WO2024122433A1 - Resin composition, prepreg, metal substrate provided with resin, and wiring board - Google Patents
Resin composition, prepreg, metal substrate provided with resin, and wiring board Download PDFInfo
- Publication number
- WO2024122433A1 WO2024122433A1 PCT/JP2023/042806 JP2023042806W WO2024122433A1 WO 2024122433 A1 WO2024122433 A1 WO 2024122433A1 JP 2023042806 W JP2023042806 W JP 2023042806W WO 2024122433 A1 WO2024122433 A1 WO 2024122433A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- hollow silica
- silica particles
- resin composition
- cured product
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 108
- 239000011347 resin Substances 0.000 title claims abstract description 108
- 239000011342 resin composition Substances 0.000 title claims abstract description 67
- 239000000758 substrate Substances 0.000 title claims description 75
- 229910052751 metal Inorganic materials 0.000 title claims description 64
- 239000002184 metal Substances 0.000 title claims description 64
- -1 prepreg Substances 0.000 title description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 190
- 238000000034 method Methods 0.000 claims abstract description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 15
- 229910052786 argon Inorganic materials 0.000 claims abstract description 13
- 229920001955 polyphenylene ether Polymers 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000011889 copper foil Substances 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 12
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- 239000009719 polyimide resin Substances 0.000 claims description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
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- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 5
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
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- 230000001678 irradiating effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Definitions
- This disclosure relates to a resin composition, a prepreg, a resin-coated metal substrate, and a wiring board.
- the electrical insulation layer of a printed wiring board is required to have properties such as a low dielectric constant, a low dielectric loss tangent, and a low linear expansion coefficient.
- a resin composition containing a thermosetting resin and silica particles has been used to manufacture an electrical insulation layer of a metal clad laminate that can be processed into a printed wiring board (see Patent Documents 1 and 2).
- a metal clad laminate is used in which a semi-cured product of the above resin composition is laminated as an electrical insulation layer on the surface of a metal substrate layer.
- a metal clad laminate is used in which a glass cloth impregnated with a resin composition is laminated as an electrical insulation layer on the surface of a metal substrate layer.
- a filler is used as a material for a prepreg using a thermosetting resin, and the filler itself usually tends to increase the relative dielectric constant of the obtained prepreg.
- a metal clad laminate using a hollow filler can reduce the relative dielectric constant compared to the case of using a solid filler, and is therefore being considered as described in Patent Documents 3 to 5.
- the present inventors have found that some conventionally known resin compositions containing hollow particles and a resin have high viscosity, and that the adhesion between the resin composition, a semi-cured product thereof, a prepreg, etc. and a substrate made of a metal, etc. is insufficient.
- the inventors have found that if the content of hollow particles is reduced in order to reduce the viscosity, a low relative dielectric constant cannot be achieved with conventional technology.
- the problem to be solved by the first embodiment of the present disclosure is to provide a resin composition capable of producing a prepreg and a cured product, which have a low dielectric constant and excellent adhesion to a substrate, as well as a prepreg, a resin-coated metal substrate, and a wiring board, which use the resin composition.
- the problem to be solved by the second embodiment of the present disclosure is to provide a resin composition capable of producing a prepreg and a cured product having a small variation in relative dielectric constant, as well as a prepreg, a resin-coated metal substrate, and a wiring board using the resin composition.
- a resin composition comprising a resin and hollow silica particles, wherein, when the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is A (g/cm 3 ), and the BET specific surface area of the hollow silica particles is B1 (m 2 /g), A ⁇ B1 is 1.0 to 120.0 m 2 /cm 3 .
- a resin composition comprising a resin and hollow silica particles, wherein when the density of the hollow silica particles and the density of the resin, which are determined by a constant volume expansion method using argon gas and a dry pycnometer, are A (g/cm 3 ) and B2 (g/cm 3 ), respectively, A/B2 is 0.3 to 1.5.
- ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6> above, wherein the content of the hollow silica particles is 10 to 70 volume% relative to the total volume of the resin composition.
- a prepreg comprising the resin composition or a semi-cured product thereof according to any one of ⁇ 1> to ⁇ 7> above, and a fibrous base material.
- the fibrous base material contains a glass component.
- a resin-coated metal substrate comprising the resin composition or a semi-cured product thereof according to any one of ⁇ 1> to ⁇ 7> above, or the prepreg according to ⁇ 8> or ⁇ 9> above, and a metal substrate layer.
- ⁇ 11> The resin-coated metal substrate according to ⁇ 10>, wherein the metal substrate layer is a copper foil.
- a wiring board comprising a cured product of the resin composition according to any one of ⁇ 1> to ⁇ 7> above and a metal wiring.
- a resin composition can be provided that has a low dielectric constant and excellent adhesion to a substrate, and can be used to produce a prepreg and a cured product.
- a prepreg, a resin-coated metal substrate, and a wiring board can be provided that use the resin composition.
- a resin composition can be provided that can be used to produce a prepreg with a small variation in relative dielectric constant.
- a prepreg, a resin-coated metal substrate, and a wiring board can be provided that use the above resin composition.
- FIG. 1 is a top view showing a pressed prepreg produced in the examples.
- each component may contain multiple types of the corresponding substance.
- the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.
- multiple types of particles corresponding to each component may be included.
- “sphericity” refers to the average value obtained by measuring the maximum diameter (DL) and the minor diameter (DS) perpendicular to the maximum diameter (DL) of each of 100 random particles in a photographic projection obtained by photographing with a scanning electron microscope (SEM) and calculating the ratio (DS/DL) of the minimum diameter (DS) to the maximum diameter (DL).
- the "dielectric tangent” and the “relative dielectric constant” are measured by a perturbation resonator method using a dedicated device (for example, "Vector Network Analyzer E5063A" manufactured by Keycom Corporation).
- the term "semi-cured product” refers to a cured product in a state where an exothermic peak associated with the curing of a thermosetting resin appears when the cured product of a resin composition is measured by differential scanning calorimetry.
- the term “semi-cured product” refers to a cured product in a state where uncured thermosetting resin remains.
- the term “cured product” refers to a cured product in a state where no exothermic peak associated with the curing of the thermosetting resin appears when the cured product of the resin composition is measured by differential scanning calorimetry.
- the term “cured product” refers to a cured product in a state where no uncured thermosetting resin remains.
- the "maximum height roughness Rz” is measured in accordance with JIS B 0601 (2013) (corresponding ISO: ISO 4287 1997).
- the "weight average molecular weight” is determined using gel permeation chromatography (GPC) in terms of polystyrene.
- composition 1 contains a resin and hollow silica particles, and when the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is A (g/cm 3 ), and the BET specific surface area of the hollow silica particles is B1 (m 2 /g), A ⁇ B1 is 1.0 to 120.0 m 2 /cm 3 .
- a prepreg and a cured product having a low dielectric constant and excellent adhesion to a substrate can be produced by using Composition 1.
- Composition 1 The reason for this is not entirely clear, but is presumed to be as follows.
- the hollow silica particles contained in composition 1 have a product of density A and BET specific surface area B1 of 1.0 to 120.0 m 2 /cm 3. This improves the dispersibility of the hollow silica particles in the resin composition and reduces the viscosity of the resin composition, which is presumably why the above-mentioned effects are achieved.
- composition 2 contains a resin and hollow silica particles, and when the densities of the hollow silica particles and the resin determined by a constant volume expansion method using argon gas and a dry pycnometer are A (g/cm 3 ) and B2 (g/cm 3 ), respectively, A/B2 is 0.3 to 1.5.
- Composition 2 It is possible to produce a prepreg and a cured product having a small variation in the relative dielectric constant by using Composition 2. The reason for this is not entirely clear, but is presumed to be as follows.
- the density ratio A/B2 of the resin and hollow silica particles contained in Composition 2 is 0.3 to 1.5. This makes it possible to suppress excessive settling or floating of the hollow silica particles in the resin composition, and to suppress the hollow silica particles from being unevenly present in the produced prepreg and cured product, which is presumably why the above-mentioned effects are achieved.
- Composition 1 and Composition 2 may be collectively referred to as “Composition.”
- the viscosity of the composition is preferably 100 to 10,000 mPa ⁇ s, more preferably 130 to 5,000 mPa ⁇ s, even 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.
- viscosity refers to a value obtained by measuring the viscosity at 30 seconds at 25°C using a rotational rheometer (e.g., Modular Rheometer Physica MCR-301 manufactured by Anton Paar) at a shear rate of 1 rpm.
- a rotational rheometer e.g., Modular Rheometer Physica MCR-301 manufactured by Anton Paar
- the composition is preferably liquid at 25°C.
- the composition may contain one type of resin or two or more types.
- the resin contained in the composition is preferably a thermosetting resin.
- the composition may contain two or more types of thermosetting resin, but preferably contains one type.
- the thermosetting resin include epoxy resin, polyphenylene ether resin, polyester resin, polyimide resin, phenol resin, resin containing a divinylbenzene skeleton, resin containing a pyrimidine skeleton, etc.
- the thermosetting resin is preferably one or more selected from epoxy resin, polyimide resin, polyphenylene ether resin, resin containing a divinylbenzene skeleton, and resin containing a pyrimidine skeleton.
- epoxy resin examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, alicyclic epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, diglycidyl ethers of polyfunctional phenols, and diglycidyl ethers of polyfunctional alcohols.
- polyimide resin examples include aromatic polyimide and aromatic polyamic acid.
- the polyphenylene ether resin may be modified polyphenylene ether or unmodified polyphenylene ether, but from the viewpoint of adhesion, 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 (2), more preferably represented by the following formula (2).
- n is an integer of 0 to 10
- Z is an arylene group
- R 1 to R 3 are each independently hydrogen or an alkyl group.
- Z is directly bonded to the end of the polyphenylene ether chain in the modified polyphenylene ether.
- R 4 is hydrogen or an alkyl group.
- the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
- the polyphenylene ether chain is preferably represented by the following formula (3):
- m is a number within the range of 1 to 50
- R 5 to 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, with a hydrogen atom or an alkyl group being preferred.
- the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
- An example of a resin containing a divinylbenzene skeleton is ODV-XET manufactured by Nippon Steel Chemical & Material Co., Ltd.
- resins containing a pyrimidine skeleton include the ELPAC HC-F series manufactured by JSR Corporation.
- 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 even more preferably 1,000 to 3,000.
- the content of the curable resin relative to the total mass of the present composition is preferably 10 to 40 mass%, more preferably 15 to 35 mass%, and even more preferably 20 to 30 mass%.
- the composition may contain resins other than thermosetting resins (hereinafter, also referred to as "other resins").
- other resins include polytetrafluoroethylene, polyethylene terephthalate, polyolefins, silicones, etc.
- the content of other resins relative to the total mass of the composition is not particularly limited, and is, for example, 1 to 50 mass%.
- the density of the resin determined by a constant volume expansion method using argon gas and a dry pycnometer is preferably 0.5 to 3.0 g/ cm3 , and more preferably 0.8 to 2.3 g/ cm3 .
- the density of the resin is measured at 25° C. after drying. In the case of a thermosetting resin, the density is measured after curing. The density can be measured by measuring the density of the cured resin with a dry pycnometer as described above.
- the density of the resin is determined by measuring the density of the composition after drying or, in the case of a thermosetting resin, after heat curing, using an Ar pycnometer.
- the present composition may contain a polymerization initiator, a polymerization accelerator, a plasticizer, and other components, as described below.
- the polymerization initiator, the polymerization accelerator, the plasticizer, and other components include a resin or a component that is incorporated into the resin by reaction, the resin or component is also included in the "resin” in calculating the density of the resin.
- the entire resin or components that are incorporated into the resin by reaction and that are included in the present composition are considered to be the "resin” in calculating the density of the resin. The same applies to the calculation of A/B2 in the present disclosure.
- the hollow silica particles have a shell layer containing silica and have a space inside the shell layer.
- the space can be confirmed by observation with a transmission electron microscope (TEM), a scanning electron microscope (SEM), or the like.
- TEM transmission electron microscope
- SEM scanning electron microscope
- "having a space inside the shell layer” means that when a cross-section of a single hollow silica particle is observed, a hollow state exists in which a single space is surrounded by a shell layer.
- the shell layer may have a single-layer structure or a multi-layer structure having two or more layers.
- the content of silica in the shell layer is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 95% by mass or more, with the upper limit of the content being 100% by mass, and preferably 99.99% by mass.
- the shell layer preferably contains at least one selected from alkali metals belonging to Groups 1 and 2 of the periodic table and their silicates.
- improving the dielectric properties of the semi-cured product and the cured product means reducing the dielectric constant and dielectric loss tangent thereof.
- the content of alkali metals belonging to Group 1 or 2 of the periodic table relative to the total mass of the shell layer is preferably 30 ppm by mass or more, more preferably 100 ppm by mass or more, even more preferably 150 ppm by mass or more, and particularly preferably 300 ppm by mass or more.
- the content is preferably 1% by mass or less, more preferably 5000 ppm by mass or less, and most preferably 1000 ppm by mass or less.
- the content of alkali metals belonging to Group 1 or 2 of the periodic table relative to the total mass of the shell layer is preferably 30 ppm by mass to 1 mass%, more preferably 100 ppm by mass to 5000 ppm by mass, and even more preferably 150 ppm by mass to 1000 ppm by mass.
