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

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

[Technical Field]

[0001] The present invention relates to a resin composition, and to a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, and the like, which use the resin composition. [Background technology]

[0002] In recent years, semiconductors, which are widely used in electronic devices, communications equipment, personal computers, etc., have become increasingly highly integrated, highly functional, and highly densely mounted. As a result, there is an ever-increasing demand for higher performance in laminates for semiconductor plastic packaging, such as low thermal expansion, drilling workability, heat resistance, and flame retardancy.

[0003] In addition, especially in recent years, there has been a strong demand for a reduction in the thermal expansion coefficient of the laminate in the plane direction. This is because if there is a large difference in the thermal expansion coefficient between the semiconductor element and the printed wiring board for the semiconductor plastic package, the difference in the thermal expansion coefficient will cause the semiconductor plastic package to warp when subjected to thermal shock, resulting in poor connections between the semiconductor element and the printed wiring board for the semiconductor plastic package, and between the semiconductor plastic package and the printed wiring board on which it is mounted.

[0004] Conventionally, in order to reduce the thermal expansion coefficient while satisfying the various properties required of a laminate, a method of compounding a relatively high amount of inorganic filler into the resin composition that constitutes the laminate has been known (see, for example, Patent Documents 1 and 2). However, these methods have had problems in that the cured resin composition becomes hard and brittle, which deteriorates drilling processability when drilling a laminate obtained using the resin composition, such as reducing hole position accuracy, accelerating drill bit wear and requiring more frequent drill bit replacement, and making the drill bit more susceptible to breakage.

[0005] On the other hand, a known method for improving the drilling processability of laminates is to blend a molybdenum compound such as zinc molybdate or calcium molybdate into a resin composition (see, for example, Patent Document 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-059643 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-120702 [Patent Document 3] International Publication No. 2013 / 047203 Brochure Summary of the Invention [Problem to be solved by the invention]

[0007] However, when the molybdenum compound described in Patent Document 3 is blended with a resin composition, the molybdenum compound or zinc oxide contained therein as an impurity acts as a curing catalyst for the cyanate ester compound, resulting in the generation of voids, which deteriorates the appearance of the molded product.

[0008] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a resin composition that combines drilling processability with good appearance, and a molded article using the same, such as a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, or a printed wiring board. [Means for solving the problem]

[0009] As a result of intensive research to solve these problems, the present inventors have found that the above-mentioned problems can be solved by containing at least a cyanate ester compound, a filler, a molybdenum compound, and zinc oxide, and by controlling the content of zinc oxide in a resin composition to a specific range or less, thereby completing the present invention.

[0010] 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, A resin composition, wherein the content of zinc oxide (D) in the resin composition is 5 mass % or less based on 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 per 100 parts by mass of the total 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 per 100 parts by mass of the total of the resin solid components in the resin composition. [4] The resin composition according to any one of the above [1] to [3], wherein the content of the zinc oxide (D) is 0.1 mass % or more and 5 mass % or less based on the total mass of the molybdenum compound particles. [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 are spherical. [7] The resin composition according to [6] above, wherein the circularity of the molybdenum compound particles is 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 resin composition according to any one of the above [1] to [8], wherein the molybdenum compound (C) is at least one selected from the group consisting of zinc molybdate, ammonium molybdate, sodium molybdate, calcium molybdate, potassium molybdate, molybdenum disulfide, molybdenum trioxide, and molybdenum hydrate.

[10] The resin composition according to any one of the above [1] to [9], wherein the cyanate ester compound (A) is at least one selected from the group consisting of phenol novolac-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds, naphthylene ether-type cyanate ester compounds, xylene resin-type cyanate ester 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.

[11] The resin composition according to any one of the above [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.

[12] The resin composition according to any one of the above [1] to

[11] , wherein the filler (B) is one or more organic fillers selected from the group consisting of silicone rubber powders and silicone composite powders.

[13] The resin composition according to any one of the above [1] to

[12] , further comprising one or more compounds selected from the group consisting of a maleimide compound (M), an epoxy compound (E), a phenol compound (F), an alkenyl-substituted nadimide compound (K), an oxacene resin (G), a benzoxazine compound (H), and a compound having a polymerizable unsaturated group (I).

[14] The resin composition according to the above item

[13] , wherein the maleimide compound (M) is at least one selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, maleimide compounds represented by the following formula (2), and maleimide compounds represented by the following formula (3):

[0011] [ka]

[0012] (In formula (2), R 1 each independently represents a hydrogen atom or a methyl group, and n1 is 1 to 10.)

[0013] [Chemical formula]

[0014] (In formula (3), multiple R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n2 is an average value and represents 1 < n2 ≦ 5.)

[15] The resin composition according to

[13] or

[14] above, 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.

[16] The resin composition according to any one of [1] to

[15] above, which is for a printed wiring board.

[17] A prepreg having a base material and the resin composition according to any one of [1] to

[15] above impregnated or coated on the base material.

[18] A resin sheet formed by shaping the resin composition according to any one of [1] to

[15] above into a sheet shape.

[19] A resin sheet with a support having a support and the resin composition according to any one of [1] to

[15] above disposed on the support.

[20] A laminate in which at least one selected from the group consisting of the prepreg according to

[17] above, the resin sheet according to

[18] above, and the resin sheet with a support according to

[19] above is laminated.

[21] At least one selected from the group consisting of the prepreg according to

[17] above, the resin sheet according to

[18] above, and the resin sheet with a support according to

[19] above, and a metal foil disposed on one or both sides of at least one material selected from the group consisting of the prepreg, a resin sheet, and a resin sheet with a support; A metal foil-clad laminate having the same. [twenty two] A printed wiring board having an insulating layer containing a cured product of the resin composition according to any one of the above [1] to

[15] , and a conductor layer formed on the surface of the insulating layer. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a resin composition that combines drilling processability and appearance, and a molded article using the same, such as a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, or a printed wiring board. DETAILED DESCRIPTION OF THE INVENTION

[0016] Below, we will explain in detail the embodiment of the present invention (hereinafter referred to as the ``present embodiment''), but the present invention is not limited to this and various modifications are possible within the scope of the gist of the present invention.

[0017] [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), wherein the molybdenum compound (C) contains molybdenum compound particles, and the content of zinc oxide (D) in the resin composition is 5 mass % or less relative to the total mass of the molybdenum compound particles.

[0018] The resin composition of this embodiment contains a molybdenum compound (C) and zinc oxide (D), and the content of zinc oxide (D) is adjusted to 5 mass% or less based on the total mass of the molybdenum compound particles. When the content of zinc oxide (D) is 5 mass% or less in terms of ZnO, voids generated by the reaction of zinc oxide with a cyanate ester compound can be suppressed, and the appearance of the molded product can be improved.

[0019] From the same viewpoint, the content of zinc oxide (D) in the resin composition is preferably 4 mass% or less relative to the total mass of the molybdenum compound particles. There is no particular lower limit to the content of zinc oxide (D) in the resin composition, but from the viewpoint of reducing production costs, it is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, even more preferably 0.3 mass% or more, particularly preferably 0.5 mass% or more, and particularly preferably 1 mass% or more.

[0020] The content of zinc oxide (D) contained in the resin composition here refers to the total mass of zinc oxide (D) contained in the resin composition. When zinc oxide (D) is mainly contained in the molybdenum compound particles, it means the content of zinc oxide contained in the molybdenum compound particles. When zinc oxide (D) is not contained in the molybdenum compound particles, it means the content of zinc oxide contained in the parts of the resin composition other than the molybdenum compound particles. When zinc oxide (D) is contained in both the molybdenum compound particles and the resin composition parts other than the molybdenum compound particles, it means the total amount of zinc oxide contained in the molybdenum compound particles and the zinc oxide contained in the parts of the resin composition other than the molybdenum compound particles.

[0021] That is, in the resin composition of this embodiment, zinc oxide (D) may be in any of the following forms: a form in which zinc oxide (D) is mainly contained in the molybdenum compound particles; a form in which zinc oxide (D) is not contained in the molybdenum compound particles but is contained in the resin composition in the portion other than the molybdenum compound particles; and a form in which zinc oxide (D) is contained in both the molybdenum compound particles and the resin composition in the portion other than the molybdenum compound particles.

