KR20240040058A - Resin composition, resin sheet, prepreg, metal foil-clad laminate and printed wiring board - Google Patents

Abstract

The present invention aims to provide a resin composition suitably used in the production of resin sheets and prepregs with excellent drillability, and resin sheets, prepregs, metal foil-clad laminates, and printed wiring boards obtained by using the resin composition. do.
The resin composition of the present invention includes a molybdenum compound (A), at least one group selected from the group consisting of a maleimide group, an amino group, an epoxy group, a carboxyl group, a vinyl group, a hydroxy group, and a (meth)acrylic group, and a polysiloxane structure. A thermosetting compound (B) containing a thermosetting resin (C) different from the thermosetting compound (B), and an inorganic filler (D) different from the molybdenum compound (A).

Description

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

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

Recently, high integration, high functionality, and high-density packaging of semiconductor packages widely used in electronic devices, communication devices, and personal computers are accelerating. In line with this, the characteristics required for printed wiring boards for semiconductor packages are becoming increasingly stringent. Such characteristics include thermal expansion coefficient, drillability, heat resistance, and flame retardancy. Among these, the demand for excellent drillability is increasing in order to realize higher density packaging.

In this regard, Patent Document 1 describes a resin composition for printed wiring boards containing a molybdenum compound. Additionally, it is described that this resin composition may contain silicone powder.

WO2013/047203

However, the cured product obtained using the resin composition described in Patent Document 1 is hard and has poor dischargeability of cutting chips (cutting powder) generated during drilling, so the hole position accuracy during drilling is low. There are problems that deteriorate drill workability, such as deterioration, accelerated wear of the drill bit, increasing the frequency of drill bit replacement, and increased risk of drill bit breakage. In addition, there is a problem that the inner diameter of the machined hole becomes non-uniform due to wear of the drill bit, and further, interlayer peeling occurs due to the unevenness of the inner diameter.

The present invention was made to solve the above-mentioned problems, and provides a resin composition suitably used in the production of resin sheets and prepregs with excellent drillability, and resin sheets, prepregs, and metal foil-clad laminates obtained by using the resin composition. and a printed wiring board.

That is, the present invention is as follows.

[1] A thermosetting compound comprising a molybdenum compound (A), at least one group selected from the group consisting of a maleimide group, an amino group, an epoxy group, a carboxyl group, a vinyl group, a hydroxy group, and a (meth)acrylic group, and a polysiloxane structure. A resin composition comprising a compound (B), a thermosetting resin (C) different from the thermosetting compound (B), and an inorganic filler (D) different from the molybdenum compound (A).

[2] The molybdenum compound (A) is molybdate, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate hydrate. The resin composition according to [1], comprising at least one member selected from the group consisting of.

[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 silicone and a structural unit derived from a maleimide compound.

[5] Any one of [1] to [4], wherein the thermosetting compound (B) is a polymer obtained by polymerizing at least an amino-modified silicone, a maleimide compound, and carboxylic acid and/or carboxylic acid anhydride. The resin composition described.

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

[Formula 1]

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

[7] The molybdenum compound (A) is molybdate, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate hydrate. It contains at least one member selected from the group consisting of, wherein the thermosetting compound (B) contains the maleimide group, and the thermosetting compound (B) contains at least a structural unit derived from amino-modified silicone and a maleimide compound. The resin composition according to [1], further comprising a structural unit, wherein the amino-modified silicone contains an amino-modified silicone represented by the following formula (1).

[Formula 2]

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

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

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

[10] The thermosetting compound (B) is a polymer obtained by polymerizing at least an alkenylphenol, an epoxy-modified silicone, and an epoxy compound other than the epoxy-modified silicone, [1], [2], [8], and [ 9] The resin composition according to any one of the above.

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

[Formula 3]

(In formula (2), R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n represents an integer from 0 to 100.)

[12] The molybdenum compound (A) is molybdate, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate hydrate. The thermosetting compound (B) contains at least one member selected from the group consisting of, the thermosetting compound (B) contains the epoxy group and/or the hydroxy group, and the thermosetting compound (B) contains at least a structural unit derived from alkenylphenol and [ 1] The resin composition described in .

[Formula 4]

(In formula (2), R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n represents an integer from 0 to 100.)

[13] The thermosetting resin (C) contains at least one member selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, alkenyl substituted nadimide compounds, and epoxy resins, [1] - The resin composition according to any one of [12].

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

[15] The maleimide compounds include bis(4-maleimidephenyl)methane, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, and bis(3-ethyl-5-methyl- In [14], comprising at least one member selected from the group consisting of 4-maleimide phenyl) methane, polytetramethylene oxide-bis (4-maleimide benzoate), and maleimide compounds represented by the following formula (4) The resin composition described.

[Formula 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 contains a maleimide compound represented by the following formula (9).

[Formula 6]

(In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer from 1 to 10.)

[17] The inorganic filler (D) includes at least one member selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide. The resin composition according to any one of [1] to [16].

[18] Any one of [1] to [17], wherein the content of the molybdenum compound (A) is 0.1 to 30 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). The resin composition described.

[19] Any one of [1] to [18], wherein the content of the thermosetting compound (B) is 5 to 50 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). The resin composition described.

[20] Any one of [1] to [19], wherein the content of the thermosetting resin (C) is 50 to 95 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). The resin composition described.

[21] Any one of [1] to [20], wherein the content of the inorganic filler (D) is 40 to 600 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). The resin composition described.

[22] The thermosetting resin (C) contains at least one member selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound, an alkenyl substituted nadimide compound, and an epoxy resin, and the thermosetting resin ( C) includes a maleimide compound, and the maleimide compound is bis(4-maleimidephenyl)methane, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, bis(3) -Ethyl-5-methyl-4-maleimide phenyl)methane, polytetramethylene oxide-bis(4-maleimide benzoate), maleimide compound represented by the following formula (4), and maleimide represented by the following formula (9) It contains at least one member selected from the group consisting of mead compounds, wherein the inorganic filler (D) is silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and hydroxide. It contains at least one member selected from the group consisting of magnesium, and the content of the molybdenum compound (A) is 0.1 to 30 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). , the content of the thermosetting compound (B) is 5 to 50 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C), and the content of the thermosetting resin (C) is The content of the inorganic filler (D) is 50 to 95 parts by mass based on a total of 100 parts by mass of the compound (B) and the thermosetting resin (C), and the content of the inorganic filler (D) is the total of the thermosetting compound (B) and the thermosetting resin (C). The resin composition according to [7], which is 40 to 600 parts by mass relative to 100 parts by mass.

[Formula 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.)

[Formula 8]

(In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer from 1 to 10.)

[23] The thermosetting resin (C) contains at least one member selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound, an alkenyl substituted nadimide compound, and an epoxy resin, and the thermosetting resin ( C) includes a maleimide compound, and the maleimide compound is bis(4-maleimidephenyl)methane, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, bis(3) -Ethyl-5-methyl-4-maleimide phenyl)methane, polytetramethylene oxide-bis(4-maleimide benzoate), maleimide compound represented by the following formula (4), and maleimide represented by the following formula (9) It contains at least one member selected from the group consisting of mead compounds, wherein the inorganic filler (D) is silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and hydroxide. It contains at least one member selected from the group consisting of magnesium, and the content of the molybdenum compound A) is 0.1 to 30 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C), The content of the thermosetting compound (B) is 5 to 50 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C),

The content of the thermosetting resin (C) is 50 to 95 parts by mass based on a 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 50 to 95 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). The resin composition according to [12], which is 40 to 600 parts by mass with respect to a total of 100 parts by mass of (B) and the thermosetting resin (C).

[Formula 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.)

[Formula 10]

(In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer from 1 to 10.)

[24] A resin sheet having a support and a resin layer disposed on one or both sides of the support, wherein the resin layer contains the resin composition according to any one of [1] to [23].

[25] A prepreg comprising a substrate and the resin composition according to any one of [1] to [23] impregnated or applied to the substrate.

[26] A metal foil-clad laminate comprising a laminate formed from the resin sheet according to [24] and metal foil disposed on one or both sides of the laminate.

[27] A metal foil-clad laminate comprising a laminate formed from the prepreg according to [25] and metal foil disposed on one or both sides of the laminate.

[28] A metal foil-clad laminate comprising a laminate formed from the resin sheet according to [24] and the prepreg according to [25], and metal foil disposed on one or both sides of the laminate.

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

[29] A printed wiring board having an insulating layer and a conductor layer formed on one or both sides of the insulating layer, wherein the insulating layer contains a cured product of the resin composition according to any one of [1] to [23].

According to the resin composition of the present invention, resin sheets, prepregs, metal foil-clad laminates, and printed wiring boards excellent in drillability can be provided.

Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as “this embodiment”) will be described in detail. The following embodiments are examples for illustrating the present invention, and are not intended to limit the present invention to the following content. The present invention can be implemented with appropriate modifications within the scope of its gist.

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

[Resin composition]

The resin composition of the present embodiment includes a molybdenum compound (A), at least one group selected from the group consisting of a maleimide group, an amino group, an epoxy group, a carboxyl group, a vinyl group, a hydroxy group, and a (meth)acrylic group, and polysiloxane It contains a thermosetting compound (B) containing a structure, a thermosetting resin (C) different from the thermosetting compound (B), and an inorganic filler (D) different from the molybdenum compound (A).

<Molybdenum compound (A)>

The resin composition of this embodiment contains a molybdenum compound (A). When the resin composition contains the molybdenum compound (A), the drillability of resin sheets, prepregs, and metal foil-clad laminates obtained by using the resin composition is improved, good hole quality is obtained, and drilling life is improved. can be extended.

The present inventors estimate as follows why drillability of resin sheets, prepregs, metal foil-clad laminates, etc. is excellent by using the resin composition of this embodiment. That is, due to the lubricity shown by the molybdenum compound (A) and the mold release effect derived from the polysiloxane structure of the thermosetting compound (B), the cutting powder generated during drilling does not form lumps and is smoothly discharged. Additionally, the 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 the thermosetting compound (B) constituting the hardened material are not thermally decomposed, and have a lubricating effect that reduces the frictional force between the tip of the tool and the workpiece to be cut, The mold release action that discharges cutting chips can be maintained. As a result, it is possible to prevent wear and breakage of the drill bit that occurs when the drill bit steps on cutting chips such as lumps. In addition, it is estimated that due to these synergistic effects, the adhesion of the drill bit to the processing target is improved, and the centripetality of the drill bit is improved, thereby improving the hole position accuracy.

The molybdenum compound (A) is not particularly limited as long as it contains molybdenum in the molecule. For example, 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, molybdic acid hydrate, and ( and zinc ammonium molybdate hydrate such as NH ₄ )Zn ₂ Mo ₂ O ₉ ·(H ₃ O). These compounds can be used individually or in appropriate combinations of two or more.

Among these, molybdic acid, zinc molybdate and zinc ammonium molybdate hydrate are preferred because they do not act as organometallic catalysts and provide better drilling properties and thermal stability.

The form of the molybdenum compound (A) when incorporated into the resin composition is not particularly limited, and may be used alone (unsupported). In the present embodiment, the non-supported type of the molybdenum compound refers to a form in which the molybdenum compound is used alone, in which no inorganic oxide or the like is formed on at least part of the surface of the core particle made of the molybdenum compound.

The average particle diameter (D50) of the molybdenum compound (unsupported type) is preferably 0.1 to 10 μm, more preferably 0.5 to 8 μm, and even more preferably 1 from the viewpoint of dispersibility in the resin composition and drillability. ~ 4 ㎛, more preferably 1 ~ 3 ㎛. In addition, in this embodiment, the average particle diameter (D50) means the median diameter, and is a value where the larger and smaller particles are equivalent when the particle size distribution of the measured powder is divided into two. The average particle diameter (D50) is determined by measuring the particle size distribution of a predetermined amount of powder injected into a dispersion medium using a laser diffraction scattering type particle size distribution measuring device, and calculating volume integration starting from the smallest particles. The value obtained when the particle size reaches 50% of the total volume. it means.

In addition, the molybdenum compound (A) may be surface-treated molybdenum particles (supported type) in which an inorganic oxide is formed on at least part of the surface of a core particle made of a molybdenum compound. The inorganic oxide may be applied to at least part of the surface of the core particle. The inorganic oxide may be provided partially 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 drillability and heat resistance, it is preferable that the inorganic oxide is uniformly applied to cover the entire surface of the core particle, that is, that the inorganic oxide film is uniformly formed on the surface of the core particle.

Surface-treated molybdenum particles (supported type) include, for example, those obtained by surface-treating particles of the molybdenum compound described above using a silane coupling agent, or those obtained by surface-treating them by methods such as the sol-gel method or liquid phase precipitation method. Examples include those obtained by treatment with an inorganic oxide. As for surface-treated molybdenum particles with inorganic oxide formed on the surface, the inorganic oxide acts effectively against heat, and the molybdenum compound acts effectively against drilling. Therefore, it becomes possible to achieve a high degree of compatibility between the two conflicting characteristics of drillability and heat resistance.

As the inorganic oxide, one having excellent heat resistance is preferable, and the type is not particularly limited, but metal oxide is more preferable. Metal oxides include, for example, 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 . there is. These can be used individually or in appropriate combination of two or more types. Among these, at least one selected from the group consisting of silica (SiO ₂ ), titania (TiO ₂ ), alumina (Al ₂ O ₃ ), and zirconia (ZrO ₂ ) is preferable in terms of heat resistance, insulation properties, cost, etc. And silica is more preferable.

That is, the molybdenum compound (A) is preferably one in which an inorganic oxide is applied to at least part or all of the surface of the core particle made of a molybdenum compound, that is, to at least part of the outer periphery or the entire outer periphery of the core particle. Among such molybdenum compounds (A), it is more preferable that silica is provided as an inorganic oxide to at least part or all of the surface of the core particle made of a molybdenum compound, that is, to at least part of the outer periphery or all of the outer periphery of the core particle. do. The core particle is 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 depending on the desired performance and is not particularly limited. In terms of forming a uniform inorganic oxide film, exhibiting the effect of improving drillability more significantly, and providing higher heat resistance, the thickness is preferably 3 to 500 nm, and more preferably. is 10 to 200 nm, more preferably 15 to 100 nm.

The average particle diameter (D50) of the surface-treated molybdenum particles is preferably 0.1 to 10 μm, more preferably 0.5 to 8 μm, and still more preferably 1 to 4 from the viewpoint of dispersibility in the resin composition and drillability. ㎛, and more preferably 1 to 3 ㎛.

Core particles made of a molybdenum compound can be produced by various known methods such as grinding or granulation, and the production method is not particularly limited. Additionally, the commercially available product may be used.

