JP7154475B2 - Resin composition for printed wiring board, prepreg, metal foil clad laminate, resin sheet and printed wiring board - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition for printed wiring boards, a prepreg, a metal foil-clad laminate, a resin sheet and a printed wiring board.

2. Description of the Related Art In recent years, semiconductors widely used in electronic devices, communication devices, personal computers, and the like are becoming increasingly highly integrated and miniaturized. Along with this, various characteristics required for semiconductor package laminates used for printed wiring boards are becoming more and more severe. Properties required include, for example, low water absorption, heat resistance after moisture absorption, flame retardancy, low dielectric constant, low dielectric loss tangent, low coefficient of thermal expansion, heat resistance, chemical resistance, and high plating peel strength.

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

WO2012/105547

Although the resin composition described in Patent Document 1 can be said to have good physical properties in terms of properties such as low water absorption and low coefficient of thermal expansion, from the viewpoint of the balance of peel strength, heat resistance and thermal conductivity, There is still room for improvement.

The present invention has been made in view of the above problems, and provides a resin composition for printed wiring boards, a prepreg, a metal foil-clad laminate, which exhibits an excellent balance of physical properties in terms of peel strength, heat resistance, and thermal conductivity. An object of the present invention is to provide a resin sheet and a printed wiring board.

The present inventors have made intensive studies to solve the above problems. As a result, the present inventors have found that the above object can be achieved by using a cyanate ester compound having a specific structure and a maleimide compound in combination, and have completed the present invention.

（式（１）中、ｎは繰り返し単位の平均値を表す。）
［２］
前記式（１）で表されるシアン酸エステル化合物（Ａ）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、１～９０質量部である、［１］に記載のプリント配線板用樹脂組成物。
［３］
前記マレイミド化合物（Ｂ）が２，２’－ビス｛４－（４－マレイミドフェノキシ）－フェニル｝プロパン、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン及び下記式（３）で表されるマレイミド化合物を含有する、［１］又は［２］に記載のプリント配線板用樹脂組成物。

（式（３）中、Ｒ₅は、各々独立して、水素原子又はメチル基を表し、ｎ₁は、１以上の整数を表す。）
［４］
さらに、充填材（Ｃ）を含有する、［１］～［３］のいずれかに記載のプリント配線板用樹脂組成物。
［５］
前記充填材（Ｃ）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、［４］に記載のプリント配線板用樹脂組成物。
［６］
さらに、前記式（１）で表されるシアン酸エステル化合物（Ａ）以外のシアン酸エステル化合物、エポキシ樹脂、フェノール樹脂、オキセタン樹脂、ベンゾオキサジン化合物、及び重合可能な不飽和基を有する化合物からなる群より選択される少なくとも一種を含有する、［１］～［５］のいずれかに記載のプリント配線板用樹脂組成物。
［７］
基材と、
前記基材に含浸又は塗布された、［１］～［６］のいずれかに記載のプリント配線板用樹脂組成物と、
を有する、プリプレグ。
［８］
少なくとも１枚以上積層された、［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］
［１］～［６］のいずれかに記載のプリント配線板用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、［１］～［６］のいずれかに記載のプリント配線板用樹脂組成物を含む、プリント配線板。 That is, the present invention includes the following aspects.
[1]
a cyanate ester compound (A) having a structure represented by the following formula (1) and having a weight average molecular weight of 340 to 2000;
a maleimide compound (B);
A resin composition for a printed wiring board containing

(In formula (1), n represents the average value of repeating units.)
[2]
The printed wiring according to [1], wherein the content of the cyanate ester compound (A) represented by the formula (1) in the resin composition is 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content. Resin composition for boards.
[3]
The maleimide compound (B) is 2,2′-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and the following formula (3) The resin composition for printed wiring boards according to [1] or [2], containing the maleimide compound represented.

(In formula (3), each R ₅ independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.)
[4]
The resin composition for printed wiring boards according to any one of [1] to [3], further comprising a filler (C).
[5]
The resin composition for a printed wiring board according to [4], wherein the content of the filler (C) in the resin composition is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.
[6]
Furthermore, it consists of a cyanate ester compound other than the cyanate ester compound (A) represented by the formula (1), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. The resin composition for printed wiring boards according to any one of [1] to [5], containing at least one selected from the group.
[7]
a base material;
The printed wiring board resin composition according to any one of [1] to [6], impregnated or applied to the substrate;
A prepreg.
[8]
The prepreg according to [7], which is laminated with at least one sheet;
A metal foil arranged on one side or both sides of the prepreg;
A metal foil clad laminate.
[9]
A resin sheet comprising the printed wiring board resin composition according to any one of [1] to [6].
[10]
an insulating layer;
a conductor layer formed on the surface of the insulating layer;
has
A printed wiring board, wherein the insulating layer comprises the resin composition for a printed wiring board according to any one of [1] to [6].

According to the present invention, a printed wiring board resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board exhibiting an excellent physical property balance in terms of peel strength, heat resistance, and thermal conductivity are provided. can be done.

1 is a GPC chart of XPL-4437E used in Synthesis Example 1. FIG. 2 is a GPC chart of XPLCN obtained in Synthesis Example 1. FIG. 3 is an IR chart of XPLCN obtained in Synthesis Example 1. FIG. 4 is a GPC chart of APG1 used in Synthesis Example 2. FIG. 5 is a GPC chart of APG1CN obtained in Synthesis Example 2. FIG. 6 is an IR chart of APG1CN obtained in Synthesis Example 2. FIG.

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

（式（１）中、ｎは繰り返し単位の平均値を表す。） [Resin composition for printed wiring board]
The printed wiring board resin composition of the present embodiment includes a cyanate ester compound (A) having a structure represented by the following formula (1) and having a weight average molecular weight of 340 to 2000, and a maleimide compound ( B) and Because of this configuration, the printed wiring board resin composition of the present embodiment can exhibit an excellent balance of physical properties in peel strength, heat resistance, and thermal conductivity.

(In formula (1), n represents the average value of repeating units.)

