JP6905682B2 - Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board - Google Patents

Description

The present invention relates to resin compositions, prepregs, metal foil-clad laminates, resin sheets and printed wiring boards.

In recent years, the 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 laminated board for a semiconductor package used for a printed wiring board are becoming more and more severe. The required characteristics include, for example, low water absorption, moisture absorption 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 have been known as resins for printed wiring boards having excellent heat resistance and electrical characteristics. In recent years, resin compositions in which an epoxy resin, a bismaleimide compound, etc. are used in combination with a cyanate ester compound have been used as semiconductor plastic packages. It is widely used as a material for high-performance printed wiring boards.
For example, Patent Document 1 describes that a resin composition composed of a cyanic acid ester compound having a specific structure and other components is excellent in properties such as low water absorption and low coefficient of thermal expansion.

International Publication No. 2012/105547

Although it can be said that the resin composition described in Patent Document 1 has good physical properties such as low water absorption and low thermal expansion rate, there is still room for improvement from the viewpoint of the balance between peel strength and dielectric properties. It has.

The present invention has been made in view of the above problems, and provides a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board, which exhibit an excellent balance of physical properties in peel strength and dielectric properties. The purpose is to do.

The present inventors have diligently studied to solve the above problems. As a result, they have found that the above problems can be achieved by using a silicon-containing polymer having a specific structure in combination with a cyanate ester compound and a maleimide compound, and have completed the present invention.

（前記式（ａ）及び（ｂ）中、Ｒ₁は、各々独立して、チオール基又はグリシジル基を表し、Ｘは、チオール基、グリシジル基、ヒドロキシル基又はメトキシ基を表し、ここで、前記Ｒ₁及びＸのうち、少なくとも１つはグリシジル基であり、かつ、少なくとも１つはチオール基であり、前記ケイ素含有重合物（Ａ）中に複数存在するＲ₁は、各々同一でも異なっていてもよく、前記ケイ素含有重合物（Ａ）中に複数存在しうるＸは、各々同一でも異なっていてもよい。）
［２］
前記ケイ素含有重合物（Ａ）が、ランダム構造である、請求項１に記載の樹脂組成物。
［３］
前記ケイ素含有重合物（Ａ）の樹脂組成物中における含有量が、樹脂固形分１００質量部に対し、１〜２５質量部である、請求項１又は２に記載の樹脂組成物。
［４］
さらに、充填材（Ｄ）を含有する、請求項１〜３のいずれか一項に記載の樹脂組成物。
［５］
前記充填材（Ｄ）が、溶融シリカ又は酸化アルミニウムである、請求項４に記載の樹脂組成物。
［６］
前記充填材（Ｄ）の樹脂組成物における含有量が、樹脂固形分１００質量部に対し、５０〜１６００質量部である、請求項４又は５に記載の樹脂組成物。
［７］
基材と、
前記基材に含浸又は塗布された、請求項１〜６のいずれか一項に記載の樹脂組成物と、
を有する、プリプレグ。
［８］
少なくとも１枚以上積層された請求項７に記載のプリプレグと、
前記プリプレグの片面又は両面に配された金属箔と、
を有する、金属箔張積層板。
［９］
請求項１〜６のいずれか一項に記載の樹脂組成物を有する、樹脂シート。
［１０］
絶縁層と、
前記絶縁層の表面に形成された導体層と、
を有し、
前記絶縁層が、請求項１〜６のいずれか一項に記載の樹脂組成物を含む、プリント配線板。 That is, the present invention includes the following aspects.
[1]
A silicon-containing polymer having a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), wherein the polymerization terminals are independently R ₁ , hydroxyl groups or alkoxy groups. A silicon-containing polymer (A) having an epoxy equivalent of 100 g / eq or more and less than 500 g / eq.
Cyanic acid ester compound (B) and
Maleimide compound (C) and
A resin composition containing.

(In the formulas (a) and (b), R ₁ independently represents a thiol group or a glycidyl group, and X represents a thiol group, a glycidyl group, a hydroxyl group or a methoxy group. of R ₁ and X, at least one is a glycidyl group, and at least one is a thiol group, R ₁ a plurality present in the silicon-containing polymer (a) in are each independently selected from the same Also, a plurality of Xs that may be present in the silicon-containing polymer (A) may be the same or different.)
[2]
The resin composition according to claim 1, wherein the silicon-containing polymer (A) has a random structure.
[3]
The resin composition according to claim 1 or 2, wherein the content of the silicon-containing polymer (A) in the resin composition is 1 to 25 parts by mass with respect to 100 parts by mass of the resin solid content.
[4]
The resin composition according to any one of claims 1 to 3, further comprising a filler (D).
[5]
The resin composition according to claim 4, wherein the filler (D) is fused silica or aluminum oxide.
[6]
The resin composition according to claim 4 or 5, wherein the content of the filler (D) in the resin composition is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.
[7]
With the base material
The resin composition according to any one of claims 1 to 6, which is impregnated or coated on the base material.
Has a prepreg.
[8]
The prepreg according to claim 7, wherein at least one of the prepregs is laminated.
With the metal foil arranged on one side or both sides of the prepreg,
With, metal leaf-clad laminate.
[9]
A resin sheet having the resin composition according to any one of claims 1 to 6.
[10]
Insulation layer and
A conductor layer formed on the surface of the insulating layer and
Have,
A printed wiring board in which the insulating layer contains the resin composition according to any one of claims 1 to 6.

According to the present invention, it is possible to provide a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board, which exhibit an excellent balance of physical properties in peel strength and dielectric properties.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto, and various modifications are made without departing from the gist thereof. Is possible.

[Resin composition]
The resin composition of the present embodiment is a silicon-containing polymer having a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), and the polymerization terminals are independent of each other. , R ₁ , a hydroxyl group or an alkoxy group, and an epoxy equivalent of 100 g / eq or more and less than 500 g / eq, a silicon-containing polymer (A), a cyanate ester compound (B), and a maleimide compound (C). , Contain. Due to this structure, the resin composition of the present embodiment can exhibit an excellent balance of physical properties in terms of peel strength and dielectric properties.

