JP7215188B2 - Resin compositions, cured products, moldings, prepregs, resin sheets, metal foil-clad laminates, printed wiring boards, semiconductor devices, sealing materials, fiber-reinforced composite materials and adhesives - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition, a cured product, a molded product, a prepreg, a resin sheet, a metal foil-clad laminate, a printed wiring board, a semiconductor device, a sealing material, a fiber-reinforced composite material, and an adhesive.

2. Description of the Related Art In recent years, semiconductors widely used in electronic devices, communication devices, personal computers, etc. have been increasingly highly integrated and miniaturized. Along with this, various characteristics required for semiconductor package laminates used for printed wiring boards are becoming more and more severe. Properties required include, for example, properties such as low water absorption, heat resistance after moisture absorption, flame retardancy, low dielectric constant, low dielectric loss tangent, low coefficient of thermal expansion, heat resistance, chemical resistance, and high plating peel strength.
A resin composition containing a radically polymerizable compound is known as a printed wiring board material having excellent properties (see, for example, Patent Document 1).

JP-A-2018-90728

However, resin compositions containing radically polymerizable compounds generally have the problem of high reactivity and poor moldability.

The present invention has been made in view of the above problems, and its object is to provide a resin composition, a cured product, a molded product, a prepreg, a resin sheet, a metal foil-clad laminate, a printed wiring board, and a semiconductor, which are excellent in moldability. An object of the present invention is to provide a device, a sealing material, a fiber-reinforced composite material, and an adhesive.

The present inventors have made intensive studies to solve such problems, and as a result, found that a resin composition containing a specific compound (B) in a radically polymerizable compound (A) can solve the above problems. arrived at the invention.

That is, the present invention includes the following contents.
[1] A resin composition comprising a radically polymerizable compound (A) and a compound (B) represented by the following general formula (1).

(In formula (1), R ₁ is a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, or the following general formula (2) Each R ₂ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, or the following general Represents an aryl group represented by formula (2), or R ₂ may combine with each other to form a carbonyl group, and Ar represents an aryl group represented by the following general formula (2).) .

(In formula (2), each R ₃ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxy group, or represents an optionally substituted linear or branched alkoxy group having 1 to 5 carbon atoms, or two adjacent R3's may be bonded to _each other to form a naphthyl group).

[2] The resin composition according to [1], wherein the content of the compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the radically polymerizable compound (A).
[3] The resin composition according to [1] or [2], wherein the radically polymerizable compound (A) contains a maleimide compound.
[4] The resin composition according to any one of [1] to [3], wherein the compound (B) contains a compound represented by the following general formula (3).

(In formula (3), each R ₄ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxy group, or represents an optionally substituted linear or branched alkoxy group having 1 to 5 carbon atoms, or two adjacent _R4 's may be bonded to each other to form a naphthyl group).

[5] The resin composition according to any one of [1] to [4], further comprising one or more selected from the group consisting of cyanate ester compounds, phenol compounds, and epoxy compounds.
[6] The resin composition according to any one of [1] to [5], further comprising an inorganic filler.
[7] According to [6], wherein the inorganic filler contains at least one selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide. of the resin composition.
[8] The resin composition according to any one of [1] to [7], which is used as an electronic material.
[9] The resin composition according to any one of [1] to [7], which is for printed wiring boards.
[10] A cured product comprising the resin composition according to any one of [1] to [7].

[11] A molded article containing the resin composition according to any one of [1] to [7].
[12] A prepreg comprising a substrate and the resin composition according to any one of [1] to [7] impregnated or applied to the substrate.
[13] A resin sheet comprising a support and the resin composition according to any one of [1] to [7] disposed on the surface of the support.
[14] A laminate formed of one or more selected from the group consisting of the prepreg described in [12] and the resin sheet described in [13], and a metal foil disposed on one or both sides of the laminate. A metal foil clad laminate comprising
[15] An insulating layer formed of one or more selected from the group consisting of the prepreg described in [12] and the resin sheet described in [13], and a conductor layer formed on the surface of the insulating layer Including printed wiring board.

[16] A semiconductor device comprising the resin composition according to any one of [1] to [7].
[17] A sealing material comprising the resin composition according to any one of [1] to [7].
[18] A fiber-reinforced composite material comprising the resin composition according to any one of [1] to [7].
[19] An adhesive comprising the resin composition according to any one of [1] to [7].

According to the present invention, a resin composition, a cured product, a molded article, a prepreg, a resin sheet, a metal foil-clad laminate, a printed wiring board, a semiconductor device, a sealing material, a fiber-reinforced composite material, and a Adhesive can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the form (only henceforth "this embodiment") for implementing this invention is demonstrated in detail. In addition, the following embodiment is an example for explaining the present invention, and the present invention is not limited only to this embodiment.

As used herein, "(meth)acrylo" means both "acrylo" and the corresponding "methacrylo". "(Meth)acrylic" means both "acrylic" and the corresponding "methacrylic". "(Meth)acrylate" means both "acrylate" and its corresponding "methacrylate". In the present embodiment, unless otherwise specified, the term "resin solid content" or "resin solid content in the resin composition" refers to other components such as additives, solvents and inorganic fillers in the resin composition. "100 parts by mass of resin solid content" means that the total of the components excluding other components such as additives, solvents and inorganic fillers in the resin composition is 100 parts by mass shall be said.

The resin composition of this embodiment contains a radically polymerizable compound (A) and a compound (B) represented by the general formula (1).
Another aspect of the present embodiment further includes one or more selected from the group consisting of cyanate ester compounds, phenol compounds, and epoxy compounds other than the radically polymerizable compound (A), in addition to the above components. It is a resin composition.
Another aspect of the present embodiment is a resin composition that further contains an inorganic filler in addition to the components described above.

[Resin composition]
[Radical polymerizable compound (A)]
The radically polymerizable compound (A) (also referred to as component (A)) is not particularly limited as long as it is a compound having a functional group that undergoes radical polymerization. The radical-polymerizable functional group is not particularly limited as long as it is a radical-polymerizable group, and examples thereof include (meth)acryl groups, maleimide groups, styryl groups, propenyl groups, norbornyl groups, and nadimide groups. Compounds having such functional groups include, for example, (meth)acrylate compounds, maleimide compounds, styryl compounds, propenyl compounds, norbornene compounds, and alkenyl-substituted nadimide compounds.

From the viewpoint of having high heat resistance, the resin composition of the present embodiment preferably contains a maleimide compound. Moreover, the resin composition of the present embodiment preferably contains an alkenyl-substituted nadimide compound from the viewpoint of reducing the coefficient of thermal expansion of the resulting cured product and improving the heat resistance.

((meth)acrylate compound)
Examples of (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tri methylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, 2,2-bis[4-((meth)acryloxymethoxy)phenyl ] Propane, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tris ((meth)acryloyloxyethyl ) isocyanurates and urethane (meth)acrylates. If necessary, a polymerization inhibitor such as hydroquinone and methyl ether hydroquinones may be used as appropriate.

(maleimide compound)
The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, fluorescein-5-maleimide, 6-maleimidohexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2′-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4′-diphenylmethanebismaleimide, bis (3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-Phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimidoethane, 1,4-bismaleimidobutane, 1,6-bismaleimidohexane, 1, 6-bismaleimido-(2,2,4-trimethyl)hexane, 1,8-bismaleimido-3,6-dioxaoctane, 1,11-bismaleimido-3,6,9-trioxaundecane, 1, 3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy) Benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4'-diphenylmethanebiscitraconimide, 2,2'-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5 -dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citraconimidophenyl)methane, polyphenylmethanemaleimide, A maleimide compound represented by the following formula (4), a maleimide compound represented by the following formula (5), a maleimide compound represented by the following formula (6), a maleimide compound represented by the following formula (7) An imide compound, a maleimide compound represented by the following formula (8), a maleimide compound represented by the following formula (9), a prepolymer obtained by polymerizing these maleimide compounds, or other compounds such as a maleimide compound and an amine compound and a prepolymer obtained by polymerizing a compound.

As the maleimide compound, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2,2′-bis{4-(4-maleimidophenoxy)phenyl, and } Propane, a maleimide compound represented by the following formula (5), and a maleimide compound represented by the following formula (6) are preferable.

As bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, commercially available products can be used, for example, BMI-70 (trade name) manufactured by K.I. Kasei Co., Ltd. can be mentioned. As 2,2'-bis{4-(4-maleimidophenoxy)phenyl}propane, a commercial product can be used, for example, BMI-80 (trade name) manufactured by K.I Kasei Co., Ltd. can be mentioned. . As the maleimide compound represented by the following formula (4), _a commercially available product can also be used. 13.6 (average)), K-I Kasei Co., Ltd. BMI-650P (trade name, n ₁ in general formula (4) = 8.8 (average)), K-I Kasei Co., Ltd. BMI-250P (trade name, n ₁ = 3 to 8 (average) in general formula (4)) manufactured by K.I Kasei Co., Ltd. CUA-4 (trade name, n in general formula (4) ₁ = 1) and the like. As the maleimide compound represented by the following formula (5), a commercially available product can be used, for example, BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. can be mentioned. As the maleimide compound represented by the following formula (6), a commercially available product can be used, for example, MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. can be mentioned. As the maleimide compound represented by the following formula (7), a commercially available product such as Designer Molecules Inc. can be used. (DMI) BMI-1500 (trade name). As the maleimide compound represented by the following formula (8), a commercially available product such as Designer Molecules Inc. can be used. (DMI) BMI-1700 (trade name). As the maleimide compound represented by the following formula (9), a commercially available product such as Designer Molecules Inc. can be used. (DMI) BMI-3000 (trade name), Designer Molecules Inc. (DMI) BMI-5000 (trade name), Designer Molecules Inc. (DMI) BMI-9000 (trade name).