As described above, the cyanate ester compound (A) in the present embodiment may have the same n in formula (1), or may be a mixture of different n in formula (1). good. Here, the mixture may contain a cyanate compound in which n=1, but in the cyanate ester compound of the present embodiment, n is greater than 1 as an average value. The value as the average value of n can be calculated, for example, based on the method described in Examples below.

In the present embodiment, the weight average molecular weight of the cyanate ester compound (A) is preferably 340 to 1500, more preferably 340, from the viewpoint of further improving the physical property balance of peel strength, heat resistance and thermal conductivity. ~600. The weight average molecular weight can be measured, for example, by the method described in Examples below.

(Method for producing cyanate ester compound (A))
The method for producing the cyanate ester compound (A) in the present embodiment is not particularly limited. For example, a hydroxy-substituted aromatic compound represented by the following formula (2) is cyanated to obtain the It is preferable to have a cyanation step for obtaining the cyanate ester compound represented by 1).

（式中、ｎは繰り返し単位の平均値を表す。）

(Wherein, n represents the average value of repeating units.)

In formula (2), n has an average value greater than 1 and is a value such that the weight-average molecular weight of the cyanate ester compound obtained by cyanation is 340-2000.

Although the hydroxy-substituted aromatic compound represented by formula (2) is not limited to the following, for example, according to the methods of Japanese Patent No. 2808034 and Japanese Patent No. 3351029, Claisen rearrangement of allyl ether of phenol novolak resins can be synthesized by

Next, the step of cyanating the hydroxy-substituted aromatic compound represented by formula (2) obtained as described above will be described.

<Cyanating step>
The cyanation step is a step of cyanating a hydroxy-substituted aromatic compound to obtain a cyanate ester compound having a structure represented by the above formula (1). Specifically, it is a step of cyanating the hydroxy group of the hydroxy-substituted aromatic compound represented by the formula (2) to obtain a cyanate ester compound having the structure represented by the above formula (1).

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

A method of reacting a hydroxy-substituted aromatic compound and a cyanogen halide in a solvent in the presence of a basic compound will be described below as an example. In this case, the hydroxy-substituted aromatic compound, which is the reaction substrate, is pre-dissolved in either the cyanogen halide solution or the basic compound solution, and then the cyanogen halide solution and the basic compound solution are brought into contact.

The method of contacting the cyanogen halide solution and the basic compound solution (contact method) is not particularly limited, but for example, (a) a method of pouring the basic compound solution into the cyanogen halide solution which has been stirred and mixed. (b) a method of pouring the cyanogen halide solution into the stirred and mixed basic compound solution; (c) a method of continuously supplying the cyanogen halide solution and the basic compound solution alternately or simultaneously. etc.
Of the methods (a), (b) and (c), the method (a) is preferred because it can suppress side reactions and yield a cyanate ester compound of higher purity in a high yield.
Moreover, the method for contacting the cyanogen halide solution and the basic compound solution may be either a semi-batch method or a continuous circulation method.
In particular, when the method (a) is used, the reaction can be completed without leaving the hydroxy group of the hydroxy-substituted aromatic compound, and a cyanate ester compound of higher purity can be obtained in a high yield. Therefore, it is preferable to pour the basic compound in divided portions. The number of divisions is not particularly limited, but preferably 1 to 5 times. Moreover, the type of basic compound may be the same or different for each division.

The cyanogen halide used in this embodiment is not particularly limited, but examples thereof include cyanogen chloride and cyanogen bromide. As the cyanogen halide, a cyanogen halide obtained by a known production method such as a method of reacting hydrogen cyanide or a metal cyanide with a halogen may be used, or a commercially available product may be used. Alternatively, a reaction solution containing cyanogen halide obtained by reacting hydrogen cyanide or metal cyanide with halogen can be used as it is.

The amount of cyanogen halide to be used for the hydroxy-substituted aromatic compound in the cyanation step in the present embodiment is preferably 0.5 to 5 mol, more preferably 1.0, per 1 mol of the hydroxy group of the hydroxy-substituted aromatic compound. ~3.5 moles.
When the content is within the above range, the yield of the cyanate ester compound tends to increase.

The solvent used for the cyanogen halide solution is not particularly limited, but examples include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, and aliphatic hydrocarbon solvents such as n-hexane, cyclohexane and isooctane. Solvents, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, dimethyl cellosolve, diglyme, tetrahydrofuran, methyltetrahydrofuran, dioxane, tetraethylene glycol dimethyl ether, dichloromethane, chloroform, carbon tetrachloride, Halogenated hydrocarbon solvents such as dichloroethane, trichloroethane, chlorobenzene, and bromobenzene; alcohol solvents such as methanol, ethanol, isopropanol, methylsolsolve, and propylene glycol monomethyl ether; N,N-dimethylformamide, N-methylpyrrolidone; , 3-dimethyl-2-imidazolidone, aprotic polar solvents such as dimethyl sulfoxide, nitrile solvents such as acetonitrile and benzonitrile, nitro solvents such as nitromethane and nitrobenzene, ester solvents such as ethyl acetate and ethyl benzoate, A water solvent is mentioned. These may be used alone or in combination of two or more depending on the reaction substrate.

As the basic compound used in the cyanation step in the present embodiment, both organic and inorganic bases can be used, and one of them can be used alone or two or more of them can be used in combination.

Organic bases include in particular trimethylamine, triethylamine, tri-n-butylamine, triamylamine, diisopropylethylamine, diethyl-n-butylamine, methyldi-n-butylamine, methylethyl-n-butylamine, dodecyldimethylamine, tribenzylamine, triethanolamine, N,N-dimethylaniline, N,N-diethylaniline, diphenylmethylamine, pyridine, diethylcyclohexylamine, tricyclohexylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8- Tertiary amines such as diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene are preferred. Among these, trimethylamine, triethylamine, tri-n-butylamine, and diisopropylethylamine are more preferable, and triethylamine is particularly preferable, because the desired product can be obtained in good yield.

The amount of the organic base to be used is preferably 0.1 to 8 mol, more preferably 1.0 to 3.5 mol, per 1 mol of the hydroxy group of the hydroxy-substituted aromatic compound.
When the content is within the above range, the yield of the cyanate ester compound tends to increase.