（前記式（ａ）及び（ｂ）中、Ｒ₁は、各々独立して、チオール基又はグリシジル基を表し、Ｘは、チオール基、グリシジル基、ヒドロキシル基又はメトキシ基を表し、ここで、前記Ｒ₁及びＸのうち、少なくとも１つはグリシジル基であり、かつ、少なくとも１つはチオール基であり、前記ケイ素含有重合物（Ａ）中に複数存在するＲ₁は、各々同一でも異なっていてもよく、前記ケイ素含有重合物（Ａ）中に複数存在しうるＸは、各々同一でも異なっていてもよい。）

(In the formulas (a) and (b), R ₁ independently represents a thiol group or a glycidyl group, and X represents a thiol group, a glycidyl group, a hydroxyl group or a methoxy group. of R ₁ and X, at least one is a glycidyl group, and at least one is a thiol group, R ₁ a plurality present in the silicon-containing polymer (a) in are each independently selected from the same Also, a plurality of Xs that may be present in the silicon-containing polymer (A) may be the same or different.)

(Silicon-containing polymer (A))
The silicon-containing polymer (A) in the present embodiment is a silicon-containing polymer having a structural unit represented by the above formulas (a) and (b), and the polymerization terminals are independently R ₁ , Hydroxyl group or alkoxy group, and epoxy equivalent is 100 g / eq or more and less than 500 g / eq. The silicon-containing polymer (A) is not particularly limited as long as such a configuration is satisfied, but preferred embodiments will be described below.

_{Since at least one of R 1} and X in the above formulas (a) and (b) is a thiol group, the resin composition of the present embodiment can exhibit excellent peel strength. From the same viewpoint, R ₁ is preferably a thiol group, and X is preferably a glycidyl group.
Further, from the viewpoint of storage stability of the polymer, the terminal of the silicon-containing polymer (A) _{needs to be one} of the above-mentioned R 1, hydroxyl group and alkoxy group. The alkoxy group in this case is not limited to the following, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

In the present embodiment, the epoxy equivalent of the silicon-containing polymer (A) needs to be 100 g / eq or more and less than 500 g / eq, preferably 200 g / eq or more and less than 400 g / eq, and more preferably 250 g. It is greater than or equal to / eq and less than 350 g / eq. When the epoxy equivalent is 500 g / eq or more, the compatibility between the silicon-containing polymer (A) and the cyanate ester compound (B) and the maleimide compound (C) is lowered, and as a result, the dielectric properties and the glass transition temperature (Tg) are reduced. ) And the physical property balance of the coefficient of thermal expansion tend to decrease.

In the present embodiment, the silicon-containing polymer (A) preferably has a random structure from the viewpoint of improving the physical balance between the peel strength and the dielectric properties. Here, the random structure means a structure in which the arrangement of the structural units is not regular and incomplete, and the fact that the silicon-containing polymer (A) has the above-mentioned structure is described by, for example, nuclear magnetic resonance. It can be confirmed by resonance (NMR), matrix-assisted laser desorption / ionization mass spectrometry (MALDI-MS), or the like.

（ここで、Ｒ₂は炭素数１〜１２の置換又は非置換の１価の炭化水素基から選ばれ、ケイ素含有重合物中の全Ｒ₂は全てが同一でも異なっていてもよい。） The silicon-containing polymer (A) preferably further has a structural unit represented by the following formula (c) from the viewpoint of achieving both fluidity and low warpage of the resin composition.

(Here, R ₂ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ₂ in the silicon-containing polymer may be the same or different.)

_{The R 2} in the general formula (c) is not limited to the following, but for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and the like. Alkyl groups such as heptyl group, octyl group, 2-ethylhexyl group, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group and other alkenyl groups, phenyl group, tolyl group, xsilyl group, naphthyl group, biphenyl group and the like. Examples thereof include an aralkyl group such as an aryl group, a benzyl group and a phenethyl group, and a methyl group or a phenyl group is preferable.

In the present embodiment, the softening point of the silicon-containing polymer (A) is preferably set to 40 ° C to 120 ° C, more preferably 50 ° C to 100 ° C. When the temperature is higher than 40 ° C., the mechanical strength of the cured product of the obtained resin composition for printed wiring boards tends to increase, and when the temperature is lower than 120 ° C., the dispersibility of the silicon-containing polymer (A) in the resin composition is improved. Tend to do. As a method for adjusting the softening point of the silicon-containing polymer (A), the molecular weight of the silicon-containing polymer (A), the constituent bond units (for example, the content ratios (a) to (c)), and the organic bonded to the silicon atom are used. For example, setting the type of the group.

The weight average molecular weight (Mw) of the silicon-containing polymer (A) is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve, and is preferably 2000 or less, more preferably. Is 1800 to 1950. When Mw is 2000 or less, the compatibility between the silicon-containing polymer (A) and the cyanate ester compound (B) and the maleimide compound (C) can be sufficiently ensured, and as a result, the dielectric properties and the glass transition can be sufficiently ensured. The physical balance between the temperature (Tg) and the coefficient of thermal expansion tends to be further improved.

The silicon-containing polymer (A) can be obtained by the production method shown below, and is available as a commercially available product as SQ502-8 manufactured by Arakawa Chemical Industry Co., Ltd.

The method for producing the silicon-containing polymer (A) is not particularly limited, and the silicon-containing polymer (A) can be produced by a known method. For example, an organochlorosilane, an organoalkoxysilane, a siloxane, or a partial hydrolysis condensation product thereof that can form the above units (a) to (c) by a hydrolysis condensation reaction is used as a raw material and an organic solvent capable of dissolving the reaction product. It can be obtained by mixing all the hydrolyzable groups of the raw materials in a mixed solution with a hydrolyzable amount of water and subjecting them to a hydrolytic condensation reaction. At this time, it is preferable to use organoalkoxysilane and / or siloxane as a raw material in order to reduce the amount of chlorine contained as an impurity in the resin composition. In this case, it is preferable to add an acid, a base, or an organometallic compound as a catalyst for promoting the reaction.
Examples of the organoalkoxysilane and / or siloxane used as the raw material of the silicon-containing polymer (A) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxy Silane, diphenyldiethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy Propyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyl (phenyl) diethoxysilane, 2- (3) 4-Epylcyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epylcyclohexyl) ethyl (methyl) diethoxysilane, 2- (3,4-epylcyclohexyl) ethyl (phenyl) dimethoxysilane, 2-( Examples thereof include 3,4-epylcyclohexyl) ethyl (phenyl) diethoxysilane and hydrolyzed condensates thereof.
Further, the thiol group contained in the silicon-containing polymer (A) can be introduced by using the thiol group-containing alkoxysilanes represented by the following formula (d) as a raw material.
R ¹ Si (OR ² ) ₃ (d)
(In the formula (d), R ¹ represents a hydrocarbon group having at least one thiol group and having 1 to 8 carbon atoms, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom and carbon. Represents a hydrocarbon group of numbers 1 to 8 or an aromatic hydrocarbon group.)
Specific examples of the thiol group-containing alkoxysilanes include, but are not limited to, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltributoxysilane, and the like. 1,4-Dimercapto-2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane, 1,4-dimercapto -2- (Tributoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2 -Mercaptomethyl-3-mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-di Examples thereof include mercaptoethyltributoxysilane. These compounds may be used alone or in combination of two or more. Among these, 3-mercaptopropyltrimethoxysilane is particularly preferable because it has high reactivity in the hydrolysis reaction and is easily available.

