Resin composition, prepreg, metal substrate with resin, and wiring board

Abstract

The resin composition according to the present disclosure contains a resin and hollow silica particles, the 20% breaking pressure of the hollow silica particles as measured by mercury intrusion is 120 MPa or more, or the charge amount of the hollow silica particles is 0.005-0.080 [mu] C / g.

Description

Technical Field

[0001] The present invention relates to a resin composition, a prepreg, a metal substrate with a resin, and a wiring board. Background Art

[0002] For the insulating layer provided in a printed wiring board, properties such as a low dielectric constant, a low dielectric loss tangent, and a low coefficient of linear expansion are required. In recent years, a resin composition containing a thermosetting resin and silica particles has been used to manufacture an insulating layer provided in a metal-clad laminate that can be processed into a printed wiring board (see Patent Documents 1 and 2). Specifically, a metal-clad laminate having a semi-cured product of the above resin composition laminated on the surface layer of a metal substrate layer is used as the insulating layer. As another example, a metal-clad laminate in which a glass cloth or the like impregnated with a resin composition is laminated on the surface of a metal substrate layer as an insulating layer is used. Here, a filler (filling material) is used as a material for a prepreg using a thermosetting resin, but the filler itself generally has a tendency to increase the relative dielectric constant of the obtained prepreg. Among them, since a metal-clad laminate using a hollow filler can reduce the relative dielectric constant as compared with the case of using a solid filler, studies have been made as described in Patent Documents 3 to 5.

[0003] Hitherto, glass spheres or the like have been used as the hollow filler. However, depending on the type of glass spheres, breakage sometimes occurs when producing a prepreg or a cured product using a resin composition, and the reduction in the relative dielectric constant is insufficient.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2013-212956

[0007] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2015-36357

[0008] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2008-31409

[0009] Patent Document 4: Japanese Patent Application Laid-Open No. 2017-522580

[0010] Patent Document 5: International Publication No. 2019-230661 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] For prepregs, cured products, etc. made of a conventionally known resin composition containing hollow particles and a resin, excellent flexural strength is required. In addition, from the viewpoints of productivity and the like, it is desired that the above resin composition has little adhesion to the apparatus during manufacturing or the like.

[0013] One problem to be solved by an embodiment of the present disclosure is to provide a resin composition capable of producing a prepreg and a cured product with a low relative dielectric constant. Another problem to be solved by other embodiments of the present disclosure is to provide a prepreg, a metal substrate with a resin, and a wiring board using the above resin composition.

[0014] One problem to be solved by an embodiment of the present disclosure is to provide a resin composition capable of producing a prepreg and a cured product with excellent flexural strength and less adhesion to a device. Another problem to be solved by other embodiments of the present disclosure is to provide a prepreg, a metal substrate with a resin, and a wiring board using the above resin composition.

[0015] Solutions to the problems

[0016] The solutions to the above problems include the following methods.

[0017] <1> A resin composition comprising a resin and hollow silica particles, wherein the 20% destruction pressure of the hollow silica particles measured by mercury intrusion porosimetry is 120 MPa or more.

[0018] <2> A resin composition comprising a resin and hollow silica particles, wherein the charge amount of the hollow silica particles is 0.005 to 0.080 μC / g.

[0019] <3> The resin composition according to the above <1> or <2>, wherein the hollow silica particles contain at least one selected from alkali metals and alkaline earth metals, and the sum of the content ratios of the alkali metals and the alkaline earth metals is 30 mass ppm to 1 mass% relative to the total mass of the shell layer of the hollow silica particles.

[0020] <4> The resin composition according to any one of the above <1> to <3>, wherein the density of the hollow silica particles is 0.35 to 2.00 g / cm 3 .

[0021] <5> The resin composition according to any one of the above <1> to <4>, wherein the BET specific surface area of the hollow silica particles is 1.0 to 100.0 m 2 / g.

[0022] <6> The resin composition according to any one of the above <1> to <5>, wherein the median particle size (d50) of the hollow silica particles is 0.1 to 10.0 μm.

[0023] <7>The resin composition according to any one of <1> to <6> above, wherein the hollow silica particles have a silica-containing shell layer, and when the diameter of the primary particles of the hollow silica particles is set to 1, the thickness of the shell layer is 0.01 to 0.3.

[0024] <8>The resin composition according to any one of <1> to <7> above, wherein the resin contains at least one selected from the group consisting of an epoxy resin, a polyimide resin, a polyphenylene ether resin, a resin containing a divinylbenzene skeleton, and a resin containing a pyrimidine skeleton.

[0025] <9>The resin composition according to any one of <1> to <8> above, wherein the content of the hollow silica particles is 10 to 70% by volume based on the total volume of the resin composition.

[0026] <10>A prepreg comprising the resin composition according to any one of <1> to <9> above or a semi-cured product thereof, and a fibrous substrate.

[0027] <11>The prepreg according to <8> above, wherein the fibrous substrate contains a glass component.

[0028] <12>A resin-coated metal substrate comprising the resin composition according to any one of <1> to <9> above or a semi-cured product thereof, or comprising the prepreg according to <10> or <11> above, and a metal substrate layer.

[0029] <13>The resin-coated metal substrate according to <12> above, wherein the metal substrate layer is a copper foil.

[0030] <14>A wiring board comprising a cured product of the resin composition according to any one of <1> to <9> above and metal wirings.

[0031] Effects of the Invention

[0032] According to one embodiment of the present disclosure, a resin composition capable of producing a prepreg and a cured product having a low relative dielectric constant can be provided. Further, according to other embodiments of the present disclosure, a prepreg, a resin-coated metal substrate, and a wiring board using the above resin composition can be provided.

[0033] According to one embodiment of the present disclosure, a resin composition capable of producing a prepreg and a cured product having excellent flexural strength and less adhesion to a device can be provided. Further, according to other embodiments of the present disclosure, a prepreg, a resin-coated metal substrate, and a wiring board using the above resin composition can be provided. Detailed Description

[0034] Hereinafter, embodiments for implementing the present disclosure will be described in detail. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, unless otherwise specifically stated, its constituent elements (including element steps, etc.) are not essential. The same applies to numerical values and their ranges, which do not limit the embodiments of the present disclosure.

[0035] In the present disclosure, in the numerical range represented by "~", the numerical values described before and after "~" are respectively included as the minimum value and the maximum value. In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may also be replaced with the upper limit value or the lower limit value of other stepwise described numerical ranges.

[0036] In the present disclosure, each component may contain a variety of corresponding substances. When there are a variety of substances corresponding to each component in the composition, unless otherwise specifically stated, the content rate or content of each component refers to the total content rate or content of the variety of substances present in the composition.

[0037] In the present disclosure, there may be a variety of particles corresponding to each component. When there are a variety of particles corresponding to each component in the composition, unless otherwise specifically stated, the particle size of each component refers to the value of the mixture of the variety of particles present in the composition.

[0038] In the present disclosure, the term "laminated" means that layers are overlapped, and two or more layers may be combined or two or more layers may be detachable.

[0039] In the present invention, unless otherwise specified, "hollow silica particles" refers to a group of a plurality of hollow silica particles.

[0040] In the present disclosure, the "BET specific surface area" is obtained by the BET method based on the nitrogen adsorption method using a specific surface area / pore size distribution measuring device (for example, "TriStarII" manufactured by Micromeritics).

[0041] In the present disclosure, the "sphericity" is represented by the following average value: For any 100 particles in the photo projection diagram obtained by photographing with a scanning electron microscope (SEM), the maximum diameter (DL) and the minor axis (DS) orthogonal thereto are measured for each, and the average value obtained by calculating the ratio (DS / DL) of the minor axis (DS) to the maximum diameter (DL) is calculated.

[0042] In the present disclosure, the "dielectric loss tangent" and the "relative dielectric constant" are measured by the perturbation mode resonator method using a dedicated device (for example, "Vector Network Analyzer E5063A" manufactured by KEYCOM Co., Ltd.).

[0043] In the present invention, the "semi-cured product" refers to a cured product in a state where a heat generation peak accompanying the curing of a thermosetting resin appears when performing differential scanning calorimetry on the cured product of the resin composition. That is, the semi-cured product refers to a cured product in a state where uncured thermosetting resin remains.