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

As a preferred method for producing surface-treated molybdenum particles, for example, molybdenum compounds (core particles) are dispersed in an alcohol solution in which metal alkoxides such as silicon alkoxide (alkoxysilane) and aluminum alkoxide are dissolved, and stirred. A mixed solution of water, alcohol and catalyst is added dropwise and the alkoxide is hydrolyzed to form a low refractive index film such as silicon oxide or aluminum oxide on the surface of the compound. Afterwards, the obtained powder is separated into solid and liquid and vacuum dried. Afterwards, a method of performing heat treatment may be mentioned. As another preferred production method, for example, a molybdenum compound (core particle) is dispersed in an alcohol solution containing a metal alkoxide such as silicon alkoxide or aluminum alkoxide, and mixed at high temperature and low pressure to cause oxidation on the surface of the compound. A method of forming a film of silicon or aluminum oxide, etc., and then vacuum drying the obtained powder and subjecting it to pulverization treatment, is an example. By these methods, molybdenum particles having a film of metal oxide such as silica or alumina on the surface of the molybdenum compound are obtained.

From the viewpoint of drillability and heat resistance, the content of the molybdenum compound (A) is preferably 0.1 to 30 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) described later and the thermosetting resin (C) described later, and is 0.3 to 0.3 parts by mass. It is more preferable that it is 10 parts by mass, and it is still more preferable that it is 0.5 to 5 parts by mass.

<Thermosetting compound (B)>

The resin composition of the present embodiment is a thermosetting compound (B) containing at least one group selected from the group consisting of a maleimide group, an amino group, an epoxy group, a carboxyl group, a vinyl group, a hydroxy group, and a (meth)acrylic group, and a polysiloxane structure. ) includes. These thermosetting compounds (B) can be used individually or in appropriate combinations of two or more types.

The thermosetting compound (B) has a polysiloxane skeleton in which siloxane bonds are repeatedly formed in the molecule, and contains at least one selected from the group consisting of a maleimide group, an amino group, an epoxy group, a carboxyl group, a vinyl group, a hydroxy group, and a (meth)acryl group. There is no particular limitation as long as it has a species flag. 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 mesh-like skeleton. Among these, a linear skeleton is preferable from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. In addition, the thermosetting compound (B) has at least one group selected from the group consisting of a maleimide group, an amino group, an epoxy group, a carboxyl group, a vinyl group, a hydroxy group, and a (meth)acryl group at both terminals in the molecule. desirable. The groups at both terminals in the molecule may be the same or different, but they are preferably the same because it facilitates control of the curing reaction and ease of handling.

The thermosetting compound (B) is preferably in a liquid state at a temperature of 23°C, or when using methyl ethyl ketone as a solvent, the solubility in the solvent at a temperature of 23°C is preferably 1% by mass or more, more preferably 5% by mass. It is more than ％. 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)) x 100 (mass%).” In this embodiment, for example, the evaluation that a total amount of 1 g or more of the thermosetting compound (B) is soluble in 99 g of methyl ethyl ketone means that the solubility of the thermosetting compound (B) in methyl ethyl ketone is “1 mass. % or more”, and the solubility is evaluated as not being high when the solubility is “less than 1% by mass.”

The thermosetting compound containing a maleimide group and a polysiloxane structure in the molecule is not particularly limited as long as it has at least one maleimide group and a polysiloxane structure in the molecule.

The thermosetting compound containing an amino group and a polysiloxane structure in the molecule is not particularly limited as long as it has at least one amino group and a polysiloxane structure 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 at least one epoxy group and a polysiloxane structure 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 at least one carboxyl group and a polysiloxane structure 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 at least one vinyl group and a polysiloxane structure in the molecule.

The thermosetting compound containing a hydroxy group and a polysiloxane structure in the molecule is not particularly limited as long as it has at least one hydroxy group and a polysiloxane structure in the molecule.

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

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

In addition, the thermosetting compound (B) contains an epoxy group and/or Alternatively, a thermosetting compound containing a hydroxy group and a polysiloxane structure is preferred.

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

The content of the thermosetting compound (B) is 100 parts by mass in total of the thermosetting compound (B) and the thermosetting resin (C) described later, since it has a superior mold release effect for discharging cutting chips and exhibits excellent heat resistance and chemical resistance. It is 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 15 to 40% by mass, based on 100% by mass of the resin solid content. % is more preferable. If the content is within the above range, the mold release action of discharging cutting chips is more excellent, and there is a tendency to exhibit excellent compatibility, low thermal expansion, and chemical resistance in a balanced manner.

(Thermosetting compound (B1))

The thermosetting compound (B) contains at least a structural unit derived from amino-modified silicone and a maleimide compound from the viewpoint of improving the reactivity of the components constituting the thermosetting compound (B) and compatibility with the thermosetting resin (C). It is preferable that it is a thermosetting compound (B1) containing the following structural units. In addition, in this specification, “structural unit derived from amino-modified silicone” and “structural unit derived from maleimide compound” refer to a thermosetting compound (B1) obtained by polymerizing each component of amino-modified silicone and maleimide compound. In addition to including structural units, it shall include structural units formed by reactions that can give the same structural units, etc. Hereinafter, in this specification, “… “Constitutive units derived from” shall be interpreted in the same way. The polymer (B1) described later is a type (specific example) of the thermosetting compound (B1), and the description below can be referred to for the amino-modified silicone and maleimide compound.

The content of the structural unit derived from amino-modified silicone is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and even more preferably 100% by mass of the total structural units in the thermosetting compound (B1). Typically, it is 15 to 45 mass%.

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 even more preferably 50 to 90% by mass, based on 100% by mass of all structural units in the thermosetting compound (B1). Typically, it is 55 to 85 mass%.

The amine titer in the thermosetting compound (B1) is preferably 2.0 mgKOH/g or less, more preferably 1.0 mgKOH/g or less, and still more preferably 0.5 mgKOH/g or less. In addition, the amine titer is the total amount of primary amine and secondary amine. If the amine value is 2.0 mgKOH/g or less, the mold release effect of discharging cutting chips is excellent, and there is a tendency to suppress the increase in viscosity of the resin composition, increase in molecular weight, gelation of the varnish, and increase in prepreg viscosity. Additionally, the smaller the amine number, the more likely it is to be able to suppress increases in viscosity and molecular weight of the resin composition. The lower limit of the amine titer is preferably 0 mgKOH/g. The amine titer is measured by a 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, and more preferably 10,000 to 15,000. When the weight average molecular weight is 5,000 or more, the thermal expansion coefficient of the prepreg tends to decrease, and when the weight average molecular weight is 20,000 or less, the mold release effect of discharging cutting chips is more excellent, the viscosity of the resin composition increases, and the molecular weight decreases. There is a tendency to suppress the increase in varnish gelation and prepreg viscosity. In order to set the weight average molecular weight of the thermosetting compound (B1) to 5,000 to 20,000, reaction conditions such as temperature and time when preparing the thermosetting compound (B1) can be controlled. In this 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 is measured by the method described in the Examples described later.

(polymer (B1))

The thermosetting compound (B) contains at least amino-modified silicone, a maleimide compound, carboxylic acid and/or carboxylic acid anhydride from the viewpoint of improving the reactivity of the components constituting it and compatibility with the thermosetting resin (C). It is preferable that it is polymer (B1) obtained by polymerizing. Polymer (B1) contains at least a structural unit derived from amino-modified silicone and a structural unit derived from a maleimide compound.

·Amino modified silicone

The amino-modified silicone is not particularly limited as long as it is a silicone having one or more amino groups in the molecule, but is preferably a silicone having two or more amino groups in the molecule, and more preferably contains an amino-modified silicone represented by the following formula (1): do. By containing a structural unit derived from amino-modified silicone, the thermosetting compound (B1) or polymer (B1) has a better mold release effect for discharging cutting chips and can exhibit excellent compatibility. Amino-modified silicones can be used individually or in appropriate combinations of two or more.

[Formula 11]

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

Examples of the alkyl group include straight-chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group; and branched alkyl groups such as isopropyl group, isobutyl group, and tert-butyl group. Among these, a methyl group is preferable.

As R _b , an alkylene group is preferable. Examples of the alkylene group include methylene group, ethylene group, trimethylene group, and tetramethylene group. Furthermore, the alkylene group is more preferably one with 1 to 4 carbon atoms in the main chain, and even more preferably a trimethylene group.

Examples of the arylene group include phenyl group, naphthyl group, indenyl group, biphenyl group, and anthryl group.

The amino group equivalent of the amino-modified silicone is preferably 130 to 6000 g/mol, more preferably 500 to 3000 g/mol, and still more preferably 600 to 2500 g/mol. When the amino group equivalent is within the above range, a cured product with a more excellent mold release effect for discharging cutting chips can be obtained. The amino group equivalent is measured by a method based on JIS K 7237:1995.

The amino-modified silicone may be a commercially available product or a product manufactured by a known method. Commercially available amino-modified silicone products include “X-22-161A” (amino group equivalent: 800 g/mol) and “X-22-161B” (amino group equivalent: 1500 g/mol) manufactured by Shin-Etsu Chemical Co., Ltd. “KF-8010” (amino group equivalent: 430 g/mol), etc. can be mentioned.

·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-maleimidephenyl)methane, and 2,2-bis(4-(4-maleimidephenoxy). -phenyl)propane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4- maleimide phenyl) methane, polytetramethylene oxide-bis(4-maleimide benzoate), maleimide compound represented by formula (4), maleimide compound represented by formula (9), prepolymer of these maleimide compounds, and Prepolymers of maleimide compounds and amine compounds can be mentioned. A maleimide compound can be used individually by 1 type or in appropriate combination of 2 or more types.

Among these, bis(4-maleimidephenyl)methane, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidephenyl) Containing at least one member selected from the group consisting of methane, polytetramethylene oxide-bis(4-maleimide benzoate), a maleimide compound represented by formula (4), and a maleimide compound represented by formula (9). It is preferable, and it is more preferable that it contains 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane.

[Formula 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.

[Formula 13]

In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer of 1 to 10.

As the maleimide compound, a commercial item may be used, or a crude product prepared by a known method may be used. Commercially available maleimide compounds include "BMI-70", "BMI-80", and "BMI-1000P" manufactured by K.I Chemical Co., Ltd., and "BMI-3000", "BMI-4000", and "BMI-3000" manufactured by Daiwa Chemical Industry Co., Ltd. Examples include "BMI-5100", "BMI-7000", and "BMI-2300", and "MIR-3000-70MT" manufactured by Nippon Explosives Co., Ltd.

·Carboxylic acid and carboxylic acid anhydride

The carboxylic acid is not particularly limited, but is preferably at least one selected from the group consisting of maleic acid, phthalic acid, succinic acid, acetic acid, and propionic acid, and more preferably at least one selected from the group consisting of maleic acid, phthalic acid, succinic acid, and acetic acid. It is preferable, and it is more preferable that it is at least one type selected from the group consisting of maleic acid, phthalic acid, and succinic acid.

The carboxylic acid anhydride is not particularly limited, but is preferably at least one selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, acetic anhydride, and propionic anhydride, and is preferably at least one selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride. It is more preferable that it is at least 1 type selected from the group consisting of maleic anhydride, phthalic anhydride, and succinic anhydride.

Among these, monovalent carboxylic acid and/or monovalent carboxylic acid anhydride, or divalent carboxylic acid and/or divalent carboxylic acid anhydride are preferable, and divalent carboxylic acid and/or divalent carboxylic acid anhydride are preferable. It is more preferable that it is an acid anhydride. The carboxylic acid and/or carboxylic acid anhydride are divalent carboxylic acid and/or divalent carboxylic acid anhydride, respectively, compared to the case where they are monovalent carboxylic acid and/or monovalent carboxylic acid anhydride. , there is a tendency to obtain a cured product with a better mold release effect for discharging cutting chips.

Carboxylic acid and carboxylic acid anhydride can be used individually or in appropriate combinations of two or more. In addition, carboxylic acid and carboxylic acid anhydride may be used individually or in combination.

In this embodiment, it is preferable to use only carboxylic acid anhydride compared to using only carboxylic acid. Since carboxylic acid anhydride has superior reactivity, it tends to be able to appropriately suppress the reactivity of polymer (B1) by reacting with the amino group in polymer (B1). As a result, the resin composition containing the polymer (B1) and the prepreg are excellent in storage stability (e.g., suppression of increase in viscosity of the resin composition, increase in molecular weight, gelation of the varnish, and increase in prepreg viscosity, etc.). And, the moldability when mixed with the thermosetting resin (C) also tends to be excellent.

The content of the structural unit derived from amino-modified silicone in the polymer (B1) is preferably 15 to 60% by mass, more preferably 20 to 60% by mass, based on 100% by mass of the total structural units in the polymer (B1). It is 55 mass%, more preferably 30 to 50 mass%.

The content of the structural unit derived from the maleimide compound in the polymer (B1) is preferably 35 to 75% by mass, more preferably 40 to 75% by mass, based on 100% by mass of all structural units in the polymer (B1). It is 70 mass%, more preferably 44 to 65 mass%.

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

· Method for producing thermosetting compound (B1) or polymer (B1)

The method for producing the thermosetting compound (B1) or polymer (B1) is not particularly limited, but includes a first reaction step of reacting an amino-modified silicone and a maleimide compound to obtain a primary polymer (hereinafter also simply referred to as the “first reaction step”) ) and a second reaction step of reacting the primary polymer with carboxylic acid and/or carboxylic acid anhydride (hereinafter, simply referred to as “second reaction step”) is a thermosetting compound that has better storage stability. (B1) or polymer (B1) is preferable in that it can be obtained.

In the first reaction step, the compounding amount of amino-modified silicone is preferably 5 to 70 mass%, more preferably 10 to 50 mass%, based on a total of 100 mass% of amino-modified silicone and maleimide compound. More preferably, it is 15 to 45 mass%.

In the first reaction step, the compounding amount of the maleimide compound is preferably 30 to 95% by mass, more preferably 50 to 90% by mass, based on a total of 100% by mass of the amino-modified silicone and the maleimide compound. More preferably, it is 55 to 85 mass%.

In the first reaction step, the mixing ratio of the maleimide compound to the amino-modified silicone is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and still more preferably 1.0 to 2.0, based on mass. When the compounding amount ratio is within the above range, the manufacturability of the thermosetting compound (B1) or polymer (B1) tends to be excellent.

The reaction temperature in the first reaction step is not particularly limited as long as it is the temperature at which the reaction between the amino-modified silicone and the maleimide compound proceeds, but is preferably 50 to 200°C, and more preferably 100 to 150°C.

The viscosity of the primary polymer obtained through the first reaction step, which is applied to the second reaction step, is 50% at a solvent-containing concentration from the viewpoint of producing a thermosetting compound (B1) or polymer (B1) with better storage stability. It is preferable that it is 100 to 500 mPa·s, and it is more preferable that it is 150 mPa·s to 400 mPa·s. Additionally, the viscosity of the primary polymer can be measured using a general viscometer. For example, it can be measured using a cone plate type viscometer (eg, ICI viscometer).

