WO2023013709A1

WO2023013709A1 - Resin composition, resin sheet, prepreg, metal foil-clad laminate, and printed wiring board

Info

Publication number: WO2023013709A1
Application number: PCT/JP2022/029869
Authority: WO
Inventors: 克哉富澤; 翔平山口; 尚義金子; 博史高橋
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2021-08-05
Filing date: 2022-08-04
Publication date: 2023-02-09
Also published as: KR20240040058A; JPWO2023013709A1; TW202313834A; CN117795016A

Abstract

A purpose of the present invention is to provide: a resin composition that can be used suitably in the production of a resin sheet and prepreg having excellent drillability; and a resin sheet, a prepreg, a metal foil-clad laminate, and a printed wiring board obtained using the resin composition. The resin composition of the present invention includes: a molybdenum compound (A); a thermally curable compound (B) that includes a polysiloxane structure and 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; a thermally curable resin (C) different from the thermally curable 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.

In recent years, semiconductor packages, which are widely used in electronic devices, communication devices, personal computers, etc., are becoming more highly integrated, highly functional, and highly densely mounted. Along with this, various characteristics required for printed wiring boards for semiconductor packages are becoming more and more severe. Such properties include coefficient of thermal expansion, drillability, heat resistance, flame retardancy, etc. Among them, the demand for excellent drillability is increasing in order to realize higher density mounting. ing.

In this regard, Patent Document 1 describes a resin composition for printed wiring boards containing a molybdenum compound. Moreover, it is described that the 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 (chips) generated during drilling. There are problems such as deterioration of drilling workability, such as deterioration of hole position accuracy, accelerated wear of the drill bit, increasing the frequency of replacement of the drill bit, and increased susceptibility to breakage of the drill bit. Further, there is a problem that the inner diameter of the machined hole becomes uneven due to wear of the drill bit, and furthermore, delamination occurs due to the unevenness of the inner diameter.

The present invention has been made to solve the above-described problems, and includes a resin composition that is suitably used for producing a resin sheet and a prepreg that are excellent in drillability, and a resin sheet that is obtained using the resin composition. , prepregs, metal foil-clad laminates, and printed wiring boards.

That is, the present invention is as follows.
[1] 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 a thermosetting compound (B) comprising a structure, a thermosetting resin (C) different from the thermosetting compound (B), an inorganic filler (D) different from the molybdenum compound (A), A resin composition comprising:

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

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

[4] The resin according to any one of [1] to [3], wherein the thermosetting compound (B) contains at least structural units derived from an amino-modified silicone and structural units derived from a maleimide compound. Composition.

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

[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).

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

[7] The molybdenum compound (A) includes molybdic acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdenum hydrate, and molybdenum. containing at least one selected from the group consisting of zinc acid ammonium hydrate, the thermosetting compound (B) containing the maleimide group, and the thermosetting compound (B) containing at least an amino-modified silicone and a structural unit derived from a maleimide compound, wherein the amino-modified silicone comprises an 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; each R _b independently represents a single bond, an alkylene group, or an arylene group; n is represents an integer from 1 to 100).

[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 the resin composition according to any one of [9].

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

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

[12] The molybdenum compound (A) contains molybdic acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdic acid hydrate, and molybdenum. containing at least one selected from the group consisting of ammonium zincate hydrate, the thermosetting compound (B) containing the epoxy group and/or the hydroxy group, and the thermosetting compound (B) containing further comprising at least a structural unit derived from an alkenylphenol, a structural unit derived from an epoxy-modified silicone, and a structural unit derived from an epoxy compound other than the epoxy-modified silicone, wherein the epoxy-modified silicone has the following formula ( The resin composition according to [1], which contains the epoxy-modified silicone represented by 2).

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

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

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

[15] The maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl ) The resin composition according to [14], which contains at least one selected from the group consisting of methane, polytetramethylene oxide-bis(4-maleimidobenzoate), and a maleimide compound represented by the following formula (4): .

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

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

(In formula (9), each R ¹³ 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.).

[17] At least the inorganic filler (D) is 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], including one.

[18] 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). [1] The resin composition according to any one of [17].

[19] The content of the thermosetting compound (B) is 5 to 50 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). [1] The resin composition according to any one of [18].

[20] 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). [1] The resin composition according to any one of [19].

[21] 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). 1] The resin composition according to any one of [20].

[22] The thermosetting resin (C) contains at least one selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, alkenyl-substituted nadimide compounds, and epoxy resins, and the thermosetting resin (C) contains a maleimide compound, and the maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3-ethyl-5 -methyl-4-maleimidophenyl)methane, polytetramethylene oxide-bis(4-maleimidobenzoate), a maleimide compound represented by the following formula (4), and a maleimide compound represented by the following formula (9). and the inorganic filler (D) is selected from silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide. containing at least one selected from the group consisting of, the content of the molybdenum compound (A) is 0 with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C) .1 to 30 parts by mass, and the content of the thermosetting compound (B) is 5 to 5 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C) 50 parts by mass, and 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). and 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), [ 7].

[23] The thermosetting resin (C) contains at least one selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, alkenyl-substituted nadimide compounds, and epoxy resins, and the thermosetting resin (C) contains a maleimide compound, and the maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3-ethyl-5 -methyl-4-maleimidophenyl)methane, polytetramethylene oxide-bis(4-maleimidobenzoate), a maleimide compound represented by the following formula (4), and a maleimide compound represented by the following formula (9). and the inorganic filler (D) is selected from silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide. containing at least one selected from the group consisting of, the content of the molybdenum compound (A) is 0 with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C) .1 to 30 parts by mass, and the content of the thermosetting compound (B) is 5 to 5 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C) 50 parts by mass,
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), and the inorganic filling The content of the material (D) is 40 to 600 parts by mass with respect to the total 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). The resin according to [12]. Composition.

[24] 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]. resin sheet.

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

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

[27] A metal foil clad laminate comprising a laminate formed of the prepreg described in [25] and a metal foil disposed on one side or both sides of the laminate.

[28] A metal foil clad laminate comprising a laminate formed of the resin sheet of [24] and the prepreg of [25], and a metal foil disposed on one or both sides of the laminate. board.
A laminate formed of at least one selected from the group consisting of the resin sheet according to [24] and the prepreg according to [25], a metal foil disposed on one side or both sides of the laminate, A metal foil clad laminate comprising:

[29] It has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer is a cured product of the resin composition according to any one of [1] to [23]. printed wiring boards, including;

According to the resin composition of the present invention, it is possible to provide resin sheets, prepregs, metal foil-clad laminates, and printed wiring boards that are excellent in drillability.

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

"(Meth)acryl" in this specification means both "acryl" and "methacryl" corresponding thereto. Further, in the present embodiment, unless otherwise specified, the "resin solid content" or "resin solid content in the resin composition" refers to the components of the resin composition excluding additives, solvents, and fillers. The phrase "100 parts by mass of resin solids" means that the total amount of components in the resin composition excluding additives, solvents, and fillers is 100 parts by mass. In addition, "100% by mass of resin solid content" means that the total amount of components excluding additives, solvents, and fillers in the resin composition is 100% by mass. In addition, a molybdenum compound (A) and an inorganic filler (D) are contained in a filler.

[Resin composition]
The resin composition of the present embodiment includes a molybdenum compound (A) and 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)acrylic group. A thermosetting compound (B) containing a group and a polysiloxane structure, a thermosetting resin (C) different from the thermosetting compound (B), and an inorganic filler different from the molybdenum compound (A) ( D) and

<Molybdenum compound (A)>
The resin composition of this embodiment contains a molybdenum compound (A). By including the molybdenum compound (A) in the resin composition, the drillability of resin sheets, prepregs, metal foil-clad laminates, etc. obtained using the resin composition is improved, and good hole quality is achieved. can be obtained, and the life of drilling can be extended.

The present inventors presume as follows about the reason why the resin sheet, prepreg, metal foil-clad laminate, and the like have excellent drillability by using the resin composition of the present embodiment. That is, due to the lubricity exhibited by the molybdenum compound (A) and the mold-releasing action derived from the polysiloxane structure of the thermosetting compound (B), the chips generated during drilling do not form lumps, etc., and are smooth. discharged to In addition, 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. have. Therefore, even if frictional heat is generated during drilling, the molybdenum compound (A) and the thermosetting compound (B) that make up the hardened material do not thermally decompose, and the gap between the cutting edge of the tool and the workpiece to be cut does not decompose. It is possible to maintain the lubricating action that reduces the frictional force and the releasing action that discharges chips. As a result, it is possible to prevent wear and breakage of the drill bit caused by the drill bit stepping on chips such as clumps. In addition, it is presumed that the synergistic effect of these factors improves the biting ability of the drill bit to the workpiece, and improves the centripetal property of the drill bit, thereby improving the hole position accuracy.

The molybdenum compound (A) is not particularly limited as long as it contains molybdenum in its molecule. _For example, molybdic acid, zinc molybdate such as _ZnMoO4 and _Zn3Mo2O9 , ammonium _molybdate , sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate hydrates such as (NH ₄ )Zn ₂ Mo ₂ O _9. (H ₃ O). These compounds can be used individually by 1 type or in combination of 2 or more types as appropriate.
Among these, molybdic acid, zinc molybdate, and zinc ammonium molybdate hydrate are preferable because they do not act as an organometallic catalyst and because better drill workability and thermal stability can be obtained.

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

The average particle size (D50) of the molybdenum compound (non-supported type) is preferably 0.1 to 10 μm, more preferably 0.5 to 8 μm, from the viewpoint of dispersibility in the resin composition and drill workability. , more preferably 1 to 4 μm, still more preferably 1 to 3 μm. In the present embodiment, the average particle diameter (D50) means the median diameter, and is a value in which the larger side and the smaller side are equal when the measured particle size distribution of the powder is divided into two. The average particle size (D50) is obtained by measuring the particle size distribution of a powder put in a predetermined amount in a dispersion medium with a laser diffraction scattering type particle size distribution measuring device, and 50% of the total volume by volume integration from small particles. means the value when it reaches

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 core particles made of a molybdenum compound. The inorganic oxide may be applied to at least part of the surface of the core particles. The inorganic oxide may be partially applied to the surfaces of the core particles, or may be applied so as to cover the entire surfaces of the core particles. From the viewpoint of both drilling workability and heat resistance, the inorganic oxide is uniformly applied so as to cover the entire surface of the core particle, that is, the inorganic oxide film is uniformly formed on the surface of the core particle. preferably.

Examples of the surface-treated molybdenum particles (supported type) include those obtained by surface-treating the molybdenum compound particles described above using a silane coupling agent, or those obtained by a method such as a sol-gel method or a liquid phase deposition method. Examples include those obtained by treating the surface with an inorganic oxide. In the surface-treated molybdenum particles having an inorganic oxide formed on the surface, the inorganic oxide acts effectively against heat, and the molybdenum compound acts effectively against drilling. Therefore, it is possible to achieve a high degree of compatibility between the two contradictory properties of drillability and heat resistance.