[0022] An example of a form in which zinc oxide (D) is mainly contained in molybdenum compound particles is when a resin composition is prepared using a molybdenum compound (C') containing molybdenum compound particles containing zinc oxide, which will be described later.

[0023] An example of a form in which zinc oxide (D) is not contained in the molybdenum compound particles but is contained in the resin composition in the portion other than the molybdenum compound particles is a case in which a molybdenum compound (C) not containing zinc oxide and zinc oxide (D) are added separately to prepare a resin composition.

[0024] An example of a form in which zinc oxide (D) is contained in both the molybdenum compound particles and the resin composition other than the molybdenum compound particles is when a mixture of molybdenum compound particles and zinc oxide is prepared in advance by kneading or the like, and then the mixture is used to prepare a resin composition. In this case, zinc oxide may be dispersed in the resin composition during preparation, and therefore zinc oxide tends to be contained in both the molybdenum compound particles and the resin composition other than the molybdenum compound particles.

[0025] Among these forms, a form in which zinc oxide (D) is mainly contained in molybdenum compound particles, and a form in which zinc oxide (D) is contained in both the molybdenum compound particles and the resin composition in the portion other than the molybdenum compound particles are preferred. 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, and a form in which a mixture of molybdenum compound particles and zinc oxide is prepared in advance by kneading or the like, and then a resin composition is prepared using the mixture are more preferred.

[0026] When the resin composition is prepared by separately adding the molybdenum compound (C) not containing zinc oxide and the zinc oxide (D), the zinc oxide is not particularly limited, and zinc oxide having various properties and particle sizes can be appropriately selected and used, and commercially available zinc oxide can be used.

[0027] When zinc oxide is kneaded with molybdenum compound particles to prepare a mixture in advance, the zinc oxide is not particularly limited, and zinc oxide having various properties and particle sizes can be appropriately selected and used, and commercially available zinc oxide can be used.

[0028] In this case, the content of zinc oxide (D) can be calculated from the charge ratio and use amount of molybdenum compound particles (molybdenum compound (C)) and zinc oxide, which are raw materials when preparing the molybdenum component to be mixed with the resin component. In this case, the content of zinc oxide (D) can be adjusted, for example, by changing the charge ratio and use amount of molybdenum compound particles (molybdenum compound (C)) and zinc oxide, which are raw materials when preparing the molybdenum component to be mixed with the resin component.

[0029] 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 raw materials used in producing the molybdenum compound (C).

[0030] [Molybdenum compounds (C)] The molybdenum compound (C) contains molybdenum in the molecule, and molybdenum oxides and molybdenum sulfides are preferred. Specific examples of the molybdenum compound (C) include, but are not limited to, zinc molybdate (e.g., ZnMoO4, Zn3Mo2O9, etc.), ammonium molybdate, sodium molybdate, calcium molybdate, potassium molybdate, molybdenum disulfide, molybdenum trioxide, and molybdenum hydrates. These compounds can be used alone or in combination of two or more. Examples of molybdenum hydrates include molybdic acid monohydrate (MoO3·H2O), ammonium molybdate tetrahydrate ((NH4)6Mo7O), and the like. 24 4H2O), zinc molybdate pentahydrate (Zn5Mo2O 11 Among the above, zinc molybdate, molybdenum disulfide, and molybdenum hydrate are preferred from the viewpoint of drill workability.

[0031] The content of the molybdenum compound (C) in the resin composition of this embodiment can be appropriately set depending on the intended application and performance, and is not particularly limited. However, from the viewpoints of heat resistance, flame retardancy, and drilling processability, the content is preferably 0.2 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of the total resin solid components in the resin composition. In this embodiment, the term "resin solid content in the resin composition" refers to the components in the resin composition excluding solvents and fillers, unless otherwise specified. Furthermore, "100 parts by mass of resin solid content" refers to 100 parts by mass of the total components in the resin composition excluding solvents and fillers.

[0032] (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 compounds listed as specific examples 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 mass%, more preferably 70 to 100 mass%, even more preferably 90 to 100 mass%, and particularly preferably 95 to 100 mass%. When the content of the molybdenum compound particles contained in the molybdenum compound (C) is within the above range, the effects of the present invention tend to be more pronounced.

[0033] The shape of the molybdenum compound particles is not particularly limited, but spherical is preferred because this increases the filling ability of the molybdenum compound (C) in the resin composition and molded articles using the same, thereby resulting in a more significant improvement in drilling processability. When the molybdenum compound particles are spherical, their circularity is preferably 0.88 to 1.00, more preferably 0.90 to 1.00, and even more preferably 0.92 to 1.00. Here, the circularity is defined as follows: circularity = 4π × (area) ÷ (perimeter) 2The circularity is an index expressed as follows: the closer the value is to 1, the more perfectly circular the particle is. The circularity can be measured using a wet flow particle size / shape analyzer. More specifically, it can be measured according to the method described in the Examples.

[0034] The average particle diameter (D50) of the molybdenum compound particles can be appropriately set depending on the desired performance and is not particularly limited. Considering drillability and dispersibility in resin components, the average particle diameter (D50) is preferably 0.1 to 10 μm, more preferably 0.5 to 8 μm. Herein, the average particle diameter (D50) refers to the median diameter, which is the value at which the volume of the larger and smaller particles is equal when the particle size distribution of a measured powder is divided into two. This average particle diameter (D50) refers to the value measured when the particle size distribution of a predetermined amount of powder introduced into an aqueous dispersion medium is measured using a laser diffraction / scattering particle size distribution analyzer, and the volume of the smaller particles is integrated to reach 50% of the total volume.

[0035] The molybdenum compound (C) containing molybdenum compound particles can be produced by various known methods such as a calcination method or a precipitation method, and the production method is not particularly limited. In addition, commercially available products may be used.

[0036] (Molybdenum compound particles containing zinc oxide) The molybdenum compound particles are preferably molybdenum compound particles containing zinc oxide. That is, as one aspect of this embodiment, the resin composition of this embodiment is a resin composition containing at least a cyanate ester compound (A), a filler (B), and a molybdenum compound (C), wherein the molybdenum compound (C) comprises molybdenum compound particles containing zinc oxide, and the content of zinc oxide contained in the molybdenum compound particles is preferably 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, resulting in a good appearance of the molded product. From the same perspective, 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. Here, "containing zinc oxide" means that the zinc oxide is incorporated into the interior of the molybdenum compound particles, or that the zinc oxide is attached to the surface of the molybdenum compound particles.

[0037] There is no particular lower limit for the zinc oxide content contained in the molybdenum compound particles, but from the viewpoint of reducing production costs, it is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, even more preferably 0.3 mass% or more, particularly preferably 0.5 mass% or more, and especially preferably 1 mass% or more. That is, the content of zinc oxide contained in the molybdenum compound particles is preferably 0.1 to 5 mass%, more preferably 0.2 to 5 mass%, even more preferably 0.3 to 5 mass%, and may be 0.5 to 4 mass%.

[0038] 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.

[0039] 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 raw materials used in producing the molybdenum compound (C') containing molybdenum compound particles containing zinc oxide.

[0040] The shape and average particle size of the molybdenum compound particles containing zinc oxide are the same as those of the molybdenum compound particles described above.

[0041] The molybdenum compound (C') containing zinc oxide-containing molybdenum compound particles can be produced by various known methods such as a calcination method or a precipitation method using a molybdenum-containing raw material and a zinc-containing raw material, and the production method is not particularly limited. In addition, commercially available products may be used. [Resin component]

[0042] The resin composition of this embodiment contains at least a cyanate ester compound (A) and a filler (B) in addition to the molybdenum compound (C) and zinc oxide (D). The cyanate ester compound (A) and filler (B) used here can be appropriately selected from known materials depending on the intended application and performance, and the type and amount of each material used are not particularly limited. For example, in the case of electrical and electronic material applications, electrical insulating material applications, machine tool material applications, and adhesive applications, they can be appropriately selected from various materials known in the respective technical fields.

[0043] [Cyanate ester compound (A)] Any known cyanate ester compound (A) can be used as long as it has two or more cyanate ester groups (cyanato groups) directly bonded to an aromatic ring in one molecule.

