WO2021192680A1

WO2021192680A1 - Resin composition, prepreg, resin sheet, laminate board, metal foil-clad laminate board, and printed wiring board

Info

Publication number: WO2021192680A1
Application number: PCT/JP2021/004891
Authority: WO
Inventors: 工藤　博章; 達郎高村; 典浩志田
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2020-03-25
Filing date: 2021-02-10
Publication date: 2021-09-30
Also published as: JPWO2021192680A1; TW202142621A; KR20220157933A; CN115335433A

Abstract

Provided is a resin composition, containing a cyanate ester compound (A), a filler (B), a molybdenum compound (C), and zinc oxide (D), wherein the molybdenum compound (C) contains molybdenum compound particles, and the zinc oxide (D) content of the resin composition is 5 wt%.

Description

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

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

In recent years, the high integration, high functionality, and high-density mounting of semiconductors widely used in electronic devices, communication devices, personal computers, etc. are accelerating. Therefore, there is an increasing demand for higher performance such as low thermal expansion, drilling workability, heat resistance, and flame retardancy in the laminated board for semiconductor plastic packages.

In addition to these, especially in recent years, there is a strong demand for reduction of the coefficient of thermal expansion in the surface direction of the laminated board. This is because if the difference in the coefficient of thermal expansion between the semiconductor element and the printed wiring board for the semiconductor plastic package is large, the semiconductor plastic package will warp due to the difference in the coefficient of thermal expansion when a thermal impact is applied, and the semiconductor element and the semiconductor plastic will warp. This is because a connection failure occurs between the printed wiring boards for the package and between the semiconductor plastic package and the printed wiring boards mounted.

Conventionally, in order to reduce the coefficient of thermal expansion while satisfying various properties required for a laminated board, a method of blending a relatively high amount of an inorganic filler into the resin composition constituting the laminated board has been known (for example). See Patent Documents 1 and 2). However, in these methods, the cured product of the resin composition becomes hard and brittle, so that when drilling the laminated plate obtained by using the cured product, the hole position accuracy is lowered, the drill bit is worn faster, and the drill bit is used. There is a problem that the drill workability is deteriorated, such as an increase in the frequency of replacement and a tendency for the drill bit to be broken.

On the other hand, as a method for improving the drilling workability of a laminated plate, a method of blending a molybdenum compound such as zinc molybdate or calcium molybdate into a resin composition is known (see, for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 2004-059643 Japanese Unexamined Patent Publication No. 2009-12702 International Publication 2013/047203 Pamphlet

However, when the molybdenum compound described in Patent Document 3 is blended in the resin composition, the molybdenum compound or zinc oxide as an impurity contained therein acts as a curing catalyst for the cyanate ester compound, and voids are generated to generate a molded product. There is a problem that the appearance of is deteriorated.

The present invention has been made in view of the above problems, and is a resin composition having both drilling workability and appearance, and a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, and a printed wiring using the same. An object of the present invention is to provide a molded product such as a plate.

As a result of diligent studies to solve such a problem, the present inventors have at least containing a cyanate ester compound, a filler, a molybdenum compound, and zinc oxide, and the zinc oxide contained in the resin composition. We have found that the above problems can be solved by setting the amount to a specific range or less, and have reached the present invention.

That is, the present invention is as follows.
[1]
A resin composition containing a cyanate ester compound (A), a filler (B), a molybdenum compound (C), and zinc oxide (D).
The molybdenum compound (C) contains molybdenum compound particles and contains molybdenum compound particles.
A resin composition in which the content of zinc oxide (D) in the resin composition is 5% by mass or less with respect to the total mass of the molybdenum compound particles.
[2]
The resin composition according to the above [1], wherein the content of the filler (B) is 10 to 500 parts by mass with respect to a total of 100 parts by mass of the resin solid components in the resin composition.
[3]
The resin composition according to the above [1] or [2], wherein the content of the molybdenum compound (C) is 0.2 to 30 parts by mass with respect to a total of 100 parts by mass of the resin solid components in the resin composition.
[4]
The resin composition according to any one of [1] to [3] above, wherein the content of zinc oxide (D) is 0.1% by mass or more and 5% by mass or less with respect to the total mass of the molybdenum compound particles. thing.
[5]
The resin composition according to any one of the above [1] to [4], wherein the zinc oxide (D) is contained in the molybdenum compound particles.
[6]
The resin composition according to any one of the above [1] to [5], wherein the molybdenum compound particles have a spherical shape.
[7]
The resin composition according to the above [6], wherein the molybdenum compound particles have a circularity of 0.90 to 1.00.
[8]
The resin composition according to any one of the above [1] to [7], wherein the molybdenum compound particles have an average particle size of 0.1 to 10 μm.
[9]
The molybdenum compound (C) is one or more selected from the group consisting of zinc molybdate, ammonium molybdate, sodium molybdate, calcium molybdate, potassium molybdenum, molybdenum disulfide, molybdenum trioxide, and molybdenum hydrate. The resin composition according to any one of the above [1] to [8].
[10]
The cyanate ester compound (A) is a phenol novolac type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, a naphthylene ether type cyanate ester compound, a xylene resin type cyanate ester compound, and a bisphenol M type cyanate ester compound. , Bisphenol A type cyanate ester compound, diallyl bisphenol A type cyanate ester compound, and one or more selected from the group consisting of biphenyl aralkyl type cyanate ester compound, any of the above [1] to [9]. The resin composition described.
[11]
The filler (B) is one or more inorganic fillers selected from the group consisting of silica, alumina, aluminum nitride, boron nitride, boehmite, aluminum hydroxide, and titanium oxide. ] The resin composition according to any one of.
[12]
The resin composition according to any one of [1] to [11] above, wherein the filler (B) is one or more organic fillers selected from the group consisting of silicone rubber powder and silicone composite powder.
[13]
Maleimide compound (M), epoxy compound (E), phenol compound (F), alkenyl-substituted nadiimide compound (K), octacene resin (G), benzoxazine compound (H), and a compound having a polymerizable unsaturated group ( The resin composition according to any one of [1] to [12] above, further comprising one or more compounds selected from the group consisting of I).
[14]
The maleimide compound (M) is bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl). ) The resin composition according to the above [13], which is one or more selected from the group consisting of methane, a maleimide compound represented by the following formula (2), and a maleimide compound represented by the following formula (3). ..

(In the formula (2), R ¹ independently represents a hydrogen atom or a methyl group, and n 1 is 1 to 10.)

In the formula (3), R ² existing in a plurality of each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, n2 is an average value, and represents 1 <n2 ≦ 5. .)
[15]
The resin according to the above [13] or [14], wherein the epoxy compound (E) is at least one selected from the group consisting of a biphenyl aralkyl type epoxy compound, a naphthalene type epoxy compound, and a naphthylene ether type epoxy resin. Composition.
[16]
The resin composition according to any one of the above [1] to [15], which is used for a printed wiring board.
[17]
A prepreg comprising a base material and the resin composition according to any one of the above [1] to [15], which is impregnated or coated on the base material.
[18]
A resin sheet obtained by molding the resin composition according to any one of the above [1] to [15] into a sheet.
[19]
A resin sheet with a support having the support and the resin composition according to any one of the above [1] to [15] arranged on the support.
[20]
A laminated board in which one or more selected from the group consisting of the prepreg according to the above [17], the resin sheet according to the above [18], and the resin sheet with a support according to the above [19] are laminated.
[21]
One or more selected from the group consisting of the prepreg according to the above [17], the resin sheet according to the above [18], and the resin sheet with a support according to the above [19].
At least one kind of metal foil arranged on one side or both sides selected from the group consisting of the prepreg, the resin sheet, and the resin sheet with a support.
Metal leaf-clad laminate with.
[22]
A printed wiring board having an insulating layer containing a cured product of the resin composition according to any one of [1] to [15] above, and a conductor layer formed on the surface of the insulating layer.

According to the present invention, there is provided a resin composition having both drilling workability and appearance, and a molded product using the same, such as a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, and a printed wiring board. Can be done.

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

[Resin composition]
The resin composition of the present embodiment is a resin composition containing a cyanate ester compound (A), a filler (B), a molybdenum compound (C), and zinc oxide (D). The molybdenum compound (C) contains molybdenum compound particles, and the content of zinc oxide (D) in the resin composition is 5% by mass or less with respect to the total mass of the molybdenum compound particles.

The resin composition of the present embodiment contains the molybdenum compound (C) and zinc oxide (D), and the content of zinc oxide (D) is 5% by mass with respect to the total mass of the molybdenum compound particles. It has been adjusted as follows. When the content of zinc oxide (D) is 5% by mass or less in terms of ZnO, voids generated by the reaction of zinc oxide with the cyanate ester compound can be suppressed, and the appearance of the molded product is improved. ..