As the inorganic base, alkali metal hydroxides are preferred. Alkali metal hydroxides include, but are not particularly limited to, industrially commonly used sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like. Sodium hydroxide is particularly preferred because it is available at low cost.

The amount of the inorganic base used is preferably 1.0 to 5.0 mol, more preferably 1.0 to 3.5 mol, per 1 mol of the hydroxy group of the hydroxy-substituted aromatic compound.
When the content is within the above range, the yield of the cyanate ester compound tends to increase.

In the reaction of this embodiment, the basic compound can be used as a solution dissolved in a solvent as described above. An organic solvent or water can be used as the solvent.

When the hydroxy-substituted aromatic compound is dissolved in the basic compound solution, the amount of the solvent used in the basic compound solution is preferably 0.1 to 100 parts by mass, based on 1 part by mass of the hydroxy-substituted aromatic compound. It is preferably 0.5 to 50 parts by mass.
When the hydroxy-substituted aromatic compound is not dissolved in the basic compound solution, the amount of the solvent used is preferably 0.1 to 100 parts by mass, more preferably 0.25 to 50 parts by mass, relative to 1 part by mass of the basic compound. Department.

The organic solvent for dissolving the basic compound is preferably used when the basic compound is an organic base. Solvents, ether solvents such as diethyl ether, dimethyl cellosolve, diglyme, tetrahydrofuran, methyltetrahydrofuran, dioxane, tetraethylene glycol dimethyl ether, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene, bromobenzene alcoholic solvents such as methanol, ethanol, isopropanol, methylsolsolve, and propylene glycol monomethyl ether; Examples include protic polar solvents, nitrile solvents such as acetonitrile and benzonitrile, nitro solvents such as nitromethane and nitrobenzene, ester solvents such as ethyl acetate and ethyl benzoate, and aliphatic hydrocarbon solvents such as cyclohexane. The organic solvent can be appropriately selected according to the basic compound, reaction substrate and solvent used for the reaction. These can be used individually by 1 type or in combination of 2 or more types.

The water in which the basic compound is dissolved is preferably used when the basic compound is an inorganic base, and is not particularly limited, and may be tap water, distilled water, or deionized water. . From the viewpoint of efficiently obtaining the desired cyanate ester compound, distilled water and deionized water containing few impurities are preferred.

When the solvent used for the basic compound solution is water, it is preferable to use a catalytic amount of an organic base as the surfactant from the viewpoint of ensuring a more sufficient reaction rate. Among them, tertiary amines with few side reactions are preferred. The tertiary amine may be alkylamine, arylamine, or cycloalkylamine, and specific examples include trimethylamine, triethylamine, tri-n-butylamine, triamylamine, diisopropylethylamine, diethyl-n-butylamine, and methyldiamine. -n-butylamine, methylethyl-n-butylamine, dodecyldimethylamine, tribenzylamine, triethanolamine, N,N-dimethylaniline, N,N-diethylaniline, diphenylmethylamine, pyridine, diethylcyclohexylamine, tricyclohexyl amines, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5- Nonene is mentioned. Among these, trimethylamine, triethylamine, tri-n-butylamine, and diisopropylethylamine are more preferable, and triethylamine is particularly preferable, from the viewpoint of solubility in water and the viewpoint of obtaining the desired product at a higher yield. These are used individually by 1 type or in combination of 2 or more types.

The total amount of the solvent used in the cyanation step in the present embodiment is 2.5 to 100 parts by mass with respect to 1 part by mass of the hydroxy-substituted aromatic compound to more uniformly dissolve the hydroxy-substituted aromatic compound. It is preferable from the viewpoint of producing the cyanate ester compound more efficiently.

The reaction temperature in the cyanation step in the present embodiment is the imide carbonate, the polymer of the cyanate ester compound, the formation of by-products such as dialkylcyanoamide, the condensation of the reaction solution, and the use of cyanogen chloride as the cyanogen halide. is preferably -20 to +50°C, more preferably -15 to 15°C, still more preferably -10 to 10°C, from the viewpoint of suppressing volatilization of cyanogen chloride.

The reaction pressure in the cyanation step in this embodiment may be normal pressure or increased pressure. If necessary, an inert gas such as nitrogen, helium or argon may be passed through the reaction system.
In addition, the reaction time is not particularly limited, but the pouring time in the case of the contact method (a) and (b) and the contact time in the case of (c) are preferably 1 minute to 20 hours, and 3 minutes to 10 hours. is more preferred. After that, it is preferable to stir while maintaining the reaction temperature for 10 minutes to 10 hours.

By setting the reaction conditions within the above range, the target cyanate ester compound can be obtained more economically and industrially.

The degree of progress of the reaction in the cyanation step can be analyzed by liquid chromatography, IR spectroscopy, or the like. Volatile components such as by-produced dicyanide and dialkylcyanoamide can be analyzed by gas chromatography.

After completion of the reaction, the target cyanate ester compound can be isolated by performing a normal post-treatment operation and, if desired, a separation/purification operation. Specifically, the organic solvent phase containing the cyanate ester compound is isolated from the reaction solution, washed with water and then concentrated, precipitated or crystallized, or washed with water and then solvent-substituted. For washing, a method using an acidic aqueous solution such as dilute hydrochloric acid can be employed in order to remove excess amines. In order to remove moisture from the sufficiently washed reaction solution, it can be dried by a general method using sodium sulfate, magnesium sulfate, or the like. During the concentration and solvent replacement, the organic solvent is distilled off by heating to a temperature of 90° C. or lower under reduced pressure in order to suppress the polymerization of the cyanate ester compound. Solvents with low solubility can be used during precipitation or crystallization. For example, a method of dripping or reverse pouring an ether solvent, a hydrocarbon solvent such as hexane, or an alcohol solvent into the reaction solution can be employed. In order to wash the obtained crude product, a method of washing the concentrate of the reaction solution or the precipitated crystals with an ether-based solvent, a hydrocarbon-based solvent such as hexane, or an alcohol-based solvent can be employed. . The crystals obtained by concentrating the reaction solution can be redissolved and then recrystallized. Crystallization may also be performed by simply concentrating or cooling the reaction solution.

