JP2023104618A - Thermosetting resin composition - Google Patents

Abstract

To provide a thermosetting resin composition to be a cured product that is low in both relative dielectric constant and dielectric loss tangent, changes little in relative dielectric constant and dielectric loss tangent after high temperature storage, and has heat resistance, wherein the thermosetting resin composition has low viscosity during heating and is easy to handle.SOLUTION: A thermosetting resin composition comprises the following component (A), component (B) and component (C): (A) a cyclic imide compound, (B) an indene compound and/or an acenaphthylene compound and (C) a polymerization initiator.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition used for encapsulating semiconductor devices such as diodes, transistors, ICs, LSIs, and super LSIs.

In recent years, the speed and capacity of signals used in mobile communication devices such as mobile phones, base station devices, network infrastructure devices such as servers and routers, and electronic devices such as large computers are progressing year by year. . Along with this, the printed wiring boards mounted on these electronic devices are required to support high frequencies such as 20 GHz, and there is a demand for substrate materials with a low dielectric constant and a low dielectric loss tangent that can reduce transmission loss. there is In addition to the electronic devices mentioned above, new systems that handle high-frequency wireless signals are being put into practical use and are being planned for use in the ITS field (related to automobiles and transportation systems) and in the indoor short-range communication field. Low transmission loss substrate materials are also required for wiring boards.

Thermosetting resins such as modified polyphenylene ether resins, maleimide resins and epoxy resins, and thermoplastic resins such as fluororesins, styrene resins and liquid crystal polymers are known as materials having a low dielectric constant and a low dielectric loss tangent. (Patent Documents 1 to 6). However, all of these materials have high melt viscosities, and the resulting cured products are hard and brittle. Therefore, although they are suitable for applications such as printed wiring boards, they are difficult to use for adhesives, semiconductor sealing materials, and the like. there were. In addition, there is a problem that the dielectric properties deteriorate due to oxidation of the resin in a high-temperature environment.

Japanese Patent Application Laid-Open No. 2019-1965 JP 2019-99710 A JP 2018-28044 A JP 2018-177931 A JP 2018-135506 A JP 2011-32463 A

Therefore, the present invention has a low dielectric constant and a low dielectric loss tangent, and has little change in the dielectric constant and dielectric loss tangent after high-temperature storage, becomes a cured product having heat resistance, has a low viscosity when heated, and is easy to handle. An object of the present invention is to provide an excellent thermosetting resin composition.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the following thermosetting resin composition can achieve the above objects, and completed the present invention.
That is, the present invention provides the following thermosetting resin composition.

（式（１）中、Ａは２価の有機基である。Ｘは独立して水素原子又はメチル基である。）

［３］
式（１）中のＡが下記構造で示される基及びダイマー酸骨格由来の炭化水素基から選ばれるものである［２］に記載の熱硬化性樹脂組成物。

（＊はイミド基中の窒素原子との結合を意味する。ｎは１～２０である。）

［４］
（Ａ）環状イミド化合物が下記式（２）で表される環状イミド化合物である［１］に記載の熱硬化性樹脂組成物。

（式（２）中、Ｂは独立して環状構造を有する４価の有機基である。Ｃ⁰は独立してヘテロ原子を含んでもよい炭素数６以上の２価の炭化水素基である。Ｘは独立して水素原子又はメチル基である。ｍは１～１０００である。）

［５］
式（２）中のＢで示される有機基が下記構造式で示される４価の有機基のいずれかである［４］に記載の熱硬化性樹脂組成物。

（上記構造式中の置換基が結合していない結合手は、式（２）において環状イミド構造を形成するカルボニル炭素と結合するものである。）

［６］
（Ａ）環状イミド化合物が下記式（３）で表される環状イミド化合物である［１］に記載の熱硬化性樹脂組成物。

（式（３）中、Ｂは独立して環状構造を含む４価の有機基を示す。Ｃ¹は独立してヘテロ原子を含んでもよい炭素数５～６０のアルキレン基又はダイマー酸骨格由来の２価炭化水素基である。Ｃ²は独立してヘテロ原子を含んでもよい炭素数６～３０のアリーレン基である。Ｘは独立して水素原子又はメチル基である。ＷはＣ¹又はＣ²である。ｍ¹は１～５００であり、ｍ²は０～５００である。）

［７］
式（３）中のＣ¹が下記構造式のいずれかで示される基及びダイマー酸骨格由来の２価炭化水素基から選ばれるものである［６］に記載の熱硬化性樹脂組成物。

（Ｒ¹は互いに独立に水素原子又は炭素数１～２０の直鎖もしくは分岐鎖のアルキル基を示す。ｐ¹及びｐ²はそれぞれ５以上の数であり、同じであっても異なっていてもよく、ｐ³及びｐ⁴はそれぞれ０以上の数であり、同じであっても異なっていてもよく、ｐ⁵は６～６０の数である。上記構造式中の置換基が結合していない結合手は、式（３）において環状イミド構造を形成する窒素原子と結合するものである。）

［８］
式（３）中のＣ²で示されるヘテロ原子を含んでもよい炭素数６～３０のアリーレン基が下記構造式のいずれかで示される基である［６］又は［７］に記載の熱硬化性樹脂組成物。

（Ｒ²は互いに独立に水素原子、ハロゲン原子又は炭素数１～６のアルキル基であり、Ｒ³は互いに独立に水素原子、ハロゲン原子、メチル基又はトリフルオロメチル基であり、Ｚは酸素原子、硫黄原子又はメチレン基である。上記構造式中の置換基が結合していない結合手は、式（３）において環状イミド構造を形成する窒素原子と結合するものである。）

［９］
（Ａ）成分を１００質量部としたときの（Ｂ）成分の質量部数が１０～９００質量部
である［１］～［８］のいずれか１項に記載の熱硬化性樹脂組成物。
[1]
A thermosetting resin composition containing the following components (A), (B) and (C).
(A) cyclic imide compound (B) indene compound and/or acenaphthylene compound (C) polymerization initiator

[2]
(A) The thermosetting resin composition according to [1], wherein the cyclic imide compound is represented by the following formula (1).