From the same viewpoint as this, the content of zinc oxide (D) contained in the resin composition is preferably 4% by mass or less with respect to the total mass of the molybdenum compound particles. The lower limit of the content of zinc oxide (D) contained in the resin composition is not particularly limited, but from the viewpoint of suppressing the production cost, it is preferably 0.1% by mass or more, and 0.2% by mass or more. More preferably, it is more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.

The content of zinc oxide (D) contained in the resin composition referred to here is the total mass of zinc oxide (D) contained in the resin composition, and zinc oxide (D) is mainly contained in the molybdenum compound particles. When it is contained, it means the content of zinc oxide contained in the molybdenum compound particles, and when zinc oxide (D) is not contained in the molybdenum compound particles, the oxidation contained in the resin composition of the portion other than the molybdenum compound particles. It means the content of zinc, and when zinc oxide (D) is contained in both the molybdenum compound particles and the resin composition of the portion other than the molybdenum compound particles, the zinc oxide contained in the molybdenum compound particles and the molybdenum compound particles It means the total amount of zinc oxide contained in the resin composition of the portion other than the above.

That is, in the resin composition of the present embodiment, zinc oxide (D) is mainly contained in the molybdenum compound particles, and zinc oxide (D) is not contained in the molybdenum compound particles, and the resin composition is a portion other than the molybdenum compound particles. The contained form or the form in which zinc oxide (D) is contained in both the molybdenum compound particles and the resin composition of the portion other than the molybdenum compound particles may be used.

Examples of the form in which zinc oxide (D) is mainly contained in the molybdenum compound particles include a case where a resin composition is prepared using a molybdenum compound (C') containing molybdenum compound particles containing zinc oxide, which will be described later.

In the form in which zinc oxide (D) is not contained in the molybdenum compound particles and is contained in the resin composition of the portion other than the molybdenum compound particles, for example, the zinc oxide-free molybdenum compound (C) and zinc oxide (D) are separately separated. A case where a resin composition is prepared by adding to the above is mentioned.

The form in which zinc oxide (D) is contained in both the molybdenum compound particles and the resin composition of the portion other than the molybdenum compound particles is prepared, for example, by preparing a mixture of molybdenum compound particles and zinc oxide in advance by kneading or the like. Examples thereof include a case where a resin composition is prepared using the mixture. In this case, zinc oxide tends to be contained in both the molybdenum compound particles and the portion other than the molybdenum compound particles because zinc oxide may be dispersed in the resin composition when the resin composition is prepared.

Among these forms, a form in which zinc oxide (D) is mainly contained in the molybdenum compound particles and a form in which zinc oxide (D) is contained in both the molybdenum compound particles and the resin composition of the portion other than the molybdenum compound particles are preferable. More specifically, a form in which a resin composition is prepared using a molybdenum compound (C') containing molybdenum compound particles containing zinc oxide, which will be described later, or a mixture of molybdenum compound particles and zinc oxide in advance by kneading or the like. After preparation, a form in which a resin composition is prepared using the mixture is more preferable.

The zinc oxide when the resin composition is prepared by separately adding the zinc oxide-free molybdenum compound (C) and zinc oxide (D) is not particularly limited, and zinc oxide having various properties and particle sizes can be used. It can be appropriately selected and used, and commercially available zinc oxide can be used.

The zinc oxide in the case of kneading zinc oxide with molybdenum compound particles to prepare a mixture in advance is not particularly limited, and zinc oxide having various properties and particle sizes can be appropriately selected and used and is commercially available. Zinc oxide can be used.

The content of zinc oxide (D) in this case is calculated from the charged ratio and amount of molybdenum compound particles (molybdenum compound (C)) and zinc oxide, which are raw materials for preparing the molybdenum component to be mixed with the resin component. can do. In this case, the content of zinc oxide (D) is, for example, the charging ratio and amount of molybdenum compound particles (molybdenum compound (C)) and zinc oxide, which are raw materials for preparing a molybdenum component to be mixed with a resin component. It can be adjusted by changing it.

On the other hand, the content of zinc oxide contained in the molybdenum compound particles can be measured by X-ray photoelectron spectroscopy (XPS) described later. The content of zinc oxide contained in the molybdenum compound particles can be adjusted, for example, by changing the charging ratio of the molybdenum-containing raw material and the zinc-containing raw material, which are the raw materials for producing the molybdenum compound (C).

[Molybdenum compound (C)]
The molybdenum compound (C) contains molybdenum in the molecule, but an oxide of molybdenum and a sulfide of molybdenum are preferable. Specific examples of the molybdenum compound (C) include zinc molybdate (for example, ZnMoO ₄ , Zn ₃ Mo ₂ O _9, etc.), ammonium molybdate, sodium molybdate, calcium molybdate, potassium molybdate, molybdenum disulfide. , Molybdenum trioxide, and molybdenum compounds such as molybdenum hydrate, but are not particularly limited. These can be used individually by 1 type or in combination of 2 or more types. The molybdenum hydrate, for example, molybdate monohydrate _{_{(MoO 3 · H 2 O)}} , ammonium molybdate tetrahydrate _{_{_{_{((NH 4) 6 Mo 7}}}} O 24 · 4H 2 O), zinc molybdate pentahydrate _{_{_{(Zn 5 Mo 2 O 11 ·}}} 5H 2 O) and the like. Among the above, zinc molybdate, molybdenum disulfide, and molybdenum hydrate are preferable from the viewpoint of drilling workability.

The content of the molybdenum compound (C) in the resin composition of the present embodiment can be appropriately set according to the intended use and performance, and is not particularly limited, but is heat resistant, flame retardant, and drilled. From the viewpoint of properties, the amount is preferably 0.2 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, still more preferably, based on 100 parts by mass of the total resin solid component in the resin composition. It is 1 to 10 parts by mass. In the present embodiment, the “resin solid content in the resin composition” refers to the components of the resin composition excluding the solvent and the filler, unless otherwise specified. Further, "100 parts by mass of resin solid content" means that the total of the components of the resin composition excluding the solvent and the filler is 100 parts by mass.

(Molybdenum compound particles)
The molybdenum compound (C) contains molybdenum compound particles. The molybdenum compound particles are particles constituting the molybdenum compound (C), and are, for example, particles containing the compound mentioned as a specific example of the molybdenum compound (C) described above. The content of the molybdenum compound particles contained in the molybdenum compound (C) is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 90 to 100% by mass. %, More preferably 95 to 100% by mass, when the content of the molybdenum compound particles contained in the molybdenum compound (C) is in the above range, the effect of the present invention tends to be more remarkable. ..

The shape of the molybdenum compound particles is not particularly limited, but the improvement in drilling workability tends to be more remarkable as the filling property of the molybdenum compound (C) in the resin composition and the molded product using the resin composition increases. , Preferably spherical. When the molybdenum compound particles are spherical, the circularity thereof is preferably 0.88 to 1.00, preferably 0.90 to 1.00, and 0.92 to 1.00. Is more preferable.
Here, the circularity is an index represented by circularity = 4π × (area) ÷ (perimeter) ² , and the closer the value is to 1, the more perfect the circle is. The circularity can be measured by a wet flow type particle size / shape analyzer. More specifically, it can be measured according to the method described in the examples.

The average particle size (D50) of the molybdenum compound particles can be appropriately set according to the desired performance and is not particularly limited. Considering the drilling workability and the dispersibility in the resin component and the like, the average particle size (D50) is preferably 0.1 to 10 μm, more preferably 0.5 to 8 μm. Here, in the present specification, the average particle size (D50) means the median size (median size), and the volume on the large side and the volume on the small side when the particle size distribution of the measured powder is divided into two. Is an equal amount. The average particle size (D50) is 50% of the total volume by measuring the particle size distribution of a predetermined amount of powder charged into the aqueous dispersion medium with a laser diffraction / scattering type particle size distribution measuring device and integrating the volume from the small particles. It means the value when it reaches.

The molybdenum compound (C) containing molybdenum compound particles can be produced by various known methods such as a firing method and a precipitation method, and the production method is not particularly limited. In addition, a commercially available product that is commercially available may be used.

(Molybdenum compound particles containing zinc oxide)
The molybdenum compound particles are preferably molybdenum compound particles containing zinc oxide. That is, as one aspect of the present embodiment, the resin composition of the present embodiment is a resin composition containing at least a cyanate ester compound (A), a filler (B), and a molybdenum compound (C). Therefore, it is preferable that the molybdenum compound (C) contains zinc oxide-containing molybdenum compound particles, and the zinc oxide content contained in the molybdenum compound particles is 5% by mass or less in terms of ZnO. In this case, the content of zinc oxide contained in the molybdenum compound particles is 5% by mass or less in terms of ZnO. When the content of zinc oxide is 5% by mass or less in terms of ZnO, voids generated by the reaction of zinc oxide with the cyanate ester compound are suppressed, and the appearance of the molded product is improved. From the same viewpoint as this, the content of zinc oxide contained in the molybdenum compound particles is preferably 4% by mass or less in terms of ZnO. The content of zinc oxide contained in the molybdenum compound particles is based on the total mass of the molybdenum compound particles. The term "containing zinc oxide" as used herein means a form in which zinc oxide is incorporated into the molybdenum compound particles or a form in which the molybdenum compound particles are attached to the surface.

