JP7154479B2 - Resin compositions, cured products, single-layer resin sheets, laminated resin sheets, prepregs, metal foil-clad laminates, printed wiring boards, 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 single-layer resin sheet, a laminated resin sheet, a prepreg, a metal foil-clad laminate, a printed wiring board, 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, and the like are becoming 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, 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.

Cyanate ester compounds have long been known as resins for printed wiring boards that are excellent in heat resistance and electrical properties.In recent years, resin compositions that combine cyanate ester compounds with epoxy resins, bismaleimide compounds, etc. have become popular for semiconductor plastic packages. It is widely used as a material for high-performance printed wiring boards, etc.
For example, Patent Literature 1 describes that a resin composition comprising a cyanate ester compound having a specific structure and other components has excellent properties such as low water absorption and a low coefficient of thermal expansion.

WO2012/105547

Although it can be said that the resin composition described in Patent Document 1 has good physical properties such as low water absorption and low coefficient of thermal expansion, there is still room for improvement from the viewpoint of thermal conductivity. be. For example, when insulating materials such as printed wiring boards and other resin sheets are used, if their thermal conductivity is not sufficient, it is difficult to apply them to applications requiring heat dissipation.

The present invention has been made in view of the above problems, and a resin composition, a cured product, a single-layer resin sheet, a laminated resin sheet, a prepreg, a metal foil-clad laminate, and a printed wiring that exhibit excellent thermal conductivity. The object is to provide plates, sealing materials, fiber reinforced composites and adhesives.

The present inventors have made intensive studies to solve the above problems. As a result, the inventors have found that a resin composition containing a cyanate ester compound (A) having a specific structure and an epoxy compound (B) having a specific structure can achieve the above object, and have completed the present invention.

That is, the present invention includes the following aspects.
[1] A resin composition comprising a cyanate ester compound (A) represented by the following formula (1) and an epoxy compound (B) represented by the following formula (3).

In formula (1), Ar ¹ , Ar ² and Ar ³ are the same or different and represent divalent groups represented by the following formula (2).

In formula (2), R ₁ represents a monovalent substituent, each independently representing a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. n represents an integer of 1-4.

In formula (3), Ar ⁴ , Ar ⁵ and Ar ⁶ are the same or different and represent a divalent group represented by formula (4) below.

In formula (4), R ₂ represents a monovalent substituent, each independently representing a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. n represents an integer of 1-4.

[2] The resin composition according to [1], wherein Ar ¹ , Ar ² , Ar ⁴ and Ar ⁵ are represented by the following formula (5).

[3] The resin composition according to [1] or [2], wherein Ar ³ and Ar ⁶ are represented by the following formula (6).

[4] A cyanate ester compound (C) other than the cyanate ester compound (A), a phenol resin, an epoxy compound other than the epoxy compound (B), an oxetane resin, a benzoxazine compound, and a polymerizable unsaturated group The resin composition according to any one of [1] to [3], further comprising one or more selected from the group consisting of compounds having
[5] The resin composition according to any one of [1] to [4], further comprising a filler.
[6] The resin composition according to [5], wherein the filler has a thermal conductivity of 3 W/(m·K) or more.
[7] The resin composition according to any one of [1] to [6], which is for a sheet-shaped molding.
[8] A cured product obtained by curing the resin composition according to any one of [1] to [7].
[9] A single-layer resin sheet obtained by molding the resin composition according to any one of [1] to [7] into a sheet.
[10] a support;
the resin composition according to any one of [1] to [7] arranged on one side or both sides of the support;
A laminated resin sheet.

[11] a substrate;
The resin composition according to any one of [1] to [7] impregnated or applied to the substrate;
A prepreg.
[12] at least one selected from the group consisting of the single-layer resin sheet described in [9], the laminated resin sheet described in [10], and the prepreg described in [11];
At least one metal foil selected from the group consisting of the single-layer resin sheet, the laminated resin sheet, and the prepreg, disposed on one side or both sides;
has
A metal foil-clad laminate comprising a cured product of a resin composition contained in at least one selected from the group consisting of the single-layer resin sheet, the resin sheet and the prepreg.
[13] an insulating layer;
a conductor layer formed on one side or both sides of the insulating layer;
has
A printed wiring board, wherein the insulating layer contains the resin composition according to any one of [1] to [7].

[14] A sealing material comprising the resin composition according to any one of [1] to [7].
[15] A fiber-reinforced composite material comprising the resin composition according to any one of [1] to [7] and reinforcing fibers.
[16] 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 single-layer resin sheet, a laminated resin sheet, a prepreg, a metal-foil-clad laminate, a printed wiring board, a sealing material, and a fiber reinforcement exhibiting excellent thermal conductivity Composite materials as well as adhesives can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited to this, and various modifications can be made without departing from the scope of the invention. is possible.

[Resin composition]
The resin composition of the present embodiment contains a cyanate ester compound (A) represented by formula (1) and an epoxy compound (B) represented by formula (3).
By having such a configuration, the resin composition of the present embodiment can exhibit excellent thermal conductivity.

[Cyanate ester compound (A)]
The cyanate ester compound (A) in the present embodiment is represented by formula (1). By using the cyanate ester compound (A) having such a structure together with the epoxy compound (B), the resin composition of the present embodiment can exhibit excellent thermal conductivity. The desired effect of this embodiment is not particularly limited, but the inventors presume as follows. In this embodiment, by applying a cyanate ester and an epoxy between terphenyl skeletons, the cyanate ester and the epoxy are likely to stack, and a regular structure resulting from a specific orientation is formed in the cured product. guessed. Therefore, it is considered that excellent thermal conductivity can be exhibited as compared with the case where the other cyanate ester compound and the epoxy compound (B) are combined.

In formula (1), Ar ¹ , Ar ² and Ar ³ are the same or different and represent a divalent group represented by formula (2) below.

In formula (2), R ₁ represents a monovalent substituent, each independently representing a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. n represents an integer of 1-4.

The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert- A butyl group is mentioned. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is even more preferable, since excellent thermal conductivity is exhibited.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.

In Ar ¹ and Ar ² in formula (1), R ₁ in formula (2) is preferably at least one group selected from a hydrogen atom and a methyl group, and exhibits excellent thermal conductivity. Therefore, it is more preferable that both Ar ¹ and Ar ² in formula (1) are divalent groups represented by the following formula (5). Ar ¹ and Ar ² in formula (1) are preferably the same.

In Ar ³ in formula (1), R ₁ in formula (2) is preferably at least one group selected from a hydrogen atom and a methyl group, and at least one group of R ₁ is a methyl group. Ar ³ in formula (1) is more preferably a divalent group represented by the following formula (6), since it exhibits excellent thermal conductivity.

Specific examples of the cyanate ester compound represented by formula (1) are not particularly limited, but include 4,4″-dicyanato-3-methylterphenyl and 4,4″-dicyanato-2-methylterphenyl. , 4,4″-dicyanato-2′-methylterphenyl, 4,4″-dicyanato-3,5-dimethylterphenyl, 4,4″-dicyanato-3,3″-dimethylterphenyl, 4,4″ -dicyanato-3-t-butylterphenyl, 4,4″-dicyanato-2-t-butylterphenyl, 4,4″-dicyanato-2′-t-butylterphenyl, 4,4″-dicyanato-3 ,5-di-t-butylterphenyl, 4,4″-dicyanato-3,3″-di-t-butylterphenyl.