- the composition of the shell layer is measured by ICP emission spectrometry, flame atomic absorption spectrometry, or the like.
- 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.
- the average primary particle diameter of the hollow silica particles is preferably 10 nm to 10 ⁇ m, more preferably 20 nm to 7 ⁇ m, even more preferably 50 nm to 5 ⁇ m, particularly preferably 70 nm to 3 ⁇ m, and most preferably 100 nm to 1 ⁇ m.
- the average primary particle size of hollow silica particles is determined by directly observing the particle diameter (diameter, the average value of the long and short sides if the particle is not spherical) by SEM observation. Specifically, the primary particle sizes of 100 hollow silica particles are measured from an SEM image, and the value at which the cumulative distribution of the primary particle sizes obtained by averaging them is 50% is estimated to be the average primary particle size of all primary particles.
- the median diameter (hereinafter also simply referred to as "d50") of the hollow silica particles is preferably 0.1 to 10.0 ⁇ m, more preferably 0.2 to 10.0 ⁇ m, even more preferably 0.25 to 8.0 ⁇ m, particularly preferably 0.3 to 7.0 ⁇ m, most preferably 0.3 to 5.0 ⁇ m, and may be 0.3 to 3.0 ⁇ m.
- d50 refers to the volume-based cumulative 50% diameter of hollow silica particles determined by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII” manufactured by Microtrack Bell Co., Ltd.). That is, d50 refers to the particle diameter at the point on the cumulative curve where the cumulative volume is 50% when the particle size distribution is measured by a laser diffraction/scattering method and a cumulative curve is calculated with the total volume of the hollow silica particles set to 100%. In the present disclosure, the d50 of the hollow silica particles is measured in a state including primary particles and secondary particles.
- the d10 of the hollow silica particles is preferably 0.1 to 2.0 ⁇ m, more preferably 0.2 to 2.0 ⁇ m, even more preferably 0.3 to 1.8 ⁇ m, and particularly preferably 0.3 to 1.5 ⁇ m.
- d10 is the volume-based cumulative 10% diameter of hollow silica particles obtained by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII” manufactured by Microtrack-Bell Co., Ltd.). That is, d10 is the particle diameter at the point where the cumulative volume is 10% on a cumulative curve obtained by measuring the particle size distribution by a laser diffraction/scattering method and assuming the total volume of the hollow silica particles to be 100%. In the present disclosure, the d10 of the hollow silica particles is measured in a state including primary particles and secondary particles.
- the d90 of the hollow silica particles is preferably 0.7 to 15.0 ⁇ m, more preferably 0.8 to 12.0 ⁇ m, even more preferably 0.9 to 10.0 ⁇ m, particularly preferably 0.9 to 8.0 ⁇ m, most preferably 0.9 to 6.0 ⁇ m, and may be 0.9 to 5.0 ⁇ m.
- d90 refers to the volume-based cumulative 90% diameter of hollow silica particles determined by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII” manufactured by Microtrack-Bell Co., Ltd.). That is, d90 refers to the particle diameter at the point on the cumulative curve where the cumulative volume is 90% when the particle size distribution is measured by a laser diffraction/scattering method and a cumulative curve is calculated with the total volume of the hollow silica particles being 100%. In the present disclosure, the d90 of the hollow silica particles is measured in a state including primary particles and secondary particles.
- d50/d10 is preferably 6.0 or less, more preferably 5.0 or less, even more preferably 3.0 or less, and particularly preferably 2.5 or less.
- the lower limit of d50/d10 is not particularly limited, and can be 1.3.
- the proportion of hollow silica particles having a particle size of 10 ⁇ m or more as measured by the Coulter Counter method is preferably 500 ppm by mass or less, more preferably 200 ppm by mass or less, even more preferably 100 ppm by mass or less, and may be 0 ppm by mass.
- the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is preferably 0.35 to 2.00 g/ cm3 , more preferably 0.35 to 1.50 g/ cm3 , and even more preferably 0.40 to 1.00 g/ cm3 .
- the density of the hollow silica particles is determined by taking a weighted average of the densities of the individual hollow silica particles.
- an AccuPycII 1340 manufactured by Micromeritics or an equivalent device can be used as the dry pycnometer.
- 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, and even more preferably 1.0 to 30.0 m 2 /g.
- a ⁇ B1 is 1.0 to 120.0 m 2 /cm 3.
- a ⁇ B1 is preferably 2.0 to 80.0 m 2 /cm 3 , more preferably 2.5 to 40.0 m 2 /cm 3 , and even more preferably 3.0 to 20.0 m 2 /cm 3 .
- a ⁇ B1 is preferably 1.0 to 120.0 m 2 /cm 3 , more preferably 2.0 to 80.0 m 2 /cm 3 , even more preferably 2.5 to 40.0 m 2 /cm 3 , and particularly preferably 3.0 to 20.0 m 2 /cm 3 .
- A/B2 is preferably 0.3 to 1.5, and more preferably 0.4 to 1.0.
- A/B2 is from 0.3 to 1.5, and from the viewpoint of further reducing the variation in the relative dielectric constant of the cured product, etc., it is preferably from 0.4 to 1.0.
- the porosity of the hollow silica particles is preferably 30 to 90%, more preferably 40 to 90%, and even more preferably 50 to 85%.
- the porosity of hollow silica particles is calculated by dividing the density of hollow silica particles by the true density of hollow silica particles and multiplying the result by 100. The true density of hollow silica particles is measured using He gas with an AccuPycII 1340 manufactured by Micromeritics or an equivalent device.
- each hollow silica particle contained in the hollow silica particles is not particularly limited and may be spherical or non-spherical, but from the viewpoint of a low dielectric tangent, a spherical shape is preferred.
- the sphericity of the spherical hollow silica particles is preferably 0.60 or more, more preferably 0.75 or more, even more preferably 0.90 or more, particularly preferably 0.93 or more, and most preferably 1.00.
- the hollow silica particles are preferably non-porous particles.
- the dielectric tangent of the hollow silica particles at a frequency of 1 GHz is preferably 0.0040 or less, more preferably 0.0030 or less, even more preferably 0.0020 or less, particularly preferably 0.0015 or less, and most preferably 0.0012 or less.
- the oil absorption of the hollow silica particles is preferably from 20 to 500 mL/100 g, more preferably from 25 to 200 mL/100 g, even more preferably from 30 to 150 mL/100 g, particularly preferably from 30 to 100 mL/100 g, and most preferably from 30 to 80 mL/100 g.
- oil absorption is measured in accordance with JIS K 5101-13-1 (2004) (corresponding ISO: ISO 787-5 1980). Note 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., oil absorption measured in accordance with JIS K 5101-13-1 (2004) ⁇ (density/true density)).
- the 20% breakdown pressure of the hollow silica particles as measured by mercury porosimetry is preferably 120 MPa or more, more preferably 150 MPa or more, even more 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, for example, 600 MPa or less.
- the "20% burst pressure” refers to the burst pressure measured by mercury porosimetry, and is the minimum pressure that indicates a 20% decrease in capacity from the maximum integrated capacity when pressure is applied from 0 to 400 MPa by mercury porosimetry.
- the 20% collapse pressure of the hollow silica particles as measured by mercury intrusion porosimeter is measured in accordance with ASTM D 3102-78.
- the charge amount of the hollow silica particles is preferably 0.005 ⁇ C/g or more, more preferably 0.010 ⁇ C/g or more, even more preferably 0.015 ⁇ C/g or more, and particularly preferably 0.020 ⁇ C/g or more.
- the upper limit of the charge amount is not particularly limited, and can be 0.080 ⁇ C/g or less.
- the charge amount is measured by the following method.
- a measuring device for example, a powder triboelectric charge measuring device NS-K100 type (manufactured by Nano Seeds Corporation) can be used.
- Each hollow silica particle may be treated with a silane coupling agent.
- a silane coupling agent By treating the surface of the hollow silica particle with a silane coupling agent, the amount of remaining silanol groups on the surface is reduced, the surface is hydrophobicized, moisture adsorption is suppressed, and the dielectric loss is improved. In addition, the affinity with the resin in the composition is improved, and the dispersibility and strength after the resin film are improved.
- the silane coupling agent include aminosilane coupling agents, methacrylsilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, etc.
- the silane coupling agents may be used alone or in combination of two or more.
- the amount of the silane coupling agent attached is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 5 parts by mass, and even more preferably 0.10 to 2 parts by mass, based on 100 parts by mass of the hollow silica particles.
- the fact that the surface of the hollow silica particles has been treated with a silane coupling agent can be confirmed by detecting a peak due to a substituent of the silane coupling agent by IR.
- the amount of the silane coupling agent attached can be measured by the amount of carbon.
- the hollow silica particles may contain impurity elements as long as the effects of the present disclosure are not hindered.
- impurity elements include Al, Fe, Ti, etc.
- the content of the hollow silica particles relative to the total volume of the present composition is preferably 10 to 70 volume %, more preferably 15 to 65 volume %, and even more preferably 18 to 60 volume %.
- the hollow silica particles may be commercially available or may be prepared by a conventional method.
- hollow silica particles prepared by the methods described in WO 2019/131658, WO 2021/006697, WO 2021/172294, etc. may be used.
- the composition may contain one or more solvents.
- the solvent 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, and cyclohexane.
- the solvent contains at least one selected from the group consisting of toluene, cyclohexanone, methyl ethyl ketone, and N-methyl-2-pyrrolidone.
- the content of the solvent relative to the total mass of the composition is not particularly limited, and may be, for example, 10 to 60% by mass.
- the surface tension of the solvent is preferably 40 mN/m or less, more preferably 35 mN/m or less, and even more preferably 30 mN/m or less.
- the lower limit of the surface tension is not particularly limited and may be, for example, 5 mN/m.
- surface tension is measured by the Wilhelmy method using a surface tensiometer for a solvent at 25°C.
- the viscosity of the solvent is preferably 10 mPa ⁇ s or less at 25°C, and more preferably 5 mPa ⁇ s or less.
- the lower limit of the viscosity of the solvent is not particularly limited, and can be 2 mPa ⁇ s or more.
- the content of the solvent relative to the total mass of the composition is not particularly limited, and can be, for example, 10% by mass to 90% by mass.
- the composition may contain one or more polymerization initiators.
- polymerization initiators include ⁇ , ⁇ '-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, and azobisisobutyronitrile.
- the content of the polymerization initiator per 100 parts by mass of resin is preferably 0.1 to 5 parts by mass.
- the composition may contain one or more polymerization accelerators.
- polymerization accelerators include trialkenyl isocyanurate compounds such as triallyl isocyanurate, 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, and vinylbenzyl compounds such as styrene having a vinylbenzyl group in the molecule.
- the content of the polymerization accelerator per 100 parts by mass of the resin is preferably 10 to 100 parts by mass.
- the composition may contain one or more plasticizers.
- plasticizers include butadiene-styrene copolymers.
- the content of the plasticizer per 100 parts by mass of resin is preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass.
- the composition may further contain other components such as surfactants, thixotropy imparting agents, pH adjusters, pH buffers, viscosity regulators, defoamers, silane coupling agents, dehydrating agents, plasticizers, weather resistance agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brightening agents, colorants, conductive materials, release agents, surface treatment agents, flame retardants, and various organic or inorganic fillers, to the extent that the effects of the composition are not impaired.
- other components such as surfactants, thixotropy imparting agents, pH adjusters, pH buffers, viscosity regulators, defoamers, silane coupling agents, dehydrating agents, plasticizers, weather resistance agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brightening agents, colorants, conductive materials, release agents, surface treatment agents, flame retardants, and various organic or inorganic fillers, to the extent that the effects of the composition are not impaired.
- This composition can be suitably used as a resin composition for producing electronic substrates for use in electronic devices such as personal computers, notebook computers, and digital cameras, and communication devices such as smartphones and game consoles.
- the resin composition of the present invention is also expected to be applied to prepregs, metal foil-clad laminates, printed wiring boards, resin sheets, adhesive layers, adhesive films, solder resists, resin compositions for bump reflow, rewiring insulating layers, die bond materials, encapsulants, underfills, mold underfills, and laminated inductors, etc., in order to reduce dielectric constant, transmission loss, moisture absorption, and improve peel strength.
- the prepreg of the present disclosure includes the present composition or a semi-cured product thereof, and a fibrous substrate.
- the fibrous substrate include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, and pulp paper.
- the fibrous substrate preferably contains a glass component.
- the thickness of the fibrous substrate is not particularly limited, and can be 12 ⁇ m to 1000 ⁇ m. Note that the present composition has been described above, so a description thereof will be omitted here.
- the prepreg of the present disclosure can be produced by applying or impregnating the present composition to a fibrous substrate. After applying or impregnating the present composition, the resin composition may be heated and semi-cured.
- the resin-coated metal substrate of the present disclosure includes the present composition or a semi-cured product thereof, or the prepreg, and a metal substrate layer.
- the metal substrate layer may be provided on one surface or both surfaces of the present composition or a semi-cured product thereof, or the prepreg.
- the type of the metal substrate layer is not particularly limited, and examples of metals constituting the metal substrate layer include copper, copper alloys, stainless steel, nickel, nickel alloys (including alloy 42), aluminum, aluminum alloys, titanium, and titanium alloys.
- the metal substrate layer is preferably a metal foil, and more preferably a copper foil such as rolled copper foil or electrolytic copper foil.