The lower limit of the content of zinc oxide contained in the molybdenum compound particles is not particularly limited, but from the viewpoint of suppressing the production cost, it is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more. It is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
That is, the content of zinc oxide contained in the molybdenum compound particles is preferably 0.1 to 5% by mass, more preferably 0.2 to 5% by mass, and 0.3 to 5% by mass. Is more preferable, and it may be 0.5 to 4% by mass.

The content of zinc oxide contained in the molybdenum compound particles can be measured by X-ray photoelectron spectroscopy (XPS). More specifically, it can be measured according to the method described in the examples.

The content of zinc oxide contained in the molybdenum compound particles changes, for example, the charging ratio of the molybdenum-containing raw material and the zinc-containing raw material, which are raw materials for producing the molybdenum compound (C') containing the molybdenum compound particles containing zinc oxide. It can be adjusted by making it.

The shape and average particle size of the molybdenum compound particles containing zinc oxide are the same as the shape and average particle size of the molybdenum compound particles described above.

A molybdenum compound (C') containing molybdenum compound particles containing zinc oxide can be produced by various known methods such as a calcining method and a precipitation method using a molybdenum-containing raw material and a zinc-containing raw material, and the production method is particularly particular. Not limited. In addition, a commercially available product that is commercially available may be used.
[Resin component]

The resin composition of the present embodiment contains at least a cyanate ester compound (A) and a filler (B) in addition to the molybdenum compound (C) and zinc oxide (D) described above. As the cyanate ester compound (A) and the filler (B) used here, known ones can be appropriately selected and used according to the intended use and performance, and the type and amount of each material used. Is not particularly limited. For example, in the case of electric / electronic material use, electric insulating material use, machine tool material use, and adhesive use, various materials known in each technical field can be appropriately selected.

[Cyanic acid ester compound (A)]
As the cyanate ester compound (A), any known compound can be appropriately used as long as it is a compound having two or more cyanate ester groups (cyanato groups) directly bonded to the aromatic ring in one molecule.

The cyanate ester compound (A) is not particularly limited, and is, for example, a phenol novolac type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, a naphthylene ether type cyanate ester compound, and a xylene resin type cyanate. Esther compounds, bisphenol M-type cyanate ester compounds, bisphenol A-type cyanate ester compounds, diallyl bisphenol A-type cyanate ester compounds, and biphenyl aralkyl-type cyanate ester compounds are listed as preferable compounds from the viewpoint of moldability and surface hardness. Be done. As the cyanate ester compound (A), one type may be used alone, or two or more types may be used in combination in any combination and ratio. Among these, bisphenol A-type cyanate ester compounds and diallyl bisphenol A-type cyanic acids are considered from the viewpoints of heat resistance, flame retardancy, low dielectric constant (low dielectric constant, low dielectric adjunct), etc., in addition to moldability and surface hardness. Ester compounds and naphthol aralkyl-type cyanate ester compounds are preferable, and naphthol aralkyl-type cyanate ester compounds are particularly preferable.

The naphthol aralkyl type cyanate ester compound is not particularly limited, but for example, a compound represented by the following formula (1) is preferable.

(In the above formula (1), R ³ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. In the above formula (1), n 3 is 1 to 10).

The content of the cyanate ester compound (A) in the resin composition of the present embodiment is preferably 1 to 99.9 parts by mass with respect to 100 parts by mass of the total resin solid content in the resin composition. It is more preferably 3 to 90 parts by mass, further preferably 5 to 80 parts by mass, and may be 10 to 70 parts by mass, 20 to 60 parts by mass, or 25 to 50 parts by mass. When the content of the cyanate ester compound (A) is within the above range, it tends to be excellent in heat resistance, low dielectric constant, low dielectric loss tangent and the like.

When the resin composition of the present embodiment contains a maleimide compound (M) described later in addition to the cyanate ester compound (A), the content of the cyanate ester compound (A) is the cyanate ester compound (A). And, with respect to 100 parts by mass of the total amount of the maleimide compound (M), it is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, and further preferably 50 to 70 parts by mass. When the content of the cyanate ester compound (A) is within the above range, in addition to heat resistance, low dielectric constant, low dielectric loss tangent, etc., moldability and copper foil peel strength tend to be further improved.

[Filler (B)]
The resin composition of the present embodiment contains a filler (B). The filler (B) is not particularly limited, and examples thereof include an inorganic filler and an organic filler. As the filler (B), one type may be used alone, or two or more types may be used in combination.

The inorganic filler is not particularly limited, and examples thereof include one or more selected from the group consisting of silica, alumina, aluminum nitride, boron nitride, boehmite, aluminum hydroxide, and titanium oxide. Among these, silica is preferably used from the viewpoint of low thermal expansion, and alumina or aluminum nitride is preferably used from the viewpoint of high thermal conductivity.

The organic filler is not particularly limited, and examples thereof include rubber powders such as styrene type powder, butadiene type powder, and acrylic type powder; core shell type rubber powder; silicone resin powder; silicone rubber powder; and silicone composite powder. Among the above, from the viewpoint of low thermal expansion and flame resistance, one or more selected from the group consisting of silicone rubber powder and silicone composite powder is preferable.

The content of the filler (B) in the resin composition of the present embodiment is preferably 10 to 500 parts by mass, more preferably 50 parts by mass, based on 100 parts by mass of the total resin solid content in the resin composition. It is about 300 parts by mass, more preferably 75 to 250 parts by mass, and particularly preferably 100 to 200 parts by mass.

The resin composition in the present embodiment includes a maleimide compound (M), an epoxy compound (E), a phenol compound (F), an alkenyl-substituted nadiimide compound (K), an octacene resin (G), a benzoxazine compound (H), and polymerization. It may further contain one or more compounds selected from the group consisting of the compound (I) having a possible unsaturated group and the like.

[Maleimide compound (M)]
As the maleimide compound (M), any known compound can be appropriately used as long as it is a compound having one or more maleimide groups in one molecule, and the type thereof is not particularly limited. The number of maleimide groups per molecule of the maleimide compound (M) is 1 or more, preferably 2 or more.

The maleimide compound (M) is not particularly limited, and is, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy)-. Phenyl} propane, bis (3,5-dimethyl-4-maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane Examples thereof include a maleimide compound represented by the following formula (2), a maleimide compound represented by the following formula (3), a prepolymer of these maleimide compounds, and a prepolymer of the above maleimide compound and an amine compound. As the maleimide compound (M), one type may be used alone, or two or more types may be used in combination in any combination and ratio. By including such a maleimide compound (M), the coefficient of thermal expansion of the obtained cured product tends to be further lowered, and the heat resistance tends to be further improved.

Among these, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, the following One or more selected from the group consisting of the maleimide compound represented by the formula (2) and the maleimide compound represented by the following formula (3) is preferable from the viewpoint of low thermal expansion and heat resistance.

In the formula (3), R ² existing in a plurality of each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, n2 is an average value, and represents 1 <n2 ≦ 5. .)

When the resin composition of the present embodiment contains the maleimide compound (M), the content of the maleimide compound (M) is preferably 1 to 99% by mass with respect to 100 parts by mass of the total resin solid content in the resin composition. It is a part, more preferably 3 to 90 parts by mass, further preferably 5 to 80 parts by mass, and may be 10 to 70 parts by mass, 20 to 60 parts by mass, and 25 to 50 parts by mass. When the content of the maleimide compound (M) is within the above range, it tends to be more excellent in heat resistance and the like.

When the resin composition of the present embodiment contains a cyanate ester compound (A) and a maleimide compound (M), the content of the maleimide compound (M) is the cyanate ester compound (A) and the maleimide compound (M). It is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and further preferably 30 to 50 parts by mass with respect to 100 parts by mass of the total amount of the above. When the content of the maleimide compound (M) is within the above range, the moldability and the copper foil peel strength tend to be further improved in addition to the heat resistance.

[Epoxy compound (E)]
As the epoxy compound (E), any known compound can be appropriately used as long as it is a compound having one or more epoxy groups in one molecule, and the type thereof is not particularly limited. The number of epoxy groups per molecule of the epoxy compound (E) is 1 or more, preferably 2 or more.