[0044] The cyanate ester compound (A) is not particularly limited, but examples thereof include phenol novolac-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds, naphthylene ether-type cyanate ester compounds, xylene resin-type cyanate ester 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. The cyanate ester compound (A) may be used alone or in any combination and ratio of two or more. Among these, bisphenol A-type cyanate ester compounds, diallyl bisphenol A-type cyanate ester compounds, and naphthol aralkyl-type cyanate ester compounds are preferred, with naphthol aralkyl-type cyanate ester compounds being particularly preferred, from the viewpoints of moldability, surface hardness, heat resistance, flame retardancy, low dielectric properties (low dielectric constant, low dielectric loss tangent), and the like.

[0045] The naphthol aralkyl cyanate ester compound is not particularly limited, but for example, a compound represented by the following formula (1) is preferred.

[0046] [ka]

[0047] (In the above formula (1), R 3 are each independently a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred. In addition, in the above formula (1), n3 is an integer of 1 to 10.

[0048] The content of the cyanate ester compound (A) in the resin composition of this embodiment is preferably 1 to 99.9 parts by mass, more preferably 3 to 90 parts by mass, and even more preferably 5 to 80 parts by mass, or may be 10 to 70 parts by mass, 20 to 60 parts by mass, or 25 to 50 parts by mass, relative to 100 parts by mass of the total resin solid content in the resin composition. When the content of the cyanate ester compound (A) is within the above range, the resin composition tends to have better heat resistance, low dielectric constant, low dielectric loss tangent, etc.

[0049] When the resin composition of this embodiment contains a maleimide compound (M) described below in addition to the cyanate ester compound (A), the content of the cyanate ester compound (A) is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, and even more preferably 50 to 70 parts by mass, relative to 100 parts by mass of the total amount of the cyanate ester compound (A) and the maleimide compound (M). When the content of the cyanate ester compound (A) is within the above range, heat resistance, low dielectric constant, low dielectric loss tangent, and the like, as well as moldability and copper foil peel strength tend to be further improved.

[0050] [Filler (B)] The resin composition of the present embodiment contains a filler (B). The filler (B) is not particularly limited, but examples thereof include inorganic fillers and organic fillers. The filler (B) may be used alone or in combination of two or more.

[0051] The inorganic filler is not particularly limited, but may be at least one selected from the group consisting of silica, alumina, aluminum nitride, boron nitride, boehmite, aluminum hydroxide, and titanium oxide. Among these, silica is preferred from the viewpoint of low thermal expansion, and alumina or aluminum nitride is preferred from the viewpoint of high thermal conductivity.

[0052] The organic filler is not particularly limited, but 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; silicone composite powder, etc. Among the above, from the viewpoints of low thermal expansion and flame resistance, one or more types selected from the group consisting of silicone rubber powder and silicone composite powder are preferred.

[0053] The content of the filler (B) in the resin composition of this embodiment is preferably 10 to 500 parts by mass, more preferably 50 to 300 parts by mass, even more preferably 75 to 250 parts by mass, and particularly preferably 100 to 200 parts by mass, relative to 100 parts by mass of the total resin solid content in the resin composition.

[0054] The resin composition in this embodiment may further contain one or more compounds selected from the group consisting of a maleimide compound (M), an epoxy compound (E), a phenol compound (F), an alkenyl-substituted nadimide compound (K), an oxacene resin (G), a benzoxazine compound (H), and a compound (I) having a polymerizable unsaturated group.

[0055] [Maleimide compound (M)] The maleimide compound (M) may be any known compound having one or more maleimide groups per molecule, and the type of the compound is not particularly limited. The number of maleimide groups per molecule of the maleimide compound (M) is 1 or more, and preferably 2 or more.

[0056] The maleimide compound (M) is not particularly limited, and examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, maleimide compounds represented by the following formula (2), maleimide compounds represented by the following formula (3), prepolymers of these maleimide compounds, and prepolymers of the above maleimide compounds and amine compounds. The maleimide compound (M) may be used alone or in any combination and ratio of two or more. The inclusion of such a maleimide compound (M) tends to further reduce the thermal expansion coefficient of the resulting cured product and further improve its heat resistance.

[0057] Among these, one or more compounds selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, maleimide compounds represented by the following formula (2), and maleimide compounds represented by the following formula (3) are preferred from the viewpoint of low thermal expansion and heat resistance.

[0058] [ka]

[0059] (In formula (2), R 1 each independently represents a hydrogen atom or a methyl group, and n1 is 1 to 10.

[0060] [ka]

[0061] (In formula (3), there are multiple R 2Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n2 is an average value and represents 1 < n2 ≤ 5.)

[0062] When the resin composition of this embodiment contains the maleimide compound (M), the content of the maleimide compound (M) is preferably 1 to 99 parts by mass, more preferably 3 to 90 parts by mass, still more 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, based on 100 parts by mass of the total resin solids in the resin composition. 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.

[0063] Also, when the resin composition of this embodiment contains the cyanate ester compound (A) and the maleimide compound (M), the content of the maleimide compound (M) is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, still more preferably 30 to 50 parts by mass, based on 100 parts by mass of the total amount of the cyanate ester compound (A) and the maleimide compound (M). When the content of the maleimide compound (M) is within the above range, in addition to heat resistance, the moldability and the copper foil peel strength tend to be further improved.

[0064] [Epoxy compound (E)] As long as the epoxy compound (E) is a compound having one or more epoxy groups in one molecule, known ones can be appropriately used, 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.

[0065] The epoxy compound (E) is not particularly limited, and conventionally known epoxy compounds and epoxy resins can be used. For example, biphenyl aralkyl epoxy compounds, naphthalene epoxy compounds, bisnaphthalene epoxy compounds, polyfunctional phenol epoxy resins, naphthylene ether epoxy resins, phenol aralkyl epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, xylene novolac epoxy resins, naphthalene skeleton-modified novolac epoxy resins, dicyclopentadiene novolac epoxy resins, biphenyl novolac epoxy resins, phenol aralkyl novolac epoxy resins, naphthol aralkyl novolac epoxy resins, aralkyl novolac epoxy resins, aromatic hydrocarbon formaldehyde epoxy compounds, anthraquinone epoxy compounds, and anthracene epoxy resins. Examples of epoxy compounds include naphthol aralkyl epoxy compounds, dicyclopentadiene epoxy resins, Xylok epoxy compounds, bisphenol A epoxy resins, bisphenol E epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol A novolac epoxy resins, phenolic epoxy compounds, biphenyl epoxy resins, aralkyl novolac epoxy resins, triazine skeleton epoxy compounds, triglycidyl isocyanurate, alicyclic epoxy resins, polyol epoxy resins, glycidyl amine, glycidyl ester resins, compounds in which the double bonds of double bond-containing compounds such as butadiene have been epoxidized, and compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin. Among these, biphenyl aralkyl epoxy compounds, naphthalene epoxy compounds, and naphthylene ether epoxy resins are preferred from the viewpoints of moldability and surface hardness. The epoxy compound (E) may be used alone or in any combination and ratio of two or more.

[0066] When the resin composition of the present embodiment contains an epoxy compound (E), the content of the epoxy compound (E) is preferably 1 to 99.9 parts by mass, more preferably 3 to 90 parts by mass, and even more preferably 4 to 80 parts by mass, or may be 10 to 70 parts by mass, 20 to 60 parts by mass, or 30 to 50 parts by mass, relative to 100 parts by mass of the total resin solid content in the resin composition. When the content of the epoxy compound (E) is within the above range, the adhesiveness, flexibility, etc. tend to be more excellent.

[0067] When the resin composition of this embodiment contains a phenol compound (F) and an epoxy compound (E) described below, the content of the epoxy compound (E) is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 40 to 60 parts by mass, relative to 100 parts by mass of the total amount of the phenol compound (F) and the epoxy compound (E). When the content of the epoxy compound (E) is within the above range, heat resistance tends to be further improved in addition to adhesiveness, flexibility, etc.

[0068] [Phenol compounds (F)] The phenol compound (F) may be any known compound having two or more phenolic hydroxyl groups in one molecule, and the type is not particularly limited.

