness of the prepreg of the present embodiment is not particularly limited, but from the viewpoint of enabling moldability and high-density wiring, it is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, More preferably, it is 0.03 to 0.1 mm.

[Resin film]
The resin film of this embodiment is a resin film containing the resin composition of this embodiment.
The resin film of the present embodiment can be produced, for example, by applying the resin composition of the present embodiment containing an organic solvent, ie, a resin varnish, to a support, followed by heating and drying.

Examples of the support include plastic films, metal foils, release papers and the like.
Examples of plastic films include films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyethylene terephthalate (hereinafter sometimes referred to as "PET"). ], polyester films such as polyethylene naphthalate; polycarbonate films, polyimide films and the like. Among these, polyethylene terephthalate film is preferable from the viewpoint of economy and handling.
Examples of metal foil include copper foil and aluminum foil. When a copper foil is used as the support, the copper foil can be used as a conductor layer to form a circuit. In this case, a rolled copper foil, an electrolytic copper foil, or the like can be used as the copper foil. When using a thin copper foil, a copper foil with a carrier may be used from the viewpoint of improving workability.
The support may be subjected to surface treatment such as matte treatment or corona treatment. Further, the support may be subjected to release treatment with a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, or the like.
The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 20 to 100 μm, still more preferably 25 to 50 μm, from the viewpoints of ease of handling and economy.

As a coating device for coating the resin varnish, for example, a coating device known to those skilled in the art such as a comma coater, bar coater, kiss coater, roll coater, gravure coater and die coater can be used. These coating apparatuses may be appropriately selected according to the film thickness to be formed.
Drying conditions after applying the resin varnish may be appropriately determined according to the content of the organic solvent, the boiling point, etc., and are not particularly limited.
For example, in the case of a resin varnish containing 40 to 60% by mass of an aromatic hydrocarbon-based solvent, the drying temperature is not particularly limited, but the productivity and the resin composition of the present embodiment are appropriately B-staged. , preferably 50 to 200°C, more preferably 100 to 190°C, still more preferably 150 to 180°C.
In the case of the above resin varnish, the drying time is not particularly limited, but from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment, it is preferably 1 to 30 minutes, more preferably 2 to 30 minutes. 15 minutes, more preferably 3 to 10 minutes.

The thickness of the resin film of the present embodiment can be appropriately determined according to the application of the resin film. 10 to 100 μm, more preferably 15 to 60 μm.

The resin film of this embodiment may have a protective film. The protective film is provided on the surface of the resin film of the present embodiment opposite to the surface on which the support is provided, and is used for the purpose of preventing foreign matter from adhering to and damaging the resin film. be. The protective film is peeled off before laminating the resin film of the present embodiment on a circuit board or the like by lamination, heat press, or the like.

The resin film of the present embodiment is preferably used for forming an insulating layer when manufacturing a multilayer printed wiring board.
For example, when manufacturing a multilayer printed wiring board, the resin film of the present embodiment is a layer that melts and flows when laminated on a circuit board and serves to embed the circuit board.
In addition, for example, when a circuit board has a through hole, a via hole, or the like, the resin film of the present embodiment flows into these holes and fills the inside of the holes.

[Laminate]
The laminate of this embodiment is a laminate containing the prepreg of this embodiment and metal foil. A laminate having metal foil is sometimes referred to as a metal-clad laminate.
The metal of the metal foil is not particularly limited as long as it is used as an electrical insulating material. Examples include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more metal elements. Examples of alloys include copper-based alloys, aluminum-based alloys, and iron-based alloys. Copper-based alloys include copper-nickel alloys and the like. Examples of iron-based alloys include iron-nickel alloys.
Among these, copper, nickel, aluminum, and iron-nickel alloys are preferred, copper and aluminum are more preferred, and copper is even more preferred, from the viewpoint of conductivity and availability.
Although the thickness of the metal foil is not particularly limited, it is preferably 1 to 200 μm, more preferably 2 to 100 μm, still more preferably 3 to 50 μm.

