WO2019031178A1

WO2019031178A1 - Resin composition, cured product, single-layer resin sheet, laminated resin sheet, prepreg, metal-foiled laminate sheet, printed circuit board, sealing material, fiber reinforced composite material, and adhesive agent

Info

Publication number: WO2019031178A1
Application number: PCT/JP2018/027009
Authority: WO
Inventors: 講平中西; 俊介片桐; 染谷　昌男
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2017-08-08
Filing date: 2018-07-19
Publication date: 2019-02-14
Also published as: TW201910429A; JP7052797B2; JPWO2019031178A1

Abstract

A resin composition comprising a cyanic ester compound represented by formula (1) and a filler having a thermal conductivity of 3W/(m∙K) or more. NCO-Ar1-Ar2-Ar3-OCN (1) (In formula (1), Ar1 and Ar3 are the same or different and represent a divalent group expressed by formula (2), and Ar2 represents a divalent group expressed by formula (3) or (4).) (2) (3) (4) (In formulas (2), (3), and (4), R1 and R2 represent monovalent substituents and each independently represents 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 to 4, and m represents an integer of 1 to 8.)

Description

Resin composition, cured product, single layer resin sheet, laminated resin sheet, prepreg, metal foil-clad laminate, printed wiring board, sealing material, fiber reinforced composite material and adhesive

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.

In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, etc. are accelerating. Along with this, various characteristics required for a laminate for a semiconductor package used for a printed wiring board are becoming increasingly severe. Examples of the required properties include properties such as low water absorption, hygroscopic heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, high plating peel strength and the like.

Conventionally, cyanate ester compounds are known as resins for printed wiring boards excellent in heat resistance and electrical properties, and in recent years, resin compositions in which an epoxy resin, a bismaleimide compound, etc. are used in combination with a cyanate ester compound are semiconductor plastic packages It is widely used for high-performance printed wiring board materials etc.
For example, Patent Document 1 describes that a resin composition composed of a cyanate ester compound having a specific structure and other components is excellent in properties such as low water absorption and low coefficient of thermal expansion.

WO 2012/105547

Although it can be said that the resin composition described in Patent Document 1 has good physical properties with respect to properties such as low water absorption and low thermal expansion coefficient, it still has room for improvement from the viewpoint of thermal conductivity. is there. For example, when it is set as an insulating material like a printed wiring board, and other resin sheets, if these heat conductivity is not enough, it is difficult to apply to the use where heat dissipation is required.

The present invention has been made in view of the above problems, and exhibits excellent thermal conductivity, a resin composition, a cured product, a single layer resin sheet, a laminated resin sheet, a prepreg, a metal foil-clad laminate, and a print. It is an object of the present invention to provide a wiring board, a sealing material, a fiber reinforced composite material and an adhesive.

The present inventors diligently studied to solve the above problems. As a result, by using together the cyanate ester compound which has a specific structure, and the filler which has a predetermined | prescribed thermal conductivity, it discovers that the said subject is solvable, and came to complete this invention.

That is, the present invention includes the following aspects.
[1]
The resin composition containing the cyanate ester compound represented by following formula (1), and the filler whose thermal conductivity is 3 W / (m * K) or more.

(In Formula (1), Ar ¹ and Ar ³ are the same or different and each represents a divalent group represented by the following Formula (2), Ar ² is represented by the following Formula (3) or (4) (Indicating a divalent group))

(In the formula (2), the formula (3) and the formula (4), R ₁ and R ₂ each represent a monovalent substituent, each independently a hydrogen atom, a linear or branched C _{1 to} C 6 chain Or an alkyl group of 1 to 4 or a halogen atom, n is an integer of 1 to 4 and m is an integer of 1 to 8)
[2]
The resin composition according to [1], wherein Ar ¹ and Ar ³ are each independently represented by the following formula (5) or (6).

[3]
The resin composition as described in [1] or [2] to which said Ar ² is represented by following formula (7) or (8).

[4]
1 type selected from the group consisting of cyanate ester compounds (A) other than the above-mentioned cyanate ester compounds, maleimide compounds, phenol resins, epoxy resins, oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group The resin composition according to any one of [1] to [3], further including the above.
[5]
The resin composition according to any one of [1] to [4], which is for a sheet-like shaped article.
[6]
A cured product obtained by curing the resin composition according to any one of [1] to [5].
[7]
A single-layer resin sheet obtained by forming the resin composition according to any one of [1] to [4] into a sheet.
[8]
A support,
The resin composition according to any one of [1] to [4], which is disposed on one side or both sides of the support.
Having a laminated resin sheet.
[9]
A substrate,
The resin composition according to any one of [1] to [4], which is impregnated or applied to the substrate.
Have a prepreg.
[10]
At least one selected from the group consisting of the single-layer resin sheet described in [7], the laminated resin sheet described in [8], and the prepreg described in [9],
At least one metal foil disposed on one side or both sides selected from the group consisting of the single-layer resin sheet, the laminated resin sheet, and the prepreg;
Have
The metal foil tension laminate board containing the hardened material of the resin composition contained in at least one sort chosen from the group which consists of the single layer resin sheet, the resin sheet, and the pre-preg.
[11]
An insulating layer,
A conductor layer formed on one side or both sides of the insulating layer;
Have
A printed wiring board, wherein the insulating layer comprises the resin composition according to any one of [1] to [4].
[12]
A sealing material comprising the resin composition according to any one of [1] to [4].
[13]
A fiber-reinforced composite material comprising the resin composition according to any one of [1] to [4] and a reinforcing fiber.
[14]
An adhesive comprising the resin composition according to any one of [1] to [4].

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 reinforced that exhibit excellent thermal conductivity. Composite materials as well as adhesives can be provided.

FIG. 1 is an IR chart of DPCCN obtained in Synthesis Example 1. FIG. 2 is a ¹ H-NMR chart of DPCCN obtained in Synthesis Example 1. FIG. 3 is a ¹³ C-NMR chart of DPCCN obtained in Synthesis Example 1. FIG. 4 is an IR chart of DPCMeCN obtained in Synthesis Example 2. FIG. 5 is a ¹ H-NMR chart of DPCMeCN obtained in Synthesis Example 2. FIG. 6 is an IR chart of TPM eCN obtained in Synthesis Example 3. FIG. 7 is a graph showing the relationship between the filler volume filling rate and the filler-containing cured product thermal conductivity in Example 3 and Example 4 and Comparative Examples 5 and 6.

Hereinafter, although a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail, the present invention is not limited to this, and various modifications can be made within the scope of the present invention. Is possible.

[Resin composition]
The resin composition of the present embodiment contains a cyanate ester compound represented by the following formula (1), and a filler having a thermal conductivity of 3 W / (m · K) or more. Since it is comprised in this way, the resin composition of this embodiment can express the outstanding thermal conductivity.

(In the formula (2), the formula (3) and the formula (4), R ₁ and R ₂ each represent a monovalent substituent, each independently a hydrogen atom, a linear or branched C _{1 to} C 6 chain Or an alkyl group of 1 to 4 or a halogen atom, n is an integer of 1 to 4 and m is an integer of 1 to 8)

(Cyanate ester compound)
The cyanate ester compound in the present embodiment is represented by the above formula (1). By having such a structure, the cyanate ester compound of the present embodiment can exhibit excellent thermal conductivity. About the desired effect of such this embodiment, although it is not the meaning limited to the following, the present inventors infer as follows. Since the cyanate ester compound in the present embodiment has the mesogen structure as described above, it exhibits a specific orientation on the surface of the filler in the present embodiment as compared to other compounds not having the mesogen structure. As a result, it is assumed that many heat conduction paths can be secured. Therefore, it is considered that the resin composition of the present embodiment can exhibit excellent thermal conductivity as compared to the case where the other compound and the filler are combined.

Specific examples of the cyanate ester compound represented by the above formula (1) are not limited to the following,
1,4-bis (4-cyanatophenyl) -1-cyclohexene,
1- (3-Methyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2-Methyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-ethyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2-ethyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-n-Propyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2-n-Propyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-isopropyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2-isopropyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-n-butyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2-n-butyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-Isobutyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2-isobutyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-s-butyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2-s-Butyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-t-butyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2-t-butyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3,6-dimethyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3,5-dimethyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2,3,6-trimethyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (2,3,5-trimethyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-isopropyl-6-methyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-isopropyl-5-methyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-t-Butyl-6-methyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3-t-Butyl-5-methyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3,5-di-t-butyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene,
1- (3,5-diisopropyl-4-cyanatophenyl) -4- (4-cyanatophenyl) -1-cyclohexene and the like can be mentioned.

In the embodiment, it is preferable that Ar ¹ and Ar ³ in the formula (1) are each independently represented by the following formula (5) or (6) from the viewpoint of expressing better thermal conductivity. From the same viewpoint, Ar ² in Formula (1) is preferably represented by the following Formula (7) or (8).

It is more preferable that the cyanate ester compound in the present embodiment is a cyanate ester compound represented by the following formula (1A) from the viewpoint of expressing a further favorable thermal conductivity, and the following formulas (1B) and ( It is even more preferable to be a cyanate ester compound represented by 1C).

(In formula (1A), R represents a monovalent substituent, and each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. N is 1 to 6 Indicates an integer of 4.)

[Method for producing cyanate ester compound]
The method for producing the cyanate ester compound of the present embodiment is not particularly limited, but the hydroxy-substituted aromatic compound represented by the following formula (9) is cyanated to be represented by the following formula (1) It is preferable to have a cyanation step to obtain a cyanate ester compound.