(In formula (1), A is a divalent organic group. X is independently a hydrogen atom or a methyl group.)

[3]
The thermosetting resin composition according to [2], wherein A in formula (1) is selected from groups represented by the following structures and hydrocarbon groups derived from dimer acid skeletons.

(* means a bond with the nitrogen atom in the imide group. n is 1 to 20.)

[4]
(A) The thermosetting resin composition according to [1], wherein the cyclic imide compound is a cyclic imide compound represented by the following formula (2).

(In formula (2), B is independently a tetravalent organic group having a cyclic structure. C ⁰ is independently a divalent hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom. X is independently a hydrogen atom or a methyl group, and m is 1 to 1000.)

[5]
The thermosetting resin composition according to [4], wherein the organic group represented by B in formula (2) is any one of the tetravalent organic groups represented by the following structural formulas.

(The bond to which no substituent is bonded in the above structural formula is bonded to the carbonyl carbon that forms the cyclic imide structure in formula (2).)

[6]
(A) The thermosetting resin composition according to [1], wherein the cyclic imide compound is a cyclic imide compound represented by the following formula (3).

(In the formula (3), B independently represents a tetravalent organic group containing a cyclic structure. C ¹ is independently an alkylene group having 5 to 60 carbon atoms which may contain a heteroatom or a dimer acid skeleton-derived is a divalent hydrocarbon group, C ² is independently an arylene group having 6 to 30 carbon atoms which may contain a hetero atom, X is independently a hydrogen atom or a methyl group, W is C ¹ or C ^2. m ¹ is 1 to 500, and m ² is 0 to 500.)

[7]
The thermosetting resin composition according to [6], wherein C ¹ in formula (3) is selected from a group represented by any one of the following structural formulas and a divalent hydrocarbon group derived from a dimer acid skeleton.

(R ¹ independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms; p ¹ and p ² each represent a number of 5 or more and may be the same or different; Each of p ³ and p ⁴ is a number of 0 or more and may be the same or different, and p ⁵ is a number of 6 to 60. The substituents in the above structural formula are not bonded. The bond is the one that binds to the nitrogen atom that forms the cyclic imide structure in formula (3).)

[8]
The thermosetting according to [6] or [7], wherein the arylene group having 6 to 30 carbon atoms which may contain a hetero atom represented by C ² in formula (3) is a group represented by any of the following structural formulas elastic resin composition.

(R ² is each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; R ³ is each independently a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group; Z is an oxygen atom; , a sulfur atom or a methylene group.The bond to which no substituent is bonded in the above structural formula is the one that bonds to the nitrogen atom that forms the cyclic imide structure in formula (3).)

[9]
The thermosetting resin composition according to any one of [1] to [8], wherein the amount of component (B) is 10 to 900 parts by mass per 100 parts by mass of component (A).

The thermosetting resin composition of the present invention has a low viscosity when heated and is excellent in handleability, and the cured product of the composition has a low dielectric constant and a low dielectric loss tangent. It has little change in temperature and high heat resistance. Therefore, the composition of the present invention is useful for applications such as adhesives, prepregs, copper-clad laminates, printed wiring boards, and semiconductor sealing materials.

The present invention will be described in detail below.

(A) Cyclic imide compound The component (A) is the main component of the present invention. By containing the component (A), it becomes possible to obtain a cured product of a thermosetting resin composition having a low dielectric constant and a low dielectric loss tangent.

Commonly known components can be used as component (A), but cyclic imide compounds represented by the following formulas (1) to (3) are preferred.

（式（１）中、Ａは２価の有機基である。Ｘは独立して水素原子又はメチル基である。）
Cyclic imide compound represented by formula (1)

(In formula (1), A is a divalent organic group. X is independently a hydrogen atom or a methyl group.)

（＊はイミド基中の窒素原子との結合を意味する。ｎは１～２０である。） The divalent organic group represented by A in formula (1) is more preferably selected from groups represented by the structures below and hydrocarbon groups derived from dimer acid skeletons.

(* means a bond with the nitrogen atom in the imide group. n is 1 to 20.)

Among the divalent organic groups represented by A, 2-methyl-1,5-diaminopentane, 2,2,4-trimethylhexamethylenediamine, 1,3-bis[2-(4-aminophenyl)- 2-propyl]benzene, 1,4-bis[2-(4-aminophenyl)-2-propyl)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 2,2-bis A group derived from a diamine such as [4-(4-aminophenoxy)phenyl]hexafluoropropane (that is, a group excluding the two amino groups of the diamine) is used from the viewpoint of dielectric properties and flexibility of the cured product. Especially preferred.

The dimer acid referred to here is a liquid dibasic acid mainly composed of dicarboxylic acid having 36 carbon atoms, which is produced by dimerization of unsaturated fatty acid having 18 carbon atoms and which is made from natural products such as vegetable oils and fats. is an acid. The dimer acid skeleton is not a single skeleton, but has multiple structures and several isomers. Typical dimer acids are classified under the names of straight chain type (a), monocyclic type (b), aromatic ring type (c), and polycyclic type (d).
As used herein, the dimer acid skeleton refers to a group derived from a dimer diamine having a structure in which the carboxy group of such a dimer acid is substituted with a primary aminomethyl group. That is, the component (A) preferably has, as a dimer acid skeleton, two carboxy groups substituted with methylene groups in each of the dimer acids shown in (a) to (d) below.
Further, when the cyclic imide compound of component (A) has a hydrocarbon group derived from a dimer acid skeleton, the hydrocarbon group derived from the dimer acid skeleton is converted into the hydrocarbon group derived from the dimer acid skeleton by a hydrogenation reaction. Those having a structure with reduced carbon-carbon double bonds are more preferable from the viewpoint of the heat resistance and reliability of the cured product.

X in formula (1) is independently a hydrogen atom or a methyl group, preferably a methyl group.

（式（２）中、Ｂは独立して環状構造を有する４価の有機基である。Ｃ⁰は独立してヘテロ原子を含んでもよい炭素数６以上の２価の炭化水素基である。Ｘは独立して水素原子又はメチル基である。ｍは１～１０００である。） Cyclic imide compound represented by formula (2)

(In formula (2), B is independently a tetravalent organic group having a cyclic structure. C ⁰ is independently a divalent hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom. X is independently a hydrogen atom or a methyl group, and m is 1 to 1000.)

