JP2014185222A - Resin composition, prepreg, laminate, and printed wiring board - Google Patents

Abstract

An object of the present invention is to solve the following problems. (1) A problem that the volume ratio of the resin composition is reduced and the fluidity is lowered, and as a result, the viscosity of the prepreg obtained by impregnating the resin composition into a substrate such as glass cloth and semi-curing is deteriorated.
(2) A moldability problem in which cracks and voids are generated in a metal foil-clad laminate in which such a prepreg is cured by overlapping with a metal foil.
(3) The problem that the moisture absorption heat resistance of a metal foil clad laminated board, an elasticity modulus, and the adhesive strength of copper foil and the insulating layer of a laminated board deteriorate.
An epoxy resin (A) represented by the formula (1), a cyanate ester compound (B), a maleimide compound (C) and an inorganic filler (D) are contained, and the inorganic filler (D) The resin composition whose content in a resin composition is contained 50-600 mass parts with respect to a total of 100 mass parts of component (A)-(C).
[Selection figure] None

Description

  The present invention relates to a resin composition, a prepreg, a laminated board, and a printed wiring board.

  As semiconductor packages widely used in electronic devices, communication devices, personal computers, and the like have become more advanced and smaller in size, higher integration and higher density mounting have been increasingly accelerated in recent years. Along with this, there are various requirements for laminated boards used in semiconductor packages, and various characteristics such as low thermal expansion, high thermal conductivity, and high elasticity are required in addition to heat resistance and reliability.

  As a method for imparting low thermal expansion and high thermal conductivity to a laminate, there is a method of highly filling an inorganic filler excellent in various properties (Patent Documents 1 to 3). In addition to providing low thermal expansion and high thermal conductivity, high filling with inorganic fillers can improve mechanical properties such as elastic modulus, flame resistance, electrical properties, and whiteness. It is used as a useful technique.

JP 2003-73543 A JP 2003-268136 A JP 2001-348488 A

However, the present inventors have found that the following problems arise when the inorganic filler is highly filled to impart characteristics such as low thermal expansion and high thermal conductivity.
(1) A problem that the volume ratio of the resin composition is reduced and the fluidity is lowered, and as a result, the viscosity of the prepreg obtained by impregnating the resin composition into a substrate such as glass cloth and semi-curing is deteriorated.
(2) A moldability problem in which cracks and voids are generated in a metal foil-clad laminate in which such a prepreg is cured by overlapping with a metal foil.
(3) The problem that the moisture absorption heat resistance of a metal foil clad laminated board, an elasticity modulus, and the adhesive strength of copper foil and the insulating layer of a laminated board deteriorate.

  In addition, when an inorganic filler having a large average particle diameter is used, the surface area is smaller than that of an inorganic filler having a small particle diameter, so that the contact area with the resin component is small and the improvement in viscosity can be suppressed. In the filler, there are particles called coarse particles whose particle diameter is particularly larger than the average, and these adversely affect the generation of voids and the insulation reliability of the laminate.

  The present invention has been made in view of the above problems, and its purpose is convenient for producing a metal foil-clad laminate with a high prepreg viscosity, although the proportion of the inorganic filler in the resin composition is large. An object of the present invention is to provide a resin composition for prepreg that is so low that a cured product can be prepared easily and with good reproducibility. Another object of the present invention is to provide a prepreg, a laminate, a printed wiring board and the like that have good moldability of the metal foil-clad laminate and good heat resistance and moisture absorption heat resistance.

  As a result of intensive studies for solving such problems, the present inventors have found that the epoxy resin (A) represented by the formula (1), the cyanate ester compound (B), the maleimide compound (C), and the inorganic filler ( D), and the resin composition containing 100 to 1000 parts by mass of the inorganic filler (D) in the resin composition with respect to a total of 100 parts by mass of the components (A) to (C). Has found that the above problems can be solved, and has reached the present invention.

（１）
（式中、Ｒは各々独立に炭素数１〜６のアルキル基であり、ｍは０〜４の整数を表し、ｎは１以上の整数を表す。）

(1)
(In the formula, each R is independently an alkyl group having 1 to 6 carbon atoms, m represents an integer of 0 to 4, and n represents an integer of 1 or more.)

  According to the present invention, a prepreg resin composition having a prepreg viscosity which is low enough to be convenient for producing a metal foil-clad laminate and capable of producing a cured product easily and with good reproducibility is obtained. It is possible to obtain a prepreg, a laminated board, a printed wiring board and the like having good moldability of the board and good heat resistance and moisture absorption heat resistance.

  Embodiments of the present invention will be described below. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

  One aspect of this embodiment contains an epoxy resin (A) represented by formula (1), a cyanate ester compound (B), a maleimide compound (C), and an inorganic filler (D), and the inorganic filler Content in (D) resin composition is a resin composition contained 100-1000 mass parts with respect to a total of 100 mass parts of component (A)-(C).

  Further, as another aspect of the present embodiment, an epoxy resin (A), a BT resin (E) obtained by prepolymerizing a cyanate ester compound (B) and a maleimide compound (C), and an inorganic filler (D) are used. It is a resin composition to contain.

  Moreover, as another aspect of this invention, in addition to the said resin composition component, it is a resin composition containing epoxy resins (F) other than Formula (1).

  Another aspect of this embodiment is a resin composition containing an imidazole compound in addition to the resin composition components.

  Furthermore, in another aspect of the present embodiment, a prepreg composed of the resin composition and a base material, a laminate using the prepreg, a resin sheet using the resin composition, and a printed wiring board are also provided.

[Epoxy resin represented by formula (1) (A)]
The epoxy resin (A) used in the present invention is represented by the formula (1). Although n is not specifically limited, It is preferable that it is an integer of 1-20, and it is more preferable that it is an integer of 1-10. m represents an integer of 0 to 4. R represents an alkyl group having 1 to 6 carbon atoms. The mass average molecular weight of the epoxy resin (A) represented by the formula (1) is not particularly limited, but the viewpoint that the melt average viscosity of the prepreg is reduced to 100 to 1000 as the polystyrene-reduced mass average molecular weight by the GPC method. The upper limit is more preferably 900 or less, still more preferably 800 or less, still more preferably 700 or less, still more preferably 600 or less, and particularly preferably 500 or less.