[0069] The phenol compound (F) is not particularly limited, and examples thereof include cresol novolac phenolic resins, biphenyl aralkyl phenolic resins represented by the following formula (4), naphthol aralkyl phenolic resins represented by the following formula (5), aminotriazine novolac phenolic resins, naphthalene phenolic resins, phenol novolac resins, alkylphenol novolac resins, bisphenol A novolac resins, dicyclopentadiene phenolic resins, Zylok phenolic resins, terpene-modified phenolic resins, and polyvinylphenols. One type of phenol compound (F) may be used alone, or two or more types may be used in any combination and ratio.

[0070] Among these, from the viewpoint of moldability and surface hardness, cresol novolac type phenolic resins, biphenyl aralkyl type phenolic resins represented by the following formula (4), naphthol aralkyl type phenolic resins represented by the following formula (5), aminotriazine novolac type phenolic resins, and naphthalene type phenolic resins are preferred, and biphenyl aralkyl type phenolic resins represented by the following formula (4) and naphthol aralkyl type phenolic resins represented by the following formula (5) are more preferred.

[0071] [ka]

[0072] (In formula (4), there are multiple R 4 each independently represents a hydrogen atom or a methyl group, and n4 is 1 to 10.

[0073] [ka]

[0074] (In formula (5), there are multiple R 5 each independently represents a hydrogen atom or a methyl group, and n5 is 1 to 10.

[0075] When the resin composition of this embodiment contains a phenolic compound (F), the content of the phenolic compound (F) is preferably 1 to 99 parts by mass, more preferably 3 to 90 parts by mass, and even more preferably 5 to 80 parts by mass, or may be 10 to 70 parts by mass, 20 to 60 parts by mass, or 30 to 50 parts by mass, relative to 100 parts by mass of the total resin solid content of the resin composition. When the content of the phenolic compound (F) is within the above range, the adhesiveness, flexibility, etc. tend to be more excellent.

[0076] When the resin composition of this embodiment contains a phenolic compound (F) and an epoxy compound (E), the content of the phenolic compound (F) is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 40 to 60 parts by mass, relative to 100 parts by mass of the total amount of the phenolic compound (F) and the epoxy compound (E). When the content of the phenolic compound (F) is within the above range, the copper foil peel strength tends to be further improved in addition to the adhesiveness, flexibility, etc.

[0077] [Alkenyl-substituted nadimide compound (K)] The alkenyl-substituted nadimide compound (K) is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadimide groups in one molecule, and examples thereof include compounds represented by the following formula (2d): The resin composition of the present embodiment tends to have improved heat resistance by containing the alkenyl-substituted nadimide compound (K).

[0078] [ka]

[0079] In the formula, each of the multiple R1s independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group or an ethyl group), and R2 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (6) or (7):

[0080] [ka]

[0081] In formula (6), R3 represents a methylene group, an isopropylidene group, CO, O, S, or SO2.

[0082] [ka]

[0083] In formula (7), a plurality of R4s each independently represent an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.

[0084] The alkenyl-substituted nadimide compound (K) may be a commercially available product or a product produced according to a known method. Examples of commercially available products include "BANI-M" and "BANI-X" manufactured by Maruzen Petrochemical Co., Ltd.

[0085] When the resin composition of the present embodiment contains an alkenyl-substituted nadimide compound (K), the content of the alkenyl-substituted nadimide compound (K) is preferably 1 to 99 parts by mass, more preferably 3 to 90 parts by mass, and even more preferably 5 to 80 parts by mass, or may be 10 to 70 parts by mass, 20 to 60 parts by mass, or 30 to 50 parts by mass, relative to 100 parts by mass of the total resin solid content of the resin composition. When the content of the alkenyl-substituted nadimide compound (K) is within the above range, the heat resistance and the like tend to be more excellent.

[0086] [Oxetane resin (G)] The oxetane resin (G) is not particularly limited, and generally known resins can be used. Specific examples of the oxetane resin (G) include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl oxetane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.), and OXT-121 (trade name, manufactured by Toagosei Co., Ltd.). These oxetane resins (G) can be used alone or in combination of two or more.

[0087] [Benzoxazine compound (H)] The benzoxazine compound (H) is not particularly limited as long as it has 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.). These benzoxazine compounds (H) can be used alone or in combination of two or more.

[0088] [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; (meth)acrylates of monohydric or polyhydric alcohols such as methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy (meth)acrylates such as bisphenol A-type epoxy (meth)acrylate and bisphenol F-type epoxy (meth)acrylate; and benzocyclobutene resins. These compounds (I) having a polymerizable unsaturated group can be used alone or in combination.

[0089] [Curing accelerator] The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, but examples thereof include imidazoles such as triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-diperphthalate; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N Examples of suitable organic compounds include tertiary amines such as methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetonate; compounds obtained by dissolving these organic metal salts in hydroxyl-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; and organic tin compounds such as dioctyltin oxide, other alkyltins, and alkyltin oxides. Among these, triphenylimidazole is particularly preferred because it accelerates the curing reaction and tends to further increase the glass transition temperature.

[0090] [Silane coupling agent and wetting / dispersing agent] The resin composition of the present embodiment may further contain a silane coupling agent and a wetting and dispersing agent. 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 examples thereof include aminosilane compounds such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; acrylic silane compounds such as γ-acryloxypropyltrimethoxysilane; cationic silane compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds. The silane coupling agents may be used alone or in combination of two or more. The wetting dispersant is not particularly limited as long as it is a dispersion stabilizer used in paints, but examples thereof include DISPERBYK-110, 111, 118, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK Japan Co., Ltd.

[0091] [Surface conditioner] The resin composition of the present embodiment may further contain a surface conditioner. The surface conditioner is not particularly limited, but examples thereof include a surface conditioner whose main component is polyester-modified polydimethylsiloxane, which reduces the surface tension of the varnish when applied to the prepreg. Surface conditioners used in paints may also be used, such as BYK-310 and 313 manufactured by BYK Japan Co., Ltd.

[0092] 〔solvent〕 The resin composition of this embodiment may further contain a solvent. The inclusion of a solvent tends to reduce the viscosity of the resin composition during preparation, improve handling, and further improve the impregnation of the resin composition into a substrate, as described below. The solvent is not particularly limited as long as it can dissolve a part or all of the resin components in the resin composition. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; and propylene glycol monomethyl ether and its acetate. One type of solvent may be used alone, or two or more types may be used in combination.

[0093] [Other ingredients] The resin composition of this embodiment may contain components other than those described above, provided that the intended properties are not impaired. Examples of such optional components include various polymeric compounds such as thermosetting resins, thermoplastic resins and their oligomers, and elastomers other than those described above, flame-retardant compounds, and various additives. These components are not particularly limited as long as they are commonly used. Examples of 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 of various additives include, but are not limited to, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, dispersants, leveling agents, gloss agents, and polymerization inhibitors. These optional components can be used alone or in combination.

[0094] [Method for producing resin composition] The method for producing the resin composition of this embodiment is not particularly limited, but examples include a method in which the cyanate ester compound (A), the filler (B), the molybdenum compound (C), the zinc oxide (D), and the optional components described above are mixed and thoroughly stirred. At this time, known processes such as stirring, mixing, and kneading can be performed to uniformly dissolve or disperse each component. Specifically, the dispersibility of the filler in the resin composition can be improved by performing the stirring and dispersion process using a stirring tank equipped with a stirrer having appropriate stirring capabilities. The stirring, mixing, and kneading processes can be appropriately performed using, for example, a mixing device such as a ball mill or a bead mill, or a known device such as a revolution or rotation type mixer.

[0095] In addition, when preparing the resin composition, a solvent can be used as needed. The type of solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples are as described above.

[0096] [Application] The resin composition of the present embodiment can be suitably used as a cured product, a prepreg, a film-like underfill material, a resin sheet, a laminate, a build-up material, a non-conductive film, a metal foil-clad laminate, a printed wiring board, a fiber-reinforced composite material, or a semiconductor device. These will be described below.