In formula (4), the average value of n ₁ is in the range of 1 or more and 30 or less. From the viewpoint of achieving the effects of the present embodiment more effectively and reliably, n ₁ is preferably 7 or more and 30 or less, more preferably 7 or more and 18 or less, as an average value.

(In formula (5), a plurality of R ₅ each independently represents a hydrogen atom or a methyl group; n ₂ represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably 1 represents an integer of ~5).

(In formula (6), a plurality of R ₆ each independently represents a hydrogen atom or a methyl group. n ₃ represents an integer of 1 or more, preferably an integer of 1 to 5.).

(In formula (7), n ₄ represents an integer of 1 or more, preferably an integer of 1 to 10).

(In formula (8), n ₅ represents an integer of 1 or more, preferably an integer of 1 to 10).

(In formula (9), n ₆ represents an integer of 1 or more, preferably an integer of 1 to 10).

When a maleimide compound is used as the radically polymerizable compound (A), the content of the maleimide compound in the resin composition is not particularly limited, but from the viewpoint of achieving both heat resistance and moldability, the resin solid content in the resin composition With respect to 100 parts by mass, preferably 1 to 99 parts by mass, more preferably 5 to 90 parts by mass, still more preferably 10 to 80 parts by mass, still more preferably 15 to 65 parts by mass .

The maleimide compound can also be included in the resin composition in the form of a prepolymer obtained by polymerizing the maleimide compound, or a prepolymer obtained by polymerizing the maleimide compound and another compound such as an amine compound. .

(styryl compound)
Examples of styryl compounds include 1,3-divinylbenzene and 1,3-dipropenylbenzene.

(propenyl compound)
Examples of propenyl compounds include monofunctional propenyl compounds such as propenylbenzene, propenylnaphthalene, propenylanthracene, propenylphenol, o-propenylphenoxybenzene, 1-cyanato-2-methoxy-4-allylbenzene (eugenol cyanate), bis Propenyl phenyl ether, 2,2′-bis[4-(o-propenylphenoxy)phenyl]propane, bis[4-(o-propenylphenoxy)phenyl]ether, bis[4-(o-propenylphenoxy)phenyl]sulfone , 4,4′-bis(o-propenylphenoxy)benzophenone, 2,2′-bis[4-(o-propenylphenoxy)phenyl]nonane, 2,2′-bis[3-tert-butyl-4-( o-propenylphenoxy)phenyl]propane, 2,2′-bis[3-secondary-butyl-4-(o-propenylphenoxy)phenyl]propane, 1,1′-bis[4-(o-propenylphenoxy)phenyl] Decane, 1,1′-bis[2-methyl-4-(o-propenylphenoxy)-5-tert-butylphenyl]-2-methylpropane, 4,4′-cyclohexylidene-bis[1-(o -propenylphenoxy)-2-(1,1-dimethylethyl)benzene], 4,4'-methylene-bis[1-(o-propenylphenoxy)-2,6-bis(1,1'-dimethylethyl) benzene], 4,4′-methylene-bis[1-(o-propenylphenoxy)-2,6-di-secondarybutylbenzene], 4,4′-cyclohexylidene-bis[1-(o-propenylphenoxy )-2-cyclohexylbenzene], 4,4′-methylene-bis[1-(o-pnopenylphenoxy)-2-nonylbenzene], 4,4′-(1-methylethylidene)-bis[1- (o-propenylphenoxy)-2,6-bis(1,1'-dimethylethyl)benzene, 4,4'-(2-ethylhexylidene)-bis[1-(o-propenylphenoxy)-benzene] , 4,4′-(1-methylheptylidene)-bis[1-(o-propenylphenoxy)-benzene], 4,4′-cyclohexylidene-bis[1-(o-propenylphenoxy)-3 -methylbenzene], 2,2′-bis[4-(o-propenylphenoxy)phenyl]-propane, 2,2′-bis[4-(o-propenylphenoxy)phenyl] -hexafluoropropane, 2,2'-bis[3-methyl-4-(o-propenylphenoxy)phenyl]-propane, 2,2'-bis[3-methyl-4-(o-propenylphenoxy)phenyl] -hexafluoropropane, 2,2'-bis[3,5-dimethyl-4-(o-propenylphenoxy)phenyl]-propane, 2,2'-bis[3,5-dimethyl-4-(o-propenyl phenoxy)phenyl]-hexafluoropropane, 2,2′-bis[3-ethyl-4-(o-propenylphenoxy)phenyl]-propane, 2,2′-bis[3-ethyl-4-(o-propenyl phenoxy)phenyl]-hexafluoropropane, bis[3-methyl-(o-propenylphenoxy)phenyl]-methane, bis[3,5-dimethyl-(o-propenylphenoxy)phenyl]-methane, bis[3-ethyl -(o-propenylphenoxy)phenyl]-methane, 3,8-bis[4-(o-propenylphenoxy)phenyl]-tricyclo-[5,2,1,0 ^2.6 ]decane, 4,8-bis [4-(o-propenylphenoxy)phenyl]-tricyclo-[5,2,1,0 ^2.6 ]decane, 3,9-bis[4-(o-propenylphenoxy)phenyl]-tricyclo-[5, 2,1,0 ^2.6 ]decane, 4,9-bis[4-(o-propenylphenoxy)phenyl]-tricyclo-[5,2,1,0 ^2.6 ]decane, 1,8-bis[ 4-(o-propenylphenoxy)phenyl]-methane, 1,8-bis[3-methyl-4-(o-propenylphenoxy)phenyl]-methane, 1,8-bis[3,5-dimethyl-4- (o-propenylphenoxy)phenyl]-methane and the like.

(Norbornene compound)
Examples of norbornene compounds include 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-( 1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2 -norbornene, 5-(5-heptenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5 -(2-ethyl-3-butenyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-5-hexenyl)-2-norbornene, 5-(3,4- Dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene, 5-(2-methyl-6-heptenyl) -2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, 5-(1,2,3-trimethyl- 4-pentenyl)-2-norbornene and the like.

(Alkenyl-Substituted Nadimide Compound)
The alkenyl-substituted nadimide compound is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadimide groups in the molecule. Among these, compounds represented by the following general formula (10) are preferable. By using such an alkenyl-substituted nadimide compound, the thermal expansion coefficient of the resulting cured product tends to be further lowered and the heat resistance tends to be further improved.

In general formula (10), each R ₇ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₈ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, represents a naphthylene group or a group represented by formula (11) or (12);

_In general formula ( ₁₁ ), R9 represents a methylene group, an isopropylidene group, or a substituent represented by CO, O, S, or SO2.

In general formula (12), each R ₁₀ independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.

The alkyl group having 1 to 6 carbon atoms in R ₇ may be a straight-chain alkyl group or a branched-chain alkyl group. Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group and 2,2-dimethylpropyl group. , a hexyl group, a trifluoromethyl group, and the like. A hydrogen atom in the alkyl group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, or the like.

The alkylene group having 1 to 6 carbon atoms in R ₈ may be a straight-chain alkylene group or a branched-chain alkylene group. Examples of alkylene groups include methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, 1-ethylpropylene, and 2,2-dimethylpropylene. group, hexylene group, and the like. A hydrogen atom in the alkylene group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, or the like.

The alkylene group having 1 to 4 carbon atoms in R ₁₀ is the same as the alkylene group described above.

Examples of the cycloalkylene group having 5 to 8 carbon atoms in R ₁₀ include cyclopentanediyl group, cyclohexanediyl group, cyclooctanediyl group and the like.

Among the compounds represented by the general formula (10), the alkenyl-substituted nadimide compounds are preferably compounds represented by the formulas (13) and/or (14). By using such an alkenyl-substituted nadimide compound, the thermal expansion coefficient of the resulting cured product tends to be further lowered and the heat resistance tends to be further improved.

In addition, a commercially available alkenyl-substituted nadimide compound can also be used. Commercially available products are not particularly limited. and the compound represented by the formula (14) manufactured by Petrochemical Co., Ltd.). These alkenyl-substituted nadimide compounds can be used singly or in combination of two or more.

When an alkenyl-substituted nadimide compound is used as the radically polymerizable compound (A), the content of the alkenyl-substituted nadimide compound in the resin composition is not particularly limited. It is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts by mass, still more preferably 20 to 40 parts by mass, based on 100 parts by mass of the resin solid content.

These radically polymerizable compounds (A) can be used singly or in combination of two or more.

The content of the radical polymerizable compound (A) in the resin composition is not particularly limited, but is preferably 1 to 99.1 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition, and more It is preferably 10 to 99.1 parts by mass, more preferably 30 to 99.1 parts by mass, even more preferably 50 to 99.1 parts by mass, even if it is 70 to 99.1 parts by mass good.

[Compound (B) represented by formula (1)]
The compound (B) (also referred to as component (B)) according to this embodiment has the structure of the following general formula (1).

(In formula (1), R ₁ is a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, or the following general formula (2) Each R ₂ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, or the following general formula: represents an aryl group represented by (2), or R ₂ may combine with each other to form a carbonyl group, and Ar represents an aryl group represented by the following general formula (2)).

(In formula (2), each R ₃ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxy group, or represents an optionally substituted linear or branched alkoxy group having 1 to 5 carbon atoms, or two adjacent R3's may be bonded to _each other to form a naphthyl group).

Generally, radically polymerizable compounds have a problem of poor moldability due to their high reactivity (particularly with heat). However, when the compound (B) according to the present embodiment is added to the radically polymerizable compound, the radical polymerization is moderately suppressed and moldability is improved. The present inventors are not sure about this mechanism of action, but presume, for example, as follows. The putative mechanism of action is explained using 1,3-diphenyl-1,3-propanedione.

