Prepreg, and metal-clad laminate and wiring board using same

Abstract

One aspect of the present invention relates to a prepreg comprising a thermosetting resin composition or a semi-cured product of the thermosetting resin composition, and a glass cloth, wherein the thermosetting resin composition contains molybdenum compound particles (A) and a maleimide compound (B), and the glass cloth contains, with respect to the total amount of components of the glass cloth, 45-55 mass% of SiO2, 20-30 mass% of Al2O3, 3.0 mass% or less of MgO, and 10-15 mass% of P2O5.

Description

Prepreg, and metal-clad laminate and wiring board using the same

[0001] The present invention relates to a prepreg, and a metal-clad laminate and a wiring board using the same.

[0002] In recent years, with the increasing performance of electronic devices and the dramatic improvement in information communication speeds, semiconductor package substrates used in network devices, servers, and AI processors are becoming thinner and larger as their performance and integration improves. This has led to an increasing demand for higher performance in semiconductor package substrates, such as drilling processability.

[0003] For example, Patent Document 1 describes a resin composition containing a cyanate ester compound, an epoxy resin, a molybdenum compound, and two types of inorganic fillers, and describes that by adjusting the ratio of the average particle sizes of the two types of inorganic fillers, it is possible to improve mechanical drilling processability (hole position accuracy).

[0004] Furthermore, as wiring boards become thinner and larger, warping occurs in semiconductor packages in which semiconductor chips are mounted on wiring boards, which increases the likelihood of mounting defects. In order to suppress warping in semiconductor packages in which semiconductor chips are mounted on wiring boards, the substrate material constituting the insulating layer of the wiring board is required to have excellent thermal expansion properties in its cured form.

[0005] For example, Patent Document 2 describes a resin composition containing a molybdic acid compound, an epoxy resin, a curing agent, and an inorganic filler, and describes a laminate that not only has excellent mechanical drilling processability (hole position accuracy) but also low thermal expansion.

[0006] However, as mentioned above, Patent Documents 1 and 2 describe the use of specific components as components of the resin composition, but only describe that general glass cloth such as T-glass, S-glass, etc. can be used for the glass cloth used in producing a wiring board or the like using the resin composition. Therefore, there is room for further improvement in terms of suppressing warpage in semiconductor packages in which semiconductor chips are mounted on wiring boards, and drill processability (drill wear rate).

[0007] Therefore, the present invention has been made in consideration of the above circumstances, and its object is to provide a prepreg having excellent drill processability (low drill wear rate) and a low coefficient of thermal expansion, as well as a metal-clad laminate and a wiring board using the same.

[0008] International Publication No. WO 2013 / 146700 International Publication No. WO 2013 / 047203

[0009] As a result of extensive research to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention through further research based on this finding.

[0010] A prepreg according to one aspect of the present invention comprises a thermosetting resin composition or a semi-cured product of the thermosetting resin composition, and glass cloth, wherein the thermosetting resin composition contains molybdenum compound particles (A) and a maleimide compound (B), and the glass cloth contains SiO ２ 45 to 55 mass% of Al ２ O ３ 20 to 30 mass %, MgO 3.0 mass % or less, P ２ O ５ Contains 10 to 15 mass % of

[0011] A metal-clad laminate according to one aspect of the present invention is characterized by comprising an insulating layer containing a cured product of the prepreg, and a metal layer.

[0012] A wiring board according to one aspect of the present invention is characterized by comprising an insulating layer containing a cured product of the prepreg, and wiring.

[0013] Fig. 1 is a schematic diagram for explaining drilling when measuring a drill wear rate in one embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing the configuration of a prepreg according to one embodiment of the present invention. Fig. 3 is a schematic cross-sectional view showing the configuration of a metal-clad laminate according to one embodiment of the present invention. Fig. 4 is a schematic cross-sectional view showing the configuration of a wiring board according to one embodiment of the present invention.

[0014] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these.

[0015] <Prepreg> The prepreg of the present embodiment comprises a thermosetting resin composition or a semi-cured product of the thermosetting resin composition, and glass cloth, wherein the thermosetting resin composition contains molybdenum compound particles (A) and a maleimide compound (B), and the glass cloth contains SiO ２ 45 to 55 mass% of Al ２ O ３ 20 to 30 mass %, MgO 3.0 mass % or less, P ２ O ５ Contains 10 to 15 mass % of

[0016] The prepreg of this embodiment having such a configuration has excellent drill processability and a low coefficient of thermal expansion, and therefore the metal-clad laminate and wiring board obtained using the prepreg of this embodiment have a low drill wear rate and are also suppressed from warping.

[0017] In this specification, excellent drilling workability means a low drill wear rate. The drill wear rate can be measured using the method shown in Figure 1. Specifically, two evaluation substrates (metal-clad laminates) 11 are stacked, an entry board 16 is placed on top of them, and 10,000 holes are drilled using a drill 15 from the entry board 16 to the evaluation substrate (metal-clad laminate) 11. The wear rate of the drill bit can be measured from the size (area) of the drill bit after drilling and the size (area) of the drill bit before drilling. More specifically, it can be measured using the method described in the Examples.

[0018] Hereinafter, each configuration of the prepreg according to this embodiment will be specifically described.

[0019] [Thermosetting Resin Composition] The thermosetting resin composition according to this embodiment (hereinafter also simply referred to as "resin composition") contains molybdenum compound particles (A) and a maleimide compound (B).

[0020] (Molybdenum Compound Particles (A)) The molybdenum compound particles (A) are a component for further improving drill machinability (low wear rate). In a preferred embodiment, the molybdenum compound particles (A) contain molybdenum compound particles (A-1) that have been surface-treated (surface-modified) with a surface treatment agent. At least a portion of the surface of the molybdenum compound particles (A-1) is surface-treated with a surface treatment agent. When the molybdenum compound particles (A) contain molybdenum compound particles (A-1) that have been surface-treated (surface-modified) with a surface treatment agent, the adhesive strength of the cured product of the resin composition can be improved. In this specification, the adhesive strength of the cured product of the resin composition means the adhesive strength with a metal layer (for example, copper foil).

[0021] Here, the term "surface treatment agent" refers to a substance that can change at least one of the properties of the surface of a substance, such as adhesion, adhesiveness, reactivity, compatibility, etc. with other substances by changing the surface properties of the substance. For example, the surface treatment agent includes a coupling agent such as a silane coupling agent.

[0022] Furthermore, the phrase "the molybdenum compound particles (A) include molybdenum compound particles (A-1) which have been surface-treated with a surface treatment agent" has two meanings.

[0023] The first meaning is that the molybdenum compound particles (A) include molybdenum compound particles (A-1) that have already been surface-treated with a surface treatment agent. The first meaning is intended to be a pretreatment method (premixing method) when producing a resin composition.

[0024] On the other hand, the second meaning means that the molybdenum compound particles (A-1) have not yet been surface-treated, but the molybdenum compound particles (A) contain molybdenum compound particles (A-1) that may be surface-treated with a coexisting surface treatment agent. The second meaning is intended for an integral blend method when producing a resin composition.