  In addition, as the epoxy resin (A) represented by the formula (1), a commercially available product can be used. EXA-7250 (epoxy equivalent 162, mass average molecular weight 462) (DIC ( ), EPPN-501H (epoxy equivalents 162 to 172), EPPN-501HY (epoxy equivalents 163 to 175, mass average molecular weight 800 to 950), EPPN-502H (epoxy equivalents 158 to 178) (Nippon Kayaku Co., Ltd.) ))). These may be used alone or in combination of two or more.

The content of the epoxy resin (A) represented by the formula (1) in the resin composition of the present embodiment is not particularly limited, but the resin composition component is an epoxy resin (A) represented by the formula (1), In a system including a cyanate ester compound (B), a maleimide compound (C) and an inorganic filler (D), an epoxy resin other than the components (A) to (C) and the formula (1) contained as an optional component It is preferable that it is 10-50 mass parts with respect to a total of 100 mass parts of (F), More preferably, it is 20-40 mass parts.
In the system in which the resin composition component includes the epoxy resin (A) represented by the formula (1), the BT resin (E), and the inorganic filler (D), the components (A), (E) and It is preferable that it is 10-90 mass parts with respect to a total of 100 mass parts of epoxy resins (F) other than Formula (1) contained as an arbitrary component, More preferably, it is 20-80 mass parts.
By making content of the epoxy resin (A) represented by Formula (1) into a preferable range, a moldability improves because a prepreg viscosity falls, a flame retardance, a glass transition temperature, a water absorption rate, and A printed wiring board having an excellent elastic modulus can be obtained.

Since the cyanate ester compound (B) used in the present invention has excellent properties such as chemical resistance and adhesiveness, it can be suitably used as a component of the resin composition in the present invention. Examples of the cyanate ester compound (B) include a naphthol aralkyl cyanate ester compound represented by the formula (2), a novolak cyanate ester, a biphenylaralkyl cyanate ester compound represented by the formula (3), and a bis (3,5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1, 3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4-cyanatophenyl) ether, bi Su (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, 2,2-bis (4-cyanatophenyl) propane, and the like. These may be used alone or in combination of two or more.
Among them, the naphthol aralkyl cyanate ester compound represented by the formula (2), the novolak cyanate ester and the biphenyl aralkyl cyanate ester compound represented by the formula (3) have excellent flame retardancy and high curability. Further, it is particularly preferable because the cured product has a low coefficient of thermal expansion.

（２）
式中、Ｒ_１は各々独立に水素原子又はメチル基を表し、中でも水素原子が好ましい。
式中、ｎは１以上の整数を示す。ｎの上限値は、通常は１０、好ましくは６である。

(2)
In the formula, each R ₁ independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
In the formula, n represents an integer of 1 or more. The upper limit value of n is usually 10, preferably 6.

（３）
式中、Ｒ_２は各々独立に水素原子又はメチル基を表し、中でも水素原子が好ましい。
式中、ｎは１以上の整数を示す。ｎの上限値は、通常は１０、好ましくは７である。

(3)
In the formula, each R ₂ independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
In the formula, n represents an integer of 1 or more. The upper limit of n is usually 10, preferably 7.

  The method for producing these cyanate ester compounds is not particularly limited, and may be produced by any existing method as cyanate ester synthesis. Specifically, for example, as described in JP-A-2009-35728, naphthol aralkyl type phenol resin represented by formula (4) and cyanogen halide are contained in an inert organic solvent in the presence of a basic compound. It can be obtained by reacting. In addition, it is possible to adopt a method of synthesizing a salt of a naphthol aralkyl type phenolic resin and a basic compound in a solution containing water and then performing a two-phase interface reaction with cyanogen halide. .

（４）
（式中、Ｒ_３は各々独立に水素原子又はメチル基を表し、ｎは１以上の整数を示す。）

(4)
(In the formula, each R ₃ independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.)

  Naphthol aralkyl cyanate compounds include naphthols such as α-naphthol and β-naphthol, p-xylylene glycol, α, α'-dimethoxy-p-xylene, 1,4-di (2-hydroxy- It can be selected from those obtained by condensing naphthol aralkyl resin obtained by reaction with 2-propyl) benzene or the like and cyanic acid.

  Further, the ratio (CN / Ep) of the number of cyanate groups of the cyanate ester compound (B) and the number of epoxy groups of all epoxy resins contained in the resin composition of the present embodiment is not particularly limited, but heat resistance and flame retardancy are not limited. From the viewpoint of the water absorption rate, it is preferably contained so as to be 0.4 to 2.5, and more preferably 0.7 to 2.0.

The content of the cyanate ester compound (B) in the resin composition of the present embodiment is not particularly limited, but is an epoxy resin (F) other than the components (A) to (C) and the formula (1) contained as an optional component. It is preferable that it is 10-50 mass parts with respect to a total of 100 mass parts, More preferably, it is 20-40 mass parts.
By setting the total content of the cyanate ester compound (B) within a preferable range, the degree of cure is increased, and a printed wiring board having flame retardancy, glass transition temperature, water absorption, and elastic modulus can be obtained.

[Maleimide compound (C)]
The maleimide compound (C) in the resin composition of the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3,5 -Dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, represented by formula (5) Examples thereof include maleimide compounds, prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, and it is also possible to use one kind or a mixture of two or more kinds as appropriate.
Among them, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, The maleimide compound represented by 5) is preferable, and the maleimide compound exemplified by the formula (5) is particularly preferable.

（５）
式中、Ｒ_４は各々独立に水素原子又はメチル基を表し、中でも水素原子が好ましい。
式中、ｎは１以上の整数を表す。ｎの上限値は、通常は１０、好ましくは７である。

(5)
In the formula, each R ₄ independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
In the formula, n represents an integer of 1 or more. The upper limit of n is usually 10, preferably 7.

