JP2024038791A - Resin composition, prepreg, copper-clad laminate, and printed wiring board - Google Patents

Abstract

To provide a resin composition characterized by a low dielectric constant and a low dielectric loss tangent, which results in a cured product exhibiting high adhesion to copper.SOLUTION: A resin composition comprises at least (a) a cyclic imide compound, (b) an epoxy compound, and (c) an imidazole compound. The counts of cyclic imide groups in the cyclic imide compound, epoxy groups in the epoxy compound, and imidazole groups in the imidazole compound each satisfy the following two formulae: 0.3≤count of cyclic imide groups/count of epoxy groups≤3.0 and 2.0≤count of epoxy groups/count of imidazole groups≤20.0.SELECTED DRAWING: None

Description

The present invention relates to resin compositions and the like.

In recent years, the speed and capacity of signals used in mobile communication devices such as mobile phones, their base stations, network infrastructure devices such as servers and routers, and electronic devices such as large computers have been increasing year by year. . Along with this, the printed wiring boards installed in these electronic devices use high frequency bands such as the 20 GHz region, so printed wiring boards with low dielectric constant, low dielectric loss tangent, low coefficient of thermal expansion, high heat resistance, and low water absorption, etc. The characteristics required of materials for wiring boards are increasing more and more.

Examples of materials that may satisfy these characteristics include modified polyphenylene ether resins, maleimide resins, and epoxy resins (Patent Documents 1 to 3). Among these, maleimide resin has a low dielectric constant, low dielectric loss tangent, and high heat resistance, so it is used as a material for printed wiring boards compatible with high frequencies (Patent Documents 4 and 5).

However, maleimide resins do not have sufficient characteristics as materials for copper-clad laminates and printed wiring boards due to their high curing temperatures and high melt viscosity. Furthermore, as the frequency band used increases, the surface roughness of the copper forming the circuit must be reduced, and higher adhesion between the resin and the copper is required.

JP 2019-1965 Publication JP 2018-28044 Publication JP 2018-44065 Publication International Publication No. 2016/114286 JP2020-45446A

Therefore, an object of the present invention is to provide a resin composition that becomes a cured product that has a low dielectric constant and a low dielectric loss tangent and has high adhesion to copper.

As a result of intensive research to solve the above-mentioned problems, the present inventors discovered that the following resin composition can achieve the above-mentioned objects, and completed the present invention.
That is, the present invention provides the following resin composition and the like.

（式（１）中、Ａは独立して環状構造を含む４価の有機基を示す。Ｑは独立してヘテロ原子を含んでもよい芳香族基を含まない炭素数６以上の２価の炭化水素基である。Ｂは独立してヘテロ原子を含んでもよい炭素数６以上のアリーレン基である。Ｘは水素原子またはメチル基であり、ｎは０～２００であり、ｍは０～２００である。）
［３］
式（１）中のＡ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［２］に記載の樹脂組成物。

（上記構造式中の置換基が結合していない結合手は、式（１）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。）
［４］
式（１）中のＱで示される２価の炭化水素基が下記構造式のいずれかで示される２価の炭化水素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［２］または［３］に記載の樹脂組成物。

（Ｒ¹は互いに独立に水素原子または炭素数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及びｐ⁶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い。上記構造式中の置換基が結合していない結合手は、式（１）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。）
［５］
式（１）中のＢで示されるアリーレン基が下記構造式のいずれかで示されるアリーレン基である［２］～［４］のいずれか１項に記載の樹脂組成物。

（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（１）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。）
［６］
（ａ）成分の環状イミド化合物が、式（１）中のｍが０である環状イミド化合物である［２］～［５］のいずれか１項に記載の樹脂組成物。
［７］
［１］～［６］のいずれか１項に記載の樹脂組成物を含有してなるプリプレグ。
［８］
［７］に記載のプリプレグを有する銅張積層板。
［９］
［８］に記載の銅張積層板を有するプリント配線板。 [1]
(a) cyclic imide compound,
(b) A resin composition comprising at least an epoxy compound and (c) an imidazole compound, in which the number of cyclic imide groups of the cyclic imide compound, the number of epoxy groups of the epoxy compound, and the number of imidazole groups of the imidazole compound satisfy the following two formulas. thing.

0.3 ≦ Number of cyclic imide groups/Number of epoxy groups ≦ 3.0

2.0 ≦ Number of epoxy groups/Number of imidazole groups ≦ 20.0

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

(In formula (1), A independently represents a tetravalent organic group containing a cyclic structure. Q independently represents a divalent carbonized group having 6 or more carbon atoms and not containing an aromatic group that may contain a hetero atom. It is a hydrogen group. B is independently an arylene group having 6 or more carbon atoms which may contain a hetero atom. X is a hydrogen atom or a methyl group, n is 0 to 200, and m is 0 to 200. be.)
[3]
The resin composition according to [2], wherein the organic group represented by A in formula (1) is any of the tetravalent organic groups represented by the following structural formula.

(The bond to which no substituent in the above structural formula is bonded is the one bonded to the carbonyl carbon forming the cyclic imide structure in formula (1).)
[4]
The divalent hydrocarbon group represented by Q in formula (1) is selected from a divalent hydrocarbon group represented by any of the following structural formulas and a divalent hydrocarbon group derived from a dimer acid skeleton [ 2] or the resin composition according to [3].

(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 are each a number of 5 or more, and may be the same or different. Often, p ³ and p ⁴ are each a number greater than or equal to 0 and may be the same or different, and p ⁵ and p ⁶ are each a number greater than or equal to 0 and may be the same or different. Good. The bond to which no substituent in the above structural formula is bonded is the one that bonds to the nitrogen atom forming the cyclic imide structure in formula (1).)
[5]
The resin composition according to any one of [2] to [4], wherein the arylene group represented by B in formula (1) is an arylene group represented by any of the following structural formulas.

