TW202313834A - Resin composition, resin sheet, prepreg, metal foil clad laminate, and printed wiring board - Google Patents

Abstract

An object of the invention is to provide a resin composition suitable for use in the production of a resin sheet and a prepreg with excellent drilling properties, and also to provide a resin sheet, a prepreg, a metal foil clad laminate, and a printed wiring board obtained using this resin composition. The resin composition of the invention comprises a molybdenum compound (A), a thermosetting compound (B) containing a polysiloxane structure and at least one group selected from the group consisting of a maleimide group, amino group, epoxy group, carboxyl group, vinyl group, hydroxy group, and (meth)acrylic group, a thermosetting resin (C) that differs from the thermosetting compound (B), and an inorganic filler (D) that differs from the molybdenum compound (A).

Description

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

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

In recent years, semiconductor packages widely used in electronic equipment, communication equipment, and personal computers have been accelerated in terms of high integration, high functionality, and high-density mounting. Along with this, many characteristics required for printed wiring boards for semiconductor packaging have become more and more stringent. Such characteristics include: thermal expansion rate, drilling processability, heat resistance, flame retardancy, etc. Among them, in order to realize higher density mounting, the requirement for excellent drilling processability is increased.

In this regard, Patent Document 1 describes a resin composition for a printed wiring board containing a molybdenum compound. In addition, it is described that the resin composition may contain silicone powder. [Prior Art Literature] [Patent Document]

[Patent Document 1] WO2013/047203

[Problem to be Solved by the Invention]

However, the cured product obtained by using the resin composition described in Patent Document 1 has a hole position during drilling due to hardness and poor discharge of chips (shavings) generated during drilling. Decreased precision, faster drill wear and increased drill replacement frequency, prone to drill breakage and other problems that deteriorate drilling processability. In addition, the inner diameter of the machined hole becomes uneven due to wear of the drill bit, and there is a problem of interlayer delamination due to irregularities in the inner diameter.

The present invention is made to solve the above-mentioned problems, and an object of the present invention is to provide a resin composition ideally used for the manufacture of a resin sheet and a prepreg excellent in drilling processability, a resin sheet using the resin composition, and a prepreg. bodies, metal foil-clad laminates, and printed wiring boards. [Means to solve the problem]

That is, the present invention is as follows. [1] A resin composition comprising: Molybdenum compound (A), The thermosetting compound (B) contains at least one group selected from the group consisting of maleimide group, amine group, epoxy group, carboxyl group, vinyl group, hydroxyl group, and (meth)acrylic group, and polysiloxane structures, A thermosetting resin (C) different from the aforementioned thermosetting compound (B), and An inorganic filler (D) different from the aforementioned molybdenum compound (A).

[2] The resin composition as described in [1], wherein the molybdenum compound (A) contains molybdenum acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, disulfide At least one selected from the group consisting of molybdenum, molybdenum trioxide, molybdic acid hydrate, and zinc ammonium molybdate hydrate.

[3] The resin composition according to [1] or [2], wherein the thermosetting compound (B) contains the maleimide group.

[4] The resin composition according to any one of [1] to [3], wherein the thermosetting compound (B) contains at least a structural unit derived from amino-modified polysiloxane and a The constituent unit of imine compound.

[5] The resin composition according to any one of [1] to [4], wherein the thermosetting compound (B) is a mixture of at least amine-modified polysiloxane, maleimide compound, A polymer obtained by polymerizing carboxylic acid and/or carboxylic anhydride.

[6] The resin composition according to [4] or [5], wherein the amine-modified polysiloxane includes an amine-modified polysiloxane represented by the following formula (1).

[chemical 1]

In formula (1), R _a each independently represents a hydrogen atom, an alkyl group, or a phenyl group, each R _b independently represents a single bond, an alkylene group, or an arylylene group, and n represents an integer of 1 to 100.

[7] The resin composition as described in [1], wherein the molybdenum compound (A) contains molybdenum acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, disulfide At least one selected from the group consisting of molybdenum, molybdenum trioxide, molybdic acid hydrate, and zinc ammonium molybdate hydrate, The aforementioned thermosetting compound (B) contains the aforementioned maleimide group, The aforementioned thermosetting compound (B) further contains at least a structural unit derived from an amino-modified polysiloxane and a structural unit derived from a maleimide compound, and The aforementioned amine-modified polysiloxane includes amine-modified polysiloxane represented by the following formula (1).

[Chem 2]

In formula (1), R _a each independently represents a hydrogen atom, an alkyl group, or a phenyl group, each R _b independently represents a single bond, an alkylene group, or an arylylene group, and n represents an integer of 1 to 100.

[8] The resin composition according to [1] or [2], wherein the thermosetting compound (B) contains the epoxy group and/or the hydroxyl group.

[9] The resin composition according to any one of [1], [2], and [8], wherein the thermosetting compound (B) contains at least a constituent unit derived from alkenylphenol, a unit derived from epoxy A structural unit of modified polysiloxane, and a structural unit derived from an epoxy compound other than the aforementioned epoxy-modified polysiloxane.

[10] The resin composition described in any one of [1], [2], [8], and [9], wherein the thermosetting compound (B) is at least alkenylphenol, epoxy Modified polysiloxane, and a polymer obtained by polymerizing epoxy compounds other than the aforementioned epoxy-modified polysiloxane.

[11] The resin composition according to any one of [8] to [10], wherein the epoxy-modified polysiloxane includes an epoxy-modified polysiloxane represented by the following formula (2).

[Chem 3]

In formula (2), R ¹ each independently represents a single bond, an alkylene group, an arylylene group, or an aralkylene group, R ² each independently represent an alkyl group or a phenyl group with 1 to 10 carbon atoms, and n represents 0 An integer of ~100.

[12] The resin composition as described in [1], wherein the molybdenum compound (A) contains molybdenum acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, disulfide At least one selected from the group consisting of molybdenum, molybdenum trioxide, molybdic acid hydrate, and zinc ammonium molybdate hydrate, The aforementioned thermosetting compound (B) contains the aforementioned epoxy group and/or the aforementioned hydroxyl group, The aforementioned thermosetting compound (B) further contains at least a constituent unit derived from alkenylphenol, a constituent unit derived from epoxy-modified polysiloxane, and a constituent unit derived from an epoxy compound other than the aforementioned epoxy-modified polysiloxane, and The aforementioned epoxy-modified polysiloxane includes epoxy-modified polysiloxane represented by the following formula (2).

[chemical 4]

In formula (2), R ¹ each independently represents a single bond, an alkylene group, an arylylene group, or an aralkylene group, R ² each independently represent an alkyl group or a phenyl group with 1 to 10 carbon atoms, and n represents 0 An integer of ~100.

[13] The resin composition according to any one of [1] to [12], wherein the thermosetting resin (C) contains a compound selected from maleimide compounds, cyanate compounds, phenol compounds, At least one selected from the group consisting of an alkenyl-substituted nadiimide compound and an epoxy resin.

[14] The resin composition according to [13], wherein the thermosetting resin (C) contains a maleimide compound.

[15] The resin composition as described in [14], wherein the maleimide compound is selected from bis(4-maleimidophenyl)methane, 2,2-bis(4-( 4-maleimidophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, polytetrahydrofuran-bis(4-maleimido) at least one of the group consisting of a maleimide compound represented by the following formula (4), and a maleimido benzoate).

[chemical 5]

In formula (4), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.

[16] The resin composition according to [14], wherein the maleimide compound includes a maleimide compound represented by the following formula (9).

[chemical 6]

In formula (9), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10.

[17] The resin composition as described in any one of [1] to [16], wherein the inorganic filler (D) contains a material selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite ), boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide at least one of the group.

[18] The resin composition according to any one of [1] to [17], wherein the content of the molybdenum compound (A) is greater than that of the thermosetting compound (B) and the thermosetting resin ( The total of 100 parts by mass of C) is 0.1 to 30 parts by mass.

[19] The resin composition according to any one of [1] to [18], wherein the content of the thermosetting compound (B) is equal to the content of the thermosetting compound (B) and the thermosetting property The total of 100 mass parts of resin (C) is 5-50 mass parts.

[20] The resin composition according to any one of [1] to [19], wherein the content of the thermosetting resin (C) is equal to the content of the thermosetting compound (B) and the thermosetting property The total of 100 mass parts of resin (C) is 50-95 mass parts.

[21] The resin composition according to any one of [1] to [20], wherein the content of the inorganic filler (D) is equal to that of the thermosetting compound (B) and the thermosetting resin (C) is 40-600 mass parts in total 100 mass parts.

[22] The resin composition as described in [7], wherein the thermosetting resin (C) contains a compound selected from the group consisting of maleimide compounds, cyanate compounds, phenol compounds, alkenyl-substituted nadicyl At least one of the group consisting of an imine compound and an epoxy resin, The aforementioned thermosetting resin (C) contains a maleimide compound, The aforementioned maleimide compound comprises bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane , bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, polytetrahydrofuran-bis(4-maleimidobenzoate), the following formula (4) At least one of the group consisting of the maleimide compound represented by and the maleimide compound represented by the following formula (9), The aforementioned inorganic filler (D) comprises silicon dioxide, aluminum hydroxide, aluminum oxide, boehmite (boehmite), boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide At least one of the groups formed, The content of the molybdenum compound (A) is 0.1 to 30 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (B) and the thermosetting resin (C), The content of the thermosetting compound (B) is 5 to 50 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (B) and the thermosetting resin (C), The content of the thermosetting resin (C) is 50 to 95 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (B) and the thermosetting resin (C), and Content of the said inorganic filler (D) is 40-600 mass parts with respect to a total of 100 mass parts of the said thermosetting compound (B) and the said thermosetting resin (C).

[chemical 7]

In formula (4), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.

[chemical 8]

In formula (9), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10.

[23] The resin composition as described in [12], wherein the thermosetting resin (C) contains a compound selected from the group consisting of maleimide compounds, cyanate compounds, phenol compounds, alkenyl-substituted nadicyl At least one of the group consisting of an imine compound and an epoxy resin, The aforementioned thermosetting resin (C) contains a maleimide compound, The aforementioned maleimide compound comprises bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane , bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, polytetrahydrofuran-bis(4-maleimidobenzoate), the following formula (4) At least one of the group consisting of the maleimide compound represented by and the maleimide compound represented by the following formula (9), The aforementioned inorganic filler (D) comprises silicon dioxide, aluminum hydroxide, aluminum oxide, boehmite (boehmite), boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide At least one of the groups formed, The content of the molybdenum compound (A) is 0.1 to 30 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (B) and the thermosetting resin (C), The content of the thermosetting compound (B) is 5 to 50 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (B) and the thermosetting resin (C), The content of the thermosetting resin (C) is 50 to 95 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (B) and the thermosetting resin (C), and Content of the said inorganic filler (D) is 40-600 mass parts with respect to a total of 100 mass parts of the said thermosetting compound (B) and the said thermosetting resin (C).

[chemical 9]

In formula (4), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.

[chemical 10]

In formula (9), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10.

[24] A resin sheet having: support, and A resin layer arranged on one or both sides of the aforementioned support; The aforementioned resin layer contains the resin composition described in any one of [1] to [23].

[25] A prepreg comprising: base material, and The resin composition described in any one of [1] to [23] impregnated or coated on the aforementioned substrate.

[26] A metal foil clad laminate comprising: A laminate formed of the resin sheet described in [24], and Metal foil arranged on one or both sides of the aforementioned laminate.

[27] A metal foil clad laminate comprising: a laminate formed from a prepreg as described in [25], and Metal foil arranged on one or both sides of the aforementioned laminate.

[28] A metal foil clad laminate comprising: A laminate formed from the resin sheet described in [24] and the prepreg described in [25], and Metal foil arranged on one or both sides of the aforementioned laminate. A metal foil-clad laminate comprising: a laminate formed of at least one kind selected from the group consisting of the resin sheet described in [24] and the prepreg described in [25], and Metal foil arranged on one or both sides of the aforementioned laminate.

[29] A printed wiring board having: insulation, and A conductor layer formed on one or both sides of the aforementioned insulating layer; The aforementioned insulating layer contains a cured product of the resin composition described in any one of [1] to [23]. [Effect of Invention]

According to the resin composition of the present invention, a resin sheet, a prepreg, a metal foil-clad laminate, and a printed wiring board having excellent drilling processability can be provided.

Hereinafter, the mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following embodiments are examples for explaining the present invention, and do not limit the present invention to the following concepts. The present invention can be appropriately modified and implemented within the scope of the gist.

In addition, "(meth)acryl" in this specification means both "acryl" and the corresponding "methacryl". In addition, in this embodiment, "resin solid content" or "resin solid content in the resin composition" refers to the components in the resin composition after excluding additives, solvents, and fillers, and "resin solid content" is used unless otherwise specified. "100 parts by mass of components" means that the total of components in the resin composition excluding additives, solvents, and fillers is 100 parts by mass. In addition, "resin solid content 100% by mass" means that the total of components in the resin composition excluding additives, solvents, and fillers is 100% by mass. Moreover, a filler contains a molybdenum compound (A) and an inorganic filler (D).

[Resin composition] The resin composition of this embodiment contains: a molybdenum compound (A), and a group selected from maleimide groups, amine groups, epoxy groups, carboxyl groups, vinyl groups, hydroxyl groups, and (meth)acrylic groups At least one of them, a thermosetting compound (B) having a polysiloxane structure, a thermosetting resin (C) different from the thermosetting compound (B), and an inorganic compound different from the molybdenum compound (A) Filler (D).

＜Molybdenum compound (A)＞ The resin composition of this embodiment contains a molybdenum compound (A). By containing the molybdenum compound (A), the resin composition can improve the drilling processability of resin sheets, prepregs, and metal foil-clad laminates obtained by using the resin composition, and obtain good hole quality , and can prolong the life of drilling.

The reason why the present inventors have excellent drilling processability of resin sheets, prepregs, metal foil-clad laminates, etc. by using the resin composition of this embodiment is estimated as follows. That is, the lubricity exerted by the molybdenum compound (A) and the release effect from the polysiloxane structure of the thermosetting compound (B) prevent the shavings generated during drilling into lumps Wait, but can be discharged smoothly. Also, a cured product obtained by curing the molybdenum compound (A), the thermosetting compound (B), the thermosetting resin (C), and the inorganic filler (D) has excellent thermal stability. Therefore, even if frictional heat is generated during drilling, the molybdenum compound (A) and thermosetting compound (B) constituting the hardened product will not be thermally decomposed, and the contact between the tool tip and the workpiece to be cut can be maintained. The lubricating effect of reducing the friction force, and the demoulding effect of discharging the shavings. As a result, wear and breakage of the drill bit caused by the drill bit passing through shavings such as agglomerates can be prevented. In addition, by utilizing these synergistic effects, the drill has good adhesion to the processing object, and the centripetal property of the drill is improved, which is inferred to improve the hole position accuracy.

The molybdenum compound (A) is not particularly limited as long as it contains molybdenum in its molecule. Examples include molybdic acid, zinc molybdate such as ZnMoO ₄ and Zn ₃ Mo ₂ O ₉ , ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdenum acid hydrate, And zinc ammonium molybdate hydrates such as (NH ₄ )Zn ₂ Mo ₂ O ₉ ･(H ₃ O), etc. These compounds can be used individually by 1 type or in appropriate combination of 2 or more types. Among them, molybdic acid, zinc molybdate, and zinc ammonium molybdate hydrate are preferable from the viewpoint of not acting as an organometallic catalyst and from the viewpoint of obtaining better drilling workability and thermal stability.

The form of the molybdenum compound (A) when blended into the resin composition is not particularly limited, and may be in a single (unsupported) form. In this embodiment, the molybdenum compound unsupported type refers to a form in which the molybdenum compound alone does not form any substance such as an inorganic oxide on at least a part of the surface of the core particle composed of the molybdenum compound.

The average particle size (D50) of the molybdenum compound (unsupported type) is preferably 0.1-10 μm, more preferably 0.5-8 μm, and more preferably 1-4 μm in view of the dispersibility of the resin composition and the drillability. Better, 1~3μm is better. In addition, in the present embodiment, the average particle diameter (D50) means the median diameter, and is a value in which the larger side and the smaller side are equivalent when the particle size distribution of the measured powder is divided into two groups. . The average particle size (D50) means that the particle size distribution of a predetermined amount of powder that has been put into the dispersion medium is measured using a laser diffraction and scattering particle size distribution measuring device, and the volume accumulation is carried out from the smaller particles and reaches The value at 50% of the total volume.

In addition, the molybdenum compound (A) may be a surface-treated molybdenum particle (supported type) in which an inorganic oxide is formed on at least a part of the surface of the core particle composed of the molybdenum compound. The inorganic oxide may be provided on at least a part of the surface of the core particle. The inorganic oxide may be partially provided on the surface of the core particle, or may be provided so as to cover the entire surface of the core particle. From the viewpoint of both drilling processability and heat resistance, the inorganic oxide should be applied uniformly so as to cover the entire surface of the core particle, that is, it is preferable to uniformly form a coating of the inorganic oxide on the surface of the core particle.

