JP2023152756A - Curable composition, cured product, prepreg, circuit board, build-up film, semiconductor sealant and semiconductor device - Google Patents

Abstract

To provide a curable composition that shows low dielectric loss tangent and low moisture absorptivity when cured, and a cured product thereof.SOLUTION: A curable composition contains a polymaleimide compound (A) including a monocyclic or fused polycyclic aromatic group combined with two or more linear or branched alkylene groups, and an unsaturated hydrocarbon compound (B) with a reactive double bond.SELECTED DRAWING: None

Description

The present disclosure relates to a curable composition, a cured product, a prepreg, a circuit board, a buildup film, a semiconductor encapsulant, and a semiconductor device.

A prepreg obtained by impregnating a glass cloth with a thermosetting resin such as an epoxy resin or a BT (bismaleimide-triazine) resin and drying it by heating, a laminate obtained by heating and curing the prepreg, and a laminate and the prepreg. Multilayer boards made by heating and curing in combination are widely used as circuit board materials for electronic devices. In particular, package substrates, which are a type of printed wiring board that plays the role of an interposer for mounting semiconductors, are becoming thinner and warping of the package substrate during mounting becomes a problem. In order to suppress this, there is a need for materials that exhibit high heat resistance.
In addition, in recent years, the speed and frequency of signals have increased, and thermosetting compositions that can maintain a sufficiently low dielectric constant and form a cured product that exhibits a sufficiently low dielectric loss tangent under these environments have been developed. It is hoped that it will be provided. Particularly recently, in various electrical materials applications, particularly in advanced materials applications, there has been a demand for further improvements in performance, typified by heat resistance and dielectric properties, as well as materials and compositions that have both of these properties. In response to these demands, maleimide resin is attracting attention as a material that has both heat resistance, low dielectric constant, and low dielectric loss tangent. However, although conventional maleimide resins exhibit high heat resistance, they are highly hygroscopic and their dielectric properties (permittivity and dielectric loss tangent) do not reach the level required for advanced material applications.
For example, Patent Document 1 discloses that a polymaleimide resin having an indane ring and triallyl cyanurate or an aromatic diamine are used as printed circuit board materials that do not impair heat resistance and have a dielectric constant of 4.0 or less as a laminate. A thermosetting composition containing the following is disclosed.

Japanese Patent Application Publication No. 5-247202

However, the thermosetting composition of Patent Document 1 does not consider the dielectric loss tangent value, so the dielectric constant and dielectric loss tangent value do not reach the level required for advanced material applications, and the thermosetting composition has low moisture absorption at high temperatures. However, it is not compatible with low dielectric constant and low dielectric loss tangent.
Therefore, the technical problem to be solved by the present disclosure is to provide a curable composition, a cured product, a prepreg, a circuit board, a build-up film, which has low hygroscopicity and exhibits a low dielectric loss tangent and a low dielectric constant when cured. An object of the present invention is to provide a semiconductor encapsulant and a semiconductor device.

As a result of extensive research to solve the above-mentioned problems, the present inventors have discovered a polycyclic polycyclic ring containing a monocyclic or fused polycyclic aromatic ring to which two or more linear or branched alkylene groups are bonded. By using a curable composition containing a maleimide compound (A) and an unsaturated hydrocarbon compound (B) having a reactive double bond, it is possible to improve hygroscopicity, low dielectric loss tangent, and low dielectric constant during curing. The present invention has been completed by discovering that both can be achieved at a high level.

According to the present disclosure, there is provided a curable composition that can achieve high levels of low hygroscopicity, low dielectric constant, and low dielectric loss tangent during curing, as well as cured products thereof, prepregs, circuit boards, build-up films, and semiconductors. A sealing material and a semiconductor device can be provided. Such a curable composition is particularly useful in applications such as electronic component sealing materials.

FIG. 1A shows the GPC measurement results of the polymaleimide compound (A-1) of this example. FIG. 1B shows the FD-MS measurement results of the polymaleimide compound (A-1) of this example. FIG. 1C shows the results of ¹³ C-NMR measurement of the polymaleimide compound (A-1) of this example.

Hereinafter, embodiments of the present invention (referred to as "the present embodiments") will be described in detail, but the present disclosure is not limited to the following description, and can be implemented with various modifications within the scope of the gist. can do.

[term]
The term "reaction raw material" as used herein refers to a compound that is used to obtain a target compound through a chemical reaction such as combination or decomposition, and that partially constitutes the chemical structure of the target compound, and is a chemical compound such as a solvent or a catalyst. Substances that play the role of auxiliaries in the reaction are excluded. In this specification, in particular, "reaction raw material" means, for example, when the target product is a polymaleimide compound (A), the polymaleimide compound (A) or its precursor compound (e.g., the aromatic amine compound (a) It refers to a precursor for obtaining an intermediate amine compound (c)) which is linked to each other via the aromatic divinyl compound (b1) through a chemical reaction.
The "aromatic group" in this specification preferably has an aromatic ring having 3 to 30 carbon atoms, and more preferably has an aromatic ring having 4 to 26 carbon atoms. The "aromatic group" in this specification means that the hydrogen atom of the aromatic ring in the aromatic group is a substituent, for example, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, It may be substituted with a group or a halogen atom. In addition, "aromatic group" includes heteroaromatic groups, and -CH ₂ - or -CH= in the "aromatic group" are substituted with -O-, -S- or -N= so that they are not adjacent to each other. It's okay.
Examples of the type of aromatic ring include a monocyclic aromatic ring and a fused polycyclic aromatic ring. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of the fused polycyclic aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, and the like. Further, the hydrogen atom of the aromatic ring in the aromatic group is, for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms,
It may be substituted with an alkoxy group having 1 to 10 carbon atoms, an aryl group having 1 to 12 carbon atoms, an aralkyl group having 1 to 12 carbon atoms, or a halogen atom.
In addition, a monovalent aromatic group refers to a group in which one hydrogen atom is removed from the "aromatic group", and a divalent aromatic group refers to a group in which any hydrogen atom in the "aromatic group" is removed. A trivalent to hexavalent aromatic group refers to a group from which 3 to 6 hydrogen atoms have been removed from the "aromatic group."
Examples of the "aralkyl group" in this specification include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group. The hydrogen atom of the aromatic ring in the aralkyl group is substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. It's okay. Note that the "aralkylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the "aralkyl group" described above.
The "alkyl group" in this specification may be linear, branched, or cyclic, and includes, for example, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group , (n-) nonyl group, (n-) decyl group, (n-) undecyl group, (n-) dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, or Examples include cyclononyl group.
In this specification, "cycloalkyl group" includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, methylcyclobutyl group, norbornyl group, or adamantyl group, etc. Can be mentioned.
Examples of the "alkylthio group" in this specification include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, an octylthio group, and a 2-ethylhexylthio group.
Examples of the "alkenyl group" in this specification include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, pentynyl group, hexynyl group, vinyl group, allyl group, and isopropenyl group.
In this specification, "alkoxy group" includes, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, or nonyloxy group. Can be mentioned.
Examples of the "aryl group" in this specification include a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, an anthryl group, an azulenyl group, a tetralinyl group, and the like. Further, the "aryl group" means that the hydrogen atom of the aromatic ring in the aryl group is, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. may be substituted with an alkenyl group or a halogen atom. Note that the "arylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the above-mentioned "aryl group."
Examples of the "aryloxy group" in this specification include a phenoxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a pyrenyloxy group, and the like.
The "arylthio group" in this specification includes arylthio groups such as phenylthio group, naphthylthio group, anthrylthio group, phenanthrylthio group, and pyrenylthio group.
Examples of the "halogen atom" in this specification include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The term "structural unit" as used herein refers to a (repeat) unit of a chemical structure formed during a reaction or polymerization. In other words, in a product compound formed by a reaction or polymerization, a unit that participates in the reaction or polymerization Refers to partial structures other than chemical bond structures, and refers to so-called residues.

[Curable composition]
The curable composition of the present embodiment is a polymaleimide compound (A) containing a monocyclic or fused polycyclic aromatic ring to which two or more linear or branched alkylene groups are bonded (hereinafter simply referred to as polymaleimide compound (A)). It contains a maleimide compound (A)) and an unsaturated hydrocarbon compound (B) having a reactive double bond (hereinafter simply referred to as an unsaturated hydrocarbon compound (B)).
Because it contains a polymaleimide compound (A) with a small proportion of polar functional groups in its chemical structure and an unsaturated hydrocarbon compound (B) having a reactive double bond, the composition as a whole has excellent low dielectric properties and low moisture absorption. You can balance your sexuality.

In the curable composition of the present embodiment, the blending ratio (parts by mass) of the components of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) having a reactive double bond is as follows: A): unsaturated hydrocarbon compound having a reactive double bond (B), preferably 90:10 to 10:90, more preferably 80:20 to 20:80, still more preferably, 75:25 to 25:75. By adjusting the blending ratio within the above range, it is possible to exhibit excellent low hygroscopicity, low dielectric constant, and low dielectric loss tangent, which is preferable.

The curable composition of the present embodiment may contain a curing agent (D) other than the unsaturated hydrocarbon compound (B) having a reactive double bond within a range that does not impair the curing of the present invention. Moreover, the curable composition of this embodiment may further contain an epoxy resin (C). The curable composition of this embodiment may contain a resin (E) other than the epoxy resin (C), a curing accelerator, or an additive. Examples of the additives include flame retardants, inorganic fillers, silane coupling agents, mold release agents, antioxidants, light stabilizers, heat stabilizers, pigments, and emulsifiers.

Hereinafter, after explaining in detail the polymaleimide compound (A) having an alkylene group containing an aromatic ring and the unsaturated hydrocarbon compound (B) which are essential components of the curable composition of the present embodiment, the optional components, The epoxy resin (C), the curing agent (D) other than the unsaturated hydrocarbon compound (B), the resin (E) other than the epoxy resin (C), the curing accelerator, and the additives will be explained.

(Polymaleimide compound (A))
The polymaleimide compound (A) according to the present embodiment is a compound having a monocyclic or condensed polycyclic aromatic ring to which two or more linear or branched alkylene groups are bonded and two or more maleimide groups. .
The above-mentioned monocyclic or fused polycyclic aromatic ring in which two or more linear or branched alkylene groups are bonded refers to a monocyclic or fused polycyclic aromatic ring in which two or more linear or branched alkylene groups having 1 to 12 carbon atoms are present. , and refers to a divalent or higher group in which one bond of the alkylene group is bonded to two or more monocyclic or fused polycyclic aromatic rings. Therefore, the number of linear or branched alkylene groups bonded to the monocyclic or fused polycyclic aromatic ring matches the valence of the alkylene group containing the aromatic ring. In this embodiment, the monocyclic or fused polycyclic aromatic ring to which two or more linear or branched alkylene groups are bonded is preferably a divalent to tetravalent group, and a divalent to trivalent group. More preferably, it is a valent group.
In this embodiment, the monocyclic or fused polycyclic aromatic ring to which two or more linear or branched alkylene groups are bonded is preferably a group represented by the following general formula (I). .

（上記一般式（Ｉ）中、Ａｒ^１は、（２＋ｈ）価の芳香族基を表し、Ｌ^１、Ｌ^２及びＬ^３はそれぞれ独立して、炭素原子数１～１２のアルキレン基を表し、ｈは０以上２以下の整数を表し、＊は他の原子との結合を表す。）
なお、上記一般式（Ｉ）において、ｈが０の場合は一般式（Ｉ）で表される基は２価であり、ｈが２の場合は一般式（Ｉ）で表される基は４価である。
前記マレイミド基とは、以下の一般式（ＩＩ）で表される基であることが好ましい。

(In the above general formula (I), Ar ¹ represents a (2+h)-valent aromatic group, L ¹ , L ² and L ³ each independently represent an alkylene group having 1 to 12 carbon atoms, h represents an integer between 0 and 2, and * represents a bond with another atom.)
In addition, in the above general formula (I), when h is 0, the group represented by general formula (I) is divalent, and when h is 2, the group represented by general formula (I) is 4. It is worth it.
The maleimide group is preferably a group represented by the following general formula (II).

（上記一般式（ＩＩ）中、Ａｒ^２は芳香族基を表し、破線は不在であるか、あるいは単結合を表し、＊は他の原子との結合を表す。）
なお、一般式（ＩＩ）中、破線は、不在であるか、あるいは単結合を表す。前記破線が不在である場合、上記一般式（ＩＩ）のマレイミド基は一価になりうる。一方、前記破線が単結合である場合、上記一般式（ＩＩ）のマレイミド基は二価になりうる。
本実施形態の好適なポリマレイミド化合物（Ａ）は、以下の一般式（１）で表される構造単位を有する化合物である、あるいはアルキル基を１以上３以下有する芳香族アミン化合物（ａ）（以下、芳香族アミン化合物（ａ）とも称する。）と、エテニル基を２つ有する芳香族ジビニル化合物（ｂ１）（以下、芳香族ジビニル化合物（ｂ１）とも称する。）と、無水マレイン酸とを反応原料（１）とする化合物である。

(In the above general formula (II), Ar ² represents an aromatic group, a broken line is absent or represents a single bond, and * represents a bond with another atom.)
In addition, in general formula (II), a broken line represents an absence or a single bond. When the dashed line is absent, the maleimide group of the general formula (II) can be monovalent. On the other hand, when the broken line is a single bond, the maleimide group of the general formula (II) can be divalent.
The preferred polymaleimide compound (A) of this embodiment is a compound having a structural unit represented by the following general formula (1), or an aromatic amine compound (a) having 1 to 3 alkyl groups ( An aromatic divinyl compound (b1) having two ethenyl groups (hereinafter also referred to as an aromatic divinyl compound (b1)) is reacted with maleic anhydride. This is a compound used as raw material (1).