In the second reaction step, the ratio of the total amount of carboxylic acid and carboxylic acid anhydride to amino-modified silicone is preferably 0.01 to 0.4, more preferably 0.01 to 0.2, and still more preferably 0.01 to 0.4, based on mass. is 0.02 to 0.1. When the compounding amount ratio is within the above range, the storage stability of polymer (B1) tends to be more excellent.

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

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

In the first process and the second process, a solvent may be used. Examples of solvents include ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide; Propylene glycol monomethyl ether and its acetate can be mentioned. Solvents can be used individually or in appropriate combinations of two or more.

(Thermosetting compound (B2))

The thermosetting compound (B) is at least derived from alkenylphenol from the viewpoint of precisely controlling compatibility with the thermosetting resin (C) and improving moldability by keeping the viscosity of the thermosetting compound (B) low. It is preferable that it is a thermosetting compound (B2) containing a structural unit, a structural unit derived from epoxy-modified silicone, and a structural unit derived from an epoxy compound other than epoxy-modified silicone. In addition, the thermosetting compound (B2) may further contain structural units derived from phenol compounds other than alkenylphenol, as needed. Polymer (B2) described later is a type (specific example) of thermosetting compound (B2), and epoxy compounds other than alkenylphenol, epoxy-modified silicone, epoxy-modified silicone, and phenol compounds other than alkenylphenol are described later. You can refer to it.

The content of the structural unit derived from alkenylphenol is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and 10 to 40% by mass, based on the total mass of the thermosetting compound (B2). It is more desirable. When the content of this structural unit is within the above range, the mold release action of discharging cutting chips is more excellent, and there is a tendency to exhibit more excellent compatibility.

The content of the structural unit derived from epoxy-modified silicone is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and 30 to 50% by mass, relative to the total mass in the thermosetting compound (B2). It is more desirable. When the content of this structural unit is within the above range, the cured product of the resin composition tends to have a more excellent mold release effect for discharging cutting chips and to exhibit excellent low thermal expansion and chemical resistance in a balanced manner.

The structural units derived from epoxy-modified silicone include epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (hereinafter also referred to as “low-equivalent epoxy-modified silicone”) and epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g/mol. It is preferable that it is a structural unit derived from epoxy-modified silicone (hereinafter also referred to as "high-equivalent epoxy-modified silicone").

The content of the structural unit derived from low-equivalent epoxy-modified silicone is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, and 10 to 17% by mass, relative to the total mass in the thermosetting compound (B2). % is more preferable.

The content of the structural unit derived from the high-equivalent epoxy-modified silicone is preferably 15 to 55% by mass, more preferably 20 to 52.5% by mass, and 25 to 50% by mass, relative to the total mass in the thermosetting compound (B2). % is more preferable.

The mass ratio of the content of the structural units derived from the high-equivalent epoxy-modified silicone to the content of the structural units derived from the low-equivalent epoxy-modified silicone is preferably 1.5 to 4, more preferably 1.7 to 3.5, and 1.9 to 3.1. It is more preferable to be When this mass ratio is within the above range, the mold release action of discharging cutting chips is more excellent, and there is a tendency to exhibit even more excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability.

The content of structural units derived from epoxy compounds other than epoxy-modified silicone is preferably 5 to 40% by mass, preferably 10 to 30% by mass, and 15 to 20% by mass, relative to the total mass in the thermosetting compound (B2). It is more preferable that it is mass%. If the content of this structural unit is within the above range, the mold release action of discharging cutting chips is more excellent, and there is a tendency to exhibit even more excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability.

In addition, the content of structural units derived from epoxy-modified silicone is preferably 5 to 95% by mass with respect to the total mass of structural units derived from epoxy-modified silicone and structural units derived from epoxy compounds other than epoxy-modified silicone. , it is more preferable that it is 10 to 90 mass%, it is still more preferable that it is 15 to 60 mass%, and it is especially preferable that it is 20 to 50 mass%. The content of structural units derived from epoxy compounds other than epoxy-modified silicone is 5 to 95% by mass with respect to the total mass of structural units derived from epoxy-modified silicone and structural units derived from epoxy compounds other than epoxy-modified silicone. It is preferable, and it is more preferable that it is 10-90 mass %, it is still more preferable that it is 40-85 mass %, and it is especially preferable that it is 50-80 mass %. When the content of these structural units has the above-mentioned relationship, the release action of discharging cutting chips is more excellent, and the excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability tend to be further improved.

The content of structural units derived from phenolic compounds other than alkenylphenol is preferably 5 to 30% by mass, preferably 10 to 27.5% by mass, and 10 to 25% by mass, relative to the total mass in the thermosetting compound (B2). It is more preferable that it is mass%. When the content of this structural unit is within the above range, the cured product of the resin composition has a more excellent mold release effect for discharging cutting chips and tends to exhibit even more excellent copper foil adhesion.

The alkenyl group equivalent weight in the thermosetting resin (B2) is preferably 300 to 1,500 g/mol, preferably 350 to 1,200 g/mol, and more preferably 400 to 1,000 g/mol. When the alkenyl group equivalent is 300 g/mol or more, the cured product of the resin composition tends to have a further lowered elastic modulus, and as a result, the thermal expansion property of a substrate or the like obtained using the cured product tends to be further reduced. When the alkenyl group equivalent is 1500 g/mol or less, the mold release action of discharging cutting chips 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 , and more preferably 3.0×10 ³ to 2.0×10 ⁴ , in terms of polystyrene in the GPC method. do. 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 mold release action of discharging cutting chips is more excellent, and the resin composition It tends to suppress the increase in viscosity, increase in molecular weight, gelation of varnish, and increase in prepreg viscosity.

(Polymer (B2))

Since the thermosetting compound (B) is said to have even better compatibility with the thermosetting resin (C), it is at least a polymer (B2) obtained by polymerizing alkenylphenol, epoxy modified silicone, and an epoxy compound other than epoxy modified silicone. It is desirable. Moreover, it is more preferable that the polymer (B2) is a polymer obtained by polymerizing at least alkenylphenol, epoxy-modified silicone, an epoxy compound other than epoxy-modified silicone, and a phenol compound other than alkenylphenol. Polymer (B2) contains at least a structural unit derived from alkenylphenol, a structural unit derived from epoxy-modified silicone, and a structural unit derived from an epoxy compound other than epoxy-modified silicone.

·Alkenylphenol

The 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. By containing a structural unit derived from alkenylphenol, the thermosetting compound (B2) or polymer (B2) has a better mold release effect for discharging cutting chips and can exhibit excellent compatibility.

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

A phenolic aromatic ring refers to one in which one or more hydroxyl groups are directly bonded to an aromatic ring, and examples 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, and is preferably 1.

The phenolic aromatic ring may have a substituent other than the alkenyl group. Such substituents include, for example, a linear alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, a cyclic alkyl group with 3 to 10 carbon atoms, a linear alkoxy group with 1 to 10 carbon atoms, and a C3 group. Examples include a branched alkoxy group having from 10 to 10 carbon atoms, a cyclic alkoxy group having from 3 to 10 carbon atoms, and a halogen atom. When the phenolic aromatic ring has a substituent other than an alkenyl group, the number of substituents directly bonded to one phenolic aromatic ring is, for example, 1 to 2. Additionally, the bonding position of the substituent to the phenolic aromatic ring is not particularly limited.

The 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 exhibiting the effects of the present embodiment, the alkenylphenol preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring, and two It is desirable to have it.

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

[Formula 14]

In formula (1A), Rxa each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxb each independently represents an alkyl group or a hydrogen atom having 1 to 10 carbon atoms, and Rxc each independently represents an alkenyl group having 2 to 8 carbon atoms. Represents an aromatic ring with 4 to 12 carbon atoms, Rxc may form a condensed structure with a benzene ring, Rxc may or may not be present, and A is an alkylene group with 1 to 6 carbon atoms, or an alkylene group with 7 to 16 carbon atoms. It represents an aralkylene group, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond), and when Rxc is not present, Rxa is attached to one benzene ring. and/or may have two or more groups of Rxb.

[Formula 15]

In formula (1B), Rxd each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxe each independently represents an alkyl group or hydrogen atom having 1 to 10 carbon atoms, and Rxf represents an alkenyl group having 4 to 12 carbon atoms. Represents an aromatic ring, Rxf may form a condensed structure with a benzene ring, Rxf may or may not be present, and if Rxf does not exist, Rxd and/or Rxe groups may be attached to one benzene ring. You may have two or more.

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

In Formula (1A) and Formula (1B), when the groups represented by Rxc and Rxf form a condensed structure with a benzene ring, for example, a compound containing a naphthol ring as a phenolic aromatic ring can be mentioned. . Moreover, in Formula (1A) and Formula (1B), examples of cases in which the groups represented by Rxc and Rxf do not exist include compounds containing a phenol ring as the phenolic aromatic ring.

In formulas (1A) and (1B), the alkyl groups having 1 to 10 carbon atoms represented by Rxb and Rxe include, for example, linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. , branched alkyl groups such as isopropyl group, isobutyl group, and tert-butyl group.

In formula (1A), examples of the alkylene group having 1 to 6 carbon atoms represented by A include methylene group, ethylene group, trimethylene group, and propylene group. Examples of the aralkylene group having 7 to 16 carbon atoms represented by A include the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar-CH ₂ -CH ₂ -, or the formula: - A group represented by CH ₂ -Ar-CH ₂ -CH ₂ - (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group) can be mentioned. Examples of the arylene group having 6 to 10 carbon atoms represented by A include a phenylene ring.

The compound represented by formula (1B) is preferably one in which Rxf is a benzene ring (a compound containing a dihydroxynaphthalene skeleton) from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.

From the viewpoint of further improving compatibility, the alkenyl phenol is preferably an alkenyl bisphenol in which one alkenyl group is bonded to two phenolic aromatic rings of bisphenols. From the same point of view, alkenylbisphenol refers to diallylbisphenol, in which one allyl group is bonded to each of two phenolic aromatic rings of bisphenols, and/or dipro, in which one propenyl group is bonded to each of two phenolic aromatic rings of bisphenols. Phenylbisphenol is preferred.

Examples of diallylbisphenol include o,o'-diallylbisphenol A (DABPA (trade name), Daiwa Chemical Industry Co., Ltd.), o,o'-diallylbisphenol F, o,o'-diallyl Bisphenol S, o,o'-diallylbisphenol fluorene can be mentioned. Dipropenylbisphenol includes, for example, o,o'-dipropenylbisphenol A (PBA01 (brand name), Gun A Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o,o '-dipropenylbisphenol S, and o,o'-dipropenylbisphenolfluorene.

The average number of phenol groups per molecule of alkenylphenol is preferably 1 to 3, more preferably 1.5 to 2.5, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. The average number of phenol groups is calculated by the following formula.

[Equation 1]

In the formula, Ai represents the number of phenol groups of the alkenylphenol having i phenol groups in the molecule, Xi represents the proportion of the alkenylphenol having i phenol groups in the molecule to all alkenylphenols, and X ₁ + X ₂ +… X _n = 1.

·Epoxy modified silicone

Epoxy-modified silicone is not particularly limited as long as it is a silicone compound or resin modified with an epoxy group-containing group. By containing a structural unit derived from epoxy-modified silicone, the thermosetting compound (B2) or polymer (B2) has a better mold release effect for discharging cutting chips and can exhibit excellent low thermal expansion and chemical resistance.

The silicone compound or resin is not particularly limited as long as it is a compound having a polysiloxane skeleton in which siloxane bonds are repeatedly formed. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a mesh-like skeleton. Among these, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment, it is preferable that the polysiloxane skeleton is a linear skeleton.

Examples of the epoxy group-containing group include group represented by the following formula (a1).

[Formula 16]

In formula (a1), R ⁰ each independently represents a single bond, an alkylene group (for example, an alkylene group having 1 to 5 carbon atoms such as a methylene group, ethylene group, or propylene group), an arylene group, or an aralkylene group. and X represents a monovalent group represented by the following formula (a2) or a monovalent group represented by the following formula (a3).

[Formula 17]

[Formula 18]

The epoxy-modified silicone preferably contains epoxy-modified silicone with an epoxy equivalent of 140 to 250 g/mol, more preferably contains epoxy-modified silicone with an epoxy equivalent of 145 to 245 g/mol, and 150 to 250 g/mol. It is more preferred to contain an epoxy modified silicone with an epoxy equivalent weight of 240 g/mol. By containing epoxy-modified silicone having an epoxy equivalent within the above range, the epoxy-modified silicone has a more excellent mold release effect for discharging cutting chips, compatibility with other resins or compounds in the resin composition, low thermal expansion property, and resistance. There is a tendency to further improve drug properties in a balanced manner.

There are two types of epoxy-modified silicone, from the viewpoint of having a superior mold release effect for discharging cutting chips and being able to further improve compatibility with other resins or compounds in the resin composition, low thermal expansion, and chemical resistance in a balanced manner. It is preferable to contain the above epoxy modified silicone. In this case, the two or more types of epoxy-modified silicones preferably have different epoxy equivalents, and include epoxy-modified silicone (low-equivalent epoxy-modified silicone) having an epoxy equivalent of 50 to 350 g/mol and 400 to 4000 g/mol. It is more preferable to contain an epoxy-modified silicone (high-equivalent epoxy-modified silicone) having an epoxy equivalent weight of It is more preferable to contain epoxy-modified silicone.

When the epoxy modified silicone contains two or more types of epoxy modified silicone, the average epoxy equivalent weight of the epoxy modified silicone is preferably 140 to 3000 g/mol, more preferably 250 to 2000 g/mol, and 300 to 1000 g/mol. It is more preferable that it is g/mol. The average epoxy equivalent is calculated by the following formula.

[Equation 2]

In the formula, Ei represents the epoxy equivalent of one type of epoxy-modified silicone among two or more types of epoxy-modified silicone, Wi represents the ratio of the epoxy-modified silicone in epoxy-modified silicone B, and W ₁ + W ₂ + . W _n = 1.

Epoxy-modified silicone has a superior mold release effect for discharging cutting chips, and from the viewpoint of being able to further improve compatibility with other resins or compounds in the resin composition, low thermal expansion property, and chemical resistance in a balanced manner, the formula is as follows: It is preferable to contain epoxy-modified silicone represented by (2).

[Formula 19]

In formula (2), R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n is Represents an integer from 0 to 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 to 12, and more preferably 1 to 4. Examples of the alkylene group include methylene group, ethylene group, or propylene group. Among these, it is preferable that R ¹ is a propylene group.