(R ² is independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, R ³ is independently a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and Z is an oxygen atom , a sulfur atom or a methylene group.The bond to which no substituent in the above structural formula is bonded is the one bonded to the nitrogen atom forming the cyclic imide structure in formula (1).)
[6]
The resin composition according to any one of [2] to [5], wherein the cyclic imide compound as component (a) is a cyclic imide compound in which m in formula (1) is 0.
[7]
A prepreg containing the resin composition according to any one of [1] to [6].
[8]
A copper-clad laminate having the prepreg according to [7].
[9]
A printed wiring board having the copper-clad laminate according to [8].

The resin composition of the present invention becomes a cured product that has a low dielectric constant and a low dielectric loss tangent, and has high adhesion to copper. Therefore, the resin composition of the present invention is suitable for use in high-frequency prepregs, copper-clad laminates, printed wiring boards, base films for flexible printed wiring boards, coverlay films, adhesives for coverlay films, heat dissipation adhesives, and electromagnetic shielding. It is useful for applications such as semiconductor encapsulation materials.

Hereinafter, the resin composition of the present invention will be explained in detail.

[(a) Cyclic imide compound]
The cyclic imide compound (a) is the main component of the resin composition of the present invention. The resin composition of the present invention contains a cyclic imide compound, and the cyclic imide group reacts to exhibit high adhesion to copper.

The cyclic imide compound as component (a) is preferably represented by the following formula (1).

（上記構造式中の置換基が結合していない結合手は、式（１）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。） The organic group represented by A in formula (1) is independently a tetravalent organic group containing a cyclic structure, and is particularly preferably any of the tetravalent organic groups represented by the following structural formula.

(The bond to which no substituent in the above structural formula is bonded is the one bonded to the carbonyl carbon forming the cyclic imide structure in formula (1).)

上記構造式中の置換基が結合していない結合手は、式（１）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。 Q in formula (1) is a divalent hydrocarbon group having 6 or more carbon atoms that does not contain an aromatic group that may independently contain a hetero atom, and is preferably 2 represented by any of the following structural formulas. It is a divalent hydrocarbon group or a divalent hydrocarbon group derived from a dimer acid skeleton.

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 (1).

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

The divalent hydrocarbon group derived from the dimer acid skeleton is a liquid whose main component is dicarboxylic acid with 36 carbon atoms, which is produced by dimerizing unsaturated fatty acids with 18 carbon atoms from natural products such as vegetable oils and fats. This is a group derived from dimer acid, which is a fatty acid. Dimer acids do not have a single skeleton, but have multiple structures, and several types of isomers exist. 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. The divalent hydrocarbon groups derived from the dimer acid skeleton have a structure in which carbon-carbon double bonds in the hydrocarbon groups derived from the dimer acid skeleton are reduced through a hydrogenation reaction, which improves the heat resistance and reliability of the cured product. More preferable from the viewpoint of sex.
In general, dimer acid may contain trimer (trimer acid) because it is made from natural products such as vegetable oils and fats, but dimer acid and trimer acid-derived The proportion of hydrocarbon groups derived from dimer acid among the hydrocarbon groups is, for example, 95% by mass or more, which means that the proportion of hydrocarbon groups derived from dimer acid is high, and the dielectric properties are excellent and the viscosity when heated is easily reduced. It is preferable because it has excellent moldability and tends to be less affected by moisture absorption.
As described above, since the dimer acid skeleton has a plurality of structures, in this specification, the divalent hydrocarbon group derived from the dimer acid skeleton may be expressed as -C ₃₆ H ₇₀ - as its average structure.

上記構造式中の置換基が結合していない結合手は、式（１）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。 B in formula (1) is independently an arylene group having 6 or more carbon atoms that may contain a hetero atom, and is preferably an arylene group 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 (1).

In the above formula, 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 a methyl group.
In the above formula, R ³ is independently a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, preferably 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.

In formula (1), X is a hydrogen atom or a methyl group.

In formula (1), n is 0 to 200, preferably 1 to 100, and more preferably 2 to 50.
In formula (1), m is 0 to 200, preferably 0 to 100, and more preferably 0 to 50.

（式（２）中、Ａ、Ｑ、Ｘ及びｎはそれぞれ式（１）と同様である。） In the above formula (1), when m=0, the cyclic imide compound of component (a) is represented by the following formula (2).

(In formula (2), A, Q, X and n are each the same as in formula (1).)

The weight average molecular weight (Mw) of the cyclic imide compound represented by formula (1) is not particularly limited, but is preferably 2,000 to 1,000,000, more preferably 3,000 to 100,000. and more preferably 3,500 to 50,000. When the weight average molecular weight (Mw) is within this range, the resin composition has sufficient strength and the terminal cyclic imide group can be reacted efficiently.

The weight average molecular weight (Mw) referred to herein refers to the weight average molecular weight measured by GPC under the following conditions using polystyrene as a standard material.
[GPC measurement conditions]
Developing solvent: tetrahydrofuran Flow rate: 0.6 mL/min
Column:TSK Guardcolumn SuperHL-L
TSKgel SuperH4000 (6.0mm I.D. x 15cm x 1)
TSKgel SuperH3000 (6.0mm I.D. x 15cm x 1)
TSKgel SuperH2000 (6.0mm I.D. x 15cm x 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40℃
Sample injection amount: 20 μL (sample concentration: 0.5% by mass-tetrahydrofuran solution)
Detector: Differential refractometer (RI)

There are no particular limitations on the method for producing the cyclic imide compound (e.g., maleimide compound, citraconimide compound, etc.) of component (a). For example, it may be produced by reacting an amine compound with excess maleic anhydride or citraconic anhydride. Alternatively, it may be produced by reacting an acid anhydride with a diamine to synthesize an amine-terminated compound, and then reacting the amine-terminated compound with excess maleic anhydride or citraconic anhydride.

Examples of acid anhydrides include pyromellitic anhydride, maleic anhydride, succinic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-diphthalic anhydride, and 4,4'-sulfonyldiphthalic anhydride. Examples include phthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, and the like. These acid anhydrides may be used alone or in combination of two or more depending on the purpose, use, etc. From the viewpoint of electrical properties of the cyclic imide compound, acid anhydrides include pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride. is preferred.