The laminate of the present embodiment can be produced, for example, by placing a metal foil on one side or both sides of the prepreg of the present embodiment, followed by heating and pressure molding.
Generally, the laminate of the present embodiment is obtained by curing the prepreg in a semi-cured state by this heating and pressure molding.
In the heat and pressure molding, only one prepreg may be used, or two or more prepregs may be laminated. In addition to prepregs and metal foils, substrates on which inner layer circuits have been processed may also be molded under heat and pressure.
For heat-press molding, for example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. can be used.
The heating temperature for hot-press molding is not particularly limited, but is preferably 100 to 300.degree. C., more preferably 150 to 280.degree. C., still more preferably 200 to 250.degree.
The heating and pressing time for the heating and pressing molding is not particularly limited, but is preferably 10 to 300 minutes, more preferably 30 to 200 minutes, still more preferably 80 to 150 minutes.
The pressure for hot-press molding is not particularly limited, but is preferably 1.5 to 5 MPa, more preferably 1.7 to 3 MPa, still more preferably 1.8 to 2.5 MPa.
However, these conditions can be appropriately adjusted according to the type of raw material used, etc., and are not particularly limited.

[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 laminate of the present embodiment.
That is, the multilayer printed wiring board of the present embodiment comprises at least a multilayer structure containing the cured prepreg of the present embodiment, the cured resin film of the present embodiment, or the laminate of the present embodiment, and a conductor circuit layer. include.
A method for manufacturing the multilayer printed wiring board of the present embodiment using the resin film of the present embodiment will be described below.

When manufacturing a multilayer printed wiring board using the resin film of this embodiment, first, the resin film of this embodiment is laminated on one side or both sides of a circuit board. After the resin film of the present embodiment is placed in contact with the circuit board, for example, the resin film of the present embodiment is laminated on the circuit board by pressure bonding to the circuit board while applying pressure and heat using a vacuum laminator. can be done.
Circuit boards used for multilayer printed wiring boards include, for example, glass epoxy, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like, on one or both sides of which a patterned conductor layer ( circuit) is formed.
From the viewpoint of adhesiveness, the surface of the conductor layer of the circuit board may be roughened in advance by blackening treatment or the like.

Next, after peeling off the support of the resin film as necessary, the resin film is cured by heating to form an insulating layer.
The heating temperature for heat curing is not particularly limited, but is preferably 100 to 300°C, more preferably 120 to 280°C, and still more preferably 150 to 250°C.
The heating time for heat curing is not particularly limited, but is preferably 2 to 300 minutes, more preferably 5 to 200 minutes, still more preferably 10 to 150 minutes.

After the insulating layer is formed by the above method, holes may be drilled if necessary. Drilling is a process of drilling holes in the circuit board and the formed insulating layer by a method such as a drill, laser, plasma, or a combination thereof to form via holes, through holes, and the like. Examples of lasers used for drilling include carbon dioxide lasers, YAG lasers, UV lasers, excimer lasers, and the like.

Then, the surface of the insulating layer may be roughened with an oxidizing agent. Further, when via holes, through holes, etc. are formed in the insulating layer and the circuit board, the so-called "smear" generated when forming these may be removed with an oxidizing agent. Roughening treatment and smear removal can be performed at the same time. The roughening treatment can form uneven anchors on the surface of the insulating layer.
Examples of the oxidizing agent include permanganates such as potassium permanganate and sodium permanganate, bichromate, ozone, hydrogen peroxide, sulfuric acid, and nitric acid. Among these, an aqueous sodium hydroxide solution of potassium permanganate and an aqueous sodium hydroxide solution of sodium permanganate, which are oxidizing agents commonly used in the manufacture of multilayer printed wiring boards by the build-up method, are preferred.

Next, a conductor layer is formed on the roughened surface of the insulating layer. The conductor layer can be formed by plating, for example.
Examples of plating methods include electroless plating and electrolytic plating. Metals for plating include, for example, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing at least one of these metal elements. Among these, copper and nickel are preferable, and copper is more preferable.
It is also possible to adopt a method of first forming a plating resist having a pattern opposite to the wiring pattern and then forming the wiring pattern only by electroless plating.
Annealing treatment may be performed after the conductor layer is formed. Annealing tends to further improve and stabilize the adhesive strength between the interlayer insulating layer and the conductor layer.

Examples of methods for patterning a conductor layer and forming a circuit include a subtractive method, a full additive method, a semi-additive method (SAP: SemiAdditive Process), a modified semi-additive method (m-SAP: modified Semi-Additive Process), and the like. A known method can be used.

[Semiconductor package]
The semiconductor package of this embodiment is obtained by mounting a semiconductor on the multilayer printed wiring board of this embodiment. The semiconductor package of this embodiment can be manufactured, for example, by mounting a semiconductor chip, a memory, etc. on the multilayer printed wiring board of this embodiment by a known method.