The content of the silicon-containing polymer (A) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of improving the physical property balance of the dielectric property, the glass transition temperature (Tg) and the coefficient of thermal expansion, the content is not particularly limited. It is preferably 1 to 25 parts by mass, more preferably 3 to 15 parts by mass, and further preferably 5 to 10 parts by mass with respect to 100 parts by mass of the resin solid content.
In the present embodiment, the "resin solid content" refers to a component of the resin composition of the present embodiment excluding the solvent and the filler, and is referred to as "100 parts by mass of the resin solid content" unless otherwise specified. Refers to mean that the total amount of the components of the resin composition of the present embodiment excluding the solvent and the filler is 100 parts by mass. That is, the mass of the silicon-containing polymer (A) is also included in the resin solid content.

(Cyanic acid ester compound (B))
The cyanate ester compound contained in the resin composition of the present embodiment is not particularly limited as long as it is a compound having an aromatic moiety substituted with at least one cyanato group (cyanic acid ester group) in the molecule. The resin composition using the cyanate ester compound has excellent properties such as glass transition temperature, low thermal expansion property, and plating adhesion when it is made into a cured product.

Examples of the cyanate ester compound include, but are not limited to, those represented by the following formula (1).

In the above formula (1), Ar ₁ represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. When there are a plurality of them, they may be the same or different from each other. Ra independently has 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. Indicates a group to which an aryl group is bonded. The aromatic ring in Ra may have a _{substituent, and the substituent in Ar 1} and Ra can be selected at any position. p _{indicates the number of cyanato groups attached to Ar 1} , and each is an integer of 1 to 3 independently. q indicates the number of Ra bonded to _{Ar 1 , 4-p when Ar 1} is a benzene ring, 6-p when it is a naphthalene ring, and 8-p when two benzene rings are single bonded. .. t indicates the average number of repetitions and is in the range of 0 to 50, and the cyanate ester compound may be a mixture of compounds having different t. When there are a plurality of X, each of them is independently a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be replaced with a hetero atom), and a divalent group having 1 to 10 nitrogen atoms. Organic group (for example, -N-RN- (where R indicates an organic group)), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxyside group ( -OC (= O) O-), sulfonyl group (-SO _2- ), divalent sulfur atom or divalent oxygen atom.

The alkyl group in Ra of the above formula (1) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group).
Further, even if the hydrogen atom in the alkyl group in the formula (1) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. 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, and the like. Examples thereof 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, a phenyl group, a xsilyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl group, and a dicyano. Examples thereof include a phenyl group, a trifluorophenyl group, a methoxyphenyl group, and an o-, m- or p-tolyl group.
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 in X of the above formula (1) are not limited to the following, but are a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, and a trimethyl group. Examples thereof include a cyclohexylene group, a biphenylylmethylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluoranyl group, a phthalidodiyl group and the like. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group or the like.
Examples of the divalent organic group having a nitrogen number of 1 to 10 in X in the above formula (1) include, but are not limited to, an imino group and a polyimide group.

Further, examples of the organic group of X in the above formula (1) include those having a structure represented by the following formula (2) or the following formula (3).

（上記式（２）中、Ａｒ₂はベンゼンテトライル基、ナフタレンテトライル基又はビフェニルテトライル基を示し、ｕが２以上の場合、互いに同一であっても異なっていてもよい。Ｒｂ、Ｒｃ、Ｒｆ、及びＲｇは各々独立に、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、トリフルオロメチル基、又はフェノール性ヒドロキシ基を少なくとも１個有するアリール基を示す。Ｒｄ及び、Ｒｅは各々独立に、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、炭素数１〜４のアルコキシル基、又はヒドロキシ基のいずれか一種から選択される。ｕは０〜５の整数を示す。）

(In the above formula (2), Ar ₂ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same or different from each other. , 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, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxy group. Rd and Re are independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a hydroxy group. U indicates an integer from 0 to 5.)

（式（３）中、Ａｒ₃はベンゼンテトライル基、ナフタレンテトライル基又はビフェニルテトライル基を示し、ｖが２以上の場合、互いに同一であっても異なっていてもよい。Ｒｉ、及びＲｊは各々独立に、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、ベンジル基、炭素数１〜４のアルコキシル基、ヒドロキシ基、トリフルオロメチル基、又はシアナト基が少なくとも１個置換されたアリール基を示す。ｖは０〜５の整数を示すが、ｖが異なる化合物の混合物であってもよい。）

(In the formula (3), Ar ₃ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when v is 2 or more, they may be the same or different from each other. Ri and Rj. Each independently has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, or a cyanato group. Indicates at least one substituted aryl group. V represents an integer from 0 to 5, but v may be a mixture of different compounds.)

Further, as X in the formula (1), a divalent group represented by the following formula can be mentioned.

（上記式中、ｚは４〜７の整数を示す。Ｒｋは各々独立に、水素原子又は炭素数１〜６のアルキル基を示す。）

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

As specific examples of Ar _{2 of the formula (2) and Ar 3} of the formula (3), two carbon atoms represented by the formula (2) or two oxygen atoms represented by the formula (3) are 1,4. The benzenetetrayl group bonded to the position or 1,3 position, the above two carbon atoms or two oxygen atoms are at the 4,4'position, 2,4'position, 2,2'position, and 2,3'position. , The biphenyltetrayl group bonded to the 3,3'position or the 3,4'position, and the above two carbon atoms or two oxygen atoms are at the 2,6, 1,5, and 1,6 positions. Examples thereof include a naphthalenetetrayl group attached to the position, 1,8, 1,3, 1,4, or 2,7.
The alkyl and aryl groups in Rb, Rc, Rd, Re, Rf and Rg of the formula (2) and Ri and Rj of the formula (3) are synonymous with those in the above formula (1).