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

In the resin composition of the present embodiment, the content of the cyanate ester compound (A) is the total of the cyanate ester compound (A) and the epoxy compound (B) from the viewpoint of obtaining better thermal conductivity and heat resistance. With respect to 100 parts by mass, it is usually 1 part by mass to 99 parts by mass, preferably 5 parts by mass to 95 parts by mass, more preferably 10 parts by mass to 90 parts by mass, and 20 parts by mass to 80 parts by mass. Parts by mass are more preferred.

[Method for producing cyanate ester compound (A)]
The method for producing the cyanate ester compound (A) of the present embodiment is not particularly limited. For example, after obtaining a hydroxy-substituted aromatic compound represented by the following formula (7), the hydroxy-substituted aromatic compound is A method including a cyanation step of obtaining the cyanate ester compound (A) represented by the above formula (1) by cyanation can be mentioned.

In formula (7), Ar ¹ , Ar ² and Ar ³ have the same meanings as in formula (1).

(Method for synthesizing hydroxy-substituted aromatic compound represented by formula (7))
Although the hydroxy-substituted aromatic compound represented by formula (7) is not particularly limited, for example, JP-A-1-168632, JP-A-1-168634, US Pat. No. 3461098, JP-A-2-212449 JP-A-2002-234856, JP-A-2002-308809, JP-A-2002-363117 and JP-A-2003-12585. More specifically, it can be produced according to the method described in Examples.

<Cyanating step>
Next, the step of cyanating the hydroxy-substituted aromatic compound represented by formula (7) obtained as described above will be described.
The method for cyanating the hydroxy-substituted aromatic compound represented by formula (7) is not particularly limited, and known methods can be applied. Specifically, a method in which a hydroxy-substituted aromatic compound and a cyanogen halide are reacted in a solvent in the presence of a basic compound, a method in which the cyanogen halide is always present in excess of the base in the solvent in the presence of a base Thus, a method of reacting a hydroxy-substituted aromatic compound with a cyanogen halide (see U.S. Pat. No. 3,553,244), or a method of using a tertiary amine as a base and using it in excess of the cyanogen halide, while using a solvent In the presence of, after adding a tertiary amine to a hydroxy-substituted aromatic compound, cyanogen halide is added dropwise, or cyanogen halide and tertiary amine are added dropwise (see Japanese Patent No. 3319061), A method of reacting a hydroxy-substituted aromatic compound, a trialkylamine and a cyanogen halide in a continuous plug flow system (see Japanese Patent No. 3905559), in which a hydroxy-substituted aromatic compound and a cyanogen halide are reacted in the presence of a quaternary amine. Below, a method of treating tert-ammonium halide, which is a by-product of the reaction in a non-aqueous solution, with a cation and anion exchange pair (see Japanese Patent No. 4055210). A tertiary amine and a cyanogen halide are simultaneously added and reacted in the presence of a liquid-capable solvent, followed by washing with water and separating the liquids, and from the obtained solution, a secondary or tertiary alcohol or a poor solvent of a hydrocarbon is added. (see Japanese Patent No. 2991054), and further, a hydroxy-substituted aromatic compound, a cyanogen halide, and a tertiary amine in a two-phase solvent of water and an organic solvent under acidic conditions. The cyanate ester compound of the present embodiment can be obtained by a method of reacting under the conditions (see Japanese Patent No. 5026727).

The obtained cyanate ester compound can be identified by a known method such as NMR (nuclear magnetic resonance spectroscopy). The purity of the cyanate ester compound can be analyzed, for example, by liquid chromatography or IR spectroscopy. Volatile components such as by-products such as dialkylcyanoamide and residual solvent in the cyanate ester compound can be quantitatively analyzed by, for example, gas chromatography. The halogen compound remaining in the cyanate ester compound can be identified by, for example, a liquid chromatograph mass spectrometer, and can also be quantitatively analyzed by ion chromatography after decomposition by potentiometric titration or combustion method using a silver nitrate solution. can be done. The polymerization reactivity of the cyanate ester compound can be evaluated, for example, by gelling time by hot plate method or torque measurement method.

[Epoxy compound (B)]
The epoxy compound (B) in this embodiment is represented by formula (3). By using the epoxy compound (B) having such a structure together with the cyanate ester compound (A), the resin composition of the present embodiment can exhibit excellent thermal conductivity.

In formula (3), Ar ⁴ , Ar ⁵ and Ar ⁶ are the same or different and represent a divalent group represented by formula (4) below.

In formula (4), R ₂ represents a monovalent substituent, each independently representing a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. n represents an integer of 1-4.

The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert- A butyl group is mentioned. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is even more preferable, since excellent thermal conductivity is exhibited.

Halogen atoms are as described above.

In Ar ⁴ and Ar ⁵ in formula (3), R ₂ in formula (4) is preferably at least one group selected from a hydrogen atom and a methyl group, and exhibits excellent thermal conductivity. Therefore, it is more preferable that both Ar ⁴ and Ar ⁵ in formula (3) are divalent groups represented by formula (5) below. Ar ⁴ and Ar ⁵ in formula (3) are preferably the same.

In Ar ⁶ in formula (3), R ₂ in formula (4) is preferably at least one group selected from a hydrogen atom and a methyl group, and at least one group among R ₂ is a methyl group. Ar ⁶ in the formula (4) is more preferably a divalent group represented by the following formula (6) because it exhibits excellent thermal conductivity.

Specific examples of the epoxy compound (B) are not particularly limited. dimethylterphenyldiglycidyl ether, 3,3″-dimethylterphenyldiglycidyl ether, 3-t-butylterphenyldiglycidyl ether, 2-t-butylterphenyldiglycidyl ether, 2′-t-butylterphenyldiglycidyl ether Glycidyl ether, 3,5-di-t-butylterphenyldiglycidyl ether, 3,3″-di-t-butylterphenyldiglycidyl ether can be mentioned.

These epoxy compounds (B) can be used individually by 1 type or in combination of 2 or more types.

In the resin composition of the present embodiment, the content of the epoxy compound (B) is 100 mass in total of the cyanate ester compound (A) and the epoxy compound (B) from the viewpoint of obtaining better thermal conductivity and heat resistance. parts, it is usually 1 part by mass to 99 parts by mass, preferably 5 parts by mass to 95 parts by mass, more preferably 10 parts by mass to 90 parts by mass, and 20 parts by mass to 80 parts by mass. is more preferable.

[Method for producing epoxy compound (B)]
Although the method for producing the epoxy compound (B) of the present embodiment is not particularly limited, it can be synthesized, for example, by the following synthesis method. That is, a substituted or unsubstituted 4,4'-dihydroxyterphenyl such as 4,4'-dihydroxy-3-methylterphenyl is reacted with an excess amount of 1-chloro-2,3-epoxypropane. can be synthesized by

Various known synthesis solvents and synthesis catalysts can be used in the above synthesis.
Specific examples of the above synthesis solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; polar solvents such as amides such as dimethylsulfoxide (DMSO), dimethylacetamide, and dimethylformamide alcoholic solvents such as methanol, ethanol, isopropanol and 1-ethoxy-2-propanol; and aromatic hydrocarbons such as toluene, xylene and anisole. These can be used singly or in combination of two or more.