[0025] The molybdenum compound particles (A) are not particularly limited, and examples thereof include molybdenum oxides and molybdenum acid compounds such as molybdenum trioxide particles, molybdenum dioxide particles, zinc molybdate particles, ammonium molybdate particles, magnesium molybdate particles, calcium molybdate particles, barium molybdate particles, sodium molybdate particles, potassium molybdate particles, phosphomolybdic acid particles, ammonium phosphomolybdate particles, sodium phosphomolybdate particles, and silicomolybdic acid particles; and molybdenum compounds such as molybdenum boride particles, molybdenum disilicide particles, molybdenum nitride particles, and molybdenum carbide particles. These may be used alone or in combination of two or more.

[0026] Among these, zinc molybdate, calcium molybdate, magnesium molybdate, etc. are preferably used from the viewpoints of chemical stability, moisture resistance, and insulating properties.

[0027] The surface treatment agent preferably contains at least one compound selected from the group consisting of fluorene compounds, phenylaminosilane compounds, styrylsilane compounds, triphenylphosphine compounds, methacrylsilane compounds, epoxysilane compounds, isocyanate compounds, vinylsilane compounds, and silicone compounds. This can further improve the adhesive strength of the cured product of the resin composition. Note that all of the compounds listed above are silane coupling agents.

[0028] The 50% volume average particle diameter (D ５０ The 50% volume average particle diameter (D) of the molybdenum compound particles (A) is preferably 0.1 μm or more and 2.0 μm or less, and more preferably 0.1 μm or more and 1.0 μm or less. ５０ When the 50% volume average particle diameter (D ) of the molybdenum compound particles (A) is 0.1 μm or more, the adhesive strength of the cured product of the resin composition can be improved. ５０ Here, the "50% volume average particle size" refers to the particle size (D) at 50% of the integrated value in the particle size distribution measured by a particle size distribution measuring device based on a laser scattering / diffraction method.５０ ) means

[0029] The 90% volume average particle diameter (D ９０ Here, the "90% volume average particle size" refers to the particle size (D) at 90% of the integrated value in the particle size distribution measured by a particle size distribution measuring device based on the laser scattering / diffraction method. ９０ ) means

[0030] (Maleimide Compound (B)) The maleimide compound (B) can be any compound having a maleimide group in the molecule. Specific examples of the maleimide compound (B) include monofunctional maleimide compounds having one maleimide group in the molecule, polyfunctional maleimide compounds having two or more maleimide groups in the molecule, and modified maleimide compounds. Examples of the modified maleimide compound include modified maleimide compounds in which a portion of the molecule is modified with an amine compound, modified maleimide compounds in which a portion of the molecule is modified with a silicone compound, and modified maleimide compounds in which a portion of the molecule is modified with an amine compound and a silicone compound.

[0031] More specific examples include maleimide compounds having two or more N-substituted maleimide groups in one molecule, maleimide compounds having an indane structure, maleimide compounds having at least one group selected from an alkyl group having 6 or more carbon atoms and an alkylene group having 6 or more carbon atoms, and maleimide compounds having a benzene ring in the molecule. Still more specific examples include compounds represented by the following formula (1) and compounds represented by the following formula (2).

[0032]

[0033] In the formula (1), s represents 1 to 5. This s is the average value of the number of repetitions (degree of polymerization).

[0034]

[0035] The maleimide compound (B) used in the present embodiment may be a commercially available product, and examples thereof include BMI-4000, BMI-2300, BMI-TMH, BMI-4000, and BMI-5100 manufactured by Daiwa Chemical Industry Co., Ltd.; MIR-3000-70MT and MIR-5000 manufactured by Nippon Kayaku Co., Ltd.; and BMI-689, BMI-1500, BMI-3000J, and BMI-5000 manufactured by Designer Molecules Inc.

[0036] As the maleimide compound (B), the above-mentioned maleimide compounds may be used alone or in combination of two or more kinds.

[0037] (Benzoxazine Compound (C)) The thermosetting resin composition preferably contains a benzoxazine compound (C). When the resin composition contains the benzoxazine compound (C), the adhesive strength of the cured product of the resin composition can be increased and the thermal expansion coefficient can be more reliably reduced. The benzoxazine compound (C) is not particularly limited as long as it is a compound having at least one benzoxazine ring. For example, a benzoxazine compound having an alkenyl group in the molecule can be mentioned.

[0038] A benzoxazine compound having an alkenyl group in its molecule has not only an alkenyl group but also a benzoxazine group in its molecule. The alkenyl group is not particularly limited, but examples include alkenyl groups having 2 to 6 carbon atoms. Specific examples of the alkenyl group include vinyl groups, allyl groups, propenyl groups, and butenyl groups. Among these, allyl groups and propenyl groups are preferred, and allyl groups are more preferred. In other words, the benzoxazine compound (C) preferably contains an allyl group-containing benzoxazine compound (C-1), which makes it easier to reduce the thermal expansion coefficient. The allyl group-containing benzoxazine compound (C-1) is a benzoxazine compound having at least one allyl group.

[0039] The benzoxazine group is not particularly limited, and examples thereof include a benzoxazine group represented by the following formula (3) and a benzoxazine group represented by the following formula (4): Examples of the benzoxazine compound (C) include not only benzoxazine compounds having a benzoxazine group represented by the following formula (3) in the molecule and benzoxazine compounds having a benzoxazine group represented by the following formula (4) in the molecule, but also benzoxazine compounds having a benzoxazine group represented by the following formula (3) and a benzoxazine group represented by the following formula (4) in the molecule.

[0040]

[0041] In the formula (3), R １ represents an allyl group, and a represents 1 to 4. a represents R １ is an average value of the degree of substitution of 1 to 4, and is preferably 1.

[0042]

[0043] In the formula (4), R ２ represents an allyl group.

[0044] More specific examples of the allyl group-containing benzoxazine compound (C-1) having the structure represented by the formulas (3) and (4) include benzoxazine compounds having the structures represented by the following formulas (5) to (7). More specific examples include the compound represented by the following formula (8).

[0045]

[0046]

[0047]

[0048]

[0049] In the formula (8), R ３ and R ４ represents an allyl group; Y represents an alkylene group; b and c each independently represent 1 to 4;

[0050] The alkylene group is not particularly limited and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octane group, an icosane group, and a hexatriacontane group. Among these, a methylene group is preferred.

[0051] In the formula (8), b is R ３ is an average value of the degree of substitution of R ４ is an average value of the degree of substitution of 1 to 4, and is preferably 1.

[0052] As the benzoxazine compound (C), commercially available products can be used, for example, Pd-type benzoxazine compound manufactured by Shikoku Chemical Industry Co., Ltd., "ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd., etc. may be used.

[0053] As the benzoxazine compound (C), the benzoxazine compounds exemplified above may be used alone or in combination of two or more kinds.

[0054] (Elastomer (D)) The thermosetting resin composition preferably contains an elastomer (D) containing at least one of a high molecular weight material (D-1) having a weight average molecular weight of 10,000 or more and 900,000 or less, and a core-shell rubber (D-2).

[0055] It is believed that the thermosetting resin composition contains a polymer (D-1) having a weight average molecular weight (Mw) of 10,000 or more and 900,000 or less, thereby making it possible to obtain a further low coefficient of thermal expansion in the cured product. The polymer (D-1) more preferably has a weight average molecular weight (Mw) of 10,000 or more and 600,000 or less. In this specification, the weight average molecular weight may be a molecular weight measured by a general molecular weight measurement method, and specific examples include values ​​measured using gel permeation chromatography (GPC).