Specific examples of the cyanato-substituted aromatic compound represented by the above formula (1) are not limited to the following, but are not limited to the following, but are not limited to cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4. -Methylbenzene, 1-Cyanato-2-, 1-Cyanato-3-, or 1-Cyanato-4-methoxybenzene, 1-Cyanato-2,3-,1-Cyanato-2,4-,1-Cyanato- 2,5-,1-Cyanato-2,6-,1-Cyanato-3,4- or 1-Cyanato-3,5-dimethylbenzene, Cyanatoethylbenzene, Cyanatobutylbenzene, Cyanatooctylbenzene, Cyanato Nonylbenzene, 2- (4-cianaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato- 2- or 1-Cyanato-3-chlorobenzene, 1-Cyanato-2,6-dichlorobenzene, 1-Cyanato-2-methyl-3-chlorobenzene, Cyanatonitrobenzene, 1-Cyanato-4-nitro-2-ethylbenzene, 1-Cyanato-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2 -Or 1-Cyanato-4-acetylbenzene, 4-Cyanatobenzaldehyde, 4-Cyanato benzoic acid methyl ester, 4-Cyanato benzoic acid phenyl ester, 1-Cyanato-4-acetaminobenzene, 4-Cyanatobenzophenone, 1 -Cyanato-2,6-di-tert-butylbenzene, 1,2-disyanatobenzene, 1,3-disyanatobenzene, 1,4-disyanatobenzene, 1,4-disyanato-2-tert-butylbenzene , 1,4-Disianato-2,4-dimethylbenzene, 1,4-Disianato-2,3,4-dimethylbenzene, 1,3-Disianato-2,4,6-trimethylbenzene, 1,3-Disianato- 5-Methylbenzene, 1-Cyanato or 2-Cyanatonaphthalene, 1-Cyanato 4-methoxynaphthalene, 2-Cyanato-6-methylnaphthalene, 2-Cyanato-7-methoxynaphthalene, 2,2'-disyanato-1, 1'-Benzene, 1,3-,1,4-,1,5-,1,6-,1,7-,2,3-,2,6- or 2,7-disianatocinaphthalene, 2 , 2'- Or 4,4'-disianatobiphenyl, 4,4'-disianato octafluorobiphenyl, 2,4'-or 4,4'-disianatodiphenylmethane, 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-bis (4-cyanato) Phenyl) Pentan, 1,1-bis (4-cyanatophenyl) -3-methylbutane, 1,1-bis (4-cyanatophenyl) -2-methylbutane, 1,1-bis (4-cyanatophenyl) -2,2-Dimethylpropane, 2,2-bis (4-cyanatophenyl) butane, 2,2-bis (4-cyanatophenyl) pentane, 2,2-bis (4-cyanatophenyl) hexane, 2,2-Bis (4-Cyanatophenyl) -3-methylbutane, 2,2-Bis (4-Cyanatophenyl) -4-methylpentane, 2,2-Bis (4-Cyanatophenyl) -3, 3-Dimethylbutane, 3,3-bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis (4-cyanatophenyl) octane, 3,3 -Bis (4-cyanatophenyl) -2-methylpentane, 3,3-bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) -2,2- Dimethylpentane, 4,4-bis (4-cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-cyanatophenyl) ) -2,2-Dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,2,4-trimethylpentane , 2,2-Bis (4-Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, Bis (4-Cyanatophenyl) Phenylmethane, 1,1-Bis (4-Si) Anatophenyl) -1-Phenyl Ruetane, bis (4-cyanatophenyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-) Cyanato-3-isopropylphenyl) propane, 1,1-bis (3-cyclohexyl-4-cyanatophenyl) cyclohexane, bis (4-cyanatophenyl) diphenylmethane, bis (4-cyanatophenyl) -2,2- Dichloroethylene, 1,3-bis [2- (4-cyanatophenyl) -2-propyl] benzene, 1,4-bis [2- (4-cyanatophenyl) -2-propyl] benzene, 1,1- Bis (4-Cyanatophenyl) -3,3,5-trimethylcyclohexane, 4- [bis (4-Cyanatophenyl) methyl] biphenyl, 4,4-disyanatobenzophenone, 1,3-bis (4-shi) Anatophenyl) -2-propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, 4-cyanato benzoic acid-4- Cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis- (4-cyanatophenyl) carbonate, 1,3-bis (4-cyanatophenyl) adamantan, 1,3-bis (4) -Cyanatophenyl) -5,7-dimethyladamantan, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (cyanate of phenolphthaline), 3,3-bis (4-) Cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (cyanate of o-cresolphthaline), 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- Tetrax (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'-( Hexafluoroisopropylidene) diphthalimide, tris (3,5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl) ) -3,3-bis (4-Cyanatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis (4-shi) Examples thereof include anatophenyl) indolin-2-one and 2-phenyl-3,3-bis (4-cyanatophenyl) indolin-2-one.

Further, as another specific example of the compound represented by the above formula (1), the phenol novolac resin and the cresol novolac resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, and the like, are not limited to the following. Formaldehyde compounds such as formalin and paraformaldehyde reacted in an acidic solution), trisphenol novolac resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorennovolak resin (fluorenone compound). When 9,9-bis (hydroxyaryl) fluorenes those reacted in the presence of an acid catalyst), phenol aralkyl resins, cresol aralkyl resin, a naphthol aralkyl resin and a biphenyl aralkyl resin (a known method, Ar ₄ - ( CH ₂ Y) ₂ (Ar ₄ indicates a phenyl group and Y indicates a halogen atom. The same shall apply hereinafter in this paragraph). A bishalogenomethyl compound and a phenol compound as represented by an acidic catalyst or no catalyst are used. obtained by reacting, Ar ₄ - (CH ₂ oR) expressed by such bis ₂ (alkoxymethyl) that a compound with a phenol compound is reacted in the presence of an acidic catalyst, or, Ar ₄ - (CH ₂ OH) _{A bis (hydroxymethyl) compound represented by 2} and a phenol compound reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound, and a phenol compound were polycondensed). , Phenol-modified xyleneformaldehyde resin (a reaction of xyleneformaldehyde resin and phenol compound in the presence of an acidic catalyst by a known method), modified naphthaleneformaldehyde resin (by a known method, naphthaleneformaldehyde resin and hydroxy-substituted aromatics). A compound in which a compound is reacted in the presence of an acidic catalyst), a phenol-modified dicyclopentadiene resin, and a phenol resin having a polynaphthylene ether structure (by a known method, many having two or more phenolic hydroxy groups in one molecule). Examples thereof include those obtained by cyanating a phenol resin such as a valent hydroxynaphthalene compound dehydrated and condensed in the presence of a basic catalyst) by the same method as described above, and prepolymers thereof.