The catalyst for synthesis is not particularly limited and can be appropriately selected from well-known catalysts. Examples thereof include basic catalysts such as sodium hydroxide, potassium hydroxide, and tetra-n-butylammonium chloride. These can be used singly or in combination of two or more.

Synthesis can be carried out using a known synthesis method and is not particularly limited. It can be carried out by reacting for about 1 to 6 hours. Also, the synthesis is preferably carried out under an inert gas atmosphere such as nitrogen, helium and argon.
The mixing ratio of substituted or unsubstituted 4,4'-dihydroxyterphenyl and 1-chloro-2,3-epoxypropane is not particularly limited, but for example, substituted or unsubstituted 4,4'-dihydroxyterphenyl The amount of 1-chloro-2,3-epoxypropane is usually 3 to 20 mol, preferably 5 to 15 mol, per 1 mol of .

[Cyanate ester compound other than cyanate ester compound (A), phenolic resin, epoxy compound other than epoxy compound (B), oxetane resin, benzoxazine compound, and compound having a polymerizable unsaturated group]
The resin composition of the present embodiment includes a cyanate ester compound other than the cyanate ester compound (A) of the present embodiment (hereinafter also referred to as "another cyanate ester compound"), a phenolic resin, and an epoxy resin of the present embodiment. One or more selected from the group consisting of epoxy compounds other than the compound (B) (hereinafter also referred to as "other epoxy compounds"), oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group. can further include:

(Other cyanate ester compounds)
Other cyanate ester compounds are not particularly limited as long as they are compounds having in the molecule an aromatic moiety substituted with at least one cyanato group (cyanate ester group). A resin composition using a cyanate ester compound has excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion when cured.

In the resin composition of the present embodiment, the content of the other cyanate ester compound can be appropriately set according to the desired properties and is not particularly limited, but the cyanate ester compound (A) and epoxy compound (B ) is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass in total.
Each of these components will be described below.

Examples of other cyanate ester compounds include, but are not particularly limited to, those represented by the following formula (8).

In formula (8) above, Ar ₁ represents an aromatic ring. When there are more than one, they may be the same or different. Examples of the aromatic ring include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a single bond of two benzene rings. Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 6 to 12 carbon atoms. Indicates a group to which an aryl group is attached. 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 each independently represents 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 from 0 to 50, and the other 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 group having 1 to 10 Organic group (for example -NRN- (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 formula (8) may have either a linear or branched chain structure or a cyclic structure (eg, cycloalkyl group, etc.).
A hydrogen atom in the alkyl group in the above formula (8) and the aryl group in Ra may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. .
Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2 , 2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl groups.
Specific examples of the aryl group include, but are not limited to, phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl groups, trifluorophenyl groups, methoxyphenyl groups, o-, m- or p-tolyl groups, and the like.
Examples of alkoxyl groups include, but are not limited to, 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 in the above formula (8) are not particularly limited, but methylene group, ethylene group, trimethylene group, dimethylmethylene group, cyclopentylene group, cyclohexylene group, trimethylcyclohexylene group, biphenylylmethylene group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, and phthalidodiyl group. 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 alkoxyl 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 in the above formula (8) are not particularly limited, but include a group represented by -NRN-, an imino group, a polyimide group, and the like. be done.

Further, examples of the organic group of X in the above formula (8) include structures represented by the following formula (9) or the following formula (10).

In formula (9), Ar ₂ represents an aromatic ring, and when u is 2 or more, they may be the same or different. Examples of the aromatic ring include, but are not particularly limited to, a benzenetetrayl group, a naphthalenetetrayl group, and a biphenyltetrayl group. Rb, Rc, Rf, and Rg 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 trifluoromethyl group, or an aryl having at least one phenolic hydroxy group indicates a group. Each of Rd and Re is 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 alkoxyl group having 1 to 4 carbon atoms, or a hydroxy group. u represents an integer of 0 to 5;

In formula (10), Ar ₃ represents a phenylene group, a naphthylene group or a biphenylene 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 alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, or It represents 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 formula (8) includes a divalent group represented by the following formula.

In the above formula, 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 formula (9) and Ar ₃ in formula (10) include a 1,4-phenylene group, a 1,3-phenylene group, a 4,4′-biphenylene group and a 2,4′-biphenylene group. , 2,2′-biphenylene group, 2,3′-biphenylene group, 3,3′-biphenylene group, 3,4′-biphenylene group, 2,6-naphthylene group, 1,5-naphthylene group, 1,6 -naphthylene group, 1,8-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group and 2,7-naphthylene group.
The alkyl group, aryl group and alkoxyl group for Rb, Rc, Rd, Re, Rf and Rg in formula (9) and Ri and Rj in formula (10) are the same as in formula (8) above. Aryl groups having at least one phenolic hydroxy group are not particularly limited, and examples include phenol, o-cresol, m-cresol, p-cresol, o-xylenol, m-xylenol, p-xylenol, o-ethyl Examples include monovalent groups obtained by removing one hydrogen atom from phenolic compounds such as phenol, m-ethylphenol, p-ethylphenol, and 2,3,5-trimethylphenol.

Specific examples of the cyanate ester compound represented by the formula (8) are not particularly limited, but cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methyl Benzene, 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, 1- Cyanato-2-methoxy-4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl 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'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis(4-cyanato-3,5-dimethylphenyl)methane, 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, 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-cyanato phenyl)-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)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-bi Su[2-(4-cyanatophenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,1-bis(4-cyanato phenyl)-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-cyanato phenyl)ethane, tetrakis(4-cyanatophenyl)methane, 2,4,6-tris(N-methyl-4-cyanatoanilino)-1,3,5-triazine, 2,4-bis(N-methyl-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-methylphenyl)- 4,4'-(Hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4- anatobenzyl)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- and bis(4-cyanatophenyl)indolin-2-one.

Other specific examples of the compound represented by the formula (8) include, but are not particularly limited to, phenol novolac resin and cresol novolac resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin or para- Formaldehyde compound such as formaldehyde 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 reacted in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins (Ar'-(CH ₂ Y) ₂ (Ar' represents a phenyl group, Y represents a halogen atom) and a phenolic compound reacted with an acidic catalyst or without a catalyst, Ar'-(CH ₂ OR) ₂ (Ar' represents a phenyl group) and a phenol compound reacted in the presence of an acidic catalyst, or Ar'-(CH ₂ OH ) ₂ (Ar' represents a phenyl group), a bis(hydroxymethyl) compound and a phenolic compound reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenolic compound polycondensation), phenol-modified xylene formaldehyde resin (by a known method, a xylene formaldehyde resin and a phenolic compound are reacted in the presence of an acidic catalyst), modified naphthalene formaldehyde resin (by a known method, Naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound reacted in the presence of an acidic catalyst), phenol-modified dicyclopentadiene resin, phenol resin having a polynaphthylene ether structure (by a known method, one phenolic hydroxy group is Polyhydric hydroxynaphthalene compounds having two or more molecules in the molecule are dehydrated and condensed in the presence of a basic catalyst), etc., cyanated by the same method as described above, and prepolymers thereof etc.