For example, when 1,3-diphenyl-1,3-propanedione is used, the conjugation of 1,3-diphenyl-1,3-propanedione spreads over the entire molecule due to the contribution of the enol type. Therefore, it is presumed that 1,3-diphenyl-1,3-propanedione easily receives radicals from the radically polymerizable compound, and as a result, the chain reaction of the radically polymerizable compound is suppressed (the following reaction formula (15)).

In addition, the present inventors have found that since 1,3-diphenyl-1,3-propanedione is susceptible to abstraction of hydrogen at the α-position, hydrogen is abstracted by radicals from the radically polymerizable compound, and the radicals move. , it is also presumed that the chain reaction of the radically polymerizable compound was suppressed (see reaction formula (16) below).

In the compound (B) represented by the general formula (1), R ₁ in the general formula (1) will be explained.
In general formula (1), R ₁ is a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, or the general formula (2) represents an aryl group represented. From the viewpoint of suppressing polymerization, R ₁ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or an aryl group represented by the general formula (2), such as a methyl group or a phenyl group. , 4-methoxyphenyl group and 4-tert-butylphenyl group are more preferable.

In R ₁ , the linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent is not particularly limited, but examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, 2,2-dimethylpropyl group, cyclopentyl group, hexyl group, trifluoromethyl group and the like. A hydrogen atom in the alkyl group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, or the like. Among the alkyl groups for R ₁ , from the viewpoint of solubility, methyl group, ethyl group, isopropyl group and tert-butyl group are preferable, and methyl group, ethyl group and tert-butyl group are more preferable. A methyl group is more preferred.

Halogen atoms in R ₁ include fluorine, chlorine, bromine and iodine atoms.

In general formula (2) for R ₁ , each R ₃ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxy group, or a linear or branched alkoxy group having 1 to 5 carbon atoms, which may have a substituent. In general formula (2) for R ₁ , two adjacent R ₃ may be bonded to each other to form a naphthyl group.
As R ₃ in general formula (2) for R ₁ , hydrogen Atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, or an optionally substituted linear or branched chain having 1 to 5 carbon atoms An alkoxy group is preferred, and a hydrogen atom, methyl group, methoxy group and tert-butyl group are more preferred.

In R ₃ in general formula (2) for R ₁ , the optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms is the same as the alkyl group for R ₁ things are mentioned. The alkyl group for R ₃ in general formula (2) for R ₁ is a tert-butyl group or a methyl group from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having appropriate reactivity). is preferred, and a tert-butyl group is more preferred.

Examples of the halogen atom for R ₃ in general formula (2) for R ₁ include the same halogen atoms as those for R ₁ .

In R ₃ in general formula (2) for R ₁ , the linear or branched alkoxy group having 1 to 5 carbon atoms, which may have a substituent, is not particularly limited, but for example, methoxy group , ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, pentyloxy group and the like. A hydrogen atom in the alkoxy group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, a cyano group, or the like. Among the alkoxy groups for R ₃ in general formula (2) for R ₁ , methoxy groups are preferred from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having moderate reactivity).

In R ₃ in general formula (2) for R _{1 , two adjacent R 3 may} be bonded to each other to form a naphthyl group. A hydrogen atom in the naphthyl group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, a cyano group, or the like.

In the general formula (1), R ₂ will be explained.
In general formula (1), each R ₂ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, or the general formula ( 2) represents an aryl group. R ₂ in general formula (1) may combine with _each other to form a carbonyl group. From the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having appropriate reactivity), R ₂ is preferably each independently a hydrogen atom or a carbonyl group in which R ₂ is bonded to each other. , is more preferably a hydrogen atom.

The linear or branched alkyl group having 1 to 10 carbon atoms in R ₂ , which may have a substituent, includes the same alkyl group as the alkyl group for R ₁ . The alkyl group for R ₂ is preferably a methyl group, an ethyl group, or an isopropyl group from the viewpoint of exhibiting the effects of the present embodiment more effectively and reliably.

The halogen atom in R ₂ is the same as the halogen atom in R ₁ above.

In general formula (2) for R ₂ , each R ₃ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxy group, or a linear or branched alkoxy group having 1 to 5 carbon atoms, which may have a substituent. In general formula (2) for R ₂ , two adjacent R _3s may combine with each other to form a naphthyl group.
As R ₃ in general formula (2) for R ₂ , hydrogen Atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, or an optionally substituted linear or branched chain having 1 to 5 carbon atoms An alkoxy group is preferred, and a hydrogen atom, methyl group, methoxy group and tert-butyl group are more preferred.

In R ₃ in general formula (2) for R ₂ , the optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms is the same as the alkyl group for R ₁ things are mentioned. The alkyl group for R ₃ in general formula (2) for R ₂ is a tert-butyl group or a methyl group from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having appropriate reactivity). is preferred, and a tert-butyl group is more preferred.

Examples of the halogen atom for R ₃ in general formula (2) for R ₂ include the same halogen atoms as those for R ₁ .

In R ₃ in general formula (2) for R ₂ , the optionally substituted linear or branched alkoxy group having 1 to 5 carbon atoms is the same as the alkoxy group for R ₁ things are mentioned. Among the alkoxy groups for R ₃ in general formula (2) for R ₂ , methoxy groups are preferred from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having appropriate reactivity).

In R ₃ in general formula (2) for R _{2 , two adjacent R 3 may} combine with each other to form a naphthyl group. A hydrogen atom in the naphthyl group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, a cyano group, or the like.

Ar in the general formula (1) will be explained.
In general formula (1), Ar represents an aryl group represented by general formula (2). In general formula (2) for Ar, each R ₃ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, or a hydroxy group. , or represents a linear or branched alkoxy group having 1 to 5 carbon atoms, which may have a substituent. In general formula (2) for Ar, two adjacent R ₃ may combine with each other to form a naphthyl group.
As R ₃ in the general formula (2) for Ar, the effects of the present embodiment are more effectively and reliably exhibited (having moderate reactivity), and the volatile matter at the reaction temperature is small, so each independently In, a hydrogen atom, optionally substituted, linear or branched alkyl group having 1 to 10 carbon atoms, halogen atom, or optionally substituted, straight chain having 1 to 5 carbon atoms A chain or branched alkoxy group is preferred, and a hydrogen atom, methyl group, tert-butyl group, fluorine atom and methoxy group are more preferred.

In R ₃ in the general formula (2) for Ar, the linear or branched alkyl group having 1 to 10 carbon atoms, which may have a substituent, is the same as the alkyl group for R ₁ above. is mentioned. The alkyl group for R ₃ in the general formula (2) for Ar is a tert-butyl group and a methyl group from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having moderate reactivity). is preferred, and a tert-butyl group is more preferred.

Examples of the halogen atom for R ₃ in Ar in general formula (2) include the same halogen atoms as those for R ₁ . From the viewpoint of compound stability, the halogen atom for R ₃ in Ar in general formula (2) is preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.

In R ₃ in general formula (2) for Ar, the linear or branched alkoxy group having 1 to 5 carbon atoms, which may have a substituent, is the same as the alkoxy group for R ₁ above. is mentioned. Among the alkoxy groups for R ₃ in the general formula (2) for Ar, the effects of the present embodiment are more effectively and reliably exhibited (having moderate reactivity), and the volatile content at the reaction temperature is small. , is preferably a methoxy group.

In R ₃ in general formula (2) for Ar, two adjacent R ₃ may combine with each other to form a naphthyl group. A hydrogen atom in the naphthyl group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, a cyano group, or the like.

Ar is not particularly limited, but for example, phenyl group, xylyl group, mesityl group, naphthyl group, methylphenyl group, ethylphenyl group, tert-butylphenyl group, trimethylphenyl group, fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluorophenyl group, trifluorophenyl group, methoxyphenyl group, tolyl group and the like. Among them, the effects of the present embodiment are more effectively and reliably exhibited (having moderate reactivity), and the volatile matter at the reaction temperature is small, so phenyl group, 3-tert-butylphenyl group, 1,3 ,5-trimethylphenyl group, 3-fluorophenyl group and 3-methoxyphenyl group are preferred.

The compound (B) represented by the general formula (1) is represented by the following general formula (3) from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having moderate reactivity). It preferably contains a compound.

In general formula (3), each R ₄ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxy group, or It represents a linear or branched alkoxy group having 1 to 5 carbon atoms, which may have a substituent. In general formula (3), two adjacent R ₄ may be bonded to each other to form a naphthyl group.
From the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having moderate reactivity), R ₄ is a hydrogen atom or a linear chain having 1 to 10 carbon atoms, which may have a substituent. Alternatively, it is preferably a branched alkyl group, or an optionally substituted linear or branched alkoxy group having 1 to 5 carbon atoms, such as a hydrogen atom, a tert-butyl group, or a methoxy group. is more preferable.

The linear or branched alkyl group having 1 to 10 carbon atoms in R ₄ , which may have a substituent, includes the same alkyl group as the alkyl group for R ₁ . The alkyl group for R ₄ is preferably a tert-butyl group or a methyl group from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having moderate reactivity), and a tert-butyl group. It is more preferable to have

Halogen atoms in R ₄ include the same halogen atoms as in R ₁ .

The linear or branched alkoxy group having 1 to 5 carbon atoms in R ₄ , which may have a substituent, includes the same alkoxy groups as the above R ₁ . The alkoxy group for R ₄ is preferably a methoxy group from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment (having moderate reactivity).

In general formula (3), two adjacent R ₄ may be bonded to each other to form a naphthyl group. A hydrogen atom in the naphthyl group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, a cyano group, or the like.

Examples of the compound (B) represented by the general formula (1) include 1,3-diphenyl-1,3-propanedione, 1,3-bis(4-methoxyphenyl)-1,3-propanedione, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione, 1-phenyl-1,3-butanedione, 1,3-diphenylpropanetrione, 1-(2- mesitylene)-1,3-butanedione, 1-(4-fluorophenyl)-1,3-butanedione, and the like.