The above-mentioned cyanate ester compounds may be used alone or in admixture of two or more.

Among the above-mentioned cyanate ester compounds, bisphenol A type cyanate ester compound, bisphenol E type cyanate ester compound, bisphenol F type cyanate ester compound and other bisphenol type cyanate ester compound, naphthol aralkyl type cyanate ester compound, and A phenol novolac type cyanate ester compound is preferable. That is, in the present embodiment, the cyanate ester compound may contain at least one selected from the group consisting of a bisphenol type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, and a phenol novolac type cyanate ester compound. preferable. Further, it is more preferable that the cyanate ester compound contains a diallyl bisphenol A type cyanate ester compound.

The content of the cyanate ester compound can be appropriately set according to the desired properties, and is not particularly limited, but from the viewpoint of further improving the physical property balance of the dielectric properties, the glass transition temperature (Tg) and the coefficient of thermal expansion. It is preferably 30 to 100 parts by mass, more preferably 35 to 80 parts by mass, and further preferably 40 to 70 parts by mass with respect to 100 parts by mass of the resin solid content.

[Maleimide compound (C)]
The maleimide compound (C) is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule, and for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, etc. 2,2-Bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane , Bis (3,5-diethyl-4-maleimidephenyl) methane, maleimide compounds represented by the following formula (4), prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. Among these, 2,2'-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane and represented by the following formula (4). At least one selected from the group consisting of maleimide compounds is preferred. By including such a maleimide compound (C), the coefficient of thermal expansion of the obtained cured product tends to be further lowered, and the glass transition temperature tends to be more excellent. From the same viewpoint, it is more preferable that the maleimide compound (C) contains at least one selected from the group consisting of maleimide compounds represented by the following formula (4).

Here, in the formula (4), R ₅ independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Further, in the equation (4), n ₁ represents an integer of 1 or more, preferably an integer of 10 or less, and more preferably an integer of 7 or less.

The content of the maleimide compound (C) in the present embodiment is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and further preferably 25 to 20 parts by mass with respect to 100 parts by mass of the resin solid content. 50 parts by mass. When the content of the maleimide compound (C) is within the above range, the coefficient of thermal expansion of the obtained cured product tends to be further lowered, and the heat resistance tends to be further improved.

The resin composition of the present embodiment can further contain one or more selected from the group consisting of an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. Hereinafter, each of these components will be described.

(Epoxy resin)
As the epoxy resin, any known epoxy resin can be appropriately used as long as it is an epoxy resin having two or more epoxy groups in one molecule, and the type thereof is not particularly limited, but the above-mentioned silicon-containing polymer (A). ) Is different. Specifically, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolac Type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol aralkyl Double bond of type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, butadiene, etc. Examples thereof include a compound obtained by epoxidizing the above, a compound obtained by reacting a hydroxyl group-containing silicone resin with epichlorohydrin, and the like. Among these epoxy resins, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin, and naphthalene type epoxy resin are preferable in terms of flame retardancy and heat resistance. These epoxy resins may be used alone or in combination of two or more.

(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, and aralkyl novolac type. Phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin , Naftor aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, hydroxyl-containing silicone resin, etc., but are particularly limited. It's not a thing. Among these phenol resins, biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, phosphorus-containing phenol resin, and hydroxyl group-containing silicone resin are preferable in terms of flame retardancy. These phenol resins can be used alone or in combination of two or more.

(Oxetane resin)
As the oxetane resin, generally known ones can be used. For example, alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoro). Methyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toa Synthetic), OXT-121 (trade name manufactured by Toa Synthetic), etc. However, it is not particularly limited. These oxetane resins can be used alone or in admixture of two or more.

(Benzooxazine compound)
As the benzoxazine compound, a generally known compound can be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (trade name manufactured by Konishi Chemicals), bisphenol F type benzoxazine BF-BXZ (trade name manufactured by Konishi Chemicals), bisphenol S type benzoxazine BS-BXZ (trade name manufactured by Konishi Chemicals), P -D type benzoxazine (trade name manufactured by Shikoku Kasei Kogyo), FA type benzoxazine (trade name manufactured by Shikoku Kasei Kogyo) and the like can be mentioned, but are not particularly limited. These benzoxazine compounds can be used alone or in admixture of two or more.

(Compound with polymerizable unsaturated group)
As the compound 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, Monovalent or polyhydric alcohol (meth) acrylates such as trimethylolpropandi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, bisphenol Examples thereof include epoxy (meth) acrylates such as A-type epoxy (meth) acrylate and bisphenol F-type epoxy (meth) acrylate, and benzocyclobutene resin, but the present invention is not particularly limited. These compounds having unsaturated groups can be used alone or in admixture of two or more. The above-mentioned "(meth) acrylate" is a concept including acrylate and the corresponding methacrylate.

[Filler (D)]
The resin composition of the present embodiment preferably further contains a filler (D) from the viewpoints of thermal expansion characteristics, dimensional stability, flame retardancy, thermal conductivity, dielectric properties and the like. As the filler (D), a known one can be appropriately used, and the type thereof is not particularly limited. In particular, a filler generally used in laminated board applications can be suitably used as the filler (D). Specific examples of the filler (D) include, but are not limited to, natural silica, molten silica, synthetic silica, amorphous silica, aerodyl, hollow silica and other silicas, white carbon, titanium white, zinc oxide, magnesium oxide, and the like. Oxides such as zirconium oxide, boron nitride, coagulated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated product (aluminum hydroxide was heat-treated to reduce a part of crystalline water. Things), boehmite, metal hydrates such as magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdenate, zinc borate, zinc tintate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc , Mica, E-Glass, A-Glass, NE-Glass, C-Glass, L-Glass, D-Glass, S-Glass, M-Glass G20, Glass Short Fibers (E-Glass, T-Glass, D-Glass, S Including fine glass powders such as glass and Q glass.), Inorganic fillers (D) such as hollow glass and spherical glass, rubber powders such as styrene type, butadiene type and acrylic type, and core shell type rubber powders. , And an organic filler (D) such as silicone resin powder, silicone rubber powder, and silicone composite powder. These fillers (D) can be used individually by 1 type or in combination of 2 or more types.
From the viewpoint of further improving the thermal conductivity of the resin composition, among the above, fused silica or aluminum oxide is preferable, and aluminum oxide is more preferable.