Examples of other cyanate ester compounds include those represented by the following formula (11).

In formula (11), Ar ₄ represents an aromatic ring, and when there are more than one, they may be the same or different. Each R ₁ independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group or an oxymethylene group, which may be linked. R ₂ represents a monovalent substituent each independently represents a hydrogen atom, an alkyl group or an aryl group; each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group, a hydroxy group or represents a hydroxymethylene group, m represents an integer of 1 or more, and n represents an integer of 0 or more. It may be a mixture of compounds in which m and n are different. The arrangement of each repeating unit is arbitrary. l represents the number of bonded cyanato groups and is an integer of 1-3. x represents the number of bonds in R ₂ , and represents the number obtained by subtracting (l+2) from the number of substitutable groups in Ar ₄ . y represents the number of bonds in R ₃ and represents the number obtained by subtracting 2 from the number of substitutable groups in Ar ₄ .

Ar ₄ in the above formula (11) is exemplified by a benzene ring, a naphthalene ring, an anthracene ring and the like, but is not particularly limited to these.
The alkyl group for R ₂ and R ₃ in formula (11) may have either a linear or branched chain structure or a cyclic structure (eg, cycloalkyl group, etc.).
Further, the hydrogen atom in the aryl group in R ₂ and R ₃ in formula (11) 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. good.
Specific examples of the alkyl group 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-dimethyl. propyl group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
Specific examples of the aryl group include a phenyl group, a xylyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl group, a dicyanophenyl group, and a trifluorophenyl group. phenyl group, methoxyphenyl group, o-, m- or p-tolyl group and the like. Furthermore, alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.

Specific examples of the cyanate compound represented by formula (11) include phenol-modified xylene formaldehyde resin (a known method in which a xylene formaldehyde resin and a phenol compound are reacted in the presence of an acidic catalyst), modified naphthalene. Examples include those obtained by converting phenolic resins such as formaldehyde resins (which are obtained by reacting naphthalene formaldehyde resins and hydroxy-substituted aromatic compounds in the presence of an acidic catalyst by a known method) into cyanate by a method similar to that described later. It is not particularly limited. These cyanate ester compounds can be used singly or in combination of two or more.

The above-described other cyanate ester compounds may be used singly or in combination of two or more.

Among the above, phenol novolak-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds, biphenyl aralkyl-type cyanate ester compounds, naphthylene ether-type cyanate ester compounds, xylene resin-type cyanate ester compounds, adamantane skeleton-type cyanate Ester compounds are preferred, and naphthol aralkyl-type cyanate ester compounds are more preferred.

(Phenolic resin)
The phenolic resin is not particularly limited, and generally known phenolic resins having two or more hydroxy 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 Examples include phenol resins, dicyclopentadiene type phenol resins, biphenyl type phenol resins, alicyclic phenol resins, polyol type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins. These can be used individually by 1 type or in combination of 2 or more types. Among these, biphenylaralkyl-type phenolic resins, naphtholaralkyl-type phenolic resins, phosphorus-containing phenolic resins, and hydroxyl-containing silicone resins are preferred from the viewpoint of flame retardancy.

In the resin composition of the present embodiment, the content of the phenolic resin can be appropriately set according to the desired properties, and is not particularly limited. It is preferably from 1 part by mass to 50 parts by mass.

(other epoxy compounds)
The other epoxy compound is not particularly limited, and any known epoxy compound having two or more epoxy groups in one molecule can be appropriately used. Other epoxy compounds may be epoxy resins other than the epoxy compound (B) of the present embodiment. For example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolak type epoxy resin, glycidyl ester type epoxy resin. , glycidylamine type epoxy resin, aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, dihydro Anthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin , isocyanuric acid-type epoxy resin, fluorene-type epoxy resin, xanthene-type epoxy resin, alicyclic epoxy resin, polyol-type epoxy resin, phosphorus-containing epoxy resin, compounds obtained by epoxidizing double bonds such as butadiene, hydroxyl-containing silicone resins and epichlorohydrin. These can be used individually by 1 type or in combination of 2 or more types. Among these, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable in terms of flame retardancy and heat resistance.

In the resin composition of the present embodiment, the content of the epoxy resin can be appropriately set according to the desired properties, and is not particularly limited. It is preferably from 1 part by mass to 50 parts by mass.

(oxetane resin)
The oxetane resin is not particularly limited, and generally known ones can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoro methyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.), OXT-121 (trade name, manufactured by Toagosei Co., Ltd.) and the like. These can be used individually by 1 type or in combination of 2 or more types.

In the resin composition of the present embodiment, the content of the oxetane resin can be appropriately set according to the desired properties, and is not particularly limited. It is preferably from 1 part by mass to 50 parts by mass.

(Benzoxazine compound)
The benzoxazine compound is not particularly limited, and generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A-type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), bisphenol F-type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), bisphenol S-type benzoxazine Oxazine BS-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), Pd type benzoxazine (trade name, manufactured by Shikoku Kasei Co., Ltd.), Fa type benzoxazine (trade name, Shikoku Kasei Kogyo Co., Ltd.) and the like. These can be used individually by 1 type or in combination of 2 or more types.

In the resin composition of the present embodiment, the content of the benzoxazine compound can be appropriately set according to the desired properties, and is not particularly limited. It is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass.

(Compound having a polymerizable unsaturated group)
The compound having a polymerizable unsaturated group is not particularly limited, and generally known compounds can be used. For example, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, Monohydric or polyhydric alcohol (meth)acrylates such as trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A-type epoxy (meth)acrylates, epoxy (meth)acrylates such as bisphenol F-type epoxy (meth)acrylates, and benzocyclobutene resins. These can be used individually by 1 type or in combination of 2 or more types. In addition, the above-mentioned "(meth)acrylate" is a concept including acrylate and its corresponding methacrylate.

In the resin composition of the present embodiment, the content of the compound having a polymerizable unsaturated group can be appropriately set according to the desired properties, and is not particularly limited. It is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of compound (B).

(filler)
It is preferable that the resin composition of the present embodiment further contains a filler from the viewpoint of exhibiting better thermal conductivity and improving thermal expansion characteristics, dimensional stability, flame retardancy, dielectric properties, and the like. . As the filler, a known filler can be used as appropriate, and the type is not particularly limited. Fillers commonly used in laminate applications can be used as fillers. Specific examples of fillers include, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, and the like. Oxides, boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, heat-treated aluminum hydroxide (heat-treated aluminum hydroxide to reduce some of the water of crystallization), boehmite , metal hydrates such as magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E -Glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (E-glass, T-glass, D-glass, S-glass, Q-glass etc.), hollow glass, spherical glass and other inorganic fillers, styrene type, butadiene type, acrylic type rubber powder, core shell type rubber powder, silicone resin powder, silicone Examples include organic fillers such as rubber powder and silicone composite powder. These can be used individually by 1 type or in combination of 2 or more types.