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

The content of the cyanate ester compound (A) can be appropriately set according to the desired properties and is not particularly limited, but from the viewpoint of obtaining a cured product with a lower thermal expansion coefficient, On the other hand, it is preferably 1 to 90 parts by mass, more preferably 30 to 70 parts by mass, still more preferably 40 to 60 parts by mass.
In the present embodiment, unless otherwise specified, the term "resin solid content" refers to the components of the printed wiring board resin composition of the present embodiment excluding the solvent and the filler. "Parts by mass" means that the total of the components excluding the solvent and the filler in the resin composition for printed wiring boards of the present embodiment is 100 parts by mass.

[Maleimide compound (B)]
The maleimide compound (B) is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Examples 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, maleimide compounds represented by the following formula (7), prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. Among these, 2,2′-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and represented by the following formula (1) At least one selected from the group consisting of maleimide compounds is preferred. By containing such a maleimide compound (B), the thermal expansion coefficient of the obtained cured product tends to be lower and the glass transition temperature tends to be more excellent. From the same point of view, the maleimide compound (B) more preferably contains at least one selected from the group consisting of maleimide compounds represented by the following formula (2).

Here, in formula (3), each R ₅ independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In formula (3), 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 (B) in the present embodiment is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 25 to 70 parts by mass, based on 100 parts by mass of the resin solid content. 50 parts by mass, particularly preferably 35 to 50 parts by mass. When the content of the maleimide compound (B) is within the above range, the resulting cured product tends to have a lower coefficient of thermal expansion and a higher heat resistance.

The printed wiring board resin composition of the present embodiment further includes a cyanate ester compound other than the cyanate ester compound represented by formula (1) of the present embodiment (hereinafter, also referred to as "another cyanate ester compound"). ), epoxy resins, phenolic resins, oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups. Each of these components will be described below.

(Other cyanate ester compounds)
Other cyanate ester compounds are not particularly limited as long as they are compounds having in the molecule an aromatic moiety substituted with at least one cyanato group (cyanate ester group).

Examples of other cyanate ester compounds include, but are not limited to, those represented by the following formula (4).

In formula (4) above, Ar ₁ represents an aromatic ring. When there are more than one, they may be the same or different. Examples of the aromatic ring include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a single bond of two benzene rings. Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 6 to 12 carbon atoms. Indicates a group to which an aryl group is attached. The aromatic ring in Ra may have a substituent, and the substituents in Ar ₁ and Ra can be selected at arbitrary positions. p represents the number of cyanato groups bonded to Ar ₁ and each independently represents an integer of 1-3. q represents the number of Ra atoms bonded to Ar ₁ , and is 4-p when Ar ₁ is a benzene ring, 6-p when it is a naphthalene ring, and 8-p when two benzene rings are single-bonded. . t indicates the average repeating number and ranges from 0 to 50, and other cyanate ester compounds may be mixtures of compounds with different t. When there are a plurality of X, each independently a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), a divalent nitrogen group having 1 to 10 Organic group (for example -NRN- (where R represents an organic group)), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxide group ( -OC(=O)O-), a sulfonyl group (-SO ₂ -), a divalent sulfur atom or a divalent oxygen atom.

The alkyl group for Ra in the above formula (4) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group, etc.).
Further, the hydrogen atom in the alkyl group in the above formula (4) 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 too.
Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl groups.
Specific examples of aryl groups include, but are not limited to, phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyano phenyl group, trifluorophenyl group, methoxyphenyl group, o-, m- or p-tolyl group, and the like.
Alkoxyl groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy groups.
Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of the above formula (4) are not limited to the following, but methylene group, ethylene group, trimethylene group, dimethylmethylene group, cyclopentylene group, cyclohexane sylene group, trimethylcyclohexylene group, biphenylylmethylene group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, phthalidodiyl group and the like. A hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.
Examples of the divalent organic group having 1 to 10 nitrogen atoms in X in the above formula (4) are not limited to the following, but a group represented by -NRN-, an imino group, a polyimide group, and the like. mentioned.

Examples of the organic group represented by X in the above formula (4) include those having structures represented by the following formula (5) or the following formula (6).

（上記式（５）中、Ａｒ₂は芳香環を示し、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。上記芳香環としては、特に限定されないが、例えば、ベンゼンテトライル基、ナフタレンテトライル基及びビフェニルテトライル基が挙げられる。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 (5), Ar ₂ represents an aromatic ring, and when u is 2 or more, they may be the same or different. The aromatic ring is not particularly limited, but for example, benzenetetra yl group, naphthalenetetrayl group and biphenyltetrayl group, wherein each of Rb, Rc, Rf and Rg is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, represents a trifluoromethyl group or an aryl group having at least one phenolic hydroxy group, wherein Rd and Re are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, selected from an alkoxyl group having 1 to 4 carbon atoms or a hydroxy group, u represents an integer of 0 to 5.)

（式（６）中、Ａｒ₃はフェニレン基、ナフチレン基又はビフェニレン基を示し、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 formula (6), Ar ₃ represents a phenylene group, a naphthylene group or a biphenylene group, and when v is 2 or more, they may be the same or different. Ri and Rj are each independently hydrogen; substituted with at least one 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 represents an aryl group, and v represents an integer of 0 to 5, but v may be a mixture of different compounds.)

Further, X in formula (4) includes a divalent group represented by the following formula.

（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. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Specific examples of Ar ₂ in formula (5) and Ar ₃ in formula (6) include a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, and a 2,4'-biphenylene group. group, 2,2′-biphenylene group, 2,3′-biphenylene group, 3,3′-biphenylene group, 3,4′-biphenylene group, 2,6-naphthylene group, 1,5-naphthylene group, 1, 6-naphthylene group, 1,8-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group and 2,7-naphthylene group.
The alkyl group and aryl group for Rb, Rc, Rd, Re, Rf and Rg in formula (5) and Ri and Rj in formula (6) are the same as in formula (4) above.