In formula (2), the arylene group represented by R ¹ may have a substituent. The number of carbon atoms of the arylene group is preferably 6 to 40, and more preferably 6 to 20. Examples of arylene groups include phenylene group, cyclohexylphenylene group, hydroxyphenylene group, cyanophenylene group, nitrophenylene group, naphthylylene group, biphenylene group, anthrylene group, pyrenylene group, and fluorescein. Nylene group, etc. can be mentioned. 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 ¹ is preferably 7 to 30, more preferably 7 to 13. Examples of the aralkylene group include a group represented by the following formula (XI).

[Formula 20]

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

In formula (2), the group represented by R ¹ may further have a substituent, and examples of the substituent include a linear alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, and a C3 to 10 alkyl group. Examples include a cyclic alkyl group of 10 carbon atoms, a linear alkoxy group of 1 to 10 carbon atoms, a branched alkoxy group of 3 to 10 carbon atoms, and a cyclic alkoxy group of 3 to 10 carbon atoms.

In formula (2), R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms. The 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 group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, and cyclohexyl group. Among these, R ² is preferably a methyl group or a phenyl group.

In formula (2), n is an integer of 0 to 100. The lower limit of n should be 1 or more from the viewpoint of superior mold release action for discharging cutting chips and further improved compatibility with other resins or compounds in the resin composition, low thermal expansion, and chemical resistance in a balanced manner. desirable. Likewise, the upper limit of n is preferably 50 or less, more preferably 30 or less, and still more preferably 20 or less.

Epoxy-modified silicone has a superior mold release effect for discharging cutting chips, and from the viewpoint of further improving compatibility with other resins or compounds in the resin composition, low thermal expansion, and chemical resistance in a balanced manner, it is used in formula (2) ) It is preferable to contain two or more types of epoxy-modified silicone represented by . In this case, it is preferable that the two or more types of epoxy-modified silicone contained each have a different n, and that n is 1 to 2 in the formula (2), and epoxy-modified silicone in which n is 5 to 20 in the formula (2). It is more preferable to contain phosphorus epoxy modified silicone.

The average number of epoxy groups per molecule of the epoxy-modified silicone is preferably 1 to 3, and more preferably 1.5 to 2.5, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. The average epoxy group number is calculated by the following formula.

[Equation 3]

In the formula, Bi represents the epoxy group number of the epoxy-modified silicone having i epoxy groups in the molecule, Yi represents the ratio of the epoxy-modified silicone having i epoxy groups in the molecule to the entire epoxy-modified silicon, and Y ₁ + Y ₂ +… Y _n = 1.

Low-equivalent epoxy-modified silicone and high-equivalent epoxy-modified silicone may be commercially available products or prepared products prepared by known methods. Commercially available low-equivalent epoxy-modified silicone products include "X-22-163" (functional group equivalent weight: 200 g/mol) manufactured by Shin-Etsu Chemical Co., Ltd. Commercially available products of high-equivalent epoxy-modified silicone include “KF-105” (functional group equivalent: 490 g/mol), “X-22-163A” (functional group equivalent: 1000 g/mol) manufactured by Shin-Etsu Chemical Co., Ltd. and “X-22-163B” (functional group equivalent: 1800 g/mol).

·Epoxy compound

An epoxy compound is an epoxy compound other than epoxy modified silicone, and more specifically, an epoxy compound that does not have a polysiloxane skeleton. By containing a structural unit derived from an epoxy compound, the thermosetting compound (B2) or polymer (B2) has a superior mold release effect for discharging cutting chips and exhibits excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability. You can.

The epoxy compound is not particularly limited as long as it is an epoxy compound other than epoxy-modified silicone. The epoxy compound is a bifunctional epoxy compound having two epoxy groups in one molecule from the viewpoint of superior mold release action for discharging cutting chips and excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability. It is preferable to contain.

Examples of bifunctional epoxy compounds include bisphenol-type epoxy resins (e.g., bisphenol A-type epoxy resins, bisphenol E-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, and bisphenol fluorene-type epoxy resins). resin), phenolic novolak-type epoxy resin (e.g., phenol novolak-type epoxy resin, bisphenol A novolak-type epoxy resin, cresol novolak-type epoxy resin), trisphenolmethane-type epoxy resin, aralkyl-type epoxy resin, Biphenyl-type epoxy resin containing a biphenyl skeleton, naphthalene-type epoxy resin containing a naphthalene skeleton, anthracene-type epoxy resin containing a dihydroanthracene skeleton, glycidyl ester-type epoxy resin, polyol-type epoxy resin, isocyanurate. epoxy resins containing a late ring, dicyclopentadiene-type epoxy resins, fluorene-type epoxy resins containing a fluorene skeleton, and epoxy resins composed of a bisphenol A-type structural unit and a hydrocarbon-based structural unit; These halogen compounds can be mentioned. These epoxy compounds are used individually or in combination of two or more types.

Examples of the aralkyl type epoxy resin include a compound represented by the following formula (b1).

[Formula 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, and R ^3a each independently represents a hydrogen atom or a methyl group. represents, and each ring may have a substituent other than a glycidyloxy group (for example, an alkyl group or a phenyl group having 1 to 5 carbon atoms).

Examples of the biphenyl type epoxy resin include a compound (compound b2) represented by the following formula (b2).

[Formula 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 group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, and cyclohexyl group.

When the biphenyl type epoxy resin is compound b2, the biphenyl type epoxy resin may be in the form of a mixture of compounds b2 with different numbers of Ra, which is an alkyl group. Specifically, a mixture of biphenyl-type epoxy resins having different numbers of Ra, which is an alkyl group, is preferable, and a mixture of compound b2, where the number of Ra, which is an alkyl group, is 0, and compound b2, where the number of Ra, which is an alkyl group, is 4, is more preferable.

Examples of the naphthalene type epoxy resin include a compound represented by the following formula (b3).

[Formula 23]

In formula (b3), R ^3b is each independently a naph group containing a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group), an aralkyl group, a benzyl group, a naphthyl group, or a glycidyloxy group. It represents a til group, and n represents an integer of 0 or more (for example, 0 to 2).

Commercially available products of the compound represented by the above formula (b3) include, for example, “HP-4032” manufactured by DIC Corporation (n = 0 in the above formula (b3)) and “HP-4710” (the above formula (b3) where n = 0 and R ^3b = a naphthylmethyl group containing at least one glycidyloxy group).

Examples of the dicyclopentadiene type epoxy resin include a compound represented by the following formula (b4).

[Formula 24]

In formula (b4), R ^3c each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group).

As the dicyclopentadiene type epoxy resin, a commercial product may be used, or a preparation prepared by a known method may be used. Commercially available products of dicyclopentadiene type epoxy resin include “EPICRON HP-7200L,” “EPICRON HP-7200,” “EPICRON HP-7200H,” and “EPICRON HP-7000HH” manufactured by Dainippon Ink Chemical Industry Co., Ltd. there is.

Examples of the epoxy resin consisting of a bisphenol A structural unit and a hydrocarbon-based structural unit include a compound represented by the following formula (b5).

[Formula 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 , ethyleneoxyethyl group, di(ethyleneoxy)ethyl group, tri(ethyleneoxy)ethyl group, propyleneoxypropyl group, di(propyleneoxy)propyl group, tri(propyleneoxy)propyl group, or alkylene group having 2 to 15 carbon atoms (e.g. For example, methylene group or ethylene group).

Among these, epoxy compounds have a better mold release effect for discharging cutting chips, and from the viewpoint of being able to exhibit even better compatibility, chemical resistance, copper foil adhesion, and insulation reliability, bisphenol-type epoxy resins and aralkyl-type epoxy resins are preferred. , it is preferably at least one selected from the group consisting of biphenyl-type epoxy resin, naphthalene-type epoxy resin, and dicyclopentadiene-type epoxy resin, and more preferably it is biphenyl-type epoxy resin and/or naphthalene-type epoxy resin.

The average number of epoxy groups per molecule of the epoxy compound is preferably 1 to 3, and more preferably 1.5 to 2.5, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. The average epoxy group number is calculated by the following formula.

[Equation 4]

In the formula, Ci represents the epoxy group number of the epoxy compound having i epoxy groups in the molecule, Zi represents the ratio of the epoxy compound having i epoxy groups in the molecule to the entire epoxy compound, and Z ₁ + Z ₂ + . Z _n = 1.

·Phenol compounds other than alkenylphenol

The thermosetting compound (B2) or polymer (B2) is a phenolic compound other than alkenylphenol (hereinafter simply referred to as “phenolic compound”) from the viewpoint of having a better mold release effect for discharging cutting chips and being able to exhibit even better copper foil adhesion. It is preferable to contain .

Phenol compounds other than alkenylphenol include bisphenol-type phenol resins (e.g., bisphenol A-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenol-type novolac resins (e.g., (phenol novolak resin, naphthol novolak resin, cresol novolak resin, etc.), glycidyl ester type phenol resin, naphthalene type phenol resin, anthracene type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic Formula phenol resin, polyol type phenol resin, aralkyl type phenol resin, phenol-modified aromatic hydrocarbon formaldehyde resin, fluorene type phenol resin, etc. are mentioned. These phenol compounds are used individually or in combination of two or more types.

Among these, the phenol compound is more excellent in the release action of discharging cutting chips and is a bifunctional phenolic compound having two phenolic hydroxyl groups in one molecule from the viewpoint of being able to exhibit even better compatibility and copper foil adhesion. desirable.

Bifunctional phenol compounds include bisphenol, biscresol, bisphenols with a fluorene skeleton (e.g., bisphenol with a fluorene skeleton, biscresol with a fluorene skeleton, etc.), biphenols (e.g., p, p'-biphenol, etc.), dihydroxydiphenyl ether (e.g., 4,4'-dihydroxydiphenyl ether, etc.), dihydroxydiphenyl ketone (e.g., 4,4'-diphenyl ketone) hydroxydiphenyl ketone, etc.), dihydroxydiphenyl sulfide (e.g., 4,4'-dihydroxydiphenyl sulfide, etc.), dihydroxyarene (e.g., hydroquinone, etc.) You can. These bifunctional phenol compounds are used individually or in combination of two or more types. Among these, bifunctional phenol compounds are more excellent in the mold release action of discharging cutting chips and can exhibit more excellent copper foil adhesion, so they are selected from the group consisting of bisphenol, biscresol, and bisphenols with a fluorene skeleton. It is preferable to include at least one selected type, and it is more preferable to include bisphenols having a fluorene skeleton. From the same viewpoint as above, bisphenol having a fluorene skeleton is preferably biscresol fluorene.

Phenol compounds other than alkenylphenol may be commercially available or products manufactured by known methods may be used. Commercially available products of phenol compounds other than alkenyl phenol include “BCF” (biscresol fluorene) manufactured by Osaka Gas Chemical Co., Ltd. and “Bisphenol M” manufactured by Mitsui Chemical Co., Ltd.

· Method for producing thermosetting compound (B2) or polymer (B2)

The method for producing the thermosetting compound (B2) or polymer (B2) is not particularly limited, but includes, for example, alkenylphenol, epoxy-modified silicone, an epoxy compound, and, if necessary, a phenol compound in the presence of a polymerization catalyst described later. It is obtained by a process of reacting under The reaction may be carried out in the presence of an organic solvent. More specifically, in the above process, an addition reaction between the epoxy group of the epoxy modified silicone and the epoxy compound and the hydroxyl group of the alkenylphenol, and the addition reaction of the hydroxyl group of the obtained addition reactant with the epoxy group of the epoxy modified silicone and the epoxy compound. By proceeding with the above, thermosetting compound (B2) or polymer (B2) can be obtained.

In the production of thermosetting compound (B2) or polymer (B2), the blending amount of alkenylphenol is selected from the viewpoint of superior mold release action for discharging cuttings and excellent compatibility. , it is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and still more preferably 5 to 30 parts by mass, relative to a total of 100 parts by mass of the epoxy modified silicone, epoxy compound, and phenol compound.

The mixing amount of the epoxy-modified silicone is that of alkenylphenol, epoxy-modified silicone, epoxy compound, and phenolic compound from the viewpoint of better mold release action for discharging cutting chips and balanced expression of excellent low thermal expansion and chemical resistance. It is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 55 parts by mass, relative to a total of 100 parts by mass.

The mixing amount of the epoxy compound is alkenylphenol, epoxy-modified silicone, epoxy compound, and It is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass, relative to a total of 100 parts by mass of the phenol compound.

The compounding amount of the phenolic compound is 100 parts by mass in total of alkenylphenol, epoxy-modified silicone, epoxy compound, and phenol compound from the viewpoint of being more excellent in the mold release action of discharging cutting chips and being able to express even more excellent copper foil adhesion. It is 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 polymer (B2) does not contain a phenol compound, the respective blending amounts of the alkenylphenol, epoxy-modified silicone, and epoxy compound described above are the sum of the alkenylphenol, epoxy-modified silicone, and epoxy compound. The mixing amount is expressed per 100 parts by mass.

Examples of polymerization catalysts include imidazole catalysts and phosphorus-based catalysts. These catalysts are used individually or in combination of two or more types. Among these, imidazole catalysts are preferable.

Imidazole catalysts include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo[1,2-a]benzoimidazole (TBZ (trade name), Shikoku Chemical Industry Co., Ltd.), and 2,4,5-triphenylimidazole (TPIZ (trade name) and imidazoles from Tokyo Chemical Industry Co., Ltd.). Among these, from the viewpoint of preventing homopolymerization of the epoxy component, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole are preferred. do.

The amount of the polymerization catalyst (preferably an imidazole catalyst) used is, for example, 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of alkenylphenol, epoxy modified silicone, 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 0.5 parts by mass or more, and more preferably 4.0 parts by mass or less.

As an organic solvent, for example, a polar solvent or a non-polar solvent can be used. Examples of polar solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Cellosolve-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; Amides such as dimethylacetamide and dimethylformamide can be mentioned. Examples of nonpolar solvents include aromatic hydrocarbons such as toluene and xylene. These solvents are used individually or in combination of two or more types.

The amount of the organic solvent used is not particularly limited, but is, for example, 50 to 150 parts by mass with respect to a total of 100 parts by mass of alkenylphenol, epoxy modified silicone, epoxy compound, and phenol compound.

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

After completion of the reaction in this step, the thermosetting compound (B2) or polymer (B2) may be separated and purified from the reaction mixture by a commonly used method.

<Thermosetting resin (C)>

The resin composition of the present embodiment contains a thermosetting resin (C) different from the thermosetting compound (B) according to the present embodiment. The thermosetting compound (B) exhibits excellent compatibility even with thermosetting resins that lack compatibility with silicone-based compounds. Therefore, even if the thermosetting compound (B) and the thermosetting resin (C) are combined, each component is not separated in the resin composition and has excellent compatibility.