（上記構造式中の置換基が結合していない結合手は、式（２）において環状イミド構造を形成するカルボニル炭素と結合するものである。） Here, the organic group represented by B in formula (2) is independently a tetravalent organic group containing a cyclic structure, and in particular any of the tetravalent organic groups represented by the following structural formulas. preferable.

(The bond to which no substituent is bonded in the above structural formula is bonded to the carbonyl carbon that forms the cyclic imide structure in formula (2).)

In formula (2), C ⁰ is independently a divalent hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom, preferably a divalent hydrocarbon group having 6 to 60 carbon atoms which may contain a heteroatom. is a hydrocarbon group of
C ⁰ is preferably an alkylene group having 6 to 60 carbon atoms which may contain a heteroatom, a divalent hydrocarbon group derived from a dimer acid skeleton or an arylene group having 6 to 30 carbon atoms which may contain a heteroatom. .

The alkylene group having 6 to 60 carbon atoms which may contain a heteroatom is preferably an alkylene group having 8 to 50 carbon atoms which may contain a heteroatom, more preferably an alkylene group having 8 to 40 carbon atoms. In addition, the alkylene group having 6 to 60 carbon atoms which may contain a heteroatom may have any of straight-chain, branched-chain and cyclic structures, and may be a group in which multiple types of these structures are combined. good too.

（上記構造式中の置換基が結合していない結合手は、式（２）において環状イミド構造を形成する窒素原子と結合するものである。） Particularly preferred examples of the alkylene group having 6 to 60 carbon atoms which may contain a heteroatom include groups represented by any of the following structural formulas.

(The bond to which no substituent is bonded in the above structural formula is bonded to the nitrogen atom forming the cyclic imide structure in formula (2).)

In the above formula, each R ¹ is independently a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. , more preferably a hydrogen atom or a straight-chain alkyl group having 1 to 10 carbon atoms.
In the above formula, p ¹ and p ² are each a number of 5 or more, preferably each a number of 5 to 12, more preferably each a number of 6 to 10, whether the same or different. good.
Each of p ³ and p ⁴ is a number of 0 or more, preferably a number of 0 to 4, more preferably a number of 0 to 2, and may be the same or different.
In the above formula, p ⁵ is a number of 6-60, preferably a number of 6-40, more preferably a number of 6-20.

Examples of the divalent hydrocarbon group derived from the dimer acid skeleton represented by C ⁰ in formula (2) include groups derived from the following groups similar to those exemplified for A in formula (1).

The arylene group having 6 to 30 carbon atoms which may contain a heteroatom is preferably an arylene group having 10 to 30 carbon atoms which may contain a heteroatom, more preferably an arylene group having 20 to 30 carbon atoms. An arylene group having 6 to 30 carbon atoms which may contain a heteroatom is a divalent group obtained by removing two hydrogen atoms bonded to carbon atoms constituting an aromatic ring from an aromatic hydrocarbon. The aromatic hydrocarbons include the following compounds.
・Monocyclic or polycyclic aromatic hydrocarbons ・Compounds in which two or more independent monocyclic or polycyclic aromatic hydrocarbons are bonded via a single bond or a divalent organic group

（上記構造式中の置換基が結合していない結合手は、式（２）において環状イミド構造を形成する窒素原子と結合するものである。） As the arylene group having 6 to 30 carbon atoms which may contain a heteroatom, groups represented by any of the following structural formulas are particularly preferred.

(The bond to which no substituent is bonded in the above structural formula is bonded to the nitrogen atom forming the cyclic imide structure in formula (2).)

In the above formula, each R ² is independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl or an ethyl group.
In the above formula, each R ³ is independently a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
In the above formula, Z is an oxygen atom, a sulfur atom or a methylene group, preferably an oxygen atom or a sulfur atom.

X in formula (2) is independently a hydrogen atom or a methyl group, preferably a hydrogen atom.

m in formula (2) is a number of 1-1000, preferably a number of 1-900.

（式（３）中、Ｂは独立して環状構造を含む４価の有機基を示す。Ｃ¹は独立してヘテロ原子を含んでもよい炭素数５～６０のアルキレン基又はダイマー酸骨格由来の２価炭化水素基である。Ｃ²は独立してヘテロ原子を含んでもよい炭素数６～３０のアリーレン基である。Ｘは独立して水素原子又はメチル基である。ＷはＣ¹又はＣ²である。ｍ¹は１～５００であり、ｍ²は０～５００である。） Cyclic imide compound represented by formula (3)

(In the formula (3), B independently represents a tetravalent organic group containing a cyclic structure. C ¹ is independently an alkylene group having 5 to 60 carbon atoms which may contain a heteroatom or a dimer acid skeleton-derived is a divalent hydrocarbon group, C ² is independently an arylene group having 6 to 30 carbon atoms which may contain a hetero atom, X is independently a hydrogen atom or a methyl group, W is C ¹ or C ^2. m ¹ is 1 to 500, and m ² is 0 to 500.)

（上記構造式中の置換基が結合していない結合手は、式（３）において環状イミド構造を形成するカルボニル炭素と結合するものである。） Examples of the tetravalent organic group containing a cyclic structure represented by B in formula (3) include the following groups similar to those exemplified for B in formula (2).

(The bond to which no substituent is bonded in the above structural formula is bonded to the carbonyl carbon that forms the cyclic imide structure in formula (3).)

The alkylene group having 6 to 60 carbon atoms which may contain a heteroatom represented by C ¹ in formula (3) is preferably an alkylene group having 8 to 50 carbon atoms which may contain a heteroatom, more preferably It is an alkylene group having 8 to 40 carbon atoms. In addition, the alkylene group having 6 to 60 carbon atoms and optionally containing a heteroatom represented by C ¹ may have a linear, branched or cyclic structure, or a combination of two or more of these structures. may be a group.