[0044] In the present invention, the "cured product" refers to a cured product in a state where a heat generation peak accompanying the curing of a thermosetting resin does not appear when performing differential scanning calorimetry on the cured product of the resin composition. That is, the cured product refers to a cured product in a state where no uncured thermosetting resin remains.

[0045] In the present disclosure, the "maximum height roughness Rz" is measured in accordance with JIS B 0601 (2013) (corresponding to ISO: ISO 4287 1997).

[0046] In the present invention, the "weight-average molecular weight" is determined by polystyrene conversion using gel permeation chromatography (GPC).

[0047] In the present disclosure, the "20% fracture pressure" refers to the fracture pressure measured by mercury intrusion porosimetry, and when applying a pressure of 0 to 400 MPa by mercury intrusion porosimetry, it represents the minimum pressure at which the volume has decreased by 20% from the maximum value of the cumulative volume.

[0048] The 20% fracture pressure of the hollow silica particles based on mercury intrusion porosimetry is measured in accordance with ASTM D 3102-78 using a mercury intrusion porosimeter (for example, AutoPore IV 9500 manufactured by MICROMERITICS INSTRUMENT Corporation).

[0049] The resin composition according to the first embodiment of the present disclosure (hereinafter also referred to as "this composition 1") contains a resin and hollow silica particles, and the 20% fracture pressure of the hollow silica particles measured by mercury intrusion porosimetry is 120 MPa or more.

[0050] According to this composition 1, a prepreg and a cured product with a low relative dielectric constant can be produced. The reason is not necessarily clear, but it is speculated as follows.

[0051] The 20% fracture pressure of the hollow silica particles contained in this composition 1 measured by mercury intrusion porosimetry is 120 MPa or more. Thus, it is possible to suppress the breakage of the hollow silica particles when producing a prepreg or the like, and as a result, it is speculated that the above effects can be exhibited.

[0052] The resin composition according to the second embodiment of the present disclosure (hereinafter also referred to as "this composition 2") contains a resin and hollow silica particles, and the charge amount of the hollow silica particles is 0.005 to 0.080 μC / g.

[0053] The composition 2 can produce prepregs and cured products with excellent flexural strength and has less adhesion to the equipment. The reason is not necessarily clear, but the speculation is as follows.

[0054] The charge amount of the hollow silica particles contained in the composition 2 is 0.005 to 0.080 μC / g. It is speculated that by making the charge amount of the hollow silica particles 0.005 μC / g or more, the electrostatic interaction with the resin contained in the composition 2 can be increased, and prepregs and cured products with excellent flexural strength can be produced. In addition, it is speculated that by making the charge amount of the hollow silica particles 0.080 μC / g or less, the adhesion of the composition 2 to the equipment during manufacturing and the like can be suppressed.

[0055] Hereinafter, the composition 1 and the composition 2 may be collectively referred to as the "composition".

[0056] In the composition 1, from the viewpoint of further reducing the relative dielectric constant, or in the composition 2, from the viewpoints of reducing the relative dielectric constant and improving the adhesion to the substrate, the viscosity of the composition is preferably 100 to 10,000 mPa·s, more preferably 130 to 5,000 mPa·s, still more preferably 150 to 3,000 mPa·s, particularly preferably 180 to 1,500 mPa·s, and most preferably 200 to 1,000 mPa·s.

[0057] In the present disclosure, the "viscosity" is a value obtained by measuring the viscosity at the 30-second time point, which is measured for 30 seconds at a shear rate of 1 rpm using a rotational rheometer (for example, manufactured by Anton paar, modular rheometer Physica MCR-301) at 25°C.

[0058] The composition is preferably liquid at 25°C.

[0059] The composition may contain one resin or may contain two or more resins. As the resin contained in the composition, a thermosetting resin is preferred. The composition may contain two or more thermosetting resins, but preferably contains one.

[0060] Examples of the thermosetting resin include epoxy resins, polyphenylene ether resins, polyester resins, polyimide resins, phenolic resins, resins containing a divinylbenzene skeleton, resins containing a pyrimidine skeleton, and the like. From the viewpoints of adhesion, heat resistance, etc., the thermosetting resin is preferably at least one selected from the group consisting of epoxy resins, polyimide resins, polyphenylene ether resins, resins containing a divinylbenzene skeleton, and resins containing a pyrimidine skeleton.

[0061] Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, diglycidyl ether compounds of polyfunctional phenols, diglycidyl ether compounds of polyfunctional alcohols, and the like.

[0062] Examples of the polyimide resin include aromatic polyimide, aromatic polyamic acid, and the like.

[0063] The polyphenylene ether resin may be a modified polyphenylene ether or an unmodified polyphenylene ether. From the viewpoint of adhesion, a modified polyphenylene ether is preferred. The modified polyphenylene ether has a polyphenylene ether chain and a substituent bonded to the end of the polyphenylene ether chain. The substituent preferably has a carbon-carbon double bond. The substituent is preferably represented by the following formula (1) or the following formula (2), and more preferably represented by the following formula (2).

[0064]

[0065] In formula (1), n is an integer from 0 to 10, Z is an arylene group, and R 1 ~R 3 are each independently hydrogen or an alkyl group. It should be noted that when n in formula (1) is 0, Z is directly bonded to the end of the polyphenylene ether chain in the modified polyphenylene ether. In formula (2), R 4 is hydrogen or an alkyl group. In formulas (1) and (2), the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

[0066] The polyphenylene ether chain is preferably represented by the following formula (3).

[0067]

[0068] In formula (3), m is a number in the range of 1 to 50, and R 5 ~R 8 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group, preferably a hydrogen atom or an alkyl group. In formula (3), the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

[0069] Examples of the resin containing a divinylbenzene skeleton include ODV-XET manufactured by NIPPON STEEL Chemical&Material Co., Ltd.

[0070] Examples of the resin containing a pyrimidine skeleton include the ELPAC HC-F series manufactured by JSR Corporation.

[0071] From the viewpoint of improving the adhesion and dielectric properties of the prepreg and the cured product, the weight average molecular weight (Mw) of the thermosetting resin is preferably 1,000 to 7,000, more preferably 1,000 to 5,000, and further preferably 1,000 to 3,000.

[0072] It should be noted that in the present invention, improving the dielectric properties of the prepreg and the cured product means reducing their relative dielectric constant and dielectric loss tangent.

[0073] From the viewpoint of improving the adhesion and dielectric properties of the prepreg and the cured product, the content rate of the curable resin relative to the total mass of the present composition is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and further preferably 20 to 30% by mass.

[0074] The present composition may contain resins other than the thermosetting resin (hereinafter also referred to as "other resins"). Examples of other resins include polytetrafluoroethylene, polyethylene terephthalate, polyolefin, silicone, etc.

[0075] The content rate of other resins relative to the total mass of the present composition is not particularly limited, and is, for example, 1 to 50% by mass.

[0076] From the viewpoint of producing a prepreg and a cured product with a small deviation in relative dielectric constant, the density of the resin determined by the constant-volume expansion method using argon and a dry pycnometer is preferably 0.5 to 3.0 g / cm 3 , more preferably 0.8 to 2.3 g / cm 3 .

[0077] It should be noted that the density of the resin is measured for the dried resin at 25°C. In the case of a thermosetting resin, it is measured for the cured resin. As a method for measuring the density, there is a method of measuring the cured resin with a dry pycnometer as described above.

[0078] It should be noted that when the present composition contains two or more resins, the density of the resin is determined by actually measuring the density of the dried composition or, in the case of a thermosetting resin, the thermally cured composition using an Ar pycnometer.

[0079] The hollow silica particles have a shell layer containing silica and a space portion inside the shell layer. The above space portion can be confirmed by observation with a transmission electron microscope (TEM), a scanning electron microscope (SEM), etc.

[0080] In the present disclosure, "having a space portion inside the shell layer" means that when observing the cross section of one hollow silica particle, there is a hollow state in which the shell layer surrounds the periphery of one space portion.

[0081] The shell layer can have a single-layer structure or a multi-layer structure with two or more layers.

[0082] The content rate of silica relative to the total mass of the shell layer is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 95% by mass or more. The upper limit of the above content rate is 100% by mass, preferably 99.99% by mass.