[0097] [Cured product] The cured product of this embodiment is obtained by curing the resin composition. The method for producing the cured product is not particularly limited, but for example, the resin composition can be melted or dissolved in a solvent, poured into a mold, and cured under normal conditions using heat, light, or the like. In the case of heat curing, the curing temperature is not particularly limited, but is preferably within the range of 120°C to 300°C from the viewpoint of efficient curing and preventing deterioration of the resulting cured product. In the case of photocuring, the wavelength range of the light is not particularly limited, but is preferably within the range of 100 nm to 500 nm, which allows efficient curing by a photopolymerization initiator, etc.

[0098] [Prepreg] The prepreg of this embodiment has a substrate and the resin composition of this embodiment impregnated into or coated on the substrate. The method for producing the prepreg can be carried out according to a conventional method and is not particularly limited. For example, the prepreg of this embodiment can be produced by impregnating or coating the substrate with the resin composition of this embodiment and then semi-curing (B-stage) the composition by heating in a dryer at 100 to 200°C for 1 to 30 minutes.

[0099] The content of the resin composition of this embodiment in the prepreg (including the filler) is preferably 30 to 90 mass %, more preferably 35 to 85 mass %, and even more preferably 40 to 80 mass %, relative to the total amount of the prepreg. When the content of the resin composition is within the above range, moldability tends to be further improved.

[0100] The substrate is not particularly limited, and known materials used in various printed wiring board materials can be appropriately selected and used depending on the intended application and performance. Specific examples of fibers constituting the substrate include, but are not limited to, glass fibers such as E-glass, D-glass, S-glass, Q-glass, spherical glass, NE-glass, L-glass, and T-glass; inorganic fibers other than glass such as quartz; wholly aromatic polyamides such as polyparaphenylene terephthalamide (Kevlar®, manufactured by DuPont Co., Ltd.) and copolyparaphenylene-3,4'-oxydiphenylene terephthalamide (Technora®, manufactured by Teijin Techno Products Co., Ltd.); polyesters such as 2,6-hydroxynaphthoic acid-parahydroxybenzoic acid (Vectran®, manufactured by Kuraray Co., Ltd.) and Zexion® (manufactured by KB Seiren Co., Ltd.); and organic fibers such as polyparaphenylene benzoxazole (Zylon®, manufactured by Toyobo Co., Ltd.) and polyimide. These substrates may be used alone or in combination of two or more.

[0101] 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 preferred.

[0102] The shape of the substrate is not particularly limited, but examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc. The weaving method of the woven fabric is not particularly limited, but examples thereof include plain weave, sieve weave, twill weave, etc., and a suitable weave can be selected from these known weaves depending on the intended use and performance. In addition, those that have been subjected to fiber opening treatment or surface treatment with a silane coupling agent or the like are preferably used. The thickness and mass of the substrate are not particularly limited, but typically those of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorbency, the substrate should have a thickness of 200 μm or less and a mass of 250 g / m 2 The following glass woven fabrics are preferred, and glass woven fabrics made of E-glass, S-glass, or T-glass glass fibers are more preferred.

[0103] [Resin sheet] The resin sheet of the present embodiment can be used to form an insulating layer of a metal foil-clad laminate, a printed wiring board, or the like, and includes both a resin sheet and a resin sheet with a support.

[0104] The resin sheet of this embodiment is obtained by molding the resin composition of this embodiment into a sheet. The manufacturing method of the resin sheet can be performed according to a conventional method and is not particularly limited. For example, it can be obtained by peeling or etching the support from a resin sheet with a support described below. Alternatively, a resin sheet can be obtained without using a sheet substrate such as a support by supplying a solution in which the resin composition of this embodiment is dissolved in a solvent into a mold having a sheet-shaped cavity and drying it to form it into a sheet.

[0105] The resin sheet with a support of this embodiment includes a support and the resin composition disposed on the support. The resin sheet with a support can be produced, for example, by directly applying the resin composition to a support such as copper foil or a resin film and drying the applied resin composition.

[0106] The support is not particularly limited, but may be any known material used in various printed wiring board materials. Examples include organic film substrates such as 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, and release films obtained by applying a release agent to the surface of these films, as well as conductive foils such as copper foil, and plate-shaped inorganic films such as glass plates, SUS plates, and FPR. Among these, electrolytic copper foil and PET film are preferred.

[0107] Examples of the application method include a method in which a solution prepared by dissolving the resin composition of the present embodiment in a solvent is applied onto a support using a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

[0108] The supported resin sheet is preferably one obtained by applying the resin composition to a support and then semi-curing (B-staged). Specific examples include a method of applying the resin composition to a support such as copper foil and then semi-curing it by, for example, heating it in a dryer at 100 to 200°C for 1 to 60 minutes, to produce a supported resin 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 supported resin sheet.

[0109] [Laminated Plate] The laminate of this embodiment is a laminate of one or more materials selected from the group consisting of the prepreg, resin sheet, and resin sheet with support. The laminate can be obtained, for example, by combining a prepreg with another layer and laminating it. The other layer is not particularly limited, but may be, for example, a separately prepared wiring board for an inner layer.

[0110] [Metal foil-clad laminate] The metal foil-clad laminate of this embodiment has one or more selected from the group consisting of the prepreg, resin sheet, and supported resin sheet, and a metal foil arranged on one or both sides of at least one selected from the group consisting of the prepreg, resin sheet, and supported resin sheet. The metal foil-clad laminate of this embodiment is, for example, a copper foil-clad laminate obtained by laminating the prepreg and copper foil and curing the laminate.

[0111] The copper foil used here is not particularly limited as long as it is used as a printed wiring board material, but known copper foils such as rolled copper foil, electrolytic copper foil, etc. are preferred. The thickness of the conductor layer is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm.

[0112] The molding method and molding conditions for the metal foil-clad laminate are not particularly limited, and general molding methods and conditions for laminates and multilayer boards for printed wiring boards can be applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used when molding the metal foil-clad laminate. In addition, when molding the metal foil-clad laminate, the temperature is 100 to 350°C, and the pressure is a surface pressure of 2 to 100 kgf / cm. 2 The heating time is generally in the range of 0.05 to 5 hours. If necessary, post-curing can be performed at a temperature of 150 to 350°C. It is also possible to form a multilayer board by combining the above-mentioned prepreg and copper foil with a separately prepared wiring board for an inner layer and laminating it.

[0113] [Printed wiring board] The printed wiring board of this embodiment includes an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes a cured product of the resin composition. The metal foil-clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal foil-clad laminate has good moldability and chemical resistance, and can be particularly effectively used as a printed wiring board for semiconductor packages where such performance is required.

[0114] Specifically, the printed wiring board of this embodiment can be manufactured, for example, by the following method. First, the above-mentioned copper foil-clad laminate is prepared. The surface of the copper foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate. The inner layer circuit surface of this inner layer substrate is then subjected to a surface treatment to enhance adhesive strength, as necessary. Next, a required number of the above-mentioned prepregs are stacked on the inner layer circuit surface, and copper foil for an outer layer circuit is further laminated on the outside of the prepreg, and the resulting laminate is integrally molded by heating and pressurizing. In this manner, a multilayer laminate is manufactured, in which an insulating layer composed of a substrate and a cured product of a resin composition is formed between the inner layer circuit and the copper foil for the outer layer circuit. Next, holes for through holes and via holes are drilled in this multilayer laminate, and then a desmear treatment is performed to remove smears, which are resin residues derived from the resin components contained in the cured product layer. A plated metal film is then formed on the wall surface of the hole to electrically connect the inner layer circuit and the copper foil for the outer layer circuit. The copper foil for the outer layer circuit is then etched to form the outer layer circuit, thereby manufacturing a printed wiring board.

[0115] The printed wiring board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on the surface of this insulating layer, and the insulating layer contains the resin composition of the present embodiment described above. In other words, the prepreg (substrate and the resin composition described above attached thereto) and the resin composition layer of the metal foil-clad laminate (layer made of the resin composition described above) constitute the insulating layer containing the resin composition described above.

[0116] In addition, when a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer that will become a circuit on the prepreg, the resin sheet, or the resin composition. In this case, the conductor layer may be formed by electroless plating.

[0117] The printed wiring board of this embodiment can be particularly effectively used as a printed wiring board for semiconductor packages, since the insulating layer has excellent isotropy of thermal conductivity.