As the inorganic oxide, one having excellent heat resistance is preferable, and the type thereof is not particularly limited, but a metal oxide is more preferable. Examples _of metal oxides include _SiO2 , _Al2O3 , _TiO2 , ZnO, _In2O3 , _SnO2 , NiO, CoO, _V2O5 , CuO, MgO _, _and _ZrO2 . These can be used individually by 1 type or in combination of 2 or more types as appropriate. Among these, it is selected from the group consisting of silica (SiO ₂ ), titania (TiO ₂ ), alumina (Al ₂ O ₃ ), and zirconia (ZrO ₂ ) in terms of heat resistance, insulating properties, cost, etc. At least one is preferred, and silica is more preferred.

That is, as the molybdenum compound (A), an inorganic oxide is applied to at least part of the surface or all of the surface of the core particle made of the molybdenum compound, that is, at least part of or all of the outer periphery of the core particle. is preferred. Among such molybdenum compounds (A), silica is added as an inorganic oxide to at least part of the surface or all of the surface of the core particles made of the molybdenum compound, i.e., at least part of or all of the outer periphery of the core particles. More preferably. More preferably, the core particles are at least one selected from the group consisting of molybdic acid, zinc molybdate, and zinc ammonium molybdate hydrate.

The thickness of the inorganic oxide on the surface can be appropriately set according to the desired performance, and is not particularly limited. The thickness is preferably 3 to 500 nm from the viewpoints of forming a uniform inorganic oxide film, exhibiting the effect of improving drillability more remarkably, and imparting higher heat resistance. , more preferably 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, from the viewpoint of dispersibility in the resin composition and drillability, It is more preferably 1 to 4 μm, and even more preferably 1 to 3 μm.

Core particles made of a molybdenum compound can be produced by various known methods such as pulverization and granulation, and the production method is not particularly limited. Moreover, you may use the commercial item.

The method for producing the surface-treated molybdenum particles is not particularly limited, and examples thereof include a sol-gel method, a liquid phase deposition method, a dip coating method, a spray coating method, a printing method, an electroless plating method, a sputtering method, a vapor deposition method, and an ion plating method. , and CVD, etc., to provide the inorganic oxide or its precursor to the surface of the core particles made of the molybdenum compound, thereby obtaining the surface-treated molybdenum particles. The method of applying the inorganic oxide or its precursor to the surface of the core particles made of the molybdenum compound may be either a wet method or a dry method.

As a suitable method for producing surface-treated molybdenum particles, for example, a molybdenum compound (core particles) is dispersed in an alcohol solution in which a metal alkoxide such as silicon alkoxide (alkoxysilane) or aluminum alkoxide is dissolved, and water and alcohol are mixed with stirring. and a mixed solution of the catalyst is added dropwise to hydrolyze the alkoxide to form a film such as silicon oxide or aluminum oxide as a low refractive index film on the surface of the compound, after which the obtained powder is solid-liquid separated, A method of performing heat treatment after vacuum drying may be mentioned. As another suitable production method, for example, a molybdenum compound (core particles) is dispersed in an alcohol solution in which a metal alkoxide such as silicon alkoxide or aluminum alkoxide is dissolved, and mixed under high temperature and low pressure to form the compound surface. A method of forming a film of silicon oxide, aluminum oxide, or the like, then vacuum-drying the obtained powder, and pulverizing may be mentioned. By these methods, molybdenum particles having a coating of metal oxide such as silica or alumina on the surface of the molybdenum compound can be obtained.

From the viewpoint of drillability and heat resistance, the content of the molybdenum compound (A) is 0 with respect to a total of 100 parts by mass of the thermosetting compound (B) described below and the thermosetting resin (C) described below. It is preferably from 0.1 to 30 parts by mass, more preferably from 0.3 to 10 parts by mass, and even more preferably from 0.5 to 5 parts by mass.

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

The thermosetting compound (B) has a polysiloxane skeleton in which siloxane bonds are repeatedly formed in the molecule, and includes a maleimide group, an amino group, an epoxy group, a carboxyl group, a vinyl group, a hydroxy group, and a (meth)acrylic There is no particular limitation as long as it has at least one group selected from the group consisting of groups. The thermosetting compound (B) exhibits good reactivity with the thermosetting resin (C) described below, and has excellent compatibility with the thermosetting resin (C). The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among these, a linear skeleton is preferred from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. In addition, the thermosetting compound (B) has, at both ends in the molecule, at least Having one group is preferred. Both terminal groups in the molecule may be the same or different, but are preferably the same because the curing reaction is easily controlled and the handling is facilitated.

The thermosetting compound (B) is preferably liquid at a temperature of 23° C., or has a solubility of 1% by mass or more in methyl ethyl ketone at a temperature of 23° C., and more Preferably, it is 5% by mass or more. Here, the solubility in methyl ethyl ketone is defined as "(total amount of thermosetting compound (B)/(total amount of thermosetting compound (B) + total amount of solvent)) x 100 (% by mass)" . In the present embodiment, for example, the total amount of 1 g or more of the thermosetting compound (B) is evaluated to dissolve in 99 g of methyl ethyl ketone because the solubility of the thermosetting compound (B) in methyl ethyl ketone is "1% by mass. or more”, and the solubility is evaluated as not 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 one or more maleimide groups and a polysiloxane structure in the molecule.

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

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

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

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

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

In addition, as the thermosetting compound (B), from the viewpoint of precisely controlling the compatibility with the thermosetting resin (C) and maintaining the viscosity of the thermosetting compound (B) low and improving the moldability , a thermosetting compound containing an epoxy group and/or a hydroxy group and a polysiloxane structure in the molecule is preferred.
As a thermosetting compound containing an epoxy group, a hydroxy group, and a polysiloxane structure, if it has one or more epoxy groups in the molecule, one or more hydroxy groups in the molecule, and a polysiloxane structure , is not particularly limited.

The content of the thermosetting compound (B) is excellent due to the release action of discharging shavings, and from the viewpoint of exhibiting excellent heat resistance and chemical resistance, the thermosetting compound (B) and the thermosetting resin described later It is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, even more preferably 15 to 40 parts by mass, based on 100 parts by mass in total with (C).

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, relative to 100% by mass of the resin solid content. More preferably, 15 to 40% by mass is even more preferable. When the content is within the above range, it tends to be more excellent in the releasing action of discharging chips, and to exhibit more excellent compatibility, low thermal expansion, and chemical resistance in a well-balanced manner.

(Thermosetting compound (B1))
The thermosetting compound (B) is composed of at least an amino-modified silicone from the viewpoint of improving the reactivity between the components constituting the thermosetting compound (B) and the compatibility with the thermosetting resin (C). It is preferably a thermosetting compound (B1) containing a unit and a structural unit derived from a maleimide compound. In the present specification, the terms “structural unit derived from amino-modified silicone” and “structural unit derived from maleimide compound” refer to each component of the amino-modified silicone and maleimide compound in the thermosetting compound (B1). In addition to containing a structural unit obtained by polymerizing, a structural unit formed by a reaction or the like that can give a similar structural unit is included. Hereinafter, in the present specification, "a structural unit derived from" shall be interpreted in the same manner. The polymer (B1) described later is one type (specific example) of the thermosetting compound (B1), and the amino-modified silicone and maleimide compound can be referred to later.

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

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

The amine value in the thermosetting compound (B1) is preferably 2.0 mgKOH/g or less, more preferably 1.0 mgKOH/g or less, still more preferably 0.5 mgKOH/g or less. The amine value is the total amount of primary amine and secondary amine. When the amine value is 2.0 mgKOH/g or less, the release effect of discharging cutting chips is excellent, and the increase in the viscosity of the resin composition, the increase in the molecular weight, the gelation of the varnish, and the increase in the prepreg viscosity tend to be suppressed. It is in. In addition, the smaller the amine value, the more likely it is that an increase in the viscosity of the resin composition and an increase in the molecular weight can be suppressed. The lower limit of the amine value is preferably 0 mgKOH/g. Amine value 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, 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. increase in molecular weight, gelation of varnish, and increase in prepreg viscosity. In order to adjust the weight average molecular weight of the thermosetting compound (B1) to 5,000 to 20,000, reaction conditions such as temperature and time in preparing the thermosetting compound (B1) may be controlled. In the present embodiment, the weight average molecular weight can be obtained as a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. Specifically, it is measured by the method described in Examples described later.

(Polymer (B1))
The thermosetting compound (B) contains at least an amino-modified silicone, a maleimide compound, a carboxylic acid and/or or a carboxylic acid anhydride, and the polymer (B1) obtained by polymerizing is preferred. The polymer (B1) contains at least structural units derived from an amino-modified silicone and structural units 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 has the following formula ( More preferably, it contains an amino-modified silicone represented by 1). Since the thermosetting compound (B1) or polymer (B1) contains structural units derived from amino-modified silicone, it is excellent in releasing action to discharge chips and can exhibit excellent compatibility. Amino-modified silicone can be used individually by 1 type or in combination of 2 or more types as appropriate.

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

Examples of alkyl groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; branched alkyl groups such as isopropyl, isobutyl, and tert-butyl. is mentioned. Among these, a methyl group is preferred.

_Rb is preferably an alkylene group. Alkylene groups include, for example, methylene, ethylene, trimethylene, and tetramethylene groups. Further, the alkylene group preferably has 1 to 4 carbon atoms in its main chain, more preferably a trimethylene group.

Arylene groups include, for example, phenyl groups, naphthyl groups, indenyl groups, biphenyl groups, and anthryl groups.

The amino group equivalent of the amino-modified silicone is preferably 130-6000 g/mol, more preferably 500-3000 g/mol, still more preferably 600-2500 g/mol. When the amino group equivalent is within the above range, it is possible to obtain a cured product that is excellent in the release action of discharging chips. An amino group equivalent is measured by a method based on JIS K 7237:1995.

Amino-modified silicone may be a commercially available product or a product manufactured by a known method. Commercial products of amino-modified silicone 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. ), and “KF-8010” (amino group equivalent: 430 g/mol).

- 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. The number of maleimide groups in the maleimide compound is preferably 2 or more. Examples of maleimide compounds include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3, 5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polytetramethylene oxide-bis( 4-maleimidobenzoate), maleimide compounds represented by formula (4), maleimide compounds represented by formula (9), prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. The maleimide compounds can be used singly or in combination of two or more.

Among these, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, poly It preferably contains at least one selected from the group consisting of tetramethylene oxide-bis(4-maleimidobenzoate), a maleimide compound represented by formula (4), and a maleimide compound represented by formula (9), More preferably, it contains 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane.

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

_R5 is preferably a hydrogen atom. The upper limit of _n1 is preferably 10, more preferably 7.

In formula (9), each R ¹³ 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 1-10.

A commercially available product or a preparation prepared by a known method may be used as the maleimide compound. Commercially available maleimide compounds include "BMI-70", "BMI-80" and "BMI-1000P" manufactured by KI Kasei Co., Ltd., and "BMI-3000" and " BMI-4000", "BMI-5100", "BMI-7000", and "BMI-2300", and Nippon Kayaku Co., Ltd. product "MIR-3000-70MT".