[0083] From the viewpoints of improving the durability of the hollow silica particles and improving the adhesion and dielectric properties of the semi-cured product and the cured product, the shell layer preferably contains at least one selected from the alkaline metal components belonging to Group 1 or Group 2 of the periodic table and their silicates.

[0084] The content rate of the alkaline metal component belonging to Group 1 or Group 2 of the periodic table relative to the total mass of the shell layer is preferably 30 mass ppm or more, more preferably 100 mass ppm or more, further preferably 150 mass ppm or more, and particularly preferably 300 mass ppm or more. In addition, it is preferably 1% by mass or less, more preferably 5000 mass ppm or less, and most preferably 1000 mass ppm or less.

[0085] That is, relative to the total mass of the shell layer, the content rate of the alkaline metal component belonging to Group 1 or Group 2 of the periodic table is preferably 30 mass ppm to 1% by mass, more preferably 100 mass ppm to 5000 mass ppm, and further preferably 150 mass ppm to 1000 mass ppm.

[0086] The composition of the shell layer is measured by ICP emission spectrometry, flame atomic absorption spectrometry, etc.

[0087] Among the alkaline metal components (alkali metals and alkaline earth metals) belonging to Group 1 or Group 2 of the periodic table, from the viewpoint of ease of acquisition, the shell layer preferably contains one or more selected from sodium, potassium, magnesium, calcium, and strontium, and more preferably contains one or more selected from sodium, magnesium, and calcium.

[0088] From the viewpoints of improving the durability of the hollow silica particles and improving the adhesion and dielectric properties of the semi-cured product and the cured product, when the diameter of the primary particles of the hollow silica particles is set to 1, the average thickness of the shell layer is preferably 0.01 to 0.3, more preferably 0.02 to 0.2, and further preferably 0.03 to 0.1.

[0089] The average thickness of the shell layer is the average value of the thicknesses of the shell layers of 20 hollow silica particles measured by TEM observation.

[0090] In this Composition 1, from the viewpoint of improving the dielectric properties of the semi-cured product and the cured product, the 20% breakdown pressure of the hollow silica particles based on the mercury intrusion method is preferably 150 MPa or more, more preferably 200 MPa or more, and further preferably 250 MPa or more. The upper limit of the 20% breakdown pressure is not particularly limited, and can be set to 600 MPa or less, for example.

[0091] In this Composition 2, from the viewpoint of improving the dielectric properties of the semi-cured product and the cured product, the 20% breakdown pressure of the hollow silica particles based on the mercury intrusion method is preferably 120 MPa or more, more preferably 150 MPa or more, further preferably 200 MPa or more, and particularly preferably 250 MPa or more. The upper limit of the 20% breakdown pressure is not particularly limited, and can be set to 600 MPa or less, for example.

[0092] From the viewpoints of producing a prepreg and a cured product with a small deviation in relative permittivity and improving the dielectric properties of the semi-cured product and the cured product, the average primary particle size of the hollow silica particles is preferably 10 nm to 10 μm, more preferably 20 nm to 7 μm, further preferably 50 nm to 5 μm, particularly preferably 70 nm to 3 μm, and most preferably 100 nm to 1 μm.

[0093] The size of the average primary particle of the hollow silica particles is determined by directly observing its particle size (diameter, or the average of the long side and the short side in the case of non-spherical particles) using SEM observation. Specifically, the size of the primary particles of 100 hollow silica particles is measured from the SEM image, and the value at which the cumulative distribution of the average primary particle size obtained by averaging them reaches 50% is presumed to be the average primary particle size of the whole primary particles.

[0094] From the viewpoints of producing a prepreg and a cured product with a small deviation in relative permittivity and improving the dielectric properties of the semi-cured product and the cured product, the median particle size (hereinafter also simply referred to as "d50") of the hollow silica particles is preferably 0.1 to 10.0 μm, more preferably 0.2 to 10.0 μm, further preferably 0.25 to 8.0 μm, particularly preferably 0.3 to 7.0 μm, most preferably 0.3 to 5.0 μm, and may also be 0.3 to 3.0 μm. In addition, by making the d50 of the hollow silica particles within the above numerical range, the smoothness of the prepreg and the cured product can be improved, and the transmission loss in the circuit when forming the insulating layer can be reduced.

[0095] In the present disclosure, "d50" is the volume-based cumulative 50% diameter of the hollow silica particles determined by a particle size distribution measuring device using laser diffraction (e.g., "MT3300EXII" manufactured by Microtrac BEL Corporation). That is, d50 is obtained by measuring the particle size distribution by the laser diffraction / scattering method, setting the total volume of the hollow silica particles to 100% to obtain a cumulative curve, and the particle diameter at the point where the cumulative volume becomes 50% on this cumulative curve.

[0096] It should be noted that in the present disclosure, the d50 of the hollow silica particles is measured in a state including primary particles and secondary particles.

[0097] From the viewpoints of producing prepregs and cured products with small deviations in relative permittivity and improving the dielectric properties of semi-cured products and cured products, the d10 of the hollow silica particles is preferably 0.1 to 2.0 μm, more preferably 0.2 to 2.0 μm, still more preferably 0.3 to 1.8 μm, particularly preferably 0.3 to 1.5 μm. In addition, by making the d10 of the hollow silica particles within the above numerical range, the smoothness of the prepregs and cured products can be improved, and the transmission loss in the circuit when forming an insulating layer can be reduced.

[0098] In the present disclosure, "d10" is the volume-based cumulative 10% diameter of the hollow silica particles determined by a particle size distribution measuring device using laser diffraction (e.g., "MT3300EXII" manufactured by Microtrac BEL Corporation). That is, d10 is obtained by measuring the particle size distribution by the laser diffraction / scattering method, setting the total volume of the hollow silica particles to 100% to obtain a cumulative curve, and the particle diameter at the point where the cumulative volume becomes 10% on this cumulative curve.

[0099] In addition, in the present invention, the d10 of the hollow silica particles is measured in a state including primary particles and secondary particles.

[0100] From the viewpoints of producing prepregs and cured products with small deviations in relative permittivity and improving the dielectric properties of semi-cured products and cured products, the d90 of the hollow silica particles is preferably 0.7 to 15.0 μm, more preferably 0.8 to 12.0 μm, still more preferably 0.9 to 10.0 μm, particularly preferably 0.9 to 8.0 μm, most preferably 0.9 to 6.0 μm, and may be 0.9 to 5.0 μm. In addition, by making the d90 of the hollow silica particles within the above numerical range, the smoothness of the prepregs and cured products can be improved, and the transmission loss in the circuit when forming an insulating layer can be reduced.

[0101] In addition, in the present invention, the d90 of the hollow silica particles is measured in a state including primary particles and secondary particles.

[0102] In the present invention, "d90" is the volume-based cumulative 90% diameter of the hollow silica particles determined by a laser diffraction type particle size distribution measuring device (for example, "MT3300EXII" manufactured by Microtrac BEL Co., Ltd.). That is, d90 is obtained by measuring the particle size distribution by the laser diffraction / scattering method, setting the total volume of the hollow silica particles to 100%, obtaining a cumulative curve, and the particle diameter at the point where the cumulative volume becomes 90% on this cumulative curve.

[0103] From the viewpoints of producing a prepreg and a cured product with a small deviation in relative permittivity and improving the dielectric properties of the semi-cured product and the cured product, d50 / d10 is preferably 6.0 or less, more preferably 5.0 or less, still more preferably 3.0 or less, and particularly preferably 2.5 or less. The lower limit value of d50 / d10 is not particularly limited and can be set to 1.3.

[0104] From the viewpoint of improving the smoothness of the semi-cured product and the cured product, the content of particles having an average particle diameter of 10 μm or more measured by the Coulter counter method in the hollow silica particles relative to the total mass of the present composition is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, still more preferably 100 mass ppm or less, and may be 0 mass ppm.

[0105] From the viewpoints of producing a prepreg and a cured product with a small deviation in relative permittivity and improving the dielectric properties of the semi-cured product and the cured product, the density of the hollow silica particles obtained by the constant volume expansion method using argon and a dry pycnometer is preferably 0.35 to 2.00 g / cm 3 , more preferably 0.35 to 1.50 g / cm 3 , still more preferably 0.40 to 1.00 g / cm 3 .