[0118] [Build-up materials] The resin composition of the present embodiment can be used as a build-up material. Here, "build-up" refers to the production of a multilayer printed wiring board by laminating prepregs or resin sheets and repeatedly performing processes such as drilling and wiring on each layer.

[0119] More specifically, a prepreg, a resin sheet, a resin sheet with a support, or a metal foil-clad laminate using the resin composition of this embodiment can be used as a build-up material for a printed wiring board. In a printed wiring board formed using the prepreg or resin sheet of this embodiment, the prepreg or resin sheet constitutes an insulating layer. In a printed wiring board formed using a metal foil-clad laminate, the prepreg (substrate and resin composition attached thereto) or resin sheet used in producing the metal foil-clad laminate constitutes an insulating layer.

[0120] Specifically, when the prepreg of the present embodiment is used as a build-up material, a metal foil-clad laminate can be produced using the prepreg by the above-described method for producing a metal foil-clad laminate, and then the printed wiring board of the present embodiment can be obtained by the above-described method. Alternatively, the prepreg may be used as it is as a build-up material for a multilayer printed wiring board.

[0121] 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, thereby obtaining the printed wiring board of the present embodiment.

[0122] Furthermore, when the metal foil-clad laminate of this embodiment is used as a build-up material, the metal foil of the metal foil-clad laminate is etched in a conventional manner, and then the layer made of prepreg (insulating layer) is surface-treated, and a wiring pattern (conductor layer) is formed on the surface of the insulating layer by plating, thereby obtaining the printed wiring board of this embodiment.

[0123] In either case, various other processes (for example, hole processing to form via holes, through holes, etc.) may be added as necessary.

[0124] [Non-conductive film] The resin composition of this embodiment can be used as a non-conductive film (NCF). Here, a "non-conductive film" refers to a film-like connecting material that simultaneously functions as an adhesive and an insulator, and is one of the film-type adhesives used when packaging electronic elements or components. For example, a non-conductive film can be used to bond the electrode surface of a semiconductor chip to the circuit surface of a substrate, and may also function as an underfill.

[0125] The form of the non-conductive film is not particularly limited, but examples thereof include a resin sheet containing the resin composition of this embodiment and a resin sheet with a support having a layer containing the resin composition of this embodiment. The method for producing the non-conductive film can be performed according to a conventional method and is not particularly limited. For example, the non-conductive film can be obtained by forming a layer containing the resin composition on a support and then removing the support.

[0126] [Fiber-reinforced composite materials] The fiber-reinforced composite material of this embodiment includes the resin composition of this embodiment and reinforcing fibers. Generally known reinforcing fibers can be used without any particular limitation. Specific examples 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 fibers; aramid fibers; boron fibers; PBO fibers; high-strength 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, nonwoven fabrics, mats, knits, braids, unidirectional strands, rovings, chopped fibers, and the like. Furthermore, the reinforcing fibers can also be in the form of preforms (layers of woven fabric base fabrics made of reinforcing fibers, or fabrics sewn together with stitching threads, or fiber structures such as three-dimensional woven fabrics and braided fabrics).

[0127] These fiber-reinforced composite materials can be produced by any known method, without any particular limitation. Specific examples include liquid composite molding, resin film infusion, filament winding, hand layup, and pultrusion. Resin transfer molding, a type of liquid composite molding, allows materials other than preforms, such as metal plates, foam cores, and honeycomb cores, to be pre-set in the mold. This makes it suitable for a variety of applications, and it is therefore preferred for the rapid mass production of composite materials with relatively complex shapes.

[0128] [Film-type underfill material] The film-like underfill material of this embodiment has a layer containing the above-described resin composition. By using the film-like underfill material, when connecting a semiconductor chip to a circuit board in semiconductor chip mounting, such as flip-chip mounting, the underfill material can be filled into the space between the semiconductor chip and the circuit board. In particular, compared to using a liquid underfill material, the use of the film-like underfill material makes it less likely for bubbles to form between the semiconductor chip and the circuit board. Therefore, even with the recent increase in the number of bumps, the narrower bump pitch, and the narrower gap between bump heights, the use of the film-like underfill material can prevent bubbles from forming between the semiconductor chip and the circuit board.

[0129] The film-like underfill material may have a release layer laminated on the layer containing the resin composition, in addition to the layer containing the resin composition. The release layer functions as a protective material that protects the layer containing the resin composition until it is used in a semiconductor packaging process, and is peeled off when, for example, a semiconductor element is attached to the underfill insulating film.

[0130] [Semiconductor Device] The semiconductor device of this embodiment includes the cured product or film-like underfill material. The semiconductor device of this embodiment can be manufactured by mounting a semiconductor chip on the conductive portion of the printed wiring board. Here, the conductive portion refers to a portion of the multilayer printed wiring board that transmits an electrical signal, and the conductive portion may be located on the surface or in an embedded location. Furthermore, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of a semiconductor material.

[0131] The method for mounting the semiconductor chip when manufacturing the semiconductor device of this embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, and a non-conductive film (NCF) mounting method. [Example]

[0132] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, the measurements and evaluations of the various physical properties were carried out as follows.

[0133] <Method for evaluating 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 in terms of ZnO from the measured element ratios. Measuring instrument: ULVAC-PHI, Inc. Quantera II X-ray source: Monochromated Al-Kα radiation Measurement area: 1000×1000μm Vacuum degree: 4.0×10 -6 Pa (Circularity) The perimeter and area of ​​the molybdenum compound particles were measured using a wet flow particle size / shape analyzer, and the circularity was calculated. Measuring instrument: Sysmex Corporation FPIA-3000S Sheath fluid: isopropanol Measurement mode: HPF Counting method: Total count 36000 (Average particle size) The particle size distribution of the molybdenum compound particles was measured using a particle size distribution measuring device, and the average particle size (D50) was calculated. Measuring instrument: Microtrac MT3300EXII manufactured by Microtrac Bell Co., Ltd. Measurement solvent: isopropanol

[0134] <Evaluation method for resin varnish> (resin curing time measurement) Using a micropipette, a resin varnish with a solid content of 75% by mass prepared in the Examples or Comparative Examples was injected into the measuring device described below, and the time until the resin hardened was measured. A resin hardening time of 200 seconds or more was considered acceptable. Measuring device: Automatic curing time measuring device Madoka manufactured by Matsuo Sangyo Co., Ltd. Hot plate temperature: 170℃ Torque judgment value: 15% Rotation speed: 190 rpm Orbital speed: 60 rpm Gap value: 0.3 mm Average score: 50 Injection volume: 500μL

[0135] <Metal foil clad laminate evaluation method> (Appearance evaluation) The copper foils on both sides of the metal foil-clad laminates prepared in the Examples and Comparative Examples were etched away to obtain samples in which all of the copper foil on the surface had been removed. These samples were visually inspected, and those in which no voids were present were evaluated as "good," and those in which voids were present were evaluated as "poor."

[0136] (Drill bit life (number of drill bit breakage holes)) A sample for evaluation was obtained by stacking a backup board, a metal foil-clad laminate prepared in the Examples or Comparative Examples, and an entry sheet in that order from the bottom. This sample was drilled 10,000 times from the top under the following drilling conditions, and then the backside of the metal foil-clad laminate was observed with a hole analyzer (manufactured by Via Mechanics Co., Ltd.) to count the statistical number of holes. Processing machine: Via Mechanics Co., Ltd. ND-1 V212 Entry sheet: Mitsubishi Gas Chemical Co., Ltd. LE900 Backup board: SPB-W manufactured by Nippon Decolux Co., Ltd. Drill bit: Union Tool MC L517AW 0.105mm x 1.8mm

[0137] (hole position accuracy) After 10,000 hits under the same drilling conditions as above, the positional deviation between the hole position on the backside of the metal foil-clad laminate and the specified coordinates was measured using a hole analyzer (manufactured by Via Mechanics Co., Ltd.) The positional deviation for all holes drilled with each drill was measured, and the average value and standard deviation (σ) were calculated, followed by the average value of the positional deviation + 3σ.

[0138] (Synthesis Example 1) Synthesis of 1-naphthol aralkyl cyanate ester resin (SNCN) 300 g of α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., manufactured by Nippon Steel Chemical Co., Ltd.) (1.28 mol in terms of hydroxy groups (OH groups)) and 194.6 g (1.92 mol) of triethylamine (1.5 mol per 1 mol of hydroxy groups) were dissolved in 1,800 g of dichloromethane, and the resulting solution was designated solution 1.