Examples of the diamine include 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3' -diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, tetramethyl-1,3-bis(3-aminopropyl)disiloxane, bis [4-(4-aminophenoxy)phenyl]sulfone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,12-diaminododecane, 1,10-diaminodecane, dimer diamine , octyldiamine, 1,3-di(aminomethyl)cyclohexane, isophoronediamine, 2,4,4-trimethylhexane-1,6-diamine, 2-methylpentane-1,5-diamine, 3(4),8 (9)-Bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane and the like. These diamines may be used alone or in combination of two or more, depending on the purpose, use, etc. From the viewpoint of electrical properties of cyclic imide compounds, diamines include 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, and 4,4' - Aromatic diamines such as diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3', 5,5'-tetraethyldiphenylmethane; tetramethyl-1,3 -bis(3-aminopropyl)disiloxane, 1,12-diaminododecane, 1,10-diaminodecane, dimer diamine, octyldiamine, 1,3-di(aminomethyl)cyclohexane, 1-amino-4-(amino Aliphatic diamines such as methyl)cyclohexane, 1,3-diaminoadamantane, isophorone diamine, 2,4,4-trimethylhexane-1,6-diamine, and 2-methylpentane-1,5-diamine are preferred; dimer diamine, Isophoronediamine is particularly preferred.

Moreover, a commercially available product may be used as the cyclic imide compound of component (a). Commercially available products include BMI-689, BMI-1400, BMI-1500, BMI-2500, BMI-3000, BMI-6100 (manufactured by Designer Molecules Inc.), SLK-6895, SLK-3000, SLK-2600, Examples include SLK-2700 and SLK-6100 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The equivalent weight of the cyclic imide group in component (a) is preferably 0.001 to 0.5 mol/100g, more preferably 0.003 to 0.4 mol/100g, and even more preferably 0.01 to 0.3 mol/100g. , 0.02 to 0.2 mol/100g is even more preferred. This range is preferable because the cured product of the resin composition has a low dielectric constant, low dielectric loss tangent, and high adhesion.

Regarding the blending amount of component (a), the ratio of the number of epoxy groups in the epoxy compound described below must satisfy the following formula.
0.3 ≦ Number of cyclic imide groups/Number of epoxy groups ≦ 3.0
Preferably, the following formula is satisfied.
0.5 ≦ Number of cyclic imide groups/Number of epoxy groups ≦ 2.5
More preferably, the following formula is satisfied.
0.7 ≦ Number of cyclic imide groups/Number of epoxy groups ≦ 2.0

If the ratio of the number of cyclic imide groups/the number of epoxy groups is smaller than 0.3, the values of the relative dielectric constant and the dielectric loss tangent will become high. Furthermore, when an imidazole compound is used as a catalyst, the cyclic imide group will not react without the epoxy group, or the reaction temperature will become high. Therefore, if the ratio of the number of cyclic imide groups/the number of epoxy groups is larger than 3.0, the cyclic imide groups will remain unreacted and the adhesive strength with copper will become low.

[(b) Epoxy compound]
The epoxy compound (b) is copolymerized with the cyclic imide compound (a) and becomes the main component of the resin composition of the present invention. By copolymerizing the epoxy group with the cyclic imide group, the cyclic imide group can be cured more quickly and the adhesiveness can be further improved.

The epoxy compound of component (b) is not particularly limited, but for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, 3,3',5,5'-tetramethyl-4,4'-biphenol type epoxy compounds, liquid polyfunctional epoxy compounds such as 4,4'-methylenebis (N,N-diglycidianiline) and 4-glycidyloxy (N,N-diglycidianiline), 4,4'-biphenol type epoxy compounds, etc. Biphenol type epoxy compound, biphenol novolac type epoxy compound, biphenylaralkyl type epoxy compound, phenol novolak type epoxy compound, cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, naphthalene diol type epoxy compound, trisphenylormethane type epoxy compound, Examples include a tetrakisphenyloethane type epoxy compound, a phenol dicyclopentadiene novolac type epoxy compound, and an epoxy compound obtained by hydrogenating the aromatic ring of a phenol dicyclopentadiene novolac type epoxy compound. Among these, liquid polyfunctional epoxy compounds, biphenol novolac type epoxy compounds, phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds, biphenylaralkyl type epoxy compounds, phenol dicyclopentadiene novolac type epoxy compounds is preferred. One type of epoxy compound may be used alone, or two or more types may be used in combination. Furthermore, if necessary, epoxy compounds other than those mentioned above can be used in combination in a certain amount depending on the purpose.

The blending amount of component (b) must satisfy the ratio with the cyclic imide group described above, and the ratio with the number of imidazole groups described below must satisfy the following formula.
2.0 ≦ Number of epoxy groups/Number of imidazole groups ≦ 20.0
Preferably, the following formula is satisfied.
4.0 ≦ Number of epoxy groups/Number of imidazole groups ≦ 17.0
More preferably, the following formula is satisfied.
6.0 ≦ Number of epoxy groups/Number of imidazole groups ≦ 15.0

If the ratio of the number of epoxy groups/the number of imidazole groups is less than 2.0, the imidazole group will open the epoxy group immediately, and the cyclic imide group will remain unreacted under normal curing conditions, resulting in poor adhesion with copper. The power becomes low. Moreover, if the ratio of the number of epoxy groups/the number of imidazole groups is larger than 20.0, the curing reaction of the entire resin composition will be delayed. Therefore, under normal curing conditions, the epoxy group and the cyclic imide group remain unreacted, resulting in low adhesive strength with copper.