- the surface of the metal foil may be rust-proofed (oxide film such as chromate) or may be roughened.
- a carrier-attached metal foil consisting of a carrier copper foil (thickness: 10 to 35 ⁇ m) and an ultra-thin copper foil (thickness: 2 to 5 ⁇ m) laminated on the carrier copper foil surface via a peeling layer may be used.
- the surface of the metal substrate layer may be treated with a silane coupling agent.
- the entire surface of the metal substrate layer may be treated with a silane coupling agent, or a part of the surface of the metal substrate layer may be treated with a silane coupling agent.
- the silane coupling agent the above-mentioned ones can be used.
- the thickness of the metal substrate layer is preferably 1 to 40 ⁇ m, more preferably 2 to 20 ⁇ m. From the viewpoint of reducing transmission loss when the resin-coated metal substrate is used as a printed wiring board, the maximum height roughness (Rz) of the metal substrate layer is preferably 6 ⁇ m or less, more preferably 4 ⁇ m or less.
- the resin-attached metal substrate of the present disclosure can be produced by applying the present composition to the surface of a metal substrate layer. After applying the present composition, the resin composition may be heated to be semi-cured.
- the resin-coated metal substrate of the present disclosure can be produced by laminating a metal substrate layer and a prepreg. Examples of a method for laminating the metal substrate layer and the prepreg include a method of thermocompression bonding them.
- the wiring board of the present disclosure includes a cured product of the present composition and metal wiring.
- the metal wiring can be produced by etching the above-mentioned metal substrate layer, etc.
- the wiring board of the present disclosure can be manufactured by a method of etching the metal substrate layer of the resin-coated metal substrate, or by a method of forming a pattern circuit on the cured surface of the present composition by electrolytic plating (semi-additive method (SAP method), modified semi-additive method (MSAP method), etc.).
- SAP method spin-additive method
- MSAP method modified semi-additive method
- particles refers to hollow silica particles, hollow particles, and/or solid particles, unless otherwise specified.
- the d50 of the particles used in each example was measured by a laser diffraction/scattering method using a particle size distribution analyzer (MT3300EXII, manufactured by Microtrac-Bell). Specifically, the secondary particles were dispersed by irradiating with ultrasonic waves for 120 seconds, and then the measurement was performed. The value at which the cumulative distribution of the particle sizes obtained was 50% was taken as d50.
- the average primary particle size of the particles used in each example was determined by directly observing the particle size (diameter, or the average of the long and short sides if the particle is not spherical) using SEM observation. Specifically, the primary particle sizes of 100 particles were measured using SEM images, and the value at which the cumulative distribution of the primary particle sizes obtained by averaging these was 50% was estimated to be the average primary particle size of all the primary particles.
- the sphericity of the particles was determined by measuring the maximum diameter (DL) and the minor diameter (DS) perpendicular to the maximum diameter (DL) of any 100 particles in a photographic projection obtained by photographing with a scanning electron microscope (SEM), calculating the ratio (DS/DL) of the minimum diameter (DS) to the maximum diameter (DL), and calculating the average.
- SEM scanning electron microscope
- the dielectric loss tangent of the particles at a frequency of 1 GHz was measured by a perturbation resonator method using a vector network analyzer E5063A manufactured by Keycom Corporation.
- the porosity of the particles was calculated by dividing the density of the particles by the true density of the particles and multiplying the result by 100.
- the true density of the particles was measured using an AccuPycII 1340 manufactured by Micromeritics.
- the density of the resin used in each example was measured as follows. - Density measurement of polyphenylene ether-containing resin - 59 parts by mass of polyphenylene ether, 16 parts by mass of butadiene-styrene random copolymer, 25 parts by mass of triallyl isocyanurate, 1 part by mass of ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, and 60 parts by mass of toluene were placed in a polyvinyl bottle and kneaded with a planetary disperser to obtain a resin.
- the resin obtained was vacuum dried at 120°C to remove the solvent, and then cured in a nitrogen oven at 200°C. It was then pulverized using a cutter mill, and the density was measured with an Ar pycnometer, which gave a density of 1.1 g/ cm3 .
- a polyimide resin (Arakawa Chemical Industries, Ltd., PIAD300, solid content 30%) was vacuum dried at 150°C to remove the solvent, and then pulverized using a cutter mill. The density was measured using an Ar pycnometer and found to be 1.5 g/ cm3 .
- Example 1-1 to 1-7 Among the following Examples 1-1 to 1-7, Examples 1 to 5 are examples of the first embodiment, and Examples 6 and 7 are comparative examples of the first embodiment.
- each component for producing a resin composition [thermosetting resin]
- Polyphenylene ether Modified polyphenylene ether in which the terminal hydroxyl groups of polyphenylene ether are modified with methacrylic groups, manufactured by SABIC, Noryl SA9000, Mw 1700, two functional groups per molecule
- the hollow silica particles A1 were prepared as follows.
- the entire 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 80° C. ion-exchanged water was added and pressure filtered again to wash the hollow silica cake. The cake after filtration was dried in a nitrogen atmosphere at 100° C. for 1 hour and then at 400° C. for 2 hours (heating rate: 10° C./min) to remove the organic matter, thereby obtaining a hollow silica precursor. The obtained hollow silica precursor was baked at 1000° C. for 1 hour (heating rate: 10° C./min) to bake and tighten the shell, thereby obtaining baked hollow silica particles.
- Hollow silica particles A2 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 2 g and the amount of sorbitan acid monooleate used was changed to 2 g.
- Hollow silica particles A3 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 10 g, sorbitan acid monooleate was not used, and the pressure in emulsification was changed to 100 bar.
- Hollow silica particles A4 were obtained in the same manner as hollow silica particles A1, except that the hollow silica precursor was calcined at 1,100° C. for 1 hour (temperature increase rate: 10° C./min).
- Hollow silica particles A5 were obtained in the same manner as hollow silica particles A1, except that the calcination conditions of the hollow silica precursor were changed to 800° C. for 1 hour (heating time: 10° C./min).
- ⁇ Hollow Particles B1> A silica-based hollow fine particle dispersion sol (Catalysts and Chemical Industries Co., Ltd., Sururia (registered trademark) 1420, average primary particle diameter 60 nm, concentration 20.5 mass%, dispersion medium: isopropanol) was subjected to vacuum drawing at 120° C. for 2 hours to dry out the solvent, thereby obtaining hollow particles B1.
- Example 1-1 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 ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, parts by mass of hollow silica particles A1 accounting for 20% by volume of the total, and 80 parts by mass of toluene were placed in a polyvinyl chloride bottle and kneaded using a planetary dispenser to obtain a resin composition. The resin composition was applied to a glass cloth of IPC spec 2116 by impregnation, and then heated and dried at 160° C.
- Examples 1-2 to 1-7 Except for changing the hollow silica particles A1 to the hollow silica particles or hollow particles shown in Table 1, a resin composition, a prepreg, and a resin-coated metal substrate were produced in the same manner as in Example 1-1.
- the cured product obtained using this composition has a low dielectric constant and excellent adhesion to the substrate.
- each component for producing a resin composition ⁇ Thermosetting resin>
- Polyphenylene ether Modified polyphenylene ether in which the terminal hydroxyl groups of polyphenylene ether are modified with methacrylic groups, manufactured by SABIC Corporation, Noryl SA9000, Mw 1700, number of functional groups per molecule: 2
- Polyimide resin Manufactured by Arakawa Chemical Industries, Ltd., PIAD300, solid content concentration 30% by mass
- the hollow silica particles A1 were prepared as follows.
- the entire 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 80° C. ion-exchanged water was added and pressure filtered again to wash the hollow silica cake. The cake after filtration was dried in a nitrogen atmosphere at 100° C. for 1 hour and then at 400° C. for 2 hours (heating rate: 10° C./min) to remove the organic matter, thereby obtaining a hollow silica precursor. The obtained hollow silica precursor was baked at 1000° C. for 1 hour (heating rate: 10° C./min) to bake and tighten the shell, thereby obtaining baked hollow silica particles.
- Hollow silica particles A2 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 2 g and the amount of sorbitan acid monooleate used was changed to 2 g.
- Hollow silica particles A3 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 10 g, sorbitan acid monooleate was not used, and the pressure in emulsification was changed to 100 bar.
- the sodium content relative to the total mass of the first shell layer and the second shell layer was 1,200 ppm by mass.
- Hollow silica particles A5 were obtained in the same manner as hollow silica particles A1, except that the calcination conditions of the hollow silica precursor were changed to 800° C. for 1 hour (heating time: 10° C./min).
- Solid particle C1> SO-C2 solid silica particles with a median diameter (d50) of 0.6 ⁇ m, Admatechs Co., Ltd. was used as is.
- Example 2-1 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 ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, parts by mass of hollow silica particles A1 accounting for 20% by volume of the total, and 80 parts by mass of toluene were placed in a polyvinyl chloride bottle and kneaded using a planetary dispenser to obtain a resin composition. The resin composition was allowed to stand in an environment of 25° C. and a relative humidity of 50% for 12 hours.
- the resin composition was applied to impregnate a glass cloth of IPC spec 2116, and then heated and dried at 160° C. for 4 minutes to obtain a prepreg.
- Three sheets of prepreg were stacked, low-profile copper foil (thickness: 18 ⁇ m, Rz: 3.5 ⁇ m, Mitsui Kinzoku Co., Ltd., 3EC-M3-V-18) was laminated on the top and bottom, and the resulting mixture was heated and molded at 230° C. and a pressure of 30 kg/cm 2 for 120 minutes to obtain a metal substrate with resin.
- A/B2 was calculated and shown in Table 2. In the subsequent examples, similar calculations were performed and the results are summarized in Table 2. In Examples 2-5 to 2-6 and Examples 3-5 to 3-6, A was used as the density of the solid particles or hollow particles, not the density of the hollow silica particles.
- Example 2-2 to 2-6 Except for changing the hollow silica particles A1 to the hollow silica particles, solid particles or hollow particles shown in Table 2, a resin composition, a prepreg and a resin-coated metal substrate were produced in the same manner as in Example 2-1.
- Example 3-1 50 parts by mass of polyimide resin (manufactured by Arakawa Chemical Industries, Ltd., PIAD300, solid content 30%), 20 parts by mass of hollow silica particles A-1 corresponding to 20 volume % of the total, and 20 parts by mass of cyclohexanone were placed in a polyvinyl bottle, and alumina balls having a diameter of 20 mm were added and mixed at 30 rpm for 12 hours. The alumina balls were then removed to obtain a resin composition. The resin composition was allowed to stand in an environment of 25° C. and a relative humidity of 50% for 12 hours. After standing, the resin composition was applied to impregnate a glass cloth of IPC spec 2116, and then heated and dried at 160° C.
- polyimide resin manufactured by Arakawa Chemical Industries, Ltd., PIAD300, solid content 30%
- alumina balls having a diameter of 20 mm were added and mixed at 30 rpm for 12 hours.
- the alumina balls were then removed to obtain a resin
- a prepreg Three sheets of prepreg were stacked, low-profile copper foil (thickness: 18 ⁇ m, Rz: 3.5 ⁇ m, Mitsui Kinzoku Co., Ltd., 3EC-M3-V-18) was laminated on top and bottom, and the resulting mixture was heated and molded at 180° C. and a pressure of 30 kg/cm 2 for 120 minutes to obtain a metal substrate with resin.
- Example 3-2 to 3-6 Except for changing the hollow silica particles A1 to the hollow silica particles, solid particles or hollow particles shown in Table 2, a resin composition, a prepreg and a resin-coated metal substrate were produced in the same manner as in Example 3-1.
- the dielectric constants were measured at three points, 1/4L, 2/4L, and 3/4L, at the center X in the short side direction of the pressed prepreg shown in Figure 1, where L is the total length in the long side direction, and the standard deviation of the dielectric constants was calculated.
- the measurement results are summarized in Table 2.
- the prepreg is indicated by the reference symbol 10.
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Abstract
A resin composition according to the present disclosure contains a resin and hollow silica particles. When A (g/cm3) is the density of the hollow silica particles as determined by a constant volume expansion method using an argon gas and a dry pycnometer, and B1 (m2/g) is the BET specific surface area of the hollow silica particles, A×B1 is 1.0 to 120.0 m2/cm3, or when A (g/cm3) and B2 (g/cm3) are respectively the density of the hollow silica particles and the density of the resin as determined by a constant volume expansion method using an argon gas and a dry pycnometer, A/B2 is 0.3 to 1.5.
Description
本開示は、樹脂組成物、プリプレグ、樹脂付き金属基材、及び配線板に関する。
This disclosure relates to a resin composition, a prepreg, a resin-coated metal substrate, and a wiring board.