[0056] The polymer (D-1) preferably contains at least one of an acrylic resin and a styrene copolymer having a weight-average molecular weight of 10,000 or more and 900,000 or less. By containing at least one of an acrylic resin and a styrene copolymer, the coefficient of thermal expansion of the polymer (D-1) can be reduced.

[0057] Specific examples of the acrylic resin in this embodiment preferably have structures represented by the following formulas (9), (10), and (11).

[0058]

[0059]

[0060]

[0061] In the above formulas (9) to (11), x, y, and z represent mole fractions, and satisfy the following: x+y+z≦1, 0<x≦0.2, 0.6≦y≦0.95, and 0.05≦z≦0.2.

[0062] In the above formula (10), R ５ is a hydrogen atom or a methyl group, R ６ contains at least one of a glycidyl group and an epoxidized alkyl group out of a hydrogen atom, an alkyl group, a glycidyl group and an epoxidized alkyl group.

[0063] In the above formula (11), R ７ is a hydrogen atom or a methyl group, R ８ is Ph (phenyl group), -COOCH ２ Ph or -COO(CH ２ ) ２ It is Ph.

[0064] Preferably, the main chain of the acrylic resin has at least one structure represented by formula (9), at least one structure represented by formula (10), and at least one structure represented by formula (11).

[0065] When the main chain of the acrylic resin has structures represented by formula (9), formula (10), and formula (11), the order of arrangement of the structures represented by formula (9), formula (10), and formula (11) is not particularly limited. In this case, in the main chain of the acrylic resin, the structure represented by formula (9) may be continuous or discontinuous, the structure represented by formula (10) may be continuous or discontinuous, and the structure represented by formula (11) may be continuous or discontinuous.

[0066] Here, R in the formula (10) ６ The meaning of containing at least one of a glycidyl group and an epoxidized alkyl group among a hydrogen atom, an alkyl group, a glycidyl group, and an epoxidized alkyl group will be explained below. ６ The acrylic resin will be described separately for cases where it has only one structure represented by formula (10) and cases where it has two or more structures represented by formula (10).

[0067] In the former case, that is, when the acrylic resin has one structure represented by formula (10), R ６ is a glycidyl group or an epoxidized alkyl group.

[0068] In the latter case, that is, when the acrylic resin has two or more structures represented by formula (10), R in at least one of the structures represented by formula (10) ６ is a glycidyl group or an epoxidized alkyl group, and R in the remaining structure represented by formula (10) ６ is a hydrogen atom or an alkyl group. R in at least one structure represented by formula (10) ６ is a glycidyl group or an epoxidized alkyl group, so that R ６ However, it may be a glycidyl group or an epoxidized alkyl group.

[0069] The structure represented by the formula (11) is a group consisting of Ph (phenyl group), —COOCH ２ Ph, -COO(CH ２ ) ２ Ph. Ph, -COOCH ２Ph, -COO(CH ２ ) ２ Ph is thermally stable, and therefore increases the strength of the cured resin composition, and can improve the heat resistance of laminates (metal-clad laminates and wiring boards).

[0070] The styrene-based copolymer that can be used in the present embodiment is a copolymer obtained by polymerizing two or more monomers including a styrene monomer, and is not particularly limited as long as the weight average molecular weight is within the above range. More specific examples include methylstyrene (ethylene / butylene) methylstyrene block copolymer, methylstyrene (ethylene-ethylene / propylene) methylstyrene block copolymer, styrene isoprene block copolymer, hydrogenated styrene isoprene styrene block copolymer, styrene (ethylene / butylene) styrene block copolymer, styrene (ethylene-ethylene / propylene) styrene block copolymer, methylstyrene (styrene / butadiene random copolymer block) methylstyrene copolymer, styrene (styrene / butadiene random copolymer block) styrene copolymer, styrene butadiene block copolymer such as styrene butadiene styrene block copolymer, styrene isobutylene styrene block copolymer, styrene (butadiene / butylene) styrene block copolymer, and hydrogenated products in which at least a portion of these is hydrogenated.

[0071] As the styrene copolymer, commercially available products may be used, such as Tuftec P1500, Tuftec H1221, Tuftec H1041, Tuftec H1517, Tuftec M1913, and Tuftec M1981 manufactured by Asahi Kasei Corporation.

[0072] The polymer (D-1) does not include the maleimide compound (B), the benzoxazine compound (C), or the core-shell rubber (D-2).

[0073] The core-shell rubber (D-2) that can be used in this embodiment is an aggregate of rubber particles, and each rubber particle has a core-shell multilayer structure. The rubber particles are formed of a core and a shell. At least one of the core and the shell has elasticity. By including such a core-shell rubber (D-2) in the resin composition, the impact resistance, thermal shock resistance, and low thermal expansion of the cured product can be improved without impairing heat resistance.

[0074] Preferably, the core-shell rubber (D-2) contains silicone in at least one of the core and the shell. This further enhances thermal shock resistance. In other words, compared to rubbers not containing silicone, impact resistance can be improved even at lower temperatures.

[0075] The core can contribute to toughening of the cured product of the resin composition. The core is a particulate rubber. The rubber may be a copolymer or a homopolymer. The polymer constituting the core is not particularly limited, but examples thereof include silicone / acrylic polymers, acrylic polymers, silicone polymers, butadiene polymers, and isoprene polymers.

[0076] The shell is highly compatible with the maleimide compound (B) and the benzoxazine compound (C), and can contribute to improving the adhesive strength of the cured resin composition. The shell is present on the surface of the core. The shell is composed of multiple graft chains. One end of each graft chain is bonded to the surface of the core and serves as a fixed end, and the other end is a free end. The graft chains may be copolymers or homopolymers. The polymer constituting the shell is not particularly limited, but examples thereof include acrylic copolymers, polymethyl methacrylate, and polystyrene.

[0077] 50% volume average particle diameter (D ５０ The 50% volume average particle diameter (D) of the core-shell rubber (D-2) is preferably 0.01 μm or more and 0.5 μm or less, more preferably 0.05 μm or more and 0.3 μm or less. ５０ When the 50% volume average particle diameter (D ) of the core-shell rubber (D-2) is 0.01 μm or more, the impact resistance of the cured product can be further improved. ５０When the diameter of the core-shell rubber (D-2) is 0.5 μm or less, the core-shell rubber (D-2) is easily dispersed uniformly in the resin composition, and as a result, the core-shell rubber (D-2) is easily dispersed uniformly in the cured product. Here, the "50% volume average particle diameter" refers to the particle diameter (D) at 50% of the cumulative value in the particle size distribution measured using a particle size distribution measuring device based on the laser scattering / diffraction method. ５０ ) means

[0078] (Inorganic Filler (E)) The resin composition of this embodiment may contain an inorganic filler (E) other than the molybdenum compound particles (A) as needed, as long as the effects of the present invention are not impaired. That is, in this embodiment, the inorganic filler (E) does not include the molybdenum compound particles (A). When the resin composition contains the inorganic filler (E), it is thought that the low thermal expansion properties of the cured product of the resin composition can be improved.