（上記一般式（１）中、Ｒ^１はそれぞれ独立して、アルキル基を表し、
Ｒ^２はそれぞれ独立して、炭素原子数１～１０のアルキル基、アルコキシ基若しくはアルキルチオ基；炭素原子数６～１０のアリール基、アリールオキシ基若しくはアリールチオ基；炭素原子数３～１０のシクロアルキル基；ハロゲン原子；水酸基；又はメルカプト基を表し、
Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立して、水素原子又はメチル基を表し、かつＲ^３及びＲ^４の一方が水素原子、他方がメチル基であり、Ｒ^５及びＲ^６の一方が水素原子、他方がメチル基であり、
Ｘ^１は、以下の一般式（ｘ）：

(In the above general formula (1), R ¹ each independently represents an alkyl group,
R ² is each independently an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; cycloalkyl having 3 to 10 carbon atoms; Represents a group; a halogen atom; a hydroxyl group; or a mercapto group;
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and one of R ³ and R ⁴ is a hydrogen atom and the other is a methyl group, and R ⁵ and R ⁶ are One is a hydrogen atom, the other is a methyl group,
X ¹ is the following general formula (x):

（一般式（ｘ）中、Ｒ^７及びＲ^８はそれぞれ独立して、水素原子又はメチル基を表し、かつＲ^７及びＲ^８の一方が水素原子、他方がメチル基であり、Ｒ^９はそれぞれ独立して、炭素原子数１～１０のアルキル基、アルコキシ基若しくはアルキルチオ基；炭素原子数６～１０のアリール基、アリールオキシ基若しくはアリールチオ基；炭素原子数３～１０のシクロアルキル基；ハロゲン原子；水酸基；又はメルカプト基を表し、ｔは０～４の整数を表す。）
で表される置換基を表し、ｒは、Ｘ^１が結合されたベンゼン環１つ当たりのＸ^１の置換数の平均値であり、０～４の数を表し、ｐは１～３の整数を表し、ｑは０～４の整数を表し、ｋは１～１００の整数を表す。）
これにより、硬化時において、低吸湿性及び低誘電正接性をより高次に両立することができる。

(In general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom and the other is a methyl group, and R ⁹ is each Independently, an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom ; represents a hydroxyl group; or a mercapto group, and t represents an integer of 0 to 4.)
represents a substituent represented by, r is the average value of the number of substitutions of X ¹ per benzene ring to which X ¹ is bonded, and represents a number from 0 to 4, p is an integer from 1 to 3 , q represents an integer from 0 to 4, and k represents an integer from 1 to 100. )
This makes it possible to achieve both low hygroscopicity and low dielectric loss tangent at a higher level during curing.

<Preferred form of polymaleimide compound (A)>
The polymaleimide compound (A) of this embodiment preferably has a structural unit represented by the above general formula (1).
Further, in the above general formula (1), when p is an integer of 2 or more, a plurality of R ^1s may be the same or different from each other. When q is an integer of 2 or more, a plurality of R ² 's may be the same or different. When t is an integer of 2 or more, a plurality of R ^9s may be the same or different.

In the above general formula (1), each R ¹ independently preferably represents an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Further, when p is an integer of 2 or more, a plurality of R ^1s may be the same or different from each other. Preferred R ¹ in general formula (1) is a methyl group, an ethyl group or an n-propyl group. Note that the benzene ring to which R ¹ in general formula (1) is bonded may be the benzene ring of the aromatic amine compound (a).
In the above general formula (1), p preferably represents 1 or 2. Note that R ¹ is preferably bonded to at least one of the 2-position, 3-position, 4-position, 5-position, or 6-position of the benzene ring to which R ¹ is bonded in general formula (1).

In the above general formula (1), R ² is each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; 3 carbon atoms It preferably represents a cycloalkyl group having ~10 atoms; a halogen atom; or a hydroxyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. Furthermore, when q is an integer of 2 or more, a plurality of ^R2s may be the same or different. Preferred R ² in general formula (1) is a methyl group, an ethyl group or an n-propyl group. Note that the benzene ring to which R ² in general formula (1) is bonded may be the benzene ring of the aromatic divinyl compound (b1). Further, in the above general formula (1), q preferably represents 0, 1 or 2.

In the above general formula (1), one of R ³ and R ⁴ is a hydrogen atom and the other is a methyl group, and one of R ⁵ and R ⁶ is a hydrogen atom and the other is a methyl group. Thereby, the reactivity of the unsaturated bonds that the polymaleimide compound (A) itself has can be maintained at a high level. When the proportion of alkyl groups in R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula (1) increases, the reactivity of the unsaturated bonds of the polymaleimide compound (A) itself increases due to steric hindrance. There is a tendency for this to decline. Therefore, if R ³ , R ⁴ , R ⁵ and R ⁶ are all alkyl groups, the reactivity of the unsaturated bonds that the polymaleimide compound (A) itself has decreases, making it impossible to form a cured product efficiently.

In the above general formula (1), it is preferable that X ¹ is represented by the above general formula (x), and in the general formula (x), R ⁷ represents a hydrogen atom and R ⁸ represents a methyl group. In the above general formula (x), R ⁹ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; It is preferable to represent a cycloalkyl group having 3 to 10 atoms; a halogen atom; or a hydroxyl group; more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; More preferably, it represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Furthermore, in the above general formula (x), t preferably represents an integer of 0 to 4, more preferably an integer of 0 to 3. In addition, when t is an integer of 2 or more, a plurality of R ⁹ 's may be the same or different from each other.

In the above general formula (1), r means the average number of substitutions of X ¹ per benzene ring to which X ¹ is bonded, and is preferably in the range of 0 to 4, preferably 0 to 3. More preferably, the range is within the range.
In the above general formula (1), k represents the number of repeating units, and is preferably an integer of 1 to 100, more preferably an integer of 1 to 90, and even more preferably an integer of 1 to 80. .

<Other preferred forms of the polymaleimide compound (A)>
Other preferable forms of the polymaleimide compound (A) of the present embodiment include an aromatic amine compound (a) having 1 or more and 3 or less alkyl groups, and an aromatic divinyl compound (b1) having 2 ethenyl groups; It may be a compound using maleic anhydride as a reaction raw material (1). At this time, in this embodiment, an aromatic monovinyl compound (b2) having one ethenyl group (hereinafter also referred to as aromatic monovinyl compound (b2)) may be further contained in the reaction raw material (1). In addition, in the polymaleimide compound (A) of the present embodiment, the aromatic amine compounds (a) having 1 or more and 3 or less alkyl groups are crosslinked with each other via the aromatic divinyl compound (b1) having 2 ethenyl groups. A polymaleimide compound (A) containing an intermediate amine compound (c) and maleic anhydride as reaction raw materials (3) is preferable. Furthermore, the intermediate amine compound (c) is optionally added to an aromatic amine compound (a) having 1 or more and 3 or less alkyl groups, and an aromatic divinyl compound (b1) having 2 ethenyl groups. It is preferable that the compound is a compound in which the reaction raw material (2) is an aromatic monovinyl compound (b2) having one ethenyl group.
In other words, the intermediate amine compound (c) in this embodiment has an amino group (including a substituted amino group in which the hydrogen atom of the amino group is further substituted with an alkyl group having 1 to 6 carbon atoms) bonded to the intermediate amine compound (c). An aromatic ring and a structural unit of an aromatic amine compound (a) having 1 or more and 3 or less alkyl groups in the aromatic ring and a structural unit of an aromatic divinyl compound (b1) having two ethenyl groups are bonded together by a chemical bond. It is preferable to have a structure in which the structural unit of the aromatic monovinyl compound (b2) is chemically bonded to the aromatic ring in the structural unit of the aromatic amine compound (a). In the polymaleimide compound (A) in this embodiment, the amino group (including -NH ₂ and substituted amino group) bonded to the aromatic ring of the intermediate amine compound (c) is bonded to the N-substituted maleimide ring. It has a substituted structure.
Therefore, in this embodiment, the "polymaleimide compound (A)" and the "intermediate amine compound (c)" which is a precursor of the "polymaleimide compound (A)" are the amino groups bonded to the aromatic ring. (containing -NH ₂ and substituted amino groups) is a polymeric compound that differs in that N-substituted maleimide ring is substituted.
Note that the structural unit of the aromatic amine compound (a) refers to a group obtained by removing two hydrogen atoms from the aromatic ring of the aromatic amine compound (a). For example, when the aromatic amine compound (a) is represented by the general formula (a) described below, the structure of the aromatic amine compound (a) is a group obtained by removing two hydrogen atoms from the benzene ring of the general formula (a). It is called a unit. Moreover, the structural unit of the aromatic divinyl compound (b1) refers to a group in which the unsaturated bonds of two ethenyl groups of the aromatic divinyl compound (b1) are cleaved.
In this embodiment, since the aromatic amine compound (a) having a specific aromatic ring structure is used as the reaction raw material, it becomes easier to control the reaction site with the aromatic divinyl compound (b1) described below, so that uniform A polymaleimide compound (A) having a chemical structure or chain length can be easily obtained, and as a result, a polymaleimide compound (A) exhibiting low hygroscopicity and low dielectric loss tangent upon curing can be provided.

Hereinafter, an aromatic amine compound (a) having 1 or more and 3 or less alkyl groups, an aromatic divinyl compound (b1) having 2 ethenyl groups, which are constituent components of the reaction raw material (1) of the polymaleimide compound (A), After explaining the aromatic monovinyl compound (b2) having one ethenyl group, which can be an optional component, and maleic anhydride, another preferred form of the polymaleimide compound (A) and a method for producing the polymaleimide compound (A) will be explained. do.

<<Aromatic amine compound (a)>>
The aromatic amine compound (a) in this embodiment has an aromatic ring to which an amino group (-NH ₂ or substituted amino group) is bonded, and one or more and three or less alkyl groups are bonded to the aromatic ring. has been done. Therefore, the aromatic amine compound (a) may be an amine compound. Further, the aromatic ring forming the central structure of the aromatic amine compound (a) is preferably monocyclic and includes an aromatic hydrocarbon ring and an aromatic heterocycle. The aromatic hydrocarbon ring is preferably a benzene ring. Examples of the aromatic heterocycle include a six-membered heterocycle such as a pyran ring or a pyridine ring. Further, the aromatic amine compound (a) in the present embodiment has an aromatic ring to which -NH ₂ is bonded and does not contain a substituted amino group, and one or more and three or less alkyl groups are bonded to the aromatic ring. It is more preferable that the

In the aromatic amine compound (a) of this embodiment, the alkyl group substituted with 1 to 3 hydrogen atoms on the aromatic ring of the aromatic amine compound (a) is an alkyl group having 1 to 10 carbon atoms. Among them, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms are more preferred. The alkyl group may be linear, branched, or cyclic. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, and the like. The smaller the molecular weight of the alkyl group, the more remarkable the effect of the present invention (lower dimensional change rate). Furthermore, the higher the molecular weight of the alkyl group, the more remarkable the effect of the present invention (low water absorption).

The upper limit of the number of alkyl groups bonded to the aromatic ring having an amino group (including -NH ₂ and substituted amino group) in the aromatic amine compound (a) is that the aromatic ring has an amino group (-NH ₂ and a substituted amino group), and from the viewpoint that two bonding hands are used for polymerization, the number is the number subtracted by 3 from the number of substitutable ring constituent atoms in the unsubstituted aromatic ring. Good to have. For example, when the aromatic ring is a benzene ring, the number of alkyl groups is 3 or less.
In addition, by setting the number of alkyl groups substituted on the aromatic ring of the aromatic amine compound (a) to 2 or more, it becomes easier to control the reaction site with the aromatic divinyl compound (b1) described below, so that uniform A polymaleimide compound (A) having a chemical structure or chain length can be easily obtained. As a result, the cured product of the polymaleimide compound (A) tends to exhibit low hygroscopicity and excellent high-frequency electrical properties.

A preferred form of the aromatic amine compound (a) will be described by taking as an example a case where the aromatic ring of the aromatic amine compound (a) in this embodiment is a benzene ring.
In this embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (a), one or more carbon atoms having the largest HOMO electron density (Hückel coefficient) are unsubstituted (or are hydrogen atoms). (substituted) is preferred.
This makes it easier to control the _ArSE reaction and molecular design using the cationoid reagent formed from the aromatic divinyl compound (b1), which will be described later. To explain in more detail, among the carbon atoms in the benzene ring constituting the aromatic amine compound (a), if the carbon atom having the largest HOMO electron density (Huckel coefficient) is unsubstituted, the largest HOMO The carbocation of the aromatic divinyl compound (b1), which is a cationoid reagent, easily reacts with carbon atoms having an electron density of . Therefore, by controlling the number, position, etc. of the alkyl groups bonded to the carbon atoms of the benzene ring, the bonding site or number of bonds with the aromatic divinyl compound (b1), etc. can be adjusted. Therefore, it is presumed that it becomes easier to design the chemical structure or molecular chain length of the obtained polymaleimide compound (A).
For example, when the aromatic amine compound (a) has an aniline skeleton having one benzene ring and one amino group, at least one carbon atom among the 2-position, 4-position and 6-position of the aniline nucleus is a hydrogen atom. It is preferable that it is substituted with . As a result, a cationoid formed from the aromatic divinyl compound (b1) described below is produced for at least one carbon atom among the 2-position, 4-position, and 6-position, which are the ortho-position and para-position with high electron density of the aniline nucleus. The reagent becomes easier to attack. In particular, when an aromatic amine compound (a) having an aniline nucleus substituted with an alkyl group at a specific position is used, the bonding site with the aromatic divinyl compound (b1) can be roughly controlled, resulting in a uniform chemical structure or chain. It becomes easier to obtain a long polymaleimide compound (A). For example, when a 2,6-dialkylamine is used as the aromatic amine compound (a), it is thought that a large amount of the polymaleimide compound (A) bonded to the aromatic divinyl compound (b1) at the 4-position can be obtained.