As the compound (B) represented by the general formula (1), a commercially available one may be used, for example, Parsol (registered trademark) 1789 (trade name) manufactured by DSM Nutrition Japan Co., Ltd. 9020 (trade name), Escalol (registered trademark) 517 (trade name) manufactured by Ashland, and the like.

These compounds (B) represented by general formula (1) can be used singly or in combination of two or more.

The content of the compound (B) represented by the general formula (1) in the resin composition is not particularly limited as long as the effect of the present embodiment is exhibited. It is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass, so that the reactivity of the radically polymerizable compound can be maintained well, and for example, a molded article having excellent chemical resistance, heat resistance, etc. can be obtained. It is more preferably 1 part by mass or more and 5.2 parts by mass or less, more preferably 1 part by mass or more and 5 parts by mass or less, and even more preferably 1 part by mass or more and less than 5 parts by mass. preferable. In the present embodiment, if the compound (B) represented by the general formula (1) is excessively added to the resin composition, the cross-linking reaction is inhibited, which may deteriorate chemical resistance and heat resistance.

[Cyanate ester compound, phenol compound, and epoxy compound]
As long as the effects of the present embodiment are exhibited, the resin composition of the present embodiment may optionally include various types of compounds other than the radically polymerizable compound (A), such as cyanate ester compounds, phenol compounds, or epoxy compounds. compound. For example, when heat resistance is required, the resin composition may contain a cyanate ester compound, a phenol compound, or an epoxy compound.
These compounds can be used singly or in admixture of two or more.

<Cyanate ester compound>
The cyanate ester compound is particularly limited as long as it is a compound or resin other than the radically polymerizable compound (A) having an aromatic moiety substituted with at least one cyanato group (cyanate ester group) in the molecule. isn't it.

For example, those represented by the general formula (17) can be mentioned.

In general formula (17), Ar ₁ represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. When there are more than one, they may be the same or different. Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. A group in which an alkyl group of 6 and an aryl group of 6 to 12 carbon atoms are bonded. The aromatic ring in Ra may have a substituent, and the substituents in Ar ₁ and Ra can be selected at arbitrary positions. p represents the number of cyanato groups bonded to Ar ₁ and is each independently an integer of 1-3. q represents the number of Ra atoms bonded to Ar ₁ , and is 4-p when Ar ₁ is a benzene ring, 6-p when it is a naphthalene ring, and 8-p when two benzene rings are single bonded. . t represents the average number of repetitions and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds with different t. When there are a plurality of X, each independently a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), a divalent nitrogen atom having 1 to 10 The organic group (for example -N-R-N- (where R represents an organic group)), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxide group (--OC(=O)O--), a sulfonyl group (--SO ₂ --), a divalent sulfur atom or a divalent oxygen atom.

The alkyl group for Ra in general formula (17) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group, etc.).
Further, the hydrogen atom in the alkyl group in the general formula (17) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group. good too.

Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl and 2,2'-dimethyl. propyl group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
Specific examples of aryl groups include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl and trifluorophenyl. groups, methoxyphenyl groups, o-, m- or p-tolyl groups, and the like. Further examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy groups.

Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of the general formula (17) include methylene group, ethylene group, trimethylene group, cyclopentylene group, cyclohexylene group, trimethylcyclohexylene group, biphenylyl methylene group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, phthalidodiyl group and the like. A hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, or the like.
Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of the general formula (17) include an imino group and a polyimide group.

Examples of the organic group for X in general formula (17) include those having structures represented by general formula (18) or (19) below.

In general formula (18), Ar ₂ represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when u is 2 or more, they may be the same or different. Rb, Rc, Rf, and Rg each independently have at least one hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or a phenolic hydroxy group represents an aryl group. Rd and Re are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group. be. u represents an integer of 0 to 5;

In general formula (19), Ar ₃ represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when v is 2 or more, they may be the same or different. Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, and a trifluoromethyl group. , or an aryl group substituted with at least one cyanato group. Although v represents an integer of 0 to 5, it may be a mixture of compounds with different v.

Further, X in general formula (17) includes a divalent group represented by the following formula.

Here, z represents an integer of 4-7. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Specific examples of Ar ₂ in general formula (18) and Ar ₃ in general formula (19) include two carbon atoms represented by general formula (18) or two oxygen atoms represented by general formula (19). , benzenediyl groups bonded to the 1,4-positions or 1,3-positions, the two carbon atoms or two oxygen atoms being 4,4′-positions, 2,4′-positions, 2,2′-positions, 2,2′-positions, biphenyldiyl groups bonded to the 3′-position, 3,3′-position, or 3,4′-position, and the two carbon atoms or two oxygen atoms attached to the 2,6-position, 1,5-position, 1 , 6-position, 1,8-position, 1,3-position, 1,4-position or 2,7-position.
The alkyl group and aryl group in Rb, Rc, Rd, Re, Rf and Rg in general formula (18) and Ri and Rj in general formula (19) are the same as those in general formula (17).

Specific examples of the cyanato-substituted aromatic compound represented by the general formula (17) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1 -cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1-cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- (4-cyanaphenyl)-2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1- Cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, methyl (4-cyanato) anatophenyl)sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, methyl 4-cyanatobenzoate ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2,6-di-tert-butylbenzene, 1,2-dicyanatobenzene, 1 ,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4-dimethylbenzene, 1,4-dicyanato-2,3 ,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2′-dicyanato-1,1′-binaphthyl, 1,3-,1,4-,1,5-,1,6 -,1,7-,2,3-,2,6- or 2,7-dicyanatocinaphthalene, 2,2'- or 4,4'-dicyanatobiphenyl, 4,4'-dicyanatooctafluoro biphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,1'-bis(4-cyanatophenyl)ethane, 1,1'-bis(4- anatophenyl)propane, 2,2′-bis(4-cyanatophenyl)propane, 2,2′-bis(4-cyanato-3-methylphenyl)propane, 2,2′-bis(2-cyanato-5 -biphenylyl)propane, 2,2′-bis(4-cyanatophenyl)hexafluoropropane, 2,2′-bis(4-cyanato-3,5-dimethylphenyl)propane, 1,1′-bis( 4-cyanatophenyl)butane, 1,1'-bis(4-cyanatophenyl)isobutane, 1,1'-bis(4-cyanatophenyl)pentane, 1,1'-bis(4-cyanatophenyl )-3-methylbutane, 1,1′-bis(4-cyanatophenyl)-2-methylbutane, 1,1′-bis(4-cyanatophenyl)-2,2′-dimethylpropane, 2,2′ -bis(4-cyanatophenyl)butane, 2,2'-bis(4-cyanatophenyl)pentane, 2,2'-bis(4-cyanatophenyl)hexane, 2,2'-bis(4- cyanatophenyl)-3-methylbutane, 2,2′-bis(4-cyanatophenyl)-4-methylpentane, 2,2′-bis(4-cyanatophenyl)-3,3′-dimethylbutane, 3,3′-bis(4-cyanatophenyl)hexane, 3,3′-bis(4-cyanatophenyl)heptane, 3,3′-bis(4-cyanatophenyl)octane, 3,3′- Bis(4-cyanatophenyl)-2-methylpentane, 3,3′-bis(4-cyanatophenyl)-2-methylhexane, 3,3′-bis(4-cyanatophenyl)-2,2 '-dimethylpentane, 4,4'-bis(4-cyanatophenyl)-3-methylheptane, 3,3'-bis(4-cyanatophenyl)-2-methylheptane, 3,3'-bis( 4-cyanatophenyl)-2,2'-dimethylhexane, 3,3'-bis(4-cyanatophenyl)-2,4-dimethylhexane, 3,3'-bis(4-cyanatophenyl)- 2,2,4-trimethylpentane, 2,2′-bis(4-cyanatophenyl)-1,1′,1″,3,3′,3″-hexafluoropropane, bis(4-cyanatophenyl) anatophenyl)phenylmethane, 1,1′-bis(4-cyanatophenyl)-1-phenylethane , bis(4-cyanatophenyl)biphenylmethane, 1,1′-bis(4-cyanatophenyl)cyclopentane, 1,1′-bis(4-cyanatophenyl)cyclohexane, 2,2′-bis( 4-cyanato-3-isopropylphenyl)propane, 1,1′-bis(3-cyclohexyl-4-cyanatophenyl)cyclohexane, bis(4-cyanatophenyl)diphenylmethane, bis(4-cyanatophenyl)-2 , 2′-dichloroethylene, 1,3-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,1′-bis(4-cyanatophenyl)-3,3′,5-trimethylcyclohexane, 4-[bis(4-cyanatophenyl)methyl]biphenyl, 4,4′-dicyanatobenzophenone, 1, 3-bis(4-cyanatophenyl)-2-propen-1-one, bis(4-cyanatophenyl) ether, bis(4-cyanatophenyl) sulfide, bis(4-cyanatophenyl) sulfone, 4 - cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis-(4-cyanatophenyl) carbonate, 1,3-bis(4-cyanatophenyl) adamantane, 1,3-bis(4-cyanatophenyl)-5,7-dimethyladamantane, 3,3′-bis(4-cyanatophenyl)isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3′-bis(4-cyanato-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9,9′-bis(4-cyanatophenyl)fluorene, 9,9'-bis(4-cyanato-3-methylphenyl)fluorene, 9,9'-bis(2-cyanato-5-biphenylyl)fluorene, tris(4-cyanatophenyl)methane, 1,1' ,1″-tris(4-cyanatophenyl)ethane, 1,1′,3-tris(4-cyanatophenyl)propane, α,α′,α″-tris(4-cyanatophenyl)- 1-ethyl-4-isopropylbenzene, 1,1′,2,2′-tetrakis(4-cyanatophenyl)ethane, tetrakis(4-cyanatophenyl)methane, 2,4,6-tris(N-methyl -4-cyanatoanilino)-1,3,5-triazine, 2,4-bis(N-methyl ru-4-cyanatoanilino)-6-(N-methylanilino)-1,3,5-triazine, bis(N-4-cyanato-2-methylphenyl)-4,4′-oxydiphthalimide, bis(N- 3-cyanato-4-methylphenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanatophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanato-2-methyl Phenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4-cyanatobenzyl)isocyanurate, 2-phenyl-3,3'-bis(4-cyanatophenyl ) phthalimidine, 2-(4-methylphenyl)-3,3′-bis(4-cyanatophenyl)phthalimidine, 2-phenyl-3,3-bis(4-cyanato-3-methylphenyl)phthalimidine, 1- methyl-3,3'-bis(4-cyanatophenyl)indolin-2-one and 2-phenyl-3,3'-bis(4-cyanatophenyl)indolin-2-one.