[0079] The inorganic filler (E) is not particularly limited as long as it can be used as an inorganic filler contained in a resin composition. Examples of the inorganic filler (E) include metal oxide particles, metal hydroxide particles, nitride particles, titanate particles, magnesium carbonate particles such as anhydrous magnesium carbonate particles, calcium carbonate particles, quartz glass particles, talc particles, aluminum borate particles, and barium sulfate particles. Examples of the metal oxide particles include silica particles, alumina particles, titanium oxide particles, magnesium oxide particles, and mica particles. Examples of the silica particles include spherical silica such as crushed silica and fused spherical silica. Examples of the metal hydroxide particles include boehmite particles, magnesium hydroxide particles, and aluminum hydroxide particles. Examples of the nitride particles include aluminum nitride particles and boron nitride particles. Examples of the titanate particles include barium titanate particles, strontium titanate particles, calcium titanate particles, and aluminum titanate particles.

[0080] Among these, the inorganic filler (E) preferably contains at least one selected from the group consisting of silica particles, aluminum hydroxide particles, talc particles, magnesium hydroxide particles, and boehmite particles.

[0081] The inorganic filler (E) may be any of the above inorganic fillers, either singly or in combination. When two or more of the above inorganic fillers are used in combination, silica particles may be used in combination with one or more inorganic fillers other than silica particles.

[0082] The inorganic filler (E) may be a surface-treated or untreated inorganic filler. Examples of the surface treatment include treatment with a silane coupling agent.

[0083] (Content) The content of the molybdenum compound particles (A) is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 35 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the resin component in the resin composition. When the content of the molybdenum compound particles (A) is 0.1 part by mass or more relative to 100 parts by mass of the resin component in the resin composition, deterioration of drilling workability can be suppressed. On the other hand, when the content of the molybdenum compound particles (A) is 40 parts by mass or less relative to 100 parts by mass of the resin component in the resin composition, the etching rate with a desmear solution can be reduced. In this specification, the term "resin component" refers to the resin component contained in the resin composition. For example, when the resin composition contains a maleimide compound (B) and a benzoxazine compound (C), the term refers to the total of the maleimide compound (B) and the benzoxazine compound (C), or when the resin composition further contains an elastomer (D) in addition to the maleimide compound (B) and the benzoxazine compound (C), the term refers to the total of the maleimide compound (B), the benzoxazine compound (C), and the elastomer (D), the total of the maleimide compound (B), the benzoxazine compound (C), and the benzoxazine compound (C).

[0084] The content of the maleimide compound (B) is preferably 15 to 75% by mass, and more preferably 30 to 50% by mass, based on the total amount of resin components in the resin composition. When the content of the maleimide compound (B) is 15% by mass or more based on the total amount of resin components in the resin composition, the thermal expansion coefficient can be reduced. When the content of the maleimide compound (B) is 75% by mass or less based on the total amount of resin components in the resin composition, a decrease in adhesive strength in a cured product of the resin composition can be suppressed.

[0085] When the thermosetting resin composition contains a benzoxazine compound (C), the content of the benzoxazine compound (C) is preferably 10 to 50 mass% and more preferably 13 to 30 mass% based on the total amount of resin components in the resin composition. By having the content of the benzoxazine compound (C) be 10 mass% or more based on the total amount of resin components in the resin composition, a decrease in adhesive strength in a cured product of the resin composition can be suppressed. By having the content of the benzoxazine compound (C) be 50 mass% or less based on the total amount of resin components in the resin composition, the thermal expansion coefficient can be reduced.

[0086] When the thermosetting resin composition contains a benzoxazine compound (C), the mass ratio (C / B) of the benzoxazine compound (C) to the maleimide compound (B) is preferably 0.2 to 1.0, more preferably 0.3 to 0.9. When the mass ratio (C / B) is 0.3 or more, a decrease in adhesive strength in a cured product of the resin composition can be suppressed. Furthermore, a decrease in drilling processability can also be suppressed. When the mass ratio (C / B) is 1.0 or less, a decrease in glass transition temperature (Tg) can be suppressed.

[0087] When the thermosetting resin composition contains elastomer (D), the content of elastomer (D) is preferably 5 to 40 mass% and more preferably 10 to 30 mass% based on the total amount of resin components in the resin composition. When the content of elastomer (D) is 5 mass% or more based on the total amount of resin components in the resin composition, the thermal expansion coefficient can be reduced. When the content of elastomer (D) is 40 mass% or less based on the total amount of resin components in the resin composition, moldability can be improved.

[0088] As described above, the resin composition may contain an inorganic filler (E). When the resin composition contains the inorganic filler (E), the content of the inorganic filler (E) is preferably 80 to 180 parts by mass, and more preferably 90 to 170 parts by mass, per 100 parts by mass of the resin component in the resin composition (excluding the molybdenum compound particles (A) and the inorganic filler (E) in the resin composition). By having the content of the inorganic filler (E) be 80 to 180 parts by mass per 100 parts by mass of the resin component in the resin composition, the thermal expansion coefficient can be reduced. Furthermore, deterioration of moldability can be suppressed.

[0089] Furthermore, when the resin composition contains an inorganic filler (E), the content of the molybdenum compound particles (A) is preferably 0.1 to 30 mass%, more preferably 1 to 15 mass%, relative to 100 mass% of the total content of the molybdenum compound particles (A) and the inorganic filler (E). When the content of the molybdenum compound particles (A) is 0.1 mass% or more relative to 100 mass% of the total content of the molybdenum compound particles (A) and the inorganic filler (E), deterioration in drilling workability can be suppressed. When the content of the molybdenum compound particles (A) is 30 mass% or less, the etching rate in a desmear solution can be reduced.

[0090] The content of the thermosetting resin composition in the prepreg of this embodiment is preferably 35 to 80 mass % and more preferably 40 to 75 mass % based on the total amount of components in the prepreg. By having the content of the thermosetting resin composition in the prepreg of 35 to 80 mass % based on the total amount of components in the prepreg, the prepreg of this embodiment can more reliably obtain the above-mentioned effects (excellent drillability, low coefficient of thermal expansion).

[0091] (Other Components) The resin composition may contain components other than the above-described components (other components) within the scope of not impairing the effects of the present invention. Examples of other components include organic components other than the above components (B) to (D), flame retardants, reaction initiators, curing accelerators, catalysts, polymerization retarders, polymerization inhibitors, dispersants, leveling agents, coupling agents, defoamers, antioxidants, heat stabilizers, antistatic agents, UV absorbers, dyes, pigments, and additives such as lubricants.

[0092] As described above, the resin composition according to this embodiment may contain an organic component other than the components (B) to (D). The organic component may be, for example, a compound that reacts with at least one of the components (B) to (D), or a compound that does not react with the components (B) to (D). Specific examples of the organic component include epoxy resins, cyanate ester compounds, and active ester compounds.

[0093] The epoxy resin is not particularly limited, but examples thereof include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, aralkyl epoxy resins, phenol novolac epoxy resins, alkylphenol novolac epoxy resins, biphenyl epoxy resins, biphenylene epoxy resins, bisphenol epoxy resins, triphenylmethane epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, and alicyclic epoxy resins. Among these, biphenylene epoxy resins and naphthalene epoxy resins are preferred. These may be used alone or in combination of two or more, depending on the circumstances.