プリント配線板が備える電気絶縁層には、低誘電率、低誘電正接、低線膨張率等の特性が要求される。近年、熱硬化性樹脂及びシリカ粒子を含む樹脂組成物は、プリント配線板に加工可能な金属張積層体が備える電気絶縁層の製造に使用されている（特許文献１及び２参照）。具体的には、金属基材層の表面に、上記樹脂組成物の半硬化物を電気絶縁層として積層した金属張積層体が使用されている。他の例としては、樹脂組成物を含浸させたガラスクロス等を電気絶縁層として、金属基材層の表面に積層した金属張積層体が使用されている。ここで、フィラーは、熱硬化性樹脂を用いたプリプレグの材料として用いられるが、フィラー自体は、通常、得られるプリプレグの比誘電率を高くする傾向にある。その中でも、中空フィラーを用いた金属張積層体は、中実フィラーを用いた場合と比べて比誘電率を低下させることが出来るため、特許文献３～５に記載されているように、検討されている。
The electrical insulation layer of a printed wiring board is required to have properties such as a low dielectric constant, a low dielectric loss tangent, and a low linear expansion coefficient. In recent years, a resin composition containing a thermosetting resin and silica particles has been used to manufacture an electrical insulation layer of a metal clad laminate that can be processed into a printed wiring board (see Patent Documents 1 and 2). Specifically, a metal clad laminate is used in which a semi-cured product of the above resin composition is laminated as an electrical insulation layer on the surface of a metal substrate layer. As another example, a metal clad laminate is used in which a glass cloth impregnated with a resin composition is laminated as an electrical insulation layer on the surface of a metal substrate layer. Here, a filler is used as a material for a prepreg using a thermosetting resin, and the filler itself usually tends to increase the relative dielectric constant of the obtained prepreg. Among them, a metal clad laminate using a hollow filler can reduce the relative dielectric constant compared to the case of using a solid filler, and is therefore being considered as described in Patent Documents 3 to 5.
本発明者は、中空粒子及び樹脂を含む従来公知の樹脂組成物には、高粘度のものが存在し、樹脂組成物、その半硬化物、プリプレグ等と、金属等から構成される基材との密着性が十分ではないとの知見を得た。また、粘度を低減するため、中空粒子の含有率を抑えると、従来の技術では低比誘電率を達成できないとの知見を得た。
本開示の第１の実施形態が解決しようとする課題は、低比誘電率であって、基材との密着性に優れる、プリプレグ及び硬化物を作製可能な樹脂組成物、並びに上記樹脂組成物を用いたプリプレグ、樹脂付き金属基材、及び配線板を提供することである。 The present inventors have found that some conventionally known resin compositions containing hollow particles and a resin have high viscosity, and that the adhesion between the resin composition, a semi-cured product thereof, a prepreg, etc. and a substrate made of a metal, etc. is insufficient. In addition, the inventors have found that if the content of hollow particles is reduced in order to reduce the viscosity, a low relative dielectric constant cannot be achieved with conventional technology.
The problem to be solved by the first embodiment of the present disclosure is to provide a resin composition capable of producing a prepreg and a cured product, which have a low dielectric constant and excellent adhesion to a substrate, as well as a prepreg, a resin-coated metal substrate, and a wiring board, which use the resin composition.
本開示の第１の実施形態が解決しようとする課題は、低比誘電率であって、基材との密着性に優れる、プリプレグ及び硬化物を作製可能な樹脂組成物、並びに上記樹脂組成物を用いたプリプレグ、樹脂付き金属基材、及び配線板を提供することである。 The present inventors have found that some conventionally known resin compositions containing hollow particles and a resin have high viscosity, and that the adhesion between the resin composition, a semi-cured product thereof, a prepreg, etc. and a substrate made of a metal, etc. is insufficient. In addition, the inventors have found that if the content of hollow particles is reduced in order to reduce the viscosity, a low relative dielectric constant cannot be achieved with conventional technology.
The problem to be solved by the first embodiment of the present disclosure is to provide a resin composition capable of producing a prepreg and a cured product, which have a low dielectric constant and excellent adhesion to a substrate, as well as a prepreg, a resin-coated metal substrate, and a wiring board, which use the resin composition.
また、本発明者は、中空粒子及び樹脂を含む従来公知の樹脂組成物を用いて、プリプレグ、硬化物等を作製する場合、樹脂組成物において、中空粒子の過度な沈降又は浮遊が生じ、凝集体を形成し、作製したプリプレグ及び硬化物中において、中空粒子が不均一に存在することとなり、測定箇所により比誘電率のばらつきが生じるおそれがあるとの知見を得た。
本開示の第２の実施形態が解決しようとする課題は、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製可能な樹脂組成物、並びに上記樹脂組成物を用いたプリプレグ、樹脂付き金属基材、及び配線板を提供することである。 Furthermore, the present inventors have found that when a prepreg, a cured product, or the like is produced using a conventionally known resin composition containing hollow particles and a resin, excessive sedimentation or floating of the hollow particles occurs in the resin composition, forming aggregates, and the hollow particles are present non-uniformly in the produced prepreg and cured product, which may result in variations in the dielectric constant depending on the measurement location.
The problem to be solved by the second embodiment of the present disclosure is to provide a resin composition capable of producing a prepreg and a cured product having a small variation in relative dielectric constant, as well as a prepreg, a resin-coated metal substrate, and a wiring board using the resin composition.
本開示の第２の実施形態が解決しようとする課題は、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製可能な樹脂組成物、並びに上記樹脂組成物を用いたプリプレグ、樹脂付き金属基材、及び配線板を提供することである。 Furthermore, the present inventors have found that when a prepreg, a cured product, or the like is produced using a conventionally known resin composition containing hollow particles and a resin, excessive sedimentation or floating of the hollow particles occurs in the resin composition, forming aggregates, and the hollow particles are present non-uniformly in the produced prepreg and cured product, which may result in variations in the dielectric constant depending on the measurement location.
The problem to be solved by the second embodiment of the present disclosure is to provide a resin composition capable of producing a prepreg and a cured product having a small variation in relative dielectric constant, as well as a prepreg, a resin-coated metal substrate, and a wiring board using the resin composition.
本開示は以下の態様を含む。
＜１＞ 樹脂及び中空シリカ粒子を含む樹脂組成物であって、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた上記中空シリカ粒子の密度をＡ（ｇ／ｃｍ３）、上記中空シリカ粒子のＢＥＴ比表面積をＢ１（ｍ２／ｇ）としたとき、Ａ×Ｂ１が、１．０～１２０．０ｍ２／ｃｍ３である、樹脂組成物。
＜２＞ 樹脂及び中空シリカ粒子を含む樹脂組成物であって、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた前記中空シリカ粒子の密度及び前記樹脂の密度を、それぞれ、Ａ（ｇ／ｃｍ３）、及びＢ２（ｇ／ｃｍ３）としたとき、Ａ／Ｂ２が、０．３～１．５である、樹脂組成物。
＜３＞ 上記中空シリカ粒子の密度が、０．３５～２．００ｇ／ｃｍ３である、上記＜１＞又は＜２＞に記載の樹脂組成物。
＜４＞ 上記中空シリカ粒子のＢＥＴ比表面積が、１．０～１００．０ｍ２／ｇである、上記＜１＞～＜３＞のいずれか１項に記載の樹脂組成物。
＜５＞ 上記中空シリカ粒子のメジアン径（ｄ５０）が０．１～１０．０μｍである、上記＜１＞～＜４＞のいずれか１つに記載の樹脂組成物。
＜６＞ 上記樹脂が、エポキシ樹脂、ポリイミド樹脂、ポリフェニレンエーテル樹脂、ジビニルベンゼン骨格を含む樹脂、及びピリミジン骨格を含む樹脂から選択される少なくとも１つを含む、上記＜１＞～＜５＞のいずれか１つに記載の樹脂組成物。
＜７＞ 樹脂組成物の総体積に対する上記中空シリカ粒子の含有量が１０～７０体積％である、上記＜１＞～＜６＞のいずれか１つに記載の樹脂組成物。
＜８＞ 上記＜１＞～＜７＞のいずれか１つに記載の樹脂組成物又はその半硬化物と、繊維質基材と、を含むプリプレグ。
＜９＞ 上記繊維質基材が、ガラス成分を含む、上記＜８＞に記載のプリプレグ。
＜１０＞ 上記＜１＞～＜７＞のいずれか１つに記載の樹脂組成物若しくはその半硬化物、又は上記＜８＞又は＜９＞に記載のプリプレグと、金属基材層と、を含む樹脂付き金属基材。
＜１１＞ 上記金属基材層が、銅箔である、上記＜１０＞に記載の樹脂付き金属基材。
＜１２＞ 上記＜１＞～＜７＞のいずれか１つに記載の樹脂組成物の硬化物と、金属配線と、を含む配線板。 The present disclosure includes the following aspects.
<1> A resin composition comprising a resin and hollow silica particles, wherein, when the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is A (g/cm 3 ), and the BET specific surface area of the hollow silica particles is B1 (m 2 /g), A×B1 is 1.0 to 120.0 m 2 /cm 3 .
<2> A resin composition comprising a resin and hollow silica particles, wherein when the density of the hollow silica particles and the density of the resin, which are determined by a constant volume expansion method using argon gas and a dry pycnometer, are A (g/cm 3 ) and B2 (g/cm 3 ), respectively, A/B2 is 0.3 to 1.5.
<3> The resin composition according to <1> or <2> above, wherein the hollow silica particles have a density of 0.35 to 2.00 g/ cm3 .
<4> The resin composition according to any one of the above <1> to <3>, wherein the hollow silica particles have a BET specific surface area of 1.0 to 100.0 m 2 /g.
<5> The resin composition according to any one of <1> to <4> above, wherein the hollow silica particles have a median diameter (d50) of 0.1 to 10.0 μm.
<6> The resin composition according to any one of <1> to <5>, wherein the resin comprises at least one selected from an epoxy resin, a polyimide resin, a polyphenylene ether resin, a resin containing a divinylbenzene skeleton, and a resin containing a pyrimidine skeleton.
<7> The resin composition according to any one of <1> to <6> above, wherein the content of the hollow silica particles is 10 to 70 volume% relative to the total volume of the resin composition.
<8> A prepreg comprising the resin composition or a semi-cured product thereof according to any one of <1> to <7> above, and a fibrous base material.
<9> The prepreg according to <8> above, wherein the fibrous base material contains a glass component.
<10> A resin-coated metal substrate comprising the resin composition or a semi-cured product thereof according to any one of <1> to <7> above, or the prepreg according to <8> or <9> above, and a metal substrate layer.
<11> The resin-coated metal substrate according to <10>, wherein the metal substrate layer is a copper foil.
<12> A wiring board comprising a cured product of the resin composition according to any one of <1> to <7> above and a metal wiring.
＜１＞ 樹脂及び中空シリカ粒子を含む樹脂組成物であって、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた上記中空シリカ粒子の密度をＡ（ｇ／ｃｍ３）、上記中空シリカ粒子のＢＥＴ比表面積をＢ１（ｍ２／ｇ）としたとき、Ａ×Ｂ１が、１．０～１２０．０ｍ２／ｃｍ３である、樹脂組成物。
＜２＞ 樹脂及び中空シリカ粒子を含む樹脂組成物であって、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた前記中空シリカ粒子の密度及び前記樹脂の密度を、それぞれ、Ａ（ｇ／ｃｍ３）、及びＢ２（ｇ／ｃｍ３）としたとき、Ａ／Ｂ２が、０．３～１．５である、樹脂組成物。
＜３＞ 上記中空シリカ粒子の密度が、０．３５～２．００ｇ／ｃｍ３である、上記＜１＞又は＜２＞に記載の樹脂組成物。
＜４＞ 上記中空シリカ粒子のＢＥＴ比表面積が、１．０～１００．０ｍ２／ｇである、上記＜１＞～＜３＞のいずれか１項に記載の樹脂組成物。
＜５＞ 上記中空シリカ粒子のメジアン径（ｄ５０）が０．１～１０．０μｍである、上記＜１＞～＜４＞のいずれか１つに記載の樹脂組成物。
＜６＞ 上記樹脂が、エポキシ樹脂、ポリイミド樹脂、ポリフェニレンエーテル樹脂、ジビニルベンゼン骨格を含む樹脂、及びピリミジン骨格を含む樹脂から選択される少なくとも１つを含む、上記＜１＞～＜５＞のいずれか１つに記載の樹脂組成物。
＜７＞ 樹脂組成物の総体積に対する上記中空シリカ粒子の含有量が１０～７０体積％である、上記＜１＞～＜６＞のいずれか１つに記載の樹脂組成物。
＜８＞ 上記＜１＞～＜７＞のいずれか１つに記載の樹脂組成物又はその半硬化物と、繊維質基材と、を含むプリプレグ。
＜９＞ 上記繊維質基材が、ガラス成分を含む、上記＜８＞に記載のプリプレグ。
＜１０＞ 上記＜１＞～＜７＞のいずれか１つに記載の樹脂組成物若しくはその半硬化物、又は上記＜８＞又は＜９＞に記載のプリプレグと、金属基材層と、を含む樹脂付き金属基材。
＜１１＞ 上記金属基材層が、銅箔である、上記＜１０＞に記載の樹脂付き金属基材。
＜１２＞ 上記＜１＞～＜７＞のいずれか１つに記載の樹脂組成物の硬化物と、金属配線と、を含む配線板。 The present disclosure includes the following aspects.
<1> A resin composition comprising a resin and hollow silica particles, wherein, when the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is A (g/cm 3 ), and the BET specific surface area of the hollow silica particles is B1 (m 2 /g), A×B1 is 1.0 to 120.0 m 2 /cm 3 .
<2> A resin composition comprising a resin and hollow silica particles, wherein when the density of the hollow silica particles and the density of the resin, which are determined by a constant volume expansion method using argon gas and a dry pycnometer, are A (g/cm 3 ) and B2 (g/cm 3 ), respectively, A/B2 is 0.3 to 1.5.