Among these, crystalline silica, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, boehmite and alumina are preferred, and alumina, aluminum nitride and boron nitride are more preferred. The use of these fillers tends to further improve the thermal conductivity of the resin composition.
In the resin composition of the present embodiment, the content of the filler can be appropriately set according to the desired properties and is not particularly limited, but from the viewpoint of providing better thermal conductivity, the cyanate ester compound ( It is preferably 50 parts by mass to 2500 parts by mass, more preferably 100 parts by mass to 2200 parts by mass, with respect to a total of 100 parts by mass of A) and the epoxy compound (B), and has excellent thermal conductivity. From the viewpoint of obtaining, it is more preferably 150 parts by mass to 2000 parts by mass.

The filler in the present embodiment preferably has a thermal conductivity of 3 W/(m K) or more, more preferably 5 W/(m K) or more, in order to exhibit better thermal conductivity. is more preferably 10 W / (m K) or more, still more preferably 15 W / (m K) or more, and even more preferably 20 W / (m K) or more, It is more preferably 25 W/(m·K) or more, and even more preferably 30 W/(m·K) or more. The filler having a thermal conductivity of 3 W/(m·K) or higher is also not particularly limited, and known fillers such as those described above can be used.
The thermal conductivity of the filler can be confirmed by referring to "Thermophysical Property Handbook" edited by the Japan Society of Thermophysical Properties, etc., and a known value can be adopted as the thermal conductivity of the filler. In addition, not all the fillers contained in the resin composition need to have a thermal conductivity of 3 W / (m K) or more, and 50% by mass or more of the fillers with respect to the total amount of the fillers contained is 3 W / It preferably has a thermal conductivity of (m·K) or more, and more preferably 75% by mass or more of the filler has a thermal conductivity of 3 W/(m·K) or more. That is, the filler may contain one having a thermal conductivity of less than 3 W/(m·K).

In incorporating the filler into the resin composition, it is preferable to use a silane coupling agent or a wetting and dispersing agent in combination. As the silane coupling agent, those generally used for surface treatment of inorganic substances can be used, and the type thereof is not particularly limited. The silane coupling agent is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-( 2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N- (2-aminoethyl)-3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino) Aminosilanes such as propyl]trimethoxysilane, [3-(N,N-dimethylamino)-propyl]trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, [8-(glycidyloxy)-n-octyl]trimethoxysilane, etc. epoxysilanes, vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane, trimethoxy(4-vinyl vinylsilanes such as phenyl)silane; methacrylsilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane; Acrylsilanes such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane, isocyanatesilanes such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, tris-(trimethoxysilyl isocyanurate silanes such as propyl)isocyanurate, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-ureidopropyltriethoxysilane ureidosilanes such as sisilane; styrylsilanes such as p-styryltrimethoxysilane; cationic silanes such as N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride; Acid anhydrides such as [3-(trimethoxysilyl)propyl]succinic anhydride, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, p-tolyltrimethoxysilane, etc. Examples include phenylsilane systems, as well as arylsilane systems such as trimethoxy(1-naphthyl)silane. Among these, 3-glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane are preferred from the viewpoint of providing superior thermal conductivity. , 3-aminopropyldimethoxymethylsilane, and 3-aminopropyldiethoxymethylsilane are preferred. These can be used individually by 1 type or in combination of 2 or more types.
In the resin composition of the present embodiment, the content of the silane coupling agent can be appropriately set according to the desired properties, and is not particularly limited. From the viewpoint of improving compatibility with the filler and providing better thermal conductivity, the amount is usually 0.1 part by mass per 100 parts by mass in total of the cyanate ester compound (A) and the epoxy compound (B). to 50 parts by mass, preferably 0.5 to 30 parts by mass.

As the wetting and dispersing agent, those generally used for paints can be used, and the type thereof is not particularly limited. As the wetting and dispersing agent, a copolymer-based wetting and dispersing agent can be used, and it may be a commercial product. Commercial products are not particularly limited, but for example, Disperbyk (registered trademark)-110, 111, 161, 180, BYK (registered trademark)-W996, BYK (registered trademark)-W9010 manufactured by BYK-Chemie Japan Co., Ltd. , BYK (registered trademark)-W903, BYK (registered trademark)-W940, and the like. These can be used individually by 1 type or in combination of 2 or more types.
In the resin composition of the present embodiment, the content of the wetting and dispersing agent can be appropriately set according to the desired properties and is not particularly limited. It is usually 0.1 to 30 parts by mass with respect to a total of 100 parts by mass of (A) and epoxy compound (B).

(Curing catalyst)
If necessary, the resin composition of the present embodiment may contain a curing catalyst for appropriately adjusting the curing speed. The curing catalyst is not particularly limited, and those commonly used as curing catalysts for cyanate ester compounds, epoxy resins, and the like can be suitably used. Curing catalysts include organic metal salts such as zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octylate, manganese octylate, phenol, xylenol, cresol, resorcinol, catechol, and octylphenol. , phenolic compounds such as nonylphenol, 1-butanol, alcohols such as 2-ethylhexanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazoles such as cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and carboxylic acids of these imidazoles or their Derivatives such as adducts of acid anhydrides, amines such as dicyandiamide, benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine compounds Peroxides such as phosphorus compounds such as phosphorus compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, Alternatively, azo compounds such as azobisisobutyronitrile can be used. These can be used individually by 1 type or in combination of 2 or more types.
In the resin composition of the present embodiment, the content of the curing catalyst can be appropriately set according to the desired properties and is not particularly limited, but from the viewpoint of providing better thermal conductivity, the cyanate ester compound ( It is usually 0.01 to 20 parts by mass per 100 parts by mass of A) and the epoxy compound (B).

(other additives)
In the resin composition of the present embodiment, other thermosetting resins, thermoplastic resins and their oligomers, various polymer compounds such as elastomers, flame retardant compounds, In addition, various additives and the like may be included. These are not particularly limited as long as they are commonly used. The flame-retardant compound is not particularly limited. Examples include nitrogen compounds such as benzoguanamine, oxazine ring-containing compounds, and silicone compounds. Various additives are not particularly limited. Sensitizers, dyes, pigments, thickeners, flow regulators, lubricants, antifoaming agents, dispersants, leveling agents, brighteners, polymerization inhibitors and the like. These can be used individually by 1 type or in combination of 2 or more types.
In the present embodiment, the content of other additives in the resin composition is not particularly limited, but is usually 0.00 parts per 100 parts by mass of the cyanate ester compound (A) and the epoxy compound (B). 01 parts by mass to 50 parts by mass.

(Organic solvent)
The resin composition of the present embodiment may contain an organic solvent, if necessary. In this case, the resin composition of the present embodiment can be used as a form (solution or varnish) in which at least part, preferably all of the various resin components described above are dissolved or compatible with an organic solvent. As the organic solvent, any known organic solvent can be appropriately used as long as it is capable of dissolving or compatible with at least a part, preferably all, of the various resin components described above, and the type thereof is not particularly limited. Examples of organic solvents include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alicyclic ketones such as cyclopentanone and cyclohexanone, cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, and ethyl lactate. , ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; polar solvents such as amides such as dimethylacetamide and dimethylformamide; toluene, xylene, etc. and non-polar solvents such as aromatic hydrocarbons. These can be used individually by 1 type or in combination of 2 or more types.