[0094] As described above, the resin composition of this embodiment may contain a reaction initiator. The reaction initiator is not particularly limited as long as it can accelerate the curing reaction of the resin composition, and examples thereof include peroxides and organic azo compounds. Examples of peroxides include α,α'-di(t-butylperoxy)diisopropylbenzene (PBP), 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, and benzoyl peroxide. Examples of organic azo compounds include azobisisobutyronitrile. Furthermore, if necessary, a metal carboxylate or the like can be used in combination. This can further accelerate the curing reaction. The reaction initiators may be used alone or in combination of two or more.

[0095] As described above, the resin composition according to this embodiment may contain a curing accelerator. The curing accelerator is not particularly limited as long as it can accelerate the curing reaction of the resin composition. Specific examples of the curing accelerator include imidazoles and their derivatives, organophosphorus compounds, amines such as secondary amines and tertiary amines, quaternary ammonium salts, organoboron compounds, and metal soaps. Examples of the imidazoles include 2-ethyl-4-methylimidazole (2E4MZ), 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, and 1-benzyl-2-methylimidazole. Examples of the organophosphorus compounds include triphenylphosphine, diphenylphosphine, phenylphosphine, tributylphosphine, and trimethylphosphine. Examples of the amines include dimethylbenzylamine, triethylenediamine, triethanolamine, and 1,8-diaza-bicyclo(5,4,0)undecene-7 (DBU). Examples of the quaternary ammonium salts include tetrabutylammonium bromide. Examples of the organoboron compounds include tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate, and tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium ethyltriphenylborate. The metal soap refers to a fatty acid metal salt, and may be either a linear fatty acid metal salt or a cyclic fatty acid metal salt. Specific examples of the metal soap include linear fatty acid metal salts and cyclic fatty acid metal salts having 6 to 10 carbon atoms. More specifically, examples of the metal soap include aliphatic metal salts composed of linear fatty acids such as stearic acid, lauric acid, ricinoleic acid, and octylic acid, or cyclic fatty acids such as naphthenic acid, and metals such as lithium, magnesium, calcium, barium, copper, and zinc. Examples of the metal soap include zinc octylate. The curing accelerators may be used alone or in combination of two or more.

[0096] [Glass Cloth] The glass cloth included in the prepreg of this embodiment contains SiO ２ 45 to 55 mass% of Al ２ O ３ 20 to 30 mass %, MgO 3.0 mass % or less, and P ２ O ５ The glass cloth contains 10 to 15 mass % of the above.

[0097] By using such glass cloth, the prepreg of this embodiment can have a low coefficient of thermal expansion and a low drill wear rate.

[0098] In the glass cloth of this embodiment, SiO ２ If the content of SiO is less than 45% by mass, it becomes difficult to obtain sufficiently low dielectric properties, and if it exceeds 55% by mass, the viscosity increases during spinning, making it difficult to form fibers. ２ The content is 47 to 53 mass %.

[0099] In the glass cloth of this embodiment, Al ２ O ３ If the content of Al is less than 20% by mass, the water resistance deteriorates, and if it exceeds 30% by mass, the spinnability deteriorates and the dielectric constant increases. ２ O ３ The content is 22 to 28 mass %.

[0100] In the glass cloth of this embodiment, if the MgO content exceeds 3 mass%, the water resistance deteriorates and it is difficult to obtain sufficiently low dielectric properties. The lower limit of the MgO content is not particularly limited, but from the viewpoint of uniformity of the glass fibers, it is preferably 0.5% or more. The MgO content relative to the total amount of the glass cloth is more preferably 0.5 to 2.8 mass%.

[0101] In the glass cloth of this embodiment, P ２ O ５ When the amount of Al is less than 10 mass %, ２ O ３ If the content of P exceeds 15% by mass, the water resistance and weather resistance may be deteriorated.２ O ５ The content is 10 to 14 mass %.

[0102] In addition to the above components, the glass cloth of the present embodiment may contain about 0.01 to 0.05 mass % of CaO. When the glass cloth contains CaO in this range, it is possible to improve the water resistance and improve the manufacturability of the glass cloth by reducing the melt viscosity of the molten glass.

[0103] The glass cloth of this embodiment is Na ２ The glass cloth may contain 0.01 to 5 mass % of O. ２ By including O, the dielectric loss tangent (Df) can be further lowered, and the melt viscosity of the molten glass can be reduced, thereby improving the productivity of the glass cloth.

[0104] Furthermore, the glass cloth of this embodiment contains Li ２ O and / or K ２ The total content of these elements relative to the total amount of the components of the glass cloth is preferably in the range of 0.03 to 0.15 mass%, more preferably in the range of 0.04 to 0.10 mass%. ２ O and / or K ２ It is believed that the inclusion of O can reduce the melt viscosity of the molten glass while maintaining a low dielectric constant, thereby improving the manufacturability of the glass cloth.

[0105] The glass cloth of this embodiment is made of Fe ２ O ３ The glass cloth may contain about 0.01 to 2 mass % of Fe. ２ O ３ By including the above, it is possible to suppress coloration of the glass cloth, while improving the degassing properties of the molten glass, thereby improving the productivity of the glass cloth.

[0106] The glass cloth of the present embodiment may contain ZnO in an amount of about 0.01 to 10 mass %. When the glass cloth contains ZnO in this range, thermal expansion can be suppressed.

[0107] The glass cloth of this embodiment is ZrO ２ The glass cloth may contain ZrO in an amount of 0.01 to 0.10 mass %. ２ By including the amount in this range, the alkali resistance of the glass cloth can be improved.

[0108] On the other hand, the glass cloth of this embodiment is B ２ O ３ , F ２ and TiO ２ Preferably, the glass cloth is substantially free of these (i.e., the content is less than 0.01% by mass), and more preferably completely free of these (i.e., the content is 0% by mass). By substantially not including these, the acid resistance of the glass cloth can be improved while maintaining a high elastic modulus of the glass cloth.

[0109] The content of each of the above components in the glass cloth of this embodiment can be measured using an X-ray fluorescence analyzer. Specifically, the content can be measured by irradiating Rh X-rays in a vacuum atmosphere with an analysis diameter of 20 mm. Alternatively, the content can be measured by ICP emission spectroscopy.

[0110] The glass cloth of the present embodiment may be a surface-treated glass cloth, and as the surface treatment agent, for example, a silane coupling agent having a functional group such as a vinyl group, a styryl group, a methacryl group, an acrylic group, or a phenylamino group can be preferably used.

[0111] The glass cloth of this embodiment is preferably a glass cloth that has been further subjected to flattening processing. Specific examples of flattening processing include a method in which the glass cloth is continuously pressed with a press roll at an appropriate pressure to compress the yarns into a flat shape. The thickness of the glass cloth of this embodiment is not particularly limited, and glass cloths of, for example, about 0.02 to 0.1 mm can be used without any particular limitations.

[0112] The proportion of the glass cloth relative to the total amount of the prepreg of this embodiment is preferably about 20 to 65 mass %. By including the glass cloth at such a content, the prepreg of this embodiment can more reliably obtain the effects described above. A more preferable proportion of the glass cloth is 25 to 60 mass %.

[0113] [Method for Producing Prepreg] Next, a method for obtaining the prepreg of this embodiment will be described. Fig. 2 is a schematic cross-sectional view showing an example of a prepreg 1 according to an embodiment of the present invention.