The thermosetting resin (C) is composed of a maleimide compound, a cyanate ester compound, a phenol compound, an alkenyl substituted nadimide compound, and an epoxy resin from the viewpoint of further improving the low thermal expansion property, chemical resistance, and copper foil adhesion of the resulting cured product. It is preferable that it contains at least one type selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound, and an epoxy resin. These thermosetting resins (C) can be used individually or in appropriate combinations of two or more types.

The content of the thermosetting resin (C) is based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C), since it has a superior mold release effect for discharging cutting chips and exhibits excellent heat resistance and chemical resistance. It 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 having a more excellent mold release effect for discharging cutting chips 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 to produce the thermosetting compound (B). Maleimide compounds can be used individually or in appropriate combinations 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, for example, a monomaleimide compound having one maleimide group in one molecule (for example, N-phenylmaleimide , N-hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleimidephenyl)methane, 2,2-bis(4-(4) -maleimidephenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3,5) -diethyl-4-maleimidephenyl)methane), m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4 -trimethyl)hexane, polytetramethylene oxide-bis(4-maleimide benzoate), a maleimide compound represented by the following formula (4), a maleimide compound represented by the formula (9), and these maleimide compounds and amine compounds. prepolymer, etc.).

[Formula 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 to 100, and more preferably 1 to 10.

[Formula 27]

In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer of 1 to 10.

It is preferable that the number of maleimide groups in a maleimide compound is 2 or more per molecule. These maleimide compounds are used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of further improving low thermal expansion and chemical resistance, maleimide compounds include bis(4-maleimidephenyl)methane, 2,2-bis(4-(4-maleimidephenoxy)-phenyl) Propane, bis(3-ethyl-5-methyl-4-maleimide phenyl)methane, polytetramethylene oxide-bis(4-maleimide benzoate), maleimide compound represented by formula (4), and formula (9) It is preferable to include at least one selected from the group consisting of maleimide compounds represented by, bis(4-maleimidephenyl)methane, 2,2-bis(4-(4-maleimidephenoxy)-phenyl) It is more preferable that it contains at least one type selected from the group consisting of propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, and a maleimide compound represented by the following formula (4).

As the maleimide compound, a commercial item may be used, or a crude product prepared by a known method may be used. Commercially available maleimide compounds include "BMI-70", "BMI-80", and "BMI-1000P" manufactured by K.I Chemical Co., Ltd., and "BMI-3000", "BMI-4000", and "BMI-3000" manufactured by Daiwa Chemical Industry Co., Ltd. Examples include "BMI-5100", "BMI-7000", and "BMI-2300", and "MIR-3000-70MT" manufactured by Nippon Explosives Co., Ltd.

The content of the maleimide compound is preferably 1 to 50 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of superior mold release action for discharging cutting chips and further improving low thermal expansion and chemical resistance. It is more preferable that it is - 40 parts by mass, and it is still more preferable that it is 10 - 40 parts by mass.

·Cyanate ester compound

The thermosetting resin (C) preferably contains a cyanate ester compound from the viewpoint of having a better mold release effect for discharging cutting chips and further improving low thermal expansion and chemical resistance.

The cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanato groups (cyanate ester groups) in one molecule. For example, naphthol aralkyl type cyanic acid such as the compound represented by formula (5). Ester compounds, novolak-type cyanate compounds such as compounds represented by formula (6) excluding the compounds represented by formula (5), biphenyl aralkyl-type cyanate esters, diallyl bisphenol-type cyanate ester compounds, bis(3) ,3-dimethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene , 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7- Dicyanatonaphthalene, 1,3,6-dicyanatonaphthalene, 4',4-dicyanatonaphthalene, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4) -cyanatophenyl)sulfone and 2,2-bis(4-cyanatophenyl)propane. These cyanate ester compounds are used individually or in combination of two or more types. Among these, cyanate ester compounds are more excellent in the mold release action of discharging cutting chips, and from the viewpoint of further improving low thermal expansion and chemical resistance, naphthol aralkyl type cyanate compounds and/or novolac type cyanic acid are used. It is preferable to include an ester compound.

Among these, the cyanate ester compound is more excellent in the mold release action of discharging cutting chips, and from the viewpoint of further improving low thermal expansion and chemical resistance, it contains the compounds represented by formula (5) and/or formula (6). It is desirable. The cyanate ester compound containing the compound represented by formula (5) has a more excellent mold release effect for discharging cutting chips, further improves low thermal expansion and chemical resistance, and further has excellent flame retardancy and a low thermal expansion coefficient. It is more desirable because it has

[Formula 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 still more preferably an integer of 1 to 6.

[Formula 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 or a hydrogen atom having 1 to 10 carbon atoms, and R _yc is , each independently represents an aromatic ring having 4 to 12 carbon atoms, R _yc may form a condensed structure with a benzene ring, R _yc may or may not be present, and A ^1a each independently represents a carbon number. Represents an alkylene group of 1 to 6 carbon atoms, an aralkylene group of 7 to 16 carbon atoms, an arylene group of 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a single bond (direct bond), R _yc When not present, one benzene ring may have two or more R _ya and/or R _yb groups. n represents an integer from 1 to 20.

In formula (6), examples of the alkenyl group having 2 to 8 carbon atoms represented by R _ya include vinyl group, allyl group, propenyl group, butenyl group, and hexenyl group.

In formula (6), examples of the alkyl group having 1 to 10 carbon atoms represented by R _yb include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group; Branched alkyl groups such as isopropyl group, isobutyl group, and tert-butyl group can be mentioned.

In formula (6), examples of the alkylene group having 1 to 6 carbon atoms represented by A ^1a include methylene group, ethylene group, trimethylene group, and propylene group. Moreover, in formula (6), the aralkylene group having 7 to 16 carbon atoms represented by A ^1a includes, for example, 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 a phenylene group, naphthylene group, or biphenylene group). In addition, examples of the arylene group having 6 to 10 carbon atoms represented by A ^1a include a phenylene ring.

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

The compound represented by formula (6) is a phenol novolak-type cyanate ester because it has a superior mold release effect for discharging cutting chips, further improves low thermal expansion and chemical resistance, and has a higher glass transition temperature. The compound is preferable, and as the phenol novolak-type cyanate ester compound, it is more preferable that it is a compound represented by formula (c1).

[Formula 30]

In formula (c1), Rx each independently represents a hydrogen atom or a methyl group, R each independently represents an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, and n is It represents an integer from 1 to 10.

These cyanate ester compounds may be produced according to known methods. Specific manufacturing methods include, for example, the methods described in Japanese Patent Application Publication No. 2017-195334 (particularly paragraphs 0052 to 0057).

The content of the cyanic acid ester compound as the thermosetting resin (C) is preferably 10 per 100 parts by mass of the resin solid content from the viewpoint of having a more excellent mold release effect for discharging cutting chips and further improving low thermal expansion and chemical resistance. It is preferably 70 to 70 parts by mass, more preferably 15 to 60 parts by mass, and even more preferably 20 to 50 parts by mass.

·Phenolic compounds

It is preferable that the thermosetting resin (C) contains a phenolic compound from the viewpoint of having a more excellent mold release effect for discharging cutting chips and further improving copper foil adhesion. The phenol compound contained in the thermosetting resin (C) may be the same as or different from the phenolic compound used to produce the thermosetting compound (B). Phenol compounds can be used individually or in appropriate combinations of two or more.

The phenolic compound is not particularly limited as long as it is a compound having two or more phenolic hydroxyl groups in one molecule, but examples include phenols and bisphenols (e.g., bisphenol A, Bisphenol E, Bisphenol F, Bisphenol S, etc.), diallylbisphenols (e.g., diallylbisphenol A, diallylbisphenol E, diallylbisphenol F, diallylbisphenol S, etc.), phenolic novolak resins (e.g. , phenol novolak resin, naphthol novolak resin, cresol novolak resin, etc.), naphthalene type phenol resin, dihydroanthracene type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, and aralkyl type phenol resin. can be mentioned. These phenol compounds are used individually or in combination of two or more types. Among these, it is preferable that the phenol compound contains an aralkyl type phenol resin from the viewpoint of further improving copper foil adhesion.

(Aralkyl type phenolic resin)

Examples of the aralkyl type phenol resin include a compound represented by formula (c2).

[Formula 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, and R ^2a each independently represents a hydrogen atom or a methyl group. represents an integer of 1 to 50, and each ring may have a substituent other than a hydroxyl group (for example, an alkyl group or phenyl group having 1 to 5 carbon atoms, etc.).

The compound represented by the formula (c2) is superior in the mold release action of discharging cutting chips, and from the viewpoint of further improving the copper foil adhesion, in the formula (c2), Ar ¹ is a naphthalene ring and Ar ² is a benzene ring. (hereinafter also referred to as “naphthol aralkyl type phenol resin”), and a compound in formula (c2) where Ar ¹ is a benzene ring and Ar ² is a biphenyl ring (hereinafter also referred to as “biphenyl aralkyl type phenol resin”) ) is desirable.

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

[Formula 32]

In the 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 phenol resin is preferably a compound represented by formula (2c).

[Formula 33]

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

The aralkyl type phenol resin may be a commercial product or a product manufactured by a known method. Commercially available aralkyl-type phenolic resins include "KAYAHARD GPH-65", "KAYAHARD GPH-78", and "KAYAHARD GPH-103" (biphenyl aralkyl-type phenol resin) manufactured by Nippon Chemical Co., Ltd., and "KAYAHARD GPH-65" manufactured by Nippon Chemical Co., Ltd. SN-495” (naphthol aralkyl type phenol resin).

The content of the phenol compound as the thermosetting resin (C) is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin solid content, from the viewpoint of superior mold release action for discharging cutting chips and further improving copper foil adhesion, It is more preferable that it is 15 to 35 parts by mass, and it is still more preferable that it is 20 to 30 parts by mass.

·Alkenyl substituted nadimide compound

The thermosetting resin (C) preferably contains an alkenyl-substituted nadimide compound from the viewpoint of having a better mold release effect for discharging cutting chips and further improving heat resistance. The alkenyl substituted nadimide compound can be used individually or in appropriate combination of two or more types.

The alkenyl substituted nadimide compound is not particularly limited as long as it is a compound having one or more alkenyl substituted nadimide groups in one molecule, but examples include compounds represented by the following formula (2d).

[Formula 34]

In formula (2d), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group or an ethyl group), and R ₂ represents an alkylene group or phenylene group having 1 to 6 carbon atoms. , a biphenylene group, a naphthylene group, or a group represented by the following formula (7) or the following formula (8).

[Formula 35]

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

[Formula 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 nadimide compound represented by formula (2d) may be a commercial product or a product manufactured according to a known method. Commercially available products include “BANI-M” and “BANI-X” manufactured by Maruzen Petrochemical Co., Ltd.

The content of the alkenyl substituted nadimide compound as the thermosetting resin (C) is preferably 1 to 45 parts by mass, more preferably 5 to 40 parts by mass, and 10 to 35 parts by mass, based on 100 parts by mass of the resin solid content. It is more desirable.

·Epoxy resin

It is preferable that the thermosetting resin (C) contains an epoxy resin from the viewpoint of having a more excellent mold release effect for discharging cutting chips 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 the epoxy compound other than the epoxy-modified silicone used to produce the thermosetting compound (B), but is an epoxy compound different from the epoxy-modified silicone. Epoxy resins are used individually or in combination of two or more types.

As an epoxy resin, typically, a bifunctional epoxy compound having two epoxy groups in one molecule or a polyfunctional epoxy compound having three or more epoxy groups in one molecule can be used. It is preferable that the epoxy resin contains a bifunctional epoxy compound and/or a polyfunctional epoxy compound from the viewpoint of having a more excellent mold release effect for discharging cutting chips and further improving chemical resistance, copper foil adhesion, and insulation reliability. .

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

[Formula 37]

In the 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, and R ^3a each independently represents a hydrogen atom or a methyl group. , k represents an integer from 1 to 50,

Here, the benzene ring or naphthalene ring in Ar ³ may further have one or more substituents, and the substituent may be a glycidyloxy group (not shown), or other substituents, for example, having 1 to 5 carbon atoms. It may be an alkyl group, phenyl group, etc.,

The benzene ring, naphthalene ring, or biphenyl ring for Ar ⁴ may further have one or more substituents, and the substituent may be a glycidyloxy group, or other substituents, for example, having 1 to 5 carbon atoms. It may be an alkyl group, a phenyl group, etc.

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

[Formula 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, and R ^3a each independently represents a hydrogen atom or a methyl group. represents,

Here, the benzene ring or naphthalene ring for Ar ³ may further have one or more substituents, and the substituents are, for example, substituted other than glycidyloxy groups such as alkyl groups having 1 to 5 carbon atoms or phenyl groups. It can also contribute,

The benzene ring, naphthalene ring, or biphenyl ring for Ar ⁴ may further have one or more substituents, and the substituents include, for example, an alkyl group having 1 to 5 carbon atoms or a glycidyloxy group such as a phenyl group. A substitution contribution may also be made.

The compound represented by formula (3a) is preferably a phenolic novolak-type epoxy resin in which Ar ⁴ in formula (3a) is at least substituted with a glycidyloxy group. There is no particular limitation on the phenolic novolak-type epoxy resin, but examples include a compound represented by the following formula (3-1) (a multifunctional epoxy resin containing a naphthalene skeleton) or a naphthalene cresol novolak-type epoxy resin. I can hear it. Naphthalene cresol novolak-type epoxy resin is preferable from the viewpoint of superior mold release action for discharging cutting chips and further improving chemical resistance, copper foil adhesion, and insulation reliability.

[Formula 39]

In formula (3-1), Ar ³¹ each independently represents a benzene ring or a naphthalene ring, Ar ⁴¹ each independently represents a benzene ring, a naphthalene ring or a biphenyl ring, and R ^31a each independently represents represents a hydrogen atom or a methyl group, kz represents an integer of 1 to 50, and each ring has a substituent other than a glycidyloxy group (for example, an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, or phenyl group), and at least one of Ar ³¹ and Ar ⁴¹ represents a naphthalene ring.

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

[Formula 40]

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

The naphthalene cresol novolak type epoxy resin is not particularly limited, but for example, a cresol/naphthol novolak type epoxy resin represented by the following formula (NE) is preferable. In addition, the compound represented by (NE) below is a random copolymer of a structural unit of cresol novolac epoxy and a structural unit of naphthol novolak epoxy, and both cresol epoxy and naphthol epoxy can be terminals.

[Formula 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, but from the viewpoint of low thermal expansion, m:n (where m+n=100) is preferably 30 to 50:70 to 50, and 45 to 55:55. ~45 is more preferable.

As the naphthalene cresol novolak-type epoxy resin, a commercial 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" manufactured by Nippon Explosives Co., Ltd., and "HP-9540" and "HP-9500" manufactured by DIC Corporation. , “HP-9540” is particularly preferable.