Specific examples of the aromatic amine compound (a) of the present embodiment include dimethylaniline (2,3-xylidine, 2,4-xylidine, 2,6-xylidine, 3,4-xylidine, or 3,5-xylidine). xylidine), diethylaniline (2,3-diethylaniline, 2,4-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline or 3,5-diethylaniline), diisopropylaniline (2,3-diisopropyl Aniline, 2,4-diisopropylaniline, 2,6-diisopropylaniline, 3,4-diisopropylaniline or 3,5-diisopropylaniline), ethylmethylaniline (for example, 2,3-position, 2,4-position, 2,6-position) cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, o, m, or p-toluidine, in which one of the 3, 4, or 3, 5 positions is a methyl group and the other is an ethyl group , o, m, or p-ethylaniline, o, m, or p-isopropylaniline, o, m, or p-propylaniline, o, m, or p-butylaniline, methylisopropylaniline (e.g. 2,3 2, 4, 2, 6, 3, 4, or 3, 5, in which one is a methyl group and the other is an isopropyl group), or ethylbutylaniline (for example, 2 , 3-position, 2-4-position, 2-6-position, 3-4-position, or 3-5-position is an ethyl group, and the other is a butyl group (ethylbutylaniline), etc. can be used. Further, the butyl includes n-butyl, tert-butyl, and sec-butyl. Note that the aromatic amine compound (a) in this embodiment may be used alone or in combination of two or more types.

For example, in the case of a chemical structure such as N-phenylmaleimide in which a maleimide group is directly bonded to an unsubstituted benzene ring, stacking occurs because the benzene ring and the five-membered maleimide ring are stable when they are aligned on the same plane. crystallinity, resulting in high crystallinity. This causes poor solvent solubility. On the other hand, in the case of the present disclosure, when the benzene ring has an alkyl group (e.g., methyl group) as a substituent, such as 2,6-dimethylaniline, the benzene ring does not form due to the steric hindrance of the methyl group. The five-membered ring of maleimide assumes a twisted conformation, making stacking difficult, resulting in lower crystallinity and improved solvent solubility, which is a preferred embodiment. However, if the steric hindrance is too large, there is a concern that the reactivity during the synthesis of maleimide may be inhibited, so for example, an aromatic amine compound (a) having an alkyl group having 1 to 6 carbon atoms may be used. is preferred.

The aromatic amine compound (a), which is essential as the reaction raw material (1) in this embodiment, can be represented by the following general formula (a), for example.

（上記一般式（ａ）中、Ｒ^１ａはアルキル基を表し、ｐ^ａは、１～３の整数を表す。複数存在するＲ^１ａは同一であっても、あるいは異なっていてもよい。）

(In the above general formula (a), R ^1a represents an alkyl group, and p ^a represents an integer of 1 to 3. A plurality of R ^1a may be the same or different.)

In the above general formula (a), the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms and the alkyl group having 1 to 3 carbon atoms are the same as above.
In the above general formula (a), p ^a is preferably 1 or 2. In addition, when multiple R ^1a 's exist, they may be the same alkyl group or different alkyl groups.
In addition, in this embodiment, the aromatic amine compound (a) represented by the above general formula (a) may be used alone or in combination of two or more types.

<<Aromatic divinyl compound (b1)>>
The aromatic divinyl compound (b1) in this embodiment has two ethenyl groups (CH ₂ ═CH-) (also referred to as a vinyl group) as substituents on the aromatic ring, and ), it can be used without any particular restrictions.
Moreover, in this embodiment, it is preferable that the reaction raw material (1) contains a mixture of the aromatic divinyl compound (b1) and the aromatic monovinyl compound (b2).
Examples of the aromatic divinyl compound (b1) include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms on the aromatic ring thereof; Examples include various compounds substituted with one or more substituents such as 10 aryl, aryloxy, or arylthio groups; cycloalkyl groups having 3 to 10 carbon atoms; halogen atoms; hydroxyl groups; or mercapto groups. A preferable form of the substituent is the same as R ² in the above general formula (1). Further, the alkyl group may be either a straight chain type or a branched type. Among these, from the viewpoint of exhibiting the effect of high heat resistance, the number of carbon atoms in the alkyl group or alkoxy group is preferably 1 to 4. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, and isobutyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like.

The aromatic divinyl compound (b1), which is the reaction raw material (1) of the polymaleimide compound (A) of the present disclosure, is preferably represented by the following formula (b1).

（上記一般式（ｂ１）中、Ｒ^２ｂはそれぞれ独立して、炭素原子数１～１０のアルキル基、アルコキシ基若しくはアルキルチオ基；炭素原子数６～１０のアリール基、アリールオキシ基若しくはアリールチオ基；炭素原子数３～１０のシクロアルキル基；ハロゲン原子；水酸基；又はメルカプト基を表し、ｑ^１ｂは０～４の整数を表す。なお、ｑ^１ｂが２以上の整数の場合、複数存在するＲ^２ｂは互いに同一であっても、あるいは異なっていてもよい。）

(In the above general formula (b1), R ^2b is each independently an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; Represents a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and q ^1b represents an integer of 0 to 4. In addition, when q ^1b is an integer of 2 or more, a plurality of R ^2b may be the same or different.)

R ^2b in the above formula (b1) can correspond to R ² in general formula (1). Therefore, as in general formula (1), R ^2b in the above general formula (b1) each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; It preferably represents an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and 1 carbon atom More preferably, it represents an alkyl group of ˜6.
In the above general formula (b1), q ^1b is preferably 0 to 2. In addition, when q ^1b is 2 or more, a plurality of R ^b1s may be the same group or different groups.

Specific examples of the aromatic divinyl compound (b1) of this embodiment include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 2,5-dimethyl-1,4- Divinylbenzene, 2,5-diethyl-1,4-divinylbenzene, cis,cis,β,β'-diethoxy-mm-divinylbenzene, 1,4-divinyl-2,5-dibutylbenzene, 1,4 -Divinylbenzenes such as divinyl-2,5-dihexylbenzene, 1,4-divinyl-2,5-dimethoxybenzene and compounds consisting of derivatives thereof, as well as 1,3-divinylnaphthalene and 1,4-divinylnaphthalene , 1,5-divinylnaphthalene, 1,6-divinylnaphthalene, 1,7-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene, 2,7-divinylnaphthalene, 3,4-divinylnaphthalene, Examples include, but are not limited to, divinylnaphthalenes such as 1,8-divinylnaphthalene, 1,5-dimethoxy-4,8-divinylnaphthalene, and compounds consisting of derivatives thereof.
Note that the aromatic divinyl compound (b1) in this embodiment may be used alone or in combination of two or more types.
In particular, from the viewpoint of fluidity, as the aromatic divinyl compound (b1), divinylbenzene and a compound having a substituent on its aromatic ring are preferable, and divinylbenzene is more preferable. Further, in the present embodiment, the substitution position of the vinyl group in divinylbenzene is not particularly limited, but it is preferable that the meta-isomer is the main component. The content of the meta substance in divinylbenzene is preferably 40% by mass or more, more preferably 50% by mass or more based on the total amount of divinylbenzene.
In the present embodiment, the structural unit of the aromatic divinyl compound (b1) preferably contains 10 to 90% by mass, and preferably contains 20 to 90% by mass with respect to the total amount (100% by mass) of the polymaleimide compound (A). It is more preferable to do so. The structural unit of the aromatic divinyl compound (b1) refers to a group obtained by removing two hydrogen atoms from each of the two ethenyl groups (total of four hydrogen atoms) of the aromatic divinyl compound (b1).

<<Aromatic monovinyl compound (b2)>>
In addition to the aromatic amine compound (a), aromatic divinyl compound (b1), and maleic anhydride, other compounds may be used as reaction raw materials for the polymaleimide compound (A) in this embodiment. Examples of the other compounds include aromatic monovinyl compounds (b2) having one ethenyl group. That is, in the embodiment, it is preferable that the aromatic amine compound (a), the aromatic divinyl compound (b1), the aromatic monovinyl compound (b2), and maleic anhydride are used as the reaction raw materials (1). By using the aromatic monovinyl compound (b2) in addition to the aromatic amine compound (a), aromatic divinyl compound (b1), and maleic anhydride as reaction raw materials, the polymaleimide compound (A) of this embodiment This is preferable because the finally obtained cured product of the polymaleimide compound (A) has an excellent low dielectric loss tangent.
Furthermore, since the aromatic monovinyl compound (b2) also generates a carbocation like the aromatic divinyl compound (b1), the most carbon atoms in the aromatic hydrocarbon ring constituting the aromatic amine compound (a) are It easily reacts with carbon atoms having a large HOMO electron density (Huckel coefficient).

The aromatic monovinyl compound (b2) in this embodiment includes, for example, vinylbenzene (styrene), vinylbiphenyl, vinylnaphthalene, and an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms on the aromatic ring thereof. ;Aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; cycloalkyl group having 3 to 10 carbon atoms; halogen atom; hydroxyl group; or various compounds substituted with one or more substituents such as mercapto group, etc. can be mentioned. The alkyl group may be either linear or branched, and may have an unsaturated bond in its structure. Among these, when low hygroscopicity is important, the alkyl group or the alkoxy group preferably has 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, and isobutyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like.

The aromatic monovinyl compound (b2) that can serve as the reaction raw material (1) of the polymaleimide compound (A) of the present disclosure can be represented by the following general formula (b2).

（上記一般式（ｂ２）中、Ｒ^９ｂはそれぞれ独立して、炭素原子数１～１０のアルキル基、アルコキシ基若しくはアルキルチオ基；炭素原子数６～１０のアリール基、アリールオキシ基若しくはアリールチオ基；炭素原子数３～１０のシクロアルキル基；ハロゲン原子；水酸基；又はメルカプト基を表し、ｔ^１ｂは０～５の整数を表す。なお、ｔ^１ｂが２以上の整数の場合、複数存在するＲ^９ｂは互いに同一であっても、あるいは異なっていてもよい。）

(In the above general formula (b2), R ^9b is each independently an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; Represents a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and t ^1b represents an integer of 0 to 5. In addition, when t ^1b is an integer of 2 or more, a plurality of R ^9b may be the same or different.)

R ^9b in the above formula (b2) can correspond to R ⁹ in the general formula (x). Therefore, as in general formula (x), R ^9b in the above general formula (b1) each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; It preferably represents an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and 1 carbon atom More preferably, it represents an alkyl group of ˜6.
In the above general formula (b1), t ^1b is preferably 1 to 4. In addition, when t ^1b is 2 or more, a plurality of R ^9b 's may be the same group or different groups.

Specific examples of the aromatic monovinyl compound (b2) of this embodiment include styrene, fluorostyrene, vinylbenzyl chloride, alkylvinylbenzene (o-, m-, p-methylstyrene, o-, m-, p- Vinylbenzenes such as compounds consisting of -ethylvinylbenzene), o-, m-, p-(chloromethyl)styrene and derivatives thereof; 4-vinylbiphenyl, 4-vinyl-p-terphenyl and derivatives thereof and vinylnaphthalenes such as compounds consisting of 1-vinylnaphthalene, 2-vinylnaphthalene, and derivatives thereof.
In particular, from the viewpoint of raw material availability, alkylvinylbenzene and a compound having a substituent on its aromatic ring are preferred, and ethylvinylbenzene is more preferred.
In addition, the substitution positions of the vinyl group and ethyl group in ethylvinylbenzene are not particularly limited, but it is preferable that the meta-isomer is the main component, and the content of the meta-isomer in ethylvinylbenzene is determined based on the total amount of ethylvinylbenzene. It is more preferably 40% by mass or more, and even more preferably 50% by mass or more.

When using an aromatic monovinyl compound (b2) as the reaction raw material (1) for the polymaleimide compound (A) in this embodiment, the aromatic monovinyl compound ( The molar ratio of b2) ((b1)/(b2)) is preferably from 99/1 to 50/50, more preferably from 98/2 to 70/30.
In this embodiment, the content of the structural unit of the aromatic monovinyl compound (b2) is preferably 0 to 40% by mass, and preferably 0 to 30% by mass with respect to the total amount (100% by mass) of the polymaleimide compound (A). It is more preferable to do so. The structural unit of the aromatic monovinyl compound (b2) refers to a group obtained by removing two hydrogen atoms from one vinyl group of the aromatic monovinyl compound (b2).