[0106] In addition, when the present composition contains two or more types of hollow silica particles, the density of the hollow silica particles is obtained by weighted averaging the densities of the respective hollow silica particles.

[0107] As the dry pycnometer, AccuPycII 1340 manufactured by Micromeritics or a device equivalent thereto can be used.

[0108] From the viewpoint of reducing the deviation in relative permittivity of the prepreg, the cured product, etc., the present composition contains a resin and hollow silica particles, and the densities of the hollow silica particles and the resin obtained by the constant volume expansion method using argon and a dry pycnometer are set to A (g / cm 3 ) and B (g / cm 3) When it is (a certain value), A / B is preferably 0.3 to 1.5, more preferably 0.4 to 1.0.

[0109] From the viewpoint of improving the dielectric properties of the prepreg and the cured product, the BET specific surface area of the hollow silica particles is preferably 1.0 to 100.0 m 2 / g, more preferably 1.0 to 50.0 m 2 / g, still more preferably 1.0 to 30.0 m 2 / g.

[0110] From the viewpoints of improving the adhesion strength of the prepreg and the cured product and reducing the relative dielectric constant, the product of the density of the hollow silica particles obtained by the constant-volume expansion method using argon and a dry pycnometer and the BET specific surface area of the hollow silica particles is preferably 1.0 to 120.0 m 2 / cm 3 , more preferably 2.0 to 80.0 m 2 / cm 3 , still more preferably 2.5 to 40.0 m 2 / cm 3 ,especially preferably 3.0 to 20.0 m 2 / cm 3 .

[0111] From the viewpoints of producing a prepreg and a cured product with a small deviation in relative dielectric constant and improving the dielectric properties of the prepreg and the cured product, the porosity of the hollow silica particles is preferably 30 to 90%, more preferably 40 to 90%, still more preferably 50 to 85%.

[0112] In the present invention, the porosity of the hollow silica particles is calculated by dividing the density of the hollow silica particles by the true density of the hollow silica particles and multiplying by 100 times. It should be noted that the true density of the hollow silica particles is measured using He gas with an AccuPycII 1340 manufactured by Micromeritics or an equivalent device.

[0113] The shape of each hollow silica particle contained in the hollow silica particles is not particularly limited, and it may be spherical or non-spherical. From the viewpoint of low dielectric loss tangent, spherical shape is preferred. From the viewpoint of low dielectric loss tangent, the sphericity of the spherical hollow silica particles is preferably 0.75 or more, more preferably 0.90 or more, still more preferably 0.93 or more, and especially preferably 1.00. In addition, from the viewpoint of low dielectric loss tangent, the hollow silica particles are preferably non-porous particles.

[0114] From the viewpoint of reducing transmission loss in a circuit when forming an insulating layer, the dielectric loss tangent of the hollow silica particles is preferably 0.0020 or less, more preferably 0.0015 or less, and further preferably 0.0012 or less at a frequency of 1 GHz.

[0115] From the viewpoints of producing a prepreg and a cured product with a small deviation in relative permittivity and improving the dielectric properties of a semi-cured product and a cured product, the oil absorption of the hollow silica particles is preferably 20 to 500 mL / 100 g, more preferably 25 to 200 mL / 100 g, further preferably 30 to 150 mL / 100 g, particularly preferably 30 to 100 mL / 100 g, and most preferably 30 to 80 mL / 100 g.

[0116] In the present invention, the "oil absorption" is measured in accordance with JIS K 5101-13-1 (2004) (corresponding to ISO: ISO 787-5 1980). It should be noted that the oil absorption in the present disclosure is a value obtained by multiplying the value measured in accordance with JIS K 5101-13-1 (2004) by the value of density / true density (i.e., the oil absorption measured in accordance with JIS K 5101-13-1 (2004) × (density / true density)).

[0117] In the present composition 1, from the viewpoint of improving the flexural strength of the semi-cured product and the cured product, the charge amount of the hollow silica particles is preferably 0.005 μC / g or more, more preferably 0.010 μC / g or more, further preferably 0.015 μC / g or more, and particularly preferably 0.020 μC / g or more. The upper limit value of the charge amount is not particularly limited and may be 0.080 μC / g or less.

[0118] In the present composition 2, from the viewpoint of improving the flexural strength of the semi-cured product and the cured product, the charge amount of the hollow silica particles is preferably 0.010 μC / g or more, more preferably 0.015 μC / g or more, further preferably 0.020 μC / g or more. The upper limit value of the charge amount is not particularly limited and may be 0.080 μC / g or less.

[0119] In the present disclosure, the charge amount is measured by the following method. It should be noted that as the measuring device, for example, a powder friction charge amount measuring device NS-K100 type (manufactured by Nanoseeds Co., Ltd.) can be used.

[0120] Put 10 g of hollow silica particles into an aluminum container (inner dimensions: Φ42 mm, depth: 70 mm), and fixedly install it on the arm for sample rotation. The left and right swing angles are 150 degrees on the left and 210 degrees on the right (the left and right swing speed is 540 deg / s), and 12 reciprocations are defined as 1 cycle (cool) (apply a powder dusting rotation action of 2 turns at the end of the middle 6 reciprocations). After applying friction stirring for 3 cycles, put the charged hollow silica particles into a Faraday cage, measure the charge amount of the hollow silica particles, and convert it into the charge amount per unit mass (charge amount of hollow silica particles / input amount of hollow silica particles 10 g).

[0121] It should be noted that the charge amount of the hollow silica particles can be adjusted by adjusting the sum of the content rates of alkaline metal components belonging to Group 1 and Group 2 of the periodic table relative to the total mass of the shell, specific surface area, primary particle size, etc.

[0122] For example, by performing surface treatment on the hollow silica particles based on a silane coupling agent, or increasing the sum of the content rates of alkaline metal components belonging to Group 1 and Group 2 of the periodic table relative to the total mass of the shell, the charge amount can be reduced.

[0123] In the present composition 1, each hollow silica particle can be treated with a silane coupling agent. By treating the surface of the hollow silica particles with a silane coupling agent, the residual amount of silanol groups on the surface becomes less, the surface is hydrophobized, water adsorption can be inhibited and the dielectric loss can be improved, and the affinity with the resin in the present composition is increased, and the dispersibility and the strength after forming a resin film can be improved.

[0124] As the types of silane coupling agents, amino-silane coupling agents, methacrylic acid-silane coupling agents, epoxy-silane coupling agents, mercapto-silane coupling agents, silane coupling agents, organosilazane compounds, etc. can be mentioned. One type of silane coupling agent can be used, or two or more types can be used in combination.

[0125] The adhesion amount of the silane coupling agent is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 5 parts by mass, and further preferably 0.10 to 2 parts by mass with respect to 100 parts by mass of the hollow silica particles.

[0126] The case where the surface of the hollow silica particles is treated with a silane coupling agent can be confirmed by detecting the peak generated by the substituent of the silane coupling agent using IR. In addition, the adhesion amount of the silane coupling agent can be measured by the carbon amount.

[0127] In addition, in the present composition 2, the obtained silica particles can be surface-treated with a conventionally known silane coupling agent, but from the viewpoint of the toughness of molded articles such as prepregs, surface treatment is preferably not performed.

[0128] In the present Composition 1, the hollow silica particles may contain impurity elements within a range that does not hinder the effects of the present disclosure. Examples of the impurity elements include Al, Fe, Ti, etc.

[0129] From the viewpoints of producing a prepreg and a cured product with a small deviation in relative permittivity, improving the dielectric properties and adhesion of the semi-cured product and the cured product, and reducing the water absorption of the present composition, the content of the hollow silica particles relative to the total volume of the present composition is preferably 10 to 70% by volume, more preferably 15 to 65% by volume, and still more preferably 18 to 60% by volume.

[0130] Commercially available hollow silica particles can be used as the hollow silica particles, or hollow silica particles produced by a conventionally known method can be used. For example, hollow silica particles produced by the methods described in International Publication No. 2019 / 131658, International Publication No. 2021 / 006697, International Publication No. 2021 / 172294, etc. can be used.