The compound represented by formula (3a) may be a compound (hereinafter also referred to as “aralkyl type epoxy resin”) that does not correspond to the phenol novolac type epoxy resin described above.

Examples of the aralkyl type epoxy resin include compounds in which Ar ³ is a naphthalene ring and Ar ⁴ is a benzene ring in formula (3a) (also referred to as “naphthol aralkyl type epoxy resin”), and Ar ³ in formula (3a) It is preferable that it is a benzene ring and Ar ⁴ is a biphenyl ring (also referred to as “biphenyl aralkyl type epoxy resin”), and more preferably it is a biphenyl aralkyl type epoxy resin.

As the naphthol aralkyl type epoxy resin, a commercial product may be used, or a product manufactured by a known method may be used. Commercially available products include, for example, "HP-5000" and "HP-9900" manufactured by DIC Corporation, and "ESN-375" and "ESN-475" manufactured by Nittetsu Chemical Corporation.

It is preferable that the biphenyl aralkyl type epoxy resin is a compound represented by formula (3b).

[Formula 42]

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

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

As the biphenyl aralkyl type epoxy resin, a commercial product may be used, or a product manufactured by a known method may be used. Commercially available products include, for example, "NC-3000", "NC-3000L", and "NC-3000FH" manufactured by Nippon Explosives Co., Ltd.

Additionally, as the epoxy resin, it is preferable to use a naphthalene type epoxy resin (excluding those corresponding to the compound represented by formula (3a)). The naphthalene type epoxy resin is preferably a naphthylene ether type epoxy resin because it has a superior mold release effect for discharging cutting chips and further improves chemical resistance, copper foil adhesion, and insulation reliability.

The naphthylene ether type epoxy resin has a better mold release effect for discharging cutting powder, and from the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, a bifunctional epoxy compound represented by formula (3-3) or the following A polyfunctional epoxy compound represented by formula (3-4) or a mixture thereof is preferable.

[Formula 43]

In formula (3-3), R ₁₃ is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (for example, a vinyl group) , allyl group, or propenyl group).

[Formula 44]

In formula (3-4), R ₁₄ is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (for example, a vinyl group) , allyl group, or propenyl group).

As the naphthylene ether type epoxy resin, a commercial product may be used, or a product manufactured by a known method may be used. Commercial products of naphthylene ether type epoxy resin include, for example, “HP-6000”, “EXA-7300”, “EXA-7310”, “EXA-7311”, “EXA-7311L”, and “EXA7311-” manufactured by DIC Corporation. G3", "EXA7311-G4", "EXA-7311G4S", "EXA-7311G5", etc., and HP-6000 is especially preferable.

Examples of the naphthalene type epoxy resin other than those mentioned above include, but are not limited to, a compound represented by the following formula (b3).

[Formula 45]

In formula (b3), R ^3b each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group), an aralkyl group, a benzyl group, a naphthyl group, or at least one glycidyloxy group. It represents a naphthyl group containing or a naphthylmethyl group containing at least one glycidyloxy group, and n represents an integer of 0 or more (for example, 0 to 2).

Commercially available products of the compound represented by the above formula (b3) include, for example, “HP-4032” manufactured by DIC Corporation (n = 0 in the above formula (b3)) and “HP-4710” (in the above formula (b3)). where n = 0 and R ^3b is a naphthylmethyl group containing at least one glycidyloxy group).

Additionally, as the epoxy resin, dicyclopentadiene type epoxy resin can be used.

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

[Formula 46]

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

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

[Formula 47]

In formula (b4), R ^3c each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group).

The dicyclopentadiene type epoxy resin may be a commercially available product or a product manufactured by a known method. Commercially available products of dicyclopentadiene type epoxy resin include “EPICRON HP-7200L,” “EPICRON HP-7200,” “EPICRON HP-7200H,” and “EPICRON HP-7000HH” manufactured by Dainippon Ink Chemical Industry Co., Ltd. there is.

Among these, the epoxy resin has a more excellent mold release effect for discharging cutting chips, and from the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, the epoxy resin represented by formula (3a), the naphthalene type epoxy resin, and It is preferable that it is at least one type selected from the group consisting of dicyclopentadiene type epoxy resin, and it is more preferable that it contains naphthalene type epoxy resin. In this case, it is preferable that the epoxy resin represented by formula (3a) contains a naphthalene cresol novolak-type epoxy resin, and the naphthalene-type epoxy resin contains a cresol/naphthol novolak-type epoxy resin represented by the formula (NE). do.

The epoxy resin may contain other epoxy resins that do not correspond to the above-mentioned epoxy resins or epoxy compounds.

Other epoxy resins are not particularly limited, but include bisphenol-type epoxy resin, trisphenolmethane-type epoxy resin, anthracene-type epoxy resin, glycidyl ester-type epoxy resin, polyol-type epoxy resin, isocyanurate ring-containing epoxy resin, and fluoride-type epoxy resin. Examples include an orene-type epoxy resin and an epoxy resin composed of a bisphenol A-type structural unit and a hydrocarbon-based structural unit.

Among the above-described epoxy resins, bisphenol-type epoxy resins may be included from the viewpoint of superior mold release action for discharging cutting chips and further improving chemical resistance, copper foil adhesion, and insulation reliability. Bisphenol-type epoxy resins include, for example, diallylbisphenol-type epoxy resins (e.g., diallylbisphenol A-type epoxy resin, diallylbisphenol E-type epoxy resin, diallylbisphenol F-type epoxy resin, diallylbisphenol S) type epoxy resin, etc.) can be used.

As an epoxy resin, one type is used individually or in combination of 2 or more types among the above-mentioned epoxy resins and epoxy compounds.

The average number of epoxy groups per molecule of the epoxy resin is preferably 1 to 3, and more preferably 1.5 to 2.5, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. The average epoxy group number is calculated by the following formula.

[Equation 5]

In the above formula, Ci represents the epoxy group number of the epoxy resin having i epoxy groups in the molecule, Zi represents the ratio of the epoxy resin having i epoxy groups in the molecule to the entire epoxy resin, and Z ₁ + Z ₂ + . Z _n = 1.

The content of the epoxy resin as the thermosetting resin (C) is preferably set to 100 parts by mass of the resin solid content from the viewpoint of superior mold release action for discharging cuttings and further improving chemical resistance, copper foil adhesion, and insulation reliability. It is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass.

·Other resins

The thermosetting resin (C) may further contain other resins as long as it does not impair the effect in the resin composition of this embodiment. Other resins include, for example, oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group. These resins or compounds are. One type can be used individually or two or more types can be used in appropriate combination.

·Oxetane resin

Oxetane resins include, for example, alkyloxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, and 3-methyl- 3-methoxymethyloxetane, 3,3'-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, Toa Examples include “OXT-101” and “OXT-121” manufactured by Synthesis Co., Ltd.

·Benzoxazine compound

The term “benzoxazine compound” as used herein refers to a compound having two or more dihydrobenzoxazine rings in one molecule. Examples of the benzoxazine compound include "Bisphenol F-type benzoxazine BF-BXZ" and "Bisphenol S-type benzoxazine BS-BXZ" manufactured by Konishi Chemical Co., Ltd.

· Compounds having a polymerizable unsaturated group

Examples of the compound having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; Methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethyl (meth)acrylates of monohydric or polyhydric alcohols, such as allpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; Epoxy (meth)acrylates such as bisphenol A-type epoxy (meth)acrylate and bisphenol F-type epoxy (meth)acrylate; Benzocyclobutene resin, etc. can be mentioned.

<Inorganic Filler (D)>

The resin composition of the present embodiment contains an inorganic filler (D) different from the molybdenum compound (A) according to the present embodiment. When the resin composition contains an inorganic filler (D), heat resistance and low thermal expansion properties tend to be further improved.

Inorganic fillers (D) include, for example, silica, silicon compounds (e.g., white carbon, etc.), metal oxides (e.g., alumina, titanium white, titanium oxide, barium titanate, zinc oxide, magnesium oxide, zirconium oxide). etc.), metal nitrides (e.g. boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, etc.), metal sulfates (e.g. barium sulfate, etc.), metal hydroxides (e.g. aluminum hydroxide, aluminum hydroxide heating) Processed products (for example, aluminum hydroxide is heat treated to reduce some of the crystal water), boehmite, magnesium hydroxide, etc.), zinc compounds (for example, zinc borate, zinc tartrate, etc.), clay, kaolin, Talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fiber ( (including glass fine powders such as E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, spherical glass, etc. These inorganic fillers (D) are used individually or in combination of two or more types. Among these, the inorganic filler (D) has a superior mold release effect for discharging cutting chips, and from the viewpoint of further improving low thermal expansion properties, silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, It is preferable that it contains at least one type selected from the group consisting of barium titanate, magnesium oxide, and magnesium hydroxide, and it is more preferable that it contains silica.

Examples of silica include natural silica, fused silica, synthetic silica, aerosil, and hollow silica. These silicas are used individually or in combination of two or more types. Among these, fused silica is preferable from the viewpoint of dispersibility in the resin composition.

Silica may be a commercially available product or a product manufactured by a known method. Commercially available silica products include “SFP-130MC” manufactured by Denka Co., Ltd., “SC-2050MB”, “SC-1050MLE”, “YA010C-MFN”, and “YA050C-MJA” manufactured by Admatex Co., Ltd. can be mentioned.

The content of the inorganic filler (D) is preferably 40 to 600 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C) from the viewpoint of suppressing wear of the drill and further improving low thermal expansion properties. And, it is more preferable that it is 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 a silane coupling agent, the dispersibility of the inorganic filler (D) and the adhesive strength between the resin composition and the substrate described later tend to be further improved.

The silane coupling agent is not particularly limited and includes silane coupling agents generally used for surface treatment of inorganic materials. For example, aminosilane-based compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane-based compounds (e.g. , γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane-based compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane-based compounds (e.g., N-β-( N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrylsilane-based compounds, and phenylsilane-based compounds. Silane coupling agents are used individually or in combination of two or more types. Among these, it is preferable that the silane coupling agent is an epoxysilane-based compound. Examples of the epoxysilane-based 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, but may be 0.1 to 10 parts by mass per 100 parts by mass of the 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 wet dispersant, the dispersibility of the filler tends to be further improved.

The wet dispersant may be any known dispersant (dispersion stabilizer) used to disperse the filler, for example, DISPERBYK (registered trademark) -110, 111, 118, 180, 161, manufactured by Big Chemie Japan Co., Ltd. BYK (registered trademark) -W996, W9010, W903, etc. are mentioned.

The content of the wetting and dispersing agent is not particularly limited, but is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin solid content.

<Curing catalyst>

The resin composition of this embodiment may further contain a curing catalyst. Examples of the curing catalyst include an imidazole catalyst and a phosphorus-based catalyst. These catalysts are used individually or in combination of two or more types. Among these, imidazole catalysts are preferable.

Examples of the imidazole catalyst include the imidazole described above. Among them, from the viewpoint of preventing homopolymerization of the epoxy component, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole ( TPIZ (trade name), Tokyo Chemical Industry Co., Ltd.) is preferred.

The amount of the curing catalyst (preferably an imidazole catalyst) used is, for example, 0.1 to 10 parts by mass per 100 parts by mass of the resin solid content.

<Solvent>

The resin composition of this embodiment may further contain a solvent. By containing a solvent, the resin composition of the present embodiment tends to lower the viscosity at the time of preparation of the resin composition, further improve handling properties, or further improve impregnation into the substrate.

The solvent is not particularly limited as long as it can dissolve part or all of each component in the resin composition. For example, ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g. toluene, xylene, etc.), amides (e.g. dimethyl formaldehyde, etc.), propylene glycol monomethyl ether and its acetate. etc. can be mentioned. These solvents are used individually or in combination of two or more types.

[Method for producing resin composition]

The method for producing the resin composition of the present embodiment is not particularly limited, but examples include a method of mixing each of the above-described components in a solvent all at once or sequentially and stirring them. At this time, known processes such as stirring, mixing, and kneading are used to uniformly dissolve or disperse each component.

[Usage]

The resin composition of this embodiment can be suitably used as a cured product, prepreg, resin sheet, laminated board, metal foil-clad laminated board, and printed wiring board. Below, these will be explained.

[Hardened product]

The cured product is obtained by curing the resin composition of this embodiment. The method for producing the cured product is not particularly limited, and can be obtained, for example, by melting or dissolving the resin composition of the present embodiment in a solvent, pouring it into a mold, and curing it under conventional conditions using heat, light, etc. there is. In the case of thermal curing, the curing temperature is preferably within the range of 120 to 300°C from the viewpoint of efficiently progressing curing and preventing deterioration of the resulting cured product.

[Resin sheet]

The resin sheet of this embodiment has a support body and a resin layer disposed on one or both surfaces of the support body, and the resin layer contains the resin composition of this embodiment. The resin sheet may be formed, for example, by applying the resin composition of this embodiment to one side or both sides of a support. The resin sheet can be manufactured, for example, by applying and drying the resin composition (varnish) of this embodiment directly onto a support such as metal foil or film.

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

The resin sheet is obtained, for example, by applying the resin composition of this embodiment to a support and then semi-curing it (B-staging). As a method for producing a resin sheet, a method for producing a composite of a B-stage resin and a support is generally preferable. Specifically, for example, after applying the resin composition to a support such as copper foil, the resin composition is semi-cured by heating for 1 to 60 minutes in a dryer at 100 to 200° C. to produce a resin sheet. I can hear it. The adhesion amount of the resin composition to the support is preferably in the range of 1.0 to 300 μm in terms of the resin thickness of the resin sheet. The resin sheet can be used as a build-up material for a printed wiring board.

[Prepreg]

The prepreg of this embodiment includes a base material and the resin composition of this embodiment impregnated or applied to the base material. The method for forming the prepreg may be a known method. Specifically, the resin composition of the present embodiment is impregnated or applied to a substrate, followed by semi-curing by heating and drying under conditions of 100 to 200°C (B-staging). ) is obtained by:

The prepreg of this embodiment also includes the form of a cured product obtained by heat curing a prepreg in a semi-cured state under the conditions of 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 is preferably 30 to 90 volume%, more preferably 35 to 85 volume%, in terms of solid content of the prepreg, relative to the total amount of prepreg, and even more preferably It is 40 to 80 volume%. When the content of the resin composition is within the above range, moldability tends to be further improved. In addition, the solid content of the prepreg referred to here refers to the component from which the solvent has been removed from the prepreg, and for example, the 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.