(In formula (9), Ar ¹ , Ar ³ and Ar ² have the same meanings as those in formula (1))

<Cyanation process>
It does not specifically limit as method to cyanate the hydroxy-substituted aromatic compound in a cyanation process, A well-known method is applicable. Specifically, a method of reacting a hydroxy-substituted aromatic compound with a cyanogen halide in the presence of a basic compound in a solvent, wherein the cyanogen halide is always present in excess of a base in the presence of a base in the solvent Thus, a method of reacting a hydroxy-substituted aromatic compound with a cyanogen halide (see US Patent 3,553,244), or using a tertiary amine as a base and using it in excess over cyanogen halide, a solvent After the tertiary amine is added to the hydroxy-substituted aromatic compound in the presence of the compound, and then the halogenated cyanogen is dropped, or the halogenated cyanogen and the tertiary amine are dropped together (see Patent No. 3319061); Method of reacting a hydroxy-substituted aromatic compound, a trialkylamine and a cyanogen halide in a continuous plug flow system (Patent No. 3 (See Japanese Patent Application Laid-Open No. 05559)), treatment of a tert-ammonium halide by-produced when reacting a hydroxy-substituted aromatic compound with a cyanogen halide in the presence of a quaternary amine in a non-aqueous solution with a cation and anion exchange pair (See Patent No. 4055210), after simultaneously adding and reacting a tertiary amine and a cyanogen halide in the presence of water and a separable solvent to a hydroxy-substituted aromatic compound Washing and liquid separation, and precipitation purification from the resulting solution using a secondary or tertiary alcohol or a hydrocarbon poor solvent (see Patent No. 2991054), further, a hydroxy-substituted aromatic compound, Method of reacting cyanogen halide and tertiary amine in a biphasic solvent of water and an organic solvent under acidic conditions (Japanese Patent No. 5026727) The irradiation) or the like, can be obtained cyanate ester compound of the present embodiment.

The obtained cyanate ester compound can be identified by a known method such as NMR. The purity of the cyanate ester compound can be analyzed by liquid chromatography or IR spectroscopy. Byproducts such as dialkyl cyanoamide in the cyanate ester compound and volatile components such as residual solvent can be quantitatively analyzed by gas chromatography. A halogen compound remaining in a cyanate ester compound can be identified by a liquid chromatograph mass spectrometer, and can be quantitatively analyzed by ion chromatography after decomposition by a potentiometric titration or combustion method using a silver nitrate solution . The polymerization reactivity of the cyanate ester compound can be evaluated by the gelation time by the hot plate method or the torque measurement method.

In the present embodiment, from the viewpoint of obtaining more excellent thermal conductivity, the content of the cyanate ester compound of the present embodiment in the resin composition is preferably 5% by mass or more, more preferably 10% by mass. It is above.

The resin composition of the present embodiment further includes a cyanate ester compound other than the cyanate ester compound of the present embodiment (hereinafter, also referred to as “cyanate ester compound (A)”), a maleimide compound, a phenol resin, an epoxy resin And at least one selected from the group consisting of oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group. Each of these components will be described below.

[Cyanate ester compound (A)]
The cyanate ester compound (A) is a cyanate ester compound other than the cyanate ester compound of the present embodiment, and is a compound having in the molecule an aromatic moiety substituted at least one cyanate ester group. If it is, it will not be limited in particular. The resin composition using a cyanate ester compound has excellent properties of glass transition temperature, low thermal expansion, plating adhesion and the like when it is a cured product.

Examples of the cyanate ester compound (A) include, but are not limited to, those represented by the following formula (10).

In the above formula (10), Ar ₁ represents an aromatic ring. When there are two or more, they may be the same or different. The aromatic ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a single benzene ring. Ra each independently represents 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 6 to 12 carbon atoms A group to which an aryl group is bonded is shown. The aromatic ring in Ra may have a substituent, and the substituent in Ar ₁ and Ra can be selected at any position. p represents the number of cyanato groups bonded to Ar ₁ and each is independently an integer of 1 to 3. q represents the number of Ra to bind to Ar _1, when Ar ₁ is 4-p, naphthalene ring when the benzene ring when those 6-p, 2 one benzene ring is a single bond is 8-p . t represents an average repeat number and is an integer of 0 to 50, and the cyanate ester compound (A) may be a mixture of compounds different in t. When there are a plurality of X's, each independently has a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), or a bivalent nitrogen having 1 to 10 Organic group (eg, -NRN- (wherein 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 at Ra in the above formula (10) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group and the like).
The hydrogen atom in the alkyl group in the above formula (10) and the aryl group in Ra is substituted by 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 It is also good.
Specific examples of the alkyl group include, but are not limited to, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, Examples include 2,2-dimethylpropyl group, cyclopentyl group, hexyl group, cyclohexyl group, and trifluoromethyl group.
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, dicyano A phenyl group, a trifluorophenyl group, a methoxyphenyl group, an o-, m- or p-tolyl group and the like can be mentioned.
Examples of the alkoxyl group include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.
Specific examples of the divalent organic group having 1 to 50 carbon atoms as X in the above-mentioned formula (10) are not limited to the following, but methylene group, ethylene group, trimethylene group, dimethylmethylene group, cyclopentylene group, cyclohexene group Examples thereof include a silene group, a trimethylcyclohexylene group, a biphenylylmethylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, and a phthalide diyl group. The hydrogen atom in the divalent organic group may be substituted by 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 a nitrogen number of 1 to 10 in X in the above formula (10) include, but are not limited to, a group represented by -NRN-, an imino group, a polyimide group, etc. It can be mentioned.

Moreover, as an organic group of X in said Formula (10), what is a structure represented with following formula (11) or following formula (12) is mentioned, for example.

(In the above formula (11), Ar ₂ represents an aromatic ring, and when u is 2 or more, they may be the same or different from each other. The aromatic ring is not particularly limited. Rb, Rc, Rf and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, And each independently represents an aryl group having at least one trifluoromethyl group or a phenolic hydroxy group, Rd and Re each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, It is selected from any one of an alkoxyl group having 1 to 4 carbon atoms or a hydroxy group, and u represents an integer of 0 to 5.)

(In the formula (12), 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 from each other. Ri and Rj are each independently hydrogen At least one substituted with an 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 a cyanato group An aryl group is shown, and v is an integer of 0 to 5, but the cyanate ester compound (A) may be a mixture of compounds different in v).

Furthermore, as X in Formula (10), the bivalent group represented by a following formula is mentioned.

(In the above formula, z represents an integer of 4 to 7. R k independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Specific examples of Ar _{2 of} Formula (11) and Ar ₃ of Formula (12) include 1,4-phenylene, 1,3-phenylene, 4,4′-biphenylene, and 2,4′-biphenylene 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 And-a naphthylene group, a 1,8-naphthylene group, a 1,3-naphthylene group, a 1,4-naphthylene group and a 2,7-naphthylene group.
The alkyl group and aryl group in Rb, Rc, Rd, Re, Rf and Rg in Formula (11), and Ri and Rj in Formula (12) have the same meanings as the alkyl group and aryl group in Ra in Formula (10) above. is there.

Specific examples of the cyanate ester compound represented by the above formula (10) include, but are not limited to, cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4- 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, Cyanatononyl Benzene, 2- (4-cyanaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyana -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-aceto Aminobenzene, 4-cyanatobenzophenone, 1-cyanato- 2,6-di-tert-butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,2 4-dicyanato-2,4-dimethylbenzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methyl Benzene, 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-disocyanatosilane, 2, 2 ' Or 4,4'-dicyanatobiphenyl, 4,4'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis (4-cyanato-3,5-dimethylphenyl) methane 1,1-bis (4-cyanatophenyl) ethane, 1,1-bis (4-cyanatophenyl) 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- (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-cyano) Anatophenyl) -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-cyanato) Phenyl) -2,2-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,2,4-trimethyl Pentane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1-bis (4- Cyanatophenyl) -1-fe Luethane, bis (4-cyanatophenyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-bis (4-cyanatophenyl) biphenylmethane) 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, 2,4-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 (Phenolphthalein cyanate), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (3 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-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 '-(hexa) Fluoroisopropylidene) 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, - 3,3-bis (4-cyanatophenyl) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one.

In addition, other specific examples of the compound represented by the above formula (10) include, but are not limited to, phenol novolac resin and cresol novolac resin (phenol, alkyl substituted phenol or halogen substituted phenol by a known method; Formaldehyde compounds such as formalin and paraformaldehyde are reacted in an acidic solution), trisphenol novolak resin (reaction of hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolac resin (fluorenone compound) And 9,9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenolaralkyl resin, cresolaralkyl resin, naphtholaralkyl resin and biphenylaralkyl resin (known methods) By, Ar '- (. (CH 2 Y) 2 Ar' represents a phenyl group, Y is below a halogen atom, similarly in this paragraph.) And bishalogenomethyl compounds represented by the phenol compound Acidic catalyst or non-catalyzed reaction, reaction of a bis (alkoxymethyl) compound such as Ar ′-(CH ₂ OR) ₂ with a phenolic compound in the presence of an acidic catalyst, or A reaction product of a bis (hydroxymethyl) compound represented by Ar ′-(CH ₂ OH) ₂ and a phenol compound in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound Polycondensation), phenol-modified xylene formaldehyde resin (xylene formaldehyde resin and phenol by a known method) A compound in which it is reacted in the presence of an acidic catalyst), a modified naphthalene formaldehyde resin (a reaction of a naphthalene formaldehyde resin and a hydroxy substituted aromatic compound in the presence of an acidic catalyst by a known method) Cyclopentadiene resin, phenol resin having a polynaphthylene ether structure (in a known method, a polyhydroxy naphthalene compound having two or more phenolic hydroxy groups in one molecule is subjected to dehydration condensation in the presence of a basic catalyst And the like, and those prepolymers and the like.

Moreover, as an example of a cyanate ester compound (A), what is represented by following formula (13) is also mentioned.

(In formula (13), Ar ₄ represents an aromatic ring, and when there are a plurality, it may be the same as or different from each other. R ₁ independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group or an oxy And R ₂ represents a monovalent substituent, each independently represents a hydrogen atom, an alkyl group or an aryl group, and R ₃ each independently represents a hydrogen atom or carbon number Is an alkyl group of 1 to 3, an aryl group, a hydroxy group or a hydroxymethylene group, m is an integer of 1 or more, n is an integer of 0 or more, and cyanate ester compounds (A) are m and n. The sequence of each repeating unit is arbitrary, l represents the number of bonded cyanato groups and is an integer of 1 to 3. x represents the number of bonded R ₂ , Ar ₄ of displaceable group From represents the number obtained by subtracting the (l + 2) .y represents a bond number of R _3, represents the number obtained by subtracting 2 from the replaceable radix Ar _4.)