[0131] The present composition may contain one or more solvents. Examples of the solvents include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-2-pyrrolidone, n-hexane, cyclohexane, etc. From the viewpoint of adhesion, etc., the solvent preferably contains at least one selected from the group consisting of toluene, cyclohexanone, methyl ethyl ketone, and N-methyl-2-pyrrolidone. The content rate of the solvent relative to the total mass of the present composition is not particularly limited, and for example, it may be 10 to 60% by mass.

[0132] From the viewpoints of suppressing aggregation of the hollow silica particles, etc., the surface tension of the solvent is preferably 40 mN / m or less, more preferably 35 mN / m or less, and still more preferably 30 mN / m or less. The lower limit of the surface tension is not particularly limited, and for example, it may be 5 mN / m.

[0133] In the present invention, the "surface tension" is measured by the Wilhelmy method for the solvent at 25°C using a surface tensiometer.

[0134] The viscosity of the solvent is preferably 10 mPa·s or less at 25°C, more preferably 5 mPa·s or less. The lower limit of the viscosity of the solvent is not particularly limited and may be 2 mPa·s or more.

[0135] The content rate of the solvent relative to the total mass of the present composition is not particularly limited, and for example, it may be 10% by mass to 90% by mass.

[0136] This composition may contain one or more than two polymerization initiators. Examples of the polymerization initiator include α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-benzosemiquinone, chloranil, 2,4,6-tri-tert-butylphenoxy, tert-butyl peroxyisopropyl monocarbonate, azobisisobutyronitrile, etc. The content of the polymerization initiator is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the resin.

[0137] This composition may contain one or more than two polymerization accelerators. Examples of the polymerization accelerator include triallyl isocyanurate and other triallyl isocyanurate compounds, polyfunctional acrylic compounds having two or more acryloyl or methacryloyl groups in the molecule, polyfunctional vinyl compounds having two or more vinyl groups in the molecule, vinylbenzyl compounds such as styrene having vinylbenzyl in the molecule, etc. The content of the polymerization accelerator is preferably 10 to 100 parts by mass relative to 100 parts by mass of the resin.

[0138] This composition may contain one or more than two plasticizers. Examples of the plasticizer include butadiene-styrene copolymer, etc. The content of the plasticizer is preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass, relative to 100 parts by mass of the resin.

[0139] In addition to the above components, this composition may further contain other components such as surfactants, thixotropy imparting agents, pH regulators, pH buffers, viscosity regulators, defoamers, silane coupling agents, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive materials, mold release agents, surface treatment agents, flame retardants, various organic or inorganic fillers, etc., within the range that does not impair its effects.

[0140] This composition can be suitably used as a resin composition for producing electronic substrates used in electronic devices such as personal computers, laptop computers, digital cameras, etc., and communication devices such as smartphones, game consoles, etc. In addition, in order to achieve low dielectric constant, low transmission loss, low moisture absorption, and improved peel strength, the resin composition of the present invention is also expected to be applied in prepregs, metal-clad laminates, printed wiring boards, resin sheets, adhesive layers, adhesive films, solder resists, resin compositions for bump reflow, rewiring insulating layers, chip bonding materials, encapsulants, underfills, mold underfills, and laminated inductors, etc.

[0141] The prepreg of the present disclosure includes the present composition or its semi-cured product and a fibrous substrate. Examples of the fibrous substrate include glass cloth, aramid cloth, polyester cloth, glass non-woven fabric, aramid non-woven fabric, polyester non-woven fabric, pulp paper, etc. As the fibrous substrate, it preferably contains a glass component. The thickness of the fibrous substrate is not particularly limited and can be 12 μm to 1000 μm. It should be noted that regarding the present composition, since it has been described above, the description is omitted here.

[0142] The prepreg of the present disclosure can be manufactured by coating or impregnating the present composition on the fibrous substrate. After the coating or impregnation of the present composition, the resin composition can be heated to semi-cure it.

[0143] The metal substrate with resin of the present disclosure includes the present composition or its semi-cured product or the above prepreg, and includes a metal substrate layer. The metal substrate layer can be provided on one surface of the present composition or its semi-cured product or the above prepreg, or can be provided on both surfaces.

[0144] The type of the metal substrate layer is not particularly limited. Examples of the metal constituting the metal substrate layer include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, titanium alloy, etc. The metal substrate layer is preferably a metal foil, more preferably a copper foil such as a rolled copper foil or an electrolytic copper foil. The surface of the metal foil can be subjected to an anti-rust treatment (such as an oxide film such as chromate), or can be roughened. As the metal foil, a carrier-bearing metal foil composed of a carrier copper foil (thickness: 10 μm to 35 μm) and an extremely thin copper foil (thickness: 2 μm to 5 μm) laminated on the surface of the carrier copper foil through a release layer can be used. The surface of the metal substrate layer can be treated with a silane coupling agent. In this case, the entire surface of the metal substrate layer can be treated with a silane coupling agent, or a part of the surface of the metal substrate layer can be treated with a silane coupling agent. As the silane coupling agent, the above substances can be used.

[0145] The thickness of the metal substrate layer is preferably 1 to 40 μm, more preferably 2 to 20 μm. From the viewpoint of being able to reduce the transmission loss when using the metal substrate with resin as a printed wiring board, the maximum height roughness (Rz) of the metal substrate layer is preferably 6 μm or less, more preferably 4 μm or less.

[0146] In one embodiment, the metal substrate with resin of the present disclosure can be manufactured by coating the present composition on the surface of the metal substrate layer. After coating the present composition, the resin composition can be heated to semi-cure it.

[0147] In other embodiments, the metal substrate with resin of the present disclosure can be manufactured by laminating a metal substrate layer and a prepreg. As a method for laminating the metal substrate layer and the prepreg, a method of thermocompression bonding them can be cited, etc.

[0148] The wiring board of the present disclosure includes a cured product of this composition and metal wiring. As the metal wiring, metal wiring manufactured by etching the above metal substrate layer or the like can be used.

[0149] The wiring board of the present disclosure can be manufactured by a method of etching the metal substrate layer included in the above metal substrate with resin, a method of forming a pattern circuit on the surface of the cured product of this composition by an electroplating method (semi-additive method (SAP method), modified semi-additive method (MSAP method), etc.), or the like.

[0150] Examples

[0151] Next, embodiments of the present disclosure will be specifically described by way of examples, but the embodiments of the present disclosure are not limited to these examples.

[0152] Examples 1-1 to 1-3 are examples in the first embodiment, and Examples 1-4 to 1-5 are comparative examples in the first embodiment.

[0153] (Method for measuring 20% fracture pressure of hollow silica particles and hollow particles)

[0154] According to ASTM D 3102-78, the 20% fracture pressure of the hollow silica particles and hollow particles used in each example was measured using a mercury intrusion porosimeter (AutoPore IV 9500 manufactured by MICROMERITICS INSTRUMENT Corporation).

[0155] (Method for measuring density of hollow silica particles and hollow particles)

[0156] The hollow silica particles and hollow particles used in each example were dried under reduced pressure at 230°C to completely remove moisture, and used as specimens. For this specimen, the density was measured using a dry specific gravity bottle (AccuPycII 1340 manufactured by Micromeritics). The measurement conditions are as described below.

[0157] (Measurement conditions)

[0158] · Sample cell: 10 cm 3 Cell

[0159] · Specimen weight: 1.0 g

[0160] · Measurement gas: argon

[0161] · Number of purge times: 10 times

[0162] · Purge treatment filling pressure: 135 kPag

[0163] · Number of cycles: 10 times

[0164] · Cycle filling pressure: 135 kPag

[0165] · Rate of ending pressure balance: 0.05 kPag / minute

[0166] (Method for measuring the BET specific surface area of hollow silica particles and hollow particles)

[0167] The hollow silica particles and hollow particles used in each example were dried under reduced pressure at 230°C to completely remove moisture and used as samples. For this sample, the specific surface area was determined by the multi-point BET method using nitrogen with an automatic specific surface area / pore size distribution measuring device "Trister II" manufactured by Micromeritics Co., Ltd.