The content of the maleimide compound (C) in the resin composition of the present embodiment is not particularly limited, but the sum of the components (A) to (C) and the epoxy resin (F) other than the formula (1) contained as an optional component. It is preferable that it is 10-50 mass parts with respect to 100 mass parts, More preferably, it is 20-40 mass parts.
By setting the content of the maleimide compound (C) within a preferable range, the degree of cure is increased, and a printed wiring board having excellent flame retardancy, glass transition temperature, water absorption, and elastic modulus can be obtained.

[Inorganic filler (D)]
The inorganic filler (D) in the resin composition of this embodiment will not be specifically limited if it is normally used in this industry. For example, natural silica, fused silica, amorphous silica, hollow silica, etc., aluminum hydroxide, aluminum hydroxide heat-treated product (aluminum hydroxide is heat-treated to reduce part of crystal water), boehmite, Metal hydrates such as magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass Examples thereof include fibers (glass fine powders such as E glass and D glass), hollow glass, spherical glass, and the like, and one or two or more kinds can be appropriately mixed and used.
Among these, silica, boehmite, magnesium hydroxide, alumina, and talc are preferable from the viewpoint of the coefficient of thermal expansion and flame resistance, and a molybdate compound coated with a molybdenum compound or an inorganic oxide is preferable from the viewpoint of drill workability.

The average particle diameter (D50) of the inorganic filler (D) is not particularly limited, but the average particle diameter (D50) is preferably 0.2 to 5 μm in consideration of dispersibility. Furthermore, as described above, the smaller the average particle diameter of the inorganic filler, the greater the surface area and the viscosity increase of the resin composition is likely to occur. Therefore, the effect of the present invention is easily obtained, and the upper limit of the average particle diameter is More preferably, it is 3 μm, and particularly preferably 1 μm.
In the present specification, the average particle diameter (D50) means the median diameter (D50), and is a value in which the larger side and the smaller side are equivalent when the particle size distribution of the measured powder is divided into two. It is. More specifically, the particle size distribution of a predetermined amount of powder introduced into the aqueous dispersion medium is measured by a laser diffraction scattering type particle size distribution measuring device, and the volume is integrated from small particles to 50% of the total volume. Means the value when reached.

The content of the inorganic filler (D) in the resin composition of the present embodiment is not particularly limited, but the resin composition component is an epoxy resin (A) represented by the formula (1), a cyanate ester compound (B). In the system including the maleimide compound (C) and the inorganic filler (D), the total of 100 masses of the epoxy resin (F) other than the components (A) to (C) and the formula (1) contained as an optional component. The amount is preferably 100 to 1000 parts by mass, more preferably 150 to 800 parts by mass, still more preferably 150 to 600 parts by mass, and particularly preferably 150 to 400 parts by mass with respect to parts.
In the system in which the resin composition component includes the epoxy resin (A) represented by the formula (1), the BT resin (E), and the inorganic filler (D), the components (A), (E) and It is preferable that it is 100-1000 mass parts with respect to a total of 100 mass parts of epoxy resins (F) other than Formula (1) contained as an arbitrary component, More preferably, it is 150-800 mass parts, More preferably, 150- 600 parts by mass, particularly preferably 150 to 400 parts by mass.
By making content of an inorganic filler (D) into a preferable range, the printed wiring board excellent in the flame retardance, a moldability, and drill workability can be obtained.

In addition to the inorganic filler (D), in order to improve the dispersibility of the inorganic filler and the adhesive strength between the resin and the inorganic filler or the glass cloth, a silane coupling agent or a wetting dispersant can be used in combination. is there.
These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for inorganic surface treatment. Specific examples include aminosilanes such as γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ -Vinyl silanes such as methacryloxypropyltrimethoxysilane, cationic silanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, phenylsilanes, etc. It is also possible to use one kind or a combination of two or more kinds as appropriate.
The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for coatings. For example, wet dispersers such as Disperbyk-110, 111, 180, 161, BYK-W996, W9010, W903 manufactured by Big Chemie Japan Co., Ltd. may be mentioned.

[BT resin (E)]
The BT resin (E) in the resin composition of the present embodiment is a solution of a cyanate ester compound and a maleimide compound in a solvent-free or organic solvent such as methyl ethyl ketone, N-methyl pyrodrine, dimethylformamide, dimethylacetamide, toluene, and xylene. Then, they are mixed by heating and prepolymerized.

The cyanate ester compound used is not particularly limited. For example, a naphthol aralkyl cyanate ester compound represented by the formula (2), a novolac cyanate ester, a biphenylaralkyl cyanate ester represented by the formula (3), a bis (3,5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1, 3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4-cyanatophenyl) ether, Bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, 2,2-bis (4-cyanatophenyl) propane, etc. may be mentioned, and one or two or more may be mixed as appropriate It is also possible to use it.
Among these, the naphthol aralkyl cyanate ester compound represented by the formula (2), the novolak cyanate ester and the biphenyl aralkyl cyanate ester represented by the formula (3) are obtained from the flame retardancy of the printed wiring board, It is preferable from the viewpoints of curability and a low thermal expansion coefficient.
The maleimide compound is not particularly limited, but N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, formula (5) Or a prepolymer of these maleimide compounds, or a prepolymer of a maleimide compound and an amine compound, or a mixture of one or more of them may be used as appropriate.
Among them, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, The maleimide compound represented by 5) is preferable, and the maleimide compound exemplified by the formula (5) is particularly preferable.

The ratio of the maleimide compound in the BT resin (E) is not particularly limited, but from the viewpoint of glass transition temperature, flame retardancy, and curability, a range of 5 to 75% by mass is preferable with respect to the total amount of the BT resin (E). A range of 10 to 70% by mass is particularly preferable.
Further, the range of the molecular weight of the prepolymer BT resin (E) is not particularly limited, but it is in the range of about 100 to 100,000 in terms of number average molecular weight from the viewpoints of handling properties, glass transition temperature, and curability. It is preferable.