[(c) Imidazole compound]
The imidazole compound (c) serves as a curing catalyst for the resin composition of the present invention.
The imidazole compound of component (c) is one used as a curing catalyst for resins, such as 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, 2-phenyl-4 -hydroxy-5-methylimidazole and the like. Furthermore, as the imidazole compound of component (c), C11Z, 2PZ, 2P4MZ, 2MZ-CN, C11Z-A, 2MA-OK, 2PHZ, 2P4MHZ (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc. may be used. Among these, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1 , 3,5-triazine, 2PHZ, and 2P4MHZ are preferred. One type of imidazole compound may be used alone, or two or more types may be used in combination. Further, if necessary, imidazole compounds other than those mentioned above can be used in combination in a certain amount depending on the purpose.
The blending amount of component (c) needs to satisfy the ratio with the number of epoxy groups mentioned above.

In the resin composition of the present invention, the content of components (a) to (c) is preferably 50 to 100% by mass, more preferably 70 to 95% by mass.

[Other ingredients]
[Polymerization initiator]
After the resin composition of the present invention is cured with the imidazole compound as component (c), it may contain other polymerization initiators in order to more completely cure it. The polymerization initiator is not particularly limited, and examples thereof include thermal radical polymerization initiators, thermal anionic polymerization initiators, and the like.

Examples of the thermal radical polymerization initiator include methyl ethyl ketone peroxide, methyl cyclohexanone 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 hydroperoxide, 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)hexine-3, iso Butyryl 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-ethylhexyl peroxydicarbonate, 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-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t -Hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy -2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate , t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl Monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butyl Peroxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, t-butylperoxyallyl monocarbonate, 3,3',4,4'-tetra(t- Organic peroxides such as butylperoxycarbonyl) 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 Examples include azo compounds such as -1,1'-azobis(1-cyclohexanecarboxylate).

Examples of thermal anionic polymerization initiators include triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo[5.4.0]undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethyl. Amine compounds such as amines; triphenylphosphine, tributylphosphine, trioctylphosphine, tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetraphenylborate, tetrabutylphosphonium acetate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium bromide , tetrabutylphosphonium bromide, tetrabutylphosphonium laurate, tetraphenylphosphonium hydrogen phthalate, bis(tetraphenylphosphonium) dihydrogenpyromellitate, bis(tetrabutylphosphonium)dihydrogenpyromellitate, etc. Can be mentioned.

Among these, thermal radical polymerization initiators are preferred, and among them, methyl ethyl ketone peroxide, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, and cinnamic acid peroxide are particularly preferred.
These polymerization initiators may be used alone or in combination of two or more. The amount of the thermal radical polymerization initiator and the thermal anionic polymerization initiator is not particularly limited, but it is preferably 0.01 to 10 parts by weight based on 100 parts by weight of component (a) in the composition of the present invention. It is more preferably 0.1 to 5 parts by weight, and even more preferably 0.3 to 3 parts by weight. Within this range, sufficient curing can be achieved without adversely affecting the physical properties of the resin composition.

[Inorganic filler]
The resin composition of the present invention may further contain an inorganic filler.
Inorganic fillers are not particularly limited, but include metal oxides such as silica, titanium dioxide, yttrium oxide, aluminum oxide, magnesium oxide, zinc oxide, and beryllium oxide; metal nitrides such as boron nitride, aluminum nitride, and silicon nitride. Carbon-containing particles such as silicon carbide, diamond, and graphene; Hollow particles such as silica balloons (hollow silica), carbon balloons, alumina balloons, and aluminosilicate balloons; gold, silver, copper, palladium, aluminum, nickel, iron, cobalt , titanium, manganese, zinc, tungsten, platinum, lead, tin, etc.; alloys such as solder, steel, stainless steel; stainless steel, Fe-Cr-Al-Si alloy, Fe-Si-Al alloy, Fe-Ni Alloy, Fe-Cu-Si alloy, Fe-Si alloy, Fe-Si-B (-Cu-Nb) alloy, Fe-Si-Cr-Ni alloy, Fe-Si-Cr alloy, Fe-Si-Al-Ni -Magnetic metal alloys such as Cr alloy; hematite (Fe ₂ O ₃ ), magnetite (Fe ₃ O ₄ ), Mn-Zn ferrite, Ni-Zn ferrite, Mg-Mn ferrite, Zr-Mn ferrite, Ti Examples include ferrites such as -Mn ferrite, Mn-Zn-Cu ferrite, barium ferrite, and strontium ferrite. These may be used alone or in combination of two or more.

By adding metal oxides, metal nitrides, and carbon-containing particles, the coefficient of linear expansion of the cured resin composition can be lowered and the thermal conductivity can be increased. It is possible to lower the relative dielectric constant, dielectric loss tangent, density, etc., it is possible to increase the electrical conductivity, thermal conductivity, etc. of the cured resin composition by adding metals and alloys, and it is possible to increase the electrical conductivity, thermal conductivity, etc. of the cured product of the resin composition. Electromagnetic wave absorption ability can be imparted to the cured product of the composition.

The shape of the inorganic filler is not particularly limited, and examples thereof include spherical, scale-like, flake-like, needle-like, rod-like, and elliptical shapes, among which spherical, scale-like, flake-like, elliptical, and rod-like shapes are preferred. , spherical, scaly, flaky, and elliptical shapes are more preferable.

The primary particle size of the inorganic filler is not particularly limited, but the median diameter measured with a laser diffraction particle size distribution analyzer is preferably 0.05 to 500 μm, more preferably 0.1 to 300 μm, and 1 to 100 μm. is even more preferable. Within this range, it is easy to uniformly disperse the inorganic filler in the resin composition, and the inorganic filler does not settle, separate, or become unevenly distributed over time, which is preferable.

The amount of the inorganic filler to be blended is not particularly limited, but it is preferably 5 to 3,000 parts by mass, and 10 to 2,500 parts by mass based on 100 parts by mass of component (a) in the composition of the present invention. It is more preferably 50 to 2,000 parts by weight, and even more preferably 50 to 2,000 parts by weight. Within this range, the function of the inorganic filler can be fully exhibited while maintaining the strength of the resin composition.