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

Further, other specific examples of the compound represented by the above formula (4) include, but are not limited to, phenol novolac resin and cresol novolac resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, 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), fluorene novolac resin (fluorenone compound and 9,9-bis(hydroxyaryl)fluorenes in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins (by known methods, Ar'-( A bishalogenomethyl compound such as CH ₂ Y) ₂ (Ar' represents a phenyl group and Y represents a halogen atom; hereinafter the same applies in this paragraph) and a phenol compound are reacted with an acidic catalyst or without a catalyst. A reaction product, a product obtained by reacting a bis(alkoxymethyl) compound represented by Ar'-(CH ₂ OR) ₂ with a phenol compound in the presence of an acidic catalyst, or Ar'-(CH ₂ OH) ₂ and a phenol compound reacted in the presence of an acidic catalyst, or polycondensation of an aromatic aldehyde compound, an aralkyl compound and a phenol compound) , phenol-modified xylene formaldehyde resin (by a known method, a xylene formaldehyde resin and a phenolic compound are reacted in the presence of an acidic catalyst), modified naphthalene formaldehyde resin (by a known method, a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound reacted in the presence of an acidic catalyst), phenol-modified dicyclopentadiene resin, phenolic resin having a polynaphthylene ether structure phenolic resins such as those obtained by dehydrating and condensing a hydroxy naphthalene compound in the presence of a basic catalyst), cyanated by the same method as described above, and prepolymers thereof.

（式（６－１）中、Ａｒ₄は芳香環を表し、複数ある場合は互いに同一であっても異なっていてもよい。Ｒ₁は各々独立にメチレン基、メチレンオキシ基、メチレンオキシメチレン基又はオキシメチレン基を表し、これらが連結していてもよい。Ｒ₂は一価の置換基を表し、各々独立に水素原子、アルキル基又はアリール基を表し、Ｒ₃は各々独立に水素原子、炭素数が１～３のアルキル基、アリール基、ヒドロキシ基又はヒドロキシメチレン基を表し、ｍは１以上の整数を表し、ｎは０以上の整数を表す。ｍ及びｎが異なる化合物の混合物であってもよい。各繰り返し単位の配列は任意である。ｌはシアナト基の結合個数を表し、１～３の整数である。ｘはＲ₂の結合個数を表し、Ａｒ₄の置換可能基数から（ｌ＋２）を引いた数を表す。ｙはＲ₃の結合個数を表し、Ａｒ₄の置換可能基数から２を引いた数を表す。） Further, examples of other cyanate ester compounds include those represented by the following formula (6-1).

(In the formula (6-1), Ar ₄ represents an aromatic ring, and when there are a plurality of them, they may be the same or different. Each R ₁ independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group. or an oxymethylene group, which may be linked together.R2 represents a monovalent substituent, each independently representing a hydrogen atom, an alkyl group or an aryl group _, R3 _each independently representing a hydrogen atom, represents an alkyl group having 1 to 3 carbon atoms, an aryl group, a hydroxy group or a hydroxymethylene group, m represents an integer of 1 or more, and n represents an integer of 0 or more, and m and n are a mixture of different compounds; The arrangement of each repeating unit is arbitrary, l represents the number of bonds of cyanato groups and is an integer of 1 to 3, x represents the number of bonds of R ₂ , and from the number of substitutable groups of Ar ₄ ( l+2) is subtracted, y represents the number of bonds in R ₃ , and represents the number of substitutable groups in Ar ₄ minus 2.)

Ar ₄ in the above formula (6-1) is exemplified by a benzene ring, a naphthalene ring, an anthracene ring and the like, but is not particularly limited thereto.
The alkyl groups for R ₂ and R ₃ in formula (6-1) may have either a linear or branched chain structure or a cyclic structure (eg, cycloalkyl group, etc.).
In addition, the hydrogen atom in the aryl group in R ₂ and R ₃ in formula (6-1) is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, or the like. may
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group and 2,2-dimethyl. propyl group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
Specific examples of the aryl group include a phenyl group, a xylyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl group, a dicyanophenyl group, and a trifluorophenyl group. phenyl group, methoxyphenyl group, o-, m- or p-tolyl group and the like. Furthermore, alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.

Specific examples of the cyanate ester compound represented by formula (6-1) include phenol-modified xylene formaldehyde resin (by a known method, a xylene formaldehyde resin and a phenol compound are reacted in the presence of an acidic catalyst), Phenolic resins such as modified naphthalene formaldehyde resin (a product obtained by reacting a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method) cyanated by a method similar to that described later, and the like. is not particularly limited. These cyanate ester compounds can be used singly or in combination of two or more.

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

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

(Epoxy resin)
As the epoxy resin, known epoxy resins having two or more epoxy groups in one molecule can be appropriately used, and the type thereof is not particularly limited. Specifically, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolak 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 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, glycidyl amine, glycidyl ester, double bond of butadiene, etc. and compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin. Among these epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable in terms of flame retardancy and heat resistance. These epoxy resins can be used singly or in combination of two or more.

(Phenolic resin)
As the phenolic resin, generally known phenolic resins having two or more hydroxy groups in one molecule can be used. Specific examples thereof include bisphenol A-type phenolic resin, bisphenol E-type phenolic resin, bisphenol F-type phenolic resin, bisphenol S-type phenolic resin, phenol novolac resin, bisphenol A novolac-type phenolic resin, glycidyl ester-type phenolic resin, and aralkyl novolak-type resin. Phenolic resins, biphenylaralkyl-type phenolic resins, cresol novolak-type phenolic resins, polyfunctional phenolic resins, naphthol resins, naphthol novolak resins, polyfunctional naphthol resins, anthracene-type phenolic resins, naphthalene skeleton-modified novolac-type phenolic resins, phenol aralkyl-type phenolic resins , naphtholaralkyl-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. not a thing Among these phenolic resins, biphenylaralkyl-type phenolic resins, naphtholaralkyl-type phenolic resins, phosphorus-containing phenolic resins, and hydroxyl group-containing silicone resins are preferred from the viewpoint of flame retardancy. These phenol resins can be used singly or in combination of two or more.

(oxetane resin)
Commonly known oxetane resins can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoro methyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toagosei), OXT-121 (trade name manufactured by Toagosei), etc. Examples include, but are not particularly limited to. These oxetane resins can be used singly or in combination of two or more.