[Method for producing resin composition]
The method for producing the resin composition of the present embodiment includes
(A) one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof;
(B) a modified conjugated diene polymer obtained by reacting (b1) a conjugated diene polymer having a vinyl group in a side chain with a (b2) compound having a phosphorus atom and an ethylenically unsaturated bond;
A method for producing a resin composition by mixing
A detailed description of each component is provided above.
When mixing each component, each component may be dissolved or dispersed while stirring. Conditions such as the order of mixing raw materials, mixing temperature, and mixing time are not particularly limited, and may be arbitrarily set according to the type of raw materials.

EXAMPLES The present embodiment will be specifically described below with reference to examples. However, this embodiment is not limited to the following examples.

In addition, in each example, the number average molecular weight was measured by the following procedures.
(Method for measuring number average molecular weight)
Number average molecular weights were calculated by gel permeation chromatography (GPC) from a standard curve using polystyrene standards. Calibration curve, standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, product name] and approximated by a cubic equation. GPC measurement conditions are shown below.
[Measurement conditions for GPC]
Apparatus: High-speed GPC apparatus HLC-8320GPC
Detector: UV absorption detector UV-8320 [manufactured by Tosoh Corporation]
Column: Guard column; TSK Guardcolumn SuperHZ-L + column; TSKgel SuperHZM-N + TSKgel SuperHZM-M + TSKgel SuperH-RC (all manufactured by Tosoh Corporation, trade name)
Column size: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column)
Eluent: Tetrahydrofuran Sample concentration: 10 mg/5 mL
Injection volume: 25 μL
Flow rate: 1.00 mL/min Measurement temperature: 40°C

[Production of modified conjugated diene polymer]
Production Examples 1-3
Into a 2-liter glass flask equipped with a thermometer, a reflux condenser, and a stirrer and capable of being heated and cooled, the amounts of each starting material shown in Table 1 and toluene as an organic solvent were charged. Then, the mixture was reacted under a nitrogen atmosphere at 90 to 100° C. for 5 hours with stirring to obtain solutions of modified conjugated diene polymers 1 to 3 (solid concentration: 35 mass %). Table 1 shows the number average molecular weight of the resulting modified conjugated diene polymer. In addition, in Table 1, the compounding amount of each component means the compounding amount of the solid content.

In addition, the details of each component described in Table 1 are as follows.
[(b1) component]
· Polybutadiene 1: 1,2-polybutadiene homopolymer, number average molecular weight = 1,200, vinyl group content = 85% or more [(b2) component]
- Phosphorus-containing monomer 1: diphenyl-(methacryloyloxymethyl) phosphine oxide [reaction catalyst]
・Organic peroxide: α,α'-bis(t-butylperoxy)diisopropylbenzene

[Preparation of resin composition]
Examples 1-3, Comparative Examples 1-2
After blending each component shown in Table 2 with toluene according to the blending amount shown in Table 2, the solid content concentration is about 50% by mass by stirring and mixing while heating at 25 ° C. or 50 to 80 ° C. was prepared. In Table 2, the unit of the compounding amount of each component is parts by mass, and in the case of solutions, it means parts by mass in terms of solid content.

[Production of resin film and resin plate with double-sided copper foil]
The resin composition obtained in each example was applied to a 38 μm thick PET film (manufactured by Teijin Limited, trade name: G2-38), and then dried by heating at 170° C. for 5 minutes to obtain a B-stage resin. A film was produced. After peeling the resin film from the PET film, it was pulverized to obtain resin powder in a B-stage state.
The resin powder obtained above was put into a Teflon (registered trademark) sheet punched into a size of 1 mm thick x 50 mm long x 35 mm wide. Company's trade name: 3EC-VLP-18) was arranged. The low-profile copper foil was arranged with the M side facing the resin powder. Subsequently, the laminate before heat and pressure molding is heat and pressure molded under the conditions of a temperature of 230 ° C., a pressure of 2.0 MPa, and a time of 120 minutes, and the resin powder is molded into a resin plate and cured. A resin plate with a copper foil was produced. The thickness of the resin plate portion of the obtained resin plate with copper foil on both sides was 1 mm.

[Measurement and evaluation method]
Using the resin compositions and resin plates with copper foils on both sides obtained in the above Examples and Comparative Examples, various measurements and evaluations were performed according to the following methods. Table 2 shows the results.

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

(2. Measurement of dielectric constant and dielectric loss tangent of cured product)
The resin plate with copper foil on both sides obtained in each example was immersed in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Company, Inc.), which is a copper etching solution, to remove the copper foil and prepare a test piece of 2 mm × 50 mm. did. Then, according to the cavity resonator perturbation method, the dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece were measured at an ambient temperature of 25° C. and in a 10 GHz band.