The epoxy compound (E) is not particularly limited, and conventionally known epoxy compounds and epoxy resins can be used. For example, biphenyl aralkyl type epoxy compound, naphthalene type epoxy compound, bisnaphthalene type epoxy compound, polyfunctional phenol type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin. , Xylene novolac type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, phenol aralkyl novolac type epoxy resin, naphthol aralkyl novolac type epoxy resin, aralkyl novolac type epoxy resin, fragrance Group hydrocarbon Formaldehyde type epoxy compound, anthraquinone type epoxy compound, anthracene type epoxy resin, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy resin, zylock type epoxy compound, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F Type epoki resin, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, phenol type epoxy compound, biphenyl type epoxy resin, aralkyl novolac type epoxy resin, triazine skeleton epoxy compound, triglycidyl isocyanurate, alicyclic epoxy resin, polyol Examples thereof include a compound obtained by epoxidizing a double bond of a double bond-containing compound such as a type epoxy resin, a glycidyl amine, a glycidyl type ester resin, and butadiene, and a compound obtained by reacting a hydroxyl group-containing silicone resin with epichlorohydrin. .. Among these, a biphenyl aralkyl type epoxy compound, a naphthalene type epoxy compound, and a naphthylene ether type epoxy resin are preferable from the viewpoint of moldability and surface hardness. As the epoxy compound (E), one type may be used alone, or two or more types may be used in combination in any combination and ratio.

When the resin composition of the present embodiment contains the epoxy compound (E), the content of the epoxy compound (E) is preferably 1 to 99. With respect to 100 parts by mass of the total resin solid content in the resin composition. It is 9 parts by mass, more preferably 3 to 90 parts by mass, further preferably 4 to 80 parts by mass, and may be 10 to 70 parts by mass, 20 to 60 parts by mass, or 30 to 50 parts by mass. .. When the content of the epoxy compound (E) is within the above range, it tends to be more excellent in adhesiveness, flexibility and the like.

When the resin composition in the present embodiment contains the phenol compound (F) and the epoxy compound (E) described later, the content of the epoxy compound (E) is 100 mass by mass of the total amount of the phenol compound (F) and the epoxy compound (E). It is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and further preferably 40 to 60 parts by mass with respect to the parts. When the content of the epoxy compound (E) is within the above range, the heat resistance tends to be further improved in addition to the adhesiveness and flexibility.

[Phenol compound (F)]
As the phenol compound (F), any known compound can be appropriately used as long as it is a compound having two or more phenolic hydroxyl groups in one molecule, and the type thereof is not particularly limited.

The phenol compound (F) is not particularly limited, and is, for example, a cresol novolac type phenol resin, a biphenyl aralkyl type phenol resin represented by the following formula (4), and a naphthol aralkyl type phenol resin represented by the following formula (5). , Aminotriazine novolac type phenol resin, naphthalene type phenol resin, phenol novolac resin, alkylphenol novolac resin, bisphenol A type novolak resin, dicyclopentadiene type phenol resin, zylock type phenol resin, terpene-modified phenol resin, polyvinylphenols, etc. Can be mentioned. As the phenol compound (F), one type may be used alone, or two or more types may be used in combination in any combination and ratio.

Among these, from the viewpoint of moldability and surface hardness, cresol novolac type phenol resin, biphenyl aralkyl type phenol resin represented by the following formula (4), naphthol aralkyl type phenol resin represented by the following formula (5), Aminotriazine novolac type phenol resin and naphthalene type phenol resin are preferable, and biphenyl aralkyl type phenol resin represented by the following formula (4) and naphthol aralkyl type phenol resin represented by the following formula (5) are more preferable.

(In the formula (4), each of a plurality of R 4s independently represents a hydrogen atom or a methyl group, and ^{n 4 is 1 to 10.)}

(In the formula (5), the plurality of ^{R 5,} each independently, represent a hydrogen atom or a methyl group, n5 is 1-10.)

When the resin composition of the present embodiment contains a phenol compound (F), the content of the phenol compound (F) is preferably 1 to 99 parts by mass with respect to a total of 100 parts by mass of the resin solid content of the resin composition. It is more preferably 3 to 90 parts by mass, further preferably 5 to 80 parts by mass, and may be 10 to 70 parts by mass, 20 to 60 parts by mass, or 30 to 50 parts by mass. When the content of the phenol compound (F) is within the above range, it tends to be more excellent in adhesiveness, flexibility and the like.

When the resin composition in the present embodiment contains the phenol compound (F) and the epoxy compound (E), the content of the phenol compound (F) is 100 parts by mass in total of the phenol compound (F) and the epoxy compound (E). On the other hand, it is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and further preferably 40 to 60 parts by mass. When the content of the phenol compound (F) is within the above range, the copper foil peel strength tends to be further improved in addition to the adhesiveness and flexibility.

[Alkaline-substituted nadiimide compound (K)]
The alkenyl-substituted nadiimide compound (K) is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadiimide groups in one molecule, and examples thereof include compounds represented by the following formula (2d). The resin composition of the present embodiment tends to have improved heat resistance by containing the alkenyl-substituted nadiimide compound (K).

Wherein a plurality of R ₁ each independently represent a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms (e.g., methyl or ethyl) represents, R ₂ is an alkylene group having 1 to 6 carbon atoms, phenylene It represents a group, a biphenylene group, a naphthylene group, or a group represented by the following formula (6) or the following formula (7).

In formula (6), R ₃ represents a methylene group, an isopropylidene group, CO, O, S or SO ₂ .

In the formula (7), a plurality of R ₄ each independently represent an alkylene group, or a cycloalkylene group having 5 to 8 carbon atoms having 1 to 4 carbon atoms.

As the alkenyl-substituted nadiimide compound (K), a commercially available product may be used, or a manufactured product manufactured according to a known method may be used. Examples of commercially available products include "BANI-M" and "BANI-X" manufactured by Maruzen Petrochemical Co., Ltd.

When the resin composition of the present embodiment contains the alkenyl-substituted nadiimide compound (K), the content of the alkenyl-substituted nadiimide compound (K) is preferably based on 100 parts by mass of the total resin solid content of the resin composition. It is 1 to 99 parts by mass, more preferably 3 to 90 parts by mass, further preferably 5 to 80 parts by mass, 10 to 70 parts by mass, 20 to 60 parts by mass, and 30 to 50 parts by mass. May be good. When the content of the alkenyl-substituted nadiimide compound (K) is within the above range, it tends to be more excellent in heat resistance and the like.

[Oxetane resin (G)]
The oxetane resin (G) is not particularly limited, and generally known ones can be used. Specific examples of the oxetane resin (G) include alkyloxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, and 3-methyl-3-methoxy. Methyl oxetane, 3,3-di (trifluoromethyl) perfluoro oxetane, 2-chloromethyl oxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name manufactured by Toa Synthetic), OXT -121 (trade name manufactured by Oxetane Synthetic) and the like can be mentioned. These oxetane resins (G) can be used alone or in admixture of two or more.

[Benzooxazine compound (H)]
The benzoxazine compound (H) is not particularly limited as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule, and generally known compounds can be used. Specific examples of the benzoxazine compound (H) include bisphenol A type benzoxazine BA-BXZ (trade name manufactured by Konishi Chemical Industry Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (trade name manufactured by Konishi Chemical Industry Co., Ltd.), and bisphenol S type benzoxazine. BS-BXZ (trade name manufactured by Konishi Chemical Industry Co., Ltd.) and the like can be mentioned. These benzoxazine compounds (H) can be used alone or in admixture of two or more.

[Compound (I) having a polymerizable unsaturated group]
The compound (I) having a polymerizable unsaturated group is not particularly limited, and generally known compounds can be used. Specific examples of the compound (I) having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl, methyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , 2-Hydroxypropyl (meth) acrylate, Polypropylene glycol di (meth) acrylate, Trimethylol propandi (meth) acrylate, Trimethylol propantri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, Dipentaerythritol hexa (meth) ) Monovalent or polyhydric alcohol (meth) acrylates such as acrylates, bisphenol A type epoxy (meth) acrylates, bisphenol F type epoxy (meth) acrylates and other epoxy (meth) acrylates, benzocyclobutene resins and the like. Be done. The compound (I) having a polymerizable unsaturated group can be used alone or in combination of two or more.

[Curing accelerator]
The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, but for example, imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate and the like. Organic peroxides; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine Tertiary amines such as pyridine, quinoline, N-methylmorpholin, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidin; phenols such as phenol, xylenol, cresol, resorcin, catechol; naphthenic acid Organic metal salts such as lead, lead stearate, zinc naphthenate, zinc octylate, manganese octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts are phenols and bisphenols. Those dissolved in a hydroxyl group-containing compound such as; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyl tin oxide and other organic tin compounds such as alkyl tin and alkyl tin oxide can be mentioned. Among these, triphenylimidazole is particularly preferable because it promotes the curing reaction and tends to further improve the glass transition temperature.

[Silane coupling agent and wet dispersant]
The resin composition of the present embodiment may further contain a silane coupling agent and a wet dispersant.
The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances, but for example, γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ. -Aminosilane compounds such as aminopropyltrimethoxysilane; epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; acrylicsilane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N-) Examples thereof include thionic silane compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds. The silane coupling agent may be used alone or in combination of two or more.
The wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints, but for example, DISPERBYK-110, 111, 118, 180, 161 and BYK-W996 manufactured by Big Chemie Japan Co., Ltd. , W9010, W903 and the like.