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

Among these, a monovalent carboxylic acid and/or a monovalent carboxylic acid anhydride, or a divalent carboxylic acid and/or a divalent carboxylic acid anhydride are preferred, and a divalent carboxylic acid and/or or a divalent carboxylic acid anhydride is more preferred. The carboxylic acid and/or carboxylic anhydride is a monovalent carboxylic acid and/or monovalent carboxylic anhydride by being a divalent carboxylic acid and/or divalent carboxylic anhydride respectively Compared to the case, there is a tendency to obtain a cured product that is excellent due to the mold release action that discharges shavings.

Carboxylic acid and carboxylic anhydride can be used singly or in appropriate combination of two or more. Carboxylic acid and carboxylic anhydride may be used alone or in combination.

In the present embodiment, using only carboxylic acid anhydride is preferable to using only carboxylic acid. Since the carboxylic anhydride is superior in reactivity, it tends to favorably suppress the reactivity of the polymer (B1) by reacting with the amino group in the polymer (B1). As a result, the resin composition containing the polymer (B1) and the prepreg have excellent storage stability (for example, suppression of increase in viscosity of the resin composition, increase in molecular weight, gelation of varnish, and increase in prepreg viscosity). , the moldability tends to be excellent when mixed with the thermosetting resin (C).

The content of structural units derived from amino-modified silicone in the polymer (B1) is preferably 15 to 60% by mass, more preferably 100% by mass of all structural units in the polymer (B1). It is 20 to 55% by mass, more preferably 30 to 50% by 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%, based on 100% by mass of all structural units in the polymer (B1). 70 mass %, more preferably 44 to 65 mass %.

The content (total content) of structural units derived from carboxylic acid and/or carboxylic anhydride in the polymer (B1) is preferably It is 0.1 to 10 mass %, more preferably 0.5 to 7 mass %, still 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 an amino-modified silicone and a maleimide compound are reacted. A first reaction step (hereinafter simply referred to as “first reaction step”) to obtain a primary polymer, and a second reaction step (hereinafter simply referred to as “second It is preferable to have a thermosetting compound (B1) or a polymer (B1) having better storage stability.

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

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

In the first reaction step, the compounding 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 even more preferably 1.0 to 2.5, on a mass basis. 1.0 to 2.0. When the blending ratio is within the above range, the productivity of the thermosetting compound (B1) or the polymer (B1) tends to be excellent.

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

The viscosity of the primary polymer obtained in the first reaction step, which is subjected to the second reaction step, is the thermosetting compound (B1) or polymer (B1) having superior storage stability, so that the solvent At a concentration of 50% containing, it is preferably 100 to 500 mPa s, more preferably 150 mPa s to 400 mPa s. In addition, the measurement method of the viscosity of a primary polymer can be measured using a general viscometer. For example, it can be measured using a cone-plate viscometer (eg, ICI viscometer).

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

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

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

A solvent may be used in the first and second steps. 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 acetate thereof. A solvent can be used individually by 1 type or in combination of 2 or more types as appropriate.

(Thermosetting compound (B2))
From the viewpoint of precisely controlling the compatibility with the thermosetting resin (C) and improving the moldability by keeping the viscosity of the thermosetting compound (B) low, the thermosetting compound (B) has at least A thermosetting compound (B2) containing 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 is preferred. Moreover, the thermosetting compound (B2) may further contain a structural unit derived from a phenol compound other than alkenylphenol, if necessary. The polymer (B2) described below is a type (specific example) of the thermosetting compound (B2), and the alkenylphenol, epoxy-modified silicone, epoxy compounds other than epoxy-modified silicone, and phenol compounds other than alkenylphenol are See below.

The content of structural units derived from alkenylphenol is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, relative to the total mass of the thermosetting compound (B2). More preferably, it is up to 40% by mass. When the content of this structural unit is within the above range, it tends to be excellent in the releasing action of discharging shavings and exhibit even better compatibility.

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

The constituent units derived from epoxy-modified silicone are an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (hereinafter also referred to as "low equivalent epoxy-modified silicone") and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g/mol. Structural units derived from silicone (hereinafter also referred to as “high equivalent weight epoxy-modified silicone”) are preferred.

The content of structural units derived from the low-equivalent epoxy-modified silicone is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, relative to the total mass in the thermosetting compound (B2). is more preferable, and 10 to 17% by mass is even 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, relative to the total mass in the thermosetting compound (B2). is more preferable, and 25 to 50% by mass is even more preferable.

The mass ratio of the content of 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, and 1.7 to 3.5. is more preferable, and 1.9 to 3.1 is even more preferable. When this mass ratio is within the above range, it tends to be more excellent in the release action of discharging chips, and more excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability can be exhibited.

The content of structural units derived from epoxy compounds other than epoxy-modified silicone is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, relative to the total mass in the thermosetting compound (B2). is preferred, and 15 to 20% by mass is more preferred. When the content of this structural unit is within the above range, it tends to be excellent in the release action of discharging shavings, and can exhibit even better compatibility, chemical resistance, copper foil adhesion, and insulation reliability. .

In addition, the content of the structural unit derived from the epoxy-modified silicone is 5 to 95% by mass with respect to the total mass of the structural unit derived from the epoxy-modified silicone and the structural unit derived from an epoxy compound other than the epoxy-modified silicone. 10 to 90% by mass is more preferable, 15 to 60% by mass is even more preferable, and 20 to 50% by mass is particularly preferable. The content of structural units derived from epoxy compounds other than epoxy-modified silicone is 5 to 95% by mass based on the total mass of structural units derived from epoxy-modified silicone and structural units derived from epoxy compounds other than epoxy-modified silicone. is preferably 10 to 90% by mass, more preferably 40 to 85% by mass, and particularly preferably 50 to 80% by mass. When the contents of these structural units have the above relationship, the mold release action for discharging shavings is excellent, and the compatibility, chemical resistance, copper foil adhesion, and insulation reliability tend to be further improved. It is in.

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, based on the total mass in the thermosetting compound (B2). preferably 10 to 25% by mass. When the content of this structural unit is within the above range, the cured product of the resin composition tends to be excellent in the releasing action of discharging chips, and can exhibit even better adhesion to the copper foil.

The alkenyl group equivalent in the thermosetting resin (B2) is preferably 300-1500 g/mol, preferably 350-1200 g/mol, and more preferably 400-1000 g/mol. When the alkenyl group equivalent is 300 g/mol or more, the elastic modulus of the cured product of the resin composition tends to be further reduced, and as a result, the thermal expansion of the substrate obtained using the cured product is further reduced. tend to be able. When the alkenyl group equivalent is 1500 g/mol or less, the releasing action of discharging chips is excellent, and the compatibility, chemical resistance, and insulation reliability of the resin composition tend to be further improved.

The weight average molecular weight (Mw) of the thermosetting resin (B2) is preferably 3.0×10 ³ to 5.0×10 ⁴ , more preferably 3.0×10 ³ to 2 in terms of polystyrene in the GPC method. 0×10 ⁴ is more preferred. When the weight-average molecular weight is 3.0×10 ³ or more, the coefficient of thermal expansion of the prepreg tends to decrease, and when the weight-average molecular weight is 5.0×10 ⁴ or less, a separator for discharging cutting chips is formed. It tends to be excellent in forming action, and can suppress increase in viscosity of the resin composition, increase in molecular weight, gelation of varnish, and increase in prepreg viscosity.

(Polymer (B2))
The thermosetting compound (B) is obtained by polymerizing at least an alkenylphenol, an epoxy-modified silicone, and an epoxy compound other than the epoxy-modified silicone for the reason that the compatibility with the thermosetting resin (C) is further excellent. It is preferable that the polymer (B2) obtained by Further, the polymer (B2) is more preferably a polymer obtained by polymerizing at least an alkenylphenol, an epoxy-modified silicone, an epoxy compound other than the epoxy-modified silicone, and a phenol compound other than the alkenylphenol. preferable. The 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 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. Since the thermosetting compound (B2) or polymer (B2) contains structural units derived from alkenylphenol, it is excellent in the release action of discharging chips and can exhibit excellent compatibility.

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

A phenolic aromatic ring is one in which one or more hydroxyl groups are directly bonded to an aromatic ring, and includes phenol rings and naphthol rings. The number of hydroxyl groups directly bonded to one phenolic aromatic ring is, for example, 1 to 2, preferably 1.

The phenolic aromatic ring may have substituents other than alkenyl groups. Examples of such substituents include linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, linear alkyl groups having 1 to 10 carbon atoms, A chain alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, and a halogen atom. When the phenolic aromatic ring has substituents other than alkenyl groups, the number of said substituents directly bonded to one phenolic aromatic ring is, for example, 1-2. Also, the bonding position of the substituent to the phenolic aromatic ring is not particularly limited.

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

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

In formula (1A), Rxa each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and Rxc is Each independently represents an aromatic ring having 4 to 12 carbon atoms, Rxc may form a fused structure with a benzene ring, Rxc may or may not exist, A represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, 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). , Rxc does not exist, one benzene ring may have two or more Rxa and/or Rxb groups.

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

Examples of alkenyl groups having 2 to 8 carbon atoms represented by Rxa and Rxd in formulas (1A) and (1B) include vinyl groups, allyl groups, propenyl groups, butenyl groups, and hexenyl groups. Rxa and Rxd are preferably allyl and/or propenyl groups, more preferably allyl groups.

In formulas (1A) and (1B), when the groups represented by Rxc and Rxf form a condensed structure with a benzene ring, examples thereof include compounds containing a naphthol ring as the phenolic aromatic ring. . Further, in the case where the groups represented by Rxc and Rxf are not present in the formulas (1A) and (1B), for example, compounds containing a phenol ring can be mentioned as the phenolic aromatic ring.

Examples of alkyl groups having 1 to 10 carbon atoms represented by Rxb and Rxe in formulas (1A) and (1B) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and the like. Branched alkyl groups such as linear alkyl groups, isopropyl groups, isobutyl groups and tert-butyl groups can be mentioned.

Examples of the alkylene group having 1 to 6 carbon atoms represented by A in the formula (1A) include a methylene group, an ethylene group, a trimethylene group and a propylene group. The aralkylene group having 7 to 16 carbon atoms represented by A includes, for example, 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. The arylene group having 6 to 10 carbon atoms represented by A includes, for example, a phenylene ring.

In the compound represented by formula (1B), Rxf is preferably a benzene ring (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, alkenylphenol is preferably alkenylbisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of bisphenols. From a similar point of view, alkenyl bisphenol is diallyl bisphenol in which two phenolic aromatic rings of bisphenols are respectively bonded to one allyl group, and/or bisphenols in which two phenolic aromatic rings are respectively bonded to one propenyl group. Dipropenyl bisphenol is preferred.

Examples of diallyl bisphenol include o, o'-diallyl bisphenol A (DABPA (trade name), Daiwa Kasei Kogyo Co., Ltd.), o, o'-diallyl bisphenol F, o, o'-diallyl bisphenol S, o, o'-diallyl bisphenol fluorene. Examples of dipropenyl bisphenol include o,o'-dipropenyl bisphenol A (PBA01 (trade name), Gunei Chemical Industry Co., Ltd.), o,o'-dipropenyl bisphenol F, o,o'-dipropenyl Bisphenol S and o,o'-dipropenyl bisphenol fluorene.