Surface-treated molybdenum particles (supported type) include, for example, those obtained by surface-treating the above-mentioned molybdenum compound particles with a silane coupling agent, or by inorganically oxidizing the surface by using sol-gel method or liquid phase precipitation method. obtained through processing. Surface-treated molybdenum particles with inorganic oxides formed on the surface Inorganic oxides effectively act on heat, and molybdenum compounds effectively act on drilling. Therefore, the two opposite characteristics of drilling workability and heat resistance can be achieved to a high degree.

The inorganic oxide is preferably one having excellent heat resistance, and its type is not particularly limited, and is more preferably a metal oxide. Examples of metal oxides include SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZnO, In ₂ O ₃ , SnO ₂ , NiO, CoO, V ₂ O ₅ , CuO, MgO, and ZrO ₂ . These can be used individually by 1 type or in appropriate combination of 2 or more types. Among them, in view of heat resistance, insulating properties, and cost, it is preferable to be selected from silicon dioxide (SiO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), and zirconia (ZrO 2 ). ₂ ) At least one of the group formed is more preferably silicon dioxide.

That is, the molybdenum compound (A) is preferably an inorganic oxide applied to at least a part or the entire surface of the core particle made of the molybdenum compound, that is, at least a part or the entire periphery of the core particle. Among such molybdenum compounds (A), it is more preferable that silicon dioxide is provided as an inorganic oxide on at least a part or the entire surface of the core particle composed of the molybdenum compound, that is, at least a part or the entire outer periphery of the core particle. The core particles are more preferably at least one selected from the group consisting of molybdic acid, zinc molybdate, and zinc ammonium molybdate hydrate.

The thickness of the inorganic oxide on the surface can be appropriately set according to the desired performance, and is not particularly limited. Considering the viewpoint of forming a uniform inorganic oxide film and the viewpoint of improving the drilling processability more significantly and imparting higher heat resistance, the thickness is preferably 3 to 500 nm, more preferably 10 to 200 nm, and is 15~100nm is even better.

The average particle size (D50) of the surface-treated molybdenum particles is preferably 0.1-10 μm, more preferably 0.5-8 μm, more preferably 1-4 μm, and more preferably 1 ~3 μm is even better.

The core particles made of a molybdenum compound can be produced by various known methods such as a pulverization method and a granulation method, and the production method is not particularly limited. Moreover, its commercial item can also be used.

The method of producing the surface-treated molybdenum particles is not particularly limited, for example, by appropriately adopting a sol-gel method, a liquid phase precipitation method, a dip coating method, a spray coating method, a printing method, an electroless plating method, a sputtering method, Surface-treated molybdenum particles can be obtained by imparting an inorganic oxide or its precursor to the surface of a core particle composed of a molybdenum compound by various known methods such as vapor deposition, ion plating, and CVD. The method of imparting the inorganic oxide or its precursor to the surface of the core particle composed of the molybdenum compound does not matter whether it is a wet method or a dry method.

The ideal method for producing surface-treated molybdenum particles includes, for example, dispersing a molybdenum compound (core particle) in an alcoholic solution in which metal alkoxides such as silane alkoxides (alkoxysilanes) and aluminum alkoxides are dissolved. Add the mixed solution of water, alcohol and catalyst dropwise while stirring, and hydrolyze the alkoxide, thereby forming a film such as silicon oxide or aluminum oxide on the surface of the compound as a low refractive index film, and then the obtained powder is solid-liquid After separation and vacuum drying, heat treatment is applied. A more ideal production method can include, for example: dispersing molybdenum compound (core particle) in alcohol solution after dissolving metal alkoxide such as silane alkoxide and aluminum alkoxide, mixing treatment under high temperature and low pressure, and mixing in the compound A method of forming a coating such as silicon oxide or aluminum oxide on the surface, and then vacuum-drying the obtained powder and performing crushing treatment. By these methods, molybdenum particles having a film of metal oxides such as silicon dioxide and aluminum oxide on the surface of the molybdenum compound can be obtained.

The content of the molybdenum compound (A) is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total of the thermosetting compound (B) described later and the thermosetting resin (C) described later, in consideration of the drillability and heat resistance. , more preferably 0.3 to 10 parts by mass, more preferably 0.5 to 5 parts by mass.

＜Thermosetting compound (B)＞ The resin composition of the present embodiment contains at least one group selected from the group consisting of maleimide group, amine group, epoxy group, carboxyl group, vinyl group, hydroxyl group, and (meth)acrylic group, And a thermosetting compound (B) with polysiloxane structure. These thermosetting compounds (B) can be used individually by 1 type or in appropriate combination of 2 or more types.

If the thermosetting compound (B) has a polysiloxane skeleton formed by repeated siloxane bonds in the molecule, and has a group selected from maleimide group, amine group, epoxy group, carboxyl group, vinyl group, hydroxyl group , and at least one of the group consisting of (meth)acrylic groups is not particularly limited. The thermosetting compound (B) exhibits good reactivity with the thermosetting resin (C) described later, and has excellent compatibility with the thermosetting resin (C). The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among them, from the viewpoint of more effectively and reliably exerting the effect of the present embodiment, a straight-chain skeleton is preferable. In addition, the thermosetting compound (B) has a group selected from the group consisting of maleimide group, amine group, epoxy group, carboxyl group, vinyl group, hydroxyl group, and (meth)acrylic group at both terminals in the molecule. At least one of them is ideal. The groups at both terminals in the molecule may be the same or different, but they are preferably the same in terms of ease of control of the curing reaction and ease of handling.

The thermosetting compound (B) is preferably liquid at a temperature of 23°C, or when methyl ethyl ketone is used as a solvent, its solubility in the solvent at a temperature of 23°C is preferably 1% by mass or more, more preferably 5% by mass or more. Here, the solubility in methyl ethyl ketone is defined as "(total amount of thermosetting compound (B)/(total amount of thermosetting compound (B)+total amount of solvent))×100 (mass %)". In this embodiment, for example, evaluating the solubility of the thermosetting compound (B) in methyl ethyl ketone (99 g) when the total amount of 1 g or more of the thermosetting compound (B) dissolves in methyl ethyl ketone is "1% by mass or more", and the solubility is evaluated Not high means that the solubility is "less than 1% by mass".

As for the thermosetting compound containing maleimide group and polysiloxane structure in the molecule, as long as it has one or more maleimide group and polysiloxane structure in the molecule, there is no special requirement. limit.

The thermosetting compound containing an amino group and a polysiloxane structure in the molecule is not particularly limited as long as it has one or more amino groups and polysiloxane structures in the molecule.

The thermosetting compound containing an epoxy group and a polysiloxane structure in the molecule is not particularly limited as long as it has one or more epoxy groups and polysiloxane structures in the molecule.

The thermosetting compound containing a carboxyl group and a polysiloxane structure in the molecule is not particularly limited as long as it has one or more carboxyl groups and polysiloxane structures in the molecule.

The thermosetting compound containing a vinyl group and a polysiloxane structure in the molecule is not particularly limited as long as it has one or more vinyl groups and polysiloxane structures in the molecule.

The thermosetting compound containing a hydroxyl group and a polysiloxane structure in the molecule is not particularly limited as long as it has one or more hydroxyl groups and a polysiloxane structure in the molecule.

As for the thermosetting compound containing (meth)acrylic group and polysiloxane structure in the molecule, as long as it has one or more (meth)acrylic group and polysiloxane structure in the molecule, there is no special requirement. limit.

The thermosetting compound (B) is preferably a thermosetting compound containing a maleimide group and a polysiloxane structure in its molecule in view of better compatibility with the thermosetting resin (C).

In addition, the thermosetting compound (B) is preferably from the viewpoint of precisely controlling the compatibility with the thermosetting resin (C), and from the viewpoint of keeping the viscosity of the thermosetting compound (B) low and improving formability. It is a thermosetting compound containing epoxy group and/or hydroxyl group and polysiloxane structure in the molecule. The thermosetting compound containing an epoxy group, a hydroxyl group, and a polysiloxane structure is not particularly limited as long as the molecule contains one or more epoxy groups, one or more hydroxyl groups, and a polysiloxane structure.

The content of the thermosetting compound (B) is considered to be more excellent in releasing the shavings, and exhibits excellent heat resistance and chemical resistance. The total of (C) is 100 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 15 to 40 parts by mass.

In addition, the total content of the polymers (B1) and (B2) described later is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and more preferably 15 to 40% by mass based on 100% by mass of the solid content of the resin. good. If the content falls within the above range, the release effect of shavings discharge will be more excellent, and a further excellent balance of compatibility, low thermal expansion, and chemical resistance will tend to be exhibited.

(thermosetting compound (B1)) The thermosetting compound (B) preferably contains at least one compound derived from an amino group-modified polymer in consideration of the reactivity of the components constituting the thermosetting compound (B) and the improvement of compatibility with the thermosetting resin (C). A thermosetting compound (B1) derived from a constituent unit of silicon oxide and a constituent unit derived from a maleimide compound. In addition, in this specification, "constituent unit derived from amino-modified polysiloxane" and "constituent unit derived from maleimide compound" refer to thermosetting compound (B1) containing amino-modified polysiloxane Oxygen, a structural unit formed by polymerization of each component of the maleimide compound, and a structural unit formed by a reaction that provides the same structural unit. Hereinafter, in this specification, "constituent unit derived from ..." is also defined and interpreted in the same way. The polymer (B1) described below is one type (specific example) of the thermosetting compound (B1), and for the amine-modified polysiloxane and maleimide compounds, refer to the following description.

The content of structural units derived from amino-modified polysiloxane is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, relative to 100 mass % of all structural units in the thermosetting compound (B1), and is 15~45% by mass is even better.

The content of the structural unit derived from the maleimide compound is preferably 30 to 95% by mass, more preferably 50 to 90% by mass, and 55% to 100% by mass of all the structural units in the thermosetting compound (B1). ~85% by mass is even better.

The amine value in the thermosetting compound (B1) is preferably at most 2.0 mgKOH/g, more preferably at most 1.0 mgKOH/g, even more preferably at most 0.5 mgKOH/g. In addition, the amine value is the total amount of a primary amine and a secondary amine. If the amine value is 2.0mgKOH/g or less, it will have a better release effect to discharge shavings, and can suppress the increase in viscosity of the resin composition, the increase in molecular weight, the gelation of the varnish, and the viscosity of the prepreg. tendency to rise. Also, the smaller the amine value, the more likely it is possible to suppress the increase in viscosity and molecular weight of the resin composition. The lower limit of the amine value is preferably 0 mgKOH/g. The amine value was measured by the method based on JIS K 7237:1995.

The weight average molecular weight (Mw) of the thermosetting compound (B1) is preferably 5,000 to 20,000, more preferably 10,000 to 15,000. When the weight average molecular weight is 5,000 or more, the thermal expansion rate of the prepreg tends to be lowered. When the weight average molecular weight is 20,000 or less, the release effect of shavings is better, and the resin composition can be suppressed. Increase in viscosity, increase in molecular weight, gelation of varnish, and increase in viscosity of prepreg. In order to set the weight average molecular weight of the thermosetting compound (B1) to 5,000 to 20,000, it is only necessary to control reaction conditions such as temperature and time when preparing the thermosetting compound (B1). In the present embodiment, the weight average molecular weight can be measured by gel permeation chromatography (GPC), and obtained as a value converted using a standard polystyrene calibration curve. Specifically, it was measured by the method described in the Example mentioned later.

(polymer (B1)) The thermosetting compound (B) considers the reactivity of the components constituting it and the compatibility improvement with the thermosetting resin (C), and at least amino-modified polysiloxane and maleimide compound , carboxylic acid and/or carboxylic anhydride polymerized polymer (B1) is preferable. The polymer (B1) contains at least a structural unit derived from an amino-modified polysiloxane and a structural unit derived from a maleimide compound.

･Amine-modified polysiloxane If the amine-modified polysiloxane is a polysiloxane with more than one amine group in the molecule, there are no special restrictions, and it is preferably a polysiloxane with more than 2 amine groups in the molecule, including the following formula (1) The amino-modified polysiloxane indicated is more preferable. When the thermosetting compound (B1) or the polymer (B1) contains the structural unit derived from the amino-modified polysiloxane, the release effect of shavings is better and can exhibit excellent compatibility. The amino-modified polysiloxane can be used alone or in appropriate combination of two or more.

[chemical 11]

In formula (1), R _a each independently represents a hydrogen atom, an alkyl group, or a phenyl group. R _b each independently represent a single bond, an alkylene group, or an arylylene group. n represents an integer from 1 to 100.

Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; and branched alkyl groups such as isopropyl, isobutyl, and tertiary butyl. Among them, a methyl group is preferable.

R _b is preferably an alkylene group. Examples of the alkylene group include methylene, ethylene, trimethylene, and tetramethylene. Also, the alkylene group has 1 to 4 carbon atoms in its main chain, more preferably trimethylene.

Examples of the aryl group include phenyl, naphthyl, indenyl, biphenyl, and anthracenyl.

The amine equivalent weight of the amine-modified polysiloxane is preferably 130-6000 g/mol, more preferably 500-3000 g/mol, and even more preferably 600-2500 g/mol. When the amine group equivalent falls within the above-mentioned range, a cured product having a more excellent release effect for discharging shavings can be obtained. The amine group equivalent is measured by the method based on JIS K 7237:1995.

As the amino-modified polysiloxane, a commercial item may be used, or a product produced by a known method may be used. Examples of commercially available amine-modified polysiloxane include "X-22-161A" (amine equivalent weight: 800 g/mol) and "X-22-161B" (amine equivalent weight) manufactured by Shin-Etsu Chemical Co., Ltd. : 1500g/mol), and "KF-8010" (amine equivalent: 430g/mol), etc.

･Maleimide compound The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. It is preferable that the number of maleimide groups in the maleimide compound is 2 or more. Examples of maleimide compounds 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-ethane Base-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polytetrahydrofuran-bis(4- Maleimido benzoate), maleimide compounds represented by formula (4), maleimide compounds represented by formula (9), prepolymers of these maleimide compounds, And the prepolymer of maleimide compound and amine compound. The maleimide compound can be used alone or in appropriate combination of two or more.

Among them, it is preferable to contain bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis (3-Ethyl-5-methyl-4-maleimidophenyl) methane, polytetrahydrofuran-bis(4-maleimido benzoate), the horsedoth represented by formula (4) At least one of the group consisting of a maleimide compound and a maleimide compound represented by formula (9), including 2,2-bis(4-(4-maleimidophenoxy ) phenyl) propane is more preferred.

[chemical 12]

In formula (4), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.

R ₅ is preferably a hydrogen atom. The upper limit of n ₁ is preferably 10, more preferably 7.

[chemical 13]

In formula (9), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10.

As the maleimide compound, a commercial item may be used, or a preparation prepared by a known method may be used. Commercially available maleimide compounds include: "BMI-70", "BMI-80" and "BMI-1000P" from K･I Chemicals Co., Ltd., "BMI-1000P" from Daiwa Chemical Industry Co., Ltd. BMI-3000", "BMI-4000", "BMI-5100", "BMI-7000", and "BMI-2300", and "MIR-3000-70MT" produced by Nippon Kayaku Co., Ltd., etc.

･Carboxylic acid and carboxylic anhydride The carboxylic acid is not particularly limited, and is preferably at least one selected from the group consisting of maleic acid, phthalic acid, succinic acid, acetic acid, and propionic acid, and is preferably selected from maleic acid, phthalic acid, and succinic acid. , and at least one selected from the group consisting of acetic acid, more preferably at least one selected from the group consisting of maleic acid, phthalic acid, and succinic acid. The carboxylic anhydride is not particularly limited, and is preferably at least one selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, acetic anhydride, and propionic anhydride. More preferably, it is at least one kind selected from the group consisting of maleic anhydride, phthalic anhydride, and acetic anhydride, and even more preferably at least one kind selected from the group consisting of maleic anhydride, phthalic anhydride, and succinic anhydride.

Among them, monobasic carboxylic acid and/or monobasic carboxylic acid anhydride, or dibasic carboxylic acid and/or dibasic carboxylic acid anhydride are preferred, and dibasic carboxylic acid and/or dibasic carboxylic anhydride are even more preferred. . Carboxylic acid and/or carboxylic acid anhydride are respectively dibasic carboxylic acid and/or dibasic carboxylic anhydride, compared to the case of unitary carboxylic acid and/or unitary carboxylic acid anhydride, it will be possible to obtain the discharge of shavings The tendency of hardened products with better demoulding effect.

A carboxylic acid and a carboxylic anhydride can be used individually by 1 type or in appropriate combination of 2 or more types. Moreover, carboxylic acid and carboxylic anhydride may be used individually or in combination, respectively.

In this embodiment, it is preferable to use only carboxylic acid anhydride rather than only carboxylic acid. The reactivity of the carboxylic acid anhydride is better, so the reaction with the amine group in the polymer (B1) tends to suppress the reactivity of the polymer (B1) ideally. As a result, the storage stability of the resin composition containing the polymer (B1) and the prepreg (such as suppressing the increase in the viscosity of the resin composition, the increase in the molecular weight, the gelation of the varnish, and the viscosity of the prepreg) rise, etc.) and tends to be excellent in moldability when mixed with a thermosetting resin (C).