<<Maleic anhydride>>
In this embodiment, maleic anhydride is an essential component of the reaction raw material (1) of the polymaleimide compound (A), and as explained in the section of the method for producing the polymaleimide compound (A) below, It is used in the reaction of converting amino groups (including -NH ₂ and substituted amino groups) derived from (a) into maleimidation.

<Preferred form of polymaleimide compound (A)>
Hereinafter, preferred embodiments of the polymaleimide compound (A) of the present disclosure will be described, taking as an example the case where each aromatic ring is a benzene ring. The following chemical structural formulas are for illustratively explaining the present disclosure, and the scope of the present disclosure is not limited to the following chemical structural formulas.

In this embodiment, the polymaleimide compound (A) is preferably represented by the following general formula (2).

（上記一般式（２）中、Ｒ^１はそれぞれ独立して、アルキル基を表し、Ｒ^２はそれぞれ独立して、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基；炭素原子数６～１０のアリール基；炭素原子数３～１０のシクロアルキル基；ハロゲン原子；又は水酸基を表し、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立して、水素原子又はメチル基を表し、かつＲ^３及びＲ^４の一方が水素原子、他方がメチル基であり、Ｒ^５及びＲ^６の一方が水素原子、他方がメチル基であり、
Ｘ^１は、以下の一般式（ｘ）：

(In the above general formula (2), R ¹ each independently represents an alkyl group, R ² each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; Aryl group having 6 ^to 10 carbon atoms ^; cycloalkyl group having ³ to ¹⁰ carbon atoms; halogen atom; represents a group, and one of R ³ and R ⁴ is a hydrogen atom and the other is a methyl group, and one of R ⁵ and R ⁶ is a hydrogen atom and the other is a methyl group,
X ¹ is the following general formula (x):

（一般式（ｘ）中、Ｒ^７及びＲ^８はそれぞれ独立して、水素原子又はメチル基を表し、かつＲ^７及びＲ^８の一方が水素原子、他方がメチル基であり、Ｒ^９は炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基；炭素原子数６～１０のアリール基；炭素原子数３～１０のシクロアルキル基；ハロゲン原子；又は水酸基を表し、ｔは０～４の整数を表す。）
で表される置換基を表し、
Ｍ^２１は水素原子又は下記一般式（ｉ）で表される基を表し、Ｍ^２２は、水素原子、下記一般式（ｉｉ）で表される基又は下記一般式（ｉｉｉ）で表される基を表し、

(In general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, and R ⁹ is a carbon an alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, and t is (Represents an integer from 0 to 4.)
represents a substituent represented by
^M21 represents a hydrogen atom or a group represented by the following general formula (i), and ^M22 represents a hydrogen atom, a group represented by the following general formula (ii), or a group represented by the following general formula (iii). represents,

［上記一般式（ｉ）中、Ｒ^９は炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基；炭素原子数６～１０のアリール基；炭素原子数３～１０のシクロアルキル基；ハロゲン原子；又は水酸基を表し、Ｒ^７及びＲ^８はそれぞれ独立して、水素原子又はメチル基を表し、かつＲ^７及びＲ^８の一方が水素原子、他方がメチル基であり、ｔは０～４の整数を表し、＊は他の原子との結合を表す。なお、ｔが２以上の整数である場合、複数存在するＲ^９は互いに同一であっても、又は異なっていてもよい。］

[In the above general formula (i), R ⁹ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cyclo group having 3 to 10 carbon atoms; represents an alkyl group; a halogen atom; or a hydroxyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom and the other is a methyl group, and t represents an integer from 0 to 4, and * represents a bond with another atom. In addition, when t is an integer of 2 or more, a plurality of R ⁹ 's may be the same or different from each other. ]

［上記一般式（ｉｉ）中、Ｒ^１ｉｉはアルキル基を表し、ｐ^ｉｉは０～４の整数を表す。なお、ｐ^ｉｉが２以上の整数である場合、複数存在するＲ^１ｉｉは互いに同一であっても、又は異なっていてもよい。上記一般式（ｉｉｉ）中、Ｒ^１ｉｉｉはアルキル基を表し、Ｒ^９は炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基；炭素原子数６～１０のアリール基；炭素原子数３～１０のシクロアルキル基；ハロゲン原子；又は水酸基を表し、Ｒ^７及びＲ^８はそれぞれ独立して、水素原子又はメチル基を表し、かつＲ^７及びＲ^８の一方が水素原子、他方がメチル基であり、ｐ^ｉｉｉは０～３の整数を表し、ｔは０～４の整数を表し、ｒ^１ｉｉｉは、Ｘ^１が結合されたベンゼン環１つ当たりの置換数の平均値であり、１～４の数を表し、＊は他の原子との結合を表す。なお、ｐ^ｉｉｉが２以上の整数である場合、複数存在するＲ^１ｉｉｉは互いに同一であっても、又は異なっていてもよく、ｔが２以上の整数である場合、複数存在するＲ^９は互いに同一であっても、又は異なっていてもよい。］
ｒは、Ｘ^１が結合されたベンゼン環１つ当たりのＸ^１の置換数の平均値であり、０～４の数を表し、ｐは１～３の整数を表し、ｑは０～４の整数を表し、ｋは１～１００の整数を表す。）
上記一般式（２）中、ｐが２以上の整数である場合、複数存在するＲ^１は互いに同一であっても、又は異なっていてもよく、ｑが２以上の整数である場合、複数存在するＲ^２は互いに同一であっても、又は異なっていてもよく、ｔが２以上の整数である場合、複数存在するＲ^９は互いに同一であっても、又は異なっていてもよい。）で表されることが好ましい。
なお、上記一般式（２）中のＲ^１～Ｒ^９、Ｘ^１、ｐ、ｑ、ｒ、ｔ及びｋの好ましい形態は、上記一般式（１）と同様である。さらには、上記一般式（ｉ）は上記一般式（ｘ）に対応し、上記一般式（ｉｉ）中のＲ^１ｉｉは上記一般式（１）中のＲ^１に対応し、上記一般式（ｉｉｉ）中のＲ^１ｉｉｉは上記一般式（１）中のＲ^１に対応する。

[In the above general formula (ii), R ¹ⁱⁱ represents an alkyl group, and p ⁱⁱ represents an integer of 0 to 4. In addition, when p ⁱⁱ is an integer of 2 or more, a plurality of R ¹ⁱⁱ may be the same or different from each other. In the above general formula (iii), R ¹ⁱⁱⁱ represents an alkyl group, R ⁹ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; Represents a cycloalkyl group having 3 to 10 atoms; a halogen atom; or a hydroxyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, p ⁱⁱⁱ represents an integer from 0 to 3, t represents an integer from 0 to 4, and r ⁱⁱⁱ is the average number of substitutions per benzene ring to which X ¹ is bonded. , represents a number from 1 to 4, and * represents a bond with another atom. In addition, when p ⁱⁱⁱ is an integer of 2 or more, the plurality of R ^1iiis may be the same or different from each other, and when t is an integer of 2 or more, the plurality of R ^9s may be the same or different from each other. They may be the same or different. ]
r is the average value of the number of substitutions of X ¹ per benzene ring to which X ¹ is bonded, and represents a number from 0 to 4, p represents an integer from 1 to 3, and q represents an integer from 0 to 4. It represents an integer, and k represents an integer from 1 to 100. )
In the above general formula (2), when p is an integer of 2 or more, a plurality of R ^1s may be the same or different from each other, and when q is an integer of 2 or more, a plurality of R 1s may be present. R ² may be the same or different, and when t is an integer of 2 or more, a plurality of R ⁹ may be the same or different. ) is preferably represented.
The preferable forms of R ¹ to R ⁹ , X ¹ , p, q, r, t and k in the above general formula (2) are the same as in the above general formula (1). Furthermore, the above general formula (i) corresponds to the above general formula (x), R ¹ⁱⁱ in the above general formula (ii) corresponds to R ¹ in the above general formula (1), and the above general formula (iii R ¹ⁱⁱⁱ in ) corresponds to R ¹ in the above general formula (1).

The number average molecular weight (Mn) of the polymaleimide compound (A) of the present disclosure is preferably in the range of 350 to 2,000, more preferably in the range of 400 to 1,500. Further, the weight average molecular weight (Mw) of the polymaleimide compound (A) is preferably in the range of 400 to 500,000, more preferably in the range of 450 to 400,000.
The polymaleimide compound (A) of the present disclosure has a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight ( Mn)) is preferably in the range of 1.001 to 500, more preferably 1.001 to 400. In addition, from the GPC chart obtained from GPC measurement, if the molecular weight distribution is wide and there are many high molecular weight components, the proportion of high molecular weight components that contribute to flexibility will be large. This is a preferred embodiment since it is possible to obtain a cured product with reduced brittleness and excellent flexibility and pliability compared to the conventional method.
The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymaleimide compound (A) of this embodiment are determined by gel permeation chromatography. (hereinafter abbreviated as "GPC") under the measurement conditions described in the Examples below.

When the polymaleimide compound (A) in this embodiment contains an indane skeleton (or a structural unit having an indane skeleton) represented by the following general formula (3), the total amount of the polymaleimide compound (A) (100 mass %), the ratio of the indane skeleton is preferably 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 0.9% by mass or less. Particularly preferred.

（上記一般式（３）中、Ｒ^３１、Ｒ^３２及びＲ^３３はそれぞれ独立して、水素原子又は炭素原子数１～３のアルキル基を表し、Ｒ^３４はそれぞれ独立して、炭素原子数１～１０のアルキル基、アルコキシ基若しくはアルキルチオ基；炭素原子数６～１０のアリール基、アリールオキシ基若しくはアリールチオ基；炭素原子数３～１０のシクロアルキル基；ハロゲン原子；水酸基；又はメルカプト基を表し、ｑ^３は、０～３の整数を表し、ｑ^３が２以上の整数の場合、複数存在するＲ^３４は、互いに同一であっても、あるいは異なっていてもよい。また、＊は他の原子との結合を表す。）
上記一般式（３）中、Ｒ^３４はそれぞれ独立して、炭素原子数１～６のアルキル基を表すことが好ましく、炭素原子数１～３のアルキル基を表すことがより好ましい。また、上記一般式（３）中、Ｒ^３１、Ｒ^３２及びＲ^３３は水素原子又はメチル基であることが好ましい。
本実施形態の硬化性組成物において、硬化性組成物全体に対して、ポリマレイミド化合物（Ａ）を３０質量％以上９５質量％以下含有することが好ましく、４０質量％以上８５質量％以下含有することがより好ましく、５０質量％以上８０質量％以下含有することが最も好ましい。ポリマレイミド化合物（Ａ）の含有量が５０質量％以上８０質量％以下の範囲であると耐熱性及び低吸湿性の観点で好ましい。

(In the above general formula (3), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³⁴ each independently represents 1 to 3 carbon atoms. ~10 alkyl group, alkoxy group or alkylthio group; aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; cycloalkyl group having 3 to 10 carbon atoms; halogen atom; hydroxyl group; or mercapto group. , q ³ represents an integer from 0 to 3, and when q ³ is an integer of 2 or more, multiple R ^34s may be the same or different from each other. (Represents a bond with an atom.)
In the above general formula (3), each R ³⁴ independently preferably represents an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Further, in the above general formula (3), R ³¹ , R ³² and R ³³ are preferably a hydrogen atom or a methyl group.
The curable composition of the present embodiment preferably contains the polymaleimide compound (A) in an amount of 30% by mass or more and 95% by mass or less, and preferably contains 40% by mass or more and 85% by mass or less, based on the entire curable composition. More preferably, the content is 50% by mass or more and 80% by mass or less. The content of the polymaleimide compound (A) is preferably in the range of 50% by mass or more and 80% by mass or less from the viewpoint of heat resistance and low hygroscopicity.

<Method for producing polymaleimide compound (A)>
The method for producing the polymaleimide compound (A) of the present disclosure will be described below.
The manufacturing method of the polymaleimide compound (A) of this embodiment is not particularly limited, and an aromatic amine compound (a), an aromatic divinyl compound (b1), and maleic anhydride are used as reaction raw materials (1). Alternatively, it may be manufactured in any manner as long as it has the structural unit represented by the above general formula (1). An example of the method for producing the polymaleimide compound (A) of the present disclosure includes, for example, a production method including the following steps (1) and (2).
Step (1): A step of reacting an aromatic amine compound (a) with an aromatic divinyl compound (b1) as a reaction raw material (2) to obtain an intermediate amine compound (c) in this embodiment;
Step (2): As a reaction raw material (3), the intermediate amine compound (c) obtained in the above step (1) is reacted with maleic anhydride to obtain the polymaleimide compound (A) of the present disclosure. Process.
Specifically, the method for producing the polymaleimide compound (A) of the present embodiment includes a step (1) of reacting an aromatic amine compound (a) and an aromatic divinyl compound (b1) under a solid acid catalyst ( It is preferable to have a step (2) (also referred to as a condensation step) of condensing the intermediate amine compound (c) produced in step (1) with maleic anhydride (also referred to as a crosslinking step).
Hereinafter, each step of the method for producing the polymaleimide compound (A) of the present disclosure will be explained in order.