Examples of Ar ₄ in the above formula (13) include a benzene ring, a naphthalene ring, an anthracene ring and the like, but are not particularly limited thereto.
The alkyl group in R ₂ and R ₃ of Formula (13) may have any of a linear or branched chain structure and a cyclic structure (eg, a cycloalkyl group etc.).
Further, even if the hydrogen atom in the aryl group in R ₂ and R ₃ in the formula (13) is substituted by 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 group A propyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group etc. are mentioned.
Specific examples of the aryl group include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluoro And phenyl group, methoxyphenyl group, o-, m- or p-tolyl group and the like. Furthermore, examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like.

Specific examples of the cyanate ester compound represented by the formula (13) include phenol-modified xylene-formaldehyde resin (in which a xylene-formaldehyde resin and a phenol compound are reacted in the presence of an acidic catalyst by a known method), modified naphthalene Although the thing which cyanated phenol resins, such as formaldehyde resin (The thing which made naphthalene formaldehyde resin and a hydroxy substituted aromatic compound react in presence of an acidic catalyst by the well-known method) by the method similar to the after-mentioned is mentioned, It is not particularly limited. These cyanate ester compounds can be used alone or in combination of two or more.

The above-mentioned cyanate ester compounds (A) can be used singly or in combination of two or more.

Among the above, phenol novolac type cyanate ester compound, naphthol aralkyl type cyanate ester compound, biphenylaralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, adamantane skeleton type cyanate Ester compounds are preferred, and naphthol aralkyl type cyanate ester compounds are particularly preferred.

(Epoxy resin)
As an epoxy resin, if it is an epoxy resin which has 2 or more epoxy groups in 1 molecule, a well-known thing can be used suitably, The kind in particular is not limited. Specifically, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl ester Type epoxy resin, aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl novolac type epoxy resin, naphthalene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy Resin, dihydroanthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol aralkyl type epoxy resin, 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, fat Cyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidyl amine type epoxy resin, compound obtained by epoxidizing double bond such as butadiene, and compound obtained by reaction of hydroxyl group-containing silicone resin with epichlorohydrin Be Among these epoxy resins, biphenylaralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable from the viewpoint of flame retardancy and heat resistance. Further, from the viewpoint of further enhancing the thermal conductivity, the resin composition of the present embodiment is at least selected from the group consisting of naphthalene type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin and isocyanuric acid type epoxy resin. It is preferred to include one epoxy resin. Examples of the naphthalene type epoxy resin include, but are not limited to, for example, trade name HP-4710, trade name HP-4700, trade name HP-4032D, etc., manufactured by DIC Corporation. Examples of the biphenyl type epoxy resin include, but are not limited to, for example, Mitsubishi Chemical Co., Ltd., trade name YX4000, trade name YL6121H, trade name YX7399, and the like. Examples of the triphenylmethane epoxy resin include, but are not limited to, Nippon Kayaku Co., Ltd., trade name EPPN-501H, trade name EPPN-501HY, trade name EPPN-502H, and the like. Examples of the isocyanuric acid type epoxy resin include, but are not limited to, for example, Nissan Chemical Industries, Ltd., trade name TEPIC-S, trade name TEPIC-VL, and the like. These epoxy resins can be used singly or in combination of two or more.

(Maleimide compound)
As the maleimide compound, generally known compounds can be used as long as they are compounds having one or more maleimide groups in one molecule. For example, 4,4-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl -4,4-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 4,4-diphenylether bismaleimide, 4,4 -Diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, polyphenylmethane maleimide, novolac maleimide, biphenylaralkyl maleimide, and these maleimide compounds Prepolymer Or although prepolymer of the maleimide compound and amine compound, but is not particularly limited. These maleimide compounds can be used alone or in combination of two or more. Among these, novolak type maleimide compounds and biphenylaralkyl type maleimide compounds are particularly preferable.

(Phenol resin)
As the phenol resin, generally known phenol resins can be used as long as they have two or more hydroxy groups in one molecule. Specific examples thereof include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type Phenol resin, biphenylaralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenolaralkyl type phenol resin Naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin Nord resins, alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, a hydroxyl group-containing silicone resins and the like, but is not particularly limited. Among these phenol resins, biphenylaralkyl type phenol resins, naphtholaralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in view of flame retardancy. These phenol resins can be used singly or in combination of two or more.

(Oxetane resin)
As the oxetane resin, those generally known can be used. For example, alkyl oxetanes such as oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, 3, 3-dimethyl oxetane, 3-methyl 3-methoxymethyl oxetane, 3, 3-di (trifluoro) Methyl) perfluoxetane, 2-chloromethyl oxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name of Toho Gosei Co., Ltd.), OXT-121 (trade name of Toho Gosei Co., Ltd.), etc. Although it may be mentioned, it is not particularly limited. These oxetane resins can be used alone or in combination of two or more.

(Benzoxazine compound)
As the benzoxazine compound, generally known compounds can be used as long as they are compounds having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (trade name of Konishi Chemical) bisphenol F type benzooxazine BF-BXZ (trade name of Konishi Chemical), bisphenol S type benzooxazine BS-BXZ (trade name of Konishi Chemical), P Examples thereof include -d-type benzoxazine (trade name of Shikoku Kasei Kogyo Co., Ltd.) and F-a type benzoxazine (trade name of Shikoku Kasei Kogyo Co., Ltd.) and the like, but not limited thereto. These benzoxazine compounds can be used alone or in combination of two or more.

(Compound having a polymerizable unsaturated group)
As compounds having a polymerizable unsaturated group, generally known compounds can be used. For example, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, (Meth) acrylates of monohydric or polyhydric alcohols such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol Epoxy (meth) acrylates such as A-type epoxy (meth) acrylate, bisphenol F-type epoxy (meth) acrylate and the like, and benzocyclobutene resin But it is not particularly limited. The compound which has these unsaturated groups can be used 1 type or in mixture of 2 or more types. In addition, the said "(meth) acrylate" is the concept containing an acrylate and the methacrylate corresponding to it.

(Filling material)
The resin composition of the present embodiment contains a filler from the viewpoint of thermal expansion characteristics, dimensional stability, flame retardancy, thermal conductivity, dielectric characteristics, and the like. The filler in the present embodiment has a thermal conductivity of 3 W / (m · K) or more. In the present embodiment, the thermal conductivity of the filler is preferably 5 W / (m · K) or more, more preferably 10 W / (m · K) or more, and 15 W / (m · K) or more Is more preferably 20 W / (m · K) or more, still more preferably 25 W / (m · K) or more, and 30 W / (m · K) or more Even more preferred.
The thermal conductivity of the filler used in the present embodiment can be confirmed with reference to “Thermal physical property handbook” edited by the Japan Society of Thermophysical Properties, etc., and a known value is adopted as the thermal conductivity of the filler. be able to. In addition, it is not necessary for all the fillers contained in the resin composition to have a thermal conductivity of 3 W / (m · K) or more, and the filler having 50 mass% or more with respect to the total amount of the contained fillers is 3 W / It is preferable to have a thermal conductivity of (m · K) or more, and it is more preferable that the filler of 75% by mass or more has a thermal conductivity of 3 W / (m · K) or more. That is, the filler may include one having a thermal conductivity of less than 3 W / (m · K).
A well-known thing can be used suitably as a filler mentioned above, About the filler which has the heat conductivity of 3 W / (m * K) or more, the heat of less than 3 W / (m * K) The type of the filler having conductivity is not particularly limited. In particular, fillers commonly used in laminate applications can be suitably used as fillers. Specific examples of the filler include natural silica, crystalline silica, synthetic silica, amorphous silica, aerosil, silicas such as hollow silica, white carbon, titanium white, oxides such as zinc oxide, magnesium oxide, zirconium oxide, boron nitride Cohesive boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated product (Aluminum hydroxide is heat-treated to reduce a part of crystal water), boehmite, magnesium hydroxide etc. Metal hydrates, 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, -In addition to inorganic fillers such as glass, M-glass G20, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, Q glass etc.), hollow glass, spherical glass etc. And rubber powders such as styrene type, butadiene type and acrylic type, core-shell type rubber powder, and organic fillers such as silicone resin powder, silicone rubber powder, silicone composite powder and the like. The fillers may be used alone or in combination of two or more.
Among the above, crystalline silica, boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, boehmite and alumina are preferable, and alumina, aluminum nitride and boron nitride are particularly preferable. The thermal conductivity of the resin composition tends to be further improved by using these fillers.
In the present embodiment, the filling amount of the filler in the composition is not particularly limited, but is preferably 40 vol% or more, more preferably 50 vol% or more, and further preferably 60 vol% or more from the viewpoint of giving more excellent thermal conductivity. Preferably, 70 vol% or more is even more preferable. Further, the filling amount is preferably 90 vol% or less, more preferably 85 vol% or less from the viewpoint of formability.

Here, when the filler is contained in the resin composition, it is preferable to use a silane coupling agent or a wetting and dispersing agent in combination. As a silane coupling agent, what is generally used for the surface treatment of an inorganic substance can be used suitably, The kind in particular is not limited. Specific examples of the silane coupling agent include, but are not limited to, aminosilanes such as, but not limited to, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycid Epoxysilanes such as xylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxypropyltrimethoxysilane, vinyl-tri (β-methoxyethoxy) silane, N Cationic silane systems, such as -β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, as well as phenylsilane systems. The silane coupling agent can be used singly or in combination of two or more. Moreover, as a wetting and dispersing agent, what is generally used for paints can be used suitably, The kind in particular is not limited. As the wetting and dispersing agent, a copolymer-based wetting and dispersing agent is preferably used, and may be a commercially available product. Specific examples of commercially available products include, but are not limited to, Disperbyk-110, 111, 161, 180, BYK-W 996, BYK-W 9010, BYK-W 903, BYK-W 940, etc., manufactured by Big Chemie Japan Ltd. Be The wetting and dispersing agents can be used alone or in combination of two or more.