The content of the structural unit derived from the amino-modified polysiloxane in the polymer (B1) is preferably 15 to 60% by mass, 20 to 55% by mass relative to 100% by mass of all the structural units in the polymer (B1) % is more preferably 30 to 50% by mass and more preferably.

The content of the structural unit derived from the maleimide compound in the polymer (B1) is preferably 35 to 75% by mass, 40 to 70% by mass relative to 100% by mass of all the structural units in the polymer (B1) More preferably, it is 44~65% by mass, and even more preferably.

The content (total content) of the structural units derived from carboxylic acid and/or carboxylic anhydride in the polymer (B1) is preferably 0.1 to 10% by mass relative to 100% by mass of all the structural units in the polymer (B1), which is It is more preferably 0.5 to 7% by mass, and more preferably 1 to 6% by mass.

･Method for producing thermosetting compound (B1) or polymer (B1) The method for producing the thermosetting compound (B1) or the polymer (B1) is not particularly limited, and includes a first reaction step ( Hereinafter also simply referred to as "the first reaction step"), and the second reaction step (hereinafter also referred to simply as "the second reaction step") in which the primary polymer is reacted with carboxylic acid and/or carboxylic anhydride, it is considered that the A thermosetting compound (B1) or a polymer (B1) having better storage stability is preferable.

In the first reaction step, the blending amount of the amino-modified polysiloxane is preferably 5-70% by mass, 10% relative to the total of the amino-modified polysiloxane and the maleimide compound (100% by mass). ~50% by mass is more preferable, 15~45% by mass is even more preferable.

In the first reaction step, the blending amount of the maleimide compound is preferably 30-95% by mass, 50-95% by mass relative to the total of the amino-modified polysiloxane and the maleimide compound (100% by mass). It is more preferably 90% by mass, and even more preferably 55 to 85% by mass.

In the first reaction step, the blending ratio of the maleimide compound to the amino-modified polysiloxane is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and 1.0 to 2.0 on a mass basis. better. There exists a tendency for the manufacturability|producibility of a thermosetting compound (B1) or a polymer (B1) to be excellent because a compounding quantity ratio falls within the said range.

The reaction temperature in the first reaction step is not particularly limited if it is the temperature at which the reaction between the amino-modified polysiloxane and the maleimide compound will proceed, and it is preferably 50-200°C, more preferably 100-150°C good.

The viscosity of the primary polymer obtained by the first reaction step used in the second reaction step is considered to be a thermosetting compound (B1) or polymer (B1) with better storage stability. The concentration of the solvent is 50%, preferably 100~500mPa･s, more preferably 150mPa･s~400mPa･s. In addition, the method of measuring the viscosity of the primary polymer can be measured using a general viscometer. For example, it can measure using a cone-plate type viscometer (for example, ICI viscometer).

In the second reaction step, the blending ratio of the total of carboxylic acid and carboxylic anhydride to the amino-modified polysiloxane is preferably 0.01-0.4 on a mass basis, more preferably 0.01-0.2, and 0.02-0.1 Even better. There exists a tendency for the storage stability of a polymer (B1) to become more excellent when a compounding quantity ratio falls within the said range.

The reaction temperature in the second reaction step is preferably 50-200°C, more preferably 100-150°C. The reaction time is preferably 0.5-5 hours, more preferably 1.5-3.5 hours.

In this embodiment, the amino-modified polysiloxane, the maleimide compound, and the carboxylic acid and/or carboxylic anhydride may be simultaneously reacted. That is, the first reaction step and the second reaction step may be carried out simultaneously.

A solvent may also be used in the first step and the second step. Examples of solvents include ketones such as acetone, methyl ethyl ketone, and methyl celluloid; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether, and acetic acid ester. A solvent can be used individually by 1 type or in appropriate combination of 2 or more types.

(thermosetting compound (B2)) The thermosetting compound (B) is at least The thermosetting compound (B2) preferably contains a structural unit derived from alkenylphenol, a structural unit derived from epoxy-modified polysiloxane, and a structural unit derived from an epoxy compound other than epoxy-modified polysiloxane. Moreover, a thermosetting compound (B2) may further contain the structural unit derived from the phenol compound other than alkenylphenol as needed. The polymer (B2) described below is one of the thermosetting compounds (B2) (specific examples), for alkenylphenol, epoxy-modified polysiloxane, epoxy compounds other than epoxy-modified polysiloxane, and alkenyl For phenolic compounds other than phenol, refer to the description below.

The content of the constituent units derived from alkenylphenol is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 10 to 40% by mass, based on the total mass of the thermosetting compound (B2). When the content of the constituent unit falls within the above-mentioned range, there is a tendency that the releasing effect of discharging shavings is more excellent, and further excellent compatibility can be exhibited.

The content of constituent units derived from epoxy-modified polysiloxane is preferably 20-60% by mass, more preferably 25-55% by mass, and 30-50% by mass relative to the total mass of the thermosetting compound (B2). Even better. When the content of the constituent unit falls within the above-mentioned range, the cured product of the resin composition tends to have a better release effect for discharging shavings and exhibit a further excellent balance between low thermal expansion and chemical resistance.

The constituent units derived from epoxy-modified polysiloxane are preferably from epoxy-modified polysiloxane with an epoxy equivalent of 50 to 350 g/mol (hereinafter also referred to as "low-equivalent epoxy-modified polysiloxane"), And a constituent unit of epoxy-modified polysiloxane having an epoxy equivalent of 400-4000 g/mol (hereinafter also referred to as "high-equivalent epoxy-modified polysiloxane").

The content of constituent units derived from low-equivalent epoxy-modified polysiloxane is preferably 5-25% by mass, more preferably 7.5-20% by mass, and 10-17% by mass relative to the total mass of the thermosetting compound (B2). Quality % is even better.

The content of constituent units derived from high-equivalent epoxy-modified polysiloxane is preferably 15-55% by mass, more preferably 20-52.5% by mass, and 25-50% by mass relative to the total mass of the thermosetting compound (B2). Quality % is even better.

The mass ratio of the content of constituent units derived from high-equivalent epoxy-modified polysiloxane relative to the content of constituent units derived from low-equivalent epoxy-modified polysiloxane is preferably 1.5-4, more preferably 1.7-3.5, and 1.9 ~3.1 is better. If the mass ratio falls within the above-mentioned range, the release effect for discharging shavings is more excellent, and further excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability tend to be exhibited.

The content of constituent units derived from epoxy compounds other than epoxy-modified polysiloxane is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total mass of the thermosetting compound (B2). 15~20% by mass is even better. If the content of the constituent unit falls within the above range, the demoulding effect of shavings discharge will be more excellent, and further excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability will be exhibited. tendency.

Also, the content of the constituent units derived from epoxy-modified polysiloxane is preferably equal to the total mass of constituent units derived from epoxy-modified polysiloxane and constituent units derived from epoxy compounds other than epoxy-modified polysiloxane. It is 5 to 95% by mass, more preferably 10 to 90% by mass, more preferably 15 to 60% by mass, and most preferably 20 to 50% by mass. The content of constituent units derived from epoxy compounds other than epoxy-modified polysiloxane relative to the total of constituent units derived from epoxy-modified polysiloxane and constituent units derived from epoxy compounds other than epoxy-modified polysiloxane The mass is preferably 5-95% by mass, more preferably 10-90% by mass, more preferably 40-85% by mass, especially preferably 50-80% by mass. If the content of these constituent units has the above-mentioned relationship, there will be a better release effect of shavings discharge, and further excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability will be further improved. tendency.

The content of constituent units derived from phenolic compounds other than alkenylphenols is preferably 5 to 30% by mass, more preferably 10 to 27.5% by mass, and 10 to 25% by mass based on the total mass of the thermosetting compound (B2). Even better. When the content of this structural unit falls within the above-mentioned range, the cured product of the resin composition tends to be more excellent in the release effect of discharging shavings, and to exhibit further excellent adhesion to copper foil.

The alkenyl equivalent in the thermosetting resin (B2) is preferably 300-1500 g/mol, more preferably 350-1200 g/mol, and even more preferably 400-1000 g/mol. When the alkenyl equivalent is 300 g/mol or more, the elastic modulus of the cured product of the resin composition tends to be further lowered, and as a result, the thermal expansion of the substrate etc. obtained by using the cured product tends to be further reduced . When the alkenyl equivalent is 1,500 g/mol or less, the release effect for discharging shavings is more excellent, and the compatibility, chemical resistance, and insulation reliability of the resin composition tend to be further improved.

The weight average molecular weight (Mw) of the thermosetting resin (B2) is preferably 3.0×10 ³ to 5.0×10 ⁴ , more preferably 3.0×10 ³ to 2.0×10 ⁴ in terms of polystyrene in the GPC method. When the weight-average molecular weight is 3.0×10 ³ or more, the thermal expansion coefficient of the prepreg tends to decrease, and when the weight-average molecular weight is 5.0×10 ⁴ or less, the release effect for discharging shavings is better, and It can suppress the tendency of the increase of the viscosity of the resin composition, the increase of the molecular weight, the gelation of the varnish, and the increase of the viscosity of the prepreg.

(polymer (B2)) The reason why the thermosetting compound (B) is further excellent in compatibility with the thermosetting resin (C) is that at least alkenylphenol, epoxy-modified polysiloxane, and epoxy-modified polysiloxane A polymer (B2) obtained by polymerizing an epoxy compound is preferable. In addition, the polymer (B2) is a polymer obtained by polymerizing at least alkenylphenol, epoxy-modified polysiloxane, epoxy compounds other than epoxy-modified polysiloxane, and phenol compounds other than alkenylphenol words are more ideal. The polymer (B2) contains at least a structural unit derived from alkenylphenol, a structural unit derived from epoxy-modified polysiloxane, and a structural unit derived from an epoxy compound other than epoxy-modified polysiloxane.

･Alkenylphenol Alkenylphenol is not particularly limited as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. When the thermosetting compound (B2) or the polymer (B2) contains the constituent unit derived from alkenylphenol, the release effect of shavings discharge is improved, and excellent compatibility can be exhibited.

Examples of the alkenyl group include alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, propenyl, butenyl, and hexenyl. Among them, the alkenyl group is preferably an allyl group and/or a propenyl group, more preferably an allyl group, from the viewpoint of more effectively and reliably exerting the effects of the present embodiment. The number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-4. From the viewpoint of more effectively and reliably exerting the effects of this embodiment, the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably 1-2, more preferably 1. Also, the position where the alkenyl group is bonded to the phenolic aromatic ring is not particularly limited.

The phenolic aromatic ring means that one or more hydroxyl groups are directly bonded to the aromatic ring, and examples thereof include a phenol ring and a naphthol ring. The number of hydroxyl groups directly bonded to one phenolic aromatic ring is, for example, 1 to 2, preferably 1.

The phenolic aromatic ring may have substituents other than alkenyl. Examples of such substituents include straight-chain alkyl groups with 1 to 10 carbons, branched alkyl groups with 3 to 10 carbons, cyclic alkyl groups with 3 to 10 carbons, and straight-chain alkyl groups with 1 to 10 carbons. Shaped alkoxy, branched alkoxy with 3 to 10 carbons, cyclic alkoxy with 3 to 10 carbons, and halogen atoms. When the phenolic aromatic ring has a substituent other than an alkenyl group, the number of the substituent directly bonded to one phenolic aromatic ring is, for example, 1-2. Also, the position where the substituent is bonded to the phenolic aromatic ring is not particularly limited.

Alkenylphenol may have one or more structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of more effectively and reliably exerting the effects of this embodiment, alkenylphenol preferably has one or two structures in which one or more alkenyl groups are directly bonded to the phenolic aromatic ring, preferably two.

The alkenylphenol may be, for example, a compound represented by the following formula (1A) or the following formula (1B).

[chemical 14]

In the formula (1A), each R _xa independently represents an alkenyl group having 2 to 8 carbon atoms, each R _xb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and each R _xc independently represents an alkenyl group having 4 to 12 carbon atoms. The aromatic ring, R _xc can also form a condensation structure with the benzene ring, R _xc may or may not exist, A represents an alkylene group with 1~6 carbons, an aralkylene group with 7~16 carbons, and an aralkylene group with 6~16 carbons Arylylene group, fenylene group, sulfonyl group, oxygen atom, sulfur atom, or direct bond (single bond) of 10, when R _xc does not exist, one benzene ring may also have two or more R _xa and/or Or the base of R _xb .

[chemical 15]

In the formula (1B), R _xd independently represents an alkenyl group with 2 to 8 carbons, R _xe independently represents an alkyl group with 1 to 10 carbons or a hydrogen atom, and R _xf represents an aromatic ring with 4 to 12 carbons , R _xf can also form a condensed structure with a benzene ring, R _xf may or may not exist, and when R _xf does not exist, one benzene ring may have two or more R _xd and/or R _xe groups.

In formula (1A) and formula (1B), the alkenyl groups having 2 to 8 carbon atoms represented by R _xa and R _xd include, for example, vinyl, allyl, propenyl, butenyl, hexenyl and the like. R _xa and R _xd are preferably allyl and/or propenyl, more preferably allyl.

In formula (1A) and formula (1B), when the groups represented by R _xc and R _xf form a condensed structure with a benzene ring, for example, a compound containing a naphthol ring as a phenolic aromatic ring is mentioned. Moreover, in formula (1A) and formula (1B), when the group represented by R _xc and R _xf does not exist, for example, the compound which contains a phenol ring as a phenolic aromatic ring is mentioned.

In formula (1A) and formula (1B), the alkyl groups with 1 to 10 carbons represented by _Rxb and _Rxe can include, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl and other linear Alkyl; branched alkyl such as isopropyl, isobutyl, tertiary butyl, etc.

In the formula (1A), the alkylene group having 1 to 6 carbon atoms represented by A includes, for example, a methylene group, an ethylene group, a trimethylene group, and a propylidene group. The aralkylene group with 7~16 carbons represented by A can be exemplified by the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar-CH ₂ -CH ₂ -, or the formula: -CH ₂ A group represented by -Ar-CH ₂ -CH ₂ - (wherein, Ar represents a phenylene group, a naphthylene group, or a biphenylene group). The arylylene group having 6 to 10 carbon atoms represented by A includes, for example, a phenylene ring.

For the compound represented by formula (1B), _Rxf is preferably a benzene ring (a compound containing a dihydroxynaphthalene skeleton) from the viewpoint of more effectively and reliably exerting the effects of the present embodiment.

The alkenyl phenol is preferably an alkenyl bisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of bisphenols in view of further improving compatibility. Considering the same point of view, alkenyl bisphenols should be diallyl bisphenols with one allyl group bonded to the two phenolic aromatic rings of bisphenols and/or two phenolic aromatic rings in bisphenols. Dipropenyl bisphenol having one propenyl group bonded to each ring.

Examples of diallyl bisphenol include o,o'-diallyl bisphenol A (DABPA (trade name), Daiwa Chemical Industry Co., Ltd.), o,o'-diallyl bisphenol F, o,o'-diallyl bisphenol S, o,o'-diallyl bisphenol terpene. Dipropylene bisphenols include, for example: o, o'-dipropylene bisphenol A (PBA01 (trade name), Qunyei Chemical Industry Co., Ltd.), o, o'-dipropylene bisphenol F, o, o'-dipropenyl bisphenol S, and o,o'-dipropenyl bisphenol terpene.

The average number of phenolic groups per molecule of alkenylphenol is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exerting the effects of the present embodiment. The average number of phenol groups was calculated using the following formula.

[number 1]

In the formula, Ai represents the number of phenolic groups of alkenylphenols with i phenolic groups in the molecule, Xi represents the proportion of alkenylphenols with i phenolic groups in the molecule to the total alkenylphenols, X ₁ +X ₂ +…X _n =1.

･Epoxy modified silicone The epoxy-modified polysiloxane is not particularly limited as long as it is a polysiloxane compound or resin modified with an epoxy group-containing group. The thermosetting compound (B2) or polymer (B2) can improve the release effect of shavings discharge by containing the constituent units derived from epoxy-modified polysiloxane, and can exhibit excellent low thermal expansion and Drug resistance.

The polysiloxane compound or resin is not particularly limited as long as it has a polysiloxane skeleton formed by repeating siloxane bonds. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among them, the polysiloxane skeleton is preferably a linear skeleton from the viewpoint of more effectively and reliably exerting the effect of the present embodiment.

As a group containing an epoxy group, the group represented by following formula (a1) is mentioned, for example.

[chemical 16]

In the formula (a1), R ⁰ each independently represent a single bond, an alkylene group (for example, an alkylene group with 1 to 5 carbons such as methylene, ethylene, and propylidene), an arylylene group, or an arylene group. In an alkyl group, X represents a monovalent group represented by the following formula (a2) or a monovalent group represented by the following formula (a3).