Although content of BT resin (E) in the resin composition of this invention is not specifically limited, A total of 100 epoxy resins (F) other than Formula (1) contained as a component (A), (E) and an arbitrary component. It is preferable that it is 10-90 mass parts with respect to a mass part, More preferably, it is 20-80 mass parts.
By setting the content of the BT resin (E) within a preferable range, the degree of cure is increased, and a printed wiring board excellent in flame retardancy, glass transition temperature, water absorption rate, and elastic modulus can be obtained.

（６）
（式中、Ａｒは各々独立に、置換基を有してもよいフェニル基、ナフタレン基、ビフェニル基、アントラセン基又はその水酸基変性物、Ｒ_５は水素原子、アルキル基又はその水酸基変性物、置換基を有してもよいアリール基を表す。） The resin composition of this embodiment may contain an imidazole compound represented by formula (6). This imidazole compound has an effect of accelerating curing and has an effect of increasing the glass transition temperature of the cured product. Examples of the substituent Ar in the formula (6) include an optionally substituted phenyl group, naphthalene group, biphenyl group, anthracene group, or a hydroxyl group-modified product thereof, among which a phenyl group is preferable.
In addition, the substituent R ₅ in the formula (6) is preferably a hydrogen atom, an alkyl group or a hydroxyl-modified product thereof, and an aryl group such as a phenyl group which may have a substituent. Further, both Ar and R ₅ are phenyl. More preferably, it is a group.

(6)
(In the formula, each Ar independently represents an optionally substituted phenyl group, naphthalene group, biphenyl group, anthracene group or a hydroxyl group-modified product thereof, and R ₅ is a hydrogen atom, an alkyl group or a hydroxyl group-modified product thereof, a substituted group. Represents an aryl group which may have a group.)

Although the content of the imidazole compound in the resin composition of the present invention is not particularly limited, the resin composition component includes an epoxy resin (A) represented by the formula (1), a cyanate ester compound (B), a maleimide compound (C ) And the inorganic filler (D) are included in the system, the component (A) to (C) and the epoxy resin (F) other than the formula (1) contained as an optional component is 100 parts by mass in total. It is preferable that it is 0.01-10 mass parts, More preferably, it is 0.1-5 mass parts.
In the system in which the resin composition component includes the epoxy resin (A) represented by the formula (1), the BT resin (E), and the inorganic filler (D), the components (A), (E) and It is preferable that it is 0.01-10 mass parts with respect to a total of 100 mass parts of epoxy resins (F) other than Formula (1) contained as an arbitrary component, More preferably, it is 0.1-5 mass parts. .
By setting the content of the imidazole compound within a preferable range, the degree of cure is increased, and a printed wiring board excellent in glass transition temperature, water absorption rate, and elastic modulus can be obtained.

  In the resin composition of the embodiment, in addition to the imidazole compound, other curing accelerators can be used in combination as long as the desired characteristics are not impaired. Examples of such compounds include organic peroxides exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, and the like; azobisnitrile The azo compound: N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine , Tertiary amines such as triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; monomeric phenols such as phenol, xylenol, cresol, resorcin, catechol; lead naphthenate, lead stearate, Naphthenic acid sub- Organic metal salts such as zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and acetylacetone iron; these organic metal salts are dissolved in monomeric hydroxyl group-containing compounds such as phenol and bisphenol Inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; Dioctyl tin oxide, and other organic tin compounds such as alkyl tin and alkyl tin oxide.

Furthermore, the resin composition of this embodiment may contain an epoxy resin (F) other than the formula (1). The epoxy resin (F) other than the formula (1) is not particularly limited as long as it does not contain a halogen atom in the molecular structure and has two or more epoxy groups in the molecule.
For example, a phenol phenyl aralkyl novolak type epoxy resin represented by formula (7), a phenol biphenyl aralkyl type epoxy resin represented by formula (8), a naphthol aralkyl type epoxy resin represented by formula (9), and thermal expansion In order to lower the anthraquinone type epoxy resin represented by formula (10), polyoxynaphthylene type epoxy resin represented by formula (11) and formula (12), bisphenol A type epoxy resin, bisphenol F type epoxy resin , Phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, trifunctional phenol epoxy resin, tetrafunctional phenol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, aralkyl novolac epoxy Examples include compounds obtained by epoxidizing double bonds such as fats, alicyclic epoxy resins, polyol-type epoxy resins, glycidyl amines, glycidyl esters, and butadienes, compounds obtained by reaction of hydroxyl group-containing silicone resins with epichlorohydrin, and the like. Among these, in order to improve flame retardancy, the phenol phenyl aralkyl novolac type epoxy resin represented by the formula (7), the phenol biphenyl aralkyl type epoxy resin represented by the formula (8), and the formula (9) The naphthol aralkyl type epoxy resin, the anthraquinone type epoxy resin represented by the formula (10), and the polyoxynaphthylene type epoxy resin represented by the formula (11) and the formula (12) are preferable.
These non-halogen epoxy resins can be used alone or in combination of two or more.

（７）
式中、Ｒ_６は各々独立に水素原子又はメチル基を表し、中でも水素原子が好ましい。
式中、ｎは１以上の整数を表す。ｎの上限値は、通常は１０、好ましくは７である。

(7)
In the formula, each R ₆ independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
In the formula, n represents an integer of 1 or more. The upper limit of n is usually 10, preferably 7.

（８）
式中、Ｒ_７は各々独立に水素原子又はメチル基を表し、中でも水素原子が好ましい。
式中、ｎは１以上の整数を表す。ｎの上限値は、通常は１０、好ましくは７である。

(8)
In the formula, each R ₇ independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
In the formula, n represents an integer of 1 or more. The upper limit of n is usually 10, preferably 7.

（９）
式中、Ｒ_８は各々独立に水素原子又はメチル基を表し、中でも水素原子が好ましい。
式中、ｎは１以上の整数を表す。ｎの上限値は、通常は１０、好ましくは７である。

(9)
In the formula, each R ₈ independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
In the formula, n represents an integer of 1 or more. The upper limit of n is usually 10, preferably 7.

（１０）

(10)

（１１）
式中、Ｒ_９は各々独立に炭素原子数１〜４のアルキル基を表し、ｎは０〜３の整数を表す。

(11)
In the formula, each R ₉ independently represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 3.