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

In the formula, A represents the number of phenol groups in alkenylphenol having i phenol groups in the molecule, Xi represents the ratio of 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. The thermosetting compound (B2) or polymer (B2) contains structural units derived from epoxy-modified silicone, so that it is excellent in releasing action to discharge cutting chips, and has excellent low thermal expansion and chemical resistance. can be expressed.

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 network skeleton. Among these, the polysiloxane skeleton is preferably a linear skeleton from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.

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

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

The epoxy-modified silicone preferably contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol, more preferably an epoxy-modified silicone having an epoxy equivalent of 145 to 245 g/mol, and an epoxy equivalent of 150 to 240 g/mol. It is more preferable to contain an epoxy-modified silicone having an epoxy equivalent of mol. By containing an epoxy-modified silicone having an epoxy equivalent within the above range, the epoxy-modified silicone is excellent in the release action of discharging cutting chips, has compatibility with other resins or compounds in the resin composition, and has low heat. It tends to be able to further improve expandability and chemical resistance in a well-balanced manner.

Epoxy-modified silicone is excellent in mold release action for discharging cutting chips, and can further improve compatibility with other resins or compounds in the resin composition, low thermal expansion, and chemical resistance in a well-balanced manner. It is preferable to contain the above epoxy-modified silicone. In this case, the two or more epoxy-modified silicones preferably have different epoxy equivalents. It is more preferable to contain an epoxy-modified silicone having an epoxy equivalent (high-equivalent epoxy-modified silicone), and an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol and an epoxy-modified epoxy having an epoxy equivalent of 450 to 3000 g/mol. It is more preferable to contain silicone.

When the epoxy-modified silicone contains two or more epoxy-modified silicones, the average epoxy equivalent of the epoxy-modified silicone is preferably 140 to 3000 g/mol, more preferably 250 to 2000 g/mol, and 300 to 300 g/mol. More preferably 1000 g/mol. The average epoxy equivalent is calculated by the following formula.

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

Epoxy-modified silicone is excellent in mold release action for discharging shavings, 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 well-balanced manner, the following formula ( It is preferable to contain an epoxy-modified silicone represented by 2).

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

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

In formula (2), the arylene group represented by R ¹ may have a substituent. The number of carbon atoms in the arylene group is preferably 6-40, more preferably 6-20. Arylene groups include, for example, phenylene groups, cyclohexylphenylene groups, hydroxyphenylene groups, cyanophenylene groups, nitrophenylene groups, naphthylene groups, biphenylene groups, anthrylene groups, pyrenylene groups, and fluorenylene groups. These groups may contain an ether bond, a ketone bond, or an ester bond.

In formula (2), the aralkylene group represented by R ¹ preferably has 7 to 30 carbon atoms, more preferably 7 to 13 carbon atoms. Examples of the aralkylene group include groups represented by the following formula (XI).

In formula (XI), * indicates 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 having 1 to 10 carbon atoms, a linear alkyl group having 3 to 10 carbon atoms, A branched alkyl group, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, and a cyclic alkoxy group having 3 to 10 carbon atoms mentioned.

In formula (2), each R ² independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. The above alkyl group and phenyl group may have a substituent. The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Alkyl groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl groups. Among these, R ² is preferably a methyl group or a phenyl group.

In formula (2), n is an integer from 0 to 100. The lower limit of n is 1 or more from the viewpoint that it is excellent in the release action of discharging shavings and can further improve compatibility with other resins or compounds in the resin composition, low thermal expansion, and chemical resistance in a well-balanced manner. is preferably Similarly, the upper limit of n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

Epoxy-modified silicone is excellent in releasing action to discharge 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 well-balanced manner, the formula ( It is preferable to contain two or more types of epoxy-modified silicone represented by 2). In this case, the epoxy-modified silicones containing two or more types preferably have different values of n. It is more preferable to contain a certain epoxy-modified silicone.

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

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

For the low-equivalent epoxy-modified silicone and high-equivalent epoxy-modified silicone, commercially available products or preparations prepared by known methods may be used. Commercially available products of low-equivalent epoxy-modified silicone include "X-22-163" (functional group equivalent: 200 g/mol) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Commercially available high-equivalent epoxy-modified silicones 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. mol), and “X-22-163B” (functional group equivalent: 1800 g/mol).

- Epoxy compound Epoxy compounds are epoxy compounds other than epoxy-modified silicone, and more specifically, epoxy compounds that do not have a polysiloxane skeleton. The thermosetting compound (B2) or polymer (B2) contains a structural unit derived from an epoxy compound, so that it has an excellent release action for discharging chips, excellent compatibility, chemical resistance, copper foil Adhesion and insulation reliability can be expressed.

The epoxy compound is not particularly limited as long as it is an epoxy compound other than epoxy-modified silicone. Epoxy compounds have two epoxy groups in one molecule from the viewpoint that they are excellent in releasing action to discharge chips, and can express more excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability. It preferably contains a bifunctional epoxy compound.

Bifunctional epoxy compounds include, for example, bisphenol type epoxy resins (e.g., bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol fluorene type epoxy resin), and phenols. Novolac-type epoxy resins (e.g., phenol novolac-type epoxy resins, bisphenol A novolak-type epoxy resins, cresol novolak-type epoxy resins), trisphenolmethane-type epoxy resins, aralkyl-type epoxy resins, biphenyl-type epoxy resins containing a biphenyl skeleton, naphthalene skeleton-containing naphthalene-type epoxy resin, dihydroanthracene-containing anthracene-type epoxy resin, glycidyl ester-type epoxy resin, polyol-type epoxy resin, isocyanurate ring-containing epoxy resin, dicyclopentadiene-type epoxy resin, fluorene-containing skeleton Fluorene-type epoxy resins, epoxy resins composed of bisphenol A-type structural units and hydrocarbon-based structural units; and halogen compounds thereof. These epoxy compounds are used individually by 1 type or in combination of 2 or more types.

Examples of aralkyl-type epoxy resins include compounds represented by the following formula (b1).

In formula (b1), Ar ³ each independently represents a benzene ring or naphthalene ring, Ar ⁴ represents a benzene ring, naphthalene ring, or biphenyl ring, and R ^3a each independently represents a hydrogen atom. or a methyl group, and each ring may have a substituent other than a glycidyloxy group (eg, an alkyl group having 1 to 5 carbon atoms or a phenyl group).

Examples of biphenyl-type epoxy resins include compounds represented by the following formula (b2) (compound b2).

In formula (b2), each Ra 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. Alkyl groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl groups.

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 having different numbers of Ra as alkyl groups. Specifically, a mixture of biphenyl-type epoxy resins having different numbers of Ra as alkyl groups is preferable, and compound b2 having 0 Ra as alkyl groups and a compound b2 having 4 Ra as alkyl groups. Mixtures of b2 are more preferred.

Examples of naphthalene-type epoxy resins include compounds represented by the following formula (b3).

In formula (b3), R ^3b each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl group or ethyl group), an aralkyl group, a benzyl group, a naphthyl group, or a glycidyloxy group. represents a contained naphthyl group, n represents an integer of 0 or more (eg, 0 to 2).

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

Examples of dicyclopentadiene-type epoxy resins include compounds represented by the following formula (b4).

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

For the dicyclopentadiene type epoxy resin, a commercially available product or a prepared product prepared by a known method may be used. Commercial products of dicyclopentadiene type epoxy resin include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H" and "EPICRON HP-7000HH" manufactured by Dainippon Ink and Chemicals. mentioned.

Examples of epoxy resins composed of bisphenol A-type structural units and hydrocarbon-based structural units include compounds represented by the following formula (b5).

In formula (b5), R ^1x and R ^2x each independently represent a hydrogen atom or a methyl group, and R ^3x to R ^6x each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. and X is an ethyleneoxyethyl group, di(ethyleneoxy)ethyl group, tri(ethyleneoxy)ethyl group, propyleneoxypropyl group, di(propyleneoxy)propyl group, tri(propyleneoxy)propyl group, or carbon It represents an alkylene group of numbers 2 to 15 (eg, methylene group or ethylene group).

Among these, epoxy compounds are excellent in mold release action for discharging shavings, and from the viewpoint of being able to express more excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability, bisphenol type epoxy resin, aralkyl type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, and dicyclopentadiene type epoxy resin. is more preferable.

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

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

・Phenolic compound other than alkenylphenol The thermosetting compound (B2) or polymer (B2) is excellent in the release action of discharging shavings, and from the viewpoint of being able to express even more excellent copper foil adhesion, It preferably contains a phenol compound (hereinafter also simply referred to as "phenol compound").

Examples of phenolic 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.), phenolic novolac resins (e.g., phenol novolak resin, naphthol novolac resin, cresol novolac resin, etc.), glycidyl ester type phenolic resin, naphthalene type phenolic resin, anthracene type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, aralkyl type Examples include phenol resins, phenol-modified aromatic hydrocarbon formaldehyde resins, and fluorene-type phenol resins. These phenol compounds are used singly or in combination of two or more.

Among these, phenolic compounds are excellent in the release action of discharging shavings, and from the viewpoint of being able to express more excellent compatibility and copper foil adhesion, a bifunctional phenolic compound having two phenolic hydroxyl groups in one molecule. is preferably

Examples of bifunctional phenol compounds include bisphenol, biscresol, bisphenols having a fluorene skeleton (e.g., bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton, etc.), biphenols (e.g., p,p'-biphenol, etc.), dihydroxy diphenyl ether (e.g., 4,4'-dihydroxydiphenyl ether, etc.), dihydroxydiphenyl ketone (e.g., 4,4'-dihydroxydiphenyl ketone, etc.), dihydroxydiphenyl sulfide (e.g., 4,4'-dihydroxydiphenyl sulfide, etc.), dihydroxyarene (eg, hydroquinone, etc.). These bifunctional phenol compounds are used singly or in combination of two or more. Among these, the bifunctional phenol compound is excellent in the release action of discharging shavings, and from the viewpoint of expressing even more excellent copper foil adhesion, from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton. It preferably contains at least one selected type, and more preferably contains a bisphenol having a fluorene skeleton. From the same viewpoint as above, bis-cresol fluorene is preferable as the bisphenols having a fluorene skeleton.

Phenol compounds other than alkenylphenol may be commercially available products or products manufactured by known methods. Examples of commercially available phenolic compounds other than alkenylphenol include "BCF" (biscresol fluorene) manufactured by Osaka Gas Chemical Co., Ltd. and "Bisphenol M" manufactured by Mitsui Chemicals, Inc.

-Method for producing thermosetting compound (B2) or polymer (B2) The method for producing the thermosetting compound (B2) or polymer (B2) is not particularly limited. , an epoxy compound and, if necessary, a phenol compound are reacted in the presence of a polymerization catalyst, which will be described later. The reaction may be performed in the presence of an organic solvent. More specifically, in the above steps, the 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 between the hydroxyl group of the resulting addition reaction product and the hydroxyl group of the epoxy-modified silicone and the epoxy compound. The thermosetting compound (B2) or polymer (B2) can be obtained by the progress of an addition reaction with an epoxy group or the like.