<3> The resin composition according to <1> or <2> above, wherein the hollow silica particles have a density of 0.35 to 2.00 g/ cm3 .
<4> The resin composition according to any one of the above <1> to <3>, wherein the hollow silica particles have a BET specific surface area of 1.0 to 100.0 m 2 /g.
<5> The resin composition according to any one of <1> to <4> above, wherein the hollow silica particles have a median diameter (d50) of 0.1 to 10.0 μm.
<6> The resin composition according to any one of <1> to <5>, wherein the resin comprises at least one selected from an epoxy resin, a polyimide resin, a polyphenylene ether resin, a resin containing a divinylbenzene skeleton, and a resin containing a pyrimidine skeleton.
<7> The resin composition according to any one of <1> to <6> above, wherein the content of the hollow silica particles is 10 to 70 volume% relative to the total volume of the resin composition.
<8> A prepreg comprising the resin composition or a semi-cured product thereof according to any one of <1> to <7> above, and a fibrous base material.
<9> The prepreg according to <8> above, wherein the fibrous base material contains a glass component.
<10> A resin-coated metal substrate comprising the resin composition or a semi-cured product thereof according to any one of <1> to <7> above, or the prepreg according to <8> or <9> above, and a metal substrate layer.
<11> The resin-coated metal substrate according to <10>, wherein the metal substrate layer is a copper foil.
<12> A wiring board comprising a cured product of the resin composition according to any one of <1> to <7> above and a metal wiring.
本開示の第１の実施形態によれば、低比誘電率であって、基材との密着性に優れる、プリプレグ及び硬化物を作製可能な樹脂組成物を提供できる。また、本開示の他の実施形態によれば、上記樹脂組成物を用いたプリプレグ、樹脂付き金属基材、及び配線板を提供できる。
According to a first embodiment of the present disclosure, a resin composition can be provided that has a low dielectric constant and excellent adhesion to a substrate, and can be used to produce a prepreg and a cured product. In addition, according to other embodiments of the present disclosure, a prepreg, a resin-coated metal substrate, and a wiring board can be provided that use the resin composition.
本開示の第２の実施形態によれば、比誘電率のばらつきが小さいプリプレグを作製可能な樹脂組成物を提供できる。また、本開示の他の実施形態によれば、上記樹脂組成物を用いたプリプレグ、樹脂付き金属基材、及び配線板を提供できる。
According to a second embodiment of the present disclosure, a resin composition can be provided that can be used to produce a prepreg with a small variation in relative dielectric constant. In addition, according to another embodiment of the present disclosure, a prepreg, a resin-coated metal substrate, and a wiring board can be provided that use the above resin composition.
以下、本開示の実施形態を実施するための形態について詳細に説明する。但し、本開示の実施形態は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本開示の実施形態を制限するものではない。
Below, the form for carrying out the embodiment of the present disclosure will be described in detail. However, the embodiment of the present disclosure is not limited to the following embodiment. In the following embodiment, the components (including element steps, etc.) are not essential unless specifically stated. The same applies to the numerical values and their ranges, and they do not limit the embodiment of the present disclosure.
本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。
本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に記載しない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において各成分に該当する粒子は複数種含まれていてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に記載しない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本開示において「積層」との語は、層を積み重ねることを示し、二以上の層が結合されていてもよく、二以上の層が着脱可能であってもよい。
本開示において、「中空シリカ粒子」とは、特に断りがない限り、複数の中空シリカ粒子の群を指す。
本開示において、「ＢＥＴ比表面積」は、比表面積・細孔分布測定装置（例えば、マイクロメリティック社製「トライスターＩＩ」等）を用いた窒素吸着法に基づくＢＥＴ法により求める。
本開示において、「真球度」は、走査型電子顕微鏡（ＳＥＭ）により写真撮影して得られる写真投影図における任意の１００個の粒子について、それぞれの最大径（ＤＬ）と、これと直交する短径（ＤＳ）とを測定し、最大径（ＤＬ）に対する最小径（ＤＳ）の比（ＤＳ／ＤＬ）を算出した平均値で表す。
本開示において、「誘電正接」及び「比誘電率」は、専用の装置（例えば、キーコム株式会社製「ベクトルネットワークアナライザ Ｅ５０６３Ａ」）を用い、摂動方式共振器法にて測定する。
本開示において、「半硬化物」とは、樹脂組成物の硬化物を示査走査熱分析測定した際に、熱硬化性樹脂の硬化に伴う発熱ピークが現れる状態にある硬化物を意味する。すなわち、半硬化物とは、未硬化の熱硬化性樹脂が残存している状態の硬化物を意味する。
本開示において、「硬化物」とは、樹脂組成物の硬化物を示査走査熱分析測定した際に、熱硬化性樹脂の硬化に伴う発熱ピークが現れない状態にある硬化物を意味する。すなわち、硬化物とは、未硬化の熱硬化性樹脂が残存していない状態の硬化物を意味する。
本開示において、「最大高さ粗さＲｚ」は、ＪＩＳ Ｂ ０６０１（２０１３）（対応ＩＳＯ：ＩＳＯ ４２８７ １９９７）に準拠して測定する。
本開示において、「重量平均分子量」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて、ポリスチレン換算により求める。 In the present disclosure, the numerical ranges indicated using "to" include the numerical values before and after "to" as the minimum and maximum values, respectively. In the numerical ranges indicated in stages in the present disclosure, the upper limit or lower limit indicated in one numerical range may be replaced with the upper limit or lower limit of another numerical range indicated in stages.
In the present disclosure, each component may contain multiple types of the corresponding substance. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.
In the present disclosure, multiple types of particles corresponding to each component may be included. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
In this disclosure, the term "lamination" refers to stacking layers, where two or more layers may be bonded together or two or more layers may be removable.
In this disclosure, the term "hollow silica particles" refers to a group of multiple hollow silica particles, unless otherwise specified.
In the present disclosure, the "BET specific surface area" is determined by the BET method based on the nitrogen adsorption method using a specific surface area/pore distribution measuring device (for example, "Tristar II" manufactured by Micromeritics, etc.).
In the present disclosure, "sphericity" refers to the average value obtained by measuring the maximum diameter (DL) and the minor diameter (DS) perpendicular to the maximum diameter (DL) of each of 100 random particles in a photographic projection obtained by photographing with a scanning electron microscope (SEM) and calculating the ratio (DS/DL) of the minimum diameter (DS) to the maximum diameter (DL).
In the present disclosure, the "dielectric tangent" and the "relative dielectric constant" are measured by a perturbation resonator method using a dedicated device (for example, "Vector Network Analyzer E5063A" manufactured by Keycom Corporation).
In the present disclosure, the term "semi-cured product" refers to a cured product in a state where an exothermic peak associated with the curing of a thermosetting resin appears when the cured product of a resin composition is measured by differential scanning calorimetry. In other words, the term "semi-cured product" refers to a cured product in a state where uncured thermosetting resin remains.
In the present disclosure, the term "cured product" refers to a cured product in a state where no exothermic peak associated with the curing of the thermosetting resin appears when the cured product of the resin composition is measured by differential scanning calorimetry. In other words, the term "cured product" refers to a cured product in a state where no uncured thermosetting resin remains.
In this disclosure, the "maximum height roughness Rz" is measured in accordance with JIS B 0601 (2013) (corresponding ISO: ISO 4287 1997).
In the present disclosure, the "weight average molecular weight" is determined using gel permeation chromatography (GPC) in terms of polystyrene.
本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に記載しない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において各成分に該当する粒子は複数種含まれていてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に記載しない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本開示において「積層」との語は、層を積み重ねることを示し、二以上の層が結合されていてもよく、二以上の層が着脱可能であってもよい。
本開示において、「中空シリカ粒子」とは、特に断りがない限り、複数の中空シリカ粒子の群を指す。
本開示において、「ＢＥＴ比表面積」は、比表面積・細孔分布測定装置（例えば、マイクロメリティック社製「トライスターＩＩ」等）を用いた窒素吸着法に基づくＢＥＴ法により求める。
本開示において、「真球度」は、走査型電子顕微鏡（ＳＥＭ）により写真撮影して得られる写真投影図における任意の１００個の粒子について、それぞれの最大径（ＤＬ）と、これと直交する短径（ＤＳ）とを測定し、最大径（ＤＬ）に対する最小径（ＤＳ）の比（ＤＳ／ＤＬ）を算出した平均値で表す。
本開示において、「誘電正接」及び「比誘電率」は、専用の装置（例えば、キーコム株式会社製「ベクトルネットワークアナライザ Ｅ５０６３Ａ」）を用い、摂動方式共振器法にて測定する。
本開示において、「半硬化物」とは、樹脂組成物の硬化物を示査走査熱分析測定した際に、熱硬化性樹脂の硬化に伴う発熱ピークが現れる状態にある硬化物を意味する。すなわち、半硬化物とは、未硬化の熱硬化性樹脂が残存している状態の硬化物を意味する。
本開示において、「硬化物」とは、樹脂組成物の硬化物を示査走査熱分析測定した際に、熱硬化性樹脂の硬化に伴う発熱ピークが現れない状態にある硬化物を意味する。すなわち、硬化物とは、未硬化の熱硬化性樹脂が残存していない状態の硬化物を意味する。
本開示において、「最大高さ粗さＲｚ」は、ＪＩＳ Ｂ ０６０１（２０１３）（対応ＩＳＯ：ＩＳＯ ４２８７ １９９７）に準拠して測定する。
本開示において、「重量平均分子量」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて、ポリスチレン換算により求める。 In the present disclosure, the numerical ranges indicated using "to" include the numerical values before and after "to" as the minimum and maximum values, respectively. In the numerical ranges indicated in stages in the present disclosure, the upper limit or lower limit indicated in one numerical range may be replaced with the upper limit or lower limit of another numerical range indicated in stages.
In the present disclosure, each component may contain multiple types of the corresponding substance. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.
In the present disclosure, multiple types of particles corresponding to each component may be included. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
In this disclosure, the term "lamination" refers to stacking layers, where two or more layers may be bonded together or two or more layers may be removable.
In this disclosure, the term "hollow silica particles" refers to a group of multiple hollow silica particles, unless otherwise specified.
In the present disclosure, the "BET specific surface area" is determined by the BET method based on the nitrogen adsorption method using a specific surface area/pore distribution measuring device (for example, "Tristar II" manufactured by Micromeritics, etc.).
In the present disclosure, "sphericity" refers to the average value obtained by measuring the maximum diameter (DL) and the minor diameter (DS) perpendicular to the maximum diameter (DL) of each of 100 random particles in a photographic projection obtained by photographing with a scanning electron microscope (SEM) and calculating the ratio (DS/DL) of the minimum diameter (DS) to the maximum diameter (DL).
In the present disclosure, the "dielectric tangent" and the "relative dielectric constant" are measured by a perturbation resonator method using a dedicated device (for example, "Vector Network Analyzer E5063A" manufactured by Keycom Corporation).
In the present disclosure, the term "semi-cured product" refers to a cured product in a state where an exothermic peak associated with the curing of a thermosetting resin appears when the cured product of a resin composition is measured by differential scanning calorimetry. In other words, the term "semi-cured product" refers to a cured product in a state where uncured thermosetting resin remains.
In the present disclosure, the term "cured product" refers to a cured product in a state where no exothermic peak associated with the curing of the thermosetting resin appears when the cured product of the resin composition is measured by differential scanning calorimetry. In other words, the term "cured product" refers to a cured product in a state where no uncured thermosetting resin remains.
In this disclosure, the "maximum height roughness Rz" is measured in accordance with JIS B 0601 (2013) (corresponding ISO: ISO 4287 1997).
In the present disclosure, the "weight average molecular weight" is determined using gel permeation chromatography (GPC) in terms of polystyrene.
第１の実施形態に係る樹脂組成物（以下、「本組成物１」とも記す。）は、樹脂及び中空シリカ粒子を含み、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた前記中空シリカ粒子の密度をＡ（ｇ／ｃｍ３）、前記中空シリカ粒子のＢＥＴ比表面積をＢ１（ｍ２／ｇ）としたとき、Ａ×Ｂ１が、１．０～１２０．０ｍ２／ｃｍ３である。
The resin composition according to the first embodiment (hereinafter also referred to as "composition 1") contains a resin and hollow silica particles, and when the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is A (g/cm 3 ), and the BET specific surface area of the hollow silica particles is B1 (m 2 /g), A×B1 is 1.0 to 120.0 m 2 /cm 3 .
本組成物１によれば、低比誘電率であり、基材との密着性に優れるプリプレグ及び硬化物が作製可能である。この理由は必ずしも明らかではないが、以下のように推測される。
本組成物１に含まれる中空シリカ粒子は、密度ＡとＢＥＴ比表面積Ｂ１との積が、１．０～１２０．０ｍ２／ｃｍ３である。これにより、樹脂組成物における、中空シリカ粒子の分散性が向上し、樹脂組成物の粘度が低下する結果、上記効果が奏されると推測される。 A prepreg and a cured product having a low dielectric constant and excellent adhesion to a substrate can be produced by using Composition 1. The reason for this is not entirely clear, but is presumed to be as follows.
The hollow silica particles contained in composition 1 have a product of density A and BET specific surface area B1 of 1.0 to 120.0 m 2 /cm 3. This improves the dispersibility of the hollow silica particles in the resin composition and reduces the viscosity of the resin composition, which is presumably why the above-mentioned effects are achieved.