[Surface conditioner]
The resin composition of the present embodiment may further contain a surface conditioner.
The surface conditioner is not particularly limited, and examples thereof include a surface conditioner whose main component is polyester-modified polydimethylsiloxane, and by containing this, the effect of lowering the surface tension of the varnish during prepreg coating is exhibited. As the surface conditioner, the surface conditioner used for paints may be used, and examples thereof include BYK-310 and 313 manufactured by Big Chemie Japan Co., Ltd.

〔solvent〕
The resin composition of the present embodiment may further contain a solvent. By containing the solvent, the viscosity of the resin composition at the time of preparation is lowered, the handleability is further improved, and the impregnation property into the substrate, which will be described later, tends to be further improved. The solvent is not particularly limited as long as it can dissolve a part or all of the resin components in the resin composition, but for example, ketones such as acetone, methyl ethyl ketone and methyl cell solve; aromatics such as toluene and xylene. Group hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and acetates thereof and the like. As the solvent, one type may be used alone, or two or more types may be used in combination.

[Other ingredients]
The resin composition of the present embodiment may contain components other than the above as long as the desired properties are not impaired. Examples of such arbitrary formulations include thermosetting resins other than the above, thermoplastic resins and their oligomers, various polymer compounds such as elastomers, flame-retardant compounds, and various additives. These are not particularly limited as long as they are generally used. For example, flame-retardant compounds include bromine compounds such as 4,4'-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, and silicon-based compounds. Examples include compounds. In addition, various additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoaming agents, dispersants, and leveling agents. , Brighteners, polymerization inhibitors and the like, but are not particularly limited thereto. Any of these formulations may be used alone or in combination of two or more.

[Manufacturing method of resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, but for example, the cyanate ester compound (A), the filler (B), the molybdenum compound (C), zinc oxide (D), and the above-mentioned. Examples thereof include a method of mixing with an arbitrary component and sufficiently stirring. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the filler in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirring machine having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading treatment can be appropriately performed using, for example, an apparatus for mixing such as a ball mill or a bead mill, or a known apparatus such as a revolving or rotating type mixing apparatus.

Further, when preparing the resin composition, a solvent can be used if necessary. The type of solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples thereof are as described above.

[Use]
The resin composition of the present embodiment includes a cured product, a prepreg, a film-like underfill material, a resin sheet, a laminated board, a build-up material, a non-conductive film, a metal foil-clad laminated board, a printed wiring board, and a fiber-reinforced composite material. Alternatively, it can be suitably used as a semiconductor device. These will be described below.

[Cured product]
The cured product of the present embodiment is obtained by curing the above resin composition. The method for producing the cured product is not particularly limited, but for example, it can be obtained by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using heat, light, or the like. Can be done. In the case of thermosetting, the curing temperature is not particularly limited, but is preferably in the range of 120 ° C. to 300 ° C. from the viewpoint of efficient curing and prevention of deterioration of the obtained cured product. In the case of photocuring, the wavelength region of light is not particularly limited, but is preferably in the range of 100 nm to 500 nm in which curing is efficiently promoted by a photopolymerization initiator or the like.

[Prepreg]
The prepreg of the present embodiment has a base material and a resin composition of the present embodiment impregnated or coated on the base material. The method for producing the prepreg can be carried out according to a conventional method, and is not particularly limited. For example, after impregnating or coating the base material with the resin composition of the present embodiment, it is semi-cured (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. , The prepreg of the present embodiment can be produced.

The content (including the filler) of the resin composition of the present embodiment in the prepreg is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, still more preferably, based on the total amount of the prepreg. Is 40 to 80% by mass. When the content of the resin composition is within the above range, the moldability tends to be further improved.

The base material is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used according to the intended use and performance. Specific examples of the fibers constituting the base material are not particularly limited, but for example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; quartz and the like. Inorganic fibers other than glass; polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technora (registered trademark), Teijin Techno Products ( Total aromatic polyamides (manufactured by Co., Ltd.); polyesters such as 2,6-hydroxynaphthoic acid / parahydroxybenzoic acid (Vectran (registered trademark), Kuraray Co., Ltd.), Zexion (registered trademark, manufactured by KB Salen); Examples thereof include organic fibers such as polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyo Spinning Co., Ltd.) and polyimide. These base materials may be used alone or in combination of two or more.

Among these, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers is preferable.

The shape of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfaced mats. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones according to the intended use and performance. .. Further, those which have been subjected to fiber opening treatment or those which have been surface-treated with a silane coupling agent or the like are preferably used. The thickness and mass of the base material are not particularly limited, but usually those having a thickness and mass of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorption, the base material is ^{preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m 2} or less, and is a glass woven fabric composed of glass fibers of E glass, S glass, or T glass. Cloth is more preferred.

[Resin sheet]
The resin sheet of the present embodiment can be used for forming an insulating layer such as a metal foil-covered laminated board or a printed wiring board, and includes both a resin sheet and a resin sheet with a support.

The resin sheet of the present embodiment is formed by molding the resin composition of the present embodiment into a sheet shape. The method for producing the resin sheet can be carried out according to a conventional method, and is not particularly limited. For example, it can be obtained by peeling or etching the support from the resin sheet with the support described later. Alternatively, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to form a sheet, thereby forming a sheet base material such as a support. It is also possible to obtain a resin sheet without using.

The resin sheet with a support of the present embodiment has a support and the above-mentioned resin composition arranged on the support. The resin sheet with a support can be produced, for example, by directly coating and drying the resin composition on a support such as a copper foil or a resin film.

The support is not particularly limited, but known materials used for various printed wiring board materials can be used. For example, polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polycarbonate film, ethylene tetrafluoroethylene copolymer film, Examples thereof include an organic film base material such as a release film in which a release agent is applied to the surface of these films, a conductor foil such as a copper foil, a glass plate, a SUS plate, and a plate-like inorganic film such as FPR. .. Among them, electrolytic copper foil and PET film are preferable.

Examples of the coating method include a method of applying a solution of the resin composition of the present embodiment in a solvent onto a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

The resin sheet with a support is preferably one in which the above resin composition is applied to a support and then semi-cured (B-staged). Specifically, for example, the resin composition is applied to a support such as a copper foil and then semi-cured by a method of heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes to obtain a resin with a support. Examples include a method of manufacturing a sheet. The amount of the resin composition adhered to the support is preferably in the range of 1 to 300 μm in terms of the thickness of the resin layer of the resin sheet with the support.

[Laminated board]
The laminated board of the present embodiment is one or more laminated plates selected from the group consisting of the prepreg, the resin sheet, and the resin sheet with a support. The laminated board can be obtained, for example, by laminating and molding a prepreg and another layer in combination. The other layer is not particularly limited, and examples thereof include a separately manufactured wiring board for the inner layer.

[Metal leaf-clad laminate]
The metal leaf-clad laminate of the present embodiment is selected from one or more selected from the group consisting of the prepreg, the resin sheet, and the resin sheet with the support, and the group consisting of the prepreg, the resin sheet, and the resin sheet with the support. It has at least one kind of metal foil arranged on one side or both sides. The metal foil-clad laminate of the present embodiment is, for example, a copper foil-clad laminate obtained by laminating and curing the prepreg and a copper foil.

The copper foil used here is not particularly limited as long as it is used as a material for a printed wiring board, but a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. The thickness of the conductor layer is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm.

The molding method of the metal foil-clad laminate and the molding conditions thereof are not particularly limited, and general molding methods and conditions for the laminated plate for printed wiring boards and the multilayer plate can be applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, or the like can be used when forming a metal foil-clad laminate. Further, in molding a metal leaf-clad laminate, the temperature is generally in the range of 100 to 350 ° C., the pressure is ^{generally in the range of 2 to 100 kgf / cm 2} , and the heating time is generally in the range of 0.05 to 5 hours. Further, if necessary, post-curing can be performed at a temperature of 150 to 350 ° C. Further, it is also possible to form a multilayer plate by laminating and molding the above-mentioned prepreg and copper foil in combination with a wiring plate for an inner layer prepared separately.

[Printed wiring board]
The printed wiring board of the present embodiment includes 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. The metal leaf-clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal leaf-clad laminate has good moldability and chemical resistance, and can be particularly effectively used as a printed wiring board for a semiconductor package in which such performance is required.