[Method for producing resin composition]
The resin composition of the present embodiment can be prepared according to a conventional method, and a method for obtaining a resin composition uniformly containing the cyanate ester compound of the present embodiment, the epoxy compound, and the other optional components described above. If so, the preparation method is not particularly limited. For example, the resin composition of the present embodiment can be easily prepared by sequentially blending the cyanate ester compound of the present embodiment, the epoxy compound, and the other optional components described above in a solvent and sufficiently stirring the mixture.

In preparing the resin composition, known treatments (heat melting, stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component can be performed. For example, when uniformly dispersing the filler, dispersibility in the resin composition can be enhanced by performing a stirring and dispersing treatment using a stirring tank equipped with a stirrer having an appropriate stirring capacity. A known melt extruder can be used for the heating and melting. The above stirring, mixing, and kneading treatments can be appropriately performed using, for example, a device for mixing such as a ball mill and a bead mill, or a known device such as a revolution/rotation type mixing device.

[Cured product]
The cured product of this embodiment is obtained by curing the resin composition of this embodiment. The cured product is not particularly limited, but can be obtained, for example, by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using heat, light, or the like. In the case of heat curing, the curing temperature is not particularly limited, but is preferably within the range of 120° C. to 300° C. from the viewpoint of efficient curing and prevention of deterioration of the resulting cured product. In the case of photocuring, the wavelength range of light is not particularly limited, but curing is preferably performed in the range of 100 nm to 500 nm where curing proceeds efficiently with a photopolymerization initiator or the like.

[Prepregs, Single-Layer Resin Sheets, Laminated Resin Sheets, Metal Foil-Clad Laminates, Printed Wiring Boards, and Materials Constituting Semiconductor Packages]
The resin composition of the present embodiment can be used as a constituent material for prepregs, single-layer resin sheets, laminated resin sheets, metal foil-clad laminates, printed wiring boards, and semiconductor packages. The resin composition of the present embodiment is preferably used for sheet-like moldings. For example, a prepreg can be obtained by impregnating or coating a base material with a solution obtained by dissolving the resin composition of the present embodiment in a solvent, followed by drying.
Alternatively, a peelable plastic film is used as a support, and a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied to the plastic film and dried to obtain a build-up film or dry film solder resist. be able to. Here, the solvent can be removed by drying at a temperature of 20° C. to 150° C. for 1 to 90 minutes.
In addition, the resin composition of the present embodiment can be used in a state (uncured state) from which the solvent has been removed, or can be used in a semi-cured (B-staged) state as necessary. .

[Resin sheet]
The laminated resin sheet of the present embodiment has a support and the resin composition of the present embodiment arranged on one side or both sides of the support. The method for producing the laminated resin sheet is not particularly limited and can be carried out according to a conventional method. For example, it can be obtained by coating a support with a solution in which the resin composition of the present embodiment is dissolved in a solvent and drying the solution.

Examples of the support include, but are not limited to, polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and a release film obtained by applying a release agent to the surface of these films. , organic film substrates such as polyimide films, conductor foils such as copper foils and aluminum foils, glass plates, SUS plates, and plate-like substrates such as FRP.

The coating method is not particularly limited, but examples thereof include a method of coating a solution obtained by dissolving the resin composition of the present embodiment in a solvent onto a support using a bar coater, die coater, doctor blade, baker applicator, or the like. be done.

The single-layer resin sheet of the present embodiment is obtained by molding the resin composition of the present embodiment into a sheet. The method for producing the single-layer resin sheet is not particularly limited and can be carried out according to a conventional method. For example, in the above-described method for producing a laminated resin sheet, there is a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is coated on a support and dried, and then the support is peeled off or etched from the laminated resin sheet. mentioned. A solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to form a sheet. A layered resin sheet (resin sheet) can also be obtained.

In the production of the single-layer resin sheet or laminated resin sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited. A temperature of 20° C. to 170° C. and a time of 1 to 90 minutes are preferable because the curing of the composition proceeds.

The thickness of the resin layer of the single layer or laminated sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the thickness of the coating, and is not particularly limited, but generally the thickness of the coating The thickness is preferably 0.1 to 500 μm because the solvent tends to remain during drying as the thickness increases.

(prepreg)
The prepreg of this embodiment will be described in detail below. The prepreg of this embodiment has a base material and a resin composition impregnated or applied to the base material. The method for producing the prepreg of the present embodiment is not particularly limited as long as it is a method of producing a prepreg by combining the resin composition of the present embodiment and a base material. Specifically, after impregnating or applying the resin composition of the present embodiment to the substrate, it is semi-cured by a method such as drying in a dryer at 120 to 220 ° C. for about 2 to 15 minutes. Prepregs of embodiments can be manufactured. At this time, the amount of the resin composition adhered to the substrate, that is, the content of the resin composition (including the filler) with respect to the total amount of the prepreg after semi-curing is preferably in the range of 20 to 99% by mass.

As the base material used when manufacturing the prepreg of the present embodiment, known materials used for various printed wiring board materials can be used. Examples of the base material include, but are not limited to, inorganic fibers other than glass such as glass fiber and quartz, organic fibers such as polyimide, polyamide and polyester, and woven fabric such as liquid crystal polyester. As the shape of the substrate, woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat and the like are known, and any of these may be used. The substrate can be used singly or in combination of two or more. Among woven fabrics, woven fabrics subjected to super-opening treatment and stuffing treatment are particularly suitable from the viewpoint of dimensional stability. A liquid crystal polyester woven fabric is preferable from the aspect of electrical properties. The thickness of the base material is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for laminate applications.

(metal foil clad laminate)
The metal foil-clad laminate of the present embodiment includes at least one selected from the group consisting of the single-layer resin sheet of the present embodiment, the laminated resin sheet of the present embodiment, and the prepreg of the present embodiment, and the single-layer resin At least one kind of metal foil selected from the group consisting of a sheet, the laminated resin sheet and the prepreg and arranged on one side or both sides, and the group consisting of the single-layer resin sheet, the laminated resin sheet and the prepreg It contains a cured product of a resin composition contained in at least one selected from. As a specific example of using a prepreg, a metal foil such as copper or aluminum is placed on one or both sides of one prepreg or a stack of a plurality of prepregs, and lamination molding is performed. It can be produced by The metal foil used here is not particularly limited as long as it is used for printed wiring board materials, but copper foils such as rolled copper foils and copper foils are preferred. Although the thickness of the metal foil is not particularly limited, it is preferably 2 to 70 μm, more preferably 3 to 35 μm. As for the molding conditions, methods used in the production of ordinary laminates and multi-layer boards for printed wiring boards can be employed. For example, using a multi-stage press machine, multi-stage vacuum press machine, continuous molding machine, autoclave molding machine, etc., the temperature is 180 to 350 ° C., the heating time is 100 to 300 minutes, and the surface pressure is 20 to 100 kg / cm ² . Thus, the metal foil-clad laminate of the present embodiment can be produced. A multilayer board can also be produced by combining the above-mentioned prepreg and a wiring board for an inner layer, which is separately produced, and performing lamination molding. As a method for producing a multilayer board, for example, 35 μm copper foil is placed on both sides of one sheet of the above-described prepreg, laminated under the above conditions, an inner layer circuit is formed, and this circuit is subjected to blackening treatment. to form an inner layer circuit board. Further, the inner layer circuit board and the prepreg are alternately arranged one by one, and a copper foil is arranged as the outermost layer, and laminated under the above conditions, preferably under vacuum. Thus, a multilayer board can be produced.