（１２）
式中、Ｒ_１０は各々独立に炭素原子数１〜４のアルキル基を表し、ｎは０〜３の整数を表す。
上記式（１１）、式（１２）のエポキシ樹脂の製品例としてはＤＩＣ株式会社製、ＥＸＡ−７３１１、ＥＸＡ−７３１１―Ｇ３、ＥＸＡ−７３１１―Ｇ４、ＥＸＡ−７３１１―Ｇ４Ｓ、ＥＸＡ−７３１１Ｌ，ＨＰ−６０００が挙げられる。

(12)
In the formula, each R ₁₀ independently represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 3.
Examples of the epoxy resin products of the above formulas (11) and (12) are DIC Corporation, EXA-7311, EXA-7311-G3, EXA-7311-G4, EXA-7311-G4S, EXA-7311L, and HP. -6000.

  Further, a phosphorus-containing epoxy resin or a brominated epoxy resin can be used in combination depending on the intended use. The brominated epoxy resin is not particularly limited as long as it is a bromine atom-containing compound having two or more epoxy groups in one molecule. Specific examples include brominated bisphenol A type epoxy resins and brominated phenol novolac type epoxy resins.

  Furthermore, the resin composition of the present embodiment may contain a solvent as necessary. For example, when an organic solvent is used, the viscosity at the time of preparing the resin composition is lowered, the handling property is improved, and the impregnation property to the glass cloth is enhanced. The kind of solvent is an epoxy resin (A) represented by the formula (1), a cyanate ester compound (B), a maleimide compound (C), or a part of a mixture of the epoxy resin (A) and the BT resin (E). Or if it can melt | dissolve all, it will not specifically limit. Specific examples thereof include ketones such as acetone, methyl ethyl ketone and methyl cellosolve, aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, propylene glycol methyl ether and acetate thereof. However, it is not particularly limited to these. A solvent can be used individually by 1 type or in combination of 2 or more types.

  The resin composition in the present invention can be prepared according to a conventional method, and includes an epoxy resin (A), a cyanate ester compound (B), a maleimide compound (C), an inorganic filler (D), and other optional components described above. If the resin composition containing the components or the epoxy resin (A), the BT resin (E), the inorganic filler (D) and the other optional components described above is obtained in a uniform manner, the preparation method is particularly It is not limited. For example, the epoxy resin represented by formula (1), a cyanate ester compound, a maleimide compound, and silica are sequentially blended in a solvent, and the resin composition of this embodiment can be easily prepared by sufficiently stirring. .

  In preparing the resin composition of the present invention, an organic solvent can be used as necessary. The type of organic solvent is an epoxy resin (A) represented by the formula (1), a cyanate ester compound (B), a maleimide compound (C), or a mixture of an epoxy resin (A) and a BT resin (E). If possible, it is not particularly limited. Specific examples thereof are as described above.

  In preparing the resin composition, known processes (such as stirring, mixing, and kneading) for uniformly dissolving or dispersing the components can be performed. For example, when the inorganic filler (D) is uniformly dispersed, the dispersibility with respect to the resin composition can be improved by performing the agitation and dispersion treatment using an agitation tank equipped with a stirrer having an appropriate agitation ability. The above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill, a bead mill or the like, or a revolution / spinning type mixing device.

  On the other hand, the prepreg of the present invention can be obtained by combining the above resin composition with a base material, specifically, impregnating or applying the above resin composition to the base material. The method for producing the prepreg can be performed according to a conventional method, and is not particularly limited. For example, after impregnating or applying the resin component in the present invention to a base material, it is heated in a dryer at 100 to 200 ° C. for 1 to 30 minutes to be semi-cured (B staged). The prepreg of the embodiment can be produced. In addition, although the prepreg of this embodiment is not specifically limited, It is preferable that the quantity of the resin composition (an inorganic filler is included) with respect to the total amount of a prepreg is the range of 30-90 mass%.

The substrate used in the present invention is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. . Specific examples thereof include glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass and T glass, inorganic fibers other than glass such as quartz, polyparaphenylene terephthalamide (Kevlar), and the like. (Registered trademark), manufactured by DuPont Co., Ltd., wholly aromatic polyamides such as copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technola (registered trademark), manufactured by Teijin Techno Products Co., Ltd.), 2,6-hydroxy Organic fibers such as polyesters such as naphthoic acid and parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), and polyimide However, it is not particularly limited to these.
Among these, E glass, T glass, S glass, and Q glass are preferable from the viewpoint of low thermal expansion.
These base materials can be used individually by 1 type or in combination of 2 or more types.
As the shape of the base material, woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat, etc., the weaving method of woven fabric is known as plain weave, Nanako weave, twill weave, etc. Depending on the intended use and performance, it can be appropriately selected and used, and those obtained by fiber opening treatment or glass woven fabric surface-treated with a silane coupling agent or the like are preferably used. Although the thickness and mass of the substrate are not particularly limited, those having a thickness of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorption, the base material is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m ² or less, and more preferably a glass woven fabric made of E-glass glass fibers.

On the other hand, the metal foil-clad laminate of the present invention can be obtained by laminating at least one or more of the prepregs described above, placing the metal foil on one side or both sides thereof, and laminating. Specifically, one or a plurality of the prepregs described above are stacked, and a metal foil such as copper or aluminum is arranged on one or both sides as desired, and this is laminated and formed as necessary. The metal foil-clad laminate of this embodiment can be produced. Although the metal foil used here will not be specifically limited if it is used for printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable. Moreover, although the thickness of metal foil is not specifically limited, 2-70 micrometers is preferable, More preferably, it is 2-35 micrometers. There are no particular limitations on the method for forming the metal foil-clad laminate and the molding conditions thereof, and general methods and conditions for a laminate for a printed wiring board and a multilayer board can be applied. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used for forming a metal foil-clad laminate, the temperature is 100 to 300 ° C., the pressure is a surface pressure of 2 to 100 kgf / cm ² and the heating time are generally in the range of 0.05 to 5 hours. Furthermore, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C. Also, a multilayer board can be formed by combining and molding the prepreg of the present embodiment and a separately prepared wiring board for an inner layer.