These cyanate ester compounds can be used singly or in combination of two or more.

Further, another specific example of the cyanate ester compound represented by the general formula (17) includes phenol novolak resin and cresol novolac resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin or Formaldehyde compound such as paraformaldehyde reacted in an acidic solution), trisphenol novolac resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorene novolak resin (fluorenone compound and 9 ,9'-bis(hydroxyaryl)fluorenes in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins (Ar ₄ -( A bishalogenomethyl compound such as CH ₂ Y) ₂ (Ar ₄ represents a phenyl group and Y represents a halogen atom; hereinafter the same applies in this paragraph) and a phenol compound are reacted with an acidic catalyst or without a catalyst. A product obtained by reacting a bis(alkoxymethyl) compound represented by Ar ₄ —(CH ₂ OR) ₂ (R represents an alkyl group) with a phenol compound in the presence of an acidic catalyst. Alternatively, a bis(hydroxymethyl) compound represented by Ar ₄ —(CH ₂ OH) ₂ and a phenolic compound are reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and phenol compound), phenol-modified xylene formaldehyde resin (by a known method, a xylene formaldehyde resin and a phenol compound are reacted in the presence of an acidic catalyst), modified naphthalene formaldehyde resin (by a known method , a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound reacted in the presence of an acidic catalyst), a phenol-modified dicyclopentadiene resin, a phenol resin having a polynaphthylene ether structure (a phenolic hydroxy group is added by a known method, Polyhydric hydroxynaphthalene compounds having two or more in one molecule are dehydrated and condensed in the presence of a basic catalyst), etc., cyanated by the same method as described above, and these prepolymers. A polymer etc. are mentioned. These are not particularly limited. These cyanate ester compounds can be used singly or in combination of two or more.

Methods for producing these cyanate ester compounds are not particularly limited, and known methods can be used. An example of such a production method includes obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton, and modifying the hydroxy group by a known technique to form a cyanate. Methods for cyanating a hydroxy group include, for example, the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

Resin cured products using these cyanate ester compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

The content of the cyanate ester compound is not particularly limited, and is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition.

<Phenol compound>
As the phenol compound, generally known phenol compounds or resins other than the radically polymerizable compound (A) having two or more hydroxyl groups in one molecule can be used. For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl Aralkyl-type phenolic resins, cresol novolac-type phenolic resins, polyfunctional phenolic resins, naphthol resins, naphthol novolak resins, polyfunctional naphthol resins, anthracene-type phenolic resins, naphthalene skeleton-modified novolac-type phenolic resins, phenol aralkyl-type phenolic resins, naphthol aralkyl-type phenolic resins Phenol resins, dicyclopentadiene type phenol resins, biphenyl type phenol resins, alicyclic phenol resins, polyol type phenol resins, phosphorus-containing phenol resins, polymerizable unsaturated hydrocarbon group-containing phenol resins, hydroxyl group-containing silicone resins, and the like. can be used, but is not particularly limited. These phenol compounds can be used singly or in admixture of two or more.

The content of the phenol compound is not particularly limited, and is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition.

<Epoxy compound>
The epoxy compound is not particularly limited as long as it is a compound or resin other than the radically polymerizable compound (A) having two or more epoxy groups in one molecule, and known compounds can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, 3 Functional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin Resins, phosphorus-containing epoxy resins, compounds obtained by epoxidizing double bonds such as glycidylamine, glycidyl esters and butadiene, and compounds obtained by reacting hydroxyl-containing silicon resins with epichlorohydrin, and the like. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin , biphenyl type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, and naphthol aralkyl type epoxy resins can be preferably used. These epoxy compounds can be used individually by 1 type or in combination of 2 or more types. Also, the epoxy compound may be in any form of monomer, oligomer and resin.

The content of the epoxy compound is not particularly limited, and is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition.

[Inorganic filler]
The resin composition of the present embodiment can contain an inorganic filler, if necessary, as long as the effects of the present embodiment are exhibited. The use of an inorganic filler is preferable because it can improve the flame resistance and thermal conductivity of the resin composition and reduce the thermal expansion coefficient.
Examples of inorganic fillers include, but are not limited to, silica (e.g., fused silica), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, aluminum nitride, etc.), magnesium compounds (e.g., magnesium oxide, hydroxide magnesium, etc.), calcium compounds (e.g., calcium carbonate, calcium sulfate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), boron nitride, barium sulfate, talc (e.g., natural talc, calcined talc, etc.), mica (mica), glass (for example, short fiber glass, spherical glass, fine powder glass (for example, E glass, T glass, D glass, etc.), etc.). One of these inorganic fillers may be used alone, or two or more thereof may be used in any combination and ratio.

Among these, from the viewpoint of improving the flame resistance of the resin composition and reducing the coefficient of thermal expansion, the inorganic fillers include silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide and magnesium hydroxide. is preferred, silica is more preferred, and among these, fused silica is particularly preferred from the viewpoint of increasing filling properties and low thermal expansion. Specific examples of fused silica include SFP-120MC (trade name) and SFP-130MC (trade name) manufactured by Denka Co., Ltd. SC1050-MLQ (trade name) and SC2050-MNU (trade name) manufactured by Admatechs Co., Ltd. (trade name), SC2050-MTX (trade name), SE2053-SQ (trade name), SC-4500SQ (trade name) and SC-5500SQ (trade name).

Although the average particle size of the inorganic filler is not particularly limited, it is preferably 3 μm or less, more preferably 1 μm or less, from the viewpoint of miniaturization of circuits. The lower limit of the average particle size is not particularly limited, but may be 10 nm, for example.
In addition, in this specification, "average particle size" shall mean a median size. Here, the median diameter is the volume of particles on the larger particle diameter side and the volume of particles on the smaller particle diameter side when the particle size distribution of powder is divided into two based on a certain particle size. means a particle size such that each accounts for 50% of the total powder. The average particle size (median size) is measured by a wet laser diffraction/scattering method.

The content of the inorganic filler is not particularly limited, but from the viewpoint of improving the flame resistance of the resin composition and reducing the coefficient of thermal expansion, it is 400 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. is preferably 300 parts by mass or less, and even more preferably 250 parts by mass or less. In addition, the content of the inorganic filler is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 50 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is 100 parts by mass or more. When two or more kinds of inorganic fillers are used in combination, the total amount thereof preferably satisfies the above content range.

[Other ingredients]
The resin composition of the present embodiment includes a radically polymerizable compound (A), a compound (B) represented by the general formula (1), a cyanate ester compound, a phenol compound, an epoxy compound, and an inorganic filler. , may contain one or more other components.

<Silane coupling agent>
The resin composition of the present embodiment may contain a silane coupling agent for the purpose of improving heat resistance after moisture absorption and improving adhesiveness. The silane coupling agent is not particularly limited as long as it is generally used for surface treatment of inorganic substances. Specific examples include epoxy-based silane coupling agents (e.g., 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane), vinylsilane-based silane coupling agents (e.g., vinyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, etc.), phenylaminosilane-based silane coupling agents (e.g., N-phenyl-3-aminopropyltrimethoxysilane, etc.) ), phenylsilane-based silane coupling agents and imidazolesilane-based silane coupling agents. One of these silane coupling agents may be used alone, or two or more thereof may be used in any combination and ratio.

As the silane coupling agent, commercially available products can be used. product name) and the like.

The content of the silane coupling agent is not particularly limited, but from the viewpoint of moisture absorption heat resistance and adhesiveness, it is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. , more preferably 0.1 to 15 parts by mass. When two or more silane coupling agents are used in combination, the total amount of these agents is preferably within the above range.

<Wetting and dispersing agent>
The resin composition of the present embodiment may contain a wetting and dispersing agent for the purpose of improving the manufacturability of the laminate and improving the dispersibility of the inorganic filler. The wetting and dispersing agent is not limited as long as it is a wetting and dispersing agent that is generally used for paints and the like. Specific examples include Disperbyk (registered trademark) -110 (trade name), -111 (trade name), -180 (trade name), -161 (trade name), BYK manufactured by Big Chemie Japan Co., Ltd. -W996 (trade name), -W9010 (trade name), -W903 (trade name), and the like. One of these wetting and dispersing agents may be used alone, or two or more thereof may be used in any combination and ratio.

The content of the wetting and dispersing agent is not particularly limited, but from the viewpoint of improving the manufacturability of the laminate, it is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler. It is more preferably 0.1 parts by mass or more and 3 parts by mass or less. In addition, when two or more kinds of wetting and dispersing agents are used in combination, it is preferable that the total amount of them is within the range of the above content.