本組成物１に含まれる中空シリカ粒子は、密度ＡとＢＥＴ比表面積Ｂ１との積が、１．０～１２０．０ｍ２／ｃｍ３である。これにより、樹脂組成物における、中空シリカ粒子の分散性が向上し、樹脂組成物の粘度が低下する結果、上記効果が奏されると推測される。 A prepreg and a cured product having a low dielectric constant and excellent adhesion to a substrate can be produced by using Composition 1. The reason for this is not entirely clear, but is presumed to be as follows.
The hollow silica particles contained in composition 1 have a product of density A and BET specific surface area B1 of 1.0 to 120.0 m 2 /cm 3. This improves the dispersibility of the hollow silica particles in the resin composition and reduces the viscosity of the resin composition, which is presumably why the above-mentioned effects are achieved.
第２の実施形態に係る樹脂組成物（以下、「本組成物２」とも記す。）は、樹脂及び中空シリカ粒子を含み、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた中空シリカ粒子及び樹脂の密度を、それぞれ、Ａ（ｇ／ｃｍ３）、及びＢ２（ｇ／ｃｍ３）としたとき、Ａ／Ｂ２が、０．３～１．５である。
The resin composition according to the second embodiment (hereinafter also referred to as "composition 2") contains a resin and hollow silica particles, and when the densities of the hollow silica particles and the resin determined by a constant volume expansion method using argon gas and a dry pycnometer are A (g/cm 3 ) and B2 (g/cm 3 ), respectively, A/B2 is 0.3 to 1.5.
本組成物２によれば、比誘電率のばらつきが小さいプリプレグ及び硬化物が作製可能である。この理由は必ずしも明らかではないが、以下のように推測される。
本組成物２に含まれる樹脂及び中空シリカ粒子の密度比Ａ／Ｂ２は０．３～１．５である。これにより、樹脂組成物において、中空シリカ粒子の過度な沈降又は浮遊を抑制でき、作製したプリプレグ及び硬化物中において、中空シリカ粒子が不均一に存在してしまうことを抑制でき、上記効果が奏されると推測される。 It is possible to produce a prepreg and a cured product having a small variation in the relative dielectric constant by using Composition 2. The reason for this is not entirely clear, but is presumed to be as follows.
The density ratio A/B2 of the resin and hollow silica particles contained in Composition 2 is 0.3 to 1.5. This makes it possible to suppress excessive settling or floating of the hollow silica particles in the resin composition, and to suppress the hollow silica particles from being unevenly present in the produced prepreg and cured product, which is presumably why the above-mentioned effects are achieved.
本組成物２に含まれる樹脂及び中空シリカ粒子の密度比Ａ／Ｂ２は０．３～１．５である。これにより、樹脂組成物において、中空シリカ粒子の過度な沈降又は浮遊を抑制でき、作製したプリプレグ及び硬化物中において、中空シリカ粒子が不均一に存在してしまうことを抑制でき、上記効果が奏されると推測される。 It is possible to produce a prepreg and a cured product having a small variation in the relative dielectric constant by using Composition 2. The reason for this is not entirely clear, but is presumed to be as follows.
The density ratio A/B2 of the resin and hollow silica particles contained in Composition 2 is 0.3 to 1.5. This makes it possible to suppress excessive settling or floating of the hollow silica particles in the resin composition, and to suppress the hollow silica particles from being unevenly present in the produced prepreg and cured product, which is presumably why the above-mentioned effects are achieved.
以下、本組成物１及び本組成物２を包括的に「本組成物」と記すことがある。
Hereinafter, Composition 1 and Composition 2 may be collectively referred to as "Composition."
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製しやすい観点から、本組成物の粘度は、１００～１０，０００ｍＰａ・ｓが好ましく、１３０～５，０００ｍＰａ・ｓがより好ましく、１５０～３，０００ｍＰａ・ｓが更に好ましく、１８０～１，５００ｍＰａ・ｓが特に好ましく、２００～１，０００ｍＰａ・ｓが最も好ましい。
本開示において「粘度」は、２５℃において、回転式レオメータ（例えば、アントンパール（Ａｎｔｏｎ ｐａａｒ）社製、モジュラーレオメーター ＰｈｙｓｉｃａＭＣＲ－３０１）を用いて、せん断速度１ｒｐｍで３０秒測定し、得られた３０秒時点での粘度を測定して得られる値である。 In composition 1, from the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate, or in composition 2, from the viewpoint of easily producing a prepreg and a cured product having a small variation in the dielectric constant, the viscosity of the composition is preferably 100 to 10,000 mPa·s, more preferably 130 to 5,000 mPa·s, even 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.
In this disclosure, "viscosity" refers to a value obtained by measuring the viscosity at 30 seconds at 25°C using a rotational rheometer (e.g., Modular Rheometer Physica MCR-301 manufactured by Anton Paar) at a shear rate of 1 rpm.
本開示において「粘度」は、２５℃において、回転式レオメータ（例えば、アントンパール（Ａｎｔｏｎ ｐａａｒ）社製、モジュラーレオメーター ＰｈｙｓｉｃａＭＣＲ－３０１）を用いて、せん断速度１ｒｐｍで３０秒測定し、得られた３０秒時点での粘度を測定して得られる値である。 In composition 1, from the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate, or in composition 2, from the viewpoint of easily producing a prepreg and a cured product having a small variation in the dielectric constant, the viscosity of the composition is preferably 100 to 10,000 mPa·s, more preferably 130 to 5,000 mPa·s, even 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.
In this disclosure, "viscosity" refers to a value obtained by measuring the viscosity at 30 seconds at 25°C using a rotational rheometer (e.g., Modular Rheometer Physica MCR-301 manufactured by Anton Paar) at a shear rate of 1 rpm.
本組成物は、２５℃において、液状であることが好ましい。
The composition is preferably liquid at 25°C.
本組成物は、樹脂を１種含んでもよく、２種以上含んでもよい。本組成物が含む樹脂としては、熱硬化性樹脂が好ましい。本組成物は、熱硬化性樹脂を２種以上含んでもよいが、１種を含むことが好ましい。
熱硬化性樹脂としては、エポキシ樹脂、ポリフェニレンエーテル樹脂、ポリエステル樹脂、ポリイミド樹脂、フェノール樹脂、ジビニルベンゼン骨格を含む樹脂、ピリミジン骨格を含む樹脂等が挙げられる。密着性、耐熱性等の観点から、熱硬化性樹脂は、エポキシ樹脂、ポリイミド樹脂、ポリフェニレンエーテル樹脂、ジビニルベンゼン骨格を含む樹脂、及びピリミジン骨格を含む樹脂から選択される１つ以上が好ましい。 The composition may contain one type of resin or two or more types. The resin contained in the composition is preferably a thermosetting resin. The composition may contain two or more types of thermosetting resin, but preferably contains one type.
Examples of the thermosetting resin include epoxy resin, polyphenylene ether resin, polyester resin, polyimide resin, phenol resin, resin containing a divinylbenzene skeleton, resin containing a pyrimidine skeleton, etc. From the viewpoint of adhesion, heat resistance, etc., the thermosetting resin is preferably one or more selected from epoxy resin, polyimide resin, polyphenylene ether resin, resin containing a divinylbenzene skeleton, and resin containing a pyrimidine skeleton.
熱硬化性樹脂としては、エポキシ樹脂、ポリフェニレンエーテル樹脂、ポリエステル樹脂、ポリイミド樹脂、フェノール樹脂、ジビニルベンゼン骨格を含む樹脂、ピリミジン骨格を含む樹脂等が挙げられる。密着性、耐熱性等の観点から、熱硬化性樹脂は、エポキシ樹脂、ポリイミド樹脂、ポリフェニレンエーテル樹脂、ジビニルベンゼン骨格を含む樹脂、及びピリミジン骨格を含む樹脂から選択される１つ以上が好ましい。 The composition may contain one type of resin or two or more types. The resin contained in the composition is preferably a thermosetting resin. The composition may contain two or more types of thermosetting resin, but preferably contains one type.
Examples of the thermosetting resin include epoxy resin, polyphenylene ether resin, polyester resin, polyimide resin, phenol resin, resin containing a divinylbenzene skeleton, resin containing a pyrimidine skeleton, etc. From the viewpoint of adhesion, heat resistance, etc., the thermosetting resin is preferably one or more selected from epoxy resin, polyimide resin, polyphenylene ether resin, resin containing a divinylbenzene skeleton, and resin containing a pyrimidine skeleton.
エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、脂環式エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、多官能フェノールのジグリシジルエーテル化物、多官能アルコールのジグリシジルエーテル化物等が挙げられる。
ポリイミド樹脂としては、芳香族ポリイミド、芳香族ポリアミック酸等が挙げられる。
ポリフェニレンエーテル樹脂は、変性ポリフェニレンエーテルであってもよく、未変性ポリフェニレンエーテルであってもよいが、密着性の観点からは、変性ポリフェニレンエーテルが好ましい。変性ポリフェニレンエーテルは、ポリフェニレンエーテル鎖及びポリフェニレンエーテル鎖の末端に結合する置換基を有する。置換基は、炭素－炭素二重結合を有することが好ましい。置換基は、下記式（１）又は下記式（２）で表されることが好ましく、下記式（２）で表されることがより好ましい。 Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, alicyclic epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, diglycidyl ethers of polyfunctional phenols, and diglycidyl ethers of polyfunctional alcohols.
Examples of the polyimide resin include aromatic polyimide and aromatic polyamic acid.
The polyphenylene ether resin may be modified polyphenylene ether or unmodified polyphenylene ether, but from the viewpoint of adhesion, 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 (2), more preferably represented by the following formula (2).
ポリイミド樹脂としては、芳香族ポリイミド、芳香族ポリアミック酸等が挙げられる。
ポリフェニレンエーテル樹脂は、変性ポリフェニレンエーテルであってもよく、未変性ポリフェニレンエーテルであってもよいが、密着性の観点からは、変性ポリフェニレンエーテルが好ましい。変性ポリフェニレンエーテルは、ポリフェニレンエーテル鎖及びポリフェニレンエーテル鎖の末端に結合する置換基を有する。置換基は、炭素－炭素二重結合を有することが好ましい。置換基は、下記式（１）又は下記式（２）で表されることが好ましく、下記式（２）で表されることがより好ましい。 Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, alicyclic epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, diglycidyl ethers of polyfunctional phenols, and diglycidyl ethers of polyfunctional alcohols.
Examples of the polyimide resin include aromatic polyimide and aromatic polyamic acid.
The polyphenylene ether resin may be modified polyphenylene ether or unmodified polyphenylene ether, but from the viewpoint of adhesion, 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 (2), more preferably represented by the following formula (2).
式（１）において、ｎは０～１０の整数であり、Ｚはアリーレン基であり、Ｒ１～Ｒ３は各々独立に水素又はアルキル基である。なお、式（１）におけるｎが０である場合は、Ｚは変性ポリフェニレンエーテルにおけるポリフェニレンエーテル鎖の末端に直接結合する。式（２）において、Ｒ４は水素又はアルキル基である。式（１）及び（２）において、アルキル基は、炭素数１～１０が好ましく、１～６がより好ましい。
In formula (1), n is an integer of 0 to 10, Z is an arylene group, and R 1 to R 3 are each independently hydrogen or an alkyl group. 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.
ポリフェニレンエーテル鎖は、下記式（３）で表されることが好ましい。
The polyphenylene ether chain is preferably represented by the following formula (3):
式（３）において、ｍは１～５０の範囲内の数であり、Ｒ５～Ｒ８は、各々独立に、水素原子、アルキル基、アルケニル基、アルキニル基、ホルミル基、アルキルカルボニル基、アルケニルカルボニル基又はアルキニルカルボニル基であり、水素原子又はアルキル基が好ましい。式（３）において、アルキル基は、炭素数１～１０が好ましく、１～６がより好ましい。
In formula (3), m is a number within the range of 1 to 50, and R 5 to 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, with a hydrogen atom or an alkyl group being preferred. In formula (3), the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
ジビニルベンゼン骨格を含む樹脂としては、日鉄ケミカル＆マテリアル株式会社製の、ＯＤＶ―ＸＥＴ等が挙げられる。
An example of a resin containing a divinylbenzene skeleton is ODV-XET manufactured by Nippon Steel Chemical & Material Co., Ltd.
ピリミジン骨格を含む樹脂としては、ＪＳＲ社製ＥＬＰＡＣ ＨＣ－Ｆシリーズ等が挙げられる。
Examples of resins containing a pyrimidine skeleton include the ELPAC HC-F series manufactured by JSR Corporation.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、半硬化物及び硬化物の密着性及び誘電特性を向上する観点から、熱硬化性樹脂の重量平均分子量（Ｍｗ）は、１，０００～７，０００が好ましく、１，０００～５，０００がより好ましく、１，０００～３，０００が更に好ましい。
In the present composition 1, from the viewpoint of further reducing the relative dielectric constant and further improving adhesion to the substrate, or in the present composition 2, from the viewpoint of improving the adhesion and dielectric properties of the semi-cured product 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 even more preferably 1,000 to 3,000.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、半硬化物及び硬化物の密着性及び誘電特性を向上する観点から、本組成物の総質量に対する硬化性樹脂の含有率は、１０～４０質量％が好ましく、１５～３５質量％がより好ましく、２０～３０質量％が更に好ましい。
In the present composition 1, from the viewpoint of further reducing the relative dielectric constant and further improving adhesion to the substrate, or in the present composition 2, from the viewpoint of improving the adhesion and dielectric properties of the semi-cured product and the cured product, the content of the curable resin relative to the total mass of the present composition is preferably 10 to 40 mass%, more preferably 15 to 35 mass%, and even more preferably 20 to 30 mass%.