[0168] (Method for measuring the d50 of hollow silica particles and hollow particles)

[0169] The d50 of the hollow silica particles and hollow particles used in each example was measured by the laser diffraction / scattering method using a particle size distribution measuring device (MT3300 EXII manufactured by Microtrac BEL Co., Ltd.). Specifically, after dispersing the secondary particles of the hollow silica particles by ultrasonic irradiation for 120 seconds, the measurement was carried out, and the value at which the cumulative distribution of the particle size of the obtained particles became 50% was set as d50.

[0170] (Method for measuring the average primary particle diameter of hollow silica particles and hollow particles)

[0171] The average primary particle diameter of the hollow silica particles and hollow particles used in each example was determined by directly observing the particle diameter (diameter, in the case of non-spherical particles, the average of the long side and the short side) through SEM observation. Specifically, the sizes of 100 primary particles of the hollow silica particles were measured from the SEM images, and the value at which the cumulative distribution of the average primary particle size obtained by averaging them reached 50% was estimated as the average primary particle diameter of the whole primary particles.

[0172] (Method for measuring the sphericity of hollow silica particles and hollow particles)

[0173] The sphericity of the hollow silica particles and the hollow particles is calculated as follows: For any 100 particles in the photograph projection obtained by photographing with a scanning electron microscope (SEM), the maximum diameter (DL) and the minor axis (DS) orthogonal thereto are measured for each, the ratio of the minimum diameter (DS) to the maximum diameter (DL) (DS / DL) is calculated, and the average thereof is calculated.

[0174] (Method for measuring the dielectric loss tangent of hollow silica particles and hollow particles)

[0175] The dielectric loss tangent at a frequency of 1 GHz of the hollow silica particles and the hollow particles is measured by the perturbation method resonator method using the "Vector Network Analyzer E5063A" manufactured by KEYCOM Co., Ltd.

[0176] (Method for measuring the porosity of hollow silica particles and hollow particles)

[0177] The porosity of the hollow silica particles is calculated by dividing the density of the hollow silica particles by the true density of the hollow silica particles and multiplying by 100 times. The true density of the hollow silica particles is measured using AccuPycII 1340 manufactured by Micromeritics. The porosity of the hollow particles is calculated in the same manner.

[0178] (Method for measuring the oil absorption of hollow silica particles and hollow particles)

[0179] The oil absorption of the hollow silica particles and the hollow particles is measured in accordance with JIS K 5101-13-1 (2004).

[0180] (Method for measuring the charge amount of hollow silica particles and hollow particles)

[0181] 10 g of the hollow silica particles or hollow particles used in each example are placed in an aluminum container (inner dimensions Φ42 mm, depth 70 mm) and fixedly installed on the arm for sample rotation. The left and right swing angles are 150 degrees to the left and 210 degrees to the right (the left and right swing speeds are 540 deg / s), and one cycle (cool) is 12 reciprocations (a powder dusting rotation action of 2 turns is applied at the end of the middle 6 reciprocations). After applying 3 cycles of friction stirring, the charged hollow silica particles or hollow particles are put into a Faraday cage, and the charge amount of the hollow silica particles or hollow particles is measured and converted into the charge amount per unit mass (charge amount of hollow silica particles or hollow particles / input amount of hollow silica particles or hollow particles 10 g).

[0182] It should be noted that a powder friction charge amount measuring device (NS-K100 type, manufactured by Nanoseeds) is used as the measuring device.

[0183] (Method for Measuring Density of Resin)

[0184] The density of the resin used in each example was measured as follows.

[0185] -Measurement of Density of Polyphenylene Oxide Resin-

[0186] 59 parts by mass of polyphenylene oxide, 16 parts by mass of butadiene-styrene random copolymer, 25 parts by mass of triallyl isocyanurate, 1 part by mass of α,α'-bis(tert-butylperoxy)diisopropylbenzene, and 60 parts by mass of toluene were added to a plastic bottle (Poly Bottle) and kneaded with a planetary disperser to obtain a resin. The obtained resin was vacuum-dried at 120 °C to remove the solvent, then crushed with a chopper, and the density was measured using an Ar pycnometer. The result showed that the density was 1.1 g / cm 3 .

[0187] 1. Preparation of Each Component for Manufacturing Resin Composition

[0188] <Thermosetting Resin>

[0189] · Polyphenylene Oxide: A modified polyphenylene oxide obtained by modifying the terminal hydroxyl groups of polyphenylene oxide with methacryloyl groups, manufactured by SABIC Corporation, Noryl SA9000, Mw 1700, and the number of functional groups per molecule is 2

[0190] <Hollow Silica Particles A1>

[0191] The hollow silica particles A1 were prepared as follows.

[0192] (Preparation of Emulsion)

[0193] 2 g of an EO-PO-EO block copolymer (manufactured by ADEKA Corporation, Pluronic (registered trademark) F68) was added to 1250 g of pure water and stirred until dissolved to obtain an aqueous solution. 42 g of n-decane in which 2 g of sorbitan monooleate (manufactured by Sanyo Chemical Industries, Ltd., Ionnet (registered trademark) S-80) was dissolved was added to this aqueous solution, and the mixture was stirred with a homogenizer manufactured by IKA Corporation until the whole liquid became uniform to prepare a crude emulsion.

[0194] Using a high-pressure emulsifier (manufactured by SMT Corporation, LAB1000), the crude emulsion was emulsified at a pressure of 50 bar to prepare an emulsion with an emulsion particle size of 1 μm.

[0195] (Curing)

[0196] The obtained emulsion was allowed to stand at 40 °C for 12 hours.

[0197] (First-stage Shell Formation)

[0198] After standing still, 23 g of a diluted aqueous sodium silicate solution (SiO2 concentration: 10.4% by mass, Na2O concentration: 3.6% by mass) and 2M hydrochloric acid were added to 1300 g of the emulsion, and the pH was adjusted to 2. The mixture was stirred while maintaining the temperature at 30 °C to obtain a mixed solution.

[0199] Next, while stirring the mixed solution, 1M aqueous sodium hydroxide solution was slowly added dropwise to adjust the pH to 6, obtaining an oil core-silica shell particle dispersion. The obtained oil core-silica shell particle dispersion was allowed to age.

[0200] (Second-stage shell formation)

[0201] The oil core-silica shell particle dispersion was heated to 70 °C, and 1M aqueous sodium hydroxide solution was slowly added while stirring to adjust the pH to 9.

[0202] Next, 330 g of a diluted aqueous sodium silicate solution (SiO2 concentration: 10.4% by mass, Na2O concentration: 3.6% by mass) and 0.5M hydrochloric acid were slowly added together until the pH reached 9.

[0203] The suspension was maintained at 80 °C for 1 day and then cooled to room temperature (25 °C) to obtain a hollow silica precursor dispersion.

[0204] (Filtration, washing, drying, firing)

[0205] The total amount of the hollow silica precursor dispersion was neutralized with 2M hydrochloric acid to pH 2, and then filtered using quantitative filter paper 5C. Then, 350 ml of ion-exchanged water at 80 °C was added, and the mixture was filtered under pressure again to wash the hollow silica filter cake.

[0206] The filtered filter cake was dried at 100 °C for 1 hour in a nitrogen atmosphere, and then dried at 400 °C for 2 hours (heating rate: 10 °C / minute) to remove organic components, thereby obtaining a hollow silica precursor.

[0207] The obtained hollow silica precursor was fired at 1000 °C for 1 hour (heating rate: 10 °C / min), thereby sintering the shell to obtain hollow silica fired particles.

[0208] (Surface treatment)

[0209] 10 g of the hollow silica fired particles, 150 ml of isopropyl alcohol, and 0.1 g of vinyltrimethoxysilane were added to a 200 ml glass beaker, and the mixture was refluxed at 100 °C for 1 hour. Thereafter, vacuum filtration was performed using a hydrophobic PTFE membrane filter, and after washing with 20 ml of isopropyl alcohol, vacuum drying was performed for 2 hours using a vacuum dryer adjusted to 150 °C to obtain surface-treated hollow silica particles A1.

[0210] The thickness of the shell formed in the first-stage shell formation and the second-stage shell formation was determined by measuring the shell thickness of each particle using a transmission electron microscope (TEM). The TEM image was obtained by dispersing the hollow silica particles on a polyvinyl formal membrane that had been hydrophilized, and observing them using an HT7700 manufactured by Hitachi, Ltd. at an acceleration voltage of 100 kV. The average value of the shell thicknesses of any 50 particles was taken as the shell thickness. The results are shown in Table 1.