[chemical 17]

[chemical 18]

Epoxy-modified polysiloxane preferably contains epoxy-modified polysiloxane with epoxy equivalent of 140~250g/mol, more preferably epoxy-modified polysiloxane with epoxy equivalent of 145~245g/mol, More preferably, it contains epoxy-modified polysiloxane having an epoxy equivalent of 150 to 240 g/mol. Epoxy-modified polysiloxane, by containing epoxy-modified polysiloxane having an epoxy equivalent within the above-mentioned range, has a more excellent release effect for discharging shavings, and further improves the resin composition. Compatibility with other resins or compounds, low thermal expansion, and balance of chemical resistance.

Epoxy-modified polysiloxane is considered to make the release effect of shavings discharge better, and can further improve the compatibility with other resins or compounds in the resin composition, the balance of low thermal expansion, and chemical resistance From the point of view, it is advisable to contain more than two kinds of epoxy-modified polysiloxane. At this time, two or more epoxy-modified polysiloxanes should have different epoxy equivalents, and epoxy-modified polysiloxanes (low-equivalent epoxy-modified polysiloxanes) with an epoxy equivalent of 50 to 350 g/mol should be used. Silicone) and epoxy-modified polysiloxane (high-equivalent epoxy-modified polysiloxane) with an epoxy equivalent of 400 to 4000 g/mol are more preferable, containing epoxy with an epoxy equivalent of 140 to 250 g/mol Modified polysiloxane and epoxy-modified polysiloxane having an epoxy equivalent of 450 to 3000 g/mol are more preferred.

When the epoxy-modified polysiloxane contains two or more epoxy-modified polysiloxanes, the average epoxy equivalent of the epoxy-modified polysiloxane should be 140~3000g/mol, more preferably 250~2000g/mol. It is more preferably 300~1000g/mol. The average epoxy equivalent was calculated using the following formula.

[number 2]

In the formula, Ei represents the epoxy equivalent of one epoxy-modified polysiloxane among the two or more epoxy-modified polysiloxanes, and Wi represents the above-mentioned epoxy-modified polysiloxane in the epoxy-modified polysiloxane. Oxygen ratio, W ₁ +W ₂ +...W _n =1.

Epoxy-modified polysiloxane is considered to make the release effect of shavings discharge better, and can further improve the compatibility with other resins or compounds in the resin composition, the balance of low thermal expansion and chemical resistance From this point of view, it is preferable to contain epoxy-modified polysiloxane represented by the following formula (2).

[chemical 19]

In formula (2), R ¹ each independently represents a single bond, an alkylene group, an arylylene group, or an aralkylene group, R ² each independently represent an alkyl group or a phenyl group with 1 to 10 carbon atoms, and n represents 0 An integer of ~100.

In formula (2), the alkylene group represented by R ¹ may be linear, branched or cyclic. The carbon number of the alkylene group is preferably 1-12, more preferably 1-4. As an alkylene group, a methylene group, an ethylene group, or a propylene group is mentioned, for example. Among them, R ¹ is preferably a propylene group.

In formula (2), the arylylene group represented by R ¹ may have a substituent. The carbon number of the extended aryl group is preferably 6-40, more preferably 6-20. Examples of the arylylene group include: phenylene, cyclohexylphenylene, hydroxyphenylene, cyanophenylene, nitrophenylene, naphthylene, biphenylene, anthracenyl, pyrenyl, and Extended base and so on. These groups may contain an ether bond, a ketone bond, or an ester bond.

In formula (2), the carbon number of the aralkylene group represented by ^R is preferably 7-30, more preferably 7-13. As an aralkylene group, the group represented by following formula (XI) is mentioned, for example.

[chemical 20]

In formula (X-I), * represents an atomic bond.

In the formula (2), the group represented by ^R1 may also have a substituent, and the substituents may include, for example: a straight-chain alkyl group with 1 to 10 carbons, a branched alkyl group with 3 to 10 carbons, a branched alkyl group with 3 carbons, Cyclic alkyl with ~10 carbons, linear alkoxy with 1 to 10 carbons, branched alkoxy with 3 to 10 carbons, and cyclic alkoxy with 3 to 10 carbons.

In formula (2), R ² each independently represent an alkyl group or phenyl group having 1 to 10 carbon atoms. The above-mentioned alkyl group and phenyl group may have a substituent. The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl. Among them, R ² is preferably methyl or phenyl.

In formula (2), n is an integer of 0-100. The lower limit of n is preferable in terms of improving the release effect of shavings and further improving the compatibility with other resins or compounds in the resin composition, low thermal expansion, and chemical resistance. 1 or more. Likewise, the upper limit of n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

Epoxy-modified polysiloxane is considered to make the release effect of shavings discharge better, and can further improve the compatibility with other resins or compounds in the resin composition, the balance of low thermal expansion, and chemical resistance. From a viewpoint, it is preferable to contain two or more epoxy-modified polysiloxanes represented by the formula (2). At this time, the two or more epoxy-modified polysiloxanes contained should have different n respectively, including epoxy-modified polysiloxanes in which n is 1~2 in formula (2) and n in formula (2) is 5~20 epoxy modified polysiloxane is better.

The average number of epoxy groups per molecule of epoxy-modified polysiloxane is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exerting the effects of this embodiment. The average number of epoxy groups was calculated by the following formula.

[number 3]

In the formula, Bi represents the number of epoxy groups of the epoxy-modified polysiloxane with i epoxy groups in the molecule, and Yi represents the epoxy-modified polysiloxane with i epoxy groups in the molecule. The proportion of the whole modified polysiloxane, Y ₁ +Y ₂ +...Y _n =1.

The low-equivalent epoxy-modified polysiloxane and the high-equivalent epoxy-modified polysiloxane can also use commercially available products, or prepared products prepared by known methods can also be used. Commercial products of low-equivalent epoxy-modified polysiloxane include "X-22-163" (functional group equivalent: 200 g/mol) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Commercial products of high-equivalent epoxy-modified polysiloxane include: "KF-105" (functional group equivalent: 490 g/mol), "X-22-163A" (functional group equivalent) manufactured by Shin-Etsu Chemical Co., Ltd. : 1000g/mol), and "X-22-163B" (functional group equivalent: 1800g/mol), etc.

･Epoxy compound The epoxy compound is an epoxy compound other than epoxy-modified polysiloxane, more specifically, an epoxy compound not having a polysiloxane skeleton. Thermosetting compound (B2) or polymer (B2) can improve the release effect of shavings by containing constituent units derived from epoxy compounds, and can exhibit excellent compatibility, chemical resistance, copper Foil adhesion, and insulation reliability.

The epoxy compound is not particularly limited as long as it is an epoxy compound other than epoxy-modified silicone. Epoxy compound, considering that it can make the release effect of shavings discharge more excellent, and can show further excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability, it is preferable to contain 1 molecule Difunctional epoxy compound with 2 epoxy groups.

The difunctional epoxy compound can enumerate for example: bisphenol type epoxy resin (such as bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol novolak type epoxy resin), phenolic novolak type epoxy resin (such as phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin), phenolic methane type epoxy resin, aralkyl type epoxy resin, biphenyl type epoxy resin containing biphenyl skeleton, naphthalene type epoxy resin containing naphthalene skeleton, anthracene type epoxy resin containing dihydroanthracene skeleton, epoxypropylene Base ester type epoxy resin, polyol type epoxy resin, epoxy resin containing isocyanurate ring, dicyclopentadiene type epoxy resin, fennel type epoxy resin containing fennel skeleton, bisphenol A type Epoxy resins composed of structural units and hydrocarbon structural units; their halogen compounds. These epoxy compounds may be used alone or in combination of two or more.

As an aralkyl type epoxy resin, the compound represented by following formula (b1) is mentioned, for example.

[chem 21]

In formula (b1), Ar ³ each independently represents a benzene ring or a naphthalene ring, Ar ⁴ represents a benzene ring, a naphthalene ring, or a biphenyl ring, R ^3a each independently represent a hydrogen atom or a methyl group, and each ring may have a ring Substituents other than oxypropoxy (such as alkyl or phenyl with 1 to 5 carbons).

As a biphenyl type epoxy resin, the compound (compound b2) represented by following formula (b2) is mentioned, for example.

[chem 22]

In formula (b2), Ra each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.

In formula (b2), the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl.

When the biphenyl type epoxy resin is the compound b2, the biphenyl type epoxy resin may be in the form of a mixture of compounds b2 in which the number of Ra of the alkyl group is different. Specifically, it is preferably a mixture of biphenyl type epoxy resins having a different number of Ra in the alkyl group, a mixture of compound b2 in which the Ra in the alkyl group is 0 and a compound b2 in which the Ra in the alkyl group is 4. good.

As a naphthalene type epoxy resin, the compound represented by following formula (b3) is mentioned, for example.

[chem 23]

In formula (b3), R ^3b each independently represent a hydrogen atom, an alkyl group (such as methyl or ethyl) with 1 to 5 carbons, an aralkyl group, benzyl group, naphthyl group, or a group containing glycidyloxy group Naphthyl, n represents an integer of 0 or more (for example, 0~2).

Commercial products of the compound represented by the above formula (b3) include, for example, "HP-4032" (n=0 in the above formula (b3)) and "HP-4710" (the above formula (b3) Among them, n=0, and R ^3b =naphthylmethyl group containing at least one glycidoxyl group) and the like.

As a dicyclopentadiene epoxy resin, the compound represented by following formula (b4) is mentioned, for example.

[chem 24]

In formula (b4), R ^3c each independently represent a hydrogen atom, or an alkyl group having 1 to 5 carbons (such as methyl or ethyl).

As the dicyclopentadiene type epoxy resin, a commercial item may be used, or a prepared product prepared by a known method may be used. Commercially available dicyclopentadiene type epoxy resins include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H", "EPICRON HP- 7000HH", etc.

As an epoxy resin which consists of a bisphenol A structural unit and a hydrocarbon structural unit, the compound represented by following formula (b5) is mentioned, for example.

[chem 25]

In formula (b5), R ^1x and R ^2x each independently represent a hydrogen atom or a methyl group, R ^3x to R ^6x each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom, and X represents an ethyleneoxyethyl group, Di(ethyleneoxy)ethyl, tri(ethyleneoxy)ethyl, propyleneoxypropyl, di(propyleneoxy)propyl, tri(propyleneoxy)propyl, or alkane with 2~15 carbons groups (such as methylene or ethylenyl).

Among them, the epoxy compound is preferable in view of being able to make the release effect of shavings discharge more excellent, and to exhibit further excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability. It is one or more selected from the group consisting of bisphenol-type epoxy resins, aralkyl-type epoxy resins, biphenyl-type epoxy resins, naphthalene-type epoxy resins, and dicyclopentadiene-type epoxy resins, More preferably, it is a biphenyl type epoxy resin and/or a naphthalene type epoxy resin.

The average number of epoxy groups per molecule of the epoxy compound is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exerting the effects of the present embodiment. The average number of epoxy groups was calculated by the following formula.

[number 4]

In the formula, Ci represents the number of epoxy groups in the epoxy compound with i epoxy groups in the molecule, Zi represents the proportion of the epoxy compound with i epoxy groups in the molecule to the overall epoxy compound, Z ₁ + Z ₂ + . . . Z _n =1.

･Phenolic compounds other than alkenylphenols The thermosetting compound (B2) or the polymer (B2) preferably contains a phenolic compound other than alkenylphenol (hereinafter Also referred to simply as "phenolic compounds").

Examples of phenolic compounds other than alkenylphenol include bisphenol-type phenolic resins (such as bisphenol A-type resins, bisphenol-E-type resins, bisphenol-F-type resins, bisphenol-S-type resins, etc.), phenolic novolak resins (such as Phenol novolak resin, naphthol novolac resin, cresol novolak resin, etc.), glycidyl ester type phenolic resin, naphthalene type phenolic resin, anthracene type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin Resin, cycloaliphatic phenolic resin, polyol type phenolic resin, aralkyl type phenolic resin, phenol modified aromatic hydrocarbon formaldehyde resin, fennel type phenolic resin, etc. These phenolic compounds may be used alone or in combination of two or more.

Among them, the phenolic compound is preferably a bifunctional one having two phenolic hydroxyl groups in one molecule in view of having a better release effect of shavings discharge and exhibiting further excellent compatibility and adhesion to copper foil. Phenolic compounds.

Examples of bifunctional phenolic compounds include bisphenol, biscresol, bisphenols with a fennel skeleton (such as bisphenol with a fennel skeleton, biscresol with a fennel skeleton, etc.), biphenols (such as p,p'-linked phenol, etc.), dihydroxydiphenyl ether (such as 4,4'-dihydroxydiphenyl ether, etc.), dihydroxybenzophenone (such as 4,4'-dihydroxybenzophenone, etc.), dihydroxy Diphenylsulfide (such as 4,4'-dihydroxydiphenylsulfide, etc.), dihydroxyaromatic hydrocarbon (such as hydroquinone, etc.). These bifunctional phenol compounds may be used alone or in combination of two or more. Among them, the bifunctional phenolic compound is preferably selected from the group consisting of bisphenol, bicresol, and fennel skeleton in view of improving the release effect of shavings discharge and exhibiting further excellent copper foil adhesion. At least one of the group consisting of bisphenols preferably includes bisphenols having a terpene skeleton. Considering the same point of view as above, the bisphenols having a fennel skeleton are preferably biscresol fennel.

As phenolic compounds other than alkenylphenol, a commercial item can also be used, and the thing manufactured by a well-known method can also be used. Commercial items of phenolic compounds other than alkenylphenol include "BCF" (bicresol) manufactured by Osaka Gas Chemical Co., Ltd., "bisphenol M" manufactured by Mitsui Chemicals Co., Ltd., and the like.

･Method for producing thermosetting compound (B2) or polymer (B2) The method for producing the thermosetting compound (B2) or the polymer (B2) is not particularly limited. For example, alkenylphenol, epoxy-modified polysiloxane, epoxy compound, and phenolic compound according to needs can be used, which will be described later It is obtained by the step of carrying out the reaction in the presence of a polymerization catalyst. This reaction can also be carried out in the presence of an organic solvent. More specifically, in the above steps, by carrying out the addition reaction of the epoxy group possessed by the epoxy-modified polysiloxane and the epoxy compound and the hydroxyl group possessed by the alkenyl phenol, and the obtained addition reaction product A thermosetting compound (B2) or a polymer (B2) can be obtained by the addition reaction of the hydroxyl group possessed by the epoxy-modified polysiloxane and the epoxy group possessed by the epoxy compound.

In the production of thermosetting compound (B2) or polymer (B2), the compounding amount of alkenyl phenol is considered to make the release effect of shavings discharge more excellent, and to show further excellent compatibility. Based on the total of 100 parts by mass of alkenylphenol, epoxy-modified polysiloxane, epoxy compound, and phenol compound, it is preferably 1-50 parts by mass, more preferably 3-40 parts by mass, and more preferably 5-30 parts by mass. better.

The blending amount of epoxy-modified polysiloxane, compared with alkenylphenol, epoxy The total of modified polysiloxane, epoxy compound, and phenol compound is 100 parts by mass, preferably 5-70 parts by mass, more preferably 10-60 parts by mass, and more preferably 20-55 parts by mass.

The blending amount of the epoxy compound is considered to make the release effect of shavings discharge better, and to show further excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability. Based on the total of 100 parts by mass of alkenylphenol, epoxy-modified polysiloxane, epoxy compound, and phenolic compound, it is preferably 5-50 parts by mass, more preferably 10-30 parts by mass, and more preferably 15-25 parts by mass. better.

The blending amount of phenolic compound is considered to make the release effect of shavings discharge more excellent, and to show further excellent copper foil adhesion. Compared with alkenylphenol, epoxy modified polysiloxane, and epoxy compound , and a total of 100 parts by mass of the phenol compound, preferably 5 to 30 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass.

In addition, when the thermosetting compound (B2) or the polymer (B2) does not contain a phenolic compound, the blending amounts of the above-mentioned alkenylphenol, epoxy-modified polysiloxane, and epoxy compound are expressed relative to alkenylphenol, A compounding amount of 100 parts by mass of epoxy-modified polysiloxane and epoxy compound in total.

As a polymerization catalyst, an imidazole catalyst and a phosphorus catalyst are mentioned, for example. These catalysts may be used alone or in combination of two or more. Among them, an imidazole catalyst is preferable.

Examples of imidazole catalysts include: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2- Phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole (TBZ (trade name), Shikoku Chemical Industry Co., Ltd.), and 2,4,5-triphenyl imidazoles (TPIZ (trade name), Tokyo Chemical Industry Co., Ltd.) and the like. Among them, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole are preferable from the viewpoint of preventing homopolymerization of the epoxy component.

The amount of the polymerization catalyst (preferably an imidazole catalyst) used is, for example, 0.1 to 10 parts by mass relative to 100 parts by mass of the total of alkenylphenol, epoxy-modified polysiloxane, epoxy compound, and phenol compound. From the viewpoint of increasing the weight average molecular weight of the thermosetting compound (B2) or polymer (B2), the amount of the polymerization catalyst used is preferably at least 0.5 parts by mass, more preferably at most 4.0 parts by mass.