本組成物は、熱硬化性樹脂以外の樹脂（以下、「その他の樹脂」とも記す。）を含んでいてもよい。その他の樹脂としては、ポリテトラフルオロエチレン、ポリエチレンテレフタラート、ポリオレフィン、シリコーン等が挙げられる。
The composition may contain resins other than thermosetting resins (hereinafter, also referred to as "other resins"). Examples of other resins include polytetrafluoroethylene, polyethylene terephthalate, polyolefins, silicones, etc.
本組成物の総質量に対するその他の樹脂の含有率は、特に限定されるものではなく、例えば、１～５０質量％である。
The content of other resins relative to the total mass of the composition is not particularly limited, and is, for example, 1 to 50 mass%.
比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点から、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた樹脂の密度は、０．５～３．０ｇ／ｃｍ３が好ましく、０．８～２．３ｇ／ｃｍ３がより好ましい。
なお、樹脂の密度測定は、２５℃において、乾燥後の樹脂に対して行う。熱硬化性樹脂の場合は、硬化後の樹脂に対して行う。密度測定の方法としては、硬化後の樹脂を上記のように乾式ピクノメーターで測定する方法が挙げられる。
なお、本組成物が、２種以上の樹脂を含む場合、樹脂の密度は、乾燥後又は熱硬化性樹脂の場合は熱硬化後の組成物の密度を、Ａｒピクノメーターによって実測して求める。
なお、本組成物は、後述するように、重合開始剤、重合促進剤、可塑剤、及び他の成分を含んでもよい。重合開始剤、重合促進剤、可塑剤、及び他の成分に、樹脂又は反応により樹脂に組み込まれる成分が含まれる場合には、当該樹脂又は成分も、樹脂の密度の算出における「樹脂」に含めるものとする。すなわち、本組成物に含まれる、樹脂又は反応により樹脂に組み込まれる成分の全体を、樹脂の密度の算出における「樹脂」とみなす。本開示におけるＡ／Ｂ２の算出についても同様である。 From the viewpoint of producing a prepreg and a cured product with small variation in the relative dielectric constant, the density of the resin determined by a constant volume expansion method using argon gas and a dry pycnometer is preferably 0.5 to 3.0 g/ cm3 , and more preferably 0.8 to 2.3 g/ cm3 .
The density of the resin is measured at 25° C. after drying. In the case of a thermosetting resin, the density is measured after curing. The density can be measured by measuring the density of the cured resin with a dry pycnometer as described above.
When the composition contains two or more resins, the density of the resin is determined by measuring the density of the composition after drying or, in the case of a thermosetting resin, after heat curing, using an Ar pycnometer.
In addition, the present composition may contain a polymerization initiator, a polymerization accelerator, a plasticizer, and other components, as described below. When the polymerization initiator, the polymerization accelerator, the plasticizer, and other components include a resin or a component that is incorporated into the resin by reaction, the resin or component is also included in the "resin" in calculating the density of the resin. In other words, the entire resin or components that are incorporated into the resin by reaction and that are included in the present composition are considered to be the "resin" in calculating the density of the resin. The same applies to the calculation of A/B2 in the present disclosure.
なお、樹脂の密度測定は、２５℃において、乾燥後の樹脂に対して行う。熱硬化性樹脂の場合は、硬化後の樹脂に対して行う。密度測定の方法としては、硬化後の樹脂を上記のように乾式ピクノメーターで測定する方法が挙げられる。
なお、本組成物が、２種以上の樹脂を含む場合、樹脂の密度は、乾燥後又は熱硬化性樹脂の場合は熱硬化後の組成物の密度を、Ａｒピクノメーターによって実測して求める。
なお、本組成物は、後述するように、重合開始剤、重合促進剤、可塑剤、及び他の成分を含んでもよい。重合開始剤、重合促進剤、可塑剤、及び他の成分に、樹脂又は反応により樹脂に組み込まれる成分が含まれる場合には、当該樹脂又は成分も、樹脂の密度の算出における「樹脂」に含めるものとする。すなわち、本組成物に含まれる、樹脂又は反応により樹脂に組み込まれる成分の全体を、樹脂の密度の算出における「樹脂」とみなす。本開示におけるＡ／Ｂ２の算出についても同様である。 From the viewpoint of producing a prepreg and a cured product with small variation in the relative dielectric constant, the density of the resin determined by a constant volume expansion method using argon gas and a dry pycnometer is preferably 0.5 to 3.0 g/ cm3 , and more preferably 0.8 to 2.3 g/ cm3 .
The density of the resin is measured at 25° C. after drying. In the case of a thermosetting resin, the density is measured after curing. The density can be measured by measuring the density of the cured resin with a dry pycnometer as described above.
When the composition contains two or more resins, the density of the resin is determined by measuring the density of the composition after drying or, in the case of a thermosetting resin, after heat curing, using an Ar pycnometer.
In addition, the present composition may contain a polymerization initiator, a polymerization accelerator, a plasticizer, and other components, as described below. When the polymerization initiator, the polymerization accelerator, the plasticizer, and other components include a resin or a component that is incorporated into the resin by reaction, the resin or component is also included in the "resin" in calculating the density of the resin. In other words, the entire resin or components that are incorporated into the resin by reaction and that are included in the present composition are considered to be the "resin" in calculating the density of the resin. The same applies to the calculation of A/B2 in the present disclosure.
中空シリカ粒子は、シリカを含むシェル層を備え、シェル層の内側に空間部を有する。上記空間部は、透過型電子顕微鏡（ＴＥＭ）観察、走査型電子顕微鏡（ＳＥＭ）等により確認できる。
本開示において、「シェル層の内側に空間部を有する」とは、１個の中空シリカ粒子の断面を観察した際に、１個の空間部の周囲をシェル層が囲んでいる中空状態が存在することを意味する。
シェル層は、単層構造を有するものであっても、２層以上の多層構造を有するものであってもよい。 The hollow silica particles have a shell layer containing silica and have a space inside the shell layer. The space can be confirmed by observation with a transmission electron microscope (TEM), a scanning electron microscope (SEM), or the like.
In the present disclosure, "having a space inside the shell layer" means that when a cross-section of a single hollow silica particle is observed, a hollow state exists in which a single space is surrounded by a shell layer.
The shell layer may have a single-layer structure or a multi-layer structure having two or more layers.
本開示において、「シェル層の内側に空間部を有する」とは、１個の中空シリカ粒子の断面を観察した際に、１個の空間部の周囲をシェル層が囲んでいる中空状態が存在することを意味する。
シェル層は、単層構造を有するものであっても、２層以上の多層構造を有するものであってもよい。 The hollow silica particles have a shell layer containing silica and have a space inside the shell layer. The space can be confirmed by observation with a transmission electron microscope (TEM), a scanning electron microscope (SEM), or the like.
In the present disclosure, "having a space inside the shell layer" means that when a cross-section of a single hollow silica particle is observed, a hollow state exists in which a single space is surrounded by a shell layer.
The shell layer may have a single-layer structure or a multi-layer structure having two or more layers.
シェル層の総質量に対するシリカの含有率は、５０質量％以上が好ましく、８０質量％以上がより好ましく、９５質量％以上が更に好ましい。上記含有率の上限は、１００質量％であるが、９９．９９質量％が好ましい。
中空シリカ粒子の耐久性を向上する観点、並びに半硬化物及び硬化物の密着性及び誘電特性を向上する観点から、シェル層は、周期表の第１族又は第２族に属するアルカリ金属分、及びこれらのケイ酸塩から選択される少なくとも１つを含むことが好ましい。なお、本開示において、半硬化物及び硬化物の誘電特性を向上するとは、これらの比誘電率及び誘電正接を低下させることを意味する。
シェル層の総質量に対する周期表の第１族又は第２族に属するアルカリ金属分の含有率は、３０質量ｐｐｍ以上が好ましく、１００質量ｐｐｍ以上がより好ましく、１５０質量ｐｐｍ以上が更に好ましく、３００質量ｐｐｍ以上が特に好ましい。また、前記含有率は、１質量％以下が好ましく、５０００質量ｐｐｍ以下がより好ましく、１０００質量ｐｐｍ以下が最も好ましい。
すなわち、シェル層の総質量に対する周期表の第１族又は第２族に属するアルカリ金属
分の含有率は、３０質量ｐｐｍ～１質量％が好ましく、１００質量ｐｐｍ～５０００質量
ｐｐｍがより好ましく、１５０質量ｐｐｍ～１０００質量ｐｐｍがさらに好ましい。
シェル層の組成は、ＩＣＰ発光分析法、フレーム原子吸光法等により測定する。
周期表の第１族又は第２族に属するアルカリ金属分（アルカリ金属及びアルカリ土類金属）の中でも、入手の容易さの観点から、シェル層は、ナトリウム、カリウム、マグネシウム、カルシウム及びストロンチウムより選択される１つ以上を含むことが好ましく、ナトリウム、マグネシウム及びカルシウムより選択される１つ以上を含むことがより好ましい。 The content of silica in the shell layer is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 95% by mass or more, with the upper limit of the content being 100% by mass, and preferably 99.99% by mass.
From the viewpoint of improving the durability of the hollow silica particles and the adhesion and dielectric properties of the semi-cured product and the cured product, the shell layer preferably contains at least one selected from alkali metals belonging to Groups 1 and 2 of the periodic table and their silicates. In the present disclosure, improving the dielectric properties of the semi-cured product and the cured product means reducing the dielectric constant and dielectric loss tangent thereof.
The content of alkali metals belonging to Group 1 or 2 of the periodic table relative to the total mass of the shell layer is preferably 30 ppm by mass or more, more preferably 100 ppm by mass or more, even more preferably 150 ppm by mass or more, and particularly preferably 300 ppm by mass or more. The content is preferably 1% by mass or less, more preferably 5000 ppm by mass or less, and most preferably 1000 ppm by mass or less.
That is, the content of alkali metals belonging to Group 1 or 2 of the periodic table relative to the total mass of the shell layer is preferably 30 ppm by mass to 1 mass%, more preferably 100 ppm by mass to 5000 ppm by mass, and even more preferably 150 ppm by mass to 1000 ppm by mass.
The composition of the shell layer is measured by ICP emission spectrometry, flame atomic absorption spectrometry, or the like.
From the viewpoint of ease of availability, among the alkali metal components (alkali metals and alkaline earth metals) belonging to Group 1 or 2 of the periodic table, 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.
中空シリカ粒子の耐久性を向上する観点、並びに半硬化物及び硬化物の密着性及び誘電特性を向上する観点から、シェル層は、周期表の第１族又は第２族に属するアルカリ金属分、及びこれらのケイ酸塩から選択される少なくとも１つを含むことが好ましい。なお、本開示において、半硬化物及び硬化物の誘電特性を向上するとは、これらの比誘電率及び誘電正接を低下させることを意味する。
シェル層の総質量に対する周期表の第１族又は第２族に属するアルカリ金属分の含有率は、３０質量ｐｐｍ以上が好ましく、１００質量ｐｐｍ以上がより好ましく、１５０質量ｐｐｍ以上が更に好ましく、３００質量ｐｐｍ以上が特に好ましい。また、前記含有率は、１質量％以下が好ましく、５０００質量ｐｐｍ以下がより好ましく、１０００質量ｐｐｍ以下が最も好ましい。
すなわち、シェル層の総質量に対する周期表の第１族又は第２族に属するアルカリ金属
分の含有率は、３０質量ｐｐｍ～１質量％が好ましく、１００質量ｐｐｍ～５０００質量
ｐｐｍがより好ましく、１５０質量ｐｐｍ～１０００質量ｐｐｍがさらに好ましい。
シェル層の組成は、ＩＣＰ発光分析法、フレーム原子吸光法等により測定する。
周期表の第１族又は第２族に属するアルカリ金属分（アルカリ金属及びアルカリ土類金属）の中でも、入手の容易さの観点から、シェル層は、ナトリウム、カリウム、マグネシウム、カルシウム及びストロンチウムより選択される１つ以上を含むことが好ましく、ナトリウム、マグネシウム及びカルシウムより選択される１つ以上を含むことがより好ましい。 The content of silica in the shell layer is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 95% by mass or more, with the upper limit of the content being 100% by mass, and preferably 99.99% by mass.
From the viewpoint of improving the durability of the hollow silica particles and the adhesion and dielectric properties of the semi-cured product and the cured product, the shell layer preferably contains at least one selected from alkali metals belonging to Groups 1 and 2 of the periodic table and their silicates. In the present disclosure, improving the dielectric properties of the semi-cured product and the cured product means reducing the dielectric constant and dielectric loss tangent thereof.
The content of alkali metals belonging to Group 1 or 2 of the periodic table relative to the total mass of the shell layer is preferably 30 ppm by mass or more, more preferably 100 ppm by mass or more, even more preferably 150 ppm by mass or more, and particularly preferably 300 ppm by mass or more. The content is preferably 1% by mass or less, more preferably 5000 ppm by mass or less, and most preferably 1000 ppm by mass or less.