[0114] 2, the prepreg 1 according to this embodiment comprises the thermosetting resin composition or a semi-cured product of the thermosetting resin composition 2, and glass cloth 3. This prepreg 1 comprises the thermosetting resin composition or the semi-cured product of the thermosetting resin composition 2, and the glass cloth 3 present in the thermosetting resin composition or the semi-cured product of the thermosetting resin composition 2.

[0115] In this embodiment, the semi-cured product refers to a thermosetting resin composition that has been partially cured to the extent that it can be further cured. That is, the semi-cured product refers to a thermosetting resin composition that has been semi-cured (B-staged). For example, when a thermosetting resin composition is heated, the viscosity initially gradually decreases, then curing begins, and then curing begins and the viscosity gradually increases. In such a case, the semi-cured state can be exemplified by the state between when the viscosity begins to increase and when the composition is completely cured.

[0116] Furthermore, the prepreg obtained using the thermosetting resin composition according to this embodiment may include a semi-cured product of the thermosetting resin composition as described above, or may include the uncured thermosetting resin composition itself. That is, it may be a prepreg including a semi-cured product of the thermosetting resin composition (the thermosetting resin composition in B stage) and glass cloth, or a prepreg including the thermosetting resin composition before curing (the thermosetting resin composition in A stage) and glass cloth. The thermosetting resin composition or the semi-cured product of the thermosetting resin composition may be obtained by drying or heat-drying the thermosetting resin composition.

[0117] When producing a prepreg, the thermosetting resin composition 2 is often prepared in the form of a varnish and used to impregnate the glass cloth 3, which is the substrate for forming the prepreg. That is, the thermosetting resin composition 2 is usually a resin varnish prepared in the form of a varnish. Such a varnish-like thermosetting resin composition (resin varnish) can be obtained, for example, by the following method. The thermosetting resin composition can be obtained by mixing the maleimide compound (B) and, if necessary, other resin components (such as the benzoxazine compound (C) and the elastomer (D)), and then adding the molybdenum compound particles (A) and, if necessary, the inorganic filler (E), and mixing the mixture.

[0118] First, the components of the thermosetting resin composition that are soluble in organic solvents, i.e., the maleimide compound (B) and, if necessary, other resin components (such as the benzoxazine compound (C) and the elastomer (D)), are added to an organic solvent and dissolved. Heating may be performed as necessary. Then, the components that are insoluble in organic solvents (such as the molybdenum compound particles (A) and the inorganic filler (E) used if necessary) are added and dispersed using a disperser or the like until a predetermined dispersion state is achieved, thereby preparing a varnish-like thermosetting resin composition. The organic solvent used here is not particularly limited, as long as it dissolves the components of the thermosetting resin composition that are soluble in organic solvents and does not inhibit the curing reaction. Specific examples include toluene and methyl ethyl ketone (MEK).

[0119] The method for producing the prepreg 1 is not particularly limited, but includes, for example, a method in which a thermosetting resin composition 2 prepared in a varnish form is impregnated into a glass cloth 3, followed by drying. The thermosetting resin composition 2 is impregnated into the glass cloth 3 by immersion, coating, or the like. Impregnation can be repeated multiple times as necessary. In this case, by repeating the impregnation using multiple resin compositions with different compositions and concentrations, it is possible to adjust the final composition and impregnation amount to the desired one.

[0120] The glass cloth 3 impregnated with the thermosetting resin composition (resin varnish) 2 is heated under desired conditions, for example, at 80°C to 180°C for 1 minute to 10 minutes. The heating provides a prepreg 1 in an uncured (A-stage) or semi-cured (B-stage) state. The heating also volatilizes the organic solvent from the resin varnish, reducing or eliminating the organic solvent.

[0121] The prepreg of this embodiment has both excellent drillability (low drill wear) and a low thermal expansion coefficient. Therefore, a wiring board having an insulating layer formed using the prepreg of this embodiment has excellent drillability (low drill wear) and little warping. Therefore, the prepreg of this embodiment can be suitably used when forming insulating layers provided in metal-clad laminates and wiring boards.

[0122] <Metal-clad laminate> FIG. 3 is a schematic cross-sectional view showing an example of a metal-clad laminate 11 according to this embodiment.

[0123] As shown in FIG. 3, the metal-clad laminate 11 is composed of an insulating layer 12 containing a cured product of the prepreg 1 shown in FIG. 2 and a metal foil 13 laminated together with the insulating layer 12. That is, the metal-clad laminate 11 has an insulating layer 12 containing a cured product of a thermosetting resin composition and a metal foil 13 provided on the insulating layer 12. The insulating layer 12 may be composed of a cured product of the thermosetting resin composition or a cured product of the prepreg. The thickness of the metal foil 13 varies depending on the performance required of the final wiring board and is not particularly limited. The thickness of the metal foil 13 can be appropriately set depending on the desired purpose, and is preferably, for example, 0.2 to 70 μm. Examples of the metal foil 13 include copper foil and aluminum foil. When the metal foil is thin, it may be a carrier-attached copper foil equipped with a release layer and a carrier to improve handling.

[0124] The method for producing the metal-clad laminate 11 is not particularly limited as long as it can produce the metal-clad laminate 11. Specifically, a method for producing the metal-clad laminate 11 using a prepreg 1 can be used. Examples of such a method include stacking one or more prepregs 1, placing a metal foil 13 such as copper foil on both sides or one side of the prepreg 1, and then heat-pressing and molding the metal foil 13 and the prepreg 1 to form an integrated laminate, thereby producing a double-sided or single-sided metal foil-clad laminate 11. That is, the metal-clad laminate 11 can be obtained by laminating the metal foil 13 on the prepreg 1 and then heat-pressing and molding the laminate. The heat-pressing conditions can be appropriately set depending on the thickness of the metal-clad laminate 11 to be produced, the type of composition of the prepreg 1, and the like. For example, the temperature can be 170 to 230°C, the pressure can be 3 to 5 MPa, and the time can be 60 to 150 minutes.

[0125] <Wiring Board> FIG. 4 is a schematic cross-sectional view showing an example of a wiring board 21 according to this embodiment.

[0126] 4, wiring board 21 according to this embodiment is composed of insulating layer 12, which is formed by curing prepreg 1 shown in FIG. 2, and wiring 14, which is laminated together with insulating layer 12 and formed by partially removing metal foil 13. Insulating layer 12 is composed of the cured product of the prepreg.

[0127] The method for manufacturing the wiring board 21 is not particularly limited as long as it can manufacture the wiring board 21. Specific examples include a method of manufacturing the wiring board 21 using the prepreg 1. Examples of this method include a method of manufacturing the wiring board 21 in which wiring is provided as a circuit on the surface of the insulating layer 12 by etching the metal foil 13 on the surface of the metal-clad laminate 11 manufactured as described above. That is, the wiring board 21 is obtained by forming a circuit by partially removing the metal foil 13 on the surface of the metal-clad laminate 11. In addition to the above methods, examples of the method for forming a circuit include circuit formation by a semi-additive process (SAP) or a modified semi-additive process (MSAP).

[0128] Metal-clad laminates and wiring boards having an insulating layer containing a cured product of the prepreg of this embodiment have the same advantages as the prepreg described above, and are therefore useful in industrial applications.