As the organic solvent, for example, a polar solvent or a nonpolar solvent can be used. Polar solvents include, for example: ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; celluloid-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, and ethyl acetate. , butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate and other ester solvents; dimethylacetamide, dimethylformamide and other amides wait. As a nonpolar solvent, aromatic hydrocarbons, such as toluene and xylene, etc. are mentioned, for example. These solvents may be used alone or in combination of two or more.

The usage-amount of an organic solvent is not specifically limited, For example, it is 50-150 mass parts with respect to a total of 100 mass parts of alkenylphenol, epoxy-modified polysiloxane, an epoxy compound, and a phenolic compound.

The heating temperature is not particularly limited, and may be, for example, 100 to 170°C. The heating time is not particularly limited, for example, it may be 3 to 8 hours.

After the reaction in this step is completed, the thermosetting compound (B2) or polymer (B2) can also be isolated and purified from the reaction mixture by a conventional method.

＜Thermosetting resin (C)＞ The resin composition of this embodiment contains the thermosetting resin (C) different from the thermosetting compound (B) of this embodiment. The thermosetting compound (B) exhibits excellent compatibility with thermosetting resins lacking in compatibility with polysiloxane compounds. Therefore, even if a thermosetting compound (B) and a thermosetting resin (C) are combined, each component will not isolate|separate in a resin composition, and compatibility is excellent.

The thermosetting resin (C) preferably contains a compound selected from maleimide compounds, cyanate compounds, At least one member selected from the group consisting of phenolic compounds, alkenyl-substituted nadicimide compounds, and epoxy resins, including maleimide compounds, cyanate compounds, phenolic compounds, and epoxy resins At least one of the group consisting of resins is more preferred. These thermosetting resins (C) can be used individually by 1 type or in appropriate combination of 2 or more types.

The content of the thermosetting resin (C) is considered to be more excellent in the release effect of shavings discharge, and to exert excellent heat resistance and chemical resistance. Compared with the thermosetting compound (B) and the thermosetting resin ( The total of 100 parts by mass of C) is preferably 50 to 95 parts by mass, more preferably 55 to 90 parts by mass, and even more preferably 60 to 85 parts by mass.

･Maleimide compound The thermosetting resin (C) preferably contains a maleimide compound from the viewpoint of improving the release effect of shavings and further improving low thermal expansion and chemical resistance. The maleimide compound contained in the thermosetting resin (C) may be the same as or different from the maleimide compound used for producing the thermosetting compound (B). The maleimide compound can be used alone or in appropriate combination of two or more.

The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, and examples thereof include monomaleimide compounds having one maleimide group in one molecule. Amide compounds (such as N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.), polymaleimides having two or more maleimide groups in one molecule Compounds (such as bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(3-ethyl -5-methyl-4-maleiminophenyl)methane, bis(3,5-dimethyl-4-maleiminophenyl)methane, bis(3,5-diethyl Base-4-maleimidophenyl) methane), m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6' -bismaleimide-(2,2,4-trimethyl)hexane, polytetrahydrofuran-bis(4-maleimidobenzoate), maleic acid represented by the following formula (4) Imide compounds, maleimide compounds represented by formula (9), prepolymers of these maleimide compounds and amine compounds, and the like.

[chem 26]

In formula (4), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.

n ₁ is 1 or more, preferably 1-100, more preferably 1-10.

[chem 27]

In formula (9), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10.

The number of maleimide groups in the maleimide compound is preferably two or more in one molecule. These maleimide compounds may be used alone or in combination of two or more. Among them, considering the point of view of further improving thermal expansion and chemical resistance, the maleimide compound preferably contains a compound selected from bis(4-maleimidophenyl)methane, 2,2-bis( 4-(4-maleimidophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, polytetrahydrofuran-bis( 4-maleimidobenzoate), a maleimide compound represented by formula (4), and a maleimide compound represented by formula (9), at least one of the group consisting of, Contains bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(3-ethyl - More preferably at least one of the group consisting of 5-methyl-4-maleimidophenyl)methane and a maleimide compound represented by the following formula (4).

As the maleimide compound, a commercial item may be used, or a preparation prepared by a known method may be used. Commercially available maleimide compounds include: "BMI-70", "BMI-80" and "BMI-1000P" from K･I Chemicals Co., Ltd., "BMI-1000P" from Daiwa Chemical Industry Co., Ltd. BMI-3000", "BMI-4000", "BMI-5100", "BMI-7000", and "BMI-2300", and "MIR-3000-70MT" produced by Nippon Kayaku Co., Ltd., etc.

The content of the maleimide compound is preferably 1 to 50 parts by mass relative to 100 parts by mass of the resin solid content, in consideration of better release effect of shavings discharge, and further improvement of low thermal expansion and chemical resistance. Parts, more preferably 5 to 40 parts by mass, more preferably 10 to 40 parts by mass.

･Cyanate compound The thermosetting resin (C) preferably contains a cyanate compound from the viewpoint of improving the release effect of shavings and further improving low thermal expansion and chemical resistance.

The cyanate compound is not particularly limited as long as it is a compound having two or more cyanooxy groups (cyanate groups) in one molecule, and examples thereof include naphthol aralkyl-type cyanide compounds such as compounds represented by formula (5). Ester compounds, compounds represented by formula (6) other than compounds represented by formula (5), novolak type cyanate compounds, biphenyl aralkyl type cyanate esters, diallyl bisphenol type cyanate esters compound, bis(3,3-dimethyl-4-cyanophenyl)methane, bis(4-cyanophenyl)methane, 1,3-dicyanooxybenzene, 1,4-dicyano Oxybenzene, 1,3,5-tricyanoxybenzene, 1,3-dicyanoxynaphthalene, 1,4-dicyanoxynaphthalene, 1,6-dicyanoxynaphthalene, 1,8- Dicyanoxynaphthalene, 2,6-dicyanoxynaphthalene, 2,7-dicyanoxynaphthalene, 1,3,6-tricyanoxynaphthalene, 4,4'-dicyanoxybiphenyl, Bis(4-cyanoxyphenyl)ether, bis(4-cyanoxyphenyl)sulfide, bis(4-cyanoxyphenyl)sulfide, 2,2-bis(4-cyanoxyphenyl) ) propane. These cyanate compounds may be used alone or in combination of two or more. Among them, the cyanate compound preferably includes a naphthol aralkyl type cyanate compound and/or from the viewpoint of improving the release effect of swarf discharge and further improving low thermal expansion and chemical resistance. or novolak-type cyanate compounds.

Among them, the cyanate compound preferably includes those represented by formula (5) and/or formula (6) from the viewpoint of making the release effect of shavings discharge more excellent, and further improving low thermal expansion and chemical resistance. compound. If the cyanate compound contains the compound represented by the formula (5), the release effect of shavings is further improved, and the low thermal expansion and chemical resistance are further improved. In addition, it has further excellent flame retardancy and low thermal expansion coefficient. , so it is more ideal.

[chem 28]

In formula (5), R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more. n ₂ is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6.

[chem 29]

In formula (6), R _ya each independently represents an alkenyl group having 2 to 8 carbon atoms, or a hydrogen atom, R _yb each independently represents an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, and R _yc each independently represents An aromatic ring with 4~12 carbons, R _yc can also form a condensed structure with a benzene ring, R _yc may or may not exist, A ^1a each independently represent an alkylene group with 1~6 carbons, an alkylene group with 7~16 carbons Aralkylene group, arylylene group with 6~10 carbons, fenylene group, sulfonyl group, oxygen atom, sulfur atom, or single bond (direct bond), when R _yc does not exist, there is also a benzene ring It may have two or more R _ya and/or R _yb groups. n represents an integer from 1 to 20.

In formula (6), the alkenyl group having 2 to 8 carbon atoms represented by R _ya includes, for example, vinyl, allyl, propenyl, butenyl, hexenyl and the like.

In formula (6), the alkyl group of carbon number 1～10 that R _yb represents can enumerate for example: methyl, ethyl, propyl group, butyl, pentyl, hexyl etc. linear alkyl; Butyl, tertiary butyl and other branched alkyl groups.

In formula (6), the alkylene group having 1 to 6 carbon atoms represented by A ^1a includes methylene, ethylene, trimethylene, and propylidene. In addition, in formula (6), the aralkylene group having 7 to 16 carbon atoms represented by A ^1a can be exemplified by the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar-CH ₂ -CH ₂ -, or a group represented by the formula: -CH ₂ -Ar-CH ₂ -CH ₂ - (wherein, Ar represents phenylene, naphthylene, or biphenylene). In addition, the arylylene group having 6 to 10 carbon atoms represented by A ^1a includes, for example, a phenylene ring.

In the formula (6), n represents an integer of 1 to 20, preferably an integer of 1 to 15, more preferably an integer of 1 to 10.

Considering that the demoulding effect of shavings discharge is better, and the low thermal expansion and chemical resistance are further improved, and the viewpoint of having a higher glass transition temperature, the compound represented by formula (6) is preferably phenol novolak type cyanate The compound, the phenol novolak type cyanate compound is more preferably a compound represented by formula (c1).

[chem 30]

In the formula (c1), Rx each independently represent a hydrogen atom or a methyl group, each R independently represents an alkenyl group having 2 to 8 carbons, an alkyl group having 1 to 10 carbons, or a hydrogen atom, and n represents a group of 1 to 10 integer.

These cyanate compounds can also be produced according to known methods. The specific production method can be, for example, the method described in JP-A-2017-195334 (particularly paragraphs 0052-0057).

The content of the cyanate compound in the thermosetting resin (C) is based on 100 parts by mass of the solid content of the resin in consideration of a better release effect for discharging shavings, and further improvement of low thermal expansion and chemical resistance. , preferably 10-70 parts by mass, more preferably 15-60 parts by mass, more preferably 20-50 parts by mass.

･Phenolic compounds It is preferable that the thermosetting resin (C) contains a phenolic compound from the viewpoint of improving the releasing effect of shavings discharge and further improving the adhesion of copper foil. The phenol compound contained in the thermosetting resin (C) and the phenol compound used for producing the thermosetting compound (B) may be the same or different. The phenolic compound can be used individually by 1 type or in appropriate combination of 2 or more types.

The phenolic compound is not particularly limited as long as it is a compound having two or more phenolic hydroxyl groups in one molecule, and examples thereof include phenols having two or more phenolic hydroxyl groups in one molecule, bisphenols (such as bisphenol A , bisphenol E, bisphenol F, bisphenol S, etc.), diallyl bisphenols (such as diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, diene Propyl bisphenol S, etc.), phenolic novolac resins (such as phenol novolac resins, naphthol novolac resins, cresol novolak resins, etc.), naphthalene-type phenolic resins, dihydroanthracene-type phenolic resins, dicyclopentadiene Type phenolic resin, biphenyl type phenolic resin, and aralkyl type phenolic resin. These phenolic compounds may be used alone or in combination of two or more. Among them, the phenolic compound preferably contains an aralkyl type phenolic resin from the viewpoint of further improving the adhesion of copper foil.

(Aralkyl type phenolic resin) As an aralkyl type phenolic resin, the compound represented by formula (c2) is mentioned, for example.

[chem 31]

In formula (c2), Ar ¹ each independently represents a benzene ring or a naphthalene ring, Ar ² represents a benzene ring, a naphthalene ring, or a biphenyl ring, R ^2a each independently represent a hydrogen atom or a methyl group, and m represents 1 to 50 Integer, and each ring may have a substituent other than hydroxyl (such as an alkyl group having 1 to 5 carbon atoms or a phenyl group, etc.).

The compound represented by the formula (c2) considers that the release effect of the shavings discharge is better, and the copper foil adhesion is further improved. In the formula (c2), Ar ¹ is a naphthalene ring, and Ar ² is a benzene ring. The compound (hereinafter also referred to as "naphthol aralkyl type phenolic resin"), and the compound in which Ar ¹ is a benzene ring and Ar ² is a biphenyl ring in formula (c2) (hereinafter also referred to as "biphenylaralkyl resin") base type phenolic resin").

The naphthol aralkyl type phenolic resin is preferably a compound represented by formula (2b).

[chem 32]

In formula (2b), R ^2a each independently represents a hydrogen atom or a methyl group (preferably a hydrogen atom), and m represents an integer of 1 to 10 (preferably an integer of 1 to 6).

The biphenyl aralkyl type phenolic resin is preferably a compound represented by formula (2c).

[chem 33]

In formula (2c), R ^{and 2b} each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbons, or a phenyl group (preferably a hydrogen atom), and m1 represents an integer of 1 to 20 (preferably an integer of 1 to 6).

As the aralkyl type phenolic resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available aralkyl type phenolic resins include: "KAYAHARD GPH-65", "KAYAHARD GPH-78", "KAYAHARD GPH-103" (biphenyl aralkyl type phenolic resins) manufactured by Nippon Kayaku Co., Ltd. ), "SN-495" (naphthol aralkyl type phenolic resin) produced by Nippon Steel Chemical Co., Ltd.

The content of the phenolic compound in the thermosetting resin (C) is preferably 10 per 100 parts by mass of the resin solids, in consideration of a better release effect for discharging shavings and further improving the adhesion of the copper foil. ~40 parts by mass, more preferably 15~35 parts by mass, more preferably 20~30 parts by mass.

･Nadic imide compound substituted by alkenyl group The thermosetting resin (C) preferably contains an alkenyl-substituted nadicimide compound in view of improving the release effect of shavings and further improving heat resistance. The alkenyl-substituted nadicimide compound can be used alone or in appropriate combination of two or more. The alkenyl-substituted nadicimide compound is not particularly limited if it is a compound having one or more alkenyl-substituted nadicimide groups in one molecule, and examples thereof include the following formula (2d): compound.

[chem 34]

In formula (2d), R ₁ each independently represents a hydrogen atom, or an alkyl group (such as methyl or ethyl) with 1 to 6 carbons, and R ₂ represents an alkylene group, phenylene group, or phenylene group with 1 to 6 carbons. A biphenylene group, a naphthylene group, or a group represented by the following formula (7) or the following formula (8).

[chem 35]

In formula (7), R ₃ represents methylene, isopropylidene, CO, O, S or SO ₂ .

[chem 36]

In formula (8), R ₄ each independently represents an alkylene group having 1 to 4 carbon atoms, or a cycloalkylene group having 5 to 8 carbon atoms.

The alkenyl-substituted nadicimide compound represented by formula (2d) may be a commercially available product, or a product produced by a known method may be used. Commercially available products include "BANI-M" and "BANI-X" produced by Maruzen Petrochemical Co., Ltd.

The content of the alkenyl-substituted nadicimide compound as the thermosetting resin (C) is preferably 1 to 45 parts by mass, more preferably 5 to 40 parts by mass, relative to 100 parts by mass of the solid content of the resin, and is 10-35 parts by mass is even better.

･Epoxy resin The thermosetting resin (C) preferably contains an epoxy resin in view of improving the release effect of swarf discharge and further improving chemical resistance, copper foil adhesion, and insulation reliability. The epoxy resin contained in the thermosetting resin (C) may be the same as or different from epoxy compounds other than the epoxy-modified polysiloxane used to produce the thermosetting compound (B). The permanent polysiloxanes are different epoxy compounds. The epoxy resins may be used alone or in combination of two or more.

As an epoxy resin, typically, the bifunctional epoxy compound which has 2 epoxy groups in 1 molecule, and the polyfunctional epoxy compound which has 3 or more epoxy groups in 1 molecule can be used. Epoxy resins should contain bifunctional epoxy compounds and/or multifunctional rings in order to improve the release effect of shavings and further improve chemical resistance, copper foil adhesion, and insulation reliability. Oxygen compounds.

The epoxy resin is not particularly limited, and a compound represented by the following formula (3a) can be used.

[chem 37]

In formula (3a), Ar ³ each independently represents a benzene ring or a naphthalene ring, Ar ⁴ represents a benzene ring, a naphthalene ring, or a biphenyl ring, R ^3a each independently represent a hydrogen atom or a methyl group, and k represents 1 to 50 Integer, here, the benzene ring or naphthalene ring in Ar ³ can also have one or more substituents, and the substituents can also be glycidyloxy groups not shown in the figure, and other substituents can also be, for example, carbon number 1 to 5 alkyl, phenyl, etc., the benzene ring in Ar ⁴ , naphthalene ring, or biphenyl ring can also have one or more substituents, the substituents can also be glycidyloxy, other substitutions The group may be, for example, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or the like.

Among the compounds represented by the above-mentioned formula (3a), examples of the bifunctional epoxy compound include compounds represented by the following formula (b1).

[chem 38]

In formula (b1), Ar ³ each independently represents a benzene ring or a naphthalene ring, Ar ⁴ represents a benzene ring, a naphthalene ring, or a biphenyl ring, R ^3a each independently represent a hydrogen atom or a methyl group, and here, in Ar ³ The benzene ring or naphthalene ring can also have one or more substituents, for example, the substituents can also be substituents other than glycidoxy groups such as alkyl groups with 1 to 5 carbon atoms, phenyl groups, etc., Ar ⁴ The benzene ring, naphthalene ring or biphenyl ring may also have one or more substituents. For example, the substituents may also be substituents other than glycidoxy groups such as alkyl groups with 1 to 5 carbon atoms and phenyl groups. .