That is, the content of alkali metals belonging to Group 1 or 2 of the periodic table relative to the total mass of the shell layer is preferably 30 ppm by mass to 1 mass%, more preferably 100 ppm by mass to 5000 ppm by mass, and even more preferably 150 ppm by mass to 1000 ppm by mass.
The composition of the shell layer is measured by ICP emission spectrometry, flame atomic absorption spectrometry, or the like.
From the viewpoint of ease of availability, among the alkali metal components (alkali metals and alkaline earth metals) belonging to Group 1 or 2 of the periodic table, 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.
中空シリカ粒子の耐久性を向上する観点、並びに半硬化物及び硬化物の密着性及び誘電特性を向上する観点から、シェル層の平均厚みは、中空シリカ粒子の一次粒子の直径を１としたとき、０．０１～０．３が好ましく、０．０２～０．２がより好ましく、０．０３～０．１が更に好ましい。
シェル層の平均厚さは、ＴＥＭ観察により測定する２０個の中空シリカ粒子のシェル層の厚さの平均値である。 From the viewpoint 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 average thickness of the shell layer is preferably 0.01 to 0.3, more preferably 0.02 to 0.2, and even more preferably 0.03 to 0.1, relative to the diameter of the primary particle of the hollow silica particles being 1.
The average thickness of the shell layer is an average value of the thicknesses of the shell layers of 20 hollow silica particles measured by TEM observation.
シェル層の平均厚さは、ＴＥＭ観察により測定する２０個の中空シリカ粒子のシェル層の厚さの平均値である。 From the viewpoint 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 average thickness of the shell layer is preferably 0.01 to 0.3, more preferably 0.02 to 0.2, and even more preferably 0.03 to 0.1, relative to the diameter of the primary particle of the hollow silica particles being 1.
The average thickness of the shell layer is an average value of the thicknesses of the shell layers of 20 hollow silica particles measured by TEM observation.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点、並びに半硬化物及び硬化物の誘電特性を向上する観点から、中空シリカ粒子の平均一次粒子径は、１０ｎｍ～１０μｍが好ましく、２０ｎｍ～７μｍがより好ましく、５０ｎｍ～５μｍが更に好ましく、７０ｎｍ～３μｍが特に好ましく、１００ｎｍ～１μｍが最も好ましい。
中空シリカ粒子の平均一次粒子の大きさは、ＳＥＭ観察によりその粒子径（直径、球状でない場合は長辺と短辺の平均値）を直接観察することによって求められる。具体的には、ＳＥＭ画像より１００個の中空シリカ粒子の一次粒子の大きさを測定し、それらを平均して得られた一次粒子の大きさの累積分布が５０％になる値を、全体の一次粒子の平均一次粒子径と推定する。 From the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate in composition 1, or from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant in composition 2, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the average primary particle diameter of the hollow silica particles is preferably 10 nm to 10 μm, more preferably 20 nm to 7 μm, even more preferably 50 nm to 5 μm, particularly preferably 70 nm to 3 μm, and most preferably 100 nm to 1 μm.
The average primary particle size of hollow silica particles is determined by directly observing the particle diameter (diameter, the average value of the long and short sides if the particle is not spherical) by SEM observation. Specifically, the primary particle sizes of 100 hollow silica particles are measured from an SEM image, and the value at which the cumulative distribution of the primary particle sizes obtained by averaging them is 50% is estimated to be the average primary particle size of all primary particles.
中空シリカ粒子の平均一次粒子の大きさは、ＳＥＭ観察によりその粒子径（直径、球状でない場合は長辺と短辺の平均値）を直接観察することによって求められる。具体的には、ＳＥＭ画像より１００個の中空シリカ粒子の一次粒子の大きさを測定し、それらを平均して得られた一次粒子の大きさの累積分布が５０％になる値を、全体の一次粒子の平均一次粒子径と推定する。 From the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate in composition 1, or from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant in composition 2, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the average primary particle diameter of the hollow silica particles is preferably 10 nm to 10 μm, more preferably 20 nm to 7 μm, even more preferably 50 nm to 5 μm, particularly preferably 70 nm to 3 μm, and most preferably 100 nm to 1 μm.
The average primary particle size of hollow silica particles is determined by directly observing the particle diameter (diameter, the average value of the long and short sides if the particle is not spherical) by SEM observation. Specifically, the primary particle sizes of 100 hollow silica particles are measured from an SEM image, and the value at which the cumulative distribution of the primary particle sizes obtained by averaging them is 50% is estimated to be the average primary particle size of all primary particles.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点、並びに半硬化物及び硬化物の誘電特性を向上する観点から、中空シリカ粒子のメジアン径（以下、単に「ｄ５０」とも記す。）は、０．１～１０．０μｍが好ましく、０．２～１０．０μｍがより好ましく、０．２５～８．０μｍが更に好ましく、０．３～７．０μｍが特に好ましく、０．３～５．０μｍが最も好ましく、０．３～３．０μｍであってもよい。また、中空シリカ粒子のｄ５０を上記数値範囲とすることにより、プリプレグ及び硬化物の平滑性を向上でき、絶縁層を形成したときの回路における伝送損失を低減できる。
本開示において、「ｄ５０」は、レーザー回折式の粒度分布測定装置（例えば、マイクロトラック・ベル株式会社製「ＭＴ３３００ＥＸＩＩ」）により求められる中空シリカ粒子の体積基準累積５０％径である。すなわち、ｄ５０は、レーザー回折・散乱法によって粒度分布を測定し、中空シリカ粒子の全体積を１００％として累積カーブを求め、その累積カーブ上で累積体積が５０％となる点の粒子径である。
なお、本開示において、中空シリカ粒子のｄ５０は、一次粒子及び二次粒子を含む状態で測定する。 From the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate in the present composition 1, or from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant in the present composition 2, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the median diameter (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, even more 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 be 0.3 to 3.0 μm. Furthermore, by setting the d50 of the hollow silica particles to the above numerical range, the smoothness of the prepreg and the cured product can be improved, and the transmission loss in the circuit when an insulating layer is formed can be reduced.
In the present disclosure, "d50" refers to the volume-based cumulative 50% diameter of hollow silica particles determined by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII" manufactured by Microtrack Bell Co., Ltd.). That is, d50 refers to the particle diameter at the point on the cumulative curve where the cumulative volume is 50% when the particle size distribution is measured by a laser diffraction/scattering method and a cumulative curve is calculated with the total volume of the hollow silica particles set to 100%.
In the present disclosure, the d50 of the hollow silica particles is measured in a state including primary particles and secondary particles.
本開示において、「ｄ５０」は、レーザー回折式の粒度分布測定装置（例えば、マイクロトラック・ベル株式会社製「ＭＴ３３００ＥＸＩＩ」）により求められる中空シリカ粒子の体積基準累積５０％径である。すなわち、ｄ５０は、レーザー回折・散乱法によって粒度分布を測定し、中空シリカ粒子の全体積を１００％として累積カーブを求め、その累積カーブ上で累積体積が５０％となる点の粒子径である。
なお、本開示において、中空シリカ粒子のｄ５０は、一次粒子及び二次粒子を含む状態で測定する。 From the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate in the present composition 1, or from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant in the present composition 2, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the median diameter (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, even more 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 be 0.3 to 3.0 μm. Furthermore, by setting the d50 of the hollow silica particles to the above numerical range, the smoothness of the prepreg and the cured product can be improved, and the transmission loss in the circuit when an insulating layer is formed can be reduced.
In the present disclosure, "d50" refers to the volume-based cumulative 50% diameter of hollow silica particles determined by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII" manufactured by Microtrack Bell Co., Ltd.). That is, d50 refers to the particle diameter at the point on the cumulative curve where the cumulative volume is 50% when the particle size distribution is measured by a laser diffraction/scattering method and a cumulative curve is calculated with the total volume of the hollow silica particles set to 100%.
In the present disclosure, the d50 of the hollow silica particles is measured in a state including primary particles and secondary particles.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点、並びに半硬化物及び硬化物の誘電特性を向上する観点から、中空シリカ粒子のｄ１０は、０．１～２．０μｍが好ましく、０．２～２．０μｍがより好ましく、０．３～１．８μｍが更に好ましく、０．３～１．５μｍが特に好ましい。また、中空シリカ粒子のｄ１０を上記数値範囲とすることにより、プリプレグ及び硬化物の平滑性を向上でき、絶縁層を形成したときの回路における伝送損失を低減できる。
本開示において、「ｄ１０」は、レーザー回折式の粒度分布測定装置（例えば、マイクロトラック・ベル株式会社製「ＭＴ３３００ＥＸＩＩ」）により求められる中空シリカ粒子の体積基準累積１０％径である。すなわち、ｄ１０は、レーザー回折・散乱法によって粒度分布を測定し、中空シリカ粒子の全体積を１００％として累積カーブを求め、その累積カーブ上で累積体積が１０％となる点の粒子径である。
なお、本開示において、中空シリカ粒子のｄ１０は、一次粒子及び二次粒子を含む状態で測定する。 From the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate in the present composition 1, or from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant in the present composition 2, and from the viewpoint of improving the dielectric properties of the semi-cured product and the cured product, the d10 of the hollow silica particles is preferably 0.1 to 2.0 μm, more preferably 0.2 to 2.0 μm, even more preferably 0.3 to 1.8 μm, and particularly preferably 0.3 to 1.5 μm. Furthermore, by setting the d10 of the hollow silica particles to the above numerical range, the smoothness of the prepreg and the cured product can be improved, and the transmission loss in the circuit when an insulating layer is formed can be reduced.
In the present disclosure, "d10" is the volume-based cumulative 10% diameter of hollow silica particles obtained by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII" manufactured by Microtrack-Bell Co., Ltd.). That is, d10 is the particle diameter at the point where the cumulative volume is 10% on a cumulative curve obtained by measuring the particle size distribution by a laser diffraction/scattering method and assuming the total volume of the hollow silica particles to be 100%.
In the present disclosure, the d10 of the hollow silica particles is measured in a state including primary particles and secondary particles.
本開示において、「ｄ１０」は、レーザー回折式の粒度分布測定装置（例えば、マイクロトラック・ベル株式会社製「ＭＴ３３００ＥＸＩＩ」）により求められる中空シリカ粒子の体積基準累積１０％径である。すなわち、ｄ１０は、レーザー回折・散乱法によって粒度分布を測定し、中空シリカ粒子の全体積を１００％として累積カーブを求め、その累積カーブ上で累積体積が１０％となる点の粒子径である。
なお、本開示において、中空シリカ粒子のｄ１０は、一次粒子及び二次粒子を含む状態で測定する。 From the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate in the present composition 1, or from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant in the present composition 2, and from the viewpoint of improving the dielectric properties of the semi-cured product and the cured product, the d10 of the hollow silica particles is preferably 0.1 to 2.0 μm, more preferably 0.2 to 2.0 μm, even more preferably 0.3 to 1.8 μm, and particularly preferably 0.3 to 1.5 μm. Furthermore, by setting the d10 of the hollow silica particles to the above numerical range, the smoothness of the prepreg and the cured product can be improved, and the transmission loss in the circuit when an insulating layer is formed can be reduced.
In the present disclosure, "d10" is the volume-based cumulative 10% diameter of hollow silica particles obtained by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII" manufactured by Microtrack-Bell Co., Ltd.). That is, d10 is the particle diameter at the point where the cumulative volume is 10% on a cumulative curve obtained by measuring the particle size distribution by a laser diffraction/scattering method and assuming the total volume of the hollow silica particles to be 100%.
In the present disclosure, the d10 of the hollow silica particles is measured in a state including primary particles and secondary particles.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点、並びに半硬化物及び硬化物の誘電特性を向上する観点から、中空シリカ粒子のｄ９０は、０．７～１５．０μｍが好ましく、０．８～１２．０μｍがより好ましく、０．９～１０．０μｍが更に好ましく、０．９～８．０μｍが特に好ましく、０．９～６．０μｍが最も好ましく、０．９～５．０μｍであってもよい。また、中空シリカ粒子のｄ９０を上記数値範囲とすることにより、プリプレグ及び硬化物の平滑性を向上でき、絶縁層を形成したときの回路における伝送損失を低減できる。
本開示において、「ｄ９０」は、レーザー回折式の粒度分布測定装置（例えば、マイクロトラック・ベル株式会社製「ＭＴ３３００ＥＸＩＩ」）により求められる中空シリカ粒子の体積基準累積９０％径である。すなわち、ｄ９０は、レーザー回折・散乱法によって粒度分布を測定し、中空シリカ粒子の全体積を１００％として累積カーブを求め、その累積カーブ上で累積体積が９０％となる点の粒子径である。
なお、本開示において、中空シリカ粒子のｄ９０は、一次粒子及び二次粒子を含む状態で測定する。 From the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate in the present composition 1, or from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant in the present composition 2, and from the viewpoint of improving the dielectric properties of the semi-cured product and the cured product, the d90 of the hollow silica particles is preferably 0.7 to 15.0 μm, more preferably 0.8 to 12.0 μm, even 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. Furthermore, by setting the d90 of the hollow silica particles to the above numerical range, the smoothness of the prepreg and the cured product can be improved, and the transmission loss in the circuit when an insulating layer is formed can be reduced.
In the present disclosure, "