<<Step (1): Manufacturing process of intermediate amine compound (c)>>
Below, the manufacturing process of the intermediate amine compound (c) in this embodiment will be explained.
Although not particularly limited, step (1) in the present embodiment includes, for example, the above-mentioned aromatic amine compound (a), the above-mentioned aromatic divinyl compound (b1) (for example, divinylbenzene), and further optionally This is a step in which other compounds such as aromatic monovinyl compound (b2) (for example, ethylvinylbenzene) are reacted in the presence of an acid catalyst. This may produce intermediate amine compound (c).

As for the blending ratio of the aromatic amine compound (a) and the aromatic divinyl compound (b1), considering the physical property balance of moldability and curability during production of the resulting cured product, the aromatic amine compound (a) and the aromatic divinyl compound (b1) are The molar ratio of the aromatic divinyl compound (b1) to 1 mol of a) is preferably 0.1 to 10 mol, more preferably 0.2 to 3 mol. Furthermore, when the aromatic monovinyl compound (b2) is used in combination, the amount of the aromatic divinyl compound (b1) and the aromatic monovinyl compound (b2) per 1 mol of the aromatic amine compound (a) is The total molar ratio is preferably 0.1 to 10 mol, more preferably 0.2 to 3 mol.
In addition, as a specific method for carrying out the above reaction, all raw materials are charged at once and reacted as is at a predetermined temperature, or the aromatic amine compound (a) and an acid catalyst are charged and a predetermined reaction is carried out. A common method is to react while maintaining the temperature while dropping the aromatic divinyl compound (b1) and other compounds (for example, the aromatic monovinyl compound (b2)). At this time, the dropping time is usually 0.1 to 12 hours, preferably 6 hours or less. After the reaction, if a solvent is used, the solvent and unreacted substances can be distilled off to obtain the intermediate amine compound (c), if necessary, and if a solvent is not used, the unreacted substances can be distilled off. By removing the compound, the desired intermediate amine compound (c) can be obtained.

The acid catalyst used in step (1) of the present embodiment includes, for example, inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid. Examples include organic acids, activated clay, acid clay, silica alumina, zeolite, solid acids such as strongly acidic ion exchange resins, heteropolyhydrochloric acid, etc., but solid acids whose catalyst can be easily removed by filtration after the reaction are It is also preferable from the viewpoint of hand linkability, and when other acids are used, it is preferable to perform neutralization with a base and washing with water after the reaction.
The amount of the acid catalyst is the total amount of the raw materials to be charged (aromatic divinyl compound (b1) or a mixture of aromatic divinyl compound (b1) and aromatic monovinyl compound (b2), and aromatic amine compound (a)). The acid catalyst is blended in an amount of 1 to 100 parts by mass, but from the viewpoint of handling and economy, 1 to 60 parts by mass is preferred. The reaction temperature may normally be in the range of 100 to 270°C, but is preferably 100 to 220°C in order to suppress the formation of isomer structures and avoid side reactions such as thermal decomposition.

In step (1) of the present embodiment, the reaction time of the aromatic divinyl compound (b1) or the mixture of the aromatic divinyl compound (b1) and the aromatic monovinyl compound (b2) and the aromatic amine compound (a); In other words, as for the crosslinking reaction time, if the reaction time is short, the reaction will not proceed completely, and if the time is too long, side reactions such as thermal decomposition of the product will occur. The total time is in the range of 1 to 48 hours, but preferably the total time is in the range of 1 to 30 hours.
In the method for producing the intermediate amine compound (c) in this embodiment, since aniline or its derivative also serves as a solvent, other solvents may not necessarily be used, but it is also possible to use a solvent. For example, when reacting divinylbenzene as a raw material, use a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene to azeotropically dehydrate the water contained in the catalyst, etc. if necessary, and then distill the solvent. Alternatively, a method may be adopted in which the reaction is carried out within the above reaction temperature range after the reaction is carried out.

The intermediate amine compound (c) obtained by the above step (1) is preferably represented by the following general formula (4), for example.

（上記一般式（４）中、Ｒ^１はそれぞれ独立して、アルキル基を表し、Ｒ^２はそれぞれ独立して、炭素原子数１～１０のアルキル基、アルコキシ基若しくはアルキルチオ基；炭素原子数６～１０のアリール基、アリールオキシ基若しくはアリールチオ基；炭素原子数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を表し、
Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立して、水素原子又はメチル基を表し、かつＲ^３及びＲ^４の一方が水素原子、他方がメチル基であり、Ｒ^５及びＲ^６の一方が水素原子、他方がメチル基であり、
Ｘ^１は、以下の一般式（ｘ）：

(In the above general formula (4), R ¹ each independently represents an alkyl group, R ² each independently represents an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; 6 carbon atoms ~10 aryl group, aryloxy group or arylthio group; cycloalkyl group having 3 to 10 carbon atoms; halogen atom; hydroxyl group or mercapto group;
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and one of R ³ and R ⁴ is a hydrogen atom and the other is a methyl group, and R ⁵ and R ⁶ are One is a hydrogen atom, the other is a methyl group,
X ¹ is the following general formula (x):

（一般式（ｘ）中、Ｒ^７及びＲ^８はそれぞれ独立して、水素原子又はメチル基を表し、かつＲ^７及びＲ^８の一方が水素原子、他方がメチル基であり、Ｒ^９はアルキル基を表し、ｔは０～４の整数を表す。）
で表される置換基を表し、ｒは、Ｘ^１が結合されたベンゼン環１つ当たりのＸ^１の置換数の平均値であり、０～４の数を表し、ｐは１～３の整数を表し、ｑは０～４の整数を表し、ｋは１～１００の整数を表す。）で表される構造単位を有することが好ましい。

(In general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, and R ⁹ is an alkyl represents a group, and t represents an integer from 0 to 4.)
represents a substituent represented by, r is the average value of the number of substitutions of X ¹ per benzene ring to which X ¹ is bonded, and represents a number from 0 to 4, p is an integer from 1 to 3 , q represents an integer from 0 to 4, and k represents an integer from 1 to 100. ) is preferable.

Further, in the above general formula (4), when p is an integer of 2 or more, a plurality of R ^1s may be the same or different from each other. When q is an integer of 2 or more, a plurality of R ² 's may be the same or different. When t is an integer of 2 or more, a plurality of R ^9s may be the same or different.

The preferable forms of R ¹ to R ⁹ , X ¹ , p, q, r, t and k in the above general formula (4) are the same as in the above general formula (1). Further, as another preferable form of the intermediate amine compound (c) obtained by the above step (1), the N-substituted maleimide group in the above general formula (2), which is also a preferable form of the polymaleimide compound (A), is Examples include structures substituted with amino groups (including -NH ₂ and substituted amino groups).

In this embodiment, the amine equivalent of the intermediate amine compound (c) is preferably 172 to 400 g/equivalent, more preferably 172 to 350 g/equivalent.
In this specification, the amine equivalent of the intermediate amine compound (c) is measured by a method based on the neutralization titration method specified in JIS K 0070 (1992).

<<Step (2): Maleimidation>>
Step (2) in this embodiment is a step of reacting the intermediate amine compound (c) obtained in step (1) with maleic anhydride. Because the amino group (including -NH ₂ and substituted amino group) of the intermediate amine compound (c) can form a chemical structure in which the amino group is substituted with an N-substituted maleimide ring by a maleimidation reaction. , the polymaleimide compound (A) of the present disclosure is obtained.
In this embodiment, the intermediate amine compound (c) represented by the above general formula (4) obtained in step (1) is charged into a reactor, dissolved in a suitable solvent, and then anhydrous in the presence of a catalyst. React with maleic acid. After the reaction, unreacted maleic anhydride or other impurities are removed by washing with water or the like, and the solvent is removed under reduced pressure to obtain the desired polymaleimide compound (A). Furthermore, a dehydrating agent may be used during the reaction if necessary.

Examples of the organic solvent used in step (2) of this embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone, N,N-dimethylformamide, N,N-dimethylacetamide, Aprotic solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane, cyclic ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, and aromatic solvents such as benzene, toluene, and xylene. Examples include solvents, and these may be used alone or in combination.

In step (2) of the present embodiment, the mixing ratio of the intermediate amine compound (c) and maleic anhydride is such that the equivalent ratio of maleic anhydride to the amino equivalent of the intermediate amine compound (c) is 1 to 5. It is preferably blended in a range of 1 to 3, more preferably 1 to 3, and the mass ratio is 0.1 to 10, preferably 0.1 to 10, based on the total amount of intermediate amine compound (c) and maleic anhydride. A preferred embodiment is to carry out the reaction in an organic solvent with a mass ratio of 2 to 5.

Catalysts that can be used in step (2) of this embodiment include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, and phosphoric acid. , inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, activated clay, acid clay, silica alumina, zeolite, and strong acidic ion exchange resins. Examples include solid acids such as, heteropolyhydrochloric acids, and toluenesulfonic acid is particularly preferably used.

The dehydrating agent used in step (2) of this embodiment includes lower aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, oxides such as phosphorus pentoxide, calcium oxide, and barium oxide, and sulfuric acid. Examples include inorganic acids such as, porous ceramics such as molecular sieve, etc., and acetic anhydride is preferably used.
There is no particular restriction on the amount of the catalyst and dehydrating agent used in step ( ₂ ) of the present embodiment, but usually the amount of catalyst is The dehydrating agent can be used in an amount of 0.0001 to 1.0 mol, preferably 0.01 to 0.3 mol, and a dehydrating agent in an amount of 1 to 3 mol, preferably 1 to 1.5 mol.
In step (2) of the present embodiment, the reaction conditions for maleimidation are as follows: the above intermediate amine compound (c) and maleic anhydride are charged, and the temperature range is 10 to 100°C, preferably 30 to 60°C. After reacting for 5 to 12 hours, preferably 1 to 4 hours, the catalyst is added and the reaction is carried out at a temperature range of 90 to 130°C, preferably 105 to 120°C, for 1 to 24 hours, preferably 1 to 10 hours. can be reacted.

(Unsaturated hydrocarbon compound (B))
The curable composition of the present disclosure contains, in addition to the polymaleimide compound (A), an unsaturated hydrocarbon compound (B) containing a group having a reactive double bond. The unsaturated hydrocarbon compound (B) has a reactive double bond (for example, an allyl group) that reacts with the maleimide group of the polymaleimide compound (A), thereby exhibiting a high crosslinking density and low polarity. Since it is possible to obtain a cured product that is moisturizing, the curable composition containing the unsaturated hydrocarbon compound (B) can be used as a molding material for electronic materials and is useful. In addition, by reaction with the polymaleimide compound (A), it acts as a curing agent, can produce three-dimensional crosslinking, and a cured product with excellent heat resistance can be obtained, which is a preferred embodiment. Furthermore, in relation to the optional component epoxy resin (C), it acts as a curing agent and improves adhesion to copper, making it useful, for example, in the production of circuit boards using copper foil.

The unsaturated hydrocarbon compound (B) of this embodiment is not particularly limited as long as it is a compound containing a group having two or more reactive double bonds (carbon-carbon unsaturated bonds) in the molecule. Examples of the group having a reactive double bond include an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, and a styrylmethyl group. Among these, allyl group, 1-propenyl group, styryl group, styrylmethyl group, etc. show good reactivity with the maleimide group of the polymaleimide compound (A) and give a cured product with high crosslink density and excellent heat resistance. This is preferable in this respect.

Moreover, the unsaturated hydrocarbon compound (B) may further have a reactive functional group other than the group having the reactive double bond. The reactive functional group is not particularly limited, but includes, for example, a cyanate group (cyanate ester group), a hydroxyl group, an epoxy group, an active ester group, an amine group, an isocyanate group, a glycidyl group, and a phosphoric acid group. . Among these, at least one selected from the group consisting of a cyanate group (cyanate ester group), a hydroxyl group, an epoxy group, and an active ester group is preferred, and a cyanate group (cyanate ester group) is more preferred. By having hydroxyl groups, cyanate groups (cyanate ester groups), epoxy groups, and active ester groups, it has high bending strength and modulus of elasticity, low dielectric constant, high glass transition temperature (Tg), and has a low coefficient of thermal expansion. Thermal conductivity tends to improve.

The unsaturated hydrocarbon compound (B) having a reactive functional group other than the group having a reactive double bond may be used alone or in combination of two or more. When using an unsaturated hydrocarbon compound (B) having a reactive functional group other than a group having two or more reactive double bonds, the reactive functional groups other than the reactive double bond may be the same. may also be different. Among these, unsaturated hydrocarbon compounds (B) in which the reactive functional group is a cyanate group (cyanate ester group) and unsaturated hydrocarbon compounds (B) in which the reactive functional group is an epoxy group are included. It is preferable. The combined use of such an unsaturated hydrocarbon compound (B) having a reactive double bond tends to further improve the bending strength, bending modulus, glass transition temperature (Tg), and thermal conductivity.

Examples of the unsaturated hydrocarbon compound (B) of this embodiment include bisphenol (B1) in which the hydrogen atom of the aromatic ring is substituted with an allyl group, bisphenol (B1) in which the hydrogen atom of the aromatic ring is substituted with an allyl group, and a phenolic hydroxyl group However, among the reactive functional groups other than the reactive double bonds mentioned above, a modified phenol compound (B2) modified with a reactive functional group other than a hydroxyl group or a polyphenylene ether compound (B3) having a reactive double bond is Can be mentioned. More specifically, examples include diallyl bisphenol A, cyanate ester compounds of diallyl bisphenol A, diallyl bisphenol A type epoxy compounds, and allylphenol terminal active ester compounds.
The bisphenol is not particularly limited, but includes, for example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, and bisphenol P. , bisphenol PH, bisphenol TMC, and bisphenol Z. Among these, bisphenol A is preferred.