The compound represented by formula (3a) is preferably a phenolic novolac epoxy resin in which Ar ⁴ is at least substituted by glycidoxy in formula (3a). Phenolic novolak-type epoxy resins are not particularly limited, and examples thereof include compounds represented by the following formula (3-1) (polyfunctional epoxy resins having a naphthalene skeleton and containing a naphthalene skeleton), naphthalene-cresol novolac-type ring oxygen resin. Considering the excellent mold release effect of shavings discharge, and the further improvement of chemical resistance, copper foil adhesion, and insulation reliability, naphthyl cresol novolak type epoxy resin is suitable.

[chem 39]

In formula (3-1), Ar ³¹ each independently represents a benzene ring or a naphthalene ring, Ar ⁴¹ each independently represent a benzene ring, a naphthalene ring or a biphenyl ring, R ^31a each independently represent a hydrogen atom or a methyl group, and kz represents An integer of 1 to 50, each ring may also have a substituent other than glycidoxy (such as an alkyl group with 1 to 5 carbons, an alkoxy group with 1 to 5 carbons, or a phenyl group), Ar ³¹ and Ar ⁴¹ At least one of them represents a naphthalene ring.

Examples of the compound represented by formula (3-1) include compounds represented by formula (3-2).

[chemical 40]

In the formula (3-2), R represents a methyl group, and kz has the same meaning as kz in the above formula (3-1).

The naphthyl cresol novolak type epoxy resin is not particularly limited, for example, a cresol/naphthol novolak type epoxy resin represented by the following formula (NE) is preferable. In addition, the compound represented by the following formula (NE) is a random copolymer of a constituent unit of a cresol novolak resin epoxy and a constituent unit of a naphthol novolac resin epoxy, and the cresol epoxy and the naphthol ring Any of the oxides may serve as the terminal.

[chem 41]

m and n in the formula (NE) each represent an integer of 1 or more. The upper limit and ratio of m and n are not particularly limited. Considering low thermal expansion, m:n (here, m+n=100) should be 30~50:70~50, 45~55:55~ 45 is better.

As the naphthylcresol novolak-type epoxy resin, a commercially available product may be used, or a product manufactured by a known method may be used. Commercially available products include, for example: "NC-7000", "NC-7300", and "NC-7300L" produced by Nippon Kayaku Co., Ltd., or "HP-9540" and "HP-9500L" produced by DIC Co., Ltd. ", etc., especially "HP-9540".

The compound represented by formula (3a) may be a compound other than the aforementioned phenolic novolac epoxy resin (hereinafter also referred to as "aralkyl epoxy resin"). The aralkyl type epoxy resin is preferably Ar in the formula (3a) ³ is a naphthalene ring, and Ar ⁴ is a compound of a benzene ring (also known as "naphthol aralkyl type epoxy resin"), and the formula (3a) Among them, Ar ³ is a benzene ring, and Ar ⁴ is a compound of a biphenyl ring (also called "biphenyl aralkyl type epoxy resin"), preferably a biphenyl aralkyl type epoxy resin.

As the naphthol aralkyl type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Examples of commercially available products include "HP-5000" and "HP-9900" produced by DIC Co., Ltd., "ESN-375" and "ESN-475" produced by Nippon Steel Chemical Co., Ltd., and the like.

The biphenyl aralkyl type epoxy resin is preferably a compound represented by formula (3b).

[chem 42]

In the formula (3b), ka represents an integer of 1 or more, preferably 1-20, more preferably 1-6.

Among the compounds represented by the above-mentioned formula (3b), examples of the bifunctional epoxy compound include compounds in which ka is 1 in the formula (3b).

As the biphenyl aralkyl type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Examples of commercially available products include "NC-3000", "NC-3000L", and "NC-3000FH" produced by Nippon Kayaku Co., Ltd.

Also, the epoxy resin is preferably a naphthalene-type epoxy resin (excluding compounds represented by the formula (3a)). Naphthalene-type epoxy resins are more suitable for naphthyl ether-type epoxy resins in view of improving the release effect of shavings and further improving chemical resistance, copper foil adhesion, and insulation reliability.

The naphthyl ether-type epoxy resin is considered to have a better release effect of shavings, and to further improve chemical resistance, copper foil adhesion, and insulation reliability. It is preferably represented by formula (3-3) A difunctional epoxy compound or a multifunctional epoxy compound represented by the following formula (3-4), or a mixture thereof.

[chem 43]

In formula (3-3), R ₁₃ each independently represents a hydrogen atom, an alkyl group with 1 to 3 carbons (such as methyl or ethyl), or an alkenyl with 2 to 3 carbons (such as vinyl, allyl, etc.) base or propenyl).

[chem 44]

In formula (3-4), R ₁₄ each independently represents a hydrogen atom, an alkyl group with 1 to 3 carbons (such as methyl or ethyl), or an alkenyl with 2 to 3 carbons (such as vinyl, allyl, etc.) base or propenyl).

As the naphthyl ether type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available naphthyl ether type epoxy resins include, for example, "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311", "EXA-7311L" of DIC Co., Ltd. ", "EXA7311-G3", "EXA7311-G4", "EXA-7311G4S", "EXA-7311G5", etc., are especially good for HP-6000.

Examples of naphthalene-type epoxy resins other than the above are not limited to the following, and compounds represented by the following formula (b3) are exemplified.

[chem 45]

In formula (b3), R ^3b each independently represent a hydrogen atom, an alkyl group (such as methyl or ethyl) with 1 to 5 carbons, an aralkyl group, a benzyl group, a naphthyl group, a glycidyl group containing at least one Naphthyl group, or naphthylmethyl group containing at least one glycidoxy group, n represents an integer of 0 or more (for example, 0~2).

Commercial products of the compound represented by the above formula (b3) include, for example, "HP-4032" (n=0 in the above formula (b3)) and "HP-4710" (the above formula (b3) Among them, n=0, and R ^3b is a naphthylmethyl group containing at least one glycidoxyl group) and the like.

Also, as the epoxy resin, a dicyclopentadiene type epoxy resin can be used.

The dicyclopentadiene epoxy resin is not particularly limited, and examples thereof include compounds represented by formula (3-5).

[chem 46]

In the formula (3-5), R ^3c each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbons, and k2 represents an integer of 0 to 10.

The compound represented by the above formula (3-5) is not particularly limited, and may be, for example, a compound represented by the following formula (b4).

[chem 47]

In formula (b4), R ^3c each independently represent a hydrogen atom, or an alkyl group having 1 to 5 carbons (such as methyl or ethyl).

As the dicyclopentadiene type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available dicyclopentadiene type epoxy resins include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H", "EPICRON HP- 7000HH", etc.

Among them, the epoxy resin should be selected from the viewpoints represented by the formula (3a) in consideration of making the release effect of shavings discharge better, and further improving the chemical resistance, copper foil adhesion, and insulation reliability. At least one type selected from the group consisting of epoxy resins, naphthalene-type epoxy resins, and dicyclopentadiene-type epoxy resins, more preferably including naphthalene-type epoxy resins. At this time, the epoxy resin represented by formula (3a) should contain naphthyl cresol novolak type epoxy resin, and the naphthalene type epoxy resin should contain the cresol/naphthol novolac type epoxy resin represented by the aforementioned formula (NE) .

The epoxy resin may also contain other epoxy resins other than the aforementioned epoxy resins or epoxy compounds. Other epoxy resins are not particularly limited, and examples include: bisphenol-type epoxy resins, paraphenolmethane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, Epoxy resins containing isocyanurate rings, fennel-type epoxy resins, and epoxy resins composed of bisphenol A-type structural units and hydrocarbon-based structural units, etc. Other epoxy resins, among the above, may contain bisphenol-type epoxy resins in consideration of the better release effect of shavings discharge, and further improvement of chemical resistance, copper foil adhesion, and insulation reliability. resin. Bisphenol type epoxy resin can use for example: diallyl bisphenol type epoxy resin (for example diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl Bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.), etc.

The epoxy resin may be used alone or in combination of two or more of the above epoxy resins and epoxy compounds.

The average number of epoxy groups per molecule of the epoxy resin is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less, in view of more effectively and reliably exerting the effect of the present embodiment. The average number of epoxy groups was calculated by the following formula.

[number 5]

In the above formula, Ci represents the number of epoxy groups of the epoxy resin with i epoxy groups in the molecule, Zi represents the proportion of the epoxy resin with i epoxy groups in the molecule to the whole epoxy resin, Z ₁ + Z ₂ + . . . Z _n =1.

As the content of the epoxy resin of the thermosetting resin (C), it is considered that the release effect of shavings discharge is more excellent, and the chemical resistance, copper foil adhesion, and insulation reliability are further improved. The solid content of the resin is 100 parts by mass, preferably 1-60 parts by mass, more preferably 3-50 parts by mass, and even more preferably 5-40 parts by mass.

･Other resins In the thermosetting resin (C), other resins may be further contained as long as the effects in the resin composition of the present embodiment are not inhibited. Other resins include, for example, oxetane resins, benzodiazepine compounds, and compounds having polymerizable unsaturated groups. These resins or compounds can be used individually by 1 type or in appropriate combination of 2 or more types.

･Oxetane resin Oxetane resins include, for example: oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3 ,3-Dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3'-bis(trifluoromethyl) Perfluorooxetane, 2-chloromethyl oxetane, 3,3-bis(chloromethyl) oxetane, biphenyl type oxetane, product of Toa Gosei Co., Ltd. "OXT-101", "OXT-121" and so on.

･Benzo 㗁𠯤 compound The term "benzohexacompound" in this specification refers to a compound having two or more dihydrobenzoxaha rings in one molecule. Examples of the benzo㗁𠯤 compound include "Bisphenol F-type benzo㗁𠯤 BF-BXZ" and "Bisphenol S-type benzo㗁𠯤BS-BXZ" produced by Konishi Chemical Co., Ltd.

･Compounds with polymerizable unsaturated groups Examples of compounds having polymerizable unsaturated groups include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, (meth)acrylic acid-2 -Hydroxyethyl ester, -2-Hydroxypropyl (meth)acrylate, Polypropylene glycol di(meth)acrylate, Trimethylolpropane di(meth)acrylate, Trimethylolpropane tri(methyl) Acrylic ester, neopentylthritol tetra(meth)acrylate, dipentynerythritol hexa(meth)acrylate and other units or (meth)acrylates of polyols; bisphenol A epoxy (methyl) ) acrylate, bisphenol F epoxy (meth)acrylate and other epoxy (meth)acrylates; benzocyclobutene resin, etc.

＜Inorganic filler (D)＞ The resin composition of this embodiment contains the inorganic filler (D) different from the molybdenum compound (A) of this embodiment. When the resin composition contains the inorganic filler (D), it tends to further improve heat resistance and low thermal expansion. Examples of inorganic fillers (D) include silicon dioxide, silicon compounds (such as white carbon, etc.), metal oxides (such as aluminum oxide, titanium dioxide, titanium oxide, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, etc. ), metal nitrides (such as boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, etc.), metal oxysulfides (such as barium sulfate, etc.), metal hydroxides (such as aluminum hydroxide, aluminum hydroxide Heat-treated products (such as heat-treated aluminum hydroxide and subtracted part of the crystal water), boehmite, magnesium hydroxide, etc.), zinc compounds (such as zinc borate, zinc stannate, etc.), clay, kaolin (kaolin ), talc (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 fiber (including E glass, T glass, D glass, S glass, Q glass and other glass powders), hollow glass, spherical glass, etc. These inorganic fillers (D) may be used alone or in combination of two or more. Among them, the inorganic filler (D) preferably contains a material selected from the group consisting of silicon dioxide, aluminum hydroxide, alumina, and boehmite in view of improving the release effect of shavings and further improving the low thermal expansion property. , boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide at least one, preferably including silicon dioxide.

Examples of silica include natural silica, fused silica, synthetic silica, aerosil, and hollow silica. These silicas may be used alone or in combination of two or more. Among them, fused silica is preferable in consideration of the dispersibility of the resin composition.

As silica, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available silica products include: "SFP-130MC" manufactured by Denka Co., Ltd., "SC-2050MB" manufactured by Admatechs Co., Ltd., "SC-1050MLE", "YA010C-MFN", and "YA050C- MJA" and so on.

The content of the inorganic filler (D) is based on 100 parts by mass of the total of the thermosetting compound (B) and the thermosetting resin (C) from the viewpoint of suppressing the wear of the drill and further improving the low thermal expansion property. It is preferably 40 to 600 parts by mass, more preferably 100 to 400 parts by mass.

＜Silane coupling agent＞ The resin composition of this embodiment may further contain a silane coupling agent. When the resin composition contains the silane coupling agent, the dispersibility of the inorganic filler (D) and the adhesive strength between the resin composition and the substrate described below tend to be further improved.

The silane coupling agent is not particularly limited, and silane coupling agents commonly used for surface treatment of inorganic substances are exemplified. Examples include: aminosilane compounds (such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane Compounds (such as γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane-based compounds (such as γ-acryloxypropyltrimethoxysilane, etc.), cationic silane-based compounds (such as N- β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrene silane compounds, phenyl silane compounds, etc. A silane coupling agent can be used individually by 1 type, or in combination of 2 or more types. Among them, the silane coupling agent is preferably an epoxy silane compound. Examples of the epoxysilane compound include "KBM-403", "KBM-303", "KBM-402", and "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.

The content of the silane coupling agent is not particularly limited, and may be 0.1 to 10 parts by mass relative to 100 parts by mass of resin solid content.

＜Wetting and Dispersing Agent＞ The resin composition of this embodiment may further contain a wetting and dispersing agent. When the resin composition contains a wetting and dispersing agent, the dispersibility of the filler tends to be further improved.

As long as the wetting and dispersing agent is a known dispersing agent (dispersion stabilizer) used to disperse the filler, examples include DISPERBYK (registered trademark)-110, 111, 118, 180, and 161 manufactured by BYK Co., Ltd. , BYK (registered trademark)-W996, W9010, W903, etc.

The content of the wetting and dispersing agent is not particularly limited, but is preferably not less than 0.5 parts by mass and not more than 5.0 parts by mass relative to 100 parts by mass of resin solids.

＜Hardening catalyst＞ The resin composition of this embodiment may further contain a curing catalyst. As a hardening catalyst, an imidazole catalyst and a phosphorus catalyst are mentioned, for example. These catalysts may be used alone or in combination of two or more. Among them, an imidazole catalyst is preferable.

As an imidazole catalyst, the said imidazole is mentioned, for example. Among them, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole ( TPIZ (trade name), Tokyo Chemical Industry Co., Ltd.).

The usage-amount of a hardening catalyst (preferably an imidazole catalyst) is 0.1-10 mass parts with respect to 100 mass parts of resin solid content, for example.

<Solvent> The resin composition of this embodiment may further contain a solvent. When the resin composition contains a solvent, the viscosity at the time of preparation of the resin composition is reduced to further improve handleability (workability), or to further improve impregnation property to the base material.

The solvent is not particularly limited as long as it can dissolve some or all of the components in the resin composition. Examples include: ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (such as toluene, xylene, etc.), amides (such as dimethylformamide, etc.), propylene glycol monomethyl ether and its acetate, etc. . These solvents may be used alone or in combination of two or more.

[Manufacturing method of resin composition] The manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mixing the above-mentioned components in a solvent one by one or one by one and stirring them is mentioned. At this time, well-known treatments such as stirring, mixing, and kneading can be used in order to dissolve or disperse each component uniformly.

[use] The resin composition of this embodiment can be ideally used as a cured product, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, or a printed wiring board. Hereinafter, these are demonstrated.

[hardened object] The cured product is obtained by curing the resin composition of this embodiment. The production method of the cured product is not particularly limited, for example, it can be obtained by melting or dissolving the resin composition of this embodiment in a solvent, pouring it into a mold, and curing it under normal conditions using heat, light, etc. . In thermosetting, the curing temperature is preferably in the range of 120 to 300° C. in consideration of efficient curing and prevention of deterioration of the obtained cured product.

[resin sheet] The resin sheet of this embodiment has a support body, and the resin layer arrange|positioned on one side or both sides of a support body, and a resin layer contains the resin composition of this embodiment. The resin sheet may be formed, for example, by applying the resin composition of the present embodiment to one or both sides of a support. The resin sheet can be produced, for example, by directly applying and drying the resin composition (varnish) of the present embodiment on a support such as a metal foil or a film.

As the support, for example, known ones used for various printed wiring board materials can be used, and resin films or metal foils are preferable. Examples of resin films and metal foils include polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, Resin films such as polypropylene (PP) film and polyethylene (PE) film, and metal foils such as aluminum foil, copper foil, and gold foil. Among them, the support is preferably electrolytic copper foil or PET film.

The resin sheet can be obtained, for example, by applying the resin composition of the present embodiment to a support, and then semi-curing (B-staging). The method for producing the resin sheet is preferably a method for usually producing a composite of a B-stage resin and a support. Specifically, for example, a method of applying a resin composition to a support such as copper foil and then heating it in a drier at 100 to 200°C for 1 to 60 minutes is used to semi-cure and produce the resin. The method of the film, etc. The adhesion amount of the resin composition to the support is preferably in the range of 1.0-300 μm in terms of the resin thickness of the resin sheet. The resin sheet can be used as a stacking material for printed wiring boards.