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

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

[Filler (C)]
From the viewpoint of thermal expansion characteristics, dimensional stability, flame retardancy, thermal conductivity, dielectric properties, etc., the printed wiring board resin composition of the present embodiment preferably further contains a filler (C). As the filler (C), known fillers can be used as appropriate, and the type thereof is not particularly limited. In particular, fillers commonly used in laminate applications can be suitably used as the filler (C). Specific examples of the filler (C) include, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, Oxides such as zirconium oxide, boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated products (heat-treated aluminum hydroxide to reduce some of the water of crystallization metal hydrates such as boehmite, magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc , mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (E-glass, T-glass, D-glass, S Inorganic fillers (C) such as hollow glass and spherical glass, styrene-, butadiene-, and acrylic-type rubber powders, and core-shell-type rubber powders , and organic fillers (C) such as silicone resin powder, silicone rubber powder, and silicone composite powder. These fillers (C) can be used individually by 1 type or in combination of 2 or more types.
Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide is suitable. Use of these fillers (C) tends to further improve properties such as thermal expansion properties, dimensional stability and flame retardancy of the resin composition.

The content of the filler (D) in the printed wiring board 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 the moldability of the resin composition, When the resin solid content is 100 parts by mass, it is preferably 50 to 1600 parts by mass, more preferably 50 to 750 parts by mass, still more preferably 50 to 300 parts by mass, and particularly preferably 50 to 200 parts by mass. part by mass.

Here, in incorporating the filler (C) into the printed wiring board resin composition, it is preferable to use a silane coupling agent or a wetting and dispersing agent in combination. As the silane coupling agent, those generally used for surface treatment of inorganic substances can be suitably 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, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycide epoxysilanes such as xypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinylsilanes such as γ-methacryloxypropyltrimethoxysilane and vinyl-tri(β-methoxyethoxy)silane; cationic silane systems such as -β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, as well as phenylsilane systems. A silane coupling agent can be used individually by 1 type or in combination of 2 or more types. As the wetting and dispersing agent, those generally used for paints can be suitably used, and the type thereof is not particularly limited. As the wetting and dispersing agent, preferably a copolymer-based wetting and dispersing agent is used, which may be a commercial product. Specific examples of commercially available products include, but are not limited to, Disperbyk-110, 111, 161, 180, BYK-W996, BYK-W9010, BYK-W903, BYK-W940 manufactured by BYK-Chemie Japan Co., Ltd. be done. Wetting and dispersing agents can be used singly or in combination of two or more.

(Curing accelerator)
Moreover, the resin composition for printed wiring boards of the present embodiment may contain a curing accelerator for appropriately adjusting the curing speed, if necessary. As the curing accelerator, those generally used as curing accelerators such as cyanate ester compounds and epoxy resins can be suitably used, and the type thereof is not particularly limited. Specific examples of curing accelerators include organic metal salts such as zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octylate, manganese octylate, phenol, xylenol, cresol, resorcinol, and catechol. , octylphenol, phenol compounds such as 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 Phosphorus compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, etc. or azo compounds such as azobisisobutyronitrile, and N,N-dimethylaminopyridine. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

(other additives)
Furthermore, the resin composition for printed wiring boards of the present embodiment can be used in other thermosetting resins, thermoplastic resins and their oligomers, various polymer compounds such as elastomers, as long as the desired properties are not impaired. A flame retardant compound and various additives can be used in combination. These are not particularly limited as long as they are commonly used. Specific examples of flame retardant compounds include, but are not 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 oxazines. Examples include ring-containing compounds and silicone compounds. Examples of various additives include, but are not limited to, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, and fluidity modifiers. , lubricants, antifoaming agents, dispersants, leveling agents, brightening agents, polymerization inhibitors and the like. These can be used individually by 1 type or in combination of 2 or more types as needed.

(Organic solvent)
In addition, the resin composition for printed wiring boards of this embodiment can contain the organic solvent as needed. In this case, the resin composition for a printed wiring board of the present embodiment can be used as a form (solution or varnish) in which at least part, preferably all of the various resin components described above are dissolved or compatible with an organic solvent. As the organic solvent, any known organic solvent can be appropriately used as long as it is capable of dissolving or compatible with at least a part, preferably all, of the various resin components described above, and the type thereof is not particularly limited. . Specific examples of organic solvents 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, and methyl hydroxyisobutyrate; polar solvents such as amides such as dimethylacetamide and dimethylformamide; and nonpolar solvents such as aromatic hydrocarbons such as toluene and xylene. be done. These can be used individually by 1 type or in combination of 2 or more types.

The printed wiring board resin composition of the present embodiment can be prepared according to a conventional method, and the cyanate ester compound (A), maleimide compound (B) and other optional components described above in the present embodiment are uniformly mixed. The preparation method is not particularly limited as long as it is a method by which a resin composition containing the resin composition can be obtained. For example, the cyanate ester compound (A), the maleimide compound (B) and the other optional components described above in the present embodiment are sequentially blended in a solvent and sufficiently stirred to obtain the printed wiring board resin composition of the present embodiment. can be easily prepared.

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

The printed wiring board resin composition of the present embodiment can be used as a constituent material for prepregs, metal foil-clad laminates, printed wiring boards, and semiconductor packages. For example, a prepreg can be obtained by impregnating or coating a substrate with a solution obtained by dissolving the resin composition for a printed wiring board of the present embodiment in a solvent, followed by drying.
In addition, using a peelable plastic film as a substrate, a solution obtained by dissolving the resin composition for a printed wiring board of the present embodiment in a solvent is applied to the plastic film and dried to form a build-up film or a dry film. A solder resist can be obtained. 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 for a printed wiring board of the present embodiment can be used in an uncured state by simply drying the solvent, or can be used in a semi-cured (B-staged) state as necessary. can also

The prepreg of this embodiment will be described in detail below. The prepreg of the present embodiment has a base material and the resin composition impregnated or applied to the base material. The method for producing the prepreg of the present embodiment is not particularly limited as long as it is a method of producing a prepreg by combining the resin composition for printed wiring board of the present embodiment and a base material. Specifically, after impregnating or applying the resin composition for a printed wiring board of the present embodiment to a substrate, it is semi-cured by drying in a dryer at 120 to 220° C. for about 2 to 15 minutes. Thus, the prepreg of this 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 (C)) with respect to the total amount of the prepreg after semi-curing is in the range of 20 to 99% by mass. is preferred.