The polyphenylene ether compound (B3) having a reactive double bond of this embodiment is not particularly limited as long as it is a polyphenylene ether compound having a reactive double bond in its molecule, but for example, the following general formula (5 ) and a partial structure represented by general formula (6), and a terminal structure containing a group having a reactive double bond bonded to the partial structure.

（上記一般式（５）及び（６）中において、Ｒ^ｄ１～Ｒ^ｄ８はそれぞれ独立して、水素原子、炭素原子数１～５のアルキル基、炭素原子数１～５のアルケニル基、炭素原子数３～５のシクロアルキル基、炭素原子数１～５のアルコキシ基、炭素原子数１～５のチオエーテル基、炭素原子数２～５のアルキルカルボニル基、炭素原子数２～５のアルキルオキシカルボニル基、炭素原子数２～５のアルキルカルボニルオキシ基又は炭素原子数１～５のアルキルスルホニル基を表し、上記一般式（６）中のＹは、フェノール性水酸基を２つ有する芳香族化合物由来の２価の芳香族基を表し、ｖは１～３０の整数値であり、ｗ及びｕは１～３０の整数値である。）
なお、上記一般式（５）及び／又は一般式（６）で表される部分構造は、その構造の末端構造に、反応性二重結合を含有する基を有する。当該反応性二重結合を含有する基としては、例えば、炭素原子数１～５のアルケニル基、（メタ）アクリロイル基、スチリル基、スチリルメチル基等が挙げられる。

(In the above general formulas (5) and (6), R ^d1 to R ^d8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a carbon atom Cycloalkyl group having 3 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, thioether group having 1 to 5 carbon atoms, alkylcarbonyl group having 2 to 5 carbon atoms, alkyloxycarbonyl group having 2 to 5 carbon atoms group, an alkylcarbonyloxy group having 2 to 5 carbon atoms, or an alkylsulfonyl group having 1 to 5 carbon atoms, and Y in the above general formula (6) is derived from an aromatic compound having two phenolic hydroxyl groups. Represents a divalent aromatic group, v is an integer value of 1 to 30, and w and u are integer values of 1 to 30.)
Note that the partial structure represented by the above general formula (5) and/or general formula (6) has a group containing a reactive double bond at the terminal structure of the structure. Examples of the group containing the reactive double bond include an alkenyl group having 1 to 5 carbon atoms, a (meth)acryloyl group, a styryl group, a styrylmethyl group, and the like.

The polyphenylene ether (PPE) contained in the structure of the polyphenylene ether compound (B3) having a reactive double bond of this embodiment has excellent dielectric properties such as dielectric constant or dielectric loss tangent, so it can be used in the high frequency range from MHz band to GHz band. It is possible to prepare a curable composition that can obtain a cured product that maintains a sufficiently low dielectric constant and exhibits a sufficiently low dielectric loss tangent even in the frequency band (high frequency region), so it is a molding material for high frequencies. It can be used as a useful tool. Further, by reaction with the polymaleimide compound (A), it acts as a curing agent, can generate three-dimensional crosslinking, and a cured product with excellent heat resistance can be obtained, which is a preferred embodiment.

The above-mentioned thioether group having 1 to 5 carbon atoms includes, but is not particularly limited to, a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a pentylthio group, and the like.

The alkylcarbonyl group having 2 to 5 carbon atoms is not particularly limited, but includes a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, an isopropylcarbonyl group, a butylcarbonyl group, and the like.

The alkyloxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, but includes methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, and the like.

The alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, but includes methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, and the like.

The above-mentioned alkylsulfonyl group having 1 to 5 carbon atoms includes, but is not particularly limited to, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group, and the like.

R ^d1 to R ^d8 in the above general formulas (5) and (6) may be the same or different, and are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and 3 to 5 carbon atoms. It is preferably a cycloalkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom, a methyl group, or an ethyl group. It is particularly preferable that there be.

Examples of Y in the above general formula (6) include a divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups.
The aromatic compound having two phenolic hydroxyl groups is not particularly limited, but catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2, Examples include 7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, and tetramethylbisphenol A. Among these, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferred, and 4,4'-biphenol and bisphenol A , and more preferably tetramethylbisphenol A.
Furthermore, since the two phenolic hydroxyl groups of the aromatic compound having two phenolic hydroxyl groups form a phenylene ether bond (two oxygen atoms bonded to Y), Y has two phenolic hydroxyl groups. It becomes a divalent aromatic group derived from an aromatic compound having In other words, a group obtained by removing two arbitrary hydrogen atoms from the aromatic compound having two phenolic hydroxyl groups is defined as a "divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups."

Furthermore, in the present embodiment, the weight average molecular weight (Mw) of the polyphenylene ether compound (B3) having a reactive double bond is preferably 1000 to 5000, more preferably 1200 to 4000, and still more preferably It is 1400-3000. If it is within the above range, it is possible to more reliably obtain a cured product with excellent dielectric properties and well-balanced heat resistance, which is a preferred embodiment. Note that the weight average molecular weight (Mw) here may be one measured by a general molecular weight measurement method, and specifically, a value measured using GPC described in the Examples section below. Can be mentioned.

In the curable composition of this embodiment, the unsaturated hydrocarbon compound (B) is preferably contained in an amount of 10% by mass or more and 70% by mass or less, and 15% by mass or more and 65% by mass or less, based on the entire curable composition. The content is more preferably 20% by mass or more and 50% by mass or less. The content of the unsaturated hydrocarbon compound (B) is preferably in the range of 20% by mass or more and 50% by mass or less from the viewpoint of heat resistance and low hygroscopicity.

(Curing agent (D) other than unsaturated hydrocarbon compound (B))
A curing agent (D) other than the unsaturated hydrocarbon compound (B) can also be added to the curable composition of the present embodiment within a range that does not impair the curing of the present invention. In addition, the curing agent (D) is preferably 2% by mass or more and 20% by mass or less, most preferably 5% by mass or more and 10% by mass or less, based on 100% by mass of the total amount of the curable composition. The content of the curing agent (D) is preferably in a range of 5% by mass or more and 10% by mass or less from the viewpoint of low hygroscopicity and low dielectric loss tangent.

Examples of the curing agent (D) of this embodiment include amine compounds, cyanate ester compounds, amide compounds, acid anhydride compounds, phenol compounds, polyphenylene ether compounds having a hydroxyl group at the end, and diene compounds. Examples include polymers. These curing agents may be used alone or in combination of two or more types.

Examples of the amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivatives.

Examples of the cyanate ester compounds include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, and phenylene ether type cyanate ester resin. , naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate Ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol condensed novolak Examples include a naphthol-cresol cocondensed novolac type cyanate ester resin, an aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate ester resin, a biphenyl-modified novolak type cyanate ester resin, an anthracene type cyanate ester resin, and the like. Each of these may be used alone, or two or more types may be used in combination.

Examples of the amide compound include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid, and ethylenediamine, and the like.

Examples of the acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, Examples include methylhexahydrophthalic anhydride.

Examples of the above-mentioned phenolic compounds include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyrock resin), and resorcin novolak resin. Polyhydric phenol novolac resins synthesized from polyhydric hydroxy compounds and formaldehyde, naphthol aralkyl resins, trimethylolmethane resins, tetraphenylolethane resins, naphthol novolac resins, naphthol-phenol cocondensed novolak resins, naphthol-cresol cocondensed novolak resins , biphenyl-modified phenolic resin (a polyhydric phenol compound with a phenol nucleus linked by a bismethylene group), biphenyl-modified naphthol resin (a polyhydric naphthol compound with a phenol nucleus linked by a bismethylene group), aminotriazine-modified phenol resin (melamine, benzoguanamine) polyhydric phenol compounds such as polyhydric phenol compounds in which the phenol nucleus is linked with phenolic compounds) and alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenol compounds in which the phenol nucleus and the alkoxy group-containing aromatic ring are linked with formaldehyde) can be mentioned.

Examples of the polyphenylene ether compounds having a hydroxyl group at the terminal include a partial structure represented by the above general formula (5) or general formula (6), and a compound in which the terminal structure bonded to the partial structure is a hydroxyl group. It will be done.

Examples of the diene polymer include unmodified diene polymers that are not modified with polar groups. Here, the polar group is a functional group that affects dielectric properties, and includes, for example, a phenol group, an amino group, an epoxy group, and the like. The diene polymer is not particularly limited, and for example, 1,2-polybutadiene, 1,4-polybutadiene, etc. can be used.

As the diene polymer, a butadiene homopolymer and its derivatives, in which 50% or more of the butadiene units in the polymer chain are 1,2-bonds, can also be used.

(Epoxy resin (C))
It is preferable that the curable composition of this embodiment further contains an epoxy resin (C). The epoxy resin (C) is useful because it has good fluidity during the preparation of the curable composition and allows the preparation of a curable composition from which a cured product with excellent adhesion can be obtained. In addition, when a polymaleimide compound (A), an unsaturated hydrocarbon compound (B), and an epoxy resin (C) are used as the curable composition of this embodiment, the adhesion to copper is improved, For example, it is useful in manufacturing circuit boards using copper foil.

The epoxy resin (C) of this embodiment is not particularly limited, but includes, for example, a phenol novolak epoxy resin, a cresol novolac epoxy resin, an α-naphthol novolac epoxy resin, a β-naphthol novolac epoxy resin, and a bisphenol A novolac. Novolak type epoxy resins such as type epoxy resins and biphenyl novolak type epoxy resins; Aralkyl type epoxy resins such as phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, and phenol biphenylaralkyl type epoxy resins; Bisphenol A type epoxy resins and bisphenol AP type Epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type Bisphenol type epoxy resins such as epoxy resins; biphenyl type epoxy resins such as biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, epoxy resins having a biphenyl skeleton and diglycidyloxybenzene skeleton; naphthalene type epoxy resins; binaphthol type epoxy resins; Binaphthyl type epoxy resin; dicyclopentadiene type epoxy resin such as dicyclopentadiene phenol type epoxy resin; tetraglycidyldiaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenylsulfone, etc. glycidyl amine type epoxy resin; diglycidyl ester type epoxy resin such as 2,6-naphthalene dicarboxylic acid diglycidyl ester type epoxy resin, glycidyl ester type epoxy resin of hexahydrophthalic anhydride; dibenzopyran, hexamethyldibenzopyran, 7- Examples include benzopyran type epoxy resins such as phenylhexamethyldibenzopyran. These may be used alone or in combination of two or more.

Among these, phenol aralkyl type epoxy resin, biphenyl novolak type epoxy resin, naphthol novolak type epoxy resin containing naphthalene skeleton, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin. type epoxy resin, crystalline biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, xanthene type epoxy resin, alkoxy group-containing aromatic ring-modified novolak type epoxy resin (formaldehyde containing glycidyl group-containing aromatic ring and alkoxy group-containing Particularly preferred are compounds in which aromatic rings are connected (compounds in which aromatic rings are connected), etc., since they yield cured products with excellent heat resistance.

In the curable composition of this embodiment, the epoxy resin (C) is preferably contained in an amount of 2% by mass or more and 30% by mass or less, and preferably 5% by mass or more and 25% by mass or less, based on the entire curable composition. is most preferred. It is preferable from the viewpoint of heat resistance that the content of the epoxy resin (C) is in the range of 5% by mass or more and 25% by mass or less.

A preferred curable composition of this embodiment is characterized by containing a polymaleimide compound (A), an unsaturated hydrocarbon compound (B), and an epoxy resin (C). The polymaleimide compound (A) has a chemical structure in which two or more maleimide groups are linked to an alkanediyl group having a monocyclic or fused polycyclic aromatic ring, and therefore has a chemical structure that is superior to conventional maleimide resins. , excellent solvent solubility, easy preparation of a curable composition, excellent handling properties, and low proportion of polar functional groups in the structure of the polymaleimide compound (A), resulting in a cured product with excellent dielectric properties. be able to. In addition, the unsaturated hydrocarbon compound (B) that acts as a curing agent can produce a cured product with a high crosslink density by reacting the reactive double bond in the unsaturated hydrocarbon compound (B) with the maleimide group. Furthermore, the epoxy resin (C) can contribute to the formation of the curable composition, and the epoxy resin (C) has good fluidity during the preparation of the curable composition, making it possible to obtain a cured product with excellent adhesion. In addition, the unsaturated hydrocarbon compound (B) that acts as a curing agent reacts with the polymaleimide compound (A) and the epoxy resin (C) to form three-dimensional crosslinks, resulting in excellent heat resistance. A cured product can be obtained, which is a preferred embodiment. Furthermore, the reaction between the unsaturated hydrocarbon compound (B) and the epoxy resin (C) improves adhesion to copper, making it useful, for example, in the production of circuit boards using copper foil.

The blending ratio (parts by mass) of the polymaleimide compound (A), the unsaturated hydrocarbon compound (B), and the epoxy resin (C) is as follows: polymaleimide compound (A): (unsaturated hydrocarbon compound (B)) + epoxy resin (C)) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, even more preferably 65:35 to 35:65, Particularly preferred is 55:45 to 45:55. By adjusting the blending ratio within the above range, heat resistance, low dielectric constant, and low dielectric loss tangent can be achieved, which is preferable.