(Hardening accelerator)
Moreover, the resin composition of this embodiment may contain the hardening accelerator for adjusting a hardening speed suitably, as needed. As this hardening accelerator, what is generally used as hardening accelerators, such as a cyanate ester compound and an epoxy resin, can be used suitably, The kind is not specifically limited. Specific examples of the curing accelerator include zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octylate, organic acid salts such as manganese octylate, phenol, xylenol, cresol, resorcinol, catechol Phenols such as octylphenol and nonylphenol, alcohols such as 1-butanol and 2-ethylhexanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, Imidazoles such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like; Derivatives such as adducts of carboxylic acids of imidazoles or their anhydrides, dicyandiamide, amines such as benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, Phosphorus compounds such as phosphonium salt compounds, diphosphine compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxy carbonate, di-2-ethylhexyl Peroxides such as peroxycarbonates or azo compounds such as azobisisobutyronitrile can be mentioned. The curing accelerator can be used singly or in combination of two or more.

(Other additives)
Furthermore, in the resin composition of the present embodiment, various polymer compounds such as other thermosetting resins, thermoplastic resins and their oligomers, elastomers, and flame retardant compounds as long as the desired properties are not impaired. And various additives etc. can be used in combination. These are not particularly limited as long as they are generally used. Specific examples of flame retardant compounds include, but are not limited to: bromine compounds such as 4,4'-dibromobiphenyl, phosphate esters, melamine phosphates, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazines Examples thereof include ring-containing compounds and silicone compounds. Moreover, as various additives, although it is not limited to the following, for example, an ultraviolet light absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, a photosensitizer, a dye, a pigment, a thickener, a flow control agent Lubricants, antifoaming agents, dispersants, leveling agents, brighteners, polymerization inhibitors and the like. These can be used singly or in combination of two or more, as desired.

(Organic solvent)
In addition, the resin composition of this embodiment can contain the organic solvent as needed. In this case, the resin composition of the present embodiment can be used as an aspect (solution or varnish) in which at least part, preferably all, of the various resin components described above are dissolved or compatible with the organic solvent. As the organic solvent, known solvents can be appropriately used so long as at least a part, preferably all of the various resin components described above can be dissolved or compatible, and the type thereof is not particularly limited. . Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate and isoamyl acetate And ester solvents such as methyl methoxypropionate and methyl hydroxyisobutyrate; polar solvents such as amides such as dimethylacetamide and dimethylformamide; and nonpolar solvents such as aromatic hydrocarbons such as toluene and xylene. These can be used singly or in combination of two or more.

The resin composition of the present embodiment can be prepared according to a conventional method, and a method of obtaining a resin composition uniformly containing the cyanate ester compound of the present embodiment, a filler, and the other optional components described above The preparation method is not particularly limited as long as 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 filler, and the other optional components described above in a solvent and sufficiently stirring.

In addition, at the time of preparation of a resin composition, the well-known process (stirring, mixing, kneading process, etc.) for dissolving or disperse | distributing each component uniformly can be performed. For example, the dispersibility with respect to a resin composition is improved by performing a stirring dispersion process using the stirring tank attached to the stirrer which has a suitable stirring capability in the case of uniform dispersion | distribution of a filler. The above-mentioned stirring, mixing, and kneading processing can be appropriately performed using, for example, a device intended for mixing such as a ball mill and a bead mill, or a known device such as a mixing device of revolution and rotation type.

Since the resin composition of the present embodiment is particularly excellent in thermal conductivity as described above, it is particularly preferable to use it for application to a sheet-like molded body.

[Cured product]
The cured product of the present embodiment is obtained by curing the resin composition of the present embodiment. The method for producing the cured product is not particularly limited. For example, after the resin composition is melted or dissolved in a solvent, it is poured into a mold and obtained by curing under normal conditions using heat or light. Can. In the case of heat curing, the curing temperature is not particularly limited, but is preferably in the range of 120 ° C. 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 it is preferable to cure in the range of 100 nm to 500 nm in which curing proceeds efficiently by a photopolymerization initiator or the like.

The resin composition of the present embodiment can be used as a constituent material of a prepreg, a single layer resin sheet, a laminated resin sheet, a metal foil-clad laminate, a printed wiring board, and a semiconductor package. For example, a prepreg can be obtained by impregnating or coating a base material with a solution in which the resin composition of the present embodiment is dissolved in a solvent, and drying.
In addition, a film obtained by dissolving the resin composition of the present embodiment in a solvent is applied to a plastic film and dried using a peelable plastic film as a support to obtain a build-up film or a 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.
Moreover, the resin composition of this embodiment can also be used in the state which removed the solvent (non-hardened state), and can also be used in the state of semi-hardening (B stage formation) as needed.

[Resin sheet]
The laminated resin sheet of the present embodiment has a support and the above-described resin composition disposed on one side or both sides of the support. The method for producing the laminated resin sheet can be performed according to a conventional method, and is not particularly limited. For example, it can be obtained by applying a solution obtained by dissolving the resin composition of the present embodiment described above in a solvent to a support and drying it.

The support used herein is not particularly limited. For example, a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a surface of these films are coated with a release agent. An organic film substrate such as a mold release film and a polyimide film, a conductor foil such as copper foil and aluminum foil, a glass plate, a SUS plate, and a plate such as FRP are exemplified, but not limited thereto.

Examples of the coating method include a method of coating a solution obtained by dissolving the resin composition of the present embodiment in a solvent on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

Moreover, the single layer resin sheet of this embodiment is formed by shaping | molding the said resin composition in a sheet form. The manufacturing method of a single layer resin sheet can be performed according to a conventional method, and is not particularly limited. For example, in the method of producing the laminated resin sheet, a method is available in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied onto a support and dried, and then the support is peeled or etched from the laminated resin sheet. It can be mentioned. In addition, using a support by forming in a sheet shape by supplying a solution obtained by dissolving the resin composition of the present embodiment in the above-described embodiment in a solvent into a mold having a sheet-like cavity and drying. It is also possible to obtain a single layer resin sheet (resin sheet).

In addition, in preparation of the single layer resin sheet or laminated resin sheet of this embodiment, although the drying conditions at the time of removing a solvent are not specifically limited, A solvent tends to remain in a resin composition as it is low temperature, It is high temperature And a temperature of 20 ° C. to 170 ° C. for 1 to 90 minutes, since curing of the resin composition proceeds.

In addition, the thickness of the resin layer of the single layer or the 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 application thickness, and is not particularly limited. When the thickness is larger, the solvent tends to remain at the time of drying, and the thickness is preferably 0.1 to 500 μm.

Hereinafter, the prepreg of the present embodiment will be described in detail. The prepreg of the present embodiment has a substrate and the above-described resin composition impregnated or coated on the substrate. 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 substrate. Specifically, after impregnating or applying the resin composition of the present embodiment to a substrate, the resin composition is semi-cured by a method such as drying in a dryer at 120 to 220 ° C. for about 2 to 15 minutes. The prepreg of the embodiment can be manufactured. At this time, the adhesion amount of the resin composition to the base material, that is, the content of the resin composition (including the filler) with respect to the total amount of the semi-cured prepreg is preferably in the range of 20 to 99% by mass.

As a base material used when manufacturing the prepreg of this embodiment, the well-known thing used for various printed wiring board materials may be used. Examples of such a substrate include glass fibers, inorganic fibers other than glass such as quartz, organic fibers such as polyimide, polyamide and polyester, and woven fabrics such as liquid crystal polyester, but are particularly limited thereto. is not. As the shape of the substrate, woven fabrics, non-woven fabrics, rovings, chopped strand mats, surfacing mats and the like are known, and any of these may be used. A base material can be used individually by 1 type or in combination of 2 or more types as appropriate. Among the woven fabrics, in particular, woven fabrics which have been subjected to super-opening treatment and filling treatment are preferable from the viewpoint of dimensional stability. Furthermore, a liquid crystalline polyester woven fabric is preferable from the viewpoint of electrical properties. Furthermore, the thickness of the substrate is not particularly limited, but in the case of laminated plate applications, the range of 0.01 to 0.2 mm is preferable.

The metal foil tension laminate sheet 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 A sheet, at least one metal foil selected from the group consisting of the laminated resin sheet and the prepreg, and a group consisting of the single-layer resin sheet, the laminated resin sheet, and the prepreg It contains the cured product of the resin composition contained in at least one selected from the above. As a specific example in the case of using a prepreg, a metal foil such as copper or aluminum is disposed on one side or both sides of one prepreg or a laminate of a plurality of prepregs as described above, and a 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 a printed wiring board material, but a copper foil such as a rolled copper foil and an electrolytic copper foil is preferable. The thickness of the metal foil is not particularly limited, but is preferably 2 to 70 μm, and more preferably 3 to 35 μm. As a molding condition, a method used at the time of producing a laminate for a general printed wiring board and a multilayer board can be adopted. For example, using a multi-stage press, multi-stage vacuum press, continuous molding machine, autoclave molding machine, etc., laminate molding is performed under conditions of temperature 180 to 350 ° C., heating time 100 to 300 minutes, and surface pressure 20 to 100 kg / cm ² Thus, the metal foil-clad laminate of the present embodiment can be manufactured. A multilayer board can also be produced by laminating and molding the above-mentioned prepreg and a wiring board for the inner layer prepared separately. As a method of manufacturing a multilayer board, for example, copper foils of 35 μm are disposed on both sides of one of the prepregs described above, and laminated under the above conditions, an inner layer circuit is formed, and the circuit is blackened. Forming an inner layer circuit board. Further, the inner layer circuit board and the above-mentioned prepreg are alternately arranged one by one, and a copper foil is further arranged as the outermost layer, and laminated and formed preferably under vacuum under the above conditions. Thus, a multilayer board can be produced.

The metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board by further forming a pattern. The printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. Hereinafter, an example of the manufacturing method of a printed wiring board is shown. First, the metal foil-clad laminate described above is prepared. Next, the surface of the metal foil-clad laminate is subjected to etching to form an inner circuit, whereby an inner substrate is produced. If necessary, the inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength, and then, the required number of the above-described prepregs is superimposed on the inner layer circuit surface. Furthermore, a metal foil for the outer layer circuit is laminated on the outer side, and heat and pressure are integrally molded. In this manner, a multilayer laminate is produced in which an insulating layer made of a cured product of a base material and a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Then, after drilling the through holes and via holes in the multilayer laminate, a plated metal film is formed on the wall surfaces of the holes so that the inner layer circuit and the outer layer circuit metal foil are conducted. 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 a configuration including an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer includes the resin composition of the above-described embodiment. Become. For example, the prepreg of the present embodiment described above (the base material and the resin composition of the present embodiment impregnated or coated with the same), the layer of the resin composition of the metal foil-clad laminate of the present embodiment described above (the present embodiment The layer made of the resin composition of the present invention can constitute an insulating layer containing the resin composition of the present embodiment.

[Sealing material]
The sealing material of the present embodiment includes the resin composition of the present embodiment. As a method for producing the sealing material, generally known methods can be appropriately applied, and are not particularly limited. For example, the sealing material can be produced by mixing the above-described resin composition and various known additives or solvents generally used in sealing material applications using a known mixer. In addition, the method of adding a cyanate ester compound, various additives, and a solvent at the time of mixing can apply a generally known method suitably, and is not particularly limited.

[Fiber-reinforced composite material]
The fiber-reinforced composite material of the present embodiment includes the resin composition of the present embodiment and reinforcing fibers. As the reinforcing fiber, a generally known one can be used, and it is not particularly limited. 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 fibers, aramid fibers, boron fibers, PBO fibers, 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 may be suitably selected from woven fabric, non-woven fabric, mat, knit, braid, unidirectional strand, roving, chopped and the like. In addition, as a form of reinforcing fiber, applying a preform (a laminated fabric base made of reinforcing fiber, or one obtained by integrally stitching the same with a stitch yarn, or a fiber structure such as a three-dimensional woven fabric or a braid) You can also.

Generally as a manufacturing method of these fiber reinforced composite materials, a publicly known method can be applied suitably, and it is not limited in particular. Specific examples thereof include a liquid composite molding method, a resin film infusion method, a filament winding method, a hand layup method, and a pultrusion method. Among these, the resin transfer molding method, which is one of the liquid composite molding methods, requires that materials other than preforms, such as metal sheets, foam cores, honeycomb cores, etc., be set in advance in the mold. Since it can correspond to various applications from what it can, it is preferably used when mass-producing relatively complex composite materials in a short time.

〔adhesive〕
The adhesive of the present embodiment includes the resin composition of the present embodiment. As a method for producing an adhesive, generally known methods can be applied as appropriate, and are not particularly limited. For example, an adhesive agent can be manufactured by mixing the above-mentioned resin composition, and various well-known additives or solvents etc. which are generally used by adhesive application using a known mixer. In addition, the method of adding a cyanate ester compound, various additives, and a solvent at the time of mixing can apply a generally known method suitably, and is not particularly limited.

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of diphenylcyclohexene-type cyanate ester compound (hereinafter abbreviated as DPCCN) A cyanate ester compound DPCCN represented by the following formula (1B) was synthesized as described below.

<Synthesis of 1,4,4-tris (4-hydroxyphenyl) cyclohexane>
1,4,4-Tris (4-hydroxyphenyl) cyclohexane represented by the following formula (14) was synthesized by the following method.

In a 1-L separable flask equipped with a nitrogen blowing port and a thermometer, 282.33 g (3.0 mol) of phenol and 46.80 g of 35% hydrochloric acid were added and heated to 55 ° C. while flowing nitrogen. A mixture of 114.14 g (0.60 mol) of 4- (4-hydroxyphenyl) cyclohexanone and 282.33 g (3.0 mol) of phenol was added over 3 hours, and the whole was added and then stirred at 55 ° C. for 4 hours. The reaction mixture was adjusted to pH 6 by adding a 16% aqueous sodium hydroxide solution, and then cooled to room temperature. 1000 L of toluene was added, and the precipitate was collected by suction filtration. After washing three times with 350 mL of toluene, it was dried to obtain 185.35 g of 90% pure 1,4,4-tris (4-hydroxyphenyl) cyclohexane.
The assignments of ¹ H-NMR for 1,4,4-tris (4-hydroxyphenyl) cyclohexane are shown below.

¹ H-NMR (500 MHz, DMSO-d6) δ (ppm): 9.18 (s, 1 H, -OH), 9.07 (d, 2 H, -OH), 7.18 (d, 2 H, ArH) 6.98 (d, 2H, ArH), 6.83 (d, 2H, ArH), 6.71 (d, 2H, ArH), 6.60 (m, 4H, ArH), 2.68 (d 2H, cyclohexyl), 2.55 (m, 1H, cyclohexyl), 1.87 (t, 2H, cyclohexyl), 1.69 (d, 2H, cyclohexyl), 1.44 (dd, 2H, cyclohexyl)

<Synthesis of diphenylcyclohexene-type bisphenol (hereinafter abbreviated as “DPCOH”)>
DPCOH represented by the following formula (9B) was synthesized by the following method.

In a 500 mL three-necked flask equipped with a nitrogen inlet and a thermometer, 45.15 g (0.125 mol) of 1,4,4-tris (4-hydroxyphenyl) cyclohexane obtained by the above method, 48% aqueous sodium hydroxide solution 1 The reaction vessel was purged with nitrogen by adding .18 g and 22.65 g of tetraethylene glycol. The pressure in the reaction vessel was reduced to 100 mmHg while stirring, and thermal decomposition was performed at 210 ° C. for 5 hours to distill off phenol. The reaction solution was cooled to room temperature, opened to the air, and adjusted to pH 6 by adding 50% aqueous acetic acid solution. 100 mL of water was added and stirred, and the precipitate was collected by suction filtration. After washing three times with 50 mL of water, it was dried to obtain a crude product. The crude product was recrystallized with methanol to give 21.41 g of DPCOH.
The assignments of ¹ H-NMR for DPCOH are shown below.

¹ H-NMR (500 MHz, DMSO-d6) δ (ppm): 9.35 (s, 1 H, -OH), 9.15 (s, 1 H, -OH), 7.25 (d, 2 H, ArH) , 7.06 (d, 2H, ArH), 6.70 (dd, 4H, ArH), 6.05 (m, 1H, -CH =), 2.68 (m, 1H, -CH-), 2 _{_{.44 (m, 2H, -CH 2}} -), 2.36 (m, 1H, -CH 2 -), 2.19 (m, 1H, -CH 2 -), 1.93 (m, 1H, - CH _2- ), 1.75 (m, 1 H, -CH _2- )

<Synthesis of DPCCN>
To a 2 L four-necked flask equipped with an argon inlet and a thermometer, 40.0 g (0.15 mol) of DPCOH obtained by the above method and 800 mL of tetrahydrofuran were added under an argon stream. Further, 44.5 g (0.42 mol) of cyanogen bromide was added, and then the internal temperature was adjusted to −10 ° C. with a dry ice / acetone bath. Triethylamine 45.5 g (0.45 mol) was added dropwise over 20 minutes so that the internal temperature did not exceed -5.degree. C., and the mixture was stirred at -5.degree. C. for 2 hours. Along the way, 400 mL of tetrahydrofuran was added. After the temperature was raised to room temperature, the reaction solution was filtered. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was dissolved in 800 mL of chloroform. The chloroform solution was washed three times with 400 mL of 2.5% brine and once with 400 mL of water, and then concentrated under reduced pressure to obtain a solid. After 600 mL of hexane was added to the obtained solid and suspended and stirred, the solid was collected by filtration and dried to obtain 45.4 g of the target cyanate ester compound DPCCN. The IR spectrum of the resulting cyanate ester compound DPCCN showed absorptions at 2252 cm ^-1 and 2287 cm ^-1 (cyanate groups) and no absorption at the hydroxy group. The IR chart is shown in FIG.
The assignments of ¹ H-NMR for the cyanate ester compound DPCCN are shown below. ^{The 1} H-NMR chart is shown in FIG.

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm): 7.34 (m, 8 H, ArH), 6.20 (m, 1 H, -CH =), 2.93 (m, 1 H, -CH) _{-), 2.55 (m, 3H} , -CH 2 -), 2.33 (m, 1H, -CH 2 -), 2.11 (m, 1H, -CH 2 -), 1.90 (m , 1H, -CH _2- )

The attributions of ¹³ C-NMR for cyanate ester compound DPCCN are shown below. ^{The 13} C-NMR chart is shown in FIG.

¹³ C-NMR (100 MHz, DMSO-d6) δ (ppm): 151.59, 151.18, 145.27, 140.71, 128.68, 126.83, 124.97, 115.20, 114. 99, 108.87, 108.67, 67.32, 77.00, 76.69, 38.73, 33.75, 29.81, 27.69

Synthesis Example 2 Synthesis of methyl-added diphenylcyclohexene type cyanate ester compound (hereinafter abbreviated as DPCMeCN) A cyanate ester compound DPCCN represented by the following formula (1C) was synthesized as described below.

<Synthesis of 1- (4-hydroxyphenyl) -4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane>
1- (4-hydroxyphenyl) -4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane represented by the following formula (15) was synthesized by the following method.