<Silicone rubber powder>
The resin composition of the present embodiment may contain silicone rubber powder. Silicone rubber powder acts as a flame-retardant aid that delays the burning time and enhances the flame-retardant effect.
Examples of silicone rubber powder include, but are not limited to, finely powdered polymethylsilsesquioxane in which siloxane bonds are crosslinked in a three-dimensional network, and addition of vinyl group-containing dimethylpolysiloxane and methylhydrogenpolysiloxane. Polymethylsilsesquioxane in which siloxane bonds are crosslinked in a three-dimensional network is coated on the surface of a finely powdered polymer, or a fine powder obtained by addition polymerization of vinyl group-containing dimethylpolysiloxane and methylhydrogenpolysiloxane. Also, the surface of an inorganic support is coated with polymethylsilsesquioxane in which siloxane bonds are crosslinked in a three-dimensional network.

Moreover, as the silicone rubber powder, a silicone composite powder obtained by disposing a silicone resin layer on the surface of the silicone rubber powder may be used. Commercially available products such as KMP-605 (trade name) and KMP-600 (trade name) manufactured by Shin-Etsu Silicone Co., Ltd. can be used as such silicone composite powders.

The average particle size (D50) of the silicone rubber powder is not particularly limited, but considering the dispersibility, the average particle size (D50) is preferably 1 to 15 μm.

Although the content of the silicone rubber powder is not particularly limited, it is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass based on 100 parts by mass of the inorganic filler, from the viewpoint of moldability. When two or more silicone rubber powders are used in combination, the total amount of these powders is preferably within the above range.

<Curing accelerator>
The resin composition of the present embodiment may contain a curing accelerator for the purpose of adjusting the curing speed. The curing accelerator is not particularly limited as long as it is known as a curing accelerator for maleimide compounds and is commonly used. Specific examples of curing accelerators include imidazoles and derivatives thereof (e.g., 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-tri phenylimidazole, etc.), tertiary amines (e.g., triethylamine, tributylamine), etc., and various organic peroxides as thermal radical polymerization initiators (e.g., dicumyl peroxide, di(2-tert-butylperoxyisopropyl ) benzene, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide). One of these curing accelerators may be used alone, or two or more thereof may be used in any combination and ratio.

The content of the curing accelerator is not particularly limited, but from the viewpoint of adjusting the curing speed, it is preferably 0.001 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. It is preferably 0.005 parts by mass or more and 2 parts by mass or less. In addition, when two or more curing accelerators are used in combination, the total amount thereof is preferably within the range of the above content.

<Additive>
The resin composition of the present embodiment may contain various additives for various purposes as long as the desired properties are not impaired. Examples of additives include flexibility imparting components, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, Leveling agents, brighteners, flame retardants, and the like. One of these additives may be used alone, or two or more of them may be used in any combination and ratio. In the resin composition of the present embodiment, the content of other additives is not particularly limited, but usually 0.1 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. It is below.

<Solvent>
The resin composition of this embodiment may further contain a solvent. By containing a solvent, the resin composition of the present embodiment has a reduced viscosity during preparation of the resin composition, further improved handling properties (handleability), and further improved impregnation properties into the substrate. There is a tendency.

The solvent is not particularly limited as long as it can dissolve some or all of the components in the resin composition, but examples include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g., toluene, xylene, etc.), amides (eg, dimethylformaldehyde, etc.), propylene glycol monomethyl ether and its acetate, and the like. These solvents are used singly or in combination of two or more.

[Method for producing resin composition]
Examples of the method for producing the resin composition of the present embodiment include a method of collectively or sequentially blending each component with a solvent and stirring the mixture. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading are used.

[Cured product]
The cured product of the present embodiment contains the resin composition of the present embodiment and is obtained by curing the resin composition of the present embodiment. The method for producing the cured product is not particularly limited. For example, the resin composition may be melted or dissolved in a solvent, poured into a mold, and cured under normal conditions using heat, light, or the like. can be done. In the case of thermosetting, the curing temperature is not particularly limited, but is preferably in the range of 120 to 300° C. from the viewpoint of efficient curing and prevention of deterioration of the obtained cured product. In the case of photocuring, the wavelength range of light is not particularly limited, but is preferably in the range of 100 nm to 500 nm where curing proceeds efficiently with a photopolymerization initiator or the like.

[Molded body]
The molded article of the present embodiment contains the resin composition of the present embodiment and is obtained by molding the resin composition of the present embodiment. Since the resin composition of the present embodiment has excellent moldability, various molded articles can be suitably obtained. The molded article of the present embodiment can be used for electrical and electronic equipment, OA equipment, optical media, automobile parts, building materials, and the like.

The molding method of the molded article of the present embodiment is not particularly limited, and examples thereof include compression molding, transfer molding, injection molding, blow molding, extrusion molding, laminate molding, and calender molding.

[Use]
The resin composition of this embodiment can exhibit excellent moldability. Therefore, the resin composition of the present embodiment can be suitably used as electronic materials such as laminates, prepregs, resin sheets, metal foil-clad laminates, printed wiring boards, and semiconductor package constituent materials.

[Prepreg]
The prepreg of this embodiment includes a substrate and the resin composition of this embodiment impregnated or applied to the substrate. The prepreg of the present embodiment may be a prepreg obtained by a known method. Specifically, after impregnating or applying the resin composition of the present embodiment to a substrate, the temperature is maintained at 100 to 200°C. It may be obtained by semi-curing (to B-stage) by heating and drying.

The prepreg of the present embodiment also includes a cured product obtained by thermally curing a semi-cured prepreg under the conditions of a heating temperature of 180 to 230° C. and a heating time of 60 to 180 minutes.

The content of the resin composition in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, and still more preferably 40 to 80% by volume in terms of solid content with respect to the total amount of the prepreg. %. When the content of the resin composition is within the above range, moldability tends to be further improved. The solid content here refers to a component of the resin composition in the prepreg from which the solvent has been removed. For example, the filler is included in the solid content of the prepreg.

The substrate is not particularly limited, and examples thereof include known substrates used as materials for various printed wiring boards. Specific examples of the substrate include glass substrates, inorganic substrates other than glass (for example, inorganic substrates composed of inorganic fibers other than glass such as quartz), organic substrates (for example, wholly aromatic polyamide, polyester , polyparaphenylenebenzoxazole, and organic base materials composed of organic fibers such as polyimide). These substrates are used singly or in combination of two or more. Among these, a glass substrate is preferable from the viewpoint of being more excellent in dimensional stability under heating.

Examples of fibers constituting the glass base material include fibers of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, HME glass, and the like. Among these, the fibers that make up the glass substrate are made of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass, from the viewpoint of being more excellent in strength and low water absorption. One or more fibers selected from the group are preferred.

The form of the substrate is not particularly limited, but examples thereof include forms such as woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave, etc. are known, and it is possible to appropriately select and use from these known ones depending on the intended use and performance. . In addition, glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used. The thickness and mass of the base material are not particularly limited, but usually about 0.01 to 0.1 mm is suitably used.

[Resin sheet]
The resin sheet of this embodiment includes a support and the resin composition of this embodiment disposed on the surface of the support. The resin sheet of the present embodiment may be formed, for example, by applying the resin composition of the present embodiment to one side or both sides of a support. The resin sheet of the present embodiment can be produced, for example, by directly coating a support such as a metal foil or film with a resin composition used for prepreg or the like and drying the resin composition.

Although the support is not particularly limited, for example, a known support used for various printed wiring board materials can be used, and a resin sheet or metal foil is preferable. Examples of resin sheets and metal foils include resin sheets such as polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, etc. and metal foils such as aluminum foil, copper foil and gold foil. Among these, the support is preferably an electrolytic copper foil or a PET film.

The resin sheet of the present embodiment can be obtained, for example, by applying the resin composition of the present embodiment to a support and then semi-curing it (making it B-stage). The method for producing the resin sheet of the present embodiment is generally preferably a method for producing a composite of a B-staged resin and a support. Specifically, for example, after the resin composition is applied to a support such as a copper foil, it is semi-cured by heating in a dryer at 100 to 200° C. for 1 to 60 minutes to produce a resin sheet. methods and the like. The amount of the resin composition adhered to the support is preferably in the range of 1.0 to 300 μm in terms of resin thickness of the resin sheet. The resin sheet of this embodiment can be used as a build-up material for printed wiring boards.

[Metal foil clad laminate]
The metal foil-clad laminate of the present embodiment includes a laminate formed of one or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a metal foil disposed on one or both sides of the laminate. including. The laminate may be formed of one prepreg or resin sheet, or may be formed of a plurality of prepregs and/or resin sheets.

The metal foil (conductor layer) may be any metal foil that is used for various printed wiring board materials, and examples thereof include metal foils of copper, aluminum, and the like. Copper foil, such as foil, is mentioned. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

The molding method and molding conditions for the metal foil-clad laminate are not particularly limited, and general techniques and conditions for printed wiring board laminates and multilayer boards can be applied. For example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when molding a laminate or a metal foil-clad laminate. In the molding of laminates or metal foil clad laminates (laminate molding), the temperature is generally 100 to 300° C., the pressure is 2 to 100 kgf/cm ² , and the heating time is generally in the range of 0.05 to 5 hours. is. Furthermore, if desired, post-curing can be performed at a temperature of 150-300°C. Particularly when a multistage press is used, the temperature is preferably 200 to 250° C., the pressure is 10 to 40 kgf/cm ² , and the heating time is 80 to 130 minutes, from the viewpoint of sufficiently accelerating the curing of the prepreg. More preferably, the pressure is 25 to 35 kgf/cm ² and the heating time is 90 to 120 minutes. Moreover, it is also possible to form a multilayer board by laminating a prepreg and a wiring board for an inner layer separately prepared in combination.

[Printed wiring board]
The printed wiring board of this embodiment includes an insulating layer formed of one or more selected from the group consisting of the prepreg and resin sheet of this embodiment, and a conductor layer formed on the surface of the insulating layer. The printed wiring board of the present embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer.