[0129] As described above, this specification discloses various aspects of the technology, but the main technologies among them are summarized below.

[0130] The prepreg in a first aspect comprises a thermosetting resin composition or a semi-cured product of the thermosetting resin composition, and a glass cloth, wherein the thermosetting resin composition contains molybdenum compound particles (A) and a maleimide compound (B), and the glass cloth contains SiO ２ 45 to 55 mass% of Al ２ O ３ 20 to 30 mass %, MgO 3.0 mass % or less, P ２ O ５ Contains 10 to 15 mass % of

[0131] The prepreg of the second embodiment is the same as the prepreg of the first embodiment, except that the molybdenum compound particles (A) contain molybdenum compound particles (A-1) that have been surface-treated with a surface treatment agent.

[0132] The prepreg according to the third embodiment is the prepreg according to the first or second embodiment, wherein the molybdenum compound particles (A) have a volume-based cumulative 50% particle size (D ５０ ) is 0.1 μm or more and 2.0 μm or less.

[0133] In a fourth aspect, in the prepreg of any one of the first to third aspects, the content of the molybdenum compound particles (A) in the thermosetting resin composition is 0.1 to 40 parts by mass per 100 parts by mass of the resin component in the thermosetting resin composition.

[0134] A prepreg in a fifth aspect is the prepreg in any one of the first to fourth aspects, wherein the thermosetting resin composition further contains a benzoxazine compound (C).

[0135] The prepreg according to a sixth embodiment is the prepreg according to the fifth embodiment, wherein the benzoxazine compound (C) comprises an allyl group-containing benzoxazine compound (C-1).

[0136] In a seventh aspect, in the prepreg of the fifth or sixth aspect, the mass ratio (C / B) of the benzoxazine compound (C) to the maleimide compound (B) is 0.2 or more and 1.0 or less.

[0137] The prepreg in an eighth aspect is the prepreg in any one of the first to seventh aspects, wherein the thermosetting resin composition comprises an elastomer (D) including at least one of a high molecular weight material (D-1) having a weight average molecular weight of 10,000 or more and 900,000 or less, and a core-shell rubber (D-2).

[0138] A ninth aspect of the prepreg is the prepreg of the eighth aspect, wherein the polymer (D-1) contains at least one of an acrylic resin and a styrene-based copolymer.

[0139] In a tenth aspect, in the prepreg of the eighth or ninth aspect, the content of the elastomer (D) in the thermosetting resin composition is 5 to 40 mass% with respect to the total amount of resin components in the thermosetting resin composition.

[0140] In an eleventh aspect, in the prepreg of any one of the first to tenth aspects, the thermosetting resin composition further contains an inorganic filler (E), and the inorganic filler (E) contains at least one selected from the group consisting of silica particles, aluminum hydroxide particles, talc particles, magnesium hydroxide particles, and boehmite particles.

[0141] In a twelfth aspect, in the prepreg of any one of the first to eleventh aspects, the content of the thermosetting resin composition in the prepreg is 35 to 80 mass% with respect to the total amount of components in the prepreg.

[0142] A metal-clad laminate according to a thirteenth aspect includes an insulating layer containing a cured product of the prepreg according to any one of the first to twelfth aspects, and a metal layer.

[0143] A wiring board according to a fourteenth aspect includes an insulating layer containing a cured product of the prepreg according to any one of the first to twelfth aspects, and wiring.

[0144] The present invention will be explained in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0145] First, the components used in preparing the thermosetting resin composition in this example will be described.

[0146] [Thermosetting Resin Composition] (Molybdenum Compound Particles (A)) Molybdenum compound particles surface-treated with phenylaminosilane (manufactured by Admatechs Co., Ltd., product name "Z4SX-A1", D ５０ : 0.8 μm, D ９０ : 1.2 μm)

[0147] (Maleimide Compound (B)) 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide represented by the formula (2) (manufactured by Daiwa Chemical Industry Co., Ltd., product name "BMI-5100")

[0148] (Benzoxazine Compound (C)) Benzoxazine Compound 1: Represented by the formula (8), R ３ and R ４ is an allyl group, Y is a methylene group, and b and c are 1 (manufactured by Shikoku Chemical Industry Co., Ltd., product name "ALP-d"); Benzoxazine compound 2: Pd-type benzoxazine compound (manufactured by Shikoku Chemical Industry Co., Ltd.);

[0149] (Elastomer (D)) High molecular weight material (D-1) (acrylic elastomer): epoxy-modified acrylic resin (manufactured by Nagase ChemteX Corporation, product name "PASR-001", weight average molecular weight Mw: 500,000)

[0150] (Epoxy resin) Multifunctional epoxy resin having a biphenylene structure (manufactured by Nippon Kayaku Co., Ltd., product name "NC3500")

[0151] (Inorganic filler (E)) Silica particles (manufactured by Admatechs Co., Ltd., product name "SC2050-MTX")

[0152] (Reaction initiator) Organic peroxide: PBP (1,3-bis(butylperoxyisopropyl)benzene; "Perbutyl P" manufactured by NOF Corporation)

[0153] (Curing accelerator) 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Corporation, product name "2E4MZ")

[0154] [Glass Cloth] (Glass Cloths 1 to 3) Three types of glass cloths 1 to 3 (thickness: 0.1 mm) having the compositions shown below were prepared. Glass cloth 1 corresponds to conventional T-glass, and glass cloth 2 corresponds to conventional S-glass. Glass cloth 1: T-glass manufactured by Nitto Boseki Co., Ltd., Cross Style 2118 (SiO ２ :66% by mass, Al ２ O ３ : 25 mass%, MgO: 7.3 mass%, and P ２ O ５ : 0 mass%) Glass cloth 2: S3 glass, Cross Style 2118 (SiO ２ :66% by mass, Al ２ O ３ : 25 mass%, MgO: 6.1 mass%, and P ２ O ５ : 0.003% by mass) Glass cloth 3: V-glass, Cross Style 2118 (SiO ２ :50% by mass, Al ２ O ３ : 25% by mass, MgO: 2.3% by mass, and P ２ O ５ :12% by mass)

[0155] [Examples 1 to 7 and Comparative Examples 1 to 3] (Preparation of Evaluation Samples) First, a resin varnish was prepared. Components other than the molybdenum compound particles and inorganic filler were added to methyl ethyl ketone (MEK) and mixed to a solids concentration of 40 to 50 mass% in the composition (parts by mass) shown in Table 1. The resulting mixture was stirred for 60 minutes. Thereafter, the molybdenum compound particles and inorganic filler were added to the resulting mixture in the composition (parts by mass) shown in Table 1, and the mixture was dispersed using a bead mill. This resulted in a varnish-like resin composition (varnish).

[0156] Next, the glass cloths shown in Table 1 were impregnated with the varnishes obtained above. Specifically, Glass Cloth 3 was used in Examples 1 to 7 and Comparative Example 3, Glass Cloth 2 in Comparative Example 1, and Glass Cloth 1 in Comparative Example 2. Prepregs were then produced by heating and drying at 130°C for 3 minutes. The content of the components that constitute the resin by the curing reaction relative to the prepreg (resin content) was adjusted to approximately 45% by mass. In other words, the content of the glass cloth relative to the total amount of prepreg was adjusted to 55% by mass. Furthermore, the thickness after curing was adjusted to 103 μm.