In a 5 L separable flask, 1080 g (10.0 mol) of o-cresol and 78 g of 35% hydrochloric acid were added and heated to 50 ° C. After adding 190 g (1.00 mol) of 4- (4-hydroxyphenyl) cyclohexanone over 2 hours and adding the whole amount, the mixture was stirred at 50 ° C. for 4 hours. The reaction mixture was adjusted to pH 6 by adding a 16% aqueous sodium hydroxide solution, and then cooled to room temperature. Toluene (1080 g) was added, and the precipitate was collected by suction filtration. The resulting solid was dried to give 299 g of 90% pure 1- (4-hydroxyphenyl) -4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane.
The ¹ H-NMR assignments of 1- (4-hydroxyphenyl) -4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane are shown below.

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm): 9.05 (s, 3 H, -OH), 7.0-6.6 (m, 12 H, ArH), 2.69 (d, 2 H) , Cyclohexyl), 2.09 (d, 6 H, -CH ₃ ), 1.84 (m, 2 H, cyclohexyl), 1.67 (m, 2 H, cyclohexyl), 1.47 (d, 2 H, cyclohexyl)

<Synthesis of methyl-added diphenylcyclohexene type bisphenol (hereinafter abbreviated as “DPCMeOH”)>
DPCMeOH represented by the following formula (9C) was synthesized by the following method.

299 g (0.770 mol) of 1- (4-hydroxyphenyl) -4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane obtained by the above method in a 2 L separable flask, 50% aqueous solution of sodium hydroxide 3.0 g and 90.0 g of tetraethylene glycol were added, the pressure in the reaction vessel was reduced to 5 Pa, and thermal decomposition was performed at 210 ° C. for 5 hours, to obtain o-cresol. After cooling to room temperature, the atmosphere was released, methyl isobutyl ketone (1.5 L) was added, and stirring was performed to dissolve the solid. The solution was transferred to a 5 L poly container, methyl isobutyl ketone (1.5 L) and distilled water (1.5 L) were added and stirred, and then the pH of the reaction solution was adjusted to 6 by addition of a 50% aqueous acetic acid solution. The mixture was transferred to a 5-L separatory funnel, the aqueous layer was removed, and the organic layer was washed three times with distilled water (1.5 L) and concentrated under reduced pressure. Toluene (2 L) was added to the obtained solid, and after suspension washing, it was recovered by suction filtration. The collected solid was dried under reduced pressure to obtain 158 g of DPCMeOH.
The assignments of ¹ H-NMR for DPCMeOH are shown below.

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm): 9.20 (s, 2 H, -OH), 7.08 (m, 4 H, ArH), 6.71 (m, 3 H, ArH), 6.03 (m, 1H, -CH = ), 2.67 (m, 1H, -CH -), 2.44 (m, 5H, -CH 2 -), 2.11 (s, 3H, -CH _{_{3), 1.91 (m, 1H}} , -CH 2 -), 1.74 (m, 1H, -CH 2 -)

<Synthesis of DPCMeCN>
To a 500 mL four-necked flask equipped with an argon inlet and a thermometer, 10.0 g (35.7 mmol) of DPCMeOH obtained by the above method and 300 mL of tetrahydrofuran were added under an argon stream. After further adding 10.6 g (100 mmol) of cyanogen bromide, the internal temperature was adjusted to −30 ° C. with a dry ice / acetone bath. 10.8 g (107 mmol) of triethylamine was added dropwise over 20 minutes so that the internal temperature did not exceed -10.degree. C., and the mixture was stirred at -10.degree. C. for 2 hours. After the temperature was raised to room temperature, the reaction solution was filtered. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was dissolved in 200 mL of chloroform. The chloroform solution was washed three times with 100 mL of 2.5% brine and once with 100 mL of water, and then concentrated under reduced pressure to obtain a solid. To the obtained solid, 300 mL of hexane was added and suspended and stirred, and then the solid was collected by filtration and dried to obtain 11.0 g of the target cyanate ester compound DPCMeCN. The IR spectrum of the resulting cyanate ester compound DPCMeCN showed absorptions at 2244 cm ^-1 and 2269 cm ^-1 (cyanate group) and no absorption at the hydroxy group. The IR chart is shown in FIG.
The assignments of ¹ H-NMR for the cyanate ester compound DPCMeCN are shown below. ^{The 1} H-NMR chart is shown in FIG.

¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.26 (m, 7 H, ArH), 6.18 (m, 1 H, -CH =), 2.93 (m, 1 H, -CH- ), 2.54 (m, 3H, -CH _2- ), 2.27 (m, 4H, -CH _3, -CH _2- ), 2.12 (m, 1 H, -CH _2- ), 91 (m, 1 H, -CH _2- )

Synthesis Example 3 Synthesis of Terphenyl Cyanate Ester Compound (hereinafter abbreviated as TPMeCN) TPMeCN represented by the following formula (16) was synthesized as described below.

<Composition of TPMeCN>
Solution 1 was prepared by dissolving 237 g of TPMeOH represented by the following formula (17) and 164.3 g (1.62 mol) of triethylamine (1.0 mol per 1 hydroxyl group) in 1540 g of tetrahydrofuran.

The hydroxy-substituted aromatic compound represented by the above formula (17) was synthesized as follows.
100 g of phenol and 16.0 g of 35% hydrochloric acid were charged into a 1 L four-necked flask equipped with a nitrogen blowing port and a dropping funnel, and the liquid temperature was raised to 55 ° C. while stirring. Then, a mixed solution of 38.2 g of 4- (4-hydroxyphenyl) cyclohexanone and 94.0 g of phenol separately prepared by heating was added dropwise over 3 hours, and after the addition, the mixture was stirred at 55 ° C. for 4 hours. After completion of the reaction, the reaction mixture was stirred at 55 ° C., and 39.1 g of a 16% aqueous solution of sodium hydroxide was added for neutralization. Further, 190 g of toluene was added, and the precipitated crystals were suction filtered at room temperature and then dried to obtain 1,4,4-tris (4-hydroxyphenyl) cyclohexane.
49.7 g of 1,4,4-tris (4-hydroxyphenyl) cyclohexane obtained above is charged in a 300 mL four-necked flask), and 0.3 g of a 48% aqueous solution of sodium hydroxide and 26.0 g of tetraethylene glycol are contained in the flask Added to. After the inside of the flask was purged with nitrogen, the pressure in the reaction vessel was reduced to 50 mmHg, and the temperature was raised to 210 ° C. to carry out a thermal decomposition reaction for about 4 hours. The end of the reaction was determined as the point at which distillation of the distillate ceased. After completion of the reaction, 50% aqueous acetic acid solution was added to the obtained reaction mixture for neutralization to obtain 66.0 g of an oily water-containing mixture.
60.0 g of α-methylstyrene and 3.5 g of a 5% palladium / carbon-supported catalyst (50 mass% water-containing product) were additionally added to 66.0 g of the above water-containing oil mixture. After the inside of the reactor was purged with nitrogen, the temperature was raised to 165 ° C., and reaction was performed for 3 hours with stirring.
After completion of the above reaction, 50 g of dimethylformamide was added to the obtained reaction mixture, and the palladium-supported catalyst was separated by filtration from this mixture. The solvent was distilled off and methanol was added to dissolve the residue, and then water was added. After crystallization filtration, the obtained solid was dried to obtain 29.7 g of 4,4 ′ ′-dihydroxy-3 ′ ′-methylterphenyl as white crystals.

While maintaining 249.5 g (4.06 mol) (2.5 mol per 1 hydroxyl group) of cyanogen chloride and 453.3 g of dichloromethane at a liquid temperature of -7 to -1 ° C while stirring, Solution 1 for 180 minutes I poured it over. Solution 1 After completion of the injection, after stirring for 30 minutes at the same temperature, a solution in which 230.0 g (2.27 mol) of triethylamine (1.0 mol per 1 hydroxyl group) is dissolved in 230 g of dichloromethane (solution 2 ) Was poured over 120 minutes. After completion of solution 2 injection, the reaction was completed by stirring for 30 minutes at the same temperature.
Thereafter, the hydrochloride of triethylamine was filtered off, and the obtained filtrate was washed with 2 liters of 0.15 N hydrochloric acid and then washed 4 times with 2 liters of water. The electric conductivity of the 4th water washing with water was 45 μS / cm, and it was confirmed by the water washing that the removable ionic compounds were sufficiently removed.
The organic phase after washing with water was concentrated under reduced pressure and concentrated to dryness at 90 ° C. for 1 hour to obtain 305 g of a light orange solid. The obtained solid was dissolved in 435 g of methyl ethyl ketone (MEK), 430 g of tetrahydrofuran and 113 g of n-hexane at 80 ° C. and then recrystallized. The resulting crystals were washed with 1 L of n-hexane and then dried under reduced pressure to obtain 86 g of the target cyanate ester compound TPMeCN (light orange crystals). The IR spectrum of the resulting cyanate ester compound TPMeCN showed absorptions of 2237 cm ^-1 and 2283 cm ^-1 (cyanate group) and no absorption of hydroxy group. The IR chart is shown in FIG.