（上記構造式中の置換基が結合していない結合手は、式（３）において環状イミド構造を形成する窒素原子と結合するものである。） As the C 6-60 alkylene group optionally containing a heteroatom represented by C ¹ , groups represented by any of the following structural formulas are particularly preferred.

(The bond to which no substituent is bonded in the above structural formula is bonded to the nitrogen atom forming the cyclic imide structure in formula (3).)

In the above formula, each R ¹ is independently a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. , more preferably a hydrogen atom or a straight-chain alkyl group having 1 to 10 carbon atoms.
In the above formula, p ¹ and p ² are each a number of 5 or more, preferably each a number of 5 to 12, more preferably each a number of 6 to 10, whether the same or different. good.
Each of p ³ and p ⁴ is a number of 0 or more, preferably a number of 0 to 4, more preferably a number of 0 to 2, and may be the same or different.
In the above formula, p ⁵ is a number of 6-60, preferably a number of 6-40, more preferably a number of 6-20.

Examples of the divalent hydrocarbon group derived from the dimer acid skeleton represented by C ¹ in formula (3) include groups derived from the following groups similar to those exemplified for A in formula (1).

In formula (3), the arylene group having 6 to 30 carbon atoms which may contain a heteroatom represented by C ² is preferably an arylene group having 10 to 30 carbon atoms which may contain a heteroatom, more preferably It is an arylene group having 20 to 30 carbon atoms. The C 6-30 arylene group optionally containing a heteroatom represented by C ² is a divalent group obtained by removing two hydrogen atoms bonded to carbon atoms constituting an aromatic ring from an aromatic hydrocarbon. The aromatic hydrocarbons include the following compounds.
・Monocyclic or polycyclic aromatic hydrocarbons ・Compounds in which two or more independent monocyclic or polycyclic aromatic hydrocarbons are bonded via a single bond or a divalent organic group

（上記構造式中の置換基が結合していない結合手は、式（３）において環状イミド構造を形成する窒素原子と結合するものである。） As the C 6-30 arylene group optionally containing a heteroatom represented by C ² , groups represented by any of the following structural formulas are preferable.

(The bond to which no substituent is bonded in the above structural formula is bonded to the nitrogen atom forming the cyclic imide structure in formula (3).)

In the above formula, each R ² is independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl or an ethyl group.
In the above formula, each R ³ is independently a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
In the above formula, Z is an oxygen atom, a sulfur atom or a methylene group, preferably an oxygen atom or a sulfur atom.

X in formula (3) is independently a hydrogen atom or a methyl group, preferably a hydrogen atom.

In formula (3), m ¹ is 1-500, preferably 1-300.
In formula (3), m ² is a number of 0-500, preferably 0-300.

The number average molecular weight (Mn) of the cyclic imide compound (A) is 200 to 100,000, preferably 250 to 50,000, more preferably 300 to 30,000, still more preferably 500 to 10,000. If the number average molecular weight is less than 200, the cyclic imide compound is likely to volatilize, resulting in a decrease in strength as a cured product. Sufficient hardening becomes difficult.

The number average molecular weight (Mn) referred to in this specification refers to the number average molecular weight measured by GPC under the following conditions using polystyrene as a standard material.
[GPC measurement conditions]
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Detector: Differential Refractive Index Detector (RI)
Column: TSK Guard column SuperH-L
TSKgel SuperHZ4000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ3000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ2000 (4.6mm I.D. x 15cm x 2)
(both manufactured by Tosoh Corporation)
Column temperature: 40°C
Sample injection volume: 5 μL (THF solution with a concentration of 0.2% by mass)

The cyclic imide compound (A) may be used singly or in combination of two or more.
In the thermosetting resin composition of the present invention, the ratio of component (A) to the total of component (A), component (B) and component (C) is preferably 20 to 95 mass%, preferably 30 to 90 % by mass is more preferred, and 40 to 85% by mass is even more preferred.
The amount of component (A) is preferably 2 to 95% by mass, more preferably 4 to 90% by mass, and even more preferably 5 to 85% by mass with respect to the total mass of the thermosetting resin composition of the present invention. .

(B) Indene compound and acenaphthylene compound (B) The indene compound and the acenaphthylene compound are added for the purpose of improving fluidity at high temperatures and heat resistance of the thermosetting resin composition.

The indene compound is not particularly limited as long as it is a compound having an indene skeleton, and generally known compounds can be used. Examples of the indene compound include indene, 3-hydroxyindene, 4-hydroxyindene, 5-hydroxyindene, 5,6-dihydroxyindene, 3-methylindene, 3-ethylindene, 3-propylindene, 4-methyl Indene, 4-ethylindene, 4-propylindene, 5-methylindene, 5-ethylindene, 5-propylindene, 3,4-dimethylindene, 5,6-dimethylindene, 3-methoxyindene, 3-ethoxyindene , 3-butoxyindene, 4-methoxyindene, 4-ethoxyindene, 4-butoxyindene, 5-methoxyindene, 5-ethoxyindene, 5-butoxyindene, 3-chloroindene, 3-bromoindene, 4-chloroindene , 4-bromoindene, 5-chloroindene, 5-bromoindene and the like. These may be used individually by 1 type, and may use 2 or more types together.

The acenaphthylene compound is not particularly limited as long as it is a compound having an acenaphthylene skeleton, and generally known compounds can be used. For example, acenaphthylene, 3-hydroxyacenaphthylene, 4-hydroxyacenaphthylene, 5-hydroxyacenaphthylene, 5,6-dihydroxyacenaphthylene, 3-methylacenaphthylene, 3-ethylacenaphthylene, 3- propylacenaphthylene, 4-methylacenaphthylene, 4-ethylacenaphthylene, 4-propylacenaphthylene, 5-methylacenaphthylene, 5-ethylacenaphthylene, 5-propylacenaphthylene, 3,8 -dimethylacenaphthylene, 5,6-dimethylacenaphthylene, 3-methoxyacenaphthylene, 3-ethoxyacenaphthylene, 3-butoxyacenaphthylene, 4-methoxyacenaphthylene, 4-ethoxyacenaphthylene, 4-butoxyacenaphthylene, 5-methoxyacenaphthylene, 5-ethoxyacenaphthylene, 5-butoxyacenaphthylene, 3-chloroacenaphthylene, 3-bromoacenaphthylene, 4-chloroacenaphthylene, 4 -bromoacenaphthylene, 5-chloroacenaphthylene, 5-bromoacenaphthylene and the like. These may be used individually by 1 type, and may use 2 or more types together.