  The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal foil-clad laminate of the present invention has a low coefficient of thermal expansion, good moldability and chemical resistance, and is particularly effectively used as a printed wiring board for semiconductor packages that require such performance. be able to.

The printed wiring board in the present invention can be manufactured, for example, by the following method. First, a metal foil-clad laminate such as a copper-clad laminate of the present invention is prepared. An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to produce an inner layer substrate. The inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, then the required number of prepregs of the present invention are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is formed on the outer side. Laminate and heat and press to form one piece. In this way, a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after this multi-layer laminate is subjected to drilling for through holes and via holes, desmear treatment is performed to remove smears, which are resin residues derived from the resin component contained in the cured product layer. . After that, a plated metal film is formed on the wall surface of this hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and the outer layer circuit is formed by etching the metal foil for the outer layer circuit to produce a printed wiring board. Is done.
The prepreg of the present invention (base material and the resin composition of the present invention attached thereto) and the resin composition layer (layer comprising the resin composition of the present invention) of the metal foil-clad laminate are the resin composition of the present invention. Insulating layers including these are formed.

  On the other hand, the laminated resin sheet of the present embodiment can be obtained by applying a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a sheet base material and drying it. Examples of the sheet substrate used here include a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a release film obtained by applying a release agent to the surface of these films, Examples thereof include organic film base materials such as polyimide film, conductor foils such as copper foil and aluminum foil, glass plates, SUS plates, and plate-like materials such as FRP, but are not particularly limited thereto. Examples of the application method include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied onto a sheet substrate with a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Moreover, it can also be set as a single layer sheet (resin sheet) by peeling or etching a sheet base material from a laminated resin sheet after drying. In addition, a sheet substrate is used by forming a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-like cavity and drying it. A single layer sheet (resin sheet) can also be obtained without any problems.

  In the production of the single layer or laminated sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but the solvent tends to remain in the resin composition at a low temperature, and the resin composition at a high temperature. Since hardening of a thing advances, 1 to 90 minutes are preferable at the temperature of 20 to 170 degreeC. In addition, the thickness of the resin layer of the single layer or laminated sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited. If the thickness is too thick, the solvent tends to remain during drying, so 0.1 to 500 μm is preferable.

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

Synthesis Example 1 Synthesis of BT Resin 1 36 parts by mass of an α-naphthol aralkyl-type cyanate compound (cyanate equivalent: 261 g / eq.) Synthesized by the method described in JP-A-2009-35728 and R ₄ in the formula (5) 26 parts by mass of a maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), all of which are hydrogen atoms and n is 0 to 1, are dissolved in dimethylacetamide and reacted at 150 ° C. with stirring to obtain BT resin 1 Got.

Synthesis Example 2 Synthesis of BT Resin 2 36 parts by mass of an α-naphthol aralkyl cyanate ester compound (cyanate equivalent: 261 g / eq.) Synthesized by the method described in JP-A-2009-35728 and a bismaleimide compound (BMI-70, 26 parts by mass (manufactured by KAI Kasei Co., Ltd.) was dissolved in dimethylacetamide and reacted at 150 ° C. with stirring to obtain BT resin 2.

Example 1
Tris (hydroxyphenyl) methane type epoxy resin (EXA-7250, epoxy equivalent: 162 g / eq., Mass average molecular weight 462, manufactured by DIC Corporation), wherein m in formula (1) is 0 and n is 0-10 60 parts by mass, α-naphthol aralkyl-type cyanate compound resin (cyanate equivalent: 261 g / eq.) Synthesized by the method described in JP-A-2009-35728, 40 parts by mass, silane coupling agent (Toray Dow Coating 5 parts by weight, 1 part by weight of a wetting and dispersing agent (disperbyk-161, manufactured by Big Chemie Japan), spherical fused silica (SC2500-SQ, average particle size: 0.5 μm, Admatex) )) Was mixed to 200 parts by mass to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated onto a 0.1 mm thick T glass woven fabric, dried by heating at 140 ° C. for 3 minutes, and a prepreg having a resin content of 50% by mass (cyanate equivalent / epoxy equivalent ratio: 0.48) was obtained.

Example 2
Except for using 40 parts by mass of 2,2-bis (4-cyanatephenyl) propane prepolymer (CA210, cyanate equivalent weight 139, manufactured by Mitsubishi Gas Chemical Co., Ltd.) instead of α-naphthol aralkyl type cyanate ester compound A prepreg (cyanate equivalent / epoxy equivalent ratio: 0.90) was obtained in the same manner as in Example 1.

Example 3
In place of the α-naphthol aralkyl cyanate ester compound, a novolak cyanate ester compound in which R ₂ in formula (3) is all hydrogen atoms (Primaset PT-30, manufactured by Lonza Japan KK, cyanate equivalent: 124 g / The prepreg (cyanate equivalent / epoxy equivalent ratio: 1.01) was obtained in the same manner as in Example 1 except that 40 parts by mass of eq.) was used.

Example 4
38 parts by mass of tris (hydroxyphenyl) methane type epoxy resin used in Example 1, 36 parts by mass of α-naphthol aralkyl type cyanate ester compound (cyanate equivalent: 261 g / eq.), Maleimide used in Synthesis Example 1 26 parts by mass of compound (BMI-2300), 5 parts by mass of silane coupling agent (Z6040), 1 part by mass of wetting and dispersing agent (disperbyk-161), 200 parts by mass of spherical fused silica (SC2500-SQ), formula A varnish was obtained by mixing 1 part by mass of 2,4,5-triphenylimidazole (Wako Pure Chemical Industries, Ltd.) in which R ₅ and Ar in (6) are all phenyl groups. This varnish was diluted with methyl ethyl ketone, impregnated onto a 0.1 mm thick T glass woven fabric, dried by heating at 140 ° C. for 3 minutes, and a prepreg having a resin content of 50% by mass (cyanate equivalent / epoxy equivalent ratio: 0.68) was obtained.