The content of the filler (D) in the resin composition of the present embodiment can be appropriately set according to the desired properties, and is not particularly limited, but from the viewpoint of moldability of the resin composition, the resin solid content may be used. When it is 100 parts by mass, it is preferably 50 to 1600 parts by mass, more preferably 50 to 750 parts by mass, further preferably 50 to 300 parts by mass, and particularly preferably 50 to 200 parts by mass. ..

Here, when the filler (D) is contained in the resin composition, it is preferable to use a silane coupling agent or a wet dispersant in combination. As the silane coupling agent, those generally used for surface treatment of inorganic substances can be preferably used, and the type thereof is not particularly limited. Specific examples of the silane coupling agent include, but are not limited to, aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxylane, and γ-glycid. Epoxysilanes such as xypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxipropyltrimethoxysilane and vinyl-tri (β-methoxyethoxy) silane, N Examples thereof include a cationic silane type such as -β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, and a phenylsilane type. The silane coupling agent may be used alone or in combination of two or more. Further, as the wet dispersant, those generally used for paints can be preferably used, and the type thereof is not particularly limited. As the wet dispersant, a copolymer-based wet dispersant is preferably used, and a commercially available product may be used. Specific examples of commercially available products include, but are not limited to, Disperbyk-110, 111, 161 and 180, BYK-W996, BYK-W9010, BYK-W903, BYK-W940, etc. manufactured by Big Chemy Japan Co., Ltd. Be done. The wet dispersant may be used alone or in combination of two or more.

(Curing accelerator)
In addition, the resin composition of the present embodiment may contain a curing accelerator for appropriately adjusting the curing rate, if necessary. As the curing accelerator, those generally used as a curing accelerator such as a cyanic acid ester compound and an epoxy resin can be preferably used, and the type thereof is not particularly limited. Specific examples of the curing accelerator include organic metal salts such as zinc octylate, zinc naphthate, cobalt naphthenate, copper naphthenate, iron acetylacetone, nickel octylate, and manganese octylate, phenol, xylenol, cresol, resorcin, and catechol. , Phenolic compounds 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 carboxylic acids of these imidazoles. Or derivatives such as adducts of acid anhydrides thereof, amines such as dicyandiamide, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine. Peroxidation of phosphorus compounds such as compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropylperoxycarbonate, di-2-ethylhexylperoxycarbonate and the like. Examples thereof include azo compounds such as azobisisobutyronitrile and N, N-dimethylaminopyridine. The curing accelerator may be used alone or in combination of two or more.

(Other additives)
Further, the resin composition of the present embodiment has various polymer compounds such as other thermosetting resins, thermoplastic resins and their oligomers, and elastomers, and flame-retardant compounds as long as the desired properties are not impaired. , And various additives and the like can be used in combination. These are not particularly limited as long as they are generally used. Specific examples of the flame-retardant compound are not limited to the following, but are limited to bromine compounds such as 4,4'-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, and oxazine. Examples include ring-containing compounds and silicone-based compounds. The various additives are not limited to the following, but are, for example, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, and flow modifiers. , Lubricants, antifoaming agents, dispersants, leveling agents, brighteners, polymerization inhibitors and the like. These can be used alone or in combination of two or more, if desired.

(Organic solvent)
The resin composition of the present embodiment may contain an organic solvent, if necessary. In this case, the resin composition of the present embodiment can be used as an embodiment (solution or varnish) in which at least a part, preferably all of the above-mentioned various resin components are dissolved or compatible with an organic solvent. As the organic solvent, known ones can be appropriately used as long as at least a part, preferably all of the above-mentioned resin components can be dissolved or compatible with each other, 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, methyl lactate, methyl acetate, ethyl acetate, butyl acetate and isoamyl acetate. , Ester solvents such as ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, polar solvents such as amides such as dimethylacetamide and dimethylformamide, and non-polar solvents such as aromatic hydrocarbons such as toluene and xylene. Be done. These can be used individually by 1 type or in combination of 2 or more types.

The resin composition of the present embodiment can be prepared according to a conventional method, and uniformly contains the cyanate ester compound (B), the maleimide compound (C), and the above-mentioned other optional components in the present embodiment. The preparation method is not particularly limited as long as it is a method for obtaining a product. For example, the resin composition of the present embodiment can be easily prepared by sequentially blending the cyanate ester compound (B), the maleimide compound (C) and the above-mentioned other optional components in the present embodiment with the solvent and sufficiently stirring the mixture. can do.

When preparing the resin composition, known treatments (stirring, mixing, kneading, etc.) for uniformly dissolving or dispersing each component can be performed. For example, in uniform dispersion of the filler (D), the dispersibility in the resin composition is enhanced by performing the stirring and dispersing treatment using a stirring tank equipped with a stirring machine having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading treatment can be appropriately performed using, for example, an apparatus for mixing such as a ball mill or a bead mill, or a known apparatus such as a revolving / rotating type mixing apparatus.

The resin composition of the present embodiment can be used as a constituent material of a prepreg, 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 of the resin composition of the present embodiment dissolved in a solvent and drying it.
Further, using a peelable plastic film as a base material, a solution prepared by dissolving the resin composition of the present embodiment in a solvent is applied to the plastic film and dried to obtain a build-up film or a dry film solder resist. be able to. Here, the solvent can be dried by drying at a temperature of 20 ° C. to 150 ° C. for 1 to 90 minutes.
Further, the resin composition of the present embodiment can be used in an uncured state in which the solvent is simply dried, or can be used in a semi-cured state (B-staged) if necessary.

Hereinafter, the prepreg of the present embodiment will be described in detail. The prepreg of the present embodiment has a base material and the above-mentioned resin composition impregnated or coated on the base material. The method for producing the prepreg of the present embodiment is not particularly limited as long as it is a method for producing the prepreg by combining the resin composition of the present embodiment and the base material. Specifically, the resin composition of the present embodiment is impregnated or coated on a base material, and then semi-cured by a method of 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 amount of the resin composition adhered to the substrate, that is, the content of the resin composition (including the filler (D)) with respect to the total amount of prepreg after semi-curing is in the range of 20 to 99% by mass. Is preferable.