The indene compound and acenaphthylene compound (B) may be used alone or in combination. The amount of component (B) is preferably 10 to 900 parts by mass, more preferably 20 to 450 parts by mass, more preferably 30 to 200 parts by mass, per 100 parts by mass of component (A). It is even more preferable to have (B) When the amounts of the indene compound and the acenaphthylene compound are within this range, a cured product having low dielectric properties (low dielectric constant and low dielectric loss tangent) can be obtained.

(C) Polymerization Initiator (C) The polymerization initiator is added for the purpose of curing the thermosetting resin composition. (C) The polymerization initiator is not particularly limited as long as it cures (A) the cyclic imide compound and (B) the indene compound and/or the acenaphthylene compound, and generally known ones can be used. Examples of the polymerization initiator include a thermal radical polymerization initiator (C1) and a thermal anionic polymerization initiator (C2).

Examples of the thermal radical polymerization initiator (C1) include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5- Trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy) Cyclohexane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t- butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroper oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, α , α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne- 3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate, di(3-methyl -3-methoxybutyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1 , 1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecano ate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethyl Butyl peroxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl Hexanoate, t-butyl peroxyisobutyrate, t-butyl peroxymaleic acid, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxyacetate, t-hexyl peroxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, t-butylperoxyallylmonocarbonate, 3,3',4,4'-tetra (t-Butylperoxycarbonyl) organic peroxides such as benzophenone; 2,2′-azobis(N-butyl-2-methylpropionamide), 2,2′-azobis(N-cyclohexyl-2-methylpropionamide) ), 2,2′-azobis[N-(2-methylpropyl)-2-methylpropionamide], 2,2′-azobis[N-(2-methylethyl)-2-methylpropionamide], 2, 2'-azobis (N-hexyl-2-methylpropionamide), 2,2'-azobis (N-propyl-2-methylpropionamide), 2,2'-azobis (N-ethyl-2-methylpropionamide ), 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2′-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2 '-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide ], dimethyl-1,1′-azobis(1-cyclohexanecarboxylate) and other azo compounds. Among these, from the viewpoint of storage stability, organic peroxides are preferred, and dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide are more preferred. These may be used individually by 1 type, and may use 2 or more types together.

Thermal anionic polymerization initiators (C2) include, for example, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine and other imidazole compounds; triethylamine, triethylenediamine, 2-(dimethyl aminomethyl)phenol, 1,8-diaza-bicyclo[5.4.0]undecene-7, tris(dimethylaminomethyl)phenol, amine compounds such as benzyldimethylamine; triphenylphosphine, tributylphosphine, trioctylphosphine, Tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetraphenylborate, tetrabutylphosphonium acetate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium laurate, tetraphenylphosphonium hydrogen Organophosphorus compounds such as phthalate, bis(tetraphenylphosphonium)dihydrogenpyromellitate, and bis(tetrabutylphosphonium)dihydrogenpyromellitate can be mentioned. Among these, imidazole compounds and organic phosphorus compounds are preferred, and 1-cyanoethyl-2-ethyl-4-methylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1 , 3,5-triazine, triphenylphosphine, tetrabutylphosphonium laurate, tetraphenylphosphonium hydrogenphthalate, bis(tetraphenylphosphonium) dihydrogenpyromellitate, bis(tetrabutylphosphonium)dihydrogenpyromellitate More preferred. These may be used individually by 1 type, and may use 2 or more types together.

The polymerization initiator of component (C) may be used alone or in combination of two or more.
The amount of the polymerization initiator of component (C) is not particularly limited, but it is preferably 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (A). is more preferable, and 0.3 to 3 parts by mass is even more preferable. Within this range, sufficient curing can be achieved without adversely affecting the physical properties of the resin composition.

[Other ingredients]
In addition to the above components (A) to (C), the thermosetting resin composition of the present invention may optionally contain other additives within a range that does not impair the objects and effects of the present invention. Such additives include epoxy resins, inorganic fillers, flame retardants, ion trapping agents, antioxidants, adhesion promoters, stress reducing agents, colorants and the like.

Epoxy resins are blended for the purpose of improving the strength and adhesive strength of the thermosetting resin composition. Examples of epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, Novolak type epoxy resins such as bisphenol F novolak type epoxy resins; alicyclic epoxy resins such as dicyclopentadiene type epoxy resins and 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate; resorcinol type epoxy resins, polyfunctional phenol type epoxy resins such as resorcinol novolac type epoxy resins; Biphenylaralkyl-type epoxy resins, naphthalene-type epoxy resins, diglycidyl ether compounds of polycyclic aromatics such as anthracene, and phosphorus-containing epoxy resins obtained by introducing a phosphorus compound into these, and the like. Among them, bisphenol A type epoxy resin, dicyclopentadiene type epoxy resin, biphenylaralkyl type epoxy resin and naphthalene type epoxy resin are preferably used.
These may be used individually by 1 type, and may use 2 or more types together.

The inorganic filler is blended for the purpose of improving resin strength of the thermosetting resin composition and reducing thermal expansion. Examples of inorganic fillers include silicas (eg, fused silica, crystalline silica, cristobalite, etc.), alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, magnesium oxide, and the like. The average particle size and shape of these inorganic fillers can be selected according to the application.

The inorganic filler is preferably surface-treated in advance with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to increase the bonding strength between the resin and the inorganic filler. Such coupling agents include epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; -β(aminoethyl)-γ-aminopropyltrimethoxysilane, reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. aminosilane; γ-mercaptosilane, γ-episulfidoxypropyltrimethoxysilane and other mercaptosilanes. The amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

The amount of the inorganic filler compounded is preferably 10 to 20,000 parts by mass, more preferably 30 to 10,000 parts by mass, per 100 parts by mass of component (A).