In the production of the thermosetting compound (B2) or the polymer (B2), the amount of alkenylphenol blended is excellent in the releasing action of discharging shavings, and from the viewpoint of expressing even more excellent compatibility, alkenylphenol, epoxy It is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and 5 to 30 parts by mass with respect to a total of 100 parts by mass of the modified silicone, epoxy compound, and phenol compound. More preferred.

The amount of the epoxy-modified silicone to be blended is the alkenylphenol, the epoxy-modified silicone, the epoxy compound, and the phenol compound from the standpoint of excellent release action for discharging cutting chips and the expression of even better low thermal expansion and chemical resistance in a well-balanced manner. It is preferably from 5 to 70 parts by mass, more preferably from 10 to 60 parts by mass, and even more preferably from 20 to 55 parts by mass with respect to the total 100 parts by mass.

The amount of the epoxy compound to be blended is, from the standpoint of excellent release action to discharge cutting chips and to express even better compatibility, chemical resistance, copper foil adhesion, and insulation reliability, alkenylphenol, epoxy-modified silicone, 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 with respect to the total 100 parts by mass of the epoxy compound and the phenol compound.

The amount of the phenolic compound is 100 parts by mass in total of alkenylphenol, epoxy-modified silicone, epoxy compound, and phenolic compound, from the viewpoint of excellent mold release action for discharging shavings and exhibiting even better copper foil adhesion. On the other hand, 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.

When the thermosetting compound (B2) or the polymer (B2) does not contain a phenol compound, the amounts of the alkenylphenol, epoxy-modified silicone and epoxy compound are the same as those of the alkenylphenol, the epoxy-modified silicone and the epoxy compound. The compounding amount is shown with respect to a total of 100 parts by mass of the compounds.

Examples of polymerization catalysts include imidazole catalysts and phosphorus catalysts. These catalysts are used individually by 1 type or in combination of 2 or more types. Among these, imidazole catalysts are preferred.

Examples of imidazole catalysts include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzo Examples include imidazoles such as imidazole (TBZ (trade name), Shikoku Kasei Kogyo Co., Ltd.) and 2,4,5-triphenylimidazole (TPIZ (trade name), Tokyo Chemical Industry Co., Ltd.). Among these, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole are preferred from the viewpoint of preventing homopolymerization of the epoxy component.

The amount of polymerization catalyst (preferably 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 4.0 parts by mass or less. is more preferable.

As the 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 solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ester solvents such as ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate; and amides such as dimethylacetamide and dimethylformamide. Examples of nonpolar solvents include aromatic hydrocarbons such as toluene and xylene. These solvents are used singly or in combination of two or more.

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

The heating temperature is not particularly limited, and may be, for example, 100-170°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 conventional method.

<Thermosetting resin (C)>
The resin composition of the present embodiment contains a thermosetting resin (C) different from the thermosetting compound (B) of the present embodiment. The thermosetting compound (B) exhibits excellent compatibility even with thermosetting resins having poor compatibility with silicone compounds. Therefore, even if the thermosetting compound (B) and the thermosetting resin (C) are combined, the components do not separate in the resin composition, and the compatibility is excellent.

The thermosetting resin (C) is a maleimide compound, a cyanate ester compound, a phenol compound, an alkenyl-substituted nadimide compound from the viewpoint of further improving the low thermal expansion property, chemical resistance, and copper foil adhesion of the resulting cured product. , and preferably at least one selected from the group consisting of epoxy resins, more preferably at least one selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, and epoxy resins. . These thermosetting resins (C) can be used individually by 1 type or in combination of 2 or more types as appropriate.

The content of the thermosetting resin (C) is excellent due to the release action of discharging shavings, and from the viewpoint of exhibiting excellent heat resistance and chemical resistance, the thermosetting compound (B) and the thermosetting resin (C ) is preferably from 50 to 95 parts by mass, more preferably from 55 to 90 parts by mass, and even more preferably from 60 to 85 parts by mass, based on the total 100 parts by mass of the above.

· Maleimide compound The thermosetting resin (C) preferably contains a maleimide compound from the viewpoint of excellent mold release action for discharging 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). The maleimide compounds can be used singly or in combination of two or more.

The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. -hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl) propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane), m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimido-(2,2,4-trimethyl)hexane, polytetramethylene oxide-bis(4-maleimidobenzoate), maleimide compounds represented by the following formula (4), maleimide compounds represented by the formula (9), prepolymers of these maleimide compounds and amine compounds, etc.).

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

The number of maleimide groups in the maleimide compound is preferably 2 or more per molecule. These maleimide compounds are used singly or in combination of two or more. Among these, from the viewpoint of further improving low thermal expansion and chemical resistance, maleimide compounds are bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane , bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, polytetramethylene oxide-bis (4-maleimidobenzoate), a maleimide compound represented by formula (4), and represented by formula (9) bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3 -Ethyl-5-methyl-4-maleimidophenyl)methane, and at least one selected from the group consisting of maleimide compounds represented by the following formula (4).

The content of the maleimide compound is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin solid content, from the viewpoint of excellent release action for discharging shavings and further improving low thermal expansion and chemical resistance. , more preferably 5 to 40 parts by mass, even more preferably 10 to 40 parts by mass.

Cyanate ester compound The thermosetting resin (C) preferably contains a cyanate ester compound from the viewpoint of excellent release action for discharging 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. cyanate ester compounds, novolak-type cyanate ester compounds such as compounds represented by formula (6) excluding 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-tricyanato benzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, 2 , 2-bis(4-cyanatophenyl)propane. These cyanate ester compounds are used singly or in combination of two or more. Among these, the cyanate ester compound is more excellent in the release action of discharging shavings, and from the viewpoint of further improving low thermal expansion and chemical resistance, a naphthol aralkyl type cyanate ester compound and / or a novolac type cyanate It preferably contains an acid ester compound.

Among these, the cyanate ester compound is excellent in the release action of discharging shavings, and from the viewpoint of further improving low thermal expansion and chemical resistance, it is represented by formula (5) and / or formula (6) It preferably contains a compound. The cyanate ester compound containing the compound represented by formula (5) is excellent in the release action of discharging swarf, further improves low thermal expansion and chemical resistance, and further exhibits excellent flame retardancy. It is more preferred because it has good flexibility and a low coefficient of thermal expansion.

In formula (5), each _R6 independently represents a hydrogen atom or a methyl group, and _n2 represents an integer of 1 or more. _n2 is preferably an integer of 1-20, more preferably an integer of 1-10, and even more preferably an integer of 1-6.

In formula (6), R _ya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and R _yb each independently represents an alkyl group having 1 to 10 carbon atoms or hydrogen represents an atom, each R _yc 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 be present , which may be absent, A ^1a each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group , an oxygen atom, a sulfur atom, or a single bond (direct bond), and when R _yc does not exist, one benzene ring may have two or more R _ya and/or R _yb groups. n represents an integer of 1-20.

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

In formula (6), the alkyl group having 1 to 10 carbon atoms represented by R _yb includes, for example, 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 C 1-6 alkylene group represented by A ^1a include methylene group, ethylene group, trimethylene group and propylene group. In formula (6), the aralkylene group having 7 to 16 carbon atoms represented by A ^1a includes, for example, the formulas: —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, a naphthylene group, or a biphenylene group). Furthermore, the arylene group having 6 to 10 carbon atoms represented by A ^1a includes, for example, a phenylene ring.

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

The compound represented by the formula (6) is a phenol novolac type cyanide because it has an excellent release action for discharging shavings, further improves low thermal expansion and chemical resistance, and has a higher glass transition temperature. An acid ester compound is preferable, and a compound represented by formula (c1) is more preferable as the phenol novolak-type cyanate ester compound.

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

These cyanate ester compounds may be produced according to known methods. Specific production methods include, for example, the method described in JP-A-2017-195334 (particularly paragraphs 0052 to 0057).

The content of the cyanate ester compound as the thermosetting resin (C) is excellent in the release action of discharging shavings, and from the viewpoint of further improving low thermal expansion and chemical resistance, the resin solid content is 100 parts by mass. On the other hand, it is preferably 10 to 70 parts by mass, more preferably 15 to 60 parts by mass, and even more preferably 20 to 50 parts by mass.

• Phenol compound The thermosetting resin (C) preferably contains a phenol compound from the viewpoint of excellent release action for discharging chips and further improving copper foil adhesion. The phenolic 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). A phenol compound can be used individually by 1 type or in combination of 2 or more types as appropriate.

The phenol compound is not particularly limited as long as it is a compound having two or more phenolic hydroxyl groups in one molecule. Examples include phenols and bisphenols (e.g., bisphenol A, bisphenol E, bisphenol F, bisphenol S, etc.), diallyl bisphenols (e.g., diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, diallyl bisphenol S, etc.), phenolic novolak resins (e.g., phenol novolak resin, naphthol novolak resins, cresol novolak resins, etc.), naphthalene-type phenol resins, dihydroanthracene-type phenol resins, dicyclopentadiene-type phenol resins, biphenyl-type phenol resins, and aralkyl-type phenol resins. These phenol compounds are used singly or in combination of two or more. Among these, the phenol compound preferably contains an aralkyl-type phenol resin from the viewpoint of further improving the copper foil adhesion.

(aralkyl-type phenolic resin)
Examples of aralkyl-type phenol resins include compounds represented by formula (c2).

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

The compound represented by the formula (c2) is excellent in the release action of discharging 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 compound having a benzene ring (hereinafter also referred to as a "naphthol aralkyl-type phenolic resin"), and a compound in which Ar ¹ is a benzene ring and Ar ² is a biphenyl ring in the formula (c2) (hereinafter referred to as a "biphenyl aralkyl-type Also referred to as "phenolic resin").

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

In formula (2b), each R ^2a 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 biphenylaralkyl-type phenolic resin is preferably a compound represented by formula (2c).

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

A commercially available product or a product manufactured by a known method may be used as the aralkyl-type phenol resin. Commercially available aralkyl-type phenolic resins include Nippon Kayaku Co., Ltd.'s "KAYAHARD GPH-65", "KAYAHARD GPH-78", "KAYAHARD GPH-103" (biphenylaralkyl-type phenolic resin), Nippon Steel Chemical Co., Ltd. The company's product "SN-495" (naphthol aralkyl type phenolic resin) can be mentioned.

The content of the phenolic compound as the thermosetting resin (C) is excellent in the release action of discharging shavings, and from the viewpoint of further improving the copper foil adhesion, the resin solid content is 100 parts by mass. It is preferably 40 parts by mass, more preferably 15 to 35 parts by mass, even more preferably 20 to 30 parts by mass.

Alkenyl-Substituted Nadimide Compound It is preferable that the thermosetting resin (C) contains an alkenyl-substituted nadimide compound from the viewpoint of excellent release action for discharging chips and further improvement of heat resistance. The alkenyl-substituted nadimide compounds can be used singly or in combination of two or more.
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, and examples thereof include compounds represented by the following formula (2d).

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

In formula (7), _R3 denotes a methylene group, an isopropylidene group, CO, O, S or _SO2 .

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

As the alkenyl-substituted nadimide compound represented by formula (2d), a commercially available product or a product manufactured according to a known method may be used. 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, based on 100 parts by mass of the resin solid content. More preferably 10 to 35 parts by mass.