[Organic filler]
The resin composition of the present invention may further contain an organic filler.
The organic filler is not particularly limited, but includes thermoplastic resin particles such as acrylic-butadiene copolymer, styrene-butadiene copolymer, acrylonitrile-styrene-butadiene copolymer, acrylic block copolymer, and carbon. Examples include fiber, cellulose fiber, silicone powder, acrylic powder, polytetrafluoroethylene powder, polyethylene powder, polypropylene powder, and the like. These may be used alone or in combination of two or more.

The shape of the organic filler is not particularly limited, and examples thereof include spherical, fibrous, flake, needle, rod, and elliptical shapes, among which spherical, fibrous, flake, elliptical, and rod shapes are preferred. , spherical, fibrous, flaky, and elliptical shapes are more preferable.

The primary particle size of the organic filler is not particularly limited, but the median diameter measured with a laser diffraction particle size distribution analyzer is preferably 0.05 to 500 μm, more preferably 0.1 to 300 μm, and 1 to 100 μm. is even more preferable. Within this range, it is easy to uniformly disperse the organic particles in the resin composition, and the organic particles do not settle, separate, or become unevenly distributed over time, which is preferable.

The amount of the organic filler to be blended is not particularly limited, but it is preferably 1 to 400 parts by weight, and 5 to 200 parts by weight, based on 100 parts by weight of component (a) in the composition of the present invention. The amount is more preferably 10 to 100 parts by mass. Within this range, it is possible to increase the strength of the resin composition.

[Adhesive agent]
The resin composition of the present invention may contain an adhesion-imparting agent as necessary in order to impart adhesiveness or tackiness (pressure-sensitive adhesiveness). Examples of the adhesion imparting agent include acrylic resin, urethane resin, phenol resin, terpene resin, and silane coupling agent. Among these, acrylic resins and silane coupling agents are preferred for imparting adhesive properties, and terpene resins are preferred for imparting tackiness (pressure-sensitive adhesiveness).

The acrylic resin is not particularly limited, but includes, for example, lauryl acrylate, stearyl acrylate, isostearyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-acryloyloxyethyl phthalic acid, - Acryloyloxyethyl acid phosphate, polyethylene glycol diacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, dioxane glycol diacrylate, 9,9-bis[4-(2-hydroxyethoxy) ) phenyl] fluorene diacrylate, lauryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol dimethacrylate, Examples include dimethylol tricyclodecane dimethacrylate.

Terpene resins are not particularly limited, but include, for example, monoterpenes such as α-pinene, β-pinene, dipentene, and limonene, sesquiterpenes such as cedrene and farnesene, and terpenes such as diterpenes such as abietic acid. homopolymers of the above, aromatic modified terpene resins which are copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene and the above terpenes, phenols such as phenol, cresol, hydroquinone, naphthol, and bisphenol A. Examples include terpene phenol resins which are copolymers of and the above-mentioned terpenes. Further, hydrogenated terpene resins obtained by hydrogenating these terpene resins can also be used.

The silane coupling agent is not particularly limited, but examples include n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, and phenyltrimethoxysilane. Ethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane, methoxytri(ethyleneoxy)propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanato Examples include silane coupling agents such as propyltrimethoxysilane.

There is no particular restriction on the amount of the adhesion imparting agent, but it is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and more preferably 1 to 5 parts by weight based on 100 parts by weight of component (a). Parts by mass are more preferred. Within this range, the adhesive force or adhesive force of the resin composition can be further improved without changing the mechanical properties of the resin composition.

[Antioxidant]
There are no particular limitations on the antioxidant, but for example, 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-hydroxyphenylacetate, 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 Phenolic antioxidants such as -5-t-butyl-4-hydroxyphenyl) propionate, 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, pentaerythrityltetrakis ( Sulfur-based antioxidants such as tridecyl phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, 2-ethylhexyldiphenyl phosphite, diphenyl Tridecyl phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, 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]dioxaphosphepine- Examples include phosphorous antioxidants such as 6-yl]oxy]-ethyl]ethanamine.

The amount of the antioxidant to be blended is not particularly limited, but is preferably 0.00001 to 5 parts by weight, more preferably 0.0001 to 4 parts by weight, and 0.001 to 4 parts by weight per 100 parts by weight of component (a). 3 parts by mass is more preferred. Within this range, oxidation of the resin composition can be prevented without changing the mechanical properties of the resin composition.

[Flame retardants]
The resin composition of the present invention may contain a flame retardant, if necessary, in order to impart flame retardancy. The flame retardant is not particularly limited, and examples thereof include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, guanidine-based flame retardants, and the like. Examples of phosphorus-based flame retardants include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus such as guanidine phosphate and phosphoric acid amide. Compound, phosphoric acid, phosphine oxide, triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylene Bis(di-2,6-xylenyl phosphate), bisphenol A-bis(diphenyl phosphate), 1,3-phenylene bis(diphenyl phosphate), divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1) phenylphosphonate -butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, bis(2-allylphenoxy)phosphazene, dicresylphosphazene and other phosphazene compounds, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate , 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Examples include oxides. Examples of metal hydrates include aluminum hydroxide hydrate, magnesium hydroxide hydrate, and the like. Examples of halogen flame retardants include hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, and tetrabromobenzene. Bromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, etc. . Examples of the guanidine flame retardant include guanidine sulfamate and guanidine phosphate.

The amount of the flame retardant to be blended is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight, and more preferably 0.1 to 3 parts by weight based on 100 parts by weight of component (a). Parts by mass are more preferred. Within this range, flame retardancy can be imparted to the resin composition without changing the mechanical properties of the resin composition.