[0211] The content rate of sodium relative to the total mass of the first-stage shell and the second-stage shell was 500 mass ppm.

[0212] <Hollow silica particle A2>

[0213] In the second-stage shell formation, the amount of the sodium silicate aqueous solution used was changed to 500 g, and otherwise, hollow silica particle A2 was obtained in the same manner as hollow silica particle A1.

[0214] <Hollow silica particle A3>

[0215] In the second-stage shell formation, the amount of the sodium silicate aqueous solution used was changed to 650 g, and otherwise, hollow silica particle A2 was obtained in the same manner as hollow silica particle A1.

[0216] <Hollow particle B1>

[0217] According to the method of Example 1 of Japanese Patent Laid-Open No. 2021-143089, aluminosilicate hollow particles were obtained.

[0218] <Hollow particle B2>

[0219] Glass Bubbles iM16K (glass spheres with a median particle diameter of 17 μm, 3M Company) was used directly.

[0220] [Example 1-1]

[0221] 59 parts by mass of a polyphenylene ether resin, 16 parts by mass of a butadiene-styrene random copolymer, 25 parts by mass of triallyl isocyanurate, 1 part by mass of α,α'-bis(tert-butylperoxy) diisopropylbenzene, the mass part of hollow silica particle A1 to make up 20% by volume of the whole, and 80 parts by mass of toluene were added to a plastic bottle and kneaded using a planetary disperser to obtain a resin composition.

[0222] The resin composition was impregnated and coated on a glass cloth of IPC specification 2116 and heated and dried at 160 °C for 4 minutes to obtain a prepreg.

[0223] Overlap three prepregs, stack low-profile copper foils (thickness: 18 μm, Rz: 3.5 μm, manufactured by Mitsui Kinzoku Co., Ltd., 3EC-M3-V-18) on the upper and lower layers, and heat and form at 230 °C under a pressure of 30 kg / cm 2 for 120 minutes to obtain a metal substrate with resin.

[0224] [Examples 1-2 to 1-5]

[0225] Change the hollow silica particles A1 to the hollow silica particles or hollow particles described in Table 1, and otherwise manufacture the resin composition, prepreg, and metal substrate with resin in the same manner as in Example 1.

[0226] [Measurement of relative dielectric constant and dielectric loss tangent]

[0227] Immerse the metal substrates with resin manufactured in Examples 1-1 to 1-5 in an etching solution (manufactured by Sunhayato Corp., H-1000A, aqueous ferric chloride solution), completely remove the copper foil on one side, and then dry in an oven at 100 °C for 10 minutes. Use a longitudinally separated dielectric resonator (manufactured by Agilent Technologies) to measure the relative dielectric constant and dielectric loss tangent (measurement frequency: 10 GHz) of the obtained pressed prepreg. The results are shown in Table 1.

[0228] [Table 1]

[0229]

[0230] As shown in Table 1, the relative dielectric constant of the prepreg obtained using Composition 1 of the present invention is reduced.

[0231] [Examples 2-1 to 2-10]

[0232] Examples 2-1 to 2-6 are examples, and Examples 2-7 to 2-10 are comparative examples.

[0233] 1. Preparation of each component for manufacturing the resin composition

[0234] [Thermosetting resin]

[0235] · Polyphenylene ether: A modified polyphenylene ether obtained by modifying the terminal hydroxyl group of polyphenylene ether with methacryloyl groups, manufactured by SABIC, Noryl SA9000, Mw 1700, and the number of functional groups per molecule is 2

[0236] [Hollow silica particles C1]

[0237] The hollow silica particles C1 are prepared as follows.

[0238] (Preparation of emulsion)

[0239] 4 g of an EO-PO-EO block copolymer (manufactured by ADEKA Corporation, Pluronic (registered trademark) F68) was added to 1250 g of pure water and stirred until dissolved to obtain an aqueous solution. 42 g of n-decane in which 4 g of sorbitan monooleate (manufactured by Sanyo Chemical Industries, Ltd., Ionnet (registered trademark) S-80) was dissolved was added to this aqueous solution, and the mixture was stirred with a homogenizer manufactured by IKA until the whole liquid became uniform to prepare a crude emulsion.

[0240] The crude emulsion was emulsified at a pressure of 50 bar using a high-pressure emulsifier (manufactured by SMT Corporation, LAB1000) to prepare an emulsion with an emulsion particle size of 1 μm.

[0241] (Curing)

[0242] The obtained emulsion was allowed to stand at 40 °C for 12 hours.

[0243] (First-stage shell formation)

[0244] After standing, 23 g of a diluted aqueous sodium silicate solution (SiO2 concentration: 10.4% by mass, Na2O concentration: 3.6% by mass) and 2 M hydrochloric acid were added to 1300 g of the emulsion to adjust the pH to 2, and the mixture was stirred while maintaining the temperature at 30 °C to obtain a mixed solution.

[0245] Next, while stirring the mixed solution, 1 M aqueous sodium hydroxide solution was slowly added dropwise to adjust the pH to 6 to obtain an oil core-silica shell particle dispersion. The obtained oil core-silica shell particle dispersion was maintained and allowed to cure.

[0246] (Second-stage shell formation)

[0247] The oil core-silica shell particle dispersion was heated to 70 °C, and 1 M aqueous sodium hydroxide solution was slowly added while stirring to adjust the pH to 9.

[0248] Next, 330 g of a diluted aqueous sodium silicate solution (SiO2 concentration: 10.4% by mass, Na2O concentration: 3.6% by mass) and 0.5 M hydrochloric acid were slowly added together to adjust the pH to 9.

[0249] After maintaining the suspension at 80 °C for 1 day, it was cooled to room temperature (25 °C) to obtain a hollow silica precursor dispersion.

[0250] (Filtration, washing, drying, firing)

[0251] The total amount of the hollow silica precursor dispersion was neutralized to pH 2 with 2 M hydrochloric acid and then filtered using quantitative filter paper 5C. Then, 350 ml of ion-exchanged water at 80 °C was added, and the mixture was filtered under pressure again to wash the hollow silica cake.

[0252] The filtered cake was dried at 100 °C for 1 hour under a nitrogen atmosphere, and then dried at 400 °C for 2 hours (heating rate: 10 °C / minute) to remove the organic components, thereby obtaining a hollow silica precursor.

[0253] The obtained hollow silica precursor was calcined at 1000 °C for 1 hour (heating rate: 10 °C / min) to sinter the shell, thereby obtaining hollow silica calcined particles.

[0254] The content rate of the alkali metal (Na) contained in the shell with respect to the total mass of the shell of the hollow silica particles C1 was 500 mass ppm.

[0255] <Hollow silica particles C2>

[0256] The amount of the EO-PO-EO block copolymer used was changed to 2 g, and the amount of sorbitan monooleate used was changed to 2 g. Otherwise, hollow silica particles C2 were obtained in the same manner as the hollow silica particles C1.

[0257] The content rate of the alkali metal (Na) contained in the shell with respect to the total mass of the shell of the hollow silica particles C2 was 500 mass ppm.

[0258] <Hollow silica particles C3>

[0259] The EO-PO-EO block copolymer (“Pluronic (registered trademark) F68” manufactured by ADEKA Corporation) was changed to 20 g, sorbitan monooleate (Ionnet (registered trademark) S-80 manufactured by Sanyo Chemical Industries, Ltd.) was not used, and the pressure during emulsification was changed to 100 bar. Otherwise, hollow silica particles C3 were obtained in the same manner as the hollow silica particles C1.

[0260] The content rate of the alkali metal (Na) contained in the shell with respect to the total mass of the shell of the hollow silica particles C3 was 50 mass ppm.

[0261] <Hollow silica particles C4>

[0262] The EO-PO-EO block copolymer (“Pluronic (registered trademark) F68” manufactured by ADEKA Corporation) was changed to 40 g, sorbitan monooleate (Ionnet (registered trademark) S-80 manufactured by Sanyo Chemical Industries, Ltd.) was not used, and the pressure during emulsification was changed to 100 bar. Otherwise, hollow silica particles C4 were obtained in the same manner as the hollow silica particles C1.