A flame retardant is added for the purpose of imparting flame retardancy. The flame retardant is not particularly limited, and any known flame retardant can be used. Molybdenum can be used.

The ion trapping agent is added for the purpose of trapping ionic impurities contained in the resin composition and preventing thermal deterioration and hygroscopic deterioration. The ion trapping agent is not particularly limited, and all known agents can be used, and hydrotalcites, bismuth hydroxide compounds, rare earth oxides and the like may be used.

The antioxidant is not particularly limited, but examples include n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, n-octadecyl-3-(3,5-di -t-butyl-4-hydroxyphenyl)acetate, neododecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, dodecyl-β-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, ethyl-α-(4-hydroxy-3,5-di-t-butylphenyl)isobutyrate, octadecyl-α-(4-hydroxy-3,5-di-t-butylphenyl)isobutyrate, Octadecyl-α-(4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-(n-octylthio)ethyl-3,5-di-t-butyl-4-hydroxyphenylacetate , 2-(n-octadecylthio)ethyl-3,5-di-t-butyl-4-hydroxyphenyl acetate, 2-(n-octadecylthio)ethyl-3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionate, 2-(2-stearoyloxyethylthio)ethyl-7-(3-methyl-5-t-butyl-4-hydroxyphenyl)heptanoate, 2-hydroxyethyl-7-(3-methyl -5-t-butyl-4-hydroxyphenyl)propionate, phenolic antioxidants such as pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; dilauryl-3, 3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, pentaerythrityl tetrakis ( 3-Lauryl thiopropionate) and other sulfur-based antioxidants; Tridecylphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, distearylpentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl) ) pentaerythritol diphosphite, 2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl ]oxy]-N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin- Phosphorus-based antioxidants such as 6-yl]oxy]-ethyl]ethanamine are included.

The tackifier is not particularly limited as long as it is a known tackifier as long as it exhibits the effects of the present invention. It may contain an imparting agent. Examples of adhesiveness imparting agents include urethane resins, phenol resins, terpene resins, silane coupling agents, and the like. Among them, a silane coupling agent is preferable for imparting adhesiveness.

The silane coupling agent is not particularly limited, but examples include n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, phenyltri ethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane, methoxytri(ethyleneoxy)propyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-amino silane coupling agents such as propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane; be done.

The amount of other additives to be blended varies depending on the purpose of the composition, but is usually 5% by mass or less of the total composition excluding inorganic fillers.

[Method for producing composition]
The thermosetting resin composition of the present invention can be produced by the method shown below.
For example, the components (A) to (C) are mixed simultaneously or separately with heat treatment if necessary, and stirred, dissolved and/or dispersed to obtain a mixture of the components (A) to (C). Preferably, a mixture of components (A) to (C) may be obtained by adding component (C) to a mixture of components (A) and (B) and stirring, dissolving and/or dispersing the mixture. Depending on the application, the mixture of components (A) to (C) may contain at least one of epoxy resin, inorganic filler, flame retardant, ion trapping agent, antioxidant, adhesion imparting agent, low stress agent, and coloring agent. Kinds may be added and mixed. Each component may be used singly or in combination of two or more.

In the method for producing the composition, there are no particular restrictions on the device for mixing, stirring and dispersing. Specifically, for example, a Raikai machine equipped with a stirring and heating device, a two-roll mill, a three-roll mill, a ball mill, a planetary mixer, or a masscolloider can be used, and these devices can be used in appropriate combination. good too.

[Use]
The thermosetting resin composition of the present invention has a low viscosity when heated and is excellent in handleability, and the cured product of the composition has a low dielectric constant and a low dielectric loss tangent. changes little and has heat resistance, it can be suitably used as adhesives, prepregs, copper-clad laminates, printed wiring boards, semiconductor encapsulants, and the like.

When used as an adhesive, each component is blended at a predetermined composition ratio as described above, and after mixing using a mixer such as a planetary mixer, use a three-roll mill to increase dispersibility as necessary. It is preferable to knead and mix.
When used as a prepreg, each component is blended in a predetermined composition ratio as described above, and after mixing using a mixer such as a planetary mixer, a three-roll mill is used to increase dispersibility as necessary. Kneading and mixing are preferred. The obtained resin composition can be used as a prepreg by impregnating a fiber base material and drying it by heating. The thickness of the prepreg of the present invention is not particularly limited, but is preferably 10-500 μm, more preferably 25-300 μm, and even more preferably 40-200 μm. If it is this range, a copper clad laminated board can be produced satisfactorily. The prepreg of the present invention may be preliminarily semi-cured (B-staged) by heating. The method for B-staging is not particularly limited, but for example, the cyclic imide resin composition of the present invention is dissolved in a solvent, impregnated into a fiber base material, dried, and then heated at a temperature of 80 to 200 ° C. B-stage can be obtained by heating for ~30 minutes.
When used as a copper-clad laminate, the above-mentioned prepreg and copper foil are superimposed, pressed, and heat-cured to be used as a copper-clad laminate. Molding conditions for the copper-clad laminate are not particularly limited, but for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc., a temperature of 100 to 400° C., a pressure of 1 to 100 MPa, and a heating time of 0.5. It can be molded in the range of 1 to 4 hours. Also, the prepreg, copper foil, and inner layer wiring board of the present invention can be combined and molded to form a copper-clad laminate.
When used as a printed wiring board, for example, when using prepreg, one or more prepregs are stacked, and metal foil such as copper foil is stacked on both sides or one side of the prepreg, and laminated by heat and pressure molding. Consolidation produces a laminate. It can be manufactured by subjecting the manufactured laminate to a circuit forming process such as perforating, metal plating, or etching of metal foil, and a multi-layer bonding process.
When used as a semiconductor encapsulating material, each component is blended in a predetermined composition ratio as described above, and the mixture is sufficiently and uniformly mixed with a mixer or the like, melted and mixed with a hot roll, a kneader, an extruder, or the like, and then cooled. It is preferably solidified and pulverized to a suitable size.