・ Epoxy resin The thermosetting resin (C) is excellent in the release action of discharging shavings, and from the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, it is possible to contain epoxy resin. preferable. 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). , is an epoxy compound different from epoxy-modified silicone. An epoxy resin is used individually by 1 type or in combination of 2 or more types.

As the 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. Epoxy resins contain bifunctional epoxy compounds and/or polyfunctional epoxy compounds from the viewpoint of further improving the release action of discharging chips and further improving chemical resistance, copper foil adhesion, and insulation reliability. preferably.

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

In formula (3a), Ar ³ each independently represents a benzene ring or naphthalene ring, Ar ⁴ represents a benzene ring, naphthalene ring, or biphenyl ring, and R ^3a each independently represents a hydrogen atom. or represents a methyl group, k represents an integer of 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 such as It may be an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.
The benzene ring, naphthalene ring, or biphenyl ring in Ar ⁴ may further have one or more substituents, which may be a glycidyloxy group, other substituents such as carbon It may be an alkyl group of number 1 to 5, a phenyl group, or the like.

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

In formula (b1), Ar ³ each independently represents a benzene ring or naphthalene ring, Ar ⁴ represents a benzene ring, naphthalene ring, or biphenyl ring, and R ^3a each independently represents a hydrogen atom. or represents a methyl group,
Here, the benzene ring or naphthalene ring in Ar ³ may further have one or more substituents, and the substituents are, for example, a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group. It may be a substituent other than
The benzene ring, naphthalene ring or biphenyl ring in Ar ⁴ may further have one or more substituents, and the substituents are, for example, a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group. It may be a substituent other than

The compound represented by formula (3a) is preferably a phenolic novolac type epoxy resin in which Ar ⁴ in formula (3a) is at least substituted with a glycidyloxy group. The phenolic novolac epoxy resin is not particularly limited, but examples thereof include a compound represented by the following formula (3-1) (a naphthalene skeleton-containing polyfunctional epoxy resin having a naphthalene skeleton) and a naphthalene cresol novolac epoxy resin. mentioned. A naphthalene cresol novolac type epoxy resin is preferable from the viewpoint of excellent mold release action for discharging chips and further improvement of chemical resistance, copper foil adhesion, and insulation reliability.

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

Compounds represented by formula (3-1) include compounds represented by formula (3-2).

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

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. The compound represented by the following formula (NE) is a random copolymer of a cresol novolak epoxy structural unit and a naphthol novolak epoxy structural unit, and both cresol epoxy and naphthol epoxy can be terminals.

m and n in formula (NE) each represent an integer of 1 or more. The upper limit of m and n and the ratio thereof are not particularly limited, but from the viewpoint of low thermal expansion, m: n (here, m + n = 100) is preferably 30 to 50: 70 to 50, and 45 to 55:55-45 is more preferred.

As the naphthalene cresol novolac type epoxy resin, a commercially available product or a product manufactured by a known method may be used. Examples of commercially available products include "NC-7000", "NC-7300" and "NC-7300L" manufactured by Nippon Kayaku Co., Ltd., and "HP-9540" and "HP-9500" manufactured by DIC Corporation. and "HP-9540" is particularly preferred.

The compound represented by formula (3a) may be a compound (hereinafter also referred to as "aralkyl epoxy resin") that does not correspond to the phenolic novolac epoxy resins described above.
Aralkyl-type epoxy resins include compounds in which Ar ³ is a naphthalene ring and Ar ⁴ is a benzene ring in the formula (3a) (also referred to as a "naphthol aralkyl- ^type epoxy resin"); It is preferably a compound in which it is a benzene ring and Ar ⁴ is a biphenyl ring (also referred to as a "biphenylaralkyl-type epoxy resin"), and more preferably a biphenylaralkyl-type epoxy resin.

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

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

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

Among the compounds represented by the above formula (3b), bifunctional epoxy compounds include, for example, compounds in which ka is 1 in formula (3b).

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

Also, as the epoxy resin, it is preferable to use a naphthalene-type epoxy resin (excluding those corresponding to the compound represented by formula (3a)). As the naphthalene-type epoxy resin, a naphthylene ether-type epoxy resin is preferable from the viewpoint of excellent release action for discharging chips and further improving chemical resistance, copper foil adhesion, and insulation reliability.

The naphthylene ether type epoxy resin is excellent in the release action of discharging cutting chips, and from the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, 2 represented by the formula (3-3) A functional epoxy compound, a polyfunctional epoxy compound represented by the following formula (3-4), or a mixture thereof is preferred.

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

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

A commercially available product or a product manufactured by a known method may be used as the naphthylene ether type epoxy resin. Commercially available naphthylene ether type epoxy resins include, for example, DIC Corporation products "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311", "EXA-7311L", " EXA7311-G3", "EXA7311-G4", "EXA-7311G4S", "EXA-7311G5", etc., and HP-6000 is particularly preferred.

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

In formula (b3), each R ^3b is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, methyl group or ethyl group), an aralkyl group, a benzyl group, a naphthyl group, at least one glycidyloxy group-containing naphthyl group or naphthyl group containing at least one glycidyloxy group, where n is an integer of 0 or greater (eg, 0 to 2).

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

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

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

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

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

A commercially available product or a product manufactured by a known method may be used as the dicyclopentadiene type epoxy resin. Commercial products of dicyclopentadiene type epoxy resin include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H" and "EPICRON HP-7000HH" manufactured by Dainippon Ink and Chemicals. mentioned.

Among these, the epoxy resin is excellent in the release action of discharging shavings, and from the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, the epoxy resin represented by the formula (3a), It is preferably one or more selected from the group consisting of naphthalene-type epoxy resins and dicyclopentadiene-type epoxy resins, and more preferably contains naphthalene-type epoxy resins. In this case, the epoxy resin represented by formula (3a) preferably contains a naphthalene cresol novolac type epoxy resin, and the naphthalene type epoxy resin preferably contains a cresol/naphthol novolak type epoxy resin represented by formula (NE).

The epoxy resin may contain other epoxy resins that do not correspond to the epoxy resins or epoxy compounds described above.
Other epoxy resins include, but are not particularly limited to, 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 fluorene-type epoxy resin. Examples thereof include resins and epoxy resins composed of bisphenol A structural units and hydrocarbon structural units.
Among the above-mentioned other epoxy resins, bisphenol-type epoxy resins may be included from the viewpoint of excellent release action for discharging chips and further improving chemical resistance, copper foil adhesion, and insulation reliability. can. As the bisphenol type epoxy resin, for example, a diallyl bisphenol type epoxy resin (for example, diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.) can be used. can be done.

As the epoxy resin, one of the above-described epoxy resins and epoxy compounds may be used alone, or two or more thereof may be used in combination.

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

In the above formula, Ci represents the number of epoxy groups 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 total epoxy resin, Z ₁ +Z ₂ + . . . Z _n =1.

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

- Other resins The thermosetting resin (C) may further contain other resins as long as the effects of the resin composition of the present embodiment are not impaired. Other resins include, for example, oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups. These resins or compounds can be used singly or in combination of two or more.

Oxetane resin Examples of the oxetane resin include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3′-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, products of Toagosei Co., Ltd. “OXT-101”, “OXT -121” and the like.

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

Compounds having a polymerizable unsaturated group Examples of compounds having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (Meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta Monohydric or polyhydric alcohol (meth)acrylates such as erythritol hexa(meth)acrylate; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; benzocyclobutene Resin etc. are mentioned.

<Inorganic filler (D)>
The resin composition of the present embodiment contains an inorganic filler (D) different from the molybdenum compound (A) of the present embodiment. When the resin composition contains the inorganic filler (D), it tends to further improve heat resistance and low thermal expansion.
Examples of inorganic fillers (D) include 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 heat treatment products (e.g. heat-treated aluminum hydroxide to partially reduce the water of crystallization), boehmite, magnesium hydroxide, etc.), zinc compounds (e.g., zinc borate, zinc stannate, 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 fibers ( glass fine powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, spherical glass, and the like. These inorganic fillers (D) are used singly or in combination of two or more. Among these, the inorganic filler (D) is excellent in the release action of discharging shavings, and from the viewpoint of further improving low thermal expansion properties, silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, oxide It preferably contains at least one selected from the group consisting of titanium, barium titanate, magnesium oxide, and magnesium hydroxide, and more preferably contains silica.

Examples of silica include natural silica, fused silica, synthetic silica, aerosil, and hollow silica. These silicas are used individually by 1 type or in combination of 2 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. Commercial products of silica include “SFP-130MC” manufactured by Denka Co., Ltd., “SC-2050MB”, “SC-1050MLE”, “YA010C-MFN”, and “YA050C-MJA” manufactured by Admatechs Co., Ltd. is mentioned.

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

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

The silane coupling agent is not particularly limited, and includes silane coupling agents that are generally used for surface treatment of inorganic substances. For example, aminosilane compounds (eg, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (eg, γ-glycidoxypropyltrimethoxysilane, silane, etc.), acrylsilane compounds (eg, γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (eg, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, hydrochloride, etc.), styrylsilane-based compounds, phenylsilane-based compounds, and the like. A silane coupling agent is used individually by 1 type or in combination of 2 or more types. Among these, the silane coupling agent is preferably an epoxysilane compound. Examples of epoxysilane compounds 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 with respect to 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. By containing a wetting and dispersing agent, the resin composition tends to further improve the dispersibility of the filler.

The wetting and dispersing agent may be a known dispersing agent (dispersion stabilizer) used for dispersing fillers, for example, DISPERBYK (registered trademark)-110, 111, 118 manufactured by BYK-Chemie Japan Co., Ltd. , 180, 161, BYK (registered trademark)-W996, W9010, W903, and the like.

Although the content of the wetting and dispersing agent is not particularly limited, it 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. Curing catalysts include, for example, imidazole catalysts and phosphorus catalysts. These catalysts are used individually by 1 type or in combination of 2 or more types. Among these, imidazole catalysts are preferred.

Examples of imidazole catalysts include the above imidazoles. 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 Kasei Kogyo Co., Ltd.) is preferred.

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

<Solvent>
The resin composition of this embodiment may further contain a solvent. By containing a solvent, the resin composition tends to have a lower viscosity during the preparation of the resin composition, further improving handling properties, and further improving the impregnating properties of the base material.

The solvent is not particularly limited as long as it can dissolve part or all of each component in the resin composition. Examples thereof include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (eg, toluene, xylene, etc.), amides (eg, dimethylformaldehyde, etc.), propylene glycol monomethyl ether and acetate thereof. These solvents are used singly or in combination of two or more.

[Method for producing resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, but an example thereof includes a method of collectively or sequentially blending each component with a solvent and stirring the mixture. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading are used.

[Use]
The resin composition of the present embodiment can be suitably used as a cured product, prepreg, resin sheet, laminate, metal foil-clad laminate, and printed wiring board. These will be described below.

[Cured product]
A cured product is obtained by curing the resin composition of the present embodiment. The method for producing the cured product is not particularly limited. For example, the resin composition of the present embodiment is melted or dissolved in a solvent, poured into a mold, and cured under normal conditions using heat or light. can be obtained by In the case of heat curing, the curing temperature is preferably in the range of 120 to 300° C. from the viewpoint of efficient curing and prevention of deterioration of the resulting cured product.