[Production method]
In the method for producing the resin composition of the present invention, components (a) to (c) and other additives added as necessary are mixed using a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) or a stirrer THINKY CONDITIONING. A method of mixing using MIXER (manufactured by Shinky Co., Ltd.) is mentioned, and preferably an organic solvent (for example, cyclopentanone, cyclopentanone, cyclohexanone, mesitylene, anisole, dibutyl ether, diphenyl ether, 1,4- Examples include a method of adding and mixing dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, etc.). By adding an organic solvent, the viscosity of the resin composition can be lowered and more uniform mixing can be achieved. A resin composition can be obtained by distilling off the organic solvent under reduced pressure after mixing, but when used as a prepreg or the like, it may be used as it is without being distilled off, or it may be adjusted to a desired concentration before use.

[Prepreg]
The resin composition of the present invention can also be used as a prepreg by dissolving it in the above-mentioned organic solvent, impregnating it into a fiber base material, and drying it by heating.
As the fiber base material, known materials used in laminates can be used. Examples include inorganic fibers such as E glass, S glass, T glass, NE glass, and Q glass (quartz glass); organic fibers such as polyethylene, polyester, polyamide, and polytetrafluoroethylene. These may be used alone or in combination of two or more. Among these, from the viewpoint of dielectric properties, inorganic fibers are preferred, and T glass, NE glass, and Q glass are more preferred.
The thickness of the fiber base material is not particularly limited, but is preferably 5 to 500 μm, more preferably 10 to 100 μm, and even more preferably 20 to 80 μm. Within this range, a prepreg with excellent flexibility, low warpage, and high strength can be obtained.
These fiber base materials may be surface-treated by heating or with a silane coupling agent or the like in order to improve dielectric properties and affinity for resins.
The content of the resin composition in the prepreg is not particularly limited, but is preferably 20 to 90% by volume, more preferably 30 to 80% by volume, and even more preferably 40 to 70% by volume. Within this range, the adhesive strength to the conductor can be increased while maintaining dielectric properties and low warpage.
The thickness of the prepreg of the present invention is not particularly limited, but is preferably 10 to 500 μm, more preferably 25 to 300 μm, and even more preferably 40 to 200 μm. Within this range, a copper-clad laminate can be produced satisfactorily.
The prepreg of the present invention may be semi-cured (B-staged) by heating in advance. There are no particular limitations on the method for forming the B-stage, but for example, the 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 for 1 to 30 minutes. B-stage can be achieved by heating for a few minutes.

[Copper-clad laminate]
The prepreg of the present invention may be used as a copper-clad laminate by stacking copper foils, pressing them, heating and curing them.
There are no particular restrictions on the method for producing a copper-clad laminate, but for example, 1 to 20 sheets, preferably 2 to 10 sheets of the prepreg are used, copper foil is placed on one or both sides of the prepreg, and the sheet is pressed and cured by heating. It can be manufactured by
The thickness of the copper foil is not particularly limited, but is preferably 3 to 70 μm, more preferably 10 to 50 μm, and even more preferably 15 to 40 μm. Within this range, it is possible to form a multilayer copper-clad laminate that maintains high reliability.
There are no particular restrictions on the molding conditions for the copper-clad laminate, but for example, a multistage press, multistage vacuum press, continuous molding, autoclave molding machine, etc. are used, the temperature is 100 to 400°C, the pressure is 1 to 100 MPa, and the heating time is 0. Molding can be carried out within a range of 1 to 4 hours. Furthermore, a copper-clad laminate can be formed by combining the prepreg of the present invention, copper foil, and wiring board for inner layer.

[Printed wiring board]
The copper-clad laminate of the present invention may be processed into a circuit and used as a printed wiring board.
There are no particular limitations on the method of circuit processing, but examples include circuit forming processing such as hole drilling, metal plating, and etching of metal foil.
Alternatively, a printed wiring board may be manufactured by a build-up method in which the resin composition or prepreg of the present invention and copper foil are sequentially laminated.

EXAMPLES Hereinafter, the present invention will be explained in more detail by showing examples and comparative examples, but the present invention is not limited to the following examples.

The molecular weights shown in the following examples are weight average molecular weights (Mw) measured by gel permeation chromatography (GPC) using polystyrene as a standard material. The measurement conditions are shown below.
[GPC measurement conditions]
Developing solvent: tetrahydrofuran Flow rate: 0.6 mL/min
Column:TSK Guardcolumn SuperHL-L
TSKgel SuperH4000 (6.0mm I.D. x 15cm x 1)
TSKgel SuperH3000 (6.0mm I.D. x 15cm x 1)
TSKgel SuperH2000 (6.0mm I.D. x 15cm x 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40℃
Sample injection amount: 20 μL (sample concentration: 0.5% by mass-tetrahydrofuran solution)
Detector: Differential refractometer (RI)

（ｎ≒８（平均値）） (a) Cyclic imide compound (a-1) Maleimide compound To 196 g of N-methylpyrrolidone, 200 g (1.0 mol) of 1,12-diaminododecane and 207 g (0.95 mol) of pyromellitic anhydride were added, and the mixture was heated at 25°C. The mixture was stirred at 150° C. for 3 hours, and then further stirred at 150° C. for 3 hours. To the obtained solution were added 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride, and the mixture was stirred at 80° C. for 1 hour. Thereafter, 500 g of toluene was added, and after further washing with water and dehydration, the solvent was distilled off under reduced pressure to obtain bismaleimide (a-1) represented by the following formula. (Weight average molecular weight 3,500, maleimide equivalent 0.057 mol/100 g)

(n≒8 (average value))

（ｎ≒２８（平均値）） (a-2) Maleimide compound To 361 g of N-methylpyrrolidone, 158 g (1.0 mol) of 2,4,4-trimethylhexane-1,6-diamine and 214 g (0.99 mol) of pyromellitic anhydride were added, The mixture was stirred at 25°C for 3 hours, and then further stirred at 150°C for 10 hours. To the obtained solution were added 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride, and the mixture was stirred at 80° C. for 1 hour. Thereafter, 1,000 g of toluene was added, and after further washing with water and dehydration, the solvent was distilled off under reduced pressure to obtain bismaleimide (a-2) represented by the following formula. (Weight average molecular weight 9,500, maleimide equivalent 0.021 mol/100 g)