[Prepreg] The prepreg of this embodiment includes: a base material, and the resin composition of this embodiment impregnated or coated on the base material. The method for forming the prepreg can also be a known method. Specifically, after impregnating or coating the substrate with the resin composition of this embodiment, heating and drying it at 100 to 200°C, and Obtained by semi-hardening (B-stage).

The prepreg of the present embodiment also includes the form of a cured product obtained by thermally curing a semi-cured prepreg at a heating temperature of 180 to 230° C. and a heating time of 60 to 180 minutes.

The content of the resin composition in the prepreg relative to the total amount of the prepreg is preferably 30~90% by volume, more preferably 35~85% by volume, and 40~80% in terms of the solid content of the prepreg. Volume % is even better. When the content of the resin composition falls within the above-mentioned range, the formability tends to be further improved. In addition, the solid content of the prepreg here refers to a component obtained by removing the solvent from the prepreg, for example, a filler is included in the solid content of the prepreg. In addition, the content of the resin composition referred to here also includes components of the cured resin composition.

As a base material, the well-known base material used for the material of various printed wiring boards is mentioned, for example. Examples include: glass substrates, inorganic substrates other than glass (for example, inorganic substrates made of inorganic fibers other than glass such as quartz), organic substrates (for example, made of wholly aromatic polyamide, polyester, Organic substrates composed of organic fibers such as phenylbenzobisoxazole and polyimide), etc. These base materials may be used alone or in combination of two or more. Among them, a glass substrate is preferable from the viewpoint of further improving heating dimensional stability.

Examples of fibers constituting the glass substrate include fibers of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among them, the fibers constituting the glass base material are preferably selected from E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass from the viewpoint of further excellent strength and low water absorption. More than one fiber in the group.

Examples of the form of the base material include forms such as woven fabric, non-woven fabric, roving, cut strand mat, and surface-treated felt. The weaving method of the woven fabric is not particularly limited, and known examples include plain weave, diagonal weave, and twill weave, and can be appropriately selected from among these known ones depending on the intended use and performance. In addition, glass woven fabrics subjected to fiber opening treatment or surface-treated with a silane coupling agent or the like can be preferably used. The thickness and mass of the base material are usually about 0.01 to 0.1 mm ideally.

[Metal Foil Clad Laminates] The metal foil-clad laminate of this embodiment includes: a laminate formed of at least one selected from the group consisting of the resin sheet of this embodiment and the prepreg of this embodiment; Metal foil on one or both sides of the body. The laminated body may be formed with one resin sheet or one prepreg, or may be formed with a plurality of resin sheets and/or a plurality of prepregs.

The metal foil (conductor layer) may be any metal foil used for various printed wiring board materials, for example, metal foils such as copper and aluminum, and copper foils include copper foils such as rolled copper foil and electrolytic copper foil. . The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

The forming method and forming conditions of the metal foil-clad laminate are not particularly limited, and methods and conditions generally used for laminates and multilayer boards of printed wiring boards can be used. For example, a multilayer press, multilayer vacuum press, continuous molding machine, high temperature and high pressure (autoclave) molding machine, etc. can be used for forming a laminate (the above-mentioned laminate) or a metal foil-clad laminate. In addition, in the forming of the laminate (the above-mentioned laminate) or the metal foil-clad laminate (lamination forming), the temperature is 100~300°C, the pressure is 2~100kgf/cm ² , and the heating time is 0.05~ The range of 5 hours is normal. In addition, post-hardening can also be performed at a temperature of 150~300°C as required. Especially when using a multi-layer press machine, considering the viewpoint of fully accelerating the hardening of the prepreg, the temperature is 200~250°C, the pressure is 10~40kgf/cm ² , and the heating time is 80~130 minutes. The temperature is 215~235°C, the pressure 25~35kgf/cm ² , preferably heating time 90~120 minutes. In addition, a multilayer board can also be produced by combining a prepreg and a wiring board for an inner layer produced separately and performing lamination molding.

[Printed Wiring Board] The printed wiring board of the present embodiment has an insulating layer, and conductor layers formed on one or both sides of the insulating layer, and the insulating layer contains a cured product of the resin composition of the present embodiment. The insulating layer is preferably formed using the resin sheet and/or prepreg of this embodiment. The printed wiring board can be formed, for example, by etching the metal foil of the metal foil-clad laminate according to the present embodiment into a predetermined wiring pattern and using it as a conductor layer.

A printed wiring board can be manufactured by the following method, for example. First, the metal foil-clad laminate of this embodiment is prepared. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to produce an inner substrate having a conductor layer (inner circuit). Then, by stacking a predetermined number of prepregs and metal foil for outer layer circuits in order on the surface of the conductor layer (inner layer circuit) of the inner layer substrate, and heat and press to form an integral body (lamination molding) to obtain stacks. In addition, the lamination forming method and its forming conditions are the same as the lamination forming method and its forming conditions of the above-mentioned laminated board and metal foil-clad laminated board. Then, the laminated body is provided with through-holes and hole-drilling processing for guide holes, and plating metal is formed on the walls of the holes formed to conduct conduction between the conductor layer (inner layer circuit) and the metal foil for outer layer circuits. film. Then, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to produce an outer layer substrate having a conductor layer (outer layer circuit). A printed wiring board is manufactured in this way.

In addition, when the metal foil-clad laminate is not used, a conductor layer as a circuit may be formed on the above-mentioned insulating layer to produce a printed wiring board. In this case, electroless plating can also be used for the formation of the conductor layer.

The printed wiring board obtained in the above-mentioned production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer is configured to contain a cured product of the resin composition of this embodiment. That is, the prepreg of the present embodiment (the cured product containing the base material and the resin composition of the present embodiment impregnated or coated on the base material), the resin composition of the metal foil-clad laminate of the present embodiment The layer (the layer containing the cured product of the resin composition of the present embodiment) is composed of an insulating layer containing the cured product of the resin composition of the present embodiment. [Example]

Hereinafter, this embodiment is demonstrated more concretely using an Example and a comparative example. This embodiment is not limited by the following examples.

[Measuring method of weight average molecular weight (Mw)] The weight average molecular weight (Mw) of a thermosetting compound is measured by the GPC method as follows. 20 μL of a solution obtained by dissolving 0.5 g of a thermosetting compound in 2 g of tetrahydrofuran (THF) was injected into a high performance liquid chromatograph (Shimadzu Corporation, pump: LC-20AD (trade name)) and analyzed. Shodex (registered trademark) GPC KF-804 (trade name, length 30 cm×inner diameter 8 mm), Shodex (registered trademark) GPC KF-803 (trade name, length 30 cm×inner diameter 8 mm), Shodex ( Registered trademark) GPC KF-802 (trade name, length 30cm×inner diameter 8mm), and Shodex (registered trademark) GPC KF-801 (trade name, length 30cm×inner diameter 8mm), a total of 4 pieces, THF (solvent ), the flow rate was set to 1 mL/min., and the detector used was RID-10A (trade name, differential refractive index detector, Shimadzu Corporation (stock)). The weight average molecular weight (Mw) was calculated|required by the GPC method using standard polystyrene as a standard substance.

[Manufacturing Example 1] Synthesis of ammonium zinc molybdate hydrate ((NH ₄ )Zn ₂ MoO ₉ ･(H ₃ O)) Dissolve 0.015 mol (30.0 g) of ammonium molybdate and 0.105 mol of zinc chloride in 100 g of pure water (14.3g). To this solution, 0.5 g of a 10 mol/L sodium hydroxide aqueous solution was added dropwise while stirring at 20° C. to obtain a precipitate. The resulting precipitate was filtered through a membrane filter and dried at 120° C. for 1 hour to obtain a white powder. The obtained powder was analyzed by an X-ray diffraction apparatus (Rigaku Co., Ltd. MiniFlex600 (trade name)), and it was confirmed that it was zinc ammonium molybdate hydrate ((NH ₄ )Zn ₂ MoO ₉ ·(H ₃ O)). Then, the obtained powder was pulverized using a jet mill mill (Nissin Engineering Co., Ltd., super jet mill SJ-500), and the powder obtained by the pulverization process was measured by a laser diffraction and scattering particle size distribution measuring device. (Microtrac MT3300EXII (trade name)), the average particle diameter (D50 particle diameter) was 2.2 micrometers after measurement.

[Manufacturing example 2] Manufacture of zinc ammonium molybdate hydrate (silicon dioxide-coated zinc ammonium molybdate hydrate) powder whose surface is coated with 15nm silicon dioxide Disperse 33 g of the zinc ammonium molybdate hydrate powder (average particle diameter: 2.2 μm) obtained in Production Example 1 in 100 ml of ethanol, and heat the container with an oil bath to maintain the liquid temperature of the obtained dispersion at 55°C. 6 g of silicon tetraethoxide and 6 g of ammonia water (29% concentration) were added thereto, and it was allowed to react for 2 hours while stirring. Thereafter, drying and heat treatment were performed to adjust the film thickness to 15 nm. Thereafter, it was diluted with ethanol, washed, filtered, and dried at 110° C. for 3 hours using a vacuum dryer. After drying, heat treatment was applied at 650° C. for 30 minutes using a rotary tube furnace, thereby obtaining silica-coated zinc ammonium molybdate hydrate powder (average particle size: 2.5 μm). The obtained silicon dioxide-coated zinc ammonium molybdate hydrate powder has a very good dispersion state.

[Synthesis Example 1] Synthesis of 1-naphthol aralkyl type cyanate compound (SN495V-CN) R in the above formula (2b) ^2a is all α-naphthol aralkyl type phenolic resin ( SN495V, OH group equivalent: 236g/mol, Nippon Steel Chemical Co., Ltd.) 300g (1.28mol in conversion of hydroxyl group (OH group)) and 194.6g (1.92mol) of triethylamine (1.5mol relative to 1mol of hydroxyl group) were dissolved In dichloromethane 1800g, make it solution 1. 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol relative to 1 mol of hydroxyl), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol relative to 1 mol of hydroxyl), and 1205.9 g of water, The solution 1 was injected over 30 minutes while maintaining the liquid temperature at -2~-0.5°C under stirring. After the injection of solution 1 was completed, after stirring at the same temperature for 30 minutes, a solution obtained by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol relative to 1 mol of hydroxyl groups) in 65 g of dichloromethane was injected over 10 minutes (solution 2). After solution 2 was injected, it was stirred at the same temperature for 30 minutes to complete the reaction. Thereafter, the reaction solution was left to stand, and the organic phase and the aqueous phase were separated. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater washed for the fifth time was 5 μS/cm, and it was confirmed that the ionic compounds that could be removed by washing with water were sufficiently removed. Concentrate the washed organic phase under reduced pressure, and finally concentrate and dry at 90°C for 1 hour to obtain the target 1-naphthol aralkyl cyanate compound (SN495V-CN, cyanate group equivalent: 261 g/mol) (orange sticky substance) 331 g. The obtained infrared absorption spectrum of SN495V-CN showed the absorption at 2250 cm ^-1 (cyanate group) and did not show the absorption of hydroxyl group.

[Example 1] (Manufacture of Polymer (B1)) Dissolve 14 parts by mass of a maleimide compound (maleimide group equivalent: 285 g/mol, BMI-80 (trade name), K･I Chemical Co., Ltd.) under the condition of heating and refluxing at 130°C In a solution of 40 parts by mass of propylene glycol monomethyl ether (KH Neochem (stock)), diamine-modified polysiloxane (amine group equivalent 1500g/mol, X-22-161B (trade name), Shin-Etsu Chemical Co., Ltd. (share)) 10 parts by mass were dissolved and reacted to obtain a primary polymer. Then, keep stirring under the condition of heating and reflux temperature of 130°C, and when the viscosity of the solution containing the primary polymer increases to 200~300mPa･s in an ICI viscometer (cone and plate type viscometer, manufactured by Towa Kogyo Co., Ltd.), A solution obtained by dissolving 1.0 parts by mass of succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 22.5 parts by mass of propylene glycol monoethyl ether acetate (manufactured by Dow Chemical Co., Ltd.) was added to the solution, and the temperature was maintained at 130° C. , and allowed to react for several hours to obtain a solution of a polymer (B1) containing a thermosetting compound (B).

It was confirmed that the obtained polymer (B1) contained a maleimide group and a polysiloxane structure in the molecule. Also, it was confirmed that the polymer (B1) contained a structural unit derived from an amino-modified polysiloxane and a structural unit derived from a maleimide compound. Moreover, when the total amount of the primary amine and the secondary amine in a polymer (B1) was measured based on JISK7237:1995, the amine value of a polymer (B1) was 0.1 mgKOH/g. In addition, the weight average molecular weight (Mw) of the polymer (B1) was 12,000 in terms of polystyrene in the GPC method as a result of measurement by the aforementioned method.

(manufacturing of prepreg) 25 parts by mass (in terms of solid content) of the obtained polymer (B1), a maleimide compound (maleimide group equivalent 186 g/mol, BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd.) 35 parts by mass, biphenyl aralkyl type epoxy resin (NC-3000H (trade name), Nippon Kayaku (stock)) 8 parts by mass, alkenyl substituted nadicimide compound (alkenyl equivalent 286g/ mol, BANI-M (trade name), 32 parts by mass of Maruzen Petrochemical Co., Ltd., 3 parts by mass of the powder of the silica-coated zinc ammonium molybdate hydrate obtained in Manufacturing Example 2, slurry silica ( SC-2050MB (trade name), Admatechs (stock)) 200 parts by mass, epoxy silane coupling agent (KBM-403 (trade name), Toray Dow Corning (stock)) 5 parts by mass, wetting dispersant (DISPERBYK- 161 (trade name), 1 part by mass of BYK (stock)), 1 part by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and methyl ethyl ketone as a solvent were mixed to obtain a varnish (resin composition ). This varnish was dip-coated on S glass woven fabric (thickness 100 μm), and heated and dried at 150° C. for 3 minutes to obtain a prepreg having a solid content (including filler) of the resin composition of 46% by mass.

(Manufacture of Metal Foil-Clad Laminate) Four obtained prepregs were laminated to obtain a laminate. Electrodeposited copper foil (3EC-III, manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 μm is placed on both sides of the laminate, and vacuum pressing is performed at a pressure of 30 kgf/cm ² at 220° C. for 120 minutes to form a laminate. , thereby producing a metal foil-clad laminate (double-sided copper-clad laminate) with an insulating layer thickness of 0.8 mm.

[Example 2] Replace 3 parts by mass of the powder of the silicon dioxide coating zinc ammonium molybdate hydrate obtained in Production Example 2 with 3 parts by mass of the powder of zinc ammonium molybdate hydrate obtained in Production Example 1, in addition, and It carried out similarly to Example 1, and obtained the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness of an insulating layer was 0.8 mm.

[Example 3] (Manufacture of Polymer (B2)) In a three-necked flask equipped with a thermometer and a Dimroth condenser, 5.3 parts by mass of diallyl bisphenol A (DABPA (trade name), Daiwa Chemical Industry (stock)) and biscresol (BCF ( Trade name), Osaka Gas Chemical Co., Ltd.) 5.8 parts by mass, epoxy-modified polysiloxane b1 (X-22-163 (trade name), Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g/mol) 4.4 parts by mass Parts, epoxy-modified polysiloxane b2 (KF-105 (trade name), Shin-Etsu Chemical Co., Ltd., functional group equivalent 490g/mol) 8.7 parts by mass, biphenyl type epoxy compound c1 (YL-6121H (commodity Name), Mitsubishi Chemical Co., Ltd.) 5.8 parts by mass, 30 parts by mass of propylene glycol monomethyl ether acetate (DOWANOL PMA (trade name), Dow Chemical Japan Co., Ltd.) as a solvent, and heated and stirred in an oil bath to 120°C. After confirming that these raw materials were dissolved in the solvent, 0.3 parts by mass of an imidazole catalyst (TBZ (trade name), Shikoku Chemical Industry Co., Ltd.) was added, the temperature was raised to 140° C., and the mixture was stirred for 5 hours. After cooling, the solution (50 mass % of solid content) of the polymer (B2) containing a thermosetting compound (B) was obtained. In addition, it is used in the preparation of polymer (B2).

In addition, diallyl bisphenol A is equivalent to "alkenyl phenol", epoxy-modified polysiloxane b1 and epoxy-modified polysiloxane b2 are equivalent to "epoxy-modified polysiloxane", and biphenyl ring Oxygen compound c1 corresponds to "epoxy compound".

It was confirmed that the obtained polymer (B2) contained an epoxy group, a hydroxyl group, and a polysiloxane structure in a molecule|numerator. Also, it was confirmed that the polymer (B2) contained a structural unit derived from alkenylphenol, a structural unit derived from epoxy-modified polysiloxane, a structural unit derived from an epoxy compound, and a structural unit derived from a phenol compound. Moreover, content of the structural unit originating in an epoxy-modified polysiloxane with respect to polymer (B2) was 43.5 mass %. Moreover, the content of the structural unit derived from an epoxy compound with respect to the total mass (100 mass %) of the structural unit derived from an epoxy-modified polysiloxane and the structural unit derived from an epoxy compound was 30.8 mass %. In addition, the alkenyl equivalent in the polymer (B2) was 872 g/mol. The weight average molecular weight (Mw) of the polymer (B2) was 11,900 in terms of polystyrene in the GPC method.