[0139] Solution 1 was added over 30 minutes to 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per mol of hydroxyl groups), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per mol of hydroxyl groups), and 1205.9 g of water while stirring and maintaining the liquid temperature at -2 to -0.5°C. After the addition of Solution 1 was completed, the mixture was stirred at the same temperature for 30 minutes, and then a solution (Solution 2) prepared by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol per mol of hydroxyl groups) in 65 g of dichloromethane was added over 10 minutes. After the addition of Solution 2 was completed, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

[0140] The reaction mixture was then allowed to stand to separate into an organic phase and an aqueous phase. The resulting organic phase was washed five times with 1300 g of water. The electrical conductivity of the wastewater after the fifth wash was 5 μS / cm, confirming that the ionic compounds had been sufficiently removed by washing with water.

[0141] 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 cyanate ester compound (SNCN) (orange viscous substance). The mass average molecular weight Mw of the obtained SNCN was 600. The infrared absorption spectrum of SNCN was measured at 2250 cm -1 The absorption of the cyanate ester group was observed, and the absorption of the hydroxyl group was not observed.

[0142] (Synthesis Example 2) Synthesis of diallyl bisphenol A cyanate ester compound (DABPACN) Solution A was obtained by dissolving 11.7 g of diallylbisphenol A (hydroxy group equivalent: 154.21 g / eq.) (0.076 mol of hydroxy group (OH group)) ("DABPA" product of Daiwa Chemical Industry Co., Ltd.) and 7.8 g (0.076 mol) of triethylamine (1.0 mol per 1 mol of hydroxy group) in 138.1 g of dichloromethane.

[0143] 7.0 g (0.114 mol) of cyanogen chloride (1.5 mol per mol of hydroxyl groups), 58.4 g of dichloromethane, 11.8 g (0.116 mol) of 36% hydrochloric acid (1.53 mol per mol of hydroxyl groups), and 153.6 g of water were stirred and the liquid temperature was kept at -2 to -0.5°C. Solution A was then added over 10 minutes. After the addition of Solution A, the mixture was stirred at the same temperature for 30 minutes, and then Solution B, prepared by dissolving 8.8 g (0.086 mol) of triethylamine (1.1 mol per mol of hydroxyl groups) in 9.3 g of dichloromethane, was added over 5 minutes. After the addition of Solution B, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

[0144] The reaction mixture was then allowed to stand to separate into an organic phase and an aqueous phase. The resulting organic phase was washed with 40 g of 0.1 N hydrochloric acid, followed by three washes with 40 g of water. The electrical conductivity of the wastewater from the third wash was 17 μS / cm, confirming that the ionic compounds that can be removed by washing with water had been sufficiently removed.

[0145] 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 13.2 g of the desired diallyl bisphenol A cyanate ester compound DABPACN (light yellow liquid). The IR spectrum of the obtained DABPACN showed an absorption at 2264 cm-1 (cyanate ester group) and no absorption of the hydroxy group. The cyanate ester group equivalent of the obtained cyanate ester compound DABPACN was 179 g / eq.

[0146] Example 1 35 parts by mass of the 1-naphthol aralkyl cyanate ester compound (cyanate ester group equivalent: 261 g / eq.) obtained in Synthesis Example 1, 25 parts by mass of polyphenylmethane maleimide (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd.), 40 parts by mass of naphthylene ether epoxy resin (HP-6000, epoxy group equivalent: 250 g / eq., manufactured by DIC Corporation), 60 parts by mass of fused spherical silica (SC4053-SQ, manufactured by Admatechs Co., Ltd.), 100 parts by mass of fused spherical silica (SFP-330MC, manufactured by Denka Co., Ltd.), and 100 parts by mass of fused spherical silica (SFP-330MC, manufactured by Denka Co., Ltd.). A resin varnish was obtained by mixing 140 parts by mass of methyl methyl methacrylate (manufactured by Admatechs Co., Ltd.), 3 parts by mass of spherical zinc molybdate (ZnO content in molybdenum compound particles: 3.7% by mass, circularity: 0.92, average particle diameter: 1.0 μm, manufactured by Admatechs Co., Ltd.), 5 parts by mass of silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by mass of wetting and dispersing agent (manufactured by BYK Japan Co., Ltd.), 1 part by mass of surface conditioner (manufactured by BYK Japan Co., Ltd.), and 1 part by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.). The thermal curing time of the obtained resin varnish was measured using the method described above. The results are shown in Table 1.

[0147] The obtained resin varnish was further diluted with methyl ethyl ketone (solvent), impregnated and coated onto a 90 μm thick E-glass cloth, and then heated and dried at 160° C. for 4 minutes to obtain a 0.1 mm thick prepreg (resin composition content: 50%). Next, eight of the obtained prepregs were stacked to form a laminate, and 12 μm thick electrolytic copper foils (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) were placed on the top and bottom surfaces of the obtained laminate, and the laminate was heated under a pressure of 20 kgf / cm. 2 The laminate was then vacuum-pressed at 220°C for 120 minutes to produce a 0.8 mm thick metal foil-clad laminate (double-sided copper-clad laminate). The resulting metal foil-clad laminate was evaluated for appearance, drill bit life, and hole position accuracy. The results are shown in Table 1.

[0148] Example 2 29 parts by mass of the diallyl bisphenol A cyanate ester compound (DABPACN, cyanate ester group equivalent: 179 g / eq.) obtained in Synthesis Example 2, 28 parts by mass of polyphenylmethane maleimide (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd.), 43 parts by mass of naphthylene ether type epoxy resin (HP-6000, epoxy group equivalent: 250 g / eq., manufactured by DIC Corporation), 60 parts by mass of fused spherical silica (SC4053-SQ, manufactured by Admatechs Co., Ltd.), 100 parts by mass of fused spherical silica (SFP-330MC, manufactured by Denso ... A resin varnish was obtained by mixing 140 parts by weight of ZnO (manufactured by Admatechs Co., Ltd.), 3 parts by weight of spherical zinc molybdate (ZnO content in molybdenum compound particles: 3.7% by weight, circularity: 0.92, average particle diameter: 1.0 μm, manufactured by Admatechs Co., Ltd.), 5 parts by weight of silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by weight of wetting and dispersing agent (manufactured by BYK Japan Co., Ltd.), 1 part by weight of surface conditioner (manufactured by BYK Japan Co., Ltd.), and 1 part by weight of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.). The thermal curing time of the obtained resin varnish was measured using the method described above. The results are shown in Table 1.

[0149] The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated onto a 90 μm thick E-glass cloth, and then heated and dried at 160° C. for 9 minutes to obtain a 0.1 mm thick prepreg (resin composition content: 50%). Next, eight of the obtained prepregs were stacked to form a laminate, and 12 μm thick electrolytic copper foils (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) were placed on the top and bottom surfaces of the obtained laminate, and the laminate was heated under a pressure of 20 kgf / cm. 2 The laminate was then vacuum-pressed at 220°C for 120 minutes to produce a 0.8 mm thick metal foil-clad laminate (double-sided copper-clad laminate). The resulting metal foil-clad laminate was evaluated for appearance, drill bit life, and hole position accuracy. The results are shown in Table 1.

[0150] Example 3 Bisphenol A cyanate ester compound (Primaset® BADCy, manufactured by Lonza Co., Ltd., cyanate ester group equivalent: 139 g / eq.) 25 parts by mass, polyphenylmethane maleimide (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd.) 33 parts by mass, naphthylene ether type epoxy resin (HP-6000, epoxy group equivalent: 250 g / eq., manufactured by DIC Corporation) 42 parts by mass, fused spherical silica (SC4053-SQ, manufactured by Admatechs Co., Ltd.) 60 parts by mass, fused spherical silica (SFP-330MC A resin varnish was obtained by mixing 140 parts by weight of 140% by weight of ZnO (manufactured by Denka Co., Ltd.), 3 parts by weight of spherical zinc molybdate (ZnO content in molybdenum compound particles: 3.7% by weight, circularity: 0.92, average particle diameter: 1.0 μm, manufactured by Admatechs Co., Ltd.), 5 parts by weight of a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by weight of a wetting and dispersing agent (manufactured by BYK Japan Co., Ltd.), 1 part by weight of a surface conditioner (manufactured by BYK Japan Co., Ltd.), and 1 part by weight of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.). The thermal curing time of the obtained resin varnish was measured using the method described above. The results are shown in Table 1.