Example 5
Tris (hydroxyphenyl) methane type epoxy resin (EPPN-501HY, epoxy equivalent: 169 g / eq., Weight average molecular weight 896, different in weight average molecular weight instead of the tris (hydroxyphenyl) methane type epoxy resin used in Example 1 A prepreg (cyanate equivalent / epoxy equivalent ratio: 0.61) was obtained in the same manner as in Example 4 except that 38 parts by mass of Nippon Kayaku Co., Ltd. was used.

Example 6
Except for using 26 parts by mass of bis (3-ethyl-5-methyl-4maleimidophenyl) methane (BMI-70) used in Synthesis Example 2 instead of the maleimide compound (BMI-2300) used in Synthesis Example 1. A prepreg (cyanate equivalent / epoxy equivalent ratio: 0.68) was obtained in the same manner as in Example 4.

Example 7
Further, a prepreg (cyanate equivalent / epoxy equivalent ratio: 0.68) was obtained in the same manner as in Example 4 except that 0.01 parts by mass of 2-ethyl-4-methylimidazole (2E4MZ) was added.

Example 8
A prepreg (cyanate) was used in the same manner as in Example 4 except that 62 parts by mass of the BT resin obtained in Synthesis Example 1 was added without using the α-naphthol aralkyl-type cyanate compound and the maleimide compound used in Synthesis Example 1. Equivalent / epoxy equivalent ratio: 0.68) was obtained.

Example 9
A prepreg (similar to Example 4) except that the α-naphthol aralkyl cyanate compound and the bismaleimide compound used in Synthesis Example 1 were not used and 62 parts by mass of the BT resin obtained in Synthesis Example 2 was added. Cyanate equivalent / epoxy equivalent ratio: 0.68) was obtained.

Comparative Example 1
Implemented except that 38 parts by mass of phenol biphenyl aralkyl type epoxy resin (NC-3000-FH, epoxy equivalent: 320 g / eq., Manufactured by Nippon Kayaku Co., Ltd.) was used instead of tris (hydroxyphenyl) methane type epoxy resin. In the same manner as in Example 4, a prepreg (cyanate equivalent / epoxy equivalent ratio: 1.16) was obtained.

Comparative Example 2
Example 4 except that 38 parts by mass of naphthalene-modified epoxy resin (ESN-175V, epoxy equivalent: 255 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.) was used instead of tris (hydroxyphenyl) methane type epoxy resin. Similarly, a prepreg (cyanate equivalent / epoxy equivalent ratio: 0.93) was obtained.

Comparative Example 3
Example 4 except that 38 parts by mass of polyoxynaphthylene type epoxy resin (HP-6000, epoxy equivalent: 250 g / eq., Manufactured by DIC Corporation) was used instead of tris (hydroxyphenyl) methane type epoxy resin. Similarly, a prepreg (cyanate equivalent / epoxy equivalent ratio: 0.91) was obtained.

Comparative Example 4
Except for using 38 parts by mass of phenol phenyl aralkyl novolak type epoxy resin (NC-2000-L, epoxy equivalent: 226 g / eq., Manufactured by Nippon Kayaku Co., Ltd.) instead of tris (hydroxyphenyl) methane type epoxy resin A prepreg (cyanate equivalent / epoxy equivalent ratio: 0.82) was obtained in the same manner as in Example 4.

Preparation of Metal Foil-Clad Laminates Two prepregs obtained in Examples 1 to 9 and Comparative Examples 1 to 4 were stacked to obtain 12 μm thick electrolytic copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.). Laminate molding was carried out at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper clad laminate having an insulating layer thickness of 0.2 mm.

  Tables 1 and 2 show the results of evaluation of moldability, Tg, heat resistance, and coefficient of thermal expansion in the surface direction using the obtained prepreg and copper clad laminate.

Method for evaluating physical properties of prepreg and metal foil-clad laminate The prepreg melt viscosity, formability, heat resistance, and coefficient of thermal expansion in the plane direction were measured by the following methods.
Prepreg melt viscosity: The obtained prepreg is loosened to remove the powder of the thermosetting resin composition, and the powder is placed in a predetermined mold and directly pressed to obtain a resin rod. Next, a resin rod was put into the heating part of the Koka type flow tester, and the melt viscosity at 120 ± 0.2 ° C. was measured.
Formability: After removing the copper foil of the copper clad laminate by etching, the surface was observed to evaluate the presence or absence of voids. The case where there was no void was marked as ◯, the case where there was a void only at the end of the ankrat plate was marked as Δ, and the case where the void was entirely void was marked as x.
Glass transition temperature (Tg): A 0.8 mm thick double-sided copper clad laminate obtained in the above examples and comparative examples was etched on the entire surface to prepare a 12 mm × 25 mm test piece, and a DMA device (TA instrument) The temperature was raised at 10 ° C./min using a dynamic viscoelasticity measuring device DMAQ400 manufactured by Mentor, and the peak position of Loss Modulus was defined as the glass transition temperature.
Heat resistance: “n” = 5, all with solder float of 260 ° C. and no swelling at 30 minutes, “◯”, and with swelling, “x”.
Thermal expansion coefficient in the plane direction: After removing the copper foil by etching the copper clad laminate, the temperature was increased from 40 ° C. to 340 ° C. at 10 ° C. per minute with a thermomechanical analyzer (manufactured by TA Instruments). The linear expansion coefficient in the plane direction from ℃ to 120 ℃ was measured. The measurement direction was the longitudinal direction (Warp) of the glass cloth of the laminate.