As the base material used when manufacturing the prepreg of the present embodiment, known materials used for various printed wiring board materials may be used. Examples of such substrates include glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, inorganic fibers other than glass such as quartz, Examples include organic fibers such as polyimide, polyamide, and polyester, and woven fabrics such as liquid crystal polyester, but the material is not particularly limited to these. As the shape of the substrate, woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat and the like are known, and any of these may be used. The base material can be used singly or in an appropriate combination of two or more. Among woven fabrics, woven fabrics subjected to super-opening treatment and stuffing treatment are particularly suitable from the viewpoint of dimensional stability. Furthermore, a glass woven fabric surface-treated with a silane coupling agent such as epoxysilane treatment or aminosilane treatment is preferable from the viewpoint of moisture absorption and heat resistance. Further, the liquid crystal polyester woven fabric is preferable from the aspect of electrical properties. Furthermore, the thickness of the base material is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for laminate applications.

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

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

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

The resin sheet of the present embodiment refers to the support and the resin composition layer (laminated sheet) disposed on the surface of the support, and only the resin composition layer (single layer sheet) from which the support is removed. ). That is, the resin sheet of this embodiment has at least the resin composition of this embodiment. This laminated sheet can be obtained by coating a support with a solution obtained by dissolving the above resin composition in a solvent and drying the solution. The support used here is not particularly limited, but examples thereof include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and a release agent coated on the surface of these films. Examples include organic film substrates such as release films and polyimide films, conductor foils such as copper foil and aluminum foil, and plate-like inorganic films such as glass plates, SUS plates, and FRP. As a coating method, for example, a solution obtained by dissolving the above resin composition in a solvent is coated on the support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like, thereby forming a support and a resin composition layer. A method of producing a laminated sheet in which are integrated is mentioned. A single-layer sheet can also be obtained by peeling off or etching the support from the resin sheet obtained by further drying after coating. A solution in which the resin composition for a printed wiring board of the present embodiment is dissolved or compatible with a solvent may be supplied into a mold having a sheet-like cavity and dried to form a sheet. It is also possible to obtain a single layer sheet without using a support.

In the production of the resin sheet or single-layer sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but drying at a temperature of 20° C. to 200° C. for 1 to 90 minutes is preferable. When it is 20°C or higher, the solvent can be prevented from remaining in the resin composition, and when it is 200°C or lower, the progress of curing of the resin composition can be suppressed. In addition, the thickness of the resin layer in the resin sheet or single-layer sheet of the present embodiment can be adjusted by the concentration and coating thickness of the solution of the resin composition for printed wiring boards of the present embodiment, 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 will be even less likely to remain during drying.

Hereinafter, the present embodiment will be described more specifically using examples and comparative examples. This embodiment is not limited at all by the following examples.

(Measurement of OH group (g/eq.) equivalent of hydroxyl group-containing aromatic compound)
The OH group equivalent (g/eq.) was determined by the pyridine-acetyl chloride method according to JIS-K0070.

(Measurement of weight average molecular weight Mw of cyanate ester compound)
10 μL of a solution obtained by dissolving 1 g of a cyanate ester compound in 100 g of tetrahydrofuran (solvent) was injected into a high performance liquid chromatography (high performance liquid chromatograph Lachrom Elite manufactured by Hitachi High-Technologies Corporation) for analysis. The columns were two TSKgel GMHHR-M (length 30 cm×inner diameter 7.8 mm) manufactured by Tosoh Corporation, the mobile phase was tetrahydrofuran, and the flow rate was 1 mL/min. , the detector was RI. The weight average molecular weight Mw was determined by GPC using polystyrene as a standard substance.

(Method for calculating number of repetitions n)
The molecular weight Mi was calculated for each component i when the repetition number n was a natural number (1, 2, 3, 4, . . . ), and a linear relational expression between the repetition number n and the molecular weight Mi was obtained. The weight average molecular weight Mw measured as described above was applied to the linear relational expression to determine the number of repetitions n.

（式中、ｎは平均値として３．１６。）

（式中、ｎは平均値として２．８８。） (Synthesis Example 1) Synthesis of allyl group-containing novolac cyanate compound 1 (formula (1-1) below; hereinafter abbreviated as “XPLCN”) containing an allyl group represented by formula (2-1) below 700 g of phenolic novolac resin (“XPL-4437E” manufactured by Gun Ei Chemical Industry Co., Ltd.; OH group equivalent 148 g/eq.; OH group conversion 4.73 mol; weight average molecular weight Mw 555 (GPC chart is shown in FIG. 1)) and triethylamine 478.6 g (4.73 mol; 1.0 mol per 1 mol of hydroxy group) was dissolved in 2100 g of dichloromethane to obtain Solution 1.
450.6 g of cyanogen chloride (7.33 mol; 1.55 mol per 1 mol of hydroxyl group), 1050 g of dichloromethane, 693.6 g of 36% hydrochloric acid (6.85 mol; 1.45 mol per 1 mol of hydroxy group), Solution 1 was poured into 3468.2 g of water over 70 minutes while stirring and maintaining the liquid temperature at -2 to -0.5°C. After pouring solution 1, the solution was stirred at the same temperature for 30 minutes, and then 622.2 g (6.15 mol; 1.3 mol per 1 mol of hydroxyl group) of triethylamine was dissolved in 622.2 g of dichloromethane (solution 2) was added over 30 minutes. After pouring solution 2, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.
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 with 2000 g of water six times. The electric conductivity of the wastewater after the sixth washing was 20 μS/cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
After washing with water, the organic phase was concentrated under reduced pressure and finally concentrated to dryness at 90° C. for 1 hour to obtain 802 g of the target cyanate ester compound XPLCN (brown viscous substance). The obtained cyanate ester compound XPLCN had a weight average molecular weight Mw of 700. A GPC chart is shown in FIG. In addition, the IR spectrum of XPLCN showed absorption at 2270 cm ^-1 (cyanate ester group) and did not show absorption of hydroxy group. An IR chart is shown in FIG.