Specifically, the printed wiring board of the present embodiment can be manufactured by, for example, the following method. First, the above-mentioned copper foil-clad laminate is prepared. An inner layer circuit is formed by etching the surface of a copper foil-clad laminate to prepare an inner layer substrate. The inner layer circuit surface of this inner layer substrate is subjected to surface treatment to increase the adhesive strength as necessary, then the required number of the above-mentioned prepregs are laminated on the inner layer circuit surface, and the copper foil for the outer layer circuit is laminated on the outer side thereof. Then, heat and pressurize to integrally mold. In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a resin composition is formed between an inner layer circuit and a copper foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in this multilayer laminated plate, desmear treatment is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer. .. After that, a plated metal film that conducts the inner layer circuit and the copper foil for the outer layer circuit is formed on the wall surface of this hole, and the copper foil for the outer layer circuit is further etched to form the outer layer circuit, and the printed wiring board is manufactured. Will be done.

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 includes the resin composition of the present embodiment described above. That is, the above-mentioned prepreg (the base material and the above-mentioned resin composition attached thereto) and the resin composition layer of the metal foil-clad laminate (the layer composed of the above-mentioned resin composition) include the above-mentioned resin composition. It will form an insulating layer.

Further, when the metal foil-clad laminate is not used, a conductor layer to be a circuit may be formed on the prepreg, the resin sheet, or the resin composition to produce a printed wiring board. At this time, an electroless plating method can also be used to form the conductor layer.

The printed wiring board of the present embodiment can be particularly effectively used as a printed wiring board for a semiconductor package because the above-mentioned insulating layer has excellent isotropic properties of thermal conductivity.

[Build-up material]
The resin composition of this embodiment can be used as a build-up material. Here, "build-up" means that a printed wiring board having a multi-layer structure is produced by laminating a prepreg or a resin sheet and repeating drilling and wiring formation for each layer.

More specifically, a prepreg, a resin sheet, a resin sheet with a support, or a metal foil-clad laminate using the resin composition of the present embodiment can be used as a build-up material for a printed wiring board. In the printed wiring board formed by using the prepreg or the resin sheet of the present embodiment, the prepreg or the resin sheet constitutes the insulating layer. Further, in the printed wiring board formed by using the metal foil-clad laminate, the prepreg (base material and the resin composition attached thereto) and the resin sheet used when producing the metal foil-clad laminate are used. It will form an insulating layer.

Specifically, when the prepreg of the present embodiment is used as a build-up material, a metal foil-clad laminate is produced using the prepreg by the above-mentioned method for manufacturing a metal foil-clad laminate, and then the present embodiment is performed by the above method. Printed wiring board can be obtained. Alternatively, the prepreg may be used as it is as a build-up material as a material for the multilayer printed wiring board.

When the resin sheet of the present embodiment is used as a build-up material, the resin composition layer (insulating layer) of the resin sheet is surface-treated by a conventional method, and a wiring pattern (conductor layer) is formed on the surface of the insulating layer by plating. By doing so, the printed wiring board of the present embodiment can be obtained.

When the metal foil-clad laminate of the present embodiment is used as a build-up material, the metal foil of the metal foil-clad laminate is etched by a conventional method, and then the layer (insulating layer) made of prepreg is surface-treated. By forming a wiring pattern (conductor layer) on the surface of the insulating layer by plating, the printed wiring board of the present embodiment can be obtained.

In any case, various other steps (for example, hole processing for forming via holes, through holes, etc.) may be added as needed.

[Non-conductive film]
The resin composition of this embodiment can be used as a non-conductive film (NCF). Here, the "non-conductive film" is a film-like connecting material having both adhesive and insulating functions at the same time, and is one of the film-type adhesives used when packaging electronic elements or parts. For example, the non-conductive film can be used for adhering the electrode surface of the semiconductor chip and the circuit surface of the substrate, and may also have an underfill function.

The mode of the non-conductive film is not particularly limited, and examples thereof include a resin sheet containing the resin composition of the present embodiment and a resin sheet with a support including a layer containing the resin composition of the present embodiment. The method for producing the non-conductive film can be carried out according to a conventional method, and is not particularly limited. For example, it can be obtained by forming a layer containing the resin composition on the support and removing the support.

[Fiber reinforced composite material]
The fiber-reinforced composite material of the present embodiment includes the resin composition of the present embodiment and the reinforcing fibers. As the reinforcing fiber, generally known fibers can be used and are not particularly limited. Specific examples thereof include glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass and spherical glass, carbon fiber, aramid fiber, boron fiber, PBO fiber and high. Examples thereof include strong polyethylene fibers, alumina fibers, and silicon carbide fibers. The form and arrangement of the reinforcing fibers are not particularly limited, and can be appropriately selected from woven fabrics, non-woven fabrics, mats, knits, braids, unidirectional strands, rovings, chopped and the like. In addition, as a form of reinforcing fibers, a preform (a laminated woven base cloth made of reinforcing fibers, a sewn-integrated one with stitch threads, or a fiber structure such as a three-dimensional woven fabric or a braid) is applied. You can also.

As a method for producing these fiber-reinforced composite materials, generally known methods can be appropriately applied and are not particularly limited. Specific examples thereof include a liquid composite molding method, a resin film infusion method, a filament winding method, a hand lay-up method, and a pull-fusion method. Among these, in the resin transfer molding method, which is one of the liquid composite molding methods, materials other than preform such as metal plates, foam cores, and honeycomb cores can be set in advance in the molding mold. Since it can be used for various purposes, it is preferably used when a composite material having a relatively complicated shape is mass-produced in a short time.

[Film-like underfill material]
The film-like underfill material of the present embodiment has a layer containing the above resin composition. By using a film-shaped underfill material, the space between the semiconductor chip and the circuit board is filled with the underfill material when the semiconductor chip and the circuit board are connected in the mounting of the semiconductor chip such as flip chip mounting. be able to. In particular, as compared with the case where a liquid underfill material is used, the use of a film-like underfill material makes it difficult for bubbles to be generated between the semiconductor chip and the circuit board. Therefore, even in the recent increase in the number of bumps, the narrowing of the bump pitch, and the narrowing of the bump height gap, bubbles are generated between the semiconductor chip and the circuit board by using the film-like underfill material. Can be suppressed.

The film-like underfill material may have a release layer laminated on the layer in addition to the layer containing the resin composition. The release layer has a function as a protective material that protects the layer containing the resin composition until it is used in the semiconductor mounting process, and is peeled off when, for example, the semiconductor element is attached onto the underfill insulating film.

[Semiconductor device]
The semiconductor device of this embodiment includes the cured product or a film-like underfill material. The semiconductor device of this embodiment can be manufactured by mounting a semiconductor chip on a conductive portion of the printed wiring board. Here, the conductive portion is a portion where an electric signal is transmitted in the multilayer printed wiring board, and the location may be a surface or an embedded portion. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bump. None Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
In the following examples and comparative examples, each physical property was measured and each evaluation was performed according to the following.

<Evaluation method of molybdenum compound particles>
(Zinc oxide content)
The element ratios constituting the molybdenum compound particles were measured by X-ray photoelectron spectroscopy (XPS). The zinc oxide content was calculated from the measured element ratio in terms of ZnO.
Measuring machine: QuanteraII manufactured by ULVAC-PHI Co., Ltd.
X-ray source: Monochromatic Al-Kα ray Measurement area: 1000 × 1000 μm
Vacuum degree: 4.0 x ^10-6 Pa
(Circularity)
The circumference and area of the molybdenum compound particles were measured with a wet flow type particle size / shape analyzer, and the circularity was calculated.
Measuring machine: FPIA-3000S manufactured by Sysmex Corporation
Sheath solution: Isopropanol Measurement mode: HPF
Counting method: Total count 36000
(Average particle size)
The particle size distribution of the molybdenum compound particles was measured with a particle size distribution measuring device, and the average particle size (D50) was calculated.
Measuring machine: Microtrack MT3300EXII manufactured by Microtrack Bell Co., Ltd.
Measuring solvent: isopropanol

<Evaluation method of resin varnish>
(Measurement of resin curing time)
Using a micropipette, the resin varnish having a solid content concentration of 75% by mass prepared in Example or Comparative Example was injected into the following measuring machine, and the time until the resin was cured was measured. It can be judged that the resin curing time of 200 seconds or more is acceptable.
Measuring machine: Matsuo Sangyo Co., Ltd. Automatic curing time measuring device Madoka hot plate temperature: 170 ° C
Torque judgment value; 15%
Rotation speed; 190 rpm
Revolution speed; 60 rpm
Gap value: 0.3 mm
Average score: 50
Injection volume: 500 μL

<Evaluation method of metal leaf-clad laminate>
(Appearance evaluation)
With respect to the metal foil-clad laminates produced in Examples or Comparative Examples, the copper foils on both sides were etched and removed to obtain a sample from which all the copper foils on the surface were removed. This sample was visually observed, and the one without voids was evaluated as "○", and the one with voids was evaluated as "x".