成形性 ◎、○：ボイド無し ×：全面ボイド
単位 プリプレグ溶融粘度：×１６ｐｓ Ｔｇ：℃ 熱膨張率：ｐｐｍ／℃

Formability ◎, ○: No void ×: Whole void unit Prepreg melt viscosity: × 16 ps Tg: ° C Thermal expansion coefficient: ppm / ° C

成形性 ◎、○：ボイド無し △：端部ボイド ×：全面ボイド
単位 プリプレグ溶融粘度：×１６ｐｓ Ｔｇ：℃ 熱膨張率：ｐｐｍ／℃

Formability ◎, ○: No void Δ: End void ×: Full void unit Prepreg melt viscosity: × 16 ps Tg: ° C Thermal expansion coefficient: ppm / ° C

Claims (26)

In the resin composition of the inorganic filler (D), the epoxy resin (A) represented by the formula (1), the cyanate ester compound (B), the maleimide compound (C) and the inorganic filler (D) are contained. Resin composition whose content is contained in 100 to 1000 parts by mass with respect to 100 parts by mass in total of components (A) to (C).

(1)
(In the formula, each R is independently an alkyl group having 1 to 6 carbon atoms, m represents an integer of 0 to 4, and n represents an integer of 1 or more.)   Furthermore, the epoxy resin (F) other than the formula (1) is contained, and the content of the inorganic filler (D) in the resin composition is an epoxy resin other than the components (A) to (C) and the formula (1). The resin composition according to claim 1, which is contained in an amount of 100 to 1000 parts by mass with respect to a total of 100 parts by mass of (F).   The resin composition according to claim 1 or 2, wherein the epoxy resin (A) represented by the formula (1) has a mass average molecular weight of 100 to 1,000. A group in which the cyanate ester compound (B) is composed of a naphthol aralkyl cyanate ester compound represented by the formula (2), a novolac cyanate ester compound and a biphenylaralkyl cyanate ester compound represented by the formula (3) The resin composition according to any one of claims 1 to 3, which is any one or more of the above.

(2)
(In the formula, each R ₁ independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.)

(3)
(In the formula, each R ₂ independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.) The resin composition as described in any one of Claims 1-4 whose said maleimide compound (C) is what is represented by Formula (5).

(5)
(In the formula, each R ₄ independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.)   The content of the epoxy resin (A) represented by the formula (1) is 10 to 10 parts by mass with respect to a total of 100 parts by mass of the components (A) to (C) and the epoxy resin (F) other than the formula (1). The resin composition according to any one of claims 1 to 5, which is 50 parts by mass.   Content of the said cyanate ester compound (B) is 10-50 mass parts with respect to 100 mass parts in total of epoxy resins (F) other than a component (A)-(C) and Formula (1), The resin composition as described in any one of Claims 1-6.   Content of the said maleimide compound (C) is 10-50 mass parts with respect to a total of 100 mass parts of epoxy resins (F) other than a component (A)-(C) and Formula (1). The resin composition as described in any one of 1-7.   Content of the said inorganic filler (D) is 150-800 mass parts with respect to a total of 100 mass parts of epoxy resins (F) other than a component (A)-(C) and Formula (1), Item 9. The resin composition according to any one of Items 1 to 8.   It contains an epoxy resin (A) represented by the formula (1), a BT resin (E) obtained by prepolymerizing a cyanate ester compound and a maleimide compound, and an inorganic filler (D), and the inorganic filler (D) The resin composition in which the content in the resin composition is 100 to 1000 parts by mass with respect to 100 parts by mass in total of the components (A) and (E).   Furthermore, the epoxy resin (F) other than the formula (1) is contained, and the content of the inorganic filler (D) in the resin composition is an epoxy resin other than the components (A), (E) and the formula (1). The resin composition according to claim 10, which is contained in an amount of 100 to 1000 parts by mass with respect to 100 parts by mass in total of (F).   The cyanate ester compound used in the BT resin (E) is a naphthol aralkyl cyanate ester compound represented by the formula (2) and / or a novolac cyanate ester compound represented by the formula (3). The resin composition according to claim 10 or 11.   The resin composition as described in any one of Claims 10-13 whose maleimide compound used for the said BT resin (E) is represented by Formula (5).   The epoxy resin (A) represented by the formula (1) has an epoxy resin (F) other than the epoxy resin (A), the BT resin (E), and the formula (1) represented by the formula (1). The resin composition according to any one of claims 10 to 13, which is 10 to 90 parts by mass with respect to 100 parts by mass in total.   The content of the BT resin (E) is 100 parts by mass in total of the epoxy resin (A) represented by the formula (1), the BT resin (E) and the epoxy resin (F) other than the formula (1). The resin composition as described in any one of Claims 10-14 which is 10-90 mass parts.   Content of the said inorganic filler (D) is 150-800 mass parts with respect to a total of 100 mass parts of epoxy resins (A), BT resin (E), and epoxy resins (F) other than Formula (1). The resin composition according to any one of claims 10 to 15. Furthermore, the resin composition as described in any one of Claims 1-16 which comprises the imidazole compound represented by Formula (6).

(6)
(In the formula, each Ar independently represents an optionally substituted phenyl group, naphthalene group, biphenyl group, anthracene group or a hydroxyl group-modified product thereof, and R ₅ is a hydrogen atom, an alkyl group or a hydroxyl group-modified product thereof, a substituted group. Represents an aryl group which may have a group.)   The resin composition according to claim 17, wherein the imidazole compound is 2,4,5-triphenylimidazole.   The inorganic filler (D) is at least one selected from the group consisting of silica, alumina, aluminum nitride, boron nitride, boehmite, aluminum hydroxide, titanium oxide, molybdenum compound, silicone rubber, and silicone composite powder. The resin composition as described in any one of Claims 1-18 which exists.   The prepreg which impregnated or apply | coated the resin composition as described in any one of Claims 1-19 on the base material.   The prepreg according to claim 19, wherein the base material is at least one of a group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers.   A laminate obtained by stacking and curing one or more prepregs according to claim 20 or 21.   A metal foil-clad laminate obtained by laminating and curing the prepreg according to claim 20 or 21 and a metal foil.   The single layer sheet formed by shape | molding the resin composition as described in any one of Claims 1-19 in a sheet form.   A laminated resin sheet obtained by coating and drying the resin composition according to any one of claims 1 to 19 on a surface of a sheet base material. It is a printed wiring board containing an insulating layer and the conductor layer formed in the surface of the said insulating layer, Comprising: The said insulating layer is a printed wiring board containing the resin composition as described in any one of Claims 1-19. .