Examples of the base material include known base materials used for materials of various printed wiring boards. For example, glass substrates, inorganic substrates other than glass (e.g., inorganic substrates made of inorganic fibers other than glass, such as quartz), organic substrates (e.g., wholly aromatic polyamide, polyester, polyparaphenylene) and organic substrates composed of organic fibers such as benzoxazole and polyimide. These base materials are used individually or in combination of two or more types. Among these, a glass substrate is preferable from the viewpoint of superior heat dimensional stability.

Examples of the fibers constituting the glass substrate include fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among these, the fibers constituting the glass substrate are selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass from the viewpoint of superior strength and low water absorption. It is preferable that at least one type of fiber is selected.

Examples of the substrate include woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, twill weave, twill weave, etc. are known, and these known weaves can be appropriately selected and used depending on the intended use or performance. In addition, glass woven fabrics that have been opened or surface-treated with a silane coupling agent or the like are preferably used. The thickness and mass of the base material are usually preferably around 0.01 to 0.1 mm.

[Metal foil clad laminate]

The metal foil-clad laminate of the present embodiment includes a laminate formed of at least one member selected from the group consisting of the resin sheet of the present embodiment and the prepreg of the present embodiment, and metal foil disposed on one or both surfaces of the laminate. do. The laminated body may be formed of one resin sheet or one prepreg, or may be formed of multiple resin sheets and/or multiple prepregs.

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

The forming method and conditions for forming the metal foil-clad laminate are not particularly limited, and general methods and conditions for laminates and multilayer boards for printed wiring boards can be applied. For example, when molding a laminate (the above-described laminate) or a metal foil-clad laminate, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used. In addition, in the molding (lamination molding) of a laminate (the above-mentioned laminate) or a metal foil-clad laminate, the temperature is 100 to 300 ° C., the pressure is in the range of 2 to 100 kgf / cm ² , and the heating time is in the range of 0.05 to 5 hours. is common. Additionally, if necessary, post-curing may be performed at a temperature of 150 to 300°C. In particular, when a multi-stage press machine is used, from the viewpoint of sufficiently promoting curing of the prepreg, a temperature of 200 to 250 ° C., a pressure of 10 to 40 kgf / cm ² , and a heating time of 80 to 130 minutes are preferable, and a temperature of 215 to 235 ° C. and a pressure of 80 to 130 minutes are preferable. 25 to 35 kgf/cm ² and a heating time of 90 to 120 minutes are more preferable. In addition, it is also possible to make a multilayer board by combining prepreg and a separately manufactured wiring board for the inner layer and lamination molding.

[Printed wiring board]

The printed wiring board of this embodiment has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer contains a cured product of the resin composition of this embodiment. The insulating layer is preferably formed from the resin sheet and/or prepreg of this embodiment. A printed wiring board can be formed, for example, by etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer.

A printed wiring board can be manufactured by, for example, the following method. 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 layer substrate having a conductor layer (inner layer circuit). Next, a predetermined number of prepregs and a metal foil for the outer layer circuit are laminated on the surface of the conductor layer (built-in circuit) of the inner layer substrate in this order, heated and pressed, and integrally molded (lamination molding) to obtain a laminate. In addition, the method of lamination molding and its molding conditions are the same as the method and molding conditions of lamination molding for the above-mentioned laminated board and metal foil-clad laminated board. Next, the laminate is subjected to hole drilling processing for through holes and via holes, and a plating metal film is formed on the wall of the hole thus formed to conduct the conductor layer (built-in circuit) and the metal foil for the outer layer circuit. . Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to produce an outer layer substrate with a conductor layer (outer layer circuit). In this way, a printed wiring board is manufactured.

In addition, when a metal foil-clad laminate is not used, a printed wiring board may be manufactured by forming a conductor layer that becomes a circuit on the insulating layer. At this time, electroless plating may be used to form the conductor layer.

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

Example

Hereinafter, this embodiment will be described in more detail using examples and comparative examples. This embodiment is not limited in any way by the examples below.

[Method for measuring weight average molecular weight (Mw)]

The weight average molecular weight (Mw) of the thermosetting compound was measured by GPC method as follows. 20 μL of a solution of 0.5 g of a thermosetting compound dissolved in 2 g of tetrahydrofuran (THF) was injected into high-performance liquid chromatography (Shimadzu Corporation, pump: LC-20AD (brand name)) for analysis. . The column is Shodex (registered trademark) GPC KF-804 (brand name, length 30 cm (registered trademark) GPC KF-802 (trade name, length 30 cm Use THF (solvent) and set the flow rate to 1 mL/min. , and the detector used was RID-10A (product name, differential refractive index detector, Shimadzu Corporation). The weight average molecular weight (Mw) was determined by GPC method using standard polystyrene as a standard material.

[Preparation Example 1] Synthesis of zinc ammonium molybdate hydrate ((NH ₄ )Zn ₂ MoO ₉ ·(H ₃ O))

0.015 mol (30.0 g) of ammonium molybdate and 0.105 mol (14.3 g) of zinc chloride were dissolved in 100 g of pure water. To this solution, 0.5 g of a 10 mol/L aqueous sodium hydroxide solution was added dropwise while stirring at 20°C to obtain a precipitate.

The resulting precipitate was filtered through a membrane filter and then dried at 120°C for 1 hour to obtain a white powder. As a result of _{analyzing the obtained} powder with _an

Subsequently, the obtained powder was subjected to pulverization using a jet mill grinder (Nissin Engineering Co., Ltd., Super Jet Mill SJ-500), and the powder obtained from the pulverization process was subjected to a laser diffraction/scattering type particle size distribution measuring device ( As a result of measurement with Microtrac MT3300EXII (brand name), the average particle diameter (D50 particle diameter) was 2.2 ㎛.

[Preparation Example 2] Preparation of powder of zinc ammonium molybdate hydrate (silica-coated zinc ammonium molybdate hydrate) whose surface is coated with 15 nm of silica.

In a container, 33 g of the powder of zinc ammonium molybdate hydrate (average particle diameter 2.2 μm) obtained in Production Example 1 was dispersed in 100 ml of ethanol, and the liquid temperature of the obtained dispersion was maintained at 55° C. by heating the container in an oil bath. To this, 6 g of silicon tetraethoxide and 6 g of aqueous ammonia (29% concentration) were added, and the mixture was allowed to react for 2 hours while stirring. Afterwards, it was dried and heat treated to adjust the film thickness to 15 nm. After that, it was diluted with ethanol, washed, filtered, and dried at 110°C for 3 hours using a vacuum dryer. After drying, heat treatment was performed at 650°C for 30 minutes using a rotary tube furnace to obtain silica-coated zinc ammonium molybdate hydrate powder (average particle diameter: 2.5 μm). The dispersion state of the obtained silica-coated zinc ammonium molybdate hydrate powder was very good.

[Synthesis Example 1] Synthesis of 1-naphthol aralkyl type cyanate ester compound (SN495V-CN)

300 g of α-naphthol aralkyl type phenol resin (SN495V, OH group equivalent: 236 g/mol, manufactured by Nippon Chemical Co., Ltd.) in which all R ^2a in the formula (2b) is a hydrogen atom (hydroxyl group ( OH group (1.28 mol) and 194.6 g (1.92 mol) of triethylamine (1.5 mol per 1 mol of hydroxy group) were dissolved in 1800 g of dichloromethane to prepare Solution 1. 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per 1 mol of hydroxyl group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of hydroxyl group), and 1205.9 g of water. Solution 1 was poured over 30 minutes while stirring and maintaining the liquid temperature at -2 to -0.5°C. After completing the addition of solution 1, stirring at the same temperature for 30 minutes, a solution (solution 2) prepared by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol for 1 mol of hydroxyl group) in 65 g of dichloromethane was added. The injection was administered over 10 minutes. After completion of adding solution 2, the reaction was completed by stirring at the same temperature for 30 minutes. Afterwards, the reaction solution was left alone to separate the organic phase and the aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater after the 5th washing with water was 5 μS/cm, and it was confirmed that ionic compounds that can be removed by washing with water were sufficiently removed. The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90°C for 1 hour to obtain the target 1-naphthol aralkyl type cyanate ester compound (SN495V-CN, cyanate ester group equivalent: 261 g/ mol) (orange viscous substance) 331 g was obtained. The obtained infrared absorption spectrum of SN495V-CN showed absorption at 2250 cm ^-1 (cyanic acid ester group) and did not show absorption of the hydroxy group.

[Example 1]

(Preparation of polymer (B1))

Maleimide compound (maleimide group equivalent weight 285 g/mol, BMI-80 (brand name), K.I Chemical Co., Ltd.) 14 parts by mass is heated to reflux with 40 parts by mass of propylene glycol monomethyl ether (KH Neochem Co., Ltd.) In a solution dissolved under conditions of a temperature of 130°C, 10 parts by mass of diamino-modified silicone (amino group equivalent 1500 g/mol, A polymer was prepared. After that, stirring was continued under the condition of a heating-reflux temperature of 130°C, and when the viscosity of the solution containing the primary polymer increased to 200 to 300 mPa·s using an ICI viscometer (cone plate type viscometer, manufactured by Towa Kogyo Co., Ltd.), To this solution, a solution prepared by dissolving 1.0 parts by mass of succinic anhydride (manufactured by Tokyo Chemical Company) in 22.5 parts by mass of propylene glycol monoethyl ether acetate (manufactured by Dow Chemical Company) was added, under the condition of a heating-reflux temperature of 130°C. The reaction was conducted for several hours to obtain a solution containing polymer (B1), which is a thermosetting compound (B).

It was confirmed that the obtained polymer (B1) contained a maleimide group and a polysiloxane structure in the molecule.

In addition, it was confirmed that the polymer (B1) contains a structural unit derived from amino-modified silicone and a structural unit derived from a maleimide compound.

In addition, based on JIS K 7237:1995, the total amount of primary amine and secondary amine in polymer (B1) was measured, and the amine value of polymer (B1) was 0.1 mgKOH/g.

Additionally, the weight average molecular weight (Mw) of polymer (B1) was measured by the method described above and was found to be 12000 in terms of polystyrene in the GPC method.

(Manufacture of prepreg)

25 parts by mass of the obtained polymer (B1) (solid content conversion), 35 parts by mass of a maleimide compound (maleimide group equivalent 186 g/mol, BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd.), and biphenyl aralkyl 8 parts by mass of type epoxy resin (NC-3000H (trade name), Nippon Kayak Co., Ltd.), and an alkenyl-substituted nadimide compound (alkenyl group equivalent weight 286 g/mol, BANI-M (trade name), Maruzen Petrochemical Co., Ltd. )) 32 parts by mass, 3 parts by mass of the powder of the silica-coated zinc ammonium molybdate hydrate obtained in Production Example 2, 200 parts by mass of slurry silica (SC-2050MB (trade name), Admatex Co., Ltd.), and epoxysilane 5 parts by mass of coupling agent (KBM-403 (brand name), Toray Dow Coating Co., Ltd.), 1 part by mass of wetting and dispersing agent (DISPERBYK-161 (brand name), Big Chemie Japan Co., Ltd.), 2, 4, 1 part by mass of 5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with methyl ethyl ketone as a solvent to obtain a varnish (resin composition). This varnish was impregnated and coated on S glass woven fabric (thickness 100 µm) and dried by heating at 150°C for 3 minutes to obtain a prepreg with a solid content (including filler) of the resin composition of 46% by mass.

(Manufacture of metal foil clad laminate)

Four sheets of the obtained prepreg were overlapped to obtain a laminate. Electrolytic copper foil (3EC-III, manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 μm was placed on both sides of this laminate, and vacuum pressing was performed at a pressure of 30 kgf/cm ² , 220° C., and 120 minutes for lamination molding. By doing so, a metal foil-clad laminate (double-sided copper-clad laminate) with an insulating layer thickness of 0.8 mm was produced.

[Example 2]

A prepreg was prepared in the same manner as in Example 1, except that 3 parts by mass of the powder of the silica-coated zinc ammonium molybdate hydrate obtained in Preparation Example 2 was used instead of 3 parts by mass of the powder of the silica-coated zinc ammonium molybdate hydrate obtained in Preparation Example 1. got it

Using the obtained prepreg, a metal foil-clad laminate (double-sided copper-clad laminate) with an insulating layer thickness of 0.8 mm was produced in the same manner as in Example 1.

[Example 3]

(Preparation of polymer (B2))

In a three-necked flask equipped with a thermometer and a dimrot, 5.3 parts by mass of diallylbisphenol A (DABPA (trade name), Daiwa Chemical Industry Co., Ltd.), biscresol fluorene (BCF (trade name), Osaka Gas Chemical Co., Ltd.) 5.8 parts by mass, epoxy-modified silicone b1 (X-22-163 (trade name), Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g/mol) 4.4 parts by mass, epoxy-modified silicone b2 (KF-105 (trade name), Shin-Etsu Chemical Co., Ltd. Kogyo Co., Ltd., functional group equivalent weight 490 g/mol) 8.7 parts by mass, biphenyl-type epoxy compound c1 (YL-6121H (trade name), Mitsubishi Chemical Co., Ltd.) 5.8 parts by mass, propylene glycol monomethyl ether acetate (DOWANOL) as solvent 30 parts by mass of PMA (trade name), Dow Chemical Japan Co., Ltd.) was added, and the mixture was 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, a solution (solid content: 50% by mass) containing polymer (B2), which is a thermosetting compound (B), was obtained. It was also used in the preparation of polymer (B2).

In addition, diallylbisphenol A corresponds to “alkenylphenol,” epoxy-modified silicone b1 and epoxy-modified silicone b2 correspond to “epoxy-modified silicone,” and biphenyl-type epoxy compound c1 corresponds to “epoxy compound C.” Equivalent to

It was confirmed that the obtained polymer (B2) contained an epoxy group, a hydroxy group, and a polysiloxane structure in the molecule.

In addition, it was confirmed that polymer (B2) contains structural units derived from alkenylphenol, structural units derived from epoxy modified silicone, structural units derived from epoxy compounds, and structural units derived from phenol compounds. .

Additionally, the content of structural units derived from epoxy-modified silicone in polymer (B2) was 43.5 mass%.

Additionally, the content of the structural unit derived from the epoxy compound relative to the total mass (100 mass%) of the structural units derived from the epoxy modified silicone and the structural units derived from the epoxy compound was 30.8 mass%.

Additionally, the alkenyl group equivalent weight in polymer (B2) was 872 g/mol.

The weight average molecular weight (Mw) of polymer (B2) was 11900 in terms of polystyrene according to the GPC method.