General molding methods using a semiconductor encapsulant include transfer molding and compression molding. In the transfer molding method, a transfer molding machine is used at a molding pressure of 5 to 20 N/mm ² , a molding temperature of 120 to 190° C. for a molding time of 30 to 500 seconds, preferably a molding temperature of 150 to 185° C. and a molding time of 30 to 180 seconds. conduct. In the compression molding method, a compression molding machine is used at a molding temperature of 120 to 190° C. for a molding time of 30 to 600 seconds, preferably at a molding temperature of 130 to 160° C. for a molding time of 120 to 300 seconds. Further, in either molding method, post-curing may be performed at 150-225° C. for 0.5-20 hours.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, in Tables 1 to 3, the compounding amount indicates parts by mass.

Components used in Examples and Comparative Examples are shown below. In the following, the number average molecular weight (Mn) is measured by gel permeation chromatography (GPC) under the following measurement conditions using polystyrene as a standard.
[GPC measurement conditions]
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Detector: Differential Refractive Index Detector (RI)
Column: TSK Guard column SuperH-L
TSKgel SuperHZ4000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ3000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ2000 (4.6mm I.D. x 15cm x 2)
(both manufactured by Tosoh Corporation)
Column temperature: 40°C
Sample injection volume: 5 μL (THF solution with a concentration of 0.2% by mass)

（式中のＣ₃₆Ｈ₇₀はダイマー酸骨格を意味する。）

（Ａ２）下記式で示される環状イミド化合物（ＢＭＩ－１５００、Ｄｅｓｉｇｎｅｒ Ｍｏｌｅｃｕｌｅｓ Ｉｎｃ．製）数平均分子量：２２００

（ｍ¹＝３（平均値）、式中のＣ₃₆Ｈ₇₀はダイマー酸骨格を意味する。）

（Ａ３）下記式で示される環状イミド化合物（Ｘ－４５－２６００、信越化学工業製）数平均分子量：６０００

（ｍ¹＝１（平均値）、ｍ^1`＝５（平均値）、式中のＣ₃₆Ｈ₇₀はダイマー酸骨格を意味する。）

合成例１（環状イミド化合物（Ａ４））
アニソール４００ｇに、３，３’，５，５’－テトラエチル－４，４’－ジアミノジフェニルメタン１５５ｇ（０．５ｍｏｌ）、プリアミン１０７５（クローダジャパン（株）製）２７７ｇ（０．５ｍｏｌ）及び４，４’－オキシジフタル酸無水物２８５ｇ（０．９２ｍｏｌ）を添加し、室温で５時間撹拌し、更に１２０℃で１２時間撹拌した。得られた溶液に、無水マレイン酸１９６ｇ（２．０ｍｏｌ）を加え、１５０℃で１時間撹拌した。その後、溶剤、未反応の無水マレイン酸を減圧留去し、下記式で示される環状イミド化合物（Ａ４）を得た。（数平均分子量１００００）

（ｍ¹＝５（平均値）、ｍ²＝５（平均値）、式中のＣ₃₆Ｈ₇₀はダイマー酸骨格を意味する。）

合成例２（環状イミド化合物（Ａ５））
攪拌機、ディーンスターク管、冷却コンデンサー及び温度計を備えた２Ｌのガラス製４つ口フラスコに、２，４，４－トリメチルヘキサンジアミン７１．２ｇ（０．４５モル）、無水シトラコン酸１１１．０ｇ（０．９９モル）及びトルエン１５０ｇを加えて反応液を調製し、８０℃で３時間撹拌することでアミック酸を合成した。その後、反応液にメタンスルホン酸４０ｇを加えたのち、１１０℃に昇温し、副生した水分を留去しながら１６時間撹拌した後、反応液を２００ｇのイオン交換水を用いて５回水洗した。その後、６０℃の減圧ストリップにより室温で褐色液状の目的物（Ａ５）を得た。（数平均分子量：３５０）

（Ａ６）ビスフェノールＡジフェニルエーテルビスマレイミド（商品名：ＢＭＩ－４０００、大和化成工業（株）製）数平均分子量：５７０
(A) Cyclic imide compound (A1) Cyclic imide compound represented by the following formula (BMI-689, manufactured by Designer Molecules Inc.) Number average molecular weight: 690

( _C36H70 in _the formula means a dimer acid skeleton.)

(A2) Cyclic imide compound represented by the following formula (BMI-1500, manufactured by Designer Molecules Inc.) Number average molecular weight: 2200

(m ¹ =3 (average value), C ₃₆ H ₇₀ in the formula means a dimer acid skeleton.)

(A3) a cyclic imide compound represented by the following formula (X-45-2600, manufactured by Shin-Etsu Chemical Co., Ltd.) number average molecular weight: 6000

(m ¹ =1 (average value), m ^1′ =5 (average value), C ₃₆ H ₇₀ in the formula means a dimer acid skeleton.)

Synthesis Example 1 (Cyclic imide compound (A4))
To 400 g of anisole, 155 g (0.5 mol) of 3,3′,5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 277 g (0.5 mol) of Priamine 1075 (manufactured by Croda Japan Co., Ltd.) and 4,4 285 g (0.92 mol) of '-oxydiphthalic anhydride was added, stirred at room temperature for 5 hours, and further stirred at 120°C for 12 hours. 196 g (2.0 mol) of maleic anhydride was added to the obtained solution, and the mixture was stirred at 150° C. for 1 hour. Thereafter, the solvent and unreacted maleic anhydride were distilled off under reduced pressure to obtain a cyclic imide compound (A4) represented by the following formula. (Number average molecular weight 10000)

(m ¹ =5 (average value), m ² =5 (average value), C ₃₆ H ₇₀ in the formula means a dimer acid skeleton.)