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

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

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

[Prepreg]
The prepreg of the present embodiment includes a substrate and the resin composition of the present embodiment impregnated or applied to the substrate. The method of forming the prepreg may be a known method. Specifically, the resin composition of the present embodiment is impregnated or applied to a substrate, and then heated and dried at 100 to 200 ° C. It is obtained by semi-curing (to B stage).

The prepreg of the present embodiment also includes the form of a cured product obtained by thermally curing a semi-cured prepreg under 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% by volume, more preferably 35 to 85% by volume, and still more preferably 40 to 40% by volume, based on the total amount of the prepreg, in terms of the solid content of the prepreg. 80% by volume. When the content of the resin composition is within the above range, moldability tends to be further improved. The solid content of the prepreg as used herein refers to a component obtained by removing the solvent from the prepreg. 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 the components of the cured resin composition.

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

Fibers constituting the glass substrate include, for example, E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, HME glass, and the like. Among these, the fibers that make up the glass substrate are made of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass, from the viewpoint of being more excellent in strength and low water absorption. One or more fibers selected from the group are preferred.

Examples of the form of the base material include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, and the like. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave, etc. are known, and it is possible to appropriately select and use from these known ones depending on the intended use and performance. . In addition, glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used. The thickness and weight of the base material are preferably about 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 selected from the group consisting of the resin sheet of the present embodiment and the prepreg of the present embodiment, and a laminate disposed on one or both sides of the laminate. and a coated metal foil. The laminate may be formed from one resin sheet or one prepreg, or may be formed from a plurality of resin sheets and/or a plurality of prepregs.

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

The molding method and molding conditions for the metal foil-clad laminate are not particularly limited, and general techniques and conditions for printed wiring board laminates and multilayer boards can be applied. For example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when molding a laminate (laminate described above) or a metal foil-clad laminate. In the molding of a laminate (laminate described above) or a metal foil-clad laminate (lamination molding), the temperature is 100 to 300° C., the pressure is 2 to 100 kgf/cm ² , and the heating time is 0.05 to 5. Time ranges are common. Furthermore, if desired, post-curing can be performed at a temperature of 150-300°C. Particularly when a multistage press is used, the temperature is preferably 200 to 250° C., the pressure is 10 to 40 kgf/cm ² , and the heating time is 80 to 130 minutes, from the viewpoint of sufficiently accelerating the curing of the prepreg. More preferably, the pressure is 25 to 35 kgf/cm ² and the heating time is 90 to 120 minutes. Moreover, it is also possible to form a multilayer board by laminating a prepreg and a wiring board for an inner layer separately prepared in combination.

[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 the present 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, for example, by the following method. First, the metal foil-clad laminate of this embodiment is prepared. An inner layer board having a conductor layer (inner layer circuit) is produced by etching the metal foil of the metal foil clad laminate into a predetermined wiring pattern. Next, on the surface of the conductor layer (inner layer circuit) of the inner layer substrate, a predetermined number of prepregs and a metal foil for the outer layer circuit are laminated in this order, and integrally molded (lamination molding) by heating and pressing. get a body The laminate molding method and molding conditions are the same as the laminate molding method and molding conditions for the laminate and the metal foil-clad laminate described above. Next, the laminate is perforated for through holes and via holes, and the wall surfaces of the holes thus formed are plated with a metal film for conducting the conductor layer (inner layer circuit) and the metal foil for the outer layer circuit. to form Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to form an outer layer substrate having a conductor layer (outer layer circuit). A printed wiring board is thus manufactured.

In addition, when a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer that becomes a circuit on the insulating layer. At this time, an electroless plating technique can 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. Become. 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 (this The layer containing the cured product of the resin composition of the embodiment) is composed of the insulating layer containing the cured product of the resin composition of the present embodiment.

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

[Method for measuring weight average molecular weight (Mw)]
The weight average molecular weight (Mw) of the thermosetting compound was measured by the GPC method as follows. 20 μL of a solution obtained by dissolving 0.5 g of a thermosetting compound in 2 g of tetrahydrofuran (THF) is injected into a high-performance liquid chromatography (Shimadzu Corporation, pump: LC-20AD (trade name)) for analysis. bottom. The columns were Shodex (registered trademark) GPC KF-804 (trade name, length 30 cm x inner diameter 8 mm) manufactured by Showa Denko, Shodex (registered trademark) GPC KF-803 (trade name, length 30 cm x inner diameter 8 mm), Shodex ( Registered trademark) GPC KF-802 (trade name, length 30 cm × inner diameter 8 mm), and Shodex (registered trademark) GPC KF-801 (trade name, length 30 cm × inner diameter 8 mm), using a total of four, the mobile phase THF (solvent) was used as a solvent, and the flow rate was 1 mL/min. As a detector, RID-10A (trade name, differential refractive index detector, Shimadzu Corporation) was used. The weight average molecular weight (Mw) was obtained by GPC method using standard polystyrene as a standard substance.

[Production 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 0.0 g of zinc chloride are added to 100 g of pure water. 105 mol (14.3 g) were dissolved. 0.5 g of a 10 mol/L sodium hydroxide aqueous solution was added dropwise to this solution while stirring at 20° C. to obtain a precipitate.
After filtering the generated precipitate with a membrane filter, it was dried at 120° C. for 1 hour to obtain a white powder. When the obtained powder was analyzed with an X-ray diffractometer (Rigaku Co., Ltd. MiniFlex 600 (trade name)), it was found that zinc ammonium molybdate hydrate ((NH ₄ )Zn ₂ MoO _9. (H ₃ O)) Confirmed that there is.
Subsequently, the obtained powder is pulverized using a jet mill pulverizer (Nisshin Engineering Co., Ltd., Super Jet Mill SJ-500), and the powder obtained by the pulverization treatment is subjected to laser diffraction. - The average particle size (D50 particle size) was 2.2 µm when measured with a scattering type particle size distribution analyzer (Microtrac MT3300EXII (trade name)).

[Production Example 2] Production of powder of zinc ammonium molybdate hydrate surface-coated with 15 nm silica (silica-coated zinc ammonium molybdate hydrate) 33 g of zinc ammonium hydrate powder (average particle size: 2.2 μm) was dispersed in 100 ml of ethanol, and the temperature of the resulting dispersion was maintained at 55° C. by heating the container with an oil bath. 6 g of silicon tetraethoxide and 6 g of aqueous ammonia (29% concentration) were added thereto, and the mixture was reacted for 2 hours while stirring. After that, drying and heat treatment were performed, and the film thickness was adjusted to 15 nm. Then, it was diluted and washed with ethanol, 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 size: 2.5 μm). The obtained powder of silica-coated ammonium zinc molybdate hydrate was in a very good state of dispersion.

[Synthesis Example 1] Synthesis of 1-naphthol aralkyl-type cyanate ester compound (SN495V-CN) α-naphthol aralkyl-type phenolic resin (SN495V, OH group equivalent: 236 g) in which all R ^2a in the above formula (2b) are hydrogen atoms / mol, manufactured by Nippon Steel Chemical Co., Ltd.) 300 g (1.28 mol in terms of hydroxy group (OH group)) and 194.6 g (1.92 mol) of triethylamine (1.5 mol per 1 mol of hydroxy group) to 1800 g of dichloromethane It was dissolved and this was designated as Solution 1. 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of hydroxy group), Solution 1 was poured into 1205.9 g of water over 30 minutes while stirring and maintaining the liquid temperature at -2 to -0.5°C. After pouring solution 1, the mixture was stirred at the same temperature for 30 minutes. I ordered over. After pouring solution 2, the mixture was stirred at the same temperature for 30 minutes to complete the reaction. After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The resulting organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater after the fifth washing was 5 μS/cm, and it was confirmed that the ionic compounds that could be removed by washing with water were sufficiently removed. The organic phase after washing with water is concentrated under reduced pressure and finally concentrated to dryness at 90° C. for 1 hour to give the desired 1-naphthol aralkyl cyanate ester compound (SN495V-CN, cyanate ester group equivalent: 261 g/ mol) (orange viscous substance) was obtained. The infrared absorption spectrum of the obtained SN495V-CN showed absorption at 2250 cm ^-1 (cyanate ester group) and no absorption of hydroxy group.

[Example 1]
(Production of polymer (B1))
14 parts by mass of a maleimide compound (maleimide group equivalent: 285 g/mol, BMI-80 (trade name), K.I. Kasei Co., Ltd.) was added to 40 parts by mass of propylene glycol monomethyl ether (KH Neochem Co., Ltd.) and heated to reflux at 130°C. 10 parts by mass of diamino-modified silicone (amino group equivalent 1500 g / mol, X-22-161B (trade name), Shin-Etsu Chemical Co., Ltd.) is dissolved and reacted in the solution dissolved under the conditions of the primary polymer was prepared. After that, stirring is continued at a heating reflux temperature of 130° C., and when the viscosity of the solution containing the primary polymer increases to 200 to 300 mPa s with an ICI viscometer (cone and plate type viscometer, manufactured by Towa Kogyo Co., Ltd.), A solution obtained by dissolving 1.0 part by mass of succinic anhydride (manufactured by Tokyo Kasei Co., Ltd.) in 22.5 parts by mass of propylene glycol monoethyl ether acetate (manufactured by Dow Chemical Co., Ltd.) was added to this solution, and heated to reflux temperature of 130. C. for several hours to obtain a solution containing the polymer (B1), which is the thermosetting compound (B).

It was confirmed that the obtained polymer (B1) contained a maleimide group and a polysiloxane structure in the molecule.
It was also confirmed that the polymer (B1) contained structural units derived from an amino-modified silicone and structural units derived from a maleimide compound.
Furthermore, when the total amount of primary amine and secondary amine in polymer (B1) was measured in accordance with JIS K 7237:1995, the amine value of polymer (B1) was 0.1 mgKOH/g. there were.
In addition, the weight average molecular weight (Mw) of the polymer (B1) was 12000 in terms of polystyrene in the GPC method as a result of measurement by the above method.

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

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

[Example 2]
Except that 3 parts by mass of the powder of zinc ammonium molybdate hydrate obtained in Production Example 1 was used instead of 3 parts by mass of the silica-coated zinc ammonium molybdate hydrate powder obtained in Production Example 2. obtained a prepreg in the same manner as in Example 1.
Using the obtained prepreg, in the same manner as in Example 1, a metal foil-clad laminate (double-sided copper-clad laminate) having an insulating layer with a thickness of 0.8 mm was produced.