(In the formula, n is 3.16 as an average value.)

(In the formula, n is 2.88 as an average value.)

（式中、ｎは平均値として１．１１。）

（式中、ｎは平均値として１．１０。） (Synthesis Example 2) Synthesis of allyl group-containing novolac cyanate compound 2 (formula (1-2) below; hereinafter abbreviated as “APG1CN”) containing allyl group represented by formula (2-2) below 700 g of phenol novolac resin (“APG1” manufactured by Gun Ei Chemical Industry Co., Ltd.; OH group equivalent: 146 g/eq.; OH group equivalent: 4.79 mol; weight average molecular weight Mw: 295 (GPC chart is shown in FIG. 4)) and triethylamine: 485 g. 2 g (4.79 mol; 1.0 mol per 1 mol of hydroxy group) was dissolved in 2100 g of dichloromethane to obtain solution 3.
456.8 g of cyanogen chloride (7.43 mol; 1.55 mol per 1 mol of hydroxyl group), 1074 g of dichloromethane, 704.1 g of 36% hydrochloric acid (6.95 mol; 1.45 mol per 1 mol of hydroxy group), Solution 3 was poured into 3520.4 g of water over 50 minutes while stirring and maintaining the liquid temperature at -2 to -0.5°C. After pouring solution 3, the mixture was stirred at the same temperature for 30 minutes. 4) was added over 30 minutes. After pouring the solution 4, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.
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 with 2000 g of water seven times. The electrical conductivity of the wastewater after the seventh water washing was 20 μS/cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
After washing with water, the organic phase was concentrated under reduced pressure and finally concentrated to dryness at 90° C. for 1 hour to obtain 803 g of the target cyanate ester compound APG1CN (pale yellow viscous substance). The obtained cyanate ester compound APG1CN had a weight average molecular weight Mw of 350. A GPC chart is shown in FIG. Also, the IR spectrum of APG1CN showed absorption at 2263 cm ^-1 (cyanate ester group) and did not show absorption of hydroxy group. An IR chart is shown in FIG.

(In the formula, n is 1.11 as an average value.)

(In the formula, n is 1.10 as an average value.)

（式（３）中、n₁は平均として１．７。） (Example 1)
50 parts by mass of XPLCN obtained in Synthesis Example 1, 50 parts by mass of a novolak-type bismaleimide compound (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300) represented by the following formula (3), epoxysilane-treated fused silica (SC2050MB, Admatechs) 100 parts by mass, 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.200 parts by mass. I got the varnish.

(In formula (3), n ₁ is 1.7 on average.)

(Example 2)
Same as Example 1, except that XPLCN obtained in Synthesis Example 1 was changed to APG1CN obtained in Synthesis Example 2, and 0.175 parts by mass of zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was mixed. and got the varnish.

(Comparative example 1)
The XPLCN obtained in Synthesis Example 1 was changed to phenol novolak-type polyfunctional cyanate ester resin PT-30 (manufactured by Lonza Japan Co., Ltd.; cyanate equivalent: 124 g / eq), and zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd.). A varnish was obtained in the same manner as in Example 1, except that 0.100 parts by mass of was mixed.

[Manufacturing method of copper-clad laminate]
The varnish obtained as described above was impregnated and coated on a 0.1 mm thick E glass cloth, and dried at 165 ° C. for 3 hours using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). After heating and drying for ~4 minutes, a prepreg having a resin composition of 46% by mass was obtained. Eight sheets of this prepreg were stacked, and 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed on both sides, and vacuum pressed 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. Table 1 shows the results of the following evaluations using the obtained copper-clad laminates.

[Measurement method and evaluation method]
(1) Copper foil peel strength Using a test piece (30 mm × 150 mm × thickness 0.8 mm) of the copper foil clad laminate with an insulating layer thickness of 0.8 mm obtained as described above, JIS C6481 printed wiring The peeling strength of the copper foil was measured three times according to the test method for copper-clad laminates for plates (see 5.7 Peeling strength), and the average value of the lower limits was taken as the measured value.

(2) Heat resistance evaluation After cutting the obtained copper foil clad laminate with an insulating layer thickness of 0.8 mm into a size of 12.7 × 30 mm with a dicing saw, the copper foil on the surface is removed by etching, and a sample for measurement is prepared. Obtained. Using this measurement sample, the storage elastic modulus E′ and loss elastic modulus E″ were measured by the DMA method with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481. and tan δ (=E''/E') were each taken as Tg to evaluate the heat resistance.

(3) Thermal conductivity The copper foil on the surface of the obtained copper-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). Then, 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

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 cyanate ester compound (A) having a structure represented by the following formula (1) and having a weight average molecular weight of 340 to 2000;
a maleimide compound (B);
contains
The maleimide compound (B) is 2,2′-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and the following formula (3) A resin composition for a printed wiring board containing at least one selected from the group consisting of maleimide compounds represented by:

(In formula (1), n represents the average value of repeating units.)

(In formula (3), each R ₅ independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.) The printed wiring according to claim 1, wherein the content of the cyanate ester compound (A) represented by the formula (1) in the resin composition is 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content. Resin composition for boards. 3. The resin composition for a printed wiring board according to claim 1, further comprising a filler (C). 4. The resin composition for a printed wiring board according to claim 3, wherein the content of the filler (C) in the resin composition is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content. Furthermore, it consists of a cyanate ester compound other than the cyanate ester compound (A) represented by the formula (1), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. The resin composition for printed wiring boards according to any one of claims 1 to 4, comprising at least one selected from the group. a substrate;
The printed wiring board resin composition according to any one of claims 1 to 5, which is impregnated or applied to the base material;
A prepreg for a printed wiring board. The prepreg according to claim 6, which is laminated with at least one or more sheets;
A metal foil arranged on one side or both sides of the prepreg;
A metal foil-clad laminate for a printed wiring board. A resin sheet for printed wiring boards, comprising the resin composition for printed wiring boards according to any one of claims 1 to 5. an insulating layer;
a conductor layer formed on the surface of the insulating layer;
has
A printed wiring board, wherein the insulating layer comprises the resin composition for a printed wiring board according to any one of claims 1 to 5.

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