Specifically, the printed wiring board of this embodiment can be produced, for example, by the following method. First, the metal foil-clad laminate of this embodiment is prepared. An inner layer board having a conductor layer (inner layer circuit) is produced by etching the metal foil of the metal foil clad laminate into a predetermined wiring pattern. Next, on the surface of the conductor layer (internal circuit) of the inner layer substrate, a predetermined number of insulating layers and a metal foil for the outer layer circuit are laminated in this order, and heat-pressed for integral molding (laminate molding). A laminate is obtained. The laminate molding method and molding conditions are the same as the laminate molding method and molding conditions for the laminate and the metal foil-clad laminate described above. Next, the laminate is perforated for through holes and via holes, and the wall surfaces of the holes thus formed are plated with a metal film for conducting the conductor layer (internal circuit) and the metal foil for the outer layer circuit. to form Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to form an outer layer substrate having a conductor layer (outer layer circuit). A printed wiring board is thus manufactured.

In the case of not using a metal foil-clad laminate, a printed wiring board may be produced by forming a conductor layer to form a circuit on the insulating layer. At this time, an electroless plating technique can be used to form the conductor layer.

[Semiconductor device]
The semiconductor device of this embodiment includes an interlayer insulating layer containing the resin composition of this embodiment, and can be specifically manufactured by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip on the conductive portion of the printed wiring board of the present embodiment. Here, the conductive portion is a portion of the printed wiring board that transmits an electric signal, and the portion may be a surface or an embedded portion. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The semiconductor chip mounting method for manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively. Examples include a mounting method using a bare buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like.

A semiconductor device can also be manufactured by forming an interlayer insulating layer containing the resin composition of the present embodiment on a semiconductor chip or a substrate on which a semiconductor chip is mounted. The shape of the substrate on which the semiconductor chips are mounted may be wafer-like or panel-like. After formation, it can be manufactured using the same method as the multilayer printed wiring board described above.

[Encapsulation material]
The encapsulating material of the present embodiment contains the resin composition of the present embodiment. As a method for producing the sealing material, generally known methods can be appropriately applied, and there is no particular limitation. For example, a sealing material can be produced by mixing the resin composition of the present embodiment with various known additives or solvents generally used for sealing material applications using a known mixer. can. The method of adding various components and solvents during mixing is not particularly limited and generally known methods can be applied as appropriate.

[Fiber-reinforced composite material]
The fiber-reinforced composite material of the present embodiment contains the resin composition of the present embodiment, preferably the resin composition of the present embodiment, and reinforcing fibers. As the reinforcing fiber, generally known ones can be used, and there is no particular limitation. Specific examples thereof include glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, carbon fiber, aramid fiber, boron fiber, PBO fiber, high Examples include strong polyethylene fibers, alumina fibers, and silicon carbide fibers. The form and arrangement of the reinforcing fibers are not particularly limited, and can be appropriately selected from woven fabrics, non-woven fabrics, mats, knits, braids, unidirectional strands, rovings, chopped and the like. In addition, as a form of reinforcing fibers, preforms (laminated fabric base fabrics made of reinforcing fibers, or those integrated by stitching with stitch threads, or fiber structures such as three-dimensional fabrics and braids) can be applied. can also

As a method for producing these fiber-reinforced composite materials, generally known methods can be appropriately applied, and there is no particular limitation. Specific examples thereof include the liquid composite molding method, the resin film infusion method, the filament winding method, the hand layup method, the pultrusion method, and the like. Among these methods, the resin transfer molding method, which is one of the liquid composite molding methods, allows materials other than preforms, such as metal plates, foam cores, and honeycomb cores, to be set in advance in the mold. Since it can be applied to various applications, it is preferably used when mass-producing composite materials with relatively complicated shapes in a short time.

〔glue〕
The adhesive of this embodiment contains the resin composition of this embodiment. As the method for producing the adhesive, generally known methods can be appropriately applied, and there is no particular limitation. For example, an adhesive can be produced by mixing the resin composition of the present embodiment with various known additives or solvents generally used for adhesives using a known mixer. The method of adding the cyanate ester compound, various additives, and solvent during mixing is not particularly limited and generally known methods can be appropriately applied.

〔others〕
Since the resin composition of the present embodiment has excellent moldability, it can be used as a highly functional polymer material, an electrical insulating material, a sealing material, an adhesive, a laminate material, a resist, a build-up laminate material, as well as civil engineering.・Preferably used for fixing materials, structural members, reinforcing agents, molding materials, etc. in fields such as construction, electricity/electronics, automobiles, railroads, ships, aircraft, sporting goods, and arts and crafts. Among these, it is suitable for electrical insulating materials, semiconductor sealing materials, adhesives for electronic parts, aircraft structural members, satellite structural members, and railway vehicle structural members.

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

〔Evaluation methods〕
(1) Automatic gel time (seconds)
Using an automatic resin curing time measuring device (2238-001 (trade name) manufactured by Cyber Co., Ltd.), the varnish (measurement solution: 0.5 mL) prepared in Examples or Comparative Examples is cured (gel , torque judgment value: 15%) was measured.

(2) Elastic modulus loss (DMA) (%)
The flexural modulus at 27° C. and 260° C. was measured according to JIS C6481, and the elastic modulus loss rate was calculated. Specifically, after removing the copper foil on both sides of the metal foil-clad laminate (50 mm × 25 mm × 0.8 mm) by etching, using an autograph (AG-Xplus manufactured by Shimadzu Corporation), the temperature was 27 ° C. and flexural modulus at 260°C were measured. The difference between the obtained bending elastic modulus (a) at 27° C. and the elastic modulus (b) of the hot bending elastic modulus at 260° C. was calculated by the following formula.
Elastic modulus loss = [(b)/(a)] x 100

(3) Linear thermal expansion coefficient (ppm/°C)
After removing the copper foil on both sides of the metal foil clad laminate (4.5 mm × 30 mm × 0.1 mm) by etching, a thermomechanical analyzer (manufactured by TA Instruments) was used to change the temperature from 40 ° C. to 340 ° C. at 10 ° C. per minute. and measured the coefficient of linear expansion in the plane direction from 60°C to 120°C. The measurement direction was the longitudinal direction (Warp) of the glass cloth of the laminate.

(Synthesis example 1)
α-naphthol aralkyl type phenolic resin (SN495V (trade name) manufactured by Nippon Steel Chemical Co., Ltd., OH group equivalent: 236 g/eq., Naphthol aralkyl repeating unit number n is 1 to 5.) 0 .47 mol (as OH group) was dissolved in 500 mL of chloroform, and 0.7 mol of triethylamine was added to this solution (solution 1).
While maintaining the temperature at −10° C., Solution 1 was added dropwise to 300 g of a chloroform solution of 0.93 mol of cyanogen chloride over 1.5 hours, followed by stirring for 30 minutes after the dropwise addition.
After that, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise into the reactor and stirred for 30 minutes to complete the reaction. After the by-produced triethylamine hydrochloride was filtered off from the reaction solution, the resulting filtrate was washed with 500 mL of 0.1N hydrochloric acid, and then washed with 500 mL of water four times. This was dried with sodium sulfate, evaporated at 75° C., and degassed under reduced pressure at 90° C. to obtain a brown solid α-naphthol aralkyl cyanate resin (SNCN). When the obtained α-naphthol aralkyl cyanate ester resin was analyzed by infrared absorption spectrum, absorption of the cyanate ester groups near 2264 cm ⁻¹ was confirmed.

(Example 1)
38 parts by mass of alkenyl-substituted nadimide (BANI-M (trade name) manufactured by Maruzen Petrochemical Co., Ltd.) and 2,2′-bis{4-(4-maleimidophenoxy)phenyl}propane (K-I Kasei Co., Ltd.) ) BMI-80 (trade name)) 31 parts by mass, a maleimide compound (Daiwa Kasei Kogyo Co., Ltd. BMI-2300 (trade name), R ₅ in the above formula (5) is all a hydrogen atom, n ₂ is 1 to 3 maleimide compound) 31 parts by mass and 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.2 parts by mass are mixed to form a resin composition After that, methyl ethyl ketone was added to this resin composition to obtain a varnish having a concentration of 50% by mass. Varnish gel time was evaluated using this varnish. As a result, it was 123 seconds.
Also, this varnish was impregnated and coated on an E-glass woven cloth, and dried by heating at 160° C. for 3 minutes to obtain a prepreg having a resin composition content of 38% by mass (in terms of solid content).

(Example 2)
Instead of 2.2 parts by mass of 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.), 1,3-bis(4-methoxyphenyl)-1,3-propanedione ( Varnish (concentration: 50% by mass) and prepreg (resin composition content: 38% by mass (solid minutes conversion)) was obtained. Using this varnish, the varnish gel time was evaluated in the same manner as in Example 1. As a result, it was 119 seconds.

(Example 3)
1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2.2 parts by mass, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl) -Varnish (concentration: 50% by mass) and prepreg (resin composition Content: 38% by mass (in terms of solid content)). Using this varnish, the varnish gel time was evaluated in the same manner as in Example 1. As a result, it was 116 seconds.

(Example 4)
1,3-diphenylpropanetrione (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2.2 parts by mass of 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.)2. A varnish (concentration: 50% by mass) and a prepreg (resin composition content: 38% by mass (in terms of solid content)) were obtained in the same manner as in Example 1, except that 4 parts by mass was used. Using this varnish, the varnish gel time was evaluated in the same manner as in Example 1. As a result, it was 98 seconds.

(Example 5)
1-phenyl-1,3-butanedione (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2.2 parts by mass of 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.) A varnish (concentration: 50% by mass) and a prepreg (resin composition content: 38% by mass (in terms of solid content)) were obtained in the same manner as in Example 1, except that 1.6 parts by mass was used. Using this varnish, the varnish gel time was evaluated in the same manner as in Example 1. As a result, it was 117 seconds.