The base material used in producing the prepreg of the present embodiment may be a known material used for various printed wiring board materials. Examples of such a base material include glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, and spherical glass, and inorganic fibers other than glass such as quartz. Examples thereof include organic fibers such as polyimide, polyamide and polyester, and woven fabrics such as liquid crystal polyester, but the present invention is not particularly limited thereto. As the shape of the base material, woven fabric, non-woven fabric, roving, chopped strand mat, surfaceing mat and the like are known, and any of these may be used. As the base material, one type can be used alone or two or more types can be used in combination as appropriate. Among the woven fabrics, a woven fabric that has been subjected to a super-spreading treatment or a filling treatment is particularly suitable from the viewpoint of dimensional stability. Further, a glass woven fabric surface-treated with an epoxy silane treatment or a silane coupling agent such as an aminosilane treatment is preferable from the viewpoint of moisture absorption and heat resistance. Further, the liquid crystal polyester woven fabric is preferable from the viewpoint of electrical characteristics. Further, the thickness of the base material is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for laminated board applications.

The metal leaf-clad laminate of the present embodiment has the above-mentioned prepreg in which at least one or more sheets are laminated, and the metal foil arranged on one side or both sides of the prepreg. Specifically, it is produced by arranging a metal foil such as copper or aluminum on one side or both sides of the above-mentioned one prepreg or a plurality of prepregs stacked and laminating. be able to. The metal foil used here is not particularly limited as long as it is used as a material for a printed wiring board, but copper foil such as rolled copper foil and decopper 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 the molding conditions, a method used when manufacturing a normal laminated board for a printed wiring board and a multilayer board can be adopted. For example, using a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like, laminating molding is performed under the conditions of ^{a temperature of 180 to 350 ° C., a heating time of 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm 2.} This makes it possible to manufacture the metal foil-clad laminate of the present embodiment. Further, a multilayer board can also be manufactured by laminating and molding the above-mentioned prepreg in combination with a separately manufactured wiring board for the inner layer. As a method for manufacturing a multilayer plate, for example, a copper foil of 35 μm is arranged on both sides of one of the above-mentioned prepregs, laminated and formed under the above conditions, an inner layer circuit is formed, and the circuit is blackened. To form an inner layer circuit board. Further, the inner layer circuit board and the above prepreg are alternately arranged one by one, and further, a copper foil is arranged on the outermost layer, and laminating molding is preferably performed under the above conditions under vacuum. In this way, the multilayer board can be produced.

The metal foil-clad laminate of the present 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. The following is an example of a method for manufacturing a printed wiring board. First, the above-mentioned metal foil-clad laminate is prepared. Next, an inner layer substrate is produced by etching the surface of the metal foil-clad laminate to form an inner layer circuit. The inner layer circuit surface of the inner layer substrate is subjected to surface treatment to increase the adhesive strength, if necessary, and then the required number of the above-mentioned prepregs is superimposed on the inner layer circuit surface. Further, a metal foil for an outer layer circuit is laminated on the outside thereof and integrally molded by heating and pressurizing. In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a resin composition is formed between an inner layer circuit and a metal foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in the multilayer laminated plate, a plated metal film for conducting the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the holes. Further, the printed wiring board is manufactured by forming the outer layer circuit by etching the metal foil for the outer layer circuit.

The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment described above. That is, the prepreg of the present embodiment described above (the base material and the resin composition of the present embodiment impregnated or coated thereto), and the layer of the resin composition of the metal leaf-clad laminate of the present embodiment described above (the present embodiment). The layer made of the resin composition of the above) is made of an insulating layer containing the resin composition of the present embodiment.

The resin sheet of the present embodiment refers to a support and the resin composition layer (laminated sheet) arranged on the surface of the support, and only the resin composition layer from which the support has been removed (single layer sheet). ) Also points. That is, the resin sheet of the present embodiment has at least the resin composition of the present embodiment. This laminated sheet can be obtained by applying a solution of the above resin composition in a solvent to a support and drying it. The support used here is not particularly limited, and for example, a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a release agent are applied to the surfaces of these films. Examples thereof include an organic film base material such as a release film and a polyimide film, a conductor foil such as a copper foil and an aluminum foil, and a plate-like inorganic film such as a glass plate, a SUS plate and an FRP. As a coating method, for example, a solution obtained by dissolving the above resin composition in a solvent is applied onto the support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like, thereby forming the support and the resin composition layer. A method of producing a laminated sheet in which the above is integrated can be mentioned. Further, a single-layer sheet can also be obtained by peeling or etching the support from the resin sheet obtained by further drying after coating. The support is formed by supplying a solution obtained by dissolving or dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-like cavity and drying the solution to form a sheet. It is also possible to obtain a single-layer sheet without using.

In the production of the resin sheet or the single-layer sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but it is preferable to dry at a temperature of 20 ° C. to 200 ° C. for 1 to 90 minutes. When the temperature is 20 ° C. or higher, the residue of the solvent in the resin composition can be further prevented, and when the temperature is 200 ° C. or lower, the progress of curing of the resin composition can be suppressed. Further, the thickness of the resin layer in the resin sheet or the single-layer 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. However, the thickness is preferably 0.1 to 500 μm. If the thickness of the resin layer is 500 μm or less, the solvent is less likely to remain during drying.

Hereinafter, the present embodiment will be described in more detail with reference to Examples and Comparative Examples. The present embodiment is not limited to the following examples.

[Synthesis Example 1] Synthesis of cyanide ester compound of diallyl bisphenol A (hereinafter abbreviated as DABPA-CN) 700 g of diallyl bisphenol A (hydroxyl group equivalent 154.2 g / eq.) (OH group equivalent 4.54 mol) (DABPA) , Daiwa Kasei Kogyo Co., Ltd.) and triethylamine 459.4 g (4.54 mol) (1.0 mol with respect to 1 mol of hydroxyl group) were dissolved in 2100 g of dichloromethane, and this was used as solution 1.
474.4 g (7.72 mol) of cyanogen chloride (1.7 mol per 1 mol of hydroxyl group), 1106.9 g of dichloromethane, 735.6 g (7.26 mol) of 36% hydrochloric acid (1. 6 mol), 4560.7 g of water was poured over 90 minutes with stirring while maintaining the liquid temperature at −2 to −0.5 ° C. After pouring 1 solution, the mixture was stirred at the same temperature for 30 minutes, and then 459.4 g (4.54 mol) of triethylamine (1.0 mol with respect to 1 mol of hydroxyl group) was dissolved in 459.4 g of dichloromethane (a solution). Solution 2) was poured over 25 minutes. After 2 pouring of the solution was completed, the reaction was completed by stirring at the same temperature for 30 minutes.
After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed with 2 L of 0.1N hydrochloric acid and then washed 6 times with 2000 g of water. The electrical conductivity of the wastewater after the sixth washing with water was 20 μS / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 805 g of the desired cyanate ester compound DABPA-CN (light yellow liquid). The IR spectrum of the obtained cyanide ester compound DABPA-CN ^{showed absorption of 2264 cm -1} (cyanic acid ester group) and no absorption of hydroxyl groups.