[0157] Next, the obtained prepreg was used to obtain an evaluation sample (metal-clad laminate). First, 10 sheets of the obtained prepreg were stacked, and 12 μm thick copper foil (3EC-VLP manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed on both sides. This was used as a pressure body, and heated to a temperature of 220 ° C. at a temperature increase rate of 3 ° C. / min, and heated and pressed at 220 ° C. for 120 minutes under a pressure of 3 MPa to obtain an evaluation substrate (metal-clad laminate) with copper foil bonded to both sides and a resin layer (insulating layer) thickness of approximately 1030 μm.

[0158] Using each prepreg and evaluation board prepared as described above, evaluation tests were carried out by the following methods.

[0159] [Evaluation Test] (Coefficient of Thermal Expansion: CTE (50 to 260°C)) In the evaluation test of the coefficient of thermal expansion, an unclad board (cured prepreg, thickness approximately 1030 µm) obtained by removing the copper foil from a copper-clad laminate of 10 prepregs by etching was used as an evaluation sample.

[0160] The evaluation sample was used as a test piece (size: 10.0 mm x 3.5 mm), and the thermal expansion coefficient in the plane direction (Y direction) of the evaluation substrate at a temperature below the glass transition temperature of the cured resin composition was measured by the TMA method (thermo-mechanical analysis). Specifically, the measurement was performed using a TMA device ("TMA / SS7100" manufactured by SII NanoTechnology Inc.) in compression mode. To eliminate the influence of thermal distortion of the test piece, the test piece was heated from 30°C to 320°C at a heating rate of 10°C / min with a load of 10 g applied in the Y direction, and then cooled to room temperature. Thereafter, the test piece was heated from 30°C to 320°C at a heating rate of 10°C / min with a load of 10 g applied in the Y direction. A temperature displacement chart was obtained during this temperature increase. The average thermal expansion coefficient from 50 to 260°C was calculated from the temperature displacement chart obtained at this time. The lower the mean coefficient of thermal expansion (CTE), the better the result. In this test, a mean coefficient of thermal expansion (CTE) of 6.5 ppm / ° C. or less was judged to be "passed."

[0161] (Drill Wear Rate) As shown in FIG. 1 , two evaluation substrates (metal-clad laminates) 11 were stacked, and an entry board 16 was placed on top of them. The evaluation substrate (metal-clad laminate) 11 with the entry board 16 placed thereon was drilled using a drill 15 under the following processing conditions, with 10,000 holes drilled from the entry board 16 to the evaluation substrate (metal-clad laminate) 11. The size (area) of the drill bit after this drilling was measured. The wear rate of the drill bit was calculated from the measured size (area) of the drill bit after drilling and the size (area) of the drill bit before drilling. In this test, a drill wear rate of 30% or less was judged to be "passed."

[0162] Entry board: LE-G0612 0.18 mm Number of layers: 1.0 mm x 2 layers Hole: Diameter 0.15 mm x Depth 2.5 mm Bit part number: NEU-L088BW Rotation speed: 200K rpm Feed speed: 12 μm / rev

[0163] The results of the above evaluations are shown in Table 1.

[0164]

[0165] [Discussion] As can be seen from Table 1, it was confirmed that the prepregs of Examples 1 to 7, which used the resin composition of this embodiment and glass cloth, had low coefficients of thermal expansion and drill wear rates. Furthermore, Examples 1 to 6, which used an allyl group-containing benzoxazine compound as the benzoxazine compound (C), had even lower coefficients of thermal expansion than Example 7, which did not use an allyl group-containing benzoxazine compound.

[0166] On the other hand, the prepregs of Comparative Examples 1 and 2, which did not use the glass cloth of the present embodiment, were inferior to the Examples in either the coefficient of thermal expansion or the drill wear rate. Furthermore, the prepreg of Comparative Example 3, which did not contain molybdenum compound particles, broke during the measurement of the drill wear rate.

[0167] This application is based on Japanese Patent Application No. 2024-056462 filed on March 29, 2024, the contents of which are incorporated herein by reference.

[0168] In order to express the present invention, the present invention has been properly and sufficiently described above through the embodiments with reference to the drawings, but it should be recognized that those skilled in the art can easily change and / or improve the above-mentioned embodiments. Therefore, unless the changes or improvements made by those skilled in the art are at a level that causes departure from the scope of the claims described in the claims, such changes or improvements are interpreted as being included in the scope of the claims.

[0169] According to the present invention, it is possible to provide a prepreg having excellent drill processability (low drill wear rate) and a low coefficient of thermal expansion, as well as a metal-clad laminate and a wiring board using the same.

Claims

1. A thermosetting resin composition or a semi-cured product of the thermosetting resin composition, and glass cloth, wherein the thermosetting resin composition contains molybdenum compound particles (A) and a maleimide compound (B), and the glass cloth contains SiO ２ 45 to 55 mass% of Al ２ O ３ 20 to 30 mass %, MgO 3.0 mass % or less, P ２ O ５ A prepreg comprising 10 to 15 mass% of the above.

2. The prepreg according to claim 1, wherein the molybdenum compound particles (A) include molybdenum compound particles (A-1) that have been surface-treated with a surface treatment agent.

3. The cumulative 50% particle size (D) on a volume basis in the particle size distribution of the molybdenum compound particles (A) ５０ 2. The prepreg according to claim 1, wherein the thickness of the prepreg is 0.1 μm or more and 2.0 μm or less.

4. The prepreg according to claim 1, wherein the content of the molybdenum compound particles (A) in the thermosetting resin composition is 0.1 to 40 parts by mass per 100 parts by mass of the resin component in the thermosetting resin composition.

5. The prepreg according to claim 1, wherein the thermosetting resin composition further contains a benzoxazine compound (C).

6. The prepreg according to claim 5, wherein the benzoxazine compound (C) includes an allyl group-containing benzoxazine compound (C-1).

7. The prepreg according to claim 5, wherein the mass ratio (C / B) of the benzoxazine compound (C) to the maleimide compound (B) is 0.2 or more and 1.0 or less.

8. The prepreg according to claim 1, wherein the thermosetting resin composition comprises an elastomer (D) containing at least one of a high molecular weight material (D-1) having a weight average molecular weight of 10,000 or more and 900,000 or less, and a core-shell rubber (D-2).

9. The prepreg according to claim 8, wherein the polymer (D-1) contains at least one of an acrylic resin and a styrene copolymer.

10. The prepreg according to claim 8, wherein the content of the elastomer (D) in the thermosetting resin composition is 5 to 40 mass % based on the total amount of resin components in the thermosetting resin composition.

11. The prepreg according to claim 1, wherein the thermosetting resin composition further contains an inorganic filler (E), and the inorganic filler (E) contains at least one selected from the group consisting of silica particles, aluminum hydroxide particles, talc particles, magnesium hydroxide particles, and boehmite particles.

12. The prepreg according to claim 1, wherein the content of the thermosetting resin composition in the prepreg is 35 to 80 mass % based on the total amount of components in the prepreg.

13. A metal-clad laminate comprising an insulating layer containing a cured product of the prepreg according to any one of claims 1 to 12, and a metal layer.

14. A wiring board comprising an insulating layer containing a cured product of the prepreg according to any one of claims 1 to 12 and wiring.

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