In the curable composition of the present invention, the blending ratio (parts by mass) of the unsaturated hydrocarbon compound (B) and the epoxy resin (C) is not particularly limited, but the properties of the resulting cured product are From the viewpoint of good performance, the ratio of unsaturated hydrocarbon compound (B) to epoxy resin (C) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and Preferably it is 65:35 to 35:65. By adjusting the blending ratio within the above range, heat resistance, low dielectric constant, and low dielectric loss tangent can be achieved, which is preferable.

(Other resin (E))
Further, other resins (E) may be contained in addition to the polymaleimide compound (A), the unsaturated hydrocarbon compound (B), and the epoxy resin (C), as long as they do not impair the purpose of the present disclosure. . Examples of the other resins (E) include bismaleimides other than the polymaleimide compound (A), allyl ether compounds, allylamine compounds, triallyl cyanurates, alkenylphenol compounds, vinyl group-containing polyolefin compounds, and phenols. Resin, active ester resin, polyphenylene ether resin, benzoxazine resin, styrene maleic anhydride copolymer, polybutadiene and its modified products, polyacetal resin, polyvinyl alcohol resin, liquid crystal polymer, fluororesin, polystyrene, polyethylene, polyimide resin, thermosetting It is also possible to appropriately blend polyimide resin, silicone gel, silicone oil, etc. The content of the other resin (E) is preferably 2% by mass or more and 20% by mass or less, most preferably 5% by mass or more and 10% by mass or less, based on 100% by mass of the total amount of the curable composition. The content of the other resin (E) is preferably in the range of 5% by mass or more and 10% by mass or less from the viewpoint of heat resistance and compatibility.

(hardening accelerator)
The curable composition of this embodiment can also be used in combination with a curing accelerator, if necessary. Various types of curing accelerators can be used; for example, it is effective to add polymerization initiators such as organic peroxides and azo compounds, or basic catalysts such as phosphine compounds and tertiary amines. . Specific examples of the curing accelerator include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, TPP-MK, TPP-K, triethylamine, imidazoles, and the like. The curing accelerator can be used alone or in combination of two or more types. The amount of the curing accelerator in this embodiment is preferably 0.05 to 5% by mass of the entire curable resin composition.

(Additive)
The curable composition of this embodiment can also contain additives as appropriate. Examples of the additives include silane coupling agents, mold release agents, pigments, emulsifiers, non-halogen flame retardants, inorganic fillers, flame retardants, and solvents. The content of the additive is preferably 1% by mass or more and 20% by mass or less, most preferably 3% by mass or more and 10% by mass or less, based on 100% by mass of the total amount of the curable composition.

Examples of the flame retardant include inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants, and non-halogen flame retardants. The curable composition of this embodiment preferably contains a non-halogen flame retardant that does not substantially contain halogen atoms in order to exhibit flame retardancy within a range that does not impair the purpose. Examples of the non-halogen flame retardant include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc., and these may be used alone or in combination. be able to.

The curable composition of this embodiment may contain an inorganic filler, if necessary. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When the amount of the inorganic filler to be blended is particularly large, it is preferable to use fused silica. The fused silica can be used either in crushed or spherical form, but in order to increase the blending amount of fused silica and to suppress the rise in melt viscosity of the molding material, it is preferable to mainly use spherical silica. Furthermore, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 30% by mass or more and 50% by mass or less based on the total amount of the curable composition. Further, when the curable composition is used for purposes such as a conductive paste described in detail below, a conductive filler such as silver powder or copper powder can be used.

In the curable composition of this embodiment, the lower limit of the total content of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) is 40% by mass with respect to the entire curable composition (100% by mass). , 42% by weight, 45% by weight, 47% by weight, 48% by weight or 50% by weight. Moreover, it is preferable that the upper limit of the said total content is 100 mass %, 99 mass %, 98 mass %, or 97 mass %. The above upper limit value and the above lower limit value can be arbitrarily combined. Therefore, for example, in the curable composition of the present embodiment, the total content of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) is 40% by mass with respect to the entire curable composition (100% by mass). % or more and 100% by mass or less, and more preferably the total content of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) is 45% by mass or more and 100% by mass or less, and the polymaleimide compound It is more preferable that the total content of (A) and the unsaturated hydrocarbon compound (B) is 50% by mass or more and 100% by mass or less.
The curable composition of this embodiment has a total content of a polymaleimide compound (A), an unsaturated hydrocarbon compound (B), an inorganic filler, and an additive with respect to the entire curable composition (100% by mass). It is preferable that the lower limit of is 70% by mass, 72% by mass, 75% by mass, 77% by mass, or 80% by mass. Moreover, it is preferable that the upper limit of the said total content is 100 mass %, 99 mass %, 98 mass %, or 97 mass %. The upper limit value and the lower limit value can be arbitrarily combined similarly to the range of the total content of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B).
The curable composition of the present embodiment contains a total of a polymaleimide compound (A), an unsaturated hydrocarbon compound (B), an epoxy resin (C), and an additive based on the entire curable composition (100% by mass). It is preferable that the lower limit of the content is 43% by mass, 45% by mass, 48% by mass, 50% by mass, or 53% by mass. Moreover, it is preferable that the upper limit of the said total content is 100 mass %, 99 mass %, 98 mass %, or 97 mass %. The upper limit value and the lower limit value can be arbitrarily combined similarly to the range of the total content of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B).

[Cured product]
The cured product of the present disclosure is preferably obtained from the curable composition. The cured product can be obtained by subjecting the curable composition to a curing reaction. The curable composition is obtained by uniformly mixing the above-mentioned components (e.g., curing agent, compounding agent), and can be easily made into a cured product by a method similar to a conventionally known method. . Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coatings, and films.
The curing (thermal curing) reaction is easily carried out without a catalyst, but if you want to make the reaction even faster, you can use a polymerization initiator such as an organic peroxide, an azo compound, a phosphine compound, or a tertiary amine. Addition of a basic catalyst such as is effective. Examples include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc., and the blending amount is preferably 0.05 to 5% by mass of the entire curable composition. .

[Heat-resistant materials and electronic materials]
The cured product obtained from the curable composition containing the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) of the present disclosure has both excellent low hygroscopicity and low dielectric properties. It can be suitably used for electronic components. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up substrates, adhesives and resist materials using conductive pastes, and the like. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg with high heat resistance or a small dimensional change rate. Furthermore, the polymaleimide compound (A) contained in the curable composition exhibits excellent solubility in various solvents and can therefore be made into a paint. The heat-resistant components and electronic components thus obtained can be suitably used for various purposes, such as industrial mechanical parts, general mechanical parts, automobile/railway/vehicle parts, space/aviation related parts, electronic/electrical parts, etc. Examples include, but are not limited to, building materials, containers/packaging members, household goods, sports/leisure goods, wind power generation casing members, etc.

Typical products (circuit boards, semiconductor sealing materials, semiconductor devices, prepregs, build-up substrates, build-up films, conductive pastes) manufactured using the curable composition of the present invention will be explained below with examples. do.

[Circuit board]
The present disclosure is a circuit board that is a laminate of prepreg and copper foil. A method for obtaining a printed circuit board from the curable composition of the present embodiment is to laminate the following prepregs in a conventional manner, overlay copper foil as appropriate, and then under a pressure of 1 to 10 MPa at 170 to 300°C for 10 minutes. A method of heat-pressing for 3 hours may be mentioned.

[Semiconductor encapsulation material]
The present disclosure is a semiconductor encapsulation material containing the curable composition of the present embodiment. The semiconductor encapsulating material obtained using the curable composition of the present embodiment has hygroscopicity and low dielectric loss tangent by using the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) of the present disclosure. Since the ratio is improved, the processability, moldability, and reflow resistance in the manufacturing process are excellent, and this is a preferred embodiment.
The curable composition of this embodiment used for the semiconductor encapsulation material may contain an inorganic filler. As for the filling rate of the inorganic filler, for example, the inorganic filler can be used in a range of 0.5 to 1200 parts by mass based on 100 parts by mass of the curable composition of the present embodiment. In addition, as described above, examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, Examples include aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, and the like.

The method for obtaining the semiconductor encapsulating material includes adding optional components such as a curing accelerator and/or additive to the curable composition of the present embodiment using an extruder, kneader, or loader. Examples include a method of sufficiently melting and mixing using a tool or the like until the mixture becomes uniform. When used as a highly thermally conductive semiconductor encapsulant for power transistors and power ICs, use high-filling materials such as crystalline silica, alumina, and silicon nitride, which have higher thermal conductivity than fused silica, or use fused silica, crystalline silica, alumina, and nitride. It is preferable to use silicon or the like. It is preferable to use the inorganic filler in a range of 30 to 95 parts by mass per 100 parts by mass of the curable composition. In order to reduce the amount, the amount is more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.

[Semiconductor device]
The present disclosure is a semiconductor device including a cured product of the semiconductor encapsulating material. Since the semiconductor device obtained using the semiconductor encapsulating material obtained using the curable composition of this embodiment uses the polymaleimide compound (A) and unsaturated hydrocarbon compound (B) of the present disclosure, it has a low It has excellent viscosity and fluidity, and has improved hygroscopicity, thermal elastic modulus, and adhesion to metal materials, so it has excellent processability, moldability, and reflow resistance in the manufacturing process, and is a preferred embodiment.

As a method for obtaining the semiconductor device, the semiconductor encapsulation material is cast, molded using a transfer molding machine, an injection molding machine, etc., and then heated and cured in a temperature range of room temperature (20°C) to 250°C. One method is to do so.

[Prepreg]
The present disclosure is a prepreg having a reinforcing base material and a semi-cured product of the curable composition of the present embodiment impregnated into the reinforcing base material. A method for obtaining a prepreg from the above-mentioned curable composition is to blend a varnished curable composition with an organic solvent to be described later and apply it to a reinforcing base material (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass After impregnating a mat, glass roving cloth, etc., the curable composition is semi-cured (or uncured) by heating at a heating temperature depending on the type of solvent used, preferably 50 to 170°C, to form a prepreg. There are several ways to obtain this. The mass ratio of the curable composition and the reinforcing base material used at this time is not particularly limited, but it is usually preferably adjusted so that the resin content in the composition in the prepreg is 20 to 60% by mass.
In the present embodiment, the semi-cured product of the curable composition is obtained by adjusting the heating temperature and heating time and stopping the curing reaction midway without completing it. Further, for example, the semi-cured material may have a degree of hardening of, for example, 85% or less and 5% or more. On the other hand, the cured product in this embodiment may have a higher degree of curing than the semi-cured product.
The degree of curing of the semi-cured product can be calculated from the following formula by measuring the curing heat value when heating the curable composition and the curing heat value of the semi-cured product using DSC.
Curing degree (%) = [1-(curing calorific value of semi-cured product/curing calorific value of curable composition)] x 100

Examples of the organic solvent used for producing the prepreg of this embodiment include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, and the like. The selection and appropriate amount used can be selected as appropriate depending on the application, but for example, when further manufacturing printed circuit boards from prepreg as described below, polar It is preferable to use a solvent, and it is also preferable to use it in a proportion such that the nonvolatile content is 40 to 80% by mass. In addition, the reinforcing base material used for manufacturing the prepreg of this embodiment is woven fabric or nonwoven fabric made of inorganic fibers such as glass fiber, polyester fiber, or polyamide fiber, or organic fiber, mat, paper, etc., and these may be used alone. Alternatively, they can be used in combination.

The conditions for the heat treatment of the prepreg of this embodiment are appropriately selected depending on the type and amount of the organic solvent, catalyst, and various additives used, but usually at a temperature of 80 to 220°C for 3 minutes. It is preferable to carry out the test for 30 minutes.

[Buildup board]
A method for obtaining a build-up substrate from the curable composition of the present embodiment includes a method that involves the following steps 1 to 3. In step 1, first, the curable composition containing rubber, filler, etc. as appropriate is applied to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured. In step 2, if necessary, holes such as predetermined through holes are made in the circuit board coated with the curable composition, and then treated with a roughening agent, and the surface is washed with hot water to remove the The substrate is made to have irregularities and is plated with metal such as copper. In step 3, the operations of steps 1 and 2 are repeated as desired to alternately build up the resin insulating layer and the conductor layer of a predetermined circuit pattern to form a buildup board. In the above process, it is preferable that the through-hole portion be formed after the outermost resin insulating layer is formed. In addition, the build-up board in this embodiment is produced by heat-pressing a resin-coated copper foil obtained by semi-curing the composition on the copper foil at 170 to 300°C onto a wiring board on which a circuit is formed. It is also possible to fabricate a build-up board by omitting the steps of forming a chemical surface and plating.

[Build-up film]
The present disclosure is a build-up film containing the curable composition of the present embodiment. The method for producing the build-up film of the present embodiment includes applying the curable composition on the support film (Y) and then drying it to form a curable composition layer on the support film (Y). An example of this method is to produce an adhesive film for a multilayer printed wiring board.
When producing a build-up film from a curable composition, the film softens under the laminating temperature conditions (usually 70 to 140°C) in the vacuum lamination method, and simultaneously laminates the circuit board and removes the via holes present in the circuit board. Alternatively, it is important that the resin exhibits fluidity (resin flow) that allows the resin to be filled in the through-hole, and it is preferable to mix the above-mentioned components so as to exhibit such characteristics. In addition, the resulting build-up films and circuit boards (copper-clad laminates, etc.) do not exhibit locally different characteristic values due to phase separation, etc., and can maintain constant performance at any location. In order to achieve this, uniformity in appearance is required.

Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to allow resin filling within this range. . Note that when laminating both sides of the circuit board, it is desirable that about 1/2 of the through holes be filled.

Specifically, the method for producing the adhesive film described above includes preparing the varnish-like curable composition, applying the varnish-like composition to the surface of the support film (Y), and further heating. Alternatively, it can be manufactured by drying the organic solvent by blowing hot air or the like to form a composition layer (X) made of a curable composition. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, and carbitol such as cellosolve and butyl carbitol. It is preferable to use tols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is also preferable to use them in a proportion such that the nonvolatile content is 30 to 60% by mass.

The thickness of the composition layer (X) to be formed is usually preferably greater than the thickness of the conductor layer. Since the thickness of a conductor layer included in a circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably in the range of 10 to 100 μm. In addition, the composition layer (X) in this embodiment may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and from scratching it.

The support film (Y) and the protective film described above are made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate, polycarbonate, polyimide, Further examples include release paper and metal foils such as copper foil and aluminum foil. Note that the support film and the protective film may be subjected to a release treatment in addition to mud treatment and corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, preferably 25 to 50 μm. Further, the thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) described above is peeled off after being laminated onto the circuit board or after forming an insulating layer by heating and curing. If the support film (Y) is peeled off after the adhesive film is cured by heating, it is possible to prevent dust and the like from adhering to the adhesive film during the curing process. When peeling is performed after curing, the support film is usually subjected to a release treatment in advance.
Note that a multilayer printed circuit board can be manufactured from the build-up film obtained as described above. For example, if the resin composition layer (X) is protected with a protective film, after peeling off the protective film, apply the resin composition layer (X) to one or both sides of the circuit board so as to be in direct contact with the circuit board. , for example, by a vacuum lamination method. The lamination method may be a batch method or a continuous method using rolls. Moreover, if necessary, the build-up film and the circuit board may be heated (preheated) before lamination. As for the laminating conditions, it is preferable that the pressure bonding temperature (laminate temperature) is 70 to 140°C, and the pressure bonding pressure is 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ). It is preferable that the lamination is carried out under a reduced air pressure of 20 mmHg (26.7 hPa) or less.

<Conductive paste>
A method for obtaining a conductive paste from the curable composition of the present invention includes, for example, a method in which conductive particles are dispersed in the composition. The above-mentioned conductive paste can be made into a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used.

The present invention will be explained in detail with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The physical properties of the synthesized polymaleimide compound (A) were measured as follows and are shown in Table 1.

(1) Amine equivalent The amine equivalent of the intermediate amine compound (c) was measured by the following measuring method.
After accurately weighing approximately 2.5 g of the sample intermediate amine compound (c), 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine into a 500 mL Erlenmeyer flask with a stopper, a cooling tube was attached. Heat and reflux for 150 minutes in an oil bath set at 120°C.
After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and titration was performed with a 0.5 mol/L potassium hydroxide-ethanol solution by potentiometric titration. A blank test was conducted in the same manner and corrections were made.
Amine equivalent (g/equivalent) = (S x 2,000)/(Blank-A)
S: Sample amount (g)
A: Consumption amount (mL) of 0.5 mol/L potassium hydroxide-ethanol solution
Blank: Consumption amount (mL) of 0.5 mol/L potassium hydroxide-ethanol solution in blank test

(2) GPC measurement Number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight of the polymaleimide compounds (A) obtained in Examples and Comparative Examples using the following measuring equipment and measurement conditions. Distribution (Mw/Mn) was calculated.
"measuring device"
"HLC-8320 GPC" manufactured by Tosoh Corporation
"Measurement condition"
Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G3000HXL” manufactured by Tosoh Corporation "TSK-GEL G4000HXL"
Detector: RI (differential refractometer)
Data processing: “GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40℃
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml/min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A tetrahydrofuran solution containing 1.0% by mass (calculated as resin solid content) of the polymaleimide compound (A) obtained in the synthesis example was filtered through a microfilter (50 μl).

(3) FD-MS measurement The FD-MS spectrum of the polymaleimide compound (A) obtained in the example was measured using the following measuring device and measurement conditions.
Measuring device: JMS-T100GC AccuTOF
Measurement conditions Measurement range: m/z = 4.00 to 2000.00
Rate of change: 51.2mA/min
Final current value: 45mA
Cathode voltage: -10kV
Recording interval: 0.07sec

(4) ¹³ C-NMR measurement The ¹³ C-NMR spectrum of the polymaleimide compound (A) obtained in the example was measured using the following measuring device and measurement conditions.
^13C -NMR: “JNM-ECZ400S” manufactured by JEOL RESONANCE
Resonance frequency: 100MHz
Accumulation count: 4000 times Solvent: Chloroform-d
Sample concentration: 12% by mass
Relaxation reagent: chromium (III) acetylacetonate

(5) Synthesis of Polymaleimide Compound (A) <Synthesis Example 1> Synthesis of Polymaleimide Compound (A-1) (I) Synthesis of Intermediate Amine Compound (c-1) Thermometer, cooling tube, Dean-Stark trap, and A flask equipped with a stirrer was charged with 242.4 g (2.0 mol) of 2-ethylaniline, 242 g of xylene, and 80 g of activated clay, heated to 130° C. with stirring, and held for 30 minutes. Thereafter, 272.0 g of DVB-810 (mixture of divinylbenzene/ethylstyrene (divinylbenzene/ethylstyrene = 81/19 (mol)%), manufactured by Nippon Steel Chemical & Materials) was added dropwise over 2 hours, and as it was. The reaction was allowed to proceed for 1 hour. Thereafter, the temperature was raised to 190° C. over 6 hours and held for 10 hours. After the reaction, the intermediate amine compound (c-1 ) was obtained. The amine equivalent of the intermediate amine compound (c-1) was 214 g/equivalent.
(II) Maleimidation 117.7 g (1.2 mol) of maleic anhydride and 700 g of toluene were charged into a 2 L flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, and the mixture was stirred at room temperature. Next, a mixed solution of 214 g (1 equivalent) of the intermediate amine compound (c-1) and 175 g of DMF was added dropwise over 1 hour, and the reaction was then allowed to proceed for 2 hours. 37.1 g of p-toluenesulfonic acid monohydrate was added to the reaction solution, heated to 115°C, and water and toluene that azeotroped under reflux were cooled and separated, and only toluene was returned to the system. The dehydration reaction was carried out for 5 hours. After air cooling to room temperature, it was neutralized with 49% NaOH. Thereafter, toluene and water were distilled off under reduced pressure at 60° C., and 600 g of MEK (methyl ethyl ketone) was added to the DMF solution remaining in the flask. The temperature of the solution was raised to 60° C., and then the salt in the solution was removed by liquid separation treatment three times with 200 g of ion-exchanged water. Further, sodium sulfate was added and after drying, the reaction product was concentrated under reduced pressure and vacuum dried at 80° C. to obtain a polymaleimide compound (A-1). The chemical structure and property analysis of the polymaleimide compound (A-1) were confirmed using GPC, FD-MS, and ¹³ C-NMR. The measurement results are shown in FIGS. 1A to 1C. From the GPC measurement results, the Mn of the polymaleimide compound (A-1) was 998, the Mw was 367,834, and the Mw/Mn was 368.697.

<Examples 1-2 and Comparative Examples 1-2>
<<Preparation of curable composition and production of cured product>>
The polymaleimide compound (A-1) obtained in the above Synthesis Example 1, a comparative maleimide (1) represented by the following formula (7) ("BMI-1000" manufactured by Daiwa Kasei Kogyo Co., Ltd.),

不飽和炭化水素化合物（Ｂ）として、不飽和炭化水素化合物（Ｂ－１）（「ＳＡ－９０００」、ＳＡＢＩＣ社製、両末端メタクリル変性ポリフェニレンエーテル）と、不飽和炭化水素化合物（Ｂ－２）（「ＮＥ－Ｖ－１１００」、ＤＩＣ社製、両末端ビニル樹脂）と、不飽和炭化水素化合物（Ｂ－３）（「ＤＡＢＰＡ」、大和化成工業株式会社製、２，２’－ジアリルビスフェノールＡ）と、エポキシ樹脂（Ｃ）として、エポキシ樹脂（Ｃ－１）（ＢＰＡ型エポキシ樹脂「８５０－Ｓ」当量：１８８ｇ／ｅｑ、ＤＩＣ株式会社製）と、ＤＣＰＯ（「パークミルＤ」、日油株式会社製、Ｄｉｃｕｍｙｌ Ｐｅｒｏｘｉｄｅ）と、を以下の表１に示す割合で配合し、実施例１～３及び比較例１～３の硬化性組成物を調製した。

As the unsaturated hydrocarbon compound (B), an unsaturated hydrocarbon compound (B-1) ("SA-9000", manufactured by SABIC, both terminals methacrylic modified polyphenylene ether) and an unsaturated hydrocarbon compound (B-2) ("NE-V-1100", manufactured by DIC Corporation, double-terminated vinyl resin) and unsaturated hydrocarbon compound (B-3) ("DABPA", manufactured by Daiwa Chemical Industries, Ltd., 2,2'-diallylbisphenol A ), and as the epoxy resin (C), epoxy resin (C-1) (BPA type epoxy resin "850-S" equivalent weight: 188 g/eq, manufactured by DIC Corporation), DCPO ("Perc Mill D", NOF Corporation) Dicumyl Peroxide (manufactured by Co., Ltd.) in the proportions shown in Table 1 below to prepare curable compositions for Examples 1 to 3 and Comparative Examples 1 to 3.

Next, by curing the curable compositions of Examples 1 to 3 and Comparative Examples 1 to 3 using the following curing conditions, a material corresponding to the curable compositions of Examples 1 to 3 and Comparative Examples 1 to 3 was obtained. Cured products were produced respectively. Then, physical properties such as dielectric constant, dielectric loss tangent, and hygroscopicity were evaluated using the following methods. The results are shown in Table 1.
<<Curing conditions>>
After heating at 200° C. for 2 hours using a vacuum press, the film was cured by heating at 250° C. for 2 hours.
Plate thickness after molding: 1.3mm
<<Evaluation of permittivity and dielectric loss tangent>>
In accordance with JIS-C-6481, using the cavity resonance method using network analyzer "E8362C" manufactured by Agilent Technologies Co., Ltd., the test piece was stored at 23°C and 50% humidity for 24 hours after being completely dried. The dielectric constant (Dk) and dielectric loss tangent (Df) were measured.
<<Evaluation of hygroscopicity>>
In the present Examples and Comparative Examples, as a method for evaluating low hygroscopicity, the moisture absorption rate (%) was calculated and evaluated by the following method.
A test piece cut into a size of 5 mm x 55 mm x 1.3 mm from the cured product obtained above was held at 85°C, 85% RH, and 1 atm for 50 hours using a pressure cooker tester, and then the following Moisture absorption rate (%) was calculated and evaluated using the formula.
Moisture absorption rate (%) = (mass of test piece after test - mass of test piece before test) / (mass of test piece before test) x 100

From the results shown in Table 1 above, when comparing Examples 1 to 3 and Comparative Examples 1 to 3, it was found that the curability of Examples 1 to 3 containing the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) was It can be confirmed that by using the composition, low dielectric constant, low dielectric loss tangent, and low moisture absorption under high temperature and high humidity conditions were achieved.

According to the present disclosure, it is possible to provide a curable composition that exhibits low dielectric properties and low moisture absorption upon curing, and a cured product thereof.

Claims (9)

A polymaleimide compound (A) containing a monocyclic or fused polycyclic aromatic group to which two or more linear or branched alkylene groups are bonded;
A curable composition containing an unsaturated hydrocarbon compound (B) having a reactive double bond. The curable composition according to claim 1, wherein the polymaleimide compound (A) has a structural unit represented by the following general formula (1).

(In the above general formula (1), R ¹ each independently represents an alkyl group,
R ² is each independently an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; cycloalkyl having 3 to 10 carbon atoms; Represents a group; a halogen atom; a hydroxyl group; or a mercapto group;
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and one of R ³ and R ⁴ is a hydrogen atom and the other is a methyl group, and R ⁵ and R ⁶ are One is a hydrogen atom, the other is a methyl group,
X ¹ is the following general formula (x):

(In general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom and the other is a methyl group, and R ⁹ is Independently, an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom ; represents a hydroxyl group; or a mercapto group, and t represents an integer of 0 to 4.)
represents a substituent represented by, r is the average value of the number of substitutions of X ¹ per benzene ring to which X ¹ is bonded, and represents a number from 0 to 4, p is an integer from 1 to 3 , q represents an integer from 0 to 4, and k represents an integer from 1 to 100. ) The curable composition according to claim 1 or 2, further comprising an epoxy resin (C). A cured product of the curable composition according to any one of claims 1 to 3. A prepreg comprising a reinforcing base material and a semi-cured product of the curable composition according to any one of claims 1 to 3 impregnated into the reinforcing base material. A circuit board comprising a laminate in which the prepreg according to claim 5 and copper foil are laminated. A build-up film containing the curable composition according to any one of claims 1 to 3. A semiconductor encapsulant containing the curable composition according to any one of claims 1 to 3. A semiconductor device comprising a cured product of the semiconductor encapsulant according to claim 8.

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