(Example 1)
DABPA-CN47.5 parts by mass, novolac type bismaleimide compound (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300) 47.5 parts by mass, silicon-containing polymer (manufactured by Arakawa Chemical Co., Ltd., SQ502-8, epoxy equivalent 276 g / eq) ) 5.0 parts by mass, epoxy silane treated molten silica (manufactured by Admatex, SC2050MB) 100.0 parts by mass, 2,4,5-Triphenylidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.5 parts by mass, octyl A varnish was obtained by mixing 0.10 parts by mass of zinc acid (manufactured by Nippon Kagaku Sangyo Co., Ltd.). The weight average molecular weight of SQ502-8 was measured and found to be 1832. The weight average molecular weight was measured as follows. That is, 4.1 g of SQ502-8 was weighed, and 10 μL of a solution dissolved in 100 g of tetrahydrofuran (solvent) was injected into high performance liquid chromatography (high performance liquid chromatograph LachromElite manufactured by Hitachi High-Technologies Corporation) for analysis. did. The columns are two TSKgel GMHR-M (length 30 cm x inner diameter 7.8 mm) manufactured by Tosoh Corporation, the mobile phase is tetrahydrofuran, and the flow velocity is 1 mL / min. , The detector was RI. The weight average molecular weight Mw was determined by the GPC method using polystyrene as a standard substance.

(Example 2)
A varnish was obtained in the same manner as in Example 1 except that the molten silica as a filler was changed to 100 parts by mass of aluminum oxide and the amount of zinc octylate used was 0.3 parts by mass.

(Comparative Example 1)
A varnish was obtained in the same manner as in Example 1 except that SQ502-8 was not used and the amounts of DABPA-CN and BMI-2300 used were changed to 50.0 parts by mass.

[Manufacturing method of copper-clad laminate]
The varnish obtained as described above is impregnated and coated on an E glass cloth having a thickness of 0.1 mm, and used in a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.) at 165 ° C., 4 It was dried by heating for a minute to obtain a prepreg having a resin composition of 46% by mass. Eight prepregs are stacked, 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Kinzoku Mining Co., Ltd.) is placed on both sides, and ^{vacuum press is performed at a pressure of 40 kg / cm 2} and a temperature of 230 ° C. for 120 minutes to obtain a thickness. A 0.8 mm 12 μm copper-clad laminate was obtained. The following evaluation was performed using the obtained copper-clad laminate.

[Copper foil peel strength]
A copper-clad laminate test method for printed wiring boards of JIS C6481 (5.7 pulls) using a test piece (30 mm × 150 mm × thickness 0.8 mm) of a double-sided copper-clad laminate with an insulating layer thickness of 0.8 mm, which will be described later. The peeling strength of the copper foil was measured three times according to the peeling strength), and the average value of the lower limit values was taken as the measured value.

[Dielectric constant (Dk)]
Using a test piece (n = 3) from which the copper foil of the copper-clad laminate was removed, the dielectric constants of 2 GHz and 10 GHz were measured by the cavity resonator perturbation method (Agient 8722ES, manufactured by Agilent Technologies), and the dielectric constants were measured three times each. The average value was calculated.

〔Thermal conductivity〕
Next, the following heat resistance evaluation was performed using the copper-clad laminate obtained from the varnish of Example 2 as described above.
The copper foil on the surface of the obtained copper foil-clad laminate having an insulating layer thickness of 0.8 mm was removed by etching to obtain a sample for measurement. The density of the obtained sample was measured, the specific heat was measured by DSC (TA Instrument Q100 type), and the thermal diffusivity was measured by a xenon flash analyzer (Bruker: LFA447 Nanoflash). Next, the thermal conductivity in the thickness direction was calculated from the following formula.
Thermal conductivity (W / m · K) = density (kg / m ³ ) x specific heat (kJ / kg · K) x thermal diffusivity (m ² / s) x 1000

(Reference example)
The following samples were prepared in order to evaluate the thermal conductivity in Example 2.
A varnish was obtained in the same manner as in Example 2 except that SQ502-8 was not used and the amounts of DABPA-CN and BMI-2300 used were changed to 50.0 parts by mass.

The resin composition of the present invention has industrial applicability as a material for prepregs, metal foil-clad laminates, resin sheets, printed wiring boards, and the like.

Claims (9)

A silicon-containing polymer having a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), wherein the polymerization terminals are independently R ₁ , hydroxyl groups or alkoxy groups. A silicon-containing polymer (A) having an epoxy equivalent of 100 g / eq or more and less than 500 g / eq.
Cyanic acid ester compound (B) and
Maleimide compound (C) and
Contains ,
The content in the resin composition of the silicon-containing polymer (A) is, with respect to resin solid content 100 parts by mass, Ru 1-25 parts by der resin composition.

(In the formulas (a) and (b), R ₁ independently represents a thiol group or a glycidyl group, and X represents a thiol group, a glycidyl group, a hydroxyl group or a methoxy group. of R ₁ and X, at least one is a glycidyl group, and at least one is a thiol group, R ₁ a plurality present in the silicon-containing polymer (a) in are each independently selected from the same Also, a plurality of Xs that may be present in the silicon-containing polymer (A) may be the same or different.) The resin composition according to claim 1, wherein the silicon-containing polymer (A) has a random structure. The resin composition according to claim 1 or 2 , further comprising a filler (D). The resin composition according to claim 3 , wherein the filler (D) is fused silica or aluminum oxide. The resin composition according to claim 3 or 4 , wherein the content of the filler (D) in the resin composition is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content. With the base material
The resin composition according to any one of claims 1 to 5 , which is impregnated or coated on the base material.
Has a prepreg. The prepreg according to claim 6 , wherein at least one of the prepregs is laminated.
With the metal foil arranged on one side or both sides of the prepreg,
With, metal leaf-clad laminate. A resin sheet having the resin composition according to any one of claims 1 to 5. Insulation layer and
A conductor layer formed on the surface of the insulating layer and
Have,
A printed wiring board in which the insulating layer contains the resin composition according to any one of claims 1 to 5.