(n≒28 (average value))

（ｎ≒３０（平均値）） (a-3) Maleimide compound 170 g (1.0 mol) of isophoronediamine and 499 g (0.96 mol) of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride were added to 263 g of N-methylpyrrolidone. and stirred at 25°C for 3 hours, then further stirred at 150°C for 5 hours. To the obtained solution were added 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride, and the mixture was stirred at 80° C. for 1 hour. Thereafter, 500 g of toluene was added, and after further washing with water and dehydration, the solvent was distilled off under reduced pressure to obtain bismaleimide (a-3) represented by the following formula. (Weight average molecular weight 20,000, maleimide equivalent 0.010mol/100g)

(n≒30 (average value))

（ｎ≒１８（平均値）） (a-4) Citraconimide compound 523 g (1.0 mol) of dimer diamine and 211 g (0.97 mol) of pyromellitic anhydride were added to 263 g of N-methylpyrrolidone, stirred at 25°C for 3 hours, and then further The mixture was stirred at 150°C for 5 hours. To the obtained solution were added 226 g (2.0 mol) of citraconic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride, and the mixture was stirred at 80° C. for 1 hour. Thereafter, 500 g of toluene was added, and after further washing with water and dehydration, the solvent was distilled off under reduced pressure to obtain citraconimide (a-4) represented by the following formula. (Weight average molecular weight 10,000, maleimide equivalent 0.020mol/100g)

(n≒18 (average value))

（ｎ１≒３（平均値）、ｎ２≒３（平均値）） (a-5) Maleimide compound Maleimide compound represented by the following formula (BMI-2500, manufactured by Designer Molecules Inc.) (weight average molecular weight 3,500, maleimide equivalent 0.057 mol/100 g)

(n1≒3 (average value), n2≒3 (average value))

（ｎ≒１８（平均値）） (a-6) Maleimide compound Maleimide compound represented by the following formula (BMI-3000, manufactured by Designer Molecules Inc.) (weight average molecular weight 10,000, maleimide equivalent 0.020 mol/100 g)

(n≒18 (average value))

（ｍ≒５０（平均値）） (a-7) Maleimide compound To 500 g of anisole, 431 g (1.05 mol) of 2,2-bis(4-(4-aminophenoxy)phenyl)propane and 4,4'-(4,4'-isopropylidenediphenoxy) ) 520 g (1.0 mol) of diphthalic anhydride was added, stirred at room temperature for 5 hours, and further stirred at 120° C. for 3 hours. 19 g (0.2 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 maleimide (a-7) represented by the following formula. (Weight average molecular weight 45,000, maleimide equivalent 0.0044 mol/100 g)

(m≒50 (average value))

(b) Epoxy compound (b-1): Biphenyl aralkyl type epoxy resin (product name: "NC-3000" (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 0.30 mol/100 g))
(b-2) Bisphenol A type epoxy resin (product name: "jER-828EL" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 0.59 mol/100 g))
(b-3) Liquid multifunctional epoxy resin (product name: "jER-630" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 1.1 mol/100 g))

(c) Imidazole compound (c-1) 2-ethyl-4-methylimidazole (imidazole equivalent: 0.91 mol/100 g)
(c-2) 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine (imidazole equivalent 0.46 mol/100 g)
(c-3) 2-phenyl-4-hydroxy-5-methylimidazole (imidazole equivalent: 0.54 mol/100 g)

(d) Polymerization initiator (d-1) Dicumyl peroxide

(e) Inorganic filler (e-1) Silica “SFP-130MC” (median primary particle size 0.6 μm) (manufactured by Denka Co., Ltd.)
(e-2) Alumina "AO-41R" (median primary particle size 6 μm) (manufactured by Admatex Co., Ltd.)

(f) Organic filler (f-1) Silicone powder "KMP-600" (median primary particle size 5 μm) (manufactured by Shin-Etsu Chemical Co., Ltd.)

(g) Adhesive agent (g-1) Silane coupling agent (3-glycidoxypropyltrimethoxysilane, trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.)
(g-2) Silane coupling agent (N-phenyl-3-aminopropyltrimethoxysilane, trade name "KBM-573", manufactured by Shin-Etsu Chemical Co., Ltd.)

(h) Antioxidant (h-1) Pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Product name: ADEKA STAB AO-60, manufactured by ADEKA Co., Ltd.) )

(i) Flame retardant (i-1) Guanidine phosphate (trade name "Apinon-303", manufactured by Sanwa Chemical Co., Ltd.)

[Method for preparing resin composition]
For Examples 1 to 17 and Comparative Examples 1 to 7, in addition to the formulations (parts by mass) shown in Tables 1 to 3, 100 parts by mass of cyclopentanone was added and mixed with respect to a total of 100 parts by mass of each component. The mixture was kneaded at 80°C for 30 minutes using a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.), and then cooled to 25°C. The obtained solution was transferred to a flask, and the solvent was distilled off under reduced pressure to prepare a resin composition.

[Relative permittivity and dielectric loss tangent]
The prepared resin composition was sandwiched between mold frames of 30 mm x 40 mm x 100 μm thick, and press cured at 180° C. for 1 hour to prepare a test sample. A network analyzer (manufactured by Keysight Corporation, E5063-2D5) and a strip line (manufactured by Keycom Corporation) were connected to the prepared test sample, and the dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured. The results are listed in Tables 1 to 3.

[Peel strength]
A resin film was prepared by coating the resin composition prepared by the above method into a film with a thickness of 25 μm, and a SUS plate, the resin film, and a copper foil with a thickness of 18 μm (product name: TQ-M4- VSP (manufactured by Mitsui Kinzoku Co., Ltd.) were stacked in this order and pressed, and heated at 180° C. for 1 hour to harden. In accordance with JIS-C-6481:1996, the standard for testing copper-clad laminates for printed wiring boards, using a Tensilon tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: Strograph VE-1D), the test was performed in a 90° direction with a width of 10 mm. The force (peel strength) when peeling the copper foil from the resin film at a speed of 50 mm/min was determined. The results are listed in Tables 1 to 3.