(Drill bit life (number of broken holes in the drill bit))
A sample for evaluation was obtained by laminating the backup board, the metal foil-clad laminate prepared in the example or the comparative example, and the entry sheet in this order from the bottom. After processing this sample for 10,000 hits from the top of the sample under the following drilling conditions, observe the back surface of the metal foil-clad laminate with a hole analyzer (manufactured by Via Mechanics, Ltd.) and count the number of statistical holes. bottom.
Processing machine; Via Mechanics, Ltd. ND-1 V212
Entry sheet; LE900 manufactured by Mitsubishi Gas Chemical Company, Inc.
Backup board: SPB-W manufactured by Nihon Decorax Co., Ltd.
Drill bit: Made by Union Tool Co., Ltd. MC L517AW 0.105mm x 1.8mm

(Hole position accuracy)
After 10000 hits under the same drilling conditions as above, the amount of positional deviation between the hole position and the designated coordinates on the back surface of the metal foil-clad laminate was measured with a hole analyzer (manufactured by Via Mechanics, Ltd.). The total amount of misalignment was measured for each drilled hole, the average value and standard deviation (σ) were calculated, and the average value of the amount of misalignment + 3σ was calculated.

(Synthesis Example 1) Synthesis of 1-naphthol aralkyl type cyanate ester resin (SNCN) α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.) 300 g (hydroxy group (hydroxy group) OH group) equivalent 1.28 mol) and triethylamine 194.6 g (1.92 mol) (1.5 mol with respect to 1 mol of hydroxy group) were dissolved in 1800 g of dichloromethane, and this was used as solution 1.

125.9 g (2.05 mol) of cyanogen chloride (1.6 mol with respect to 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol with respect to 1 mol of hydroxy group), Solution 1 was poured over 30 minutes while maintaining a liquid temperature of −2 to −0.5 ° C. under stirring with 1205.9 g of water. After pouring 1 solution, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy groups) was dissolved in 65 g of dichloromethane was added for 10 minutes. I poured it over. After 2 pouring of the solution was completed, the reaction was completed by stirring at the same temperature for 30 minutes.

After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater after the fifth washing with water was 5 μS / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 331 g of the target 1-naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance). The mass average molecular weight Mw of the obtained SNCN was 600. Infrared absorption spectrum of SNCN showed absorption of 2250 cm ^-1 (cyanic acid ester group) and no absorption of hydroxy group.

(Synthesis Example 2) Synthesis of diallyl bisphenol A type cyanate ester compound (DABPACCN) 11.7 g of diallyl bisphenol A (hydroxy group equivalent 154.21 g / eq.) (Hydroxy group (OH group) equivalent 0.076 mol) (Daiwa Kasei Kogyo Co., Ltd.) The product "DABPA") and 7.8 g (0.076 mol) of triethylamine (1.0 mol with respect to 1 mol of hydroxy group) were dissolved in 138.1 g of dichloromethane to obtain Solution A.

7.0 g (0.114 mol) of cyanide chloride (1.5 mol with respect to 1 mol of hydroxy group), 58.4 g of dichloromethane, 11.8 g (0.116 mol) of 36% hydrochloric acid (1.53 mol with respect to 1 mol of hydroxy group), Solution A was poured over 10 minutes while maintaining a liquid temperature of −2 to −0.5 ° C. with stirring 153.6 g of water. After the injection of the solution A was completed, the mixture was stirred at the same temperature for 30 minutes, and then the solution B in which 8.8 g (0.086 mol) of triethylamine (1.1 mol with respect to 1 mol of the hydroxy group) was dissolved in 9.3 g of dichloromethane was added. It was poured over 5 minutes. After the injection of the solution B was completed, the reaction was completed by stirring at the same temperature for 30 minutes.

After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed with 40 g of 0.1N hydrochloric acid and then washed with 40 g of water three times. The electrical conductivity of the wastewater after the third washing with water was 17 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 obtain 13.2 g of the target diallyl bisphenol A type cyanate ester compound DABPACS (light yellow liquid). rice field. The IR spectrum of the obtained DABPACN showed absorption of 2264 cm-1 (cyanic acid ester group) and no absorption of hydroxy group. The cyanate ester group equivalent of the obtained cyanate ester compound DABPACN was 179 g / eq.

(Example 1)
35 parts by mass of the 1-naphthol aralkyl type cyanate ester compound (cyanic acid ester group equivalent: 261 g / eq.) Obtained in Synthesis Example 1, polyphenylmethane maleimide (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 25 Parts by mass, naphthylene ether type epoxy resin (HP-6000, epoxy group equivalent: 250 g / eq., Made by DIC Co., Ltd.) 40 parts by mass, molten spherical silica (SC4053-SQ, manufactured by Admatex Co., Ltd.) 60 mass 1. 0 μm, 3 parts by mass of Admatex Co., Ltd., 5 parts by mass of silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3 parts by mass of wet dispersant (manufactured by Big Chemie Japan Co., Ltd.), A resin varnish was obtained by mixing 1 part by mass of a surface conditioner (manufactured by Big Chemie Japan Co., Ltd.) and 1 part by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.). The thermosetting time of the obtained resin varnish was measured by the above method. The results are shown in Table 1.

The obtained resin varnish is further diluted with methyl ethyl ketone (solvent), impregnated and coated on an E glass cloth having a thickness of 90 μm, and heated and dried at 160 ° C. for 4 minutes to obtain a prepreg having a thickness of 0.1 mm. (Resin composition content 50%). Next, eight obtained prepregs were laminated to form a laminate, and an electrolytic copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) having a thickness of 12 μm was placed on the upper and lower surfaces of the obtained laminate. A metal foil-clad laminate (double-sided copper-clad laminate) having a thickness of 0.8 mm was produced by performing a vacuum press at a pressure of 20 kgf / cm ^{2 and a temperature of 220 ° C. for 120 minutes for laminating and molding.} The appearance of the obtained metal foil-clad laminate was evaluated, the drill bit life, and the hole position accuracy were evaluated. The results are shown in Table 1.

(Example 2)
29 parts by mass of diallyl bisphenol A type cyanate ester compound (DABPACC, cyanate ester group equivalent: 179 g / eq.) Obtained in Synthesis Example 2, polyphenylmethane maleimide (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 28 parts by mass, naphthylene ether type epoxy resin (HP-6000, epoxy group equivalent: 250 g / eq., DIC Co., Ltd.) 43 parts by mass, molten spherical silica (SC4053-SQ, manufactured by Admatex Co., Ltd.) 60 Parts by mass, molten spherical silica (SFP-330MC, manufactured by Denka Co., Ltd.) 140 parts by mass, spherical zinc molybdate (ZnO content in molybdenum compound particles 3.7% by mass, circularity 0.92, average particle diameter 1 .0 μm, 3 parts by mass of Admatex Co., Ltd., 5 parts by mass of silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3 parts by mass of wet dispersant (manufactured by Big Chemie Japan Co., Ltd.) , 1 part by mass of a surface conditioner (manufactured by Big Chemie Japan Co., Ltd.) and 1 part by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed to obtain a resin varnish. The thermosetting time of the obtained resin varnish was measured by the above method. The results are shown in Table 1.

The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated on an E glass cloth having a thickness of 90 μm, and dried by heating at 160 ° C. for 9 minutes to obtain a prepreg having a thickness of 0.1 mm (resin). Composition content 50%). Next, eight obtained prepregs were laminated to form a laminate, and an electrolytic copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) having a thickness of 12 μm was placed on the upper and lower surfaces of the obtained laminate. A metal foil-clad laminate (double-sided copper-clad laminate) having a thickness of 0.8 mm was produced by performing a vacuum press at a pressure of 20 kgf / cm ^{2 and a temperature of 220 ° C. for 120 minutes for laminating and molding.} The appearance of the obtained metal foil-clad laminate was evaluated, the drill bit life, and the hole position accuracy were evaluated. The results are shown in Table 1.

(Example 3)
Bisphenol A type cyanate ester compound (manufactured by Ronza Co., Ltd., Primacet® BADCy, cyanate ester group equivalent: 139 g / eq.) 25 parts by mass, polyphenylmethane maleimide (BMI-2300, Daiwa Kasei Kogyo Co., Ltd.) ) 33 parts by mass, naphthylene ether type epoxy resin (HP-6000, epoxy group equivalent: 250 g / eq., DIC Co., Ltd.) 42 parts by mass, molten spherical silica (SC4053-SQ, Admatex Co., Ltd.) (Manufactured) 60 parts by mass, molten spherical silica (SFP-330MC, manufactured by Denka Co., Ltd.) 140 parts by mass, spherical zinc molybdate (ZnO content in molybdenum compound particles 3.7 mass%, circularity 0.92, average Particle size 1.0 μm, 3 parts by mass of Admatex Co., Ltd., 5 parts by mass of silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), wet dispersant (manufactured by Big Chemie Japan Co., Ltd.) A resin varnish is obtained by mixing 3 parts by mass, 1 part by mass of a surface conditioner (manufactured by Big Chemie Japan Co., Ltd.), and 1 part by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.). rice field. The thermosetting time of the obtained resin varnish was measured by the above method. The results are shown in Table 1.