[Example 3]
(Production of polymer (B2))
In a three-necked flask equipped with a thermometer and a Dimroth, 5.3 parts by mass of diallyl bisphenol A (DABPA (trade name), Daiwa Kasei Kogyo 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., functional group equivalent 490 g / mol) 8.7 parts by weight, biphenyl-type epoxy compound c1 (YL-6121H (trade name), Mitsubishi Chemical Corporation) 5.8 parts by weight , 30 parts by mass of propylene glycol monomethyl ether acetate (DOWANOL PMA (trade name), Dow Chemical Japan Co., Ltd.) was added as a solvent, and heated to 120°C with stirring in an oil bath. After confirming that these raw materials were dissolved in the solvent, 0.3 parts by mass of an imidazole catalyst (TBZ (trade name), Shikoku Kasei Kogyo Co., Ltd.) was added, and the mixture was heated to 140° C. and stirred for 5 hours. After cooling, a solution (solid content: 50% by mass) containing the polymer (B2), which is the thermosetting compound (B), was obtained. In addition, it was used for the preparation of the polymer (B2).

In addition, diallyl bisphenol 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".

It was confirmed that the obtained polymer (B2) contained an epoxy group, a hydroxy group and a polysiloxane structure in its molecule.
Further, it was confirmed that the polymer (B2) contains a structural unit derived from an alkenylphenol, a structural unit derived from an epoxy-modified silicone, a structural unit derived from an epoxy compound, and a structural unit derived from a phenol compound. bottom.
Furthermore, the content of structural units derived from epoxy-modified silicone relative to the polymer (B2) was 43.5% by mass.
Further, the content of the structural unit derived from the epoxy compound was 30.8% by mass with respect to the total mass (100% by mass) of the structural unit derived from the epoxy-modified silicone and the structural unit derived from the epoxy compound.
The alkenyl group equivalent in the polymer (B2) was 872 g/mol.
The weight average molecular weight (Mw) of the polymer (B2) was 11,900 in terms of polystyrene in the GPC method.

(Manufacture of prepreg)
26 parts by mass of the 1-naphtholaralkyl-type cyanate ester compound obtained in Synthesis Example 1 and a novolac-type maleimide compound (BMI-2300 (trade name), Daiwa Kasei Kogyo Co., Ltd.) 17 parts by mass, naphthalene cresol novolac type epoxy resin (epoxy group (functional group) equivalent weight: 244 g / eq, HP-9540 (trade name), DIC Corporation) 27 parts by mass, 3 parts by mass of the silica-coated zinc ammonium molybdate hydrate powder obtained in Production Example 2, slurry silica (SC-2050MB (trade name), Admatechs Co., Ltd.) 200 parts by mass, Epoxysilane coupling agent (KBM-403 (trade name), Dow Toray Coatings Co., Ltd.) 5 parts by mass, wetting and dispersing agent (DISPERBYK-161 (trade name), BYK Chemie Japan Co., Ltd.) 1 part by mass , 2,4,5-triphenylimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and methyl ethyl ketone as a solvent were mixed to obtain a varnish (resin composition). This varnish was impregnated and applied to an S glass woven fabric (thickness 100 μm) and dried by heating at 150° C. for 3 minutes to obtain a prepreg having a resin composition solid content (including filler) content of 46% by mass. .

(Manufacturing of metal foil-clad laminate)
Four sheets of the obtained prepreg were laminated to obtain a laminate. Electrodeposited copper foil (3EC-III (trade name), manufactured by Mitsui Mining & Smelting Co., Ltd.) having a thickness of 12 μm is placed on both sides of this laminate, and vacuum pressed at 30 kgf/cm ² at 220° C. for 120 minutes to laminate. By molding, a metal foil-clad laminate (double-sided copper-clad laminate) having an insulating layer thickness of 0.8 mm was produced.

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

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

[Comparative Example 3]
Instead of using the silica-coated zinc ammonium molybdate hydrate powder obtained in Production Example 2, 25 parts by mass of silicone composite powder (KMP-605 (trade name), Shin-Etsu Chemical Co., Ltd.) was used instead of 15 parts by mass. A prepreg was obtained in the same manner as in Comparative Example 2, except that parts by mass were blended.
Using the obtained prepreg, a metal foil-clad laminate (double-sided copper-clad laminate) having 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 silica-coated zinc ammonium molybdate hydrate powder obtained in Production Example 2 was not used.
Using the obtained prepreg, in the same manner as in Example 1, a metal foil-clad laminate (double-sided copper-clad laminate) having an insulating layer with a thickness of 0.8 mm was produced.

〔evaluation〕
Using the metal foil-clad laminates obtained in Examples and Comparative Examples, drillability was evaluated by the following method. Table 1 shows the results.

(drillability)
Using the metal foil-clad laminates obtained in Examples and Comparative Examples, drillability (hole position accuracy) was evaluated. Evaluation was performed under the following drilling conditions. Table 1 shows the results.
Entry sheet (Mitsubishi Gas Chemical Co., Ltd. LE R12F3 (trade name)), 3 metal foil clad laminates (base material thickness & stack: 0.8 mm x 3), and backup board (Nippon Decorax Co., Ltd.) SPB-W (trade name) manufactured by Hitachi Via Mechanics Co., Ltd.) are stacked in this order and drilled under the following conditions using a processing machine (ND-1 V212 (trade name) manufactured by Hitachi Via Mechanics Co., Ltd.). The positional displacement amount of the holes was measured. This amount of misalignment was the amount of misalignment on the back side of the lowest metal-foil-clad laminate among the three metal-foil-clad laminates processed. The amount of positional deviation was measured for all drilled holes 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 (trade name) manufactured by Union Tool Co., Ltd. 0.15 mm × 2.7 mm
Bit diameter: 0.15mm
RPM: 160krpm
Feeding speed: 1.6m/min
Pull-in speed: 25.4m/min
Thrust amount: 0.3mm
Number of processing holes: 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 incorporated herein by reference.

INDUSTRIAL APPLICABILITY According to the present invention, a resin composition suitably used for producing a resin sheet and a prepreg having excellent drillability, a resin sheet, a prepreg, a metal foil-clad laminate, and a printed wiring obtained using the resin composition boards can be provided.

Claims

a molybdenum compound (A);
A thermosetting compound (B )and,
a thermosetting resin (C) different from the thermosetting compound (B);
and an inorganic filler (D) different from the molybdenum compound (A),
Resin composition.
The molybdenum compound (A) includes molybdic acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate. The resin composition according to claim 1, comprising at least one selected from the group consisting of hydrates.
The resin composition according to claim 1, wherein the thermosetting compound (B) contains the maleimide group.
The resin composition according to claim 1, wherein the thermosetting compound (B) contains at least structural units derived from an amino-modified silicone and structural units derived from a maleimide compound.
The resin according to claim 1, wherein the thermosetting compound (B) is a polymer obtained by polymerizing at least an amino-modified silicone, a maleimide compound, a carboxylic acid and/or a carboxylic anhydride. Composition.
The resin composition according to claim 4, wherein the amino-modified silicone contains an 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, each R b independently represents a single bond, an alkylene group, or an arylene group, and n is represents an integer from 1 to 100).
The molybdenum compound (A) includes molybdic acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate. including at least one selected from the group consisting of hydrates,
The thermosetting compound (B) contains the maleimide group,
The thermosetting compound (B) further comprises at least a structural unit derived from an amino-modified silicone and a structural unit derived from a maleimide compound,
The resin composition according to claim 1, wherein the amino-modified silicone contains an 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; each R b independently represents a single bond, an alkylene group, or an arylene group; n is represents an integer from 1 to 100).
The resin composition according to claim 1, wherein the thermosetting compound (B) contains the epoxy group and/or the hydroxy group.
The thermosetting compound (B) comprises at least structural units derived from alkenylphenol, structural units derived from epoxy-modified silicone, and structural units derived from an epoxy compound other than the epoxy-modified silicone. Item 1. The resin composition according to item 1.
The resin composition according to claim 1, wherein 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. thing.
The resin composition according to claim 8, wherein the epoxy-modified silicone contains an epoxy-modified silicone represented by the following formula (2).

(In formula (2), each R 1 independently represents a single bond, an alkylene group, an arylene group, or an aralkylene group, and each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. and n is an integer from 0 to 100).
The molybdenum compound (A) includes molybdic acid, zinc molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenum disulfide, molybdenum trioxide, molybdate hydrate, and zinc ammonium molybdate. including at least one selected from the group consisting of hydrates,
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,
The resin composition according to claim 1, wherein the epoxy-modified silicone contains an epoxy-modified silicone represented by the following formula (2).

(In formula (2), each R 1 independently represents a single bond, an alkylene group, an arylene group, or an aralkylene group; each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group; and n is an integer from 0 to 100).
The resin composition according to claim 1, wherein the thermosetting resin (C) contains at least one selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, alkenyl-substituted nadimide compounds, and epoxy resins. thing.
The resin composition according to claim 13, wherein the thermosetting resin (C) contains a maleimide compound.
The maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 15. The resin composition according to claim 14, comprising at least one selected from the group consisting of polytetramethylene oxide-bis(4-maleimidobenzoate) and a maleimide compound represented by the following formula (4).

(In formula (4), each R 5 independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.).
The resin composition according to claim 14, wherein the maleimide compound contains a maleimide compound represented by the following formula (9).

(In formula (9), each R 13 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.).
The inorganic filler (D) contains at least one 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 of claim 1, comprising:
Claim 1, wherein 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 resin composition according to .
Claim 1, wherein the content of the thermosetting compound (B) is 5 to 50 parts by mass with respect to a total of 100 parts by mass of the thermosetting compound (B) and the thermosetting resin (C). The resin composition according to .
Claim 1, wherein 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). The resin composition according to .
Claim 1, wherein 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). The described resin composition.
The thermosetting resin (C) contains at least one selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, alkenyl-substituted nadimide compounds, and epoxy resins,
The thermosetting resin (C) contains a maleimide compound,
The maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, At least one selected from the group consisting of polytetramethylene oxide-bis(4-maleimidobenzoate), a maleimide compound represented by the following formula (4), and a maleimide compound represented by the following formula (9),
The inorganic filler (D) contains at least one selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide. including
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 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 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),
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). The described resin composition.

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

(In formula (9), each R 13 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.).
The thermosetting resin (C) contains at least one selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, alkenyl-substituted nadimide compounds, and epoxy resins,
The thermosetting resin (C) contains a maleimide compound,
The maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, At least one selected from the group consisting of polytetramethylene oxide-bis(4-maleimidobenzoate), a maleimide compound represented by the following formula (4), and a maleimide compound represented by the following formula (9),
The inorganic filler (D) contains at least one selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide. including
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 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 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),
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). The described resin composition.

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

(In formula (9), each R 13 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.).
a support;
a resin layer arranged on one side or both sides of the support,
The resin layer contains the resin composition according to any one of claims 1 to 23,
resin sheet.
a substrate;
impregnated or applied to the base material, and the resin composition according to any one of claims 1 to 23,
prepreg.
A laminate formed of the resin sheet according to claim 24;
a metal foil disposed on one or both sides of the laminate,
Metal foil clad laminate.
A laminate formed of the prepreg according to claim 25;
a metal foil disposed on one or both sides of the laminate,
Metal foil clad laminate.
A laminate formed of the resin sheet according to claim 24 and the prepreg according to claim 25,
a metal foil disposed on one or both sides of the laminate,
Metal foil clad laminate.
an insulating layer;
a conductor layer formed on one side or both sides of the insulating layer,
The insulating layer comprises a cured product of the resin composition according to any one of claims 1 to 23,
printed wiring board.