(Manufacture of prepreg)

To 30 parts by mass (in terms of solid content) of the solution containing the obtained polymer (B2), 26 parts by mass of the 1-naphthol aralkyl type cyanate compound obtained in Synthesis Example 1 and a novolac type maleimide compound (BMI-2300 ( Product name), Daiwa Chemical Industry Co., Ltd.) 17 parts by mass, naphthalene cresol novolac type epoxy resin (epoxy group (functional group) equivalent weight: 244 g/eq, HP-9540 (product name), DIC Co., Ltd.) 27 parts by mass , 3 parts by mass of the powder of the silica-coated zinc ammonium molybdate hydrate obtained in Production Example 2, 200 parts by mass of slurry silica (SC-2050MB (trade name), Admatex Co., Ltd.), and an epoxy silane coupling agent (KBM-403) (brand name), Toray Dow Coating Co., Ltd.) 5 parts by mass, wetting and dispersing agent (DISPERBYK-161 (brand name), Big Chemi Japan Co., Ltd.) 1 part by mass, and 2,4,5-triphenyl imida 0.5 parts by mass of sol (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with methyl ethyl ketone as a solvent to obtain a varnish (resin composition). This varnish was impregnated and coated on S glass woven fabric (thickness 100 µm) and dried by heating at 150°C for 3 minutes to obtain a prepreg with a solid content (including filler) of the resin composition of 46% by mass.

(Manufacture of metal foil clad laminate)

Four sheets of the obtained prepreg were overlapped to obtain a laminate. Electrolytic copper foil (3EC-III, manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 ㎛ is placed on both sides of this laminate, and vacuum pressed at a pressure of 30 kgf/cm ² at 220° C. for 120 minutes to form a laminate. , a metal foil-clad laminate (double-sided copper-clad laminate) with an insulating layer thickness of 0.8 mm was produced.

[Comparative Example 1]

(Manufacture of prepreg)

Bismaleimide compound (BMI-70 (trade name), K.I Chemical Co., Ltd.) 21.2 parts by mass, naphthalene type phenol resin (HPC-9500-60M (trade name), DIC Co., Ltd.) 16.8 parts by mass, ratio 16.8 parts by mass of phenyl aralkyl type phenol resin (GPH-103 (trade name), Nippon Kayak Co., Ltd.), and 42.2 parts by mass of biphenyl aralkyl type epoxy resin (NC-3000H (trade name), Nippon Kayak Co., Ltd.) , 5 parts by mass of talc powder (average particle diameter 3 μm, KEMGARD911C, manufactured by Sherwin Williams) whose surface was coated with zinc molybdate, 3 parts by mass of powder of zinc ammonium molybdate hydrate obtained in Production Example 1, and slurry silica (SC) -2050MB (trade name), 120 parts by mass of Admatex Co., Ltd.), 5 parts by mass of epoxysilane coupling agent (KBM-403 (trade name), Toray Dow Coating Co., Ltd.), and wetting and dispersing agent (DISPERBYK-161 ( 1 part by mass of (brand name), Big Chemie Japan Co., Ltd.), 0.5 parts by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and methyl ethyl ketone as a solvent were mixed to prepare a varnish (resin). composition) was obtained. This varnish was impregnated and coated on S glass woven fabric (thickness 100 µm) and dried by heating at 150°C for 3 minutes to obtain a prepreg with a solid content (including filler) of the resin composition of 46% by mass.

(Manufacture of metal foil clad laminate)

Four sheets of the obtained prepreg were overlapped to obtain a laminate. Electrolytic copper foil (3EC-III, manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 ㎛ is placed on both sides of this laminate, and vacuum pressed at a pressure of 30 kgf/cm ² at 220° C. for 120 minutes to form a laminate. , a metal foil-clad laminate (double-sided copper-clad laminate) with an insulating layer thickness of 0.8 mm was produced.

[Comparative Example 2]

(Manufacture of prepreg)

37 parts by mass of the 1-naphthol aralkyl type cyanate compound obtained in Synthesis Example 1, 24 parts by mass of a novolak type maleimide compound (BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd.), and naphthalene cresol 39 parts by mass of rock-type epoxy resin (epoxy group (functional group) equivalent: 244 g/eq, HP-9540 (brand name), DIC Co., Ltd.) and 3 parts by mass of powder of silica-coated zinc ammonium molybdate hydrate obtained in Production Example 2 200 parts by mass of slurry silica (SC-2050MB (trade name), Admatex Co., Ltd.), 15 parts by mass of silicon composite powder (KMP-605 (trade name), Shin-Etsu Chemical Co., Ltd.), and an epoxy silane couple. Ringing agent (KBM-403 (brand name), Toray Dow Coating Co., Ltd.) 5 parts by mass, wetting and dispersing agent (DISPERBYK-161 (brand name), Big Chemi Japan Co., Ltd.) 1 part by mass, 2, 4, 5 -0.5 parts by mass of triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with methyl ethyl ketone as a solvent to obtain a varnish (resin composition). This varnish was impregnated and coated on S glass woven fabric (thickness 100 µm) and dried by heating at 150°C for 3 minutes to obtain a prepreg with a solid content (including filler) of the resin composition of 46% by mass.

(Manufacture of metal foil clad laminate)

Four sheets of the obtained prepreg were overlapped to obtain a laminate. Electrolytic copper foil (3EC-III, manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 ㎛ is placed on both sides of this laminate, and vacuum pressed at a pressure of 30 kgf/cm ² at 220° C. for 120 minutes to form a laminate. , a metal foil-clad laminate (double-sided copper-clad laminate) with an insulating layer thickness of 0.8 mm was produced.

[Comparative Example 3]

Except that the powder of the silica-coated zinc ammonium molybdate hydrate obtained in Production Example 2 was not used, and 25 parts by mass of silicon composite powder (KMP-605 (trade name), Shin-Etsu Chemical Co., Ltd.) was added instead of 15 parts by mass. A prepreg was obtained in the same manner as in Comparative Example 2.

Using the obtained prepreg, a metal foil-clad laminate (double-sided copper-clad laminate) with an insulating layer thickness of 0.8 mm was produced in the same manner as in Comparative Example 2.

[Comparative Example 4]

A prepreg was obtained in the same manner as in Example 1, except that the powder of the silica-coated zinc ammonium molybdate hydrate obtained in Production Example 2 was not used.

Using the obtained prepreg, a metal foil-clad laminate (double-sided copper-clad laminate) with an insulating layer thickness of 0.8 mm was produced in the same manner as in Example 1.

〔evaluation〕

Using the metal foil-clad laminates obtained in Examples and Comparative Examples, drill workability was evaluated by the following method. The results are shown in Table 1.

(Drill machinability)

Drill workability (hole position accuracy) was evaluated using the metal foil-clad laminates obtained in the examples and comparative examples. The evaluation was conducted under the following drilling conditions. The results are shown in Table 1.

Entry sheet (LE R12F3 (product name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 3 sheets of metal foil-clad laminate (base thickness & stack: 0.8 mm × 3), and backing board (SPB-W (product name) manufactured by Nippon Decorax Co., Ltd. ) were stacked in this order, drilling was performed using a processing machine (ND-1 V212 (trade name) manufactured by Hitachi Via Mechanics Co., Ltd.) under the following conditions, and the amount of positional deviation of the drilled hole was measured. This positional deviation amount was set as the positional deviation amount on the back side of the lowest metal foil clad laminate among three metal foil clad laminates processed by stacking them. In addition, the amount of positional deviation is measured for all holes processed per drill, and the measurement results in Table 1 show the average value of the amount of positional deviation + 3σ (σ represents the standard deviation value).

(processing conditions)

Drill bit: MC L692BWU manufactured by Union Tool Co., Ltd. (Product name) 0.15 mm × 2.7 mm

Bit diameter: 0.15 mm

Rotation speed: 160 krpm

Feed speed: 1.6 m/min

Retraction speed: 25.4 m/min

Injection amount: 0.3 mm

Number of holes processed: 5000 (hit) or 10000 (hit)

This application is based on a Japanese patent application (Japanese Patent Application No. 2021-128685) filed on August 5, 2021, the contents of which are hereby incorporated by reference.

According to the present invention, it is possible to provide a resin composition suitably used in the production of resin sheets and prepregs with excellent drillability, and resin sheets, prepregs, metal foil-clad laminates, and printed wiring boards obtained by using the resin composition. .

Claims (29)

Molybdenum compound (A) and,
A thermosetting compound (B) comprising at least one group selected from the group consisting of a maleimide group, an amino group, an epoxy group, a carboxyl group, a vinyl group, a hydroxy group, and a (meth)acrylic group, and a polysiloxane structure,
A thermosetting resin (C) different from the thermosetting compound (B),
A resin composition containing an inorganic filler (D) different from the molybdenum compound (A). According to claim 1,
The molybdenum compound (A) is a group consisting of molybdate, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate hydrate. A resin composition containing at least one member selected from the following. According to claim 1,
A resin composition in which the thermosetting compound (B) contains the maleimide group. According to claim 1,
A resin composition in which the thermosetting compound (B) contains at least a structural unit derived from amino-modified silicone and a structural unit derived from a maleimide compound. According to claim 1,
A resin composition in which the thermosetting compound (B) is a polymer obtained by polymerizing at least an amino-modified silicone, a maleimide compound, and carboxylic acid and/or carboxylic acid anhydride. According to claim 4,
A resin composition in which the amino-modified silicone contains amino-modified silicone represented by the following formula (1).

(In formula (1), R _a each independently represents a hydrogen atom, an alkyl group or a phenyl group, R _b each independently represents a single bond, an alkylene group or an arylene group, and n is an integer of 1 to 100. represents.) According to claim 1,
The molybdenum compound (A) is a group consisting of molybdate, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate hydrate. Contains at least one species selected from,
The thermosetting compound (B) contains the maleimide group,
The thermosetting compound (B) further contains at least a structural unit derived from amino-modified silicone and a structural unit derived from a maleimide compound,
A resin composition in which the amino-modified silicone contains amino-modified silicone represented by the following formula (1).

(In formula (1), R _a each independently represents a hydrogen atom, an alkyl group or a phenyl group, R _b each independently represents a single bond, an alkylene group or an arylene group, and n is an integer of 1 to 100. represents.) According to claim 1,
A resin composition in which the thermosetting compound (B) contains the epoxy group and/or the hydroxy group. According to claim 1,
A resin composition in which the thermosetting compound (B) contains at least a structural unit derived from alkenylphenol, a structural unit derived from epoxy-modified silicone, and a structural unit derived from an epoxy compound other than the epoxy-modified silicone. According to claim 1,
A resin composition in which the thermosetting compound (B) is a polymer obtained by polymerizing at least an alkenylphenol, an epoxy-modified silicone, and an epoxy compound other than the epoxy-modified silicone. According to claim 8,
A resin composition in which the epoxy-modified silicone contains epoxy-modified silicone represented by the following formula (2).

(In formula (2), R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n represents an integer from 0 to 100.) According to claim 1,
The molybdenum compound (A) is a group consisting of molybdate, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate hydrate. Contains at least one species selected from,
The thermosetting compound (B) contains the epoxy group and/or the hydroxy group,
The thermosetting compound (B) further comprises at least a structural unit derived from alkenylphenol, a structural unit derived from epoxy-modified silicone, and a structural unit derived from an epoxy compound other than the epoxy-modified silicone,
A resin composition in which the epoxy-modified silicone contains epoxy-modified silicone represented by the following formula (2).

(In formula (2), R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n represents an integer from 0 to 100.) According to claim 1,
A resin composition in which the thermosetting resin (C) contains at least one member selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound, an alkenyl substituted nadimide compound, and an epoxy resin. According to claim 13,
A resin composition in which the thermosetting resin (C) contains a maleimide compound. According to claim 14,
The maleimide compound is bis(4-maleimidephenyl)methane, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-malei) A resin composition containing at least one member selected from the group consisting of midphenyl)methane, polytetramethylene oxide-bis(4-maleimide benzoate), and a maleimide compound 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.) According to claim 14,
A resin composition in which the maleimide compound contains a maleimide compound represented by the following formula (9).

(In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer from 1 to 10.) According to claim 1,
A resin wherein the inorganic filler (D) contains at least one member selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide. Composition. According to claim 1,
A resin composition in which the content of the molybdenum compound (A) is 0.1 to 30 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). According to claim 1,
A resin composition in which the content of the thermosetting compound (B) is 5 to 50 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). According to claim 1,
A resin composition in which the content of the thermosetting resin (C) is 50 to 95 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). According to claim 1,
A resin composition in which the content of the inorganic filler (D) is 40 to 600 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). According to claim 7,
The thermosetting resin (C) contains at least one member selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound, an alkenyl substituted nadimide compound, and an epoxy resin,
The thermosetting resin (C) contains a maleimide compound,
The maleimide compound is bis(4-maleimidephenyl)methane, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-malei) At least one selected from the group consisting of midphenyl)methane, polytetramethylene oxide-bis(4-maleimide benzoate), a maleimide compound represented by the following formula (4), and a maleimide compound represented by the following formula (9) Includes species,
The inorganic filler (D) contains at least one member selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide,
The content of the molybdenum compound (A) is 0.1 to 30 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C),
The content of the thermosetting compound (B) is 5 to 50 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C),
The content of the thermosetting resin (C) is 50 to 95 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C),
A resin composition in which the content of the inorganic filler (D) is 40 to 600 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C).

(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.)

(In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer from 1 to 10.) According to claim 12,
The thermosetting resin (C) contains at least one member selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound, an alkenyl substituted nadimide compound, and an epoxy resin,
The thermosetting resin (C) contains a maleimide compound,
The maleimide compound is bis(4-maleimidephenyl)methane, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-malei) At least one selected from the group consisting of midphenyl)methane, polytetramethylene oxide-bis(4-maleimide benzoate), a maleimide compound represented by the following formula (4), and a maleimide compound represented by the following formula (9) Includes species,
The inorganic filler (D) contains at least one member selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide,
The content of the molybdenum compound (A) is 0.1 to 30 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C),
The content of the thermosetting compound (B) is 5 to 50 parts by mass based on a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C),
The content of the thermosetting resin (C) is 50 to 95 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C),
A resin composition in which the content of the inorganic filler (D) is 40 to 600 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C).

(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.)

(In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer from 1 to 10.) A support body,
It has a resin layer disposed on one or both sides of the support,
A resin sheet in which the resin layer contains the resin composition according to any one of claims 1 to 23. With equipment,
A prepreg comprising the resin composition according to any one of claims 1 to 23, impregnated or applied to the substrate. A laminate formed from the resin sheet according to claim 24,
A metal foil-clad laminate comprising metal foil disposed on one or both sides of the laminate. A laminate formed from the prepreg according to claim 25,
A metal foil-clad laminate comprising metal foil disposed on one or both sides of the laminate. A laminate formed from the resin sheet according to claim 24 and the prepreg according to claim 25,
A metal foil-clad laminate comprising metal foil disposed on one or both sides of the laminate. an insulating layer,
It has a conductor layer formed on one or both sides of the insulating layer,
A printed wiring board in which the insulating layer contains a cured product of the resin composition according to any one of claims 1 to 23.