(Printed wiring board)
The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by further forming a pattern. A printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not specifically limited. An example of a method for manufacturing a printed wiring board is shown below.
First, the above metal foil-clad laminate is prepared. Next, an inner layer substrate is produced by etching the surface of the metal foil-clad laminate to form an inner layer circuit. The surface of the inner layer circuit of this inner layer substrate is subjected to a surface treatment for increasing the adhesive strength, if necessary, and then the required number of prepregs are laminated on the surface of the inner layer circuit. Further, a metal foil for an outer layer circuit is laminated on the outer side of the laminate, and the laminate is integrally formed by heating and pressing. In this manner, a multilayer laminate is produced in which an insulating layer composed of the base material and the cured product of the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this multi-layer laminate, a plated metal film is formed on the walls of the holes for conducting metal foils for inner layer circuits and outer layer circuits. Furthermore, the printed wiring board is manufactured by etching the metal foil for the outer layer circuit to form the outer layer circuit.

The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment. For example, the prepreg of the present embodiment (the base material and the resin composition of the present embodiment impregnated or applied thereto), the layer of the resin composition of the metal foil-clad laminate of the present embodiment (the resin composition of the present embodiment layer) can constitute an insulating layer containing the resin composition of the present embodiment.

[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. Incidentally, the method of adding the cyanate ester compound, epoxy compound, various additives, and solvent during mixing is not particularly limited and generally known methods can be appropriately applied.

[Fiber-reinforced composite material]
The fiber-reinforced composite material of this embodiment includes the resin composition of this 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.

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

The materials used for preparing the resin composition and their abbreviations are shown below.
(Thermosetting resin)
- A terphenyl-type cyanate ester compound represented by the following formula (12) (abbreviated as TP-Me-CN)
TP-Me-CN was synthesized based on Example 1 of JP-A-2018-70553.

- A terphenyl-type epoxy compound represented by the following formula (13) (abbreviated as DGETP-Me)
DGETP-Me was synthesized based on Experimental in JOURNAL OF Applied Polymer SCIENCE, 2015, vol. 132, 41296.

・2,2-bis(4-cyanatophenyl)propane (manufactured by Mitsubishi Gas Chemical Company, Inc., abbreviated as TA)
・ 1,1-bis(4-cyanatophenyl)ethane (manufactured by Mitsubishi Gas Chemical Company, Inc., abbreviated as E-CN)
・Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) 828)
・ Phenylmethane type maleimide resin (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300)

(curing agent)
・ 4,4-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd., abbreviated as DDM)

(catalyst)
・ Zinc octylate (Nippon Kagaku Sangyo Co., Ltd., Nikka Octix Zinc (trade name), metal content 18%)
· 2-ethyl-4-methylimidazole (manufactured by Wako Pure Chemical Industries, Ltd., abbreviated as 2E4MZ)

(filler)
・ FAN-f50 (manufactured by Furukawa Denshi Co., Ltd., aluminum nitride particles, thermal conductivity 200 W / m K)
・ AA-18 (manufactured by Sumitomo Chemical Co., Ltd., alumina particles, thermal conductivity 30 W / m K)
・ AA-3 (manufactured by Sumitomo Chemical Co., Ltd., alumina particles, thermal conductivity 30 W / m K)
・ AA-03 (manufactured by Sumitomo Chemical Co., Ltd., alumina particles, thermal conductivity 30 W / m K)

(Silane coupling agent)
・3-Glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-2940)
<Preparation of resin composition and production of cured product>
[Example 1]
Terphenyl-type cyanate ester compound (TP-Me-CN) 45.6 parts by mass, terphenyl-type epoxy compound (DGETP-Me) 54.4 parts by mass and 2-ethyl-4-methylimidazole (2E4MZ) 1.0 Parts by mass were mixed and melted by heating to obtain a resin composition.
A mold was filled with the obtained resin composition, and a cured product was produced by vacuum heat pressing (220° C., 90 minutes, press pressure 7 MPa).

[Comparative Example 1]
100 parts by mass of a terphenyl-type cyanate ester compound (TP-Me-CN) and 0.05 parts by mass of zinc octylate (Nikka Octix Zinc (trade name), metal content 18%, manufactured by Nihon Kagaku Sangyo Co., Ltd.) were mixed and melted by heating to obtain a resin composition.
A mold was filled with the obtained resin composition, and a cured product was produced by vacuum heat pressing (220° C., 90 minutes, press pressure 7 MPa).

[Comparative Example 2]
Comparative Example except that 100 parts by mass of 2,2-bis(4-cyanatophenyl)propane (TA) was used instead of 100 parts by mass of terphenyl-type cyanate ester compound (TP-Me-CN). A cured product was obtained in the same manner as in 1.

[Comparative Example 3]
Instead of using 100 parts by mass of terphenyl-type cyanate ester compound (TP-Me-CN), 1,1-bis(4-cyanatophenyl)ethane (E-CN) was used in 100 parts by mass. A curable material was obtained in the same manner as in Example 1.

[Comparative Example 4]
Terphenyl type cyanate ester compound (TP-Me-CN) 46.3 parts by mass, bisphenol A type epoxy resin compound (jER (registered trademark) 828) 53.7 parts by mass and 2-ethyl-4-methylimidazole (2E4MZ ) was mixed with 1.0 part by mass and heated and melted to obtain a resin composition.
A mold was filled with the obtained resin composition, and a cured product was produced by vacuum heat pressing (220° C., 90 minutes, press pressure 7 MPa).

[Comparative Example 5]
Terphenyl-type epoxy compound (DGETP-Me) 58.3 parts by mass, 2,2-bis(4-cyanatophenyl)propane (TA) 41.7 parts by mass and 2-ethyl-4-methylimidazole (2E4MZ) 1 0 parts by mass were mixed and melted by heating to obtain a resin composition.
A mold was filled with the obtained resin composition, and a cured product was produced by vacuum heat pressing (220° C., 90 minutes, press pressure 7 MPa).

[Comparative Example 6]
80.0 parts by mass of a terphenyl-type epoxy compound (DGETP-Me) and 20.0 parts by mass of 4,4-diaminodiphenylmethane (DDM) were mixed and melted by heating to obtain a resin composition.
A mold was filled with the obtained resin composition, and a cured product was produced by vacuum heat pressing (220° C., 90 minutes, press pressure 7 MPa).