[0263] The content rate of the alkali metal (Na) contained in the shell with respect to the total mass of the shell of the hollow silica particles C4 is 300 mass ppm.

[0264] <Hollow silica particles C5>

[0265] The hollow silica filter cake was washed with 350 ml of tap water instead of ion-exchanged water, and except for this, hollow silica particles C5 were obtained in the same manner as the hollow silica particles C4.

[0266] The content rate of the alkali metal (Na) contained in the shell with respect to the total mass of the shell of the hollow silica particles C5 is 300 mass ppm.

[0267] <Hollow silica particles C6>

[0268] To 10 g of the hollow silica particles C1, a solution prepared by dissolving 0.1 g of hexamethyldisilazane in 100 ml of toluene was added, and the mixture was placed in a 200 ml beaker and stirred with a propeller stirring blade for 60 minutes. The resulting solution was distilled to remove the solvent to 0.1% or less using a rotary evaporator to obtain surface-treated hollow silica particles C6.

[0269] The content rate of the alkali metal (Na) contained in the shell with respect to the total mass of the shell of the hollow silica particles C6 is 500 mass ppm.

[0270] <Hollow particles D1>

[0271] According to the method of Example 1 of Japanese Patent Application Laid-Open No. 2021-143089, aluminosilicate hollow particles were obtained.

[0272] The content rate of the alkali metals (Na, K, Ca, Mg) contained in the shell with respect to the total mass of the shell of the hollow particles D1 is 1 mass% or more.

[0273] <Hollow particles D2>

[0274] Glass Bubbles iM16K (glass spheres with a median particle size of 17 μm, 3M Company) was used directly.

[0275] The content rate of the alkali metals (Na, K, Ca, Mg) contained in the shell with respect to the total mass of the shell of the hollow particles D2 is 1 mass% or more.

[0276] <Hollow particles D3>

[0277] The hollow silica filter cake was washed with 3500 ml of tap water instead of ion-exchanged water, and except for this, hollow particles D3 were obtained in the same manner as the hollow silica particles C4.

[0278] The content rate of the alkali metal (Na) contained in the shell layer with respect to the total mass of the shell layer of the hollow particle D3 is 1500 mass ppm or more.

[0279] <Hollow particle D4>

[0280] The EO-PO-EO block copolymer (“Pluronic F68” manufactured by ADEKA Corporation) was changed to 50 g, sorbitan monooleate (Ionnet S-80 manufactured by Sanyo Chemical Industries, Ltd.) was not used, and the pressure during emulsification was changed to 100 bar. Except for these, hollow particle D4 was obtained in the same manner as the hollow silica particle C1.

[0281] The content rate of the alkali metal (Na) contained in the shell layer with respect to the total mass of the shell layer of the hollow particle D4 is 1500 mass ppm or more.

[0282] [Example 2-1]

[0283] 59 parts by mass of polyphenylene ether resin, 16 parts by mass of butadiene-styrene random copolymer, 25 parts by mass of triallyl isocyanurate, 1 part by mass of α,α'-bis(tert-butylperoxy)diisopropylbenzene, the mass part of the hollow silica particle C1 to be 20 vol% of the whole, and 80 parts by mass of toluene were added to a plastic bottle and kneaded with a planetary disperser to obtain a resin composition.

[0284] After standing, the resin composition was impregnated and coated on a glass cloth of IPC standard 2116 and heated and dried at 160 °C for 4 minutes to obtain a prepreg.

[0285] Three prepregs were overlapped, and low-profile copper foils (thickness: 18 μm, Rz: 3.5 μm, manufactured by Mitsui Mining & Smelting Co., Ltd., 3EC-M3-V-18) were laminated on the upper and lower layers, and heated and molded at 230 °C and a pressure of 30 kg / cm 2 for 120 minutes to obtain a metal substrate with resin.

[0286] [Examples 2-2 to 2-10]

[0287] The hollow silica particle C1 was changed to the hollow silica particle or hollow particle described in Table 1, and except for this, a resin composition, a prepreg, and a metal substrate with resin were manufactured in the same manner as in Example 2-1.

[0288] For Example 2-10, compared with Examples 2-1 to 2-6, a large amount of attachment of hollow particles D4 to a planetary disperser, etc. was observed.

[0289] <Measurement of flexural strength>

[0290] Using TENSILON (manufactured by A&D Company, Limited, RTF-1350), in accordance with JIS K 7171 (2016) (corresponding to ISO: ISO 178 2010), the flexural modulus of the resin-containing metal substrates manufactured in Examples 2-1 to 2-10 was measured under the conditions of a load cell rating of 10 kN, a distance between fulcrums of 64 mm, and a speed of 2 mm / minute. The measurement results are shown in Table 1.

[0291] For Example 10, there was too much adhesion to the apparatus and measurement was not possible, so it is marked as "-" in Table 2.

[0292] <Measurement of relative permittivity and dielectric loss tangent>

[0293] The resin-containing metal substrates manufactured in Examples 2-1 to 2-10 were immersed in an etching solution (manufactured by Sunhayato Corp., H-1000A, aqueous ferric chloride solution). After completely removing the copper foil on one side, they were dried in an oven at 100 °C for 10 minutes. The relative permittivity and dielectric loss tangent (measurement frequency: 10 GHz) of the obtained prepregs were measured using a longitudinally separated dielectric resonator (manufactured by Agilent Technologies). The results are shown in Table 2.

[0294] [Table 2]

[0295]

[0296] As shown in Table 2, Composition 2 of the present invention has little adhesion to the apparatus during production, and in addition, the cured product of the prepreg obtained using the present composition has excellent flexural strength.

[0297] The disclosures of Japanese Patent Application No. 2022-194211 and Japanese Patent Application No. 2022-194213, filed on December 5, 2022, are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard had been specifically and separately indicated to be incorporated by reference.

Claims

1. A resin composition comprising a resin and hollow silica particles, The 20% breakdown pressure of the hollow silica particles measured by mercury intrusion porosimetry is 120 MPa or more.

2. A resin composition comprising a resin and hollow silica particles, the charge amount of the hollow silica particles being 0.005 to 0.080 μC / g.

3. The resin composition according to claim 1 or 2, wherein, The hollow silica particles contain at least one selected from alkali metals and alkaline earth metals, and the sum of the content ratios of the alkali metals and the alkaline earth metals is 30 mass ppm to 1 mass% with respect to the total mass of the shell layer of the hollow silica particles.

4. The resin composition according to claim 1 or 2, wherein The density of the hollow silica particles is 0.35 to 2.00 g / cm 3 .

5. The resin composition according to claim 1 or 2, wherein, The BET specific surface area of the hollow silica particles is 1.0 to 100.0 m 2 / g.

6. The resin composition according to claim 1 or 2, wherein The median particle size d50 of the hollow silica particles is 0.1 to 10.0 μm.

7. The resin composition according to claim 1 or 2, wherein, The hollow silica particles have a shell layer containing silica, and when the diameter of the primary particles of the hollow silica particles is set to 1, the thickness of the shell layer is 0.01 to 0.

3.

8. The resin composition according to claim 1 or 2, wherein, The resin contains at least one selected from the group consisting of epoxy resins, polyimide resins, polyphenylene ether resins, resins containing a divinylbenzene skeleton, and resins containing a pyrimidine skeleton.

9. The resin composition according to claim 1 or 2, wherein The content of the hollow silica particles is 10 to 70% by volume with respect to the total volume of the resin composition.

10. A prepreg comprising the resin composition or its semi-cured product according to claim 1 or 2 and a fibrous substrate.

11. The prepreg according to claim 10, wherein, The fibrous substrate contains a glass component.

12. A metal substrate with a resin, comprising the resin composition or its semi-cured product according to claim 1 or 2 and a metal substrate layer.

13. A metal substrate with a resin, comprising the prepreg according to claim 10 and a metal substrate layer.

14. The metal substrate with resin according to claim 12, wherein, The metal substrate layer is a copper foil.

15. The metal substrate with resin according to claim 13, wherein, The metal substrate layer is a copper foil.

16. A wiring board comprising a cured product of the resin composition according to claim 1 or 2 and metal wirings.

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