In Examples 1 to 17, the cured products had a low dielectric constant and a low dielectric loss tangent, and had high peel strength.
In Comparative Examples 1, 2, and 6, there was no component containing an epoxy group in the composition, or the value of the number of cyclic imide groups/the number of epoxy groups was large, resulting in insufficient curing, resulting in low peel strength and poor dielectric strength. The coefficient and dielectric loss tangent were also increased.
In Comparative Example 3, the relative dielectric constant and dielectric loss tangent were high because the value of the number of cyclic imide groups/the number of epoxy groups was small.
In Comparative Example 4, the peel strength was low because the value of the number of epoxy groups/the number of imidazole groups was small.
In Comparative Examples 5 and 7, the peel strength was low because the value of the number of epoxy groups/the number of imidazole groups was large.

[Prepreg manufacturing method]
In Examples 18 to 21 and Comparative Examples 8 and 9, 1,000 g of each resin composition prepared in Examples 1 to 4 and Comparative Examples 3 and 4 and 1,000 g of cyclopentanone were mixed, and quartz glass cloth SQX2116AC ( A prepreg having a thickness of 90 μm (manufactured by Shin-Etsu Chemical Co., Ltd.) was impregnated and heated at 120° C. for 5 minutes to volatilize cyclopentanone. The content (mass%) of the resin composition and the thickness of the prepreg are listed in Table 4.

[Method for manufacturing copper-clad laminates]
10 sheets of the prepreg obtained above and 9 sheets of 18 μm thick copper foil (product name: TQ-M4-VSP, manufactured by Mitsui Kinzoku Co., Ltd.) were stacked alternately, and further copper foil was stacked on the top and bottom outermost surfaces. and heated at 180° C. for 1 hour to produce a double-sided copper-clad laminate.

[Manufacturing method of printed wiring board]
Dry resist films (NIT430E, manufactured by Nikko Materials Co., Ltd.) having a thickness of 30 μm were vacuum laminated and pasted together at 80° C. for 60 seconds on both surfaces of the double-sided copper-clad laminate obtained above. Thereafter, a mask on which a circuit pattern was formed was brought into contact with the mask, and UV was irradiated from above and below at an illuminance of 500 mW for 10 seconds. Thereafter, the film was developed by being immersed in a 10% aqueous sodium hydrogen carbonate solution at 40°C for 10 minutes. Thereafter, it was etched by being impregnated with an etching solution (H-1000A, manufactured by Sanhayato Co., Ltd.) at 40° C. for 10 minutes. Thereafter, a printed wiring board with circuits formed on both sides was manufactured by impregnating and cleaning it in a 10% aqueous sodium hydroxide solution at 40° C. for 20 minutes.

[Transmission loss]
Using a network analyzer (manufactured by Keysight Technologies, product number E5071C), the conductor length was 400 mm, the copper foil thickness was 18 μm, the line width was 0.12 mm, the insulating layer thickness was 0.20 mm, and the characteristic impedance was was adjusted to 50Ω, and the transmission loss at 40GHz was measured. The results are listed in Table 4.

In Examples 18 to 21, the transmission losses were all low.
In Comparative Examples 8 and 9, as shown in Comparative Examples 3 and 4, the relative permittivity and dielectric loss tangent were high, so the transmission loss was a high value.

Claims (9)

(a) cyclic imide compound,
(b) A resin composition containing an epoxy compound and (c) an imidazole compound, in which the number of cyclic imide groups of the cyclic imide compound, the number of epoxy groups of the epoxy compound, and the number of imidazole groups of the imidazole compound satisfy the following two formulas. .

0.3 ≦ Number of cyclic imide groups/Number of epoxy groups ≦ 3.0

2.0 ≦ Number of epoxy groups/Number of imidazole groups ≦ 20.0
The resin composition according to claim 1, wherein the cyclic imide compound (a) is represented by the following formula (1):

(In formula (1), A independently represents a tetravalent organic group containing a cyclic structure. Q independently represents a divalent hydrocarbon group having 6 or more carbon atoms which does not contain an aromatic group which may contain a heteroatom. B independently represents an arylene group having 6 or more carbon atoms which may contain a heteroatom. X independently represents a hydrogen atom or a methyl group, n is 0 to 200, and m is 0 to 200.) The resin composition according to claim 2, wherein the organic group represented by A in formula (1) is any of the tetravalent organic groups represented by the following structural formula.

(The bond to which no substituent in the above structural formula is bonded is the one bonded to the carbonyl carbon forming the cyclic imide structure in formula (1).) A claim in which the divalent hydrocarbon group represented by Q in formula (1) is selected from a divalent hydrocarbon group represented by any of the following structural formulas and a divalent hydrocarbon group derived from a dimer acid skeleton. Item 2. The resin composition according to item 2.

(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 are each a number of 5 or more, and may be the same or different. Often, p ³ and p ⁴ are each a number greater than or equal to 0 and may be the same or different, and p ⁵ and p ⁶ are each a number greater than or equal to 0 and may be the same or different. Good. The bond to which no substituent in the above structural formula is bonded is the one that bonds to the nitrogen atom forming the cyclic imide structure in formula (1).) The resin composition according to claim 2, wherein the arylene group represented by B in formula (1) is an arylene group represented by any of the following structural formulas.

(R ² is independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, R ³ is independently a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and Z is an oxygen atom , a sulfur atom or a methylene group.The bond to which no substituent in the above structural formula is bonded is the one bonded to the nitrogen atom forming the cyclic imide structure in formula (1).) 3. The resin composition according to claim 2, wherein the cyclic imide compound as component (a) is a cyclic imide compound in which m in formula (1) is 0. A prepreg comprising the resin composition according to any one of claims 1 to 6. A copper-clad laminate comprising the prepreg according to claim 7. A printed wiring board comprising the copper-clad laminate according to claim 8.