(3. Evaluation of flame retardancy)
The outer layer copper foil of the double-sided copper-clad laminate was removed by immersion in a copper etching solution (10% by mass solution of ammonium persulfate, manufactured by Mitsubishi Gas Chemical Company, Inc.), and cut into a length of 127 mm and a width of 12.7 mm. was used as a test piece. Next, in accordance with the UL94 test method (V method), the lower end of the test piece held vertically was exposed to a 20 mm flame for 10 seconds twice, and the flame retardancy was evaluated according to the UL94 V method standards. did. In addition, when the test piece was burned out by the test, it was described as "×"

The details of each component shown in Table 2 are as follows.
[(A) component]
- Aromatic bismaleimide compound containing an indane ring: number average molecular weight = 1,300
[(B) Component]
- Modified conjugated diene polymer 1: Modified conjugated diene polymer 1 obtained in Production Example 1
- Modified conjugated diene polymer 2: Modified conjugated diene polymer 2 obtained in Production Example 2
- Modified conjugated diene polymer 3: Modified conjugated diene polymer 3 obtained in Production Example 3
[(B') component]
Conjugated diene polymer: 1,2-polybutadiene homopolymer, number average molecular weight = 1,200, vinyl group content = 85% or more [(C) component]
・ Styrene-based elastomer: trade name “Tuftec (registered trademark) H1221” (manufactured by Asahi Kasei Corporation), hydrogenated styrene-based thermoplastic elastomer (SEBS; styrene-ethylene-butylene-styrene copolymer), styrene unit content = 12 Mass %, 230 ° C., MFR under measurement conditions of 2.16 kgf load = 4.5 g / 10 min, number average molecular weight = 170,000

As can be seen from Table 2, the resin compositions obtained in Examples 1 to 3 of the present embodiment have low dielectric constants and dielectric loss tangents, and excellent compatibility and flame retardancy. From this, it can be seen that the resin composition of the present embodiment is excellent in dielectric properties, compatibility and flame retardancy in a high frequency band of 10 GHz or higher. On the other hand, the resin composition obtained in Comparative Example 1 was inferior in dielectric properties, compatibility and flame retardancy, and the resin composition obtained in Comparative Example 2 was inferior in compatibility and flame retardancy. rice field.

A cured product produced from the resin composition of the present embodiment is excellent in dielectric properties, compatibility and flame retardancy in a high frequency band of 10 GHz or higher. Therefore, the resin composition of the present embodiment is used for fifth-generation mobile communication system (5G) antennas in which radio waves in the frequency band exceeding 6 GHz are used, and millimeter wave radars in which radio waves in the frequency band of 30 to 300 GHz are used. It is useful for multilayer printed wiring boards and the like.

Claims (13)

(A) one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof;
(B) a modified conjugated diene polymer obtained by reacting (b1) a conjugated diene polymer having a vinyl group in a side chain with a (b2) compound having a phosphorus atom and an ethylenically unsaturated bond;
A resin composition containing 2. The resin composition according to claim 1, wherein the component (b2) is a compound having a phosphine oxide group and an ethylenically unsaturated bond. The resin composition according to claim 2, wherein the compound having a phosphine oxide group and an ethylenically unsaturated bond is a phosphine oxide group-containing (meth)acrylate compound. The resin composition according to any one of claims 1 to 3, wherein the component (b1) is polybutadiene having a 1,2-vinyl group. The resin composition according to any one of claims 1 to 4, further comprising a styrene elastomer. At least one selected from the group consisting of maleimide compounds wherein the component (A) contains a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and has two or more N-substituted maleimide groups, and derivatives thereof. The resin composition according to any one of claims 1 to 5. A prepreg containing the resin composition according to any one of claims 1 to 6. A laminate comprising the prepreg according to claim 7 and a metal foil. A resin film comprising the resin composition according to any one of claims 1 to 6. A multilayer printed wiring board comprising one or more selected from the group consisting of the prepreg according to claim 7, the laminate according to claim 8, and the resin film according to claim 9. A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 10 . A method for producing the resin composition according to any one of claims 1 to 6,
(A) one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof;
(B) a modified conjugated diene polymer obtained by reacting (b1) a conjugated diene polymer having a vinyl group in a side chain with a (b2) compound having a phosphorus atom and an ethylenically unsaturated bond;
A method for producing a resin composition by mixing (b1) A modified conjugated diene polymer obtained by reacting a conjugated diene polymer having a vinyl group in a side chain with (b2) a compound having a phosphorus atom and an ethylenically unsaturated bond.