[0151] The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated onto a 90 μm thick E-glass cloth, and then heated and dried at 160° C. for 5 minutes to obtain a 0.1 mm thick prepreg (resin composition content: 50%). Next, eight of the obtained prepregs were stacked to form a laminate, and 12 μm thick electrolytic copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed on the top and bottom surfaces of the obtained laminate, and the laminate was heated under a pressure of 20 kgf / cm. 2 The laminate was then vacuum-pressed at 220°C for 120 minutes to produce a 0.8 mm thick metal foil-clad laminate (double-sided copper-clad laminate). The resulting metal foil-clad laminate was evaluated for appearance, drill bit life, and hole position accuracy. The results are shown in Table 1.

[0152] Example 4 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) of zinc molybdate (manufactured by Kojundo Chemical Laboratory Co., Ltd., circularity 0.91, average particle diameter 3.8 μm) and zinc oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was used as the molybdenum compound instead of spherical zinc molybdate. The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated onto a 90 μm thick E-glass cloth, and heated and dried at 130° C. for 3 minutes to obtain a 0.1 mm thick prepreg. The obtained prepreg was used to obtain a 0.8 mm thick metal foil-clad laminate in the same manner as in Example 1. The physical property measurements of the obtained resin varnish and metal foil-clad laminate are shown in Table 1.

[0153] Example 5 A resin varnish was obtained in the same manner as in Example 1, except that 12 parts by mass of a mixture of molybdenum disulfide (M-5 powder, manufactured by Daizo Co., Ltd., circularity 0.91, average particle diameter 2.9 μm) and zinc oxide (manufactured by Kojundo Chemical Research Institute Co., Ltd.) (ZnO content 1.0 mass%) was used as the molybdenum compound instead of spherical zinc molybdate. The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated onto a 90 μm thick E-glass cloth, and heated and dried at 130°C for 3 minutes to obtain a 0.1 mm thick prepreg. The obtained prepreg was used to obtain a 0.8 mm thick metal foil-clad laminate in the same manner as in Example 1. The physical property measurements of the obtained resin varnish and metal foil-clad laminate are shown in Table 1.

[0154] (Comparative Example 1) A resin varnish was obtained in the same manner as in Example 1, except that spherical zinc molybdate was not used. The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated onto a 90 μm thick E-glass cloth, and then heated and dried at 160° C. for 10 minutes to obtain a prepreg with a thickness of 0.1 mm. The obtained prepreg was used to obtain a metal foil-clad laminate with a thickness of 0.8 mm in the same manner as in Example 1. The physical property measurements of the obtained resin varnish and metal foil-clad laminate are shown in Table 1.

[0155] (Comparative Example 2) A resin varnish was obtained in the same manner as in Example 1, except that 3 parts by mass of basic zinc molybdate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) heated at 300°C for 1 hour (ZnO content in the molybdenum compound particles: 27.6% by mass, circularity: 0.87, average particle diameter: 2.5 μm) was used instead of spherical zinc molybdate. The obtained resin varnish was further diluted with methyl ethyl ketone, impregnated and coated onto a 90 μm thick E-glass cloth, and then heated and dried at 130°C for 3 minutes to obtain a 0.1 mm thick prepreg. The obtained prepreg was used to obtain a 0.8 mm thick metal foil-clad laminate in the same manner as in Example 1. The physical property measurements of the obtained resin varnish and metal foil-clad laminate are shown in Table 1.

[0156] [Table 1] As is clear from Table 1, it was confirmed that the metal foil-clad laminates obtained using the resin compositions of Examples 1 to 5 were excellent in both drilling processability and appearance evaluation. The metal foil-clad laminate obtained using the resin composition of Comparative Example 1 was inferior in hole position accuracy during drilling, and the metal foil-clad laminate obtained using the resin composition of Comparative Example 2 was inferior in appearance evaluation.

[0157] This application is based on a Japanese patent application (Patent Application No. 2020-054954) filed with the Japan Patent Office on March 25, 2020, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0158] The resin composition of the present invention has industrial applicability as a material for prepregs and the like.

Claims

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, A resin composition, wherein the content of zinc oxide (D) in the resin composition is 0.1 mass % or more and 5 mass % or less relative to the total mass of the molybdenum compound particles.

2. 2. The resin composition according to claim 1, wherein the content of the filler (B) is 10 to 500 parts by mass per 100 parts by mass of the total of the resin solid components in the resin composition.

3. 3. The resin composition according to claim 1, wherein the content of the molybdenum compound (C) is 0.2 to 30 parts by mass per 100 parts by mass of the total of the resin solid components in the resin composition.

4. The resin composition according to any one of claims 1 to 3, wherein the zinc oxide (D) is contained in the molybdenum compound particles.

5. The resin composition according to any one of claims 1 to 4, wherein the molybdenum compound particles are spherical in shape.

6. 6. The resin composition according to claim 5, wherein the circularity of the molybdenum compound particles is 0.90 to 1.

00.

7. The resin composition according to any one of claims 1 to 6, wherein the molybdenum compound particles have an average particle size of 0.1 to 10 µm.

8. The resin composition according to any one of claims 1 to 7, wherein the molybdenum compound (C) is at least one selected from the group consisting of zinc molybdate, ammonium molybdate, sodium molybdate, calcium molybdate, potassium molybdate, molybdenum disulfide, molybdenum trioxide, and molybdenum hydrate.

9. The resin composition according to any one of claims 1 to 8, wherein the cyanate ester compound (A) is at least one selected from the group consisting of phenol novolac-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds, naphthylene ether-type cyanate ester compounds, xylene resin-type cyanate ester 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.

10. The resin composition according to any one of claims 1 to 9, 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.

11. The resin composition according to any one of claims 1 to 10, wherein the filler (B) is one or more organic fillers selected from the group consisting of silicone rubber powders and silicone composite powders.

12. The resin composition according to any one of claims 1 to 11, further comprising one or more compounds selected from the group consisting of a maleimide compound (M), an epoxy compound (E), a phenol compound (F), an alkenyl-substituted nadimide compound (K), an oxacene resin (G), a benzoxazine compound (H), and a compound (I) having a polymerizable unsaturated group.

13. The resin composition according to claim 12, wherein the maleimide compound (M) is at least one selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by the following formula (2), and a maleimide compound represented by the following formula (3): 【Chemistry 1】 (In formula (2), R 1 each independently represents a hydrogen atom or a methyl group, and n1 is 1 to 10. 【Chemistry 2】 (In formula (3), there are multiple R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n2 is an average value and satisfies 1<n2≦5.

14. 14. The resin composition according to claim 12, wherein the epoxy compound (E) is at least one selected from the group consisting of biphenylaralkyl epoxy compounds, naphthalene epoxy compounds, and naphthylene ether epoxy resins.

15. The resin composition according to any one of claims 1 to 14, which is for use in a printed wiring board.

16. A prepreg comprising a substrate and the resin composition according to any one of claims 1 to 14 impregnated into or coated on the substrate.

17. A resin sheet obtained by molding the resin composition according to any one of claims 1 to 14 into a sheet.

18. A resin sheet with a support, comprising: a support; and the resin composition according to any one of claims 1 to 14, disposed on the support.

19. A laminated plate obtained by laminating at least one selected from the group consisting of the prepreg according to claim 16, the resin sheet according to claim 17, and the resin sheet with a support according to claim 18.

20. One or more selected from the group consisting of the prepreg according to claim 16, the resin sheet according to claim 17, and the resin sheet with a support according to claim 18; a metal foil disposed on one or both sides of at least one material selected from the group consisting of the prepreg, a resin sheet, and a resin sheet with a support; A metal foil-clad laminate having the same.

21. A printed wiring board having an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 14, and a conductor layer formed on the surface of the insulating layer.

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