<Preparation of filler-containing cured product>
The filler used for preparation of a filler containing hardened | cured material below is shown.
・ FAN-f50: Aluminum nitride particles, manufactured by Furukawa Electronics Co., Ltd., thermal conductivity 200 W / m · K
· AA-18: Alumina particles, manufactured by Sumitomo Chemical Co., Ltd., thermal conductivity 30 W / m · K
· AA-3: alumina particles, manufactured by Sumitomo Chemical Co., Ltd., thermal conductivity 30 W / m · K
· AA-03: Alumina particles, manufactured by Sumitomo Chemical Co., Ltd., thermal conductivity 30 W / m · K
・ AZ 35-75: Alumina particles, manufactured by Nippon Steel & Sumikin Materials Co., Ltd. Micron Company, thermal conductivity 30 W / m K
・ AZ 10-75: Alumina particles, manufactured by Nippon Steel & Sumikin Materials Co., Ltd. Micron Company, thermal conductivity 30 W / m K
· PT 110: boron nitride particles, manufactured by Momentive Performance Materials Japan Ltd., thermal conductivity 200 W / m · K
· FB-940: Fused silica particles, manufactured by Denka Co., thermal conductivity 1 W / m · K

Example 1
100.0 parts by mass of cyanate ester compound DPCCN obtained in Synthesis Example 1, 0.05 parts by mass of zinc octylate (Nihon Kagaku Sangyo Co., Ltd., trade mark zinc with a nickel content of 18%), aluminum nitride particles ( 57. 0 parts by mass of Furukawa Electronics Co., Ltd., FAN-f50, 88.3 parts by mass of alumina particles (AA-18, manufactured by Sumitomo Chemical Co., Ltd.), alumina particles (AA-3, manufactured by Sumitomo Chemical Co., Ltd.) 88. 3 parts by mass, 88.3 parts by mass of alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA-03), and 8.3 parts by mass of 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-2940) And diluted with methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., special grade reagent) to prepare a varnish.
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 130 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got Copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., 18 μm thick) is overlaid on the copper foil with B-stage resin composition so that the rough surface faces the resin composition, and vacuum heat press (220 ° C, 90 minutes, press) A cured product with double-sided copper foil was produced by a pressure of 20 MPa. The copper foil on both sides was peeled off from the cured product with double-sided copper foil, to obtain a filler-containing cured product (containing 75 volume% of filler).

Example 2
100.0 parts by mass of cyanate ester compound DPCCN obtained in Synthesis Example 1, 0.05 parts by mass of zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name zinc with a trademark of 18% of metal content), boron nitride particles ( 290.0 parts by mass of Momentive Performance Materials Japan Ltd. (PT 110) and 4.4 parts by mass of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., special grade reagent) To make a varnish.
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 130 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The obtained resin composition powder is filled in a die for powder molding (DT 5025-1525, manufactured by NP System Co., Ltd.) and pressurized to 50 MPa using a manual hydraulic pump (P-16B, manufactured by Riken Seiki Co., Ltd.) The pellet was made. The obtained pellet was vacuum hot pressed (220 ° C., 90 minutes, pressing pressure 10 MPa) to obtain a filler-containing cured product (containing 61 volume% of filler).

[Example 3]
100.0 parts by mass of cyanate ester compound DPCMeCN obtained in Synthesis Example 2, 0.05 parts by mass of zinc octylate (Nihon Kagaku Sangyo Co., Ltd., trade name zinc with a trademark of 18% of metal content), boron nitride particles ( 294.7 parts by mass of Momentive Performance Materials Japan Ltd. (PT 110) and 4.4 parts by mass of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., special grade reagent) To make a varnish.
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 130 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The obtained resin composition powder is filled in a die for powder molding (DT 5025-1525, manufactured by NP System Co., Ltd.) and pressurized to 50 MPa using a manual hydraulic pump (P-16B, manufactured by Riken Seiki Co., Ltd.) The pellet was made. The obtained pellet was vacuum hot pressed (220 ° C., 90 minutes, pressing pressure 10 MPa) to obtain a filler-containing cured product (containing 61 volume% of filler).

Example 4
100.0 parts by mass of cyanate ester compound DPCCN obtained in Synthesis Example 1, 0.05 parts by mass of zinc octylate (Nihon Kagaku Sangyo Co., Ltd., trade name zinc with a nickel content of 18%), alumina particles (Nippon Iron Corp. 190.7 parts by mass of Sumikin Material Co., Ltd. manufactured by Micron Company, AZ 35-75, 190.7 parts by mass of alumina particles (manufactured by Nippon Steel & Sumikin Material Co., Ltd., manufactured by Micron Company, AZ 10-75), Alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA -03) 95.3 parts by mass, 4.8 parts by mass of 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-2940) are mixed, and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., special grade reagent) The varnish was prepared by dilution with
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 130 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The obtained resin composition powder was filled in a mold, and a filler-containing cured product (containing 60 volume% of filler) was obtained by a vacuum heat press (220 ° C., 90 minutes, press pressure 10 MPa).

[Example 5]
100.0 parts by mass of cyanate ester compound DPCCN obtained in Synthesis Example 1, 0.05 parts by mass of zinc octylate (Nihon Kagaku Sangyo Co., Ltd., trade name zinc with a nickel content of 18%), alumina particles (Nippon Iron Corp. 127.3 parts by mass of Sumikin Material Co., Ltd. manufactured by Micron Company, AZ 35-75, 127.3 parts by mass of alumina particles (manufactured by Nippon Steel & Sumikin Material Co., Ltd. manufactured by Micron Company, AZ 10-75), Alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA -03) 63.6 parts by mass, 3.2 parts by mass of 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-2940) are mixed, and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., special grade reagent) The varnish was prepared by dilution with
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 130 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The obtained resin composition powder was filled in a mold, and a filler-containing cured product (containing 50 volume% of filler) was obtained by vacuum heat press (220 ° C., 90 minutes, press pressure 10 MPa).

[Example 6]
100.0 parts by mass of cyanate ester compound DPCMeCN obtained in Synthesis Example 2, 0.05 parts by mass of zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name zinc with a trademark of 18% of metal content), alumina particles (Nippon Iron Corp. 194.0 parts by mass of Sumikin Material Co., Ltd. Micron Company, AZ 35-75, 194.0 parts by mass of alumina particles (Nippon Steel & Sumikin Material Co., Ltd. Micron Company, AZ 10-75), alumina particles (Sumitomo Chemical Co., Ltd., AA -03) 97.0 parts by mass, 4.9 parts by mass of 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-2940) are mixed, and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., special grade reagent) The varnish was prepared by dilution with
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 130 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The obtained resin composition powder was filled in a mold, and a filler-containing cured product (containing 60 volume% of filler) was obtained by a vacuum heat press (220 ° C., 90 minutes, press pressure 10 MPa).

[Example 7]
100.0 parts by mass of cyanate ester compound DPCMeCN obtained in Synthesis Example 2, 0.05 parts by mass of zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name zinc with a trademark of 18% of metal content), alumina particles (Nippon Iron Corp. 129.5 parts by mass of Sumikin Material Co., Ltd. manufactured by Micron Company, AZ 35-75, 129.5 parts by mass of alumina particles (Nippon Steel & Sumikin Material Co., Ltd. manufactured by Micron Company, AZ 10-75), Alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA -03) 64.8 parts by mass, 3.2 parts by mass of 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-2940) are mixed, and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., special grade reagent) The varnish was prepared by dilution with
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 130 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The obtained resin composition powder was filled in a mold, and a filler-containing cured product (containing 50 volume% of filler) was obtained by vacuum heat press (220 ° C., 90 minutes, press pressure 10 MPa).

Comparative Example 1
47.8 parts by mass of TPMeCN obtained in Synthesis Example 3, 52.2 parts by mass of phenylmethane maleimide (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nickomatics Zinc) Metal content: 18%) 0.1 parts by mass, aluminum nitride particles (Furukawa Electronics Co., Ltd., FAN-f50) 550.0 parts by mass, alumina particles (Sumitomo Chemical Co., Ltd., AA-18) 85.3 mass Parts, 85.3 parts by mass of alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA-3), 85.3 parts by mass of alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA-03), 3-glycidoxypropyltrimethoxysilane ( Shin-Etsu Chemical Co., Ltd. product, LS-2940) 8.0 parts by mass is mixed, diluted with methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., reagent special grade) and varnished It was produced.
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 100 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got Copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., 18 μm thick) is overlaid on the copper foil with B-stage resin composition so that the rough surface faces the resin composition, and vacuum heat press (220 ° C, 90 minutes, press) A cured product with double-sided copper foil was produced by a pressure of 30 MPa. The copper foil on both sides was peeled off from the cured product with double-sided copper foil, to obtain a filler-containing cured product (containing 75 volume% of filler).

Comparative Example 2
2,8-bis (4-cyanatophenyl) propane (manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter abbreviated as TA) 43.8 parts by mass, phenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300) 56.2 0.1 parts by mass, zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: zinc nicks with a metal content of 18%), 0.1 parts by mass, aluminum nitride particles (Furukawa Electronics Co., Ltd., FAN-f50) 557.5 parts Parts, 86.4 parts by mass of alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA-18), 86.4 parts by mass of alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA-3), alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA -03) 86.4 parts by mass, 8.1 parts by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS-2940) are mixed, and methyl ethyl carbonate is mixed. Emissions (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) was diluted with to prepare a varnish.
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 100 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The obtained resin composition powder was filled in a mold, and a filler-containing cured product (containing 75 volume% of filler) was obtained by a vacuum heat press (220 ° C., 90 minutes, press pressure 5 MPa).

Comparative Example 3
100.0 parts by mass of cyanate ester compound DPCCN obtained in Synthesis Example 1, 0.05 parts by mass of zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name zinc with a nickel content of 18%), fused silica particles ( Denka Co., Ltd., FB-940) 526.7 parts by mass, 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-2940) 5.3 parts by mass are mixed, and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.) The varnish was prepared by diluting with a reagent grader (manufactured by Kogyo Co., Ltd.).
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 130 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The obtained resin composition powder was filled in a mold, and a filler-containing cured product (containing 75 vol% of filler) was obtained by vacuum heat press (220 ° C., 90 minutes, press pressure 10 MPa).

Comparative Example 4
61.4 parts by mass of triphenylmethane type epoxy resin (Nippon Kayaku Co., Ltd., EPPN-501H), 38.6 parts by mass of phenol novolac resin (Miwa Kasei Co., Ltd., DL-92), tetraphenylphosphonium tetraphenylborate 0.06 parts by mass (manufactured by Wako Pure Chemical Industries, Ltd.), 305.9 parts by mass of boron nitride particles (manufactured by Momentive Performance Materials Japan LLC, PT 110), phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 4 6 parts by mass was mixed and diluted with methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., special grade reagent) to prepare a varnish.
The varnish produced is coated on a rough surface of copper foil (3EC-VLP, 18 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) using an applicator, and dried at 130 ° C. for 10 minutes to obtain a copper foil with a B-stage resin composition. I got The B-stage resin composition was peeled off from the copper foil and ground in a mortar. The obtained resin composition powder is filled in a die for powder molding (DT 5025-1525, manufactured by NP System Co., Ltd.) and pressurized to 50 MPa using a manual hydraulic pump (P-16B, manufactured by Riken Seiki Co., Ltd.) The pellet was made. The obtained pellet was vacuum hot pressed (220 ° C., 90 minutes, pressing pressure 10 MPa) to obtain a filler-containing cured product (containing 61 volume% of filler).