The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated on an E glass cloth having a thickness of 90 μm, and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a thickness of 0.1 mm (resin). Composition content 50%). Next, eight obtained prepregs were laminated to form a laminate, and an electrolytic copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) having a thickness of 12 μm was placed on the upper and lower surfaces of the obtained laminate. A metal foil-clad laminate (double-sided copper-clad laminate) having a thickness of 0.8 mm was produced by performing a vacuum press at a pressure of 20 kgf / cm ^{2 and a temperature of 220 ° C. for 120 minutes for laminating and molding.} The appearance of the obtained metal foil-clad laminate was evaluated, the drill bit life, and the hole position accuracy were evaluated. The results are shown in Table 1.

(Example 4)
Instead of spherical zinc molybdate, zinc molybdate as a molybdate compound (manufactured by High Purity Chemical Laboratory Co., Ltd., circularity 0.91, average particle size 3.8 μm) and zinc oxide (High Purity Chemical Laboratory Co., Ltd.) A resin varnish was obtained in the same manner as in Example 1 except that 3 parts by mass of a mixture (ZnO content: 0.3% by mass) with (Z) was used. The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated on an E glass cloth having a thickness of 90 μm, and dried by heating at 130 ° C. for 3 minutes to obtain a prepreg having a thickness of 0.1 mm. Using the obtained prepreg, a metal leaf-clad laminate having a thickness of 0.8 mm was obtained in the same manner as in Example 1. Table 1 shows the results of measuring the physical properties of the obtained resin varnish and metal foil-clad laminate.

(Example 5)
Instead of spherical zinc molybdate, molybdate disulfide (M-5 powder, manufactured by Daizo Co., Ltd., circularity 0.91, average particle size 2.9 μm) and zinc oxide (High Purity Chemical Laboratory (High Purity Chemical Laboratory) A resin varnish was obtained in the same manner as in Example 1 except that 12 parts by mass of a mixture (ZnO content: 1.0% by mass) with (manufactured by Co., Ltd.) was used. The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated on an E glass cloth having a thickness of 90 μm, and dried by heating at 130 ° C. for 3 minutes to obtain a prepreg having a thickness of 0.1 mm. Using the obtained prepreg, a metal leaf-clad laminate having a thickness of 0.8 mm was obtained in the same manner as in Example 1. Table 1 shows the results of measuring the physical properties of the obtained resin varnish and metal foil-clad laminate.

(Comparative Example 1)
A resin varnish was obtained in the same manner as in Example 1 except that spherical zinc molybdate was not used in Example 1. The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated on an E glass cloth having a thickness of 90 μm, and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a thickness of 0.1 mm. Using the obtained prepreg, a metal leaf-clad laminate having a thickness of 0.8 mm was obtained in the same manner as in Example 1. Table 1 shows the results of measuring the physical properties of the obtained resin varnish and metal foil-clad laminate.

(Comparative Example 2)
In Example 1, as the molybdate compound, basic zinc molybdate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was heated at 300 ° C. for 1 hour instead of spherical zinc molybdate (ZnO content in molybdate compound particles). A resin varnish was obtained in the same manner as in Example 1 except that 3 parts by mass (27.6% by mass, circularity 0.87, average particle diameter 2.5 μm) was used. The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated on an E glass cloth having a thickness of 90 μm, and dried by heating at 130 ° C. for 3 minutes to obtain a prepreg having a thickness of 0.1 mm. Using the obtained prepreg, a metal leaf-clad laminate having a thickness of 0.8 mm was obtained in the same manner as in Example 1. Table 1 shows the results of measuring the physical properties of the obtained resin varnish and metal foil-clad laminate.

As is clear from Table 1, it was confirmed that the metal foil-clad laminates obtained by using the resin compositions of Examples 1 to 5 were excellent in both drilling workability and appearance evaluation. The metal foil-clad laminate obtained by using the resin composition of Comparative Example 1 is inferior in hole position accuracy during drilling, and the metal foil-clad laminate obtained by using the resin composition of Comparative Example 2 is inferior. It was inferior in appearance evaluation.

This application is based on a Japanese patent application (Japanese Patent Application No. 2020-054954) filed with the Japan Patent Office on March 25, 2020, the contents of which are incorporated herein by reference.

The resin composition of the present invention has industrial applicability as a material for prepregs and the like.

Claims

A resin composition containing a cyanate ester compound (A), a filler (B), a molybdenum compound (C), and zinc oxide (D).
The molybdenum compound (C) contains molybdenum compound particles and contains molybdenum compound particles.
A resin composition in which the content of zinc oxide (D) in the resin composition is 5% by mass or less with respect to the total mass of the molybdenum compound particles.
The resin composition according to claim 1, wherein the content of the filler (B) is 10 to 500 parts by mass with respect to a total of 100 parts by mass of the resin solid components in the resin composition.
The resin composition according to claim 1 or 2, wherein the content of the molybdenum compound (C) is 0.2 to 30 parts by mass with respect to a total of 100 parts by mass of the resin solid components in the resin composition.
The resin composition according to any one of claims 1 to 3, wherein the content of zinc oxide (D) is 0.1% by mass or more and 5% by mass or less with respect to the total mass of the molybdenum compound particles. ..
The resin composition according to any one of claims 1 to 4, wherein the zinc oxide (D) is contained in the molybdenum compound particles.
The resin composition according to any one of claims 1 to 5, wherein the molybdenum compound particles have a spherical shape.
The resin composition according to claim 6, wherein the molybdenum compound particles have a circularity of 0.90 to 1.00.
The resin composition according to any one of claims 1 to 7, wherein the molybdenum compound particles have an average particle size of 0.1 to 10 μm.
The molybdenum compound (C) is one or more selected from the group consisting of zinc molybdate, ammonium molybdate, sodium molybdate, calcium molybdate, potassium molybdate, molybdenum disulfide, molybdenum trioxide, and molybdenum hydrate. The resin composition according to any one of claims 1 to 8.
The cyanate ester compound (A) is a phenol novolac type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, a naphthylene ether type cyanate ester compound, a xylene resin type cyanate ester compound, and a bisphenol M type cyanate ester compound. , One or more selected from the group consisting of a bisphenol A type cyanate ester compound, a diallyl bisphenol A type cyanate ester compound, and a biphenyl aralkyl type cyanate ester compound, according to any one of claims 1 to 9. Resin composition.
Any of claims 1 to 10, wherein the filler (B) is one or more inorganic fillers selected from the group consisting of silica, alumina, aluminum nitride, boron nitride, boehmite, aluminum hydroxide, and titanium oxide. The resin composition according to item 1.
The resin composition according to any one of claims 1 to 11, wherein the filler (B) is one or more organic fillers selected from the group consisting of silicone rubber powder and silicone composite powder.
Maleimide compound (M), epoxy compound (E), phenol compound (F), alkenyl-substituted nadiimide compound (K), octacene resin (G), benzoxazine compound (H), and a compound having a polymerizable unsaturated group ( The resin composition according to any one of claims 1 to 12, further comprising one or more compounds selected from the group consisting of I).
The maleimide compound (M) is bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl). The resin composition according to claim 13, wherein the resin composition is one or more selected from the group consisting of methane, a maleimide compound represented by the following formula (2), and a maleimide compound represented by the following formula (3).

(In the formula (2), R 1 independently represents a hydrogen atom or a methyl group, and n 1 is 1 to 10.)

In the formula (3), R 2 existing in a plurality of each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, n2 is an average value, and represents 1 <n2 ≦ 5. .)
The resin composition according to claim 13 or 14, wherein the epoxy compound (E) is at least one selected from the group consisting of a biphenyl aralkyl type epoxy compound, a naphthalene type epoxy compound, and a naphthylene ether type epoxy resin.
The resin composition according to any one of claims 1 to 15, which is used for a printed wiring board.
A prepreg comprising a base material and the resin composition according to any one of claims 1 to 15, which is impregnated or coated on the base material.
A resin sheet obtained by molding the resin composition according to any one of claims 1 to 15 into a sheet.
A resin sheet with a support having the support and the resin composition according to any one of claims 1 to 15 arranged on the support.
A laminated board in which one or more selected from the group consisting of the prepreg according to claim 17, the resin sheet according to claim 18, and the resin sheet with a support according to claim 19 are laminated.
One or more selected from the group consisting of the prepreg according to claim 17, the resin sheet according to claim 18, and the resin sheet with a support according to claim 19.
At least one kind of metal foil arranged on one side or both sides selected from the group consisting of the prepreg, the resin sheet, and the resin sheet with a support.
Metal leaf-clad laminate with.
A printed wiring board having an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 15 and a conductor layer formed on the surface of the insulating layer.