(Example 6)
Instead of 2.2 parts by mass of 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-(2-mesitylene)-1,3-butanedione (Tokyo Chemical Industry Co., Ltd. ) company) in the same manner as in Example 1, except that 2.0 parts by mass of varnish (concentration: 50% by mass) and prepreg (resin composition content: 38% by mass (in terms of solid content)) were added. Obtained. Using this varnish, the varnish gel time was evaluated in the same manner as in Example 1. As a result, it was 97 seconds.

(Example 7)
Instead of 2.2 parts by mass of 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-(4-fluorophenyl)-1,3-butanedione (Tokyo Chemical Industry Co., Ltd. ( Co., Ltd.) was used in the same manner as in Example 1 except that 1.8 parts by mass of varnish (concentration: 50% by mass) and prepreg (resin composition content: 38% by mass (in terms of solid content)) got Using this varnish, the varnish gel time was evaluated in the same manner as in Example 1. As a result, it was 96 seconds.

(Comparative example 1)
38 parts by mass of alkenyl-substituted nadimide (BANI-M (trade name) manufactured by Maruzen Petrochemical Co., Ltd.) and 2,2′-bis{4-(4-maleimidophenoxy)phenyl}propane (K-I Kasei Co., Ltd.) ) BMI-80 (trade name)) 31 parts by mass, a maleimide compound (Daiwa Kasei Kogyo Co., Ltd. BMI-2300 (trade name), R ₅ in the above formula (5) is all a hydrogen atom, n ₂ 31 parts by mass of a maleimide compound having a value of 1 to 3) were mixed to form a resin composition, and methyl ethyl ketone was added to the resin composition to obtain a varnish having a concentration of 50% by mass. Varnish gel time was evaluated using this varnish. As a result, it was 78 seconds.
Also, this varnish was impregnated and coated on an E-glass woven cloth, and dried by heating at 160° C. for 3 minutes to obtain a prepreg having a resin composition content of 38% by mass (in terms of solid content).

(Comparative example 2)
Instead of 2.2 parts by mass of 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4′-dimethoxybenzyl (manufactured by Tokyo Chemical Industry Co., Ltd., p- Anisil) was used in the same manner as in Example 1, except that 2.7 parts by mass of anisil) was used to obtain a varnish (concentration: 50% by mass) and a prepreg (resin composition content: 38% by mass (in terms of solid content)). . Using this varnish, the varnish gel time was evaluated in the same manner as in Example 1. As a result, it was 75 seconds.

(Comparative Example 3)
Instead of 2.2 parts by mass of 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.1 parts by mass of benzyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were used. A varnish (concentration: 50% by mass) and a prepreg (resin composition content: 38% by mass (in terms of solid content)) were obtained in the same manner as in Example 1 except for this. Using this varnish, the varnish gel time was evaluated in the same manner as in Example 1. As a result, it was 89 seconds.

(Comparative Example 4)
3,5'-heptanedione (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2.2 parts by mass of 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.)1. A varnish (concentration: 50% by mass) and a prepreg (resin composition content: 38% by mass (as solid content)) were obtained in the same manner as in Example 1, except that 3 parts by mass were used. Using this varnish, the varnish gel time was evaluated in the same manner as in Example 1. As a result, it was 77 seconds.

(Example 8)
10 parts by mass of the α-naphthol aralkyl cyanate ester resin (SNCN) obtained in Synthesis Example 1, 34 parts by mass of alkenyl-substituted nadimide (BANI-M (trade name) manufactured by Maruzen Petrochemical Co., Ltd.), 46 parts by mass of a maleimide compound (BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd., a maleimide compound in which all R ₅ in the formula (5) are hydrogen atoms and n ₂ is 1 to 3), and biphenyl Aralkyl-type epoxy resin (Nippon Kayaku Co., Ltd. NC-3000FH (trade name), epoxy equivalent: 290 g / eq.) 10 parts by mass, fused silica (Denka Co., Ltd. SFP-130MC, average particle size : 0.7 μm) 100 parts by mass, fused silica (SC-4500SQ manufactured by Admatechs Co., Ltd., average particle size: 1.3 μm) 100 parts by mass, silicone composite powder (KMP manufactured by Shin-Etsu Chemical Co., Ltd. -605 (trade name)) 25 parts by mass, a wetting and dispersing agent (DISPERBYK-161 manufactured by BYK Chemie Japan Co., Ltd.) 1 part by mass, and a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. KBM-403 (product Name))) 5 parts by mass and 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.) 3 parts by mass After mixing to form a resin composition, methyl ethyl ketone was added to the resin composition to obtain a varnish having a concentration of 50% by mass. Varnish gel time was evaluated using this varnish. As a result, it was 234 seconds.
Also, this varnish was impregnated and coated on an E-glass woven fabric, and dried by heating at 160° C. for 3 minutes to obtain a prepreg having a resin composition content of 46% by mass (in terms of solid content).

After that, one sheet or eight sheets of each of the obtained prepregs were stacked, and 12 μm-thick electrolytic copper foils (3EC-III (trade name) manufactured by Mitsui Kinzoku Mining Co., Ltd.) were arranged above and below, and a pressure of 30 kgf/cm ² was applied. Lamination molding was performed at a temperature of 220° C. for 120 minutes to obtain a metal foil clad laminate having an insulating layer thickness of 0.1 mm or 0.8 mm. Elastic modulus loss and linear thermal expansion coefficient were measured using the metal foil-clad laminate. As a result, the elastic modulus loss rate was 90% and the linear thermal expansion coefficient was 3.2 ppm/°C.

(Comparative Example 5)
10 parts by mass of the α-naphthol aralkyl cyanate ester resin (SNCN) obtained in Synthesis Example 1, 34 parts by mass of alkenyl-substituted nadimide (BANI-M (trade name) manufactured by Maruzen Petrochemical Co., Ltd.), 46 parts by mass of a maleimide compound (BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd., a maleimide compound in which all R ₅ in the formula (5) are hydrogen atoms and n ₂ is 1 to 3), and biphenyl Aralkyl-type epoxy resin (Nippon Kayaku Co., Ltd. NC-3000FH (trade name), epoxy equivalent: 290 g / eq.) 10 parts by mass, fused silica (Denka Co., Ltd. SFP-130MC, average particle size : 0.7 μm) 100 parts by mass, fused silica (SC-4500SQ manufactured by Admatechs Co., Ltd., average particle size: 1.3 μm) 100 parts by mass, silicone composite powder (KMP manufactured by Shin-Etsu Chemical Co., Ltd. -605 (trade name)) 25 parts by mass, a wetting and dispersing agent (DISPERBYK-161 manufactured by BYK Chemie Japan Co., Ltd.) 1 part by mass, and a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. KBM-403 (product 5 parts by mass of No.)) were mixed to form a resin composition, and methyl ethyl ketone was added to the resin composition to obtain a varnish having a concentration of 50% by mass. Using this varnish, the varnish gel time was evaluated in the same manner as in Example 8. As a result, it was 201 seconds.
Also, in the same manner as in Example 8, a prepreg (resin composition content: 46% by mass (solid content)) and a metal foil clad laminate were obtained, and the elastic modulus loss and linear thermal expansion coefficient were measured. As a result, the elastic modulus loss rate was 90% and the linear thermal expansion coefficient was 3.1 ppm/°C.

Claims (18)

a radically polymerizable compound (A);
and a compound (B) represented by the following general formula (1) ,
The radically polymerizable compound (A) contains a maleimide compound ,
Resin composition.

(In formula (1), R ₁ is a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, or the following general formula (2) represents an aryl group represented by
Each R ₂ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, or represented by the following general formula (2) represents an aryl group, or R ₂ may combine with each other to form a carbonyl group,
Ar represents an aryl group represented by the following general formula (2). ).

(In formula (2), each R ₃ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxy group, or represents an optionally substituted linear or branched alkoxy group having 1 to 5 carbon atoms, or two adjacent R3's may be bonded to _each other to form a naphthyl group). 2. The resin composition according to claim 1, wherein the content of the compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the radically polymerizable compound (A). The resin composition according to claim 1 or 2 , wherein the compound (B) contains a compound represented by the following general formula (3).

(In formula (3), each R ₄ is independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxy group, or represents an optionally substituted linear or branched alkoxy group having 1 to 5 carbon atoms, or two adjacent _R4 's may be bonded to each other to form a naphthyl group). The resin composition according to any one of claims 1 to 3 , further comprising one or more selected from the group consisting of cyanate ester compounds, phenol compounds, and epoxy compounds. The resin composition according to any one of claims 1 to 4 , further comprising an inorganic filler. The resin composition according to claim 5 , wherein the inorganic filler contains at least one selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide. thing. The resin composition according to any one of claims 1 to 6 , which is for electronic materials. The resin composition according to any one of claims 1 to 6 , which is for printed wiring boards. A cured product comprising the resin composition according to any one of claims 1 to 6 . A molded article comprising the resin composition according to any one of claims 1 to 6 . A prepreg comprising a base material and the resin composition according to any one of claims 1 to 6 impregnated or applied to the base material. A resin sheet comprising a support and the resin composition according to any one of claims 1 to 6 disposed on the surface of the support. A laminate formed of one or more selected from the group consisting of the prepreg according to claim 11 and the resin sheet according to claim 12 , and a metal foil disposed on one or both sides of the laminate. Metal foil clad laminate. Printed wiring comprising an insulating layer formed of one or more selected from the group consisting of the prepreg according to claim 11 and the resin sheet according to claim 12 , and a conductor layer formed on the surface of the insulating layer board. A semiconductor device comprising the resin composition according to any one of claims 1 to 6 . A sealing material comprising the resin composition according to any one of claims 1 to 6 . A fiber-reinforced composite material comprising the resin composition according to any one of claims 1 to 6 . An adhesive comprising the resin composition according to any one of claims 1 to 6 .