<Preparation of cured product containing filler>
[Example 2]
Terphenyl-type cyanate ester compound (TP-Me-CN) 45.7 parts by mass, terphenyl-type epoxy compound (DGETP-Me) 54.3 parts by mass, 2-ethyl-4-methylimidazole (2E4MZ) 0.2 Parts by mass, aluminum nitride particles (FAN-f50) 562.1 parts by mass, alumina particles (AA-18) 87.1 parts by mass, alumina particles (AA-3) 87.1 parts by mass, alumina particles (AA-03) 87.1 parts by mass of 3-glycidoxypropyltrimethoxysilane (LS-2940) and 8.2 parts by mass of 3-glycidoxypropyltrimethoxysilane (LS-2940) were mixed and diluted with methyl ethyl ketone (special reagent grade, Wako Pure Chemical Industries, Ltd.) to prepare a varnish.
The prepared varnish is applied to a rough surface of copper foil (3EC-VLP, thickness 18 μm, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, dried at 100 ° C. for 10 minutes, and B-stage resin composition-attached copper foil. got Copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., 3EC-VLP, thickness 18 μm) is placed on the B-stage resin composition-attached copper foil so that the rough surface faces the resin composition, and vacuum hot press (220 ° C., 90 minutes, press A cured product with copper foils on both sides was produced under a pressure of 20 MPa). The copper foils on both sides were peeled off from the cured product with copper foils on both sides to obtain a cured product containing filler (containing 75% by volume of filler).

[Comparative Example 7]
2,2-bis(4-cyanatophenyl)propane (TA) 43.7 parts by mass, phenylmethane type maleimide resin (BMI-2300) 56.3 parts by mass, zinc octylate (Nippon Kagaku Sangyo Co., Ltd., Nikka Octix Zinc (trade name), metal content 18%) 0.1 parts by mass, aluminum nitride particles (FAN-f50) 557.5 parts by mass, alumina particles (AA-18) 86.4 parts by mass, alumina particles ( AA-3) 86.4 parts by mass, 86.4 parts by mass of alumina particles (AA-03), and 8.1 parts by mass of 3-glycidoxypropyltrimethoxysilane (LS-2940) are mixed, and methyl ethyl ketone (Wako Pure Yakukogyo Co., Ltd., reagent special grade) was diluted to prepare a varnish.
The prepared varnish is applied to a rough surface of copper foil (3EC-VLP, thickness 18 μm, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, dried at 100 ° C. for 10 minutes, and B-stage resin composition-attached copper foil. got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The resulting resin composition powder was filled in a mold and subjected to vacuum heat pressing (220° C., 90 minutes, press pressure 5 MPa) to obtain a filler-containing cured product (filler content of 75% by volume).

[Evaluation method of cured product]
The properties of the resulting cured product and filler-containing cured product were evaluated by the following methods.
<Thermal conductivity of cured product>
The thermal diffusivity is measured by setting a cured product processed to a size of 1 cm square on a sample holder in a xenon flash method thermal diffusivity measuring device (LFA447 NanoFlash manufactured by NETZSCH) at 25° C. in the atmosphere. sought by doing.
The specific heat was obtained using a DSC (manufactured by Seiko Instruments Inc., EXSTAR6000 DSC6220) according to JIS K7123 (Method for measuring specific heat capacity of plastics).
Density was determined by an underwater substitution method using a density measuring instrument (MS-DNY-43 manufactured by Mettler Toledo Co., Ltd.).
From the obtained thermal diffusion coefficient, specific heat, and density, the thermal conductivity of the obtained cured product and filler-containing cured product was determined by the following equation.
Formula: λ=α・Cp・ρ
[λ: Thermal conductivity (W/m·K), α: Thermal diffusion coefficient (m ² /s), Cp: Specific heat (J/g·K), ρ: Density (kg/m ³ )]

<Evaluation result of cured product>
The evaluation results of the cured product were as shown in Tables 1 and 2 below. In Tables 1 and 2, "-" means that the corresponding raw material is not blended.

As is clear from Table 1, the cured product of the curable resin composition containing the terphenyl-type cyanate ester compound and the terphenyl-type epoxy compound of the present invention is higher than that using a single cyanate ester compound. It was confirmed that it has excellent thermal conductivity (comparison of Example 1 and Comparative Examples 1 to 3).
In addition, compared with a resin cured product containing a terphenyl-type cyanate ester compound and a conventional epoxy compound, and a resin cured product containing a terphenyl-type epoxy compound and a conventional cyanate ester compound or an amine-based curing agent, It was confirmed that the resin cured product of the present invention has excellent thermal conductivity (compare Example 1 and Comparative Examples 4 to 6).

As is clear from Table 2, the terphenyl-type cyanate ester compound of the present invention, the terphenyl-type epoxy compound, the aluminum nitride having a thermal conductivity of 3 W / (m K) or more, and the thermal conductivity of 3 W / (m · K) It was confirmed that the resin composition of the present invention containing alumina that is above has excellent thermal conductivity

INDUSTRIAL APPLICABILITY The resin composition of the present invention exhibits excellent thermal conductivity and is therefore industrially useful.

Claims (14)

A resin composition comprising a cyanate ester compound (A) represented by the following formula (1) and an epoxy compound (B) represented by the following formula (3).

(In formula (1), Ar ¹ and Ar ² both represent a divalent group represented by the following formula (5), and Ar ³ represents a divalent group represented by the following formula (6) .)

(In formula (3), Ar ⁴ and Ar ⁵ both represent a divalent group represented by formula (5) above, and Ar ⁶ represents a divalent group represented by formula (6) above .) . From a cyanate ester compound (C) other than the cyanate ester compound (A), a phenol resin, an epoxy compound other than the epoxy compound (B), an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group The resin composition according to claim 1 , further comprising one or more selected from the group consisting of: 3. The resin composition according to claim 1, further comprising a filler. The resin composition according to claim 3 , wherein the filler has a thermal conductivity of 3 W/(m·K) or more. 5. The resin composition according to any one of claims 1 to 4 , which is used for a sheet-shaped molding. A cured product obtained by curing the resin composition according to any one of claims 1 to 5 . A single-layer resin sheet obtained by molding the resin composition according to any one of claims 1 to 5 into a sheet. a support;
The resin composition according to any one of claims 1 to 5 , which is arranged on one side or both sides of the support;
A laminated resin sheet. a substrate;
The resin composition according to any one of claims 1 to 5 , impregnated or applied to the base material,
A prepreg. at least one selected from the group consisting of the single-layer resin sheet according to claim 7 , the laminated resin sheet according to claim 8 , and the prepreg according to claim 9 ;
At least one metal foil selected from the group consisting of the single-layer resin sheet, the laminated resin sheet, and the prepreg, disposed on one side or both sides;
has
A metal foil-clad laminate comprising a cured product of a resin composition contained in at least one selected from the group consisting of the single-layer resin sheet, the laminated resin sheet and the prepreg. an insulating layer;
a conductor layer formed on one side or both sides of the insulating layer;
has
A printed wiring board, wherein the insulating layer comprises a cured product of the resin composition according to any one of claims 1 to 5 . A sealing material comprising the resin composition according to any one of claims 1 to 5 . A fiber-reinforced composite material comprising the resin composition according to any one of claims 1 to 5 and reinforcing fibers. An adhesive comprising the resin composition according to any one of claims 1 to 5 .