(manufacturing of prepreg) In 30 parts by mass (in terms of solid content) of a solution containing the obtained polymer (B2), 26 parts by mass of the 1-naphthol aralkyl type cyanate compound obtained in Synthesis Example 1, 26 parts by mass of the novolak type maleimide Amine compound (BMI-2300 (trade name), Daiwa Kasei Kogyo Co., Ltd.) 17 parts by mass, naphthyl cresol novolak type epoxy resin (epoxy group (functional group) equivalent: 244 g/eq, HP-9540 (commercial product) name), DIC (stock)) 27 parts by mass, 3 parts by mass of the powder of the silicon dioxide-coated zinc ammonium molybdate hydrate obtained in Production Example 2, slurry silicon dioxide (SC-2050MB (trade name), Admatechs (stock)) 200 parts by mass, epoxy silane coupling agent (KBM-403 (trade name), Toray Dow Corning (stock)) 5 parts by mass, wetting and dispersing agent (DISPERBYK-161 (trade name), BYK (stock) )) 1 part by mass, 0.5 parts by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and methyl ethyl ketone as a solvent to obtain a varnish (resin composition). This varnish was dip-coated on S glass woven fabric (thickness 100 μm), and heated and dried at 150° C. for 3 minutes to obtain a prepreg having a solid content (including filler) of the resin composition of 46% by mass.

(Manufacture of Metal Foil-Clad Laminate) Four obtained prepregs were laminated to obtain a laminate. Electrodeposited copper foil (3EC-III (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 μm was arranged on both sides of the laminate, and vacuum pressing was carried out at a pressure of 30 kgf/cm ² at 220° C. for 120 minutes. Lamination was formed, whereby a metal foil-clad laminate (double-sided copper-clad laminate) having an insulating layer thickness of 0.8 mm was produced.

[Comparative example 1] (manufacturing of prepreg) 21.2 parts by mass of bismaleimide compound (BMI-70 (trade name), K･I Chemicals (stock)), 16.8 parts by mass of naphthalene-type phenolic resin (HPC-9500-60M (trade name), DIC (stock)) Parts by mass, biphenyl aralkyl type phenolic resin (GPH-103 (trade name), Nippon Kayaku (stock)) 16.8 parts by mass, biphenyl aralkyl type epoxy resin (NC-3000H (trade name), Japan Kayaku Co., Ltd.) 42.2 parts by mass, 5 parts by mass of talc powder (average particle diameter 3 μm, KEMGARD911C, manufactured by Sherwin-Williams) after coating the surface with zinc molybdate, zinc ammonium molybdate hydrate obtained in Production Example 1 3 parts by mass of powder, 120 parts by mass of silicon dioxide slurry (SC-2050MB (trade name), Admatechs (stock)), epoxy silane coupling agent (KBM-403 (trade name), Toray Dow Corning ( stock)) 5 parts by mass, wetting and dispersing agent (DISPERBYK-161 (trade name), BYK (stock)) 1 part by mass, 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.5 parts by mass, and Methyl ethyl ketone as a solvent was mixed to obtain a varnish (resin composition). This varnish was dip-coated on S glass woven fabric (thickness 100 μm), and heated and dried at 150° C. for 3 minutes to obtain a prepreg having a solid content (including filler) of the resin composition of 46% by mass.

(Manufacture of Metal Foil-Clad Laminate) Four obtained prepregs were laminated to obtain a laminate. Electrodeposited copper foil (3EC-III (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 μm was arranged on both sides of the laminate, and vacuum pressing was carried out at a pressure of 30 kgf/cm ² at 220° C. for 120 minutes. Lamination was formed, whereby a metal foil-clad laminate (double-sided copper-clad laminate) having an insulating layer thickness of 0.8 mm was produced.

[Comparative example 2] (manufacturing of prepreg) 37 parts by mass of 1-naphthol aralkyl type cyanate compound obtained in Synthesis Example 1, 24 parts by mass of novolac type maleimide compound (BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd.) , Naphthalene cresol novolac type epoxy resin (epoxy group (functional group) equivalent: 244g/eq, HP-9540 (trade name), DIC (stock)) 39 parts by mass, silica coating obtained in Production Example 2 3 parts by mass of powder of zinc ammonium molybdate hydrate, 200 parts by mass of silicon dioxide slurry (SC-2050MB (trade name), Admatechs (stock)), polysiloxane composite powder (KMP-605 (trade name) , Shin-Etsu Chemical Co., Ltd.) 15 parts by mass, epoxy silane coupling agent (KBM-403 (trade name), Toray Dow Corning Co., Ltd.) 5 parts by mass, wetting and dispersing agent (DISPERBYK-161 (trade name) , BYK (stock)) 1 part by mass, 0.5 part by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and methyl ethyl ketone as a solvent were mixed to obtain a varnish (resin composition). This varnish was dip-coated on S glass woven fabric (thickness 100 μm), and heated and dried at 150° C. for 3 minutes to obtain a prepreg having a solid content (including filler) of the resin composition of 46% by mass.

(Manufacture of Metal Foil-Clad Laminate) Four obtained prepregs were laminated to obtain a laminate. Electrodeposited copper foil (3EC-III (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 μm was arranged on both sides of the laminate, and vacuum pressing was carried out at a pressure of 30 kgf/cm ² at 220° C. for 120 minutes. Lamination was formed, whereby a metal foil-clad laminate (double-sided copper-clad laminate) having an insulating layer thickness of 0.8 mm was produced.

[Comparative example 3] Instead of using the powder of silica-coated zinc ammonium molybdate hydrate obtained in Manufacturing Example 2, 15 parts by mass of polysiloxane composite powder (KMP-605 (trade name), Shin-Etsu Chemical Co., Ltd.) was replaced with Except having blended 25 mass parts, it carried out similarly to the comparative example 2, and obtained the prepreg. Using the obtained prepreg, it carried out similarly to the comparative example 2, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness of an insulating layer was 0.8 mm.

[Comparative example 4] A prepreg was obtained in the same manner as in Example 1 except that the silica-coated zinc ammonium molybdate hydrate powder obtained in Production Example 2 was not used. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness of an insulating layer was 0.8 mm.

[evaluate] Drillability was evaluated by the following method using the metal foil-clad laminates obtained in Examples and Comparative Examples. The results are shown in Table 1.

(drillability) Drillability (hole position accuracy) was evaluated using the metal foil-clad laminates obtained in Examples and Comparative Examples. The evaluation was carried out under the following drilling conditions. The results are shown in Table 1. Drilling entry sheet (entry sheet, Mitsubishi Gas Chemical Co., Ltd. LE R12F3 (trade name)), 3 sheets of metal foil-clad laminate (substrate thickness & stacking: 0.8mm×3), and drilling backing sheet (Backup board, SPB-W (trade name) manufactured by NIHON DECOLUXE Co., Ltd.) were stacked in order, and drilling was performed using a processing machine (ND-1 V212 (trade name) manufactured by Hitachi Via Mechanics Co., Ltd.) under the following conditions, Measure the misalignment of drilled holes. The amount of misalignment is defined as the amount of misalignment inside the lowermost metal foil-clad laminate among metal foil-clad laminates processed by stacking three sheets. In addition, the amount of misalignment was measured for all holes processed by one drill, and the measurement results in Table 1 represent the average value of the amount of misalignment + 3σ (σ represents the standard deviation value).

(Processing conditions) Drill: MC L692BWU (trade name) manufactured by UNION TOOL Co., Ltd. 0.15mm×2.7mm Drill diameter: 0.15mm Speed: 160krpm Feed speed: 1.6m/min Pulling speed: 25.4m/min Push amount: 0.3mm Processing holes: 5000(hit) or 10000(hit)

[Table 1] Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Hole position accuracy -5000hit AVE+3σ all 23.5 24.1 32.4 42.2 45.7 112.1 40.8 Hole position accuracy -10000hit AVE+3σ all 31.7 31.2 33.8 damaged damaged damaged damaged

This application is based on the Japanese patent application (Japanese Patent Application No. 2021-128685) filed on August 5, 2021, and the contents thereof are incorporated herein by reference. [industrial availability]

According to the present invention, it is possible to provide a resin composition ideally used for manufacturing a resin sheet and a prepreg excellent in drilling processability, a resin sheet, a prepreg, and a metal foil-clad laminate obtained by using the resin composition , and printed wiring boards.

Claims (27)

A resin composition comprising: Molybdenum compound (A), The thermosetting compound (B) contains at least one group selected from the group consisting of maleimide group, amine group, epoxy group, carboxyl group, vinyl group, hydroxyl group, and (meth)acrylic group, and polysiloxane structures, a thermosetting resin (C) different from the thermosetting compound (B), and An inorganic filler (D) different from the molybdenum compound (A). The resin composition as in claim 1, wherein the molybdenum compound (A) comprises molybdenum acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide , molybdic acid hydrate, and at least one of the group consisting of zinc ammonium molybdate hydrate. The resin composition according to claim 1 or 2, wherein the thermosetting compound (B) contains the maleimide group. The resin composition according to claim 1 or 2, wherein the thermosetting compound (B) contains at least a structural unit derived from an amino-modified polysiloxane and a structural unit derived from a maleimide compound. The resin composition according to claim 1 or 2, wherein the thermosetting compound (B) is obtained by polymerizing at least amino-modified polysiloxane, maleimide compound, carboxylic acid and/or carboxylic anhydride of polymers. The resin composition according to claim 4, wherein the amino-modified polysiloxane comprises the amino-modified polysiloxane represented by the following formula (1);

In formula (1), R _a each independently represents a hydrogen atom, an alkyl group, or a phenyl group, each R _b independently represents a single bond, an alkylene group, or an arylylene group, and n represents an integer of 1 to 100. The resin composition as in claim 1, wherein the molybdenum compound (A) comprises molybdenum acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide , molybdic acid hydrate, and at least one of the group consisting of zinc ammonium molybdate hydrate, the thermosetting compound (B) contains the maleimide group, and the thermosetting compound (B) is at least more Contains structural units derived from amine-modified polysiloxane and structural units derived from maleimide compounds, and the amine-modified polysiloxane includes amine-modified polysiloxane represented by the following formula (1);

In formula (1), R _a each independently represents a hydrogen atom, an alkyl group, or a phenyl group, each R _b independently represents a single bond, an alkylene group, or an arylylene group, and n represents an integer of 1 to 100. The resin composition according to claim 1 or 2, wherein the thermosetting compound (B) contains the epoxy group and/or the hydroxyl group. The resin composition according to claim 1 or 2, wherein the thermosetting compound (B) contains at least a constituent unit derived from alkenylphenol, a constituent unit derived from epoxy-modified polysiloxane, and a constituent unit derived from the epoxy-modified Constituent units of epoxy compounds other than polysiloxane. The resin composition according to claim 1 or 2, wherein the thermosetting compound (B) is at least alkenylphenol, epoxy-modified polysiloxane, and an epoxy compound other than the epoxy-modified polysiloxane A polymer obtained by polymerization. The resin composition according to claim 8, wherein the epoxy-modified polysiloxane comprises epoxy-modified polysiloxane represented by the following formula (2);

(2) In the formula (2), R ¹ each independently represent a single bond, an alkylene group, an arylylene group, or an aralkylene group, and R ² each independently represent an alkyl group or a phenyl group with 1 to 10 carbon atoms, n represents an integer from 0 to 100. The resin composition as in claim 1, wherein the molybdenum compound (A) comprises molybdenum acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide , molybdic acid hydrate, and zinc ammonium molybdate hydrate, the thermosetting compound (B) contains the epoxy group and/or the hydroxyl group, the thermosetting compound (B) It further contains at least a constituent unit derived from alkenylphenol, a constituent unit derived from epoxy-modified polysiloxane, and a constituent unit derived from an epoxy compound other than the epoxy-modified polysiloxane, and the epoxy-modified polysiloxane Oxygen contains epoxy-modified polysiloxane represented by the following formula (2);

(2) In the formula (2), R ¹ each independently represent a single bond, an alkylene group, an arylylene group, or an aralkylene group, and R ² each independently represent an alkyl group or a phenyl group with 1 to 10 carbon atoms, n represents an integer from 0 to 100. The resin composition as claimed in item 1 or 2, wherein, the thermosetting resin (C) comprises a maleimide compound, a cyanate compound, a phenolic compound, an alkenyl-substituted nadicamide ( nadiimide) compound, and at least one of the group consisting of epoxy resin. The resin composition according to claim 13, wherein the thermosetting resin (C) contains a maleimide compound. The resin composition as claimed in claim 14, wherein the maleimide compound comprises bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimide Iminophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, polytetrahydrofuran-bis(4-maleimido Benzoate), and at least one of the group consisting of maleimide compounds represented by the following formula (4);

In formula (4), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more. The resin composition as claimed in item 14, wherein the maleimide compound comprises a maleimide compound represented by the following formula (9);

In formula (9), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10. The resin composition according to claim 1 or 2, wherein the inorganic filler (D) comprises silicon dioxide, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, oxide At least one selected from the group consisting of titanium, barium titanate, magnesium oxide, and magnesium hydroxide. The resin composition according to claim 1 or 2, wherein the content of the molybdenum compound (A) is 0.1 to 100 parts by mass relative to the total of the thermosetting compound (B) and the thermosetting resin (C). 30 parts by mass. The resin composition according to claim 1 or 2, wherein the content of the thermosetting compound (B) relative to the total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C) is: 5~50 parts by mass. The resin composition according to claim 1 or 2, wherein the content of the thermosetting resin (C) relative to the total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C) is: 50~95 parts by mass. The resin composition according to claim 1 or 2, wherein the content of the inorganic filler (D) is 40 parts by mass relative to the total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). ~600 parts by mass. The resin composition according to claim 7, wherein the thermosetting resin (C) comprises a maleimide compound, a cyanate compound, a phenol compound, an alkenyl-substituted nadicamide compound, and At least one of the group consisting of epoxy resins, the thermosetting resin (C) contains a maleimide compound, and the maleimide compound contains a compound selected from bis(4-maleimidobenzene base) methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimido Phenyl)methane, polytetrahydrofuran-bis(4-maleimidobenzoate), a maleimide compound represented by the following formula (4), and a maleimide compound represented by the following formula (9) At least one of the group consisting of amine compounds, the inorganic filler (D) containing silicon dioxide, aluminum hydroxide, alumina, boehmite (boehmite), boron nitride, aluminum nitride, titanium oxide , barium titanate, magnesium oxide, and magnesium hydroxide, the content of the molybdenum compound (A) relative to the thermosetting compound (B) and the thermosetting resin (C) The total of 100 parts by mass is 0.1 to 30 parts by mass, and the content of the thermosetting compound (B) relative to the total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C) is: 5 to 50 parts by mass, the content of the thermosetting resin (C) is 50 to 95 parts by mass relative to the total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C), and The content of the inorganic filler (D) is 40 to 600 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (B) and the thermosetting resin (C);

In formula (4), R ₅ each independently represent a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more;

In formula (9), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10. The resin composition according to claim 12, wherein the thermosetting resin (C) comprises a maleimide compound, a cyanate compound, a phenol compound, an alkenyl-substituted nadicamide compound, and At least one of the group consisting of epoxy resins, the thermosetting resin (C) contains a maleimide compound, and the maleimide compound contains a compound selected from bis(4-maleimidobenzene base) methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimido Phenyl)methane, polytetrahydrofuran-bis(4-maleimidobenzoate), a maleimide compound represented by the following formula (4), and a maleimide compound represented by the following formula (9) At least one of the group consisting of amine compounds, the inorganic filler (D) containing silicon dioxide, aluminum hydroxide, alumina, boehmite (boehmite), boron nitride, aluminum nitride, titanium oxide , barium titanate, magnesium oxide, and magnesium hydroxide, the content of the molybdenum compound (A) relative to the thermosetting compound (B) and the thermosetting resin (C) The total of 100 parts by mass is 0.1 to 30 parts by mass, and the content of the thermosetting compound (B) relative to the total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C) is: 5 to 50 parts by mass, the content of the thermosetting resin (C) is 50 to 95 parts by mass relative to the total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C), and The content of the inorganic filler (D) is 40 to 600 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (B) and the thermosetting resin (C);

In formula (4), R ₅ each independently represent a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more;

In formula (9), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10. A resin sheet having: support, and A resin layer disposed on one or both sides of the support; The resin layer contains the resin composition according to any one of claims 1 to 23. A prepreg comprising: base material, and The resin composition according to any one of claims 1 to 23 impregnated or coated on the substrate. A metal foil-clad laminate comprising: A laminate formed of at least one kind selected from the group consisting of the resin sheet according to claim 24 and the prepreg according to claim 25, and Metal foil arranged on one or both sides of the laminate. A printed wiring board having: insulation, and A conductor layer formed on one or both sides of the insulating layer; The insulating layer contains a cured product of the resin composition according to any one of claims 1 to 23.