Comparative Example 5
Bisphenol A type epoxy resin (manufactured by DIC Corporation, 850-S) 64.3 parts by mass, Phenolic novolak resin (manufactured by Meiwa Kasei Kogyo Co., Ltd., DL-92) 35.7 parts by mass, 2-phenylimidazole (Wako Pure Chemical Industries, Ltd. 0.2 parts by mass, manufactured by Kogyo Co., Ltd., 400 parts by mass of alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA-3), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS-2940) 4 0 parts by mass was mixed and diluted with methyl ethyl ketone (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a varnish.
The varnish produced is coated on a rough surface of a copper foil (3EC-VLP, 18 μm thick, made by Mitsui Metal Mining Co., Ltd.) using an applicator, and dried at 120 ° C. for 20 minutes to obtain a copper foil with a B-stage resin composition. I got Copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., 18 μm thick) is overlaid on the copper foil with B-stage resin composition so that the rough surface faces the resin composition, and vacuum heat press (190 ° C, 30 minutes, press) A cured product with double-sided copper foil was produced by a pressure of 5 MPa. The copper foils on both sides were peeled off from the cured product with double-sided copper foil to obtain a filler-containing cured product (containing 55 volume% of filler).

Comparative Example 6
Bisphenol A type epoxy resin (manufactured by DIC Corporation, 850-S) 64.3 parts by mass, Phenolic novolak resin (manufactured by Meiwa Kasei Kogyo Co., Ltd., DL-92) 35.7 parts by mass, 2-phenylimidazole (Wako Pure Chemical Industries, Ltd. 0.2 parts by mass, manufactured by Kogyo Co., Ltd., 233.3 parts by mass of alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA-3), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS-2940) 2.3 parts by mass were mixed and diluted with methyl ethyl ketone (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a varnish.
The varnish produced is coated on a rough surface of a copper foil (3EC-VLP, 18 μm thick, made by Mitsui Metal Mining Co., Ltd.) using an applicator, and dried at 120 ° C. for 20 minutes to obtain a copper foil with a B-stage resin composition. I got Copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., 18 μm thick) is overlaid on the copper foil with B-stage resin composition so that the rough surface faces the resin composition, and vacuum heat press (190 ° C, 30 minutes, press) A cured product with double-sided copper foil was produced by a pressure of 5 MPa. The copper foils on both sides were peeled off from the cured product with double-sided copper foil to obtain a filler-containing cured product (containing 41 volume% of filler).

<Creation of cured resin>
Comparative Example 7
100.0 parts by mass of cyanate ester compound DPCCN obtained in Synthesis Example 1 and 0.05 parts by mass of zinc octylate (manufactured by Nippon Chemical Industrial Co., Ltd., trade name zinc with a trademark of 18% metal content) Thus, a curable resin composition was obtained.
The obtained curable resin composition was filled in a mold, and a cured resin was produced by a vacuum heat press (220 ° C., 90 minutes, press pressure 10 MPa).

Comparative Example 8
100.0 parts by mass of cyanate ester compound DPCMeCN obtained in Synthesis Example 2 and 0.05 parts by mass of zinc octylate (Nihon Kagaku Sangyo Co., Ltd., trade name zinc with a trademark of 18% of metal content) are heated and melted. Thus, a curable resin composition was obtained.
The obtained curable resin composition was filled in a mold, and a cured resin was produced by a vacuum heat press (220 ° C., 90 minutes, press pressure 10 MPa).

Comparative Example 9
Bisphenol A type epoxy resin (manufactured by DIC Corporation, 850-S) 64.3 parts by mass, Phenolic novolak resin (manufactured by Meiwa Kasei Kogyo Co., Ltd., DL-92) It heat-melted (made by Kogyo Co., Ltd. make) 0.2 mass part, and obtained curable resin composition.
The obtained curable resin composition was filled in a mold, and a cured resin was produced by vacuum heat press (190 ° C., 30 minutes, press pressure 2 MPa).

<Evaluation of thermal conductivity of filler-containing cured product and resin part of the cured product>
The characteristics of the filler-containing cured product and the resin cured product obtained as described above were evaluated by the following methods.
Thermal diffusion coefficient: A cured product processed to a size of 1 cm square is set in a sample holder in a xenon flash thermal diffusivity measurement device (manufactured by NETZSCH, LFA 447 NanoFlash), and measurement is performed at 25 ° C. in the atmosphere. It asked by.
Specific heat: Determined according to JIS K 7123 (method of measuring specific heat capacity of plastic) using DSC (manufactured by Seiko Instruments Inc., EXSTAR 6000 DSC 6220).
Density: It was determined by a water displacement method using a densitometer (MS-DNY-43, manufactured by METTLER TOLEDO Co., Ltd.).
Thermal conductivity: The thermal conductivity of the cured product was determined by the following equation from the determined thermal diffusion coefficient, specific heat, and density.
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 )]

Further, from the thermal conductivity of the filler-containing cured product obtained in the above-described Example 4, Example 5, Example 6, Example 7, Comparative Example 5, and Comparative Example 6, the resin portion in the filler-containing cured product The thermal conductivity of was calculated using the following equation (X).
Formula (X): 1-phi = [(lambda c-lambda f) / (lambda m-lambda f)] x (lambda m / lambda c) ^1/3
[Φ: volume filling ratio of filler (volume%), λc: thermal conductivity of cured material containing filler (W / m · K), λf: thermal conductivity of alumina (30 W / m · K), λm: filling Conductivity (W / m · K) of resin part in hardened material containing material

The evaluation results were as shown in Tables 1 to 3 below. In Tables 1 to 3, the description of “-” means that there is no blending of the corresponding raw materials.

As apparent from Table 1, the cyanate ester compound represented by the formula (1) according to one aspect of the present embodiment, and aluminum nitride and alumina having a thermal conductivity of 3 W / (m · K) or more The resin composition of the present embodiment containing the above showed excellent thermal conductivity.

As apparent from Table 2, according to one aspect of the present embodiment, the cyanate ester compound represented by the formula (1) and boron nitride having a thermal conductivity of 3 W / (m · K) or more The resin composition contained showed excellent thermal conductivity.

As apparent from Table 3, the thermal conductivity of the resin portion converted from the filler-containing cured product constituted of the resin composition of the present embodiment is the resin cured product containing no filler (Comparative Example 7, It showed a higher value than the thermal conductivity of 8). On the other hand, the thermal conductivity of the resin part converted from Comparative Example 5 and Comparative Example 6 using a general-purpose epoxy resin was equivalent to that of a cured resin containing no filler (see Comparative Example 9). From the above results, it was proved that the cyanate ester compound represented by the formula (1) has improved thermal conductivity in the presence of a filler having a thermal conductivity of 3 W / (m · K) or more . The relationship between the filler volume filling ratio and the filler-containing cured product thermal conductivity in Example 4, Example 5, Example 6, Example 7, Comparative Example 5 and Comparative Example 6 is shown in FIG.

This application is based on Japanese Patent Application (Japanese Patent Application No. 2017-153275) filed on Aug. 8, 2017 to the Japanese Patent Office, the contents of which are incorporated herein by reference.

Claims

The resin composition containing the cyanate ester compound represented by following formula (1), and the filler whose thermal conductivity is 3 W / (m * K) or more.

(In Formula (1), Ar 1 and Ar 3 are the same or different and each represents a divalent group represented by the following Formula (2), Ar 2 is represented by the following Formula (3) or (4) (Indicating a divalent group))

(In the formula (2), the formula (3) and the formula (4), R 1 and R 2 each represent a monovalent substituent, each independently a hydrogen atom, a linear or branched C 1 to C 6 chain Or an alkyl group of 1 to 4 or a halogen atom, n is an integer of 1 to 4 and m is an integer of 1 to 8)
The resin composition according to claim 1, wherein Ar 1 and Ar 3 are each independently represented by the following formula (5) or (6).
The resin composition according to claim 1, wherein Ar 2 is represented by the following formula (7) or (8).
1 type selected from the group consisting of cyanate ester compounds (A) other than the above-mentioned cyanate ester compounds, maleimide compounds, phenol resins, epoxy resins, oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group The resin composition according to any one of claims 1 to 3, further comprising the above.
The resin composition according to any one of claims 1 to 4, which is for a sheet-like shaped body.
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 forming the resin composition according to any one of claims 1 to 4 into a sheet.
A support,
The resin composition according to any one of claims 1 to 4, which is disposed on one side or both sides of the support.
Having a laminated resin sheet.
A substrate,
The resin composition according to any one of claims 1 to 4, which is impregnated or applied to the substrate.
Have a prepreg.
A single-layer resin sheet according to claim 7, a laminated resin sheet according to claim 8, and at least one selected from the group consisting of a prepreg according to claim 9.
At least one metal foil disposed on one side or both sides selected from the group consisting of the single-layer resin sheet, the laminated resin sheet, and the prepreg;
Have
The metal foil tension laminate board containing the hardened material of the resin composition contained in at least one sort chosen from the group which consists of the single layer resin sheet, the resin sheet, and the pre-preg.
An insulating layer,
A conductor layer formed on one side or both sides of the insulating layer;
Have
A printed wiring board, wherein the insulating layer comprises the resin composition according to any one of claims 1 to 4.
A sealing material comprising the resin composition according to any one of claims 1 to 4.
A fiber-reinforced composite material comprising the resin composition according to any one of claims 1 to 4 and a reinforcing fiber.
An adhesive comprising the resin composition according to any one of claims 1 to 4.