Synthesis Example 2 (Cyclic imide compound (A5))
Into a 2 L four-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser and thermometer, 71.2 g (0.45 mol) of 2,4,4-trimethylhexanediamine, 111.0 g of citraconic anhydride ( 0.99 mol) and 150 g of toluene were added to prepare a reaction solution, and the amic acid was synthesized by stirring at 80° C. for 3 hours. After that, 40 g of methanesulfonic acid was added to the reaction solution, the temperature was raised to 110° C., and the reaction solution was stirred for 16 hours while distilling off by-produced moisture, and then the reaction solution was washed five times with 200 g of deionized water. bottom. After that, vacuum stripping at 60° C. gave the desired product (A5) in the form of a brown liquid at room temperature. (Number average molecular weight: 350)

(A6) Bisphenol A diphenyl ether bismaleimide (trade name: BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) number average molecular weight: 570

(B) Indene compound and acenaphthylene compound (B1) acenaphthylene compound (acenaphthylene: JFE Chemical Co., Ltd.)
(B2) Indene compound (indene: manufactured by JFE Chemical Company)

(C) polymerization initiator (C1) dicumyl peroxide (Perkadox BC-FF: manufactured by Kayaku Nourion Co., Ltd.)
(C2) 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine (2MZ-A: manufactured by Shikoku Kasei Co., Ltd.)

Other additives Bisphenol A type epoxy resin (jER828EL: manufactured by Mitsubishi Chemical Corporation, liquid at 25°C, epoxy group equivalent 189)

A thermosetting resin composition was obtained by mixing each of the above components in the amounts (parts by mass) shown in Tables 1 to 3.

1. Fluidity Each thermosetting resin composition was heated on a hot plate set at 100°C. The results are shown in Tables 1 to 3, with ○ indicating fluidity of the resin at 100°C and x indicating no fluidity.

2. Relative permittivity, dielectric loss tangent A frame with a diameter of 200 mm and a thickness of 150 μm was prepared, and each thermosetting resin composition of Examples and Comparative Examples was sandwiched between release-treated PET films (E7006, manufactured by Toyobo) with a thickness of 50 μm. Then, using a vacuum press (manufactured by Nikko Materials), molding was performed at 180° C. for 20 minutes to obtain a cured product. The cured product was taken out from the PET film and further cured under conditions of 180° C. for 2 hours to obtain a cured resin film.
Using the cured resin film, a network analyzer (E5063-2D5 manufactured by Keysight Corporation) and a stripline (manufactured by Keycom Corporation) were connected to measure the dielectric constant and dielectric loss tangent of the cured resin film at a frequency of 10 GHz. The results are shown in Tables 1-3.

3. Dielectric loss tangent change rate after high temperature storage A test piece (cured resin film) prepared in the same manner as the above cured resin film was stored in an oven at 150 ° C. for 150 hours, cooled to room temperature, and measured for dielectric loss tangent at a frequency of 10 GHz. bottom. More specifically, the dielectric loss tangent change rate after high-temperature storage was calculated by the following formula.

4. Glass transition temperature The storage modulus (MPa) of a test piece (cured resin film) prepared in the same manner as the cured resin film was measured in the range of 0 ° C to 300 ° C using DMA Q800 (manufactured by TA Instruments Co., Ltd.). , the peak top temperature obtained from a graph plotting Tan δ values derived from the obtained values of storage elastic modulus and loss elastic modulus was taken as the glass transition temperature (Tg). The measurement conditions were a test sample (cured material) of 20 mm×5 mm×50 μm thickness, temperature increase rate of 5° C./min, multi-frequency mode, tension mode, and amplitude of 15 μm. The results are shown in Tables 1-3.

Claims (9)

A thermosetting resin composition containing the following components (A), (B) and (C).
(A) cyclic imide compound (B) indene compound and/or acenaphthylene compound (C) polymerization initiator 2. The thermosetting resin composition according to claim 1, wherein (A) the cyclic imide compound is a cyclic imide compound represented by the following formula (1).

(In formula (1), A is a divalent organic group. X is independently a hydrogen atom or a methyl group.) 3. The thermosetting resin composition according to claim 2, wherein A in formula (1) is selected from groups represented by the following structures and hydrocarbon groups derived from dimer acid skeletons.

(* means a bond with the nitrogen atom in the imide group. n is 1 to 20.) 2. The thermosetting resin composition according to claim 1, wherein (A) the cyclic imide compound is a cyclic imide compound represented by the following formula (2).

(In formula (2), B is independently a tetravalent organic group having a cyclic structure. C ⁰ is independently a divalent hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom. X is independently a hydrogen atom or a methyl group, and m is 1 to 1000.)
5. The thermosetting resin composition according to claim 4, wherein the organic group represented by B in formula (2) is any one of the tetravalent organic groups represented by the following structural formulas.

(The bond to which no substituent is bonded in the above structural formula is bonded to the carbonyl carbon that forms the cyclic imide structure in formula (2).) 2. The thermosetting resin composition according to claim 1, wherein (A) the cyclic imide compound is a cyclic imide compound represented by the following formula (3).

(In the formula (3), B independently represents a tetravalent organic group containing a cyclic structure. C ¹ is independently an alkylene group having 5 to 60 carbon atoms which may contain a heteroatom or a dimer acid skeleton-derived is a divalent hydrocarbon group, C ² is independently an arylene group having 6 to 30 carbon atoms which may contain a hetero atom, X is independently a hydrogen atom or a methyl group, W is C ¹ or C ^2. m ¹ is 1 to 500, and m ² is 0 to 500.)
7. The thermosetting resin composition according to claim 6, wherein C ¹ in formula (3) is selected from a group represented by any of the following structural formulas and a divalent hydrocarbon group derived from a dimer acid skeleton.

(R ¹ independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms; p ¹ and p ² each represent a number of 5 or more and may be the same or different; Each of p ³ and p ⁴ is a number of 0 or more and may be the same or different, and p ⁵ is a number of 6 to 60. The substituents in the above structural formula are not bonded. The bond is the one that binds to the nitrogen atom that forms the cyclic imide structure in formula (3).) The thermosetting resin according to claim 6 or 7, wherein the arylene group having 6 to 30 carbon atoms which may contain a hetero atom represented by C ² in formula (3) is a group represented by any one of the following structural formulas. Composition.

(R ² is each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; R ³ is each independently a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group; Z is an oxygen atom; , a sulfur atom or a methylene group.The bond to which no substituent is bonded in the above structural formula is the one that bonds to the nitrogen atom that forms the cyclic imide structure in formula (3).) The thermosetting resin composition according to any one of claims 1 to 8, wherein the component (B) is contained in an amount of 10 to 900 parts by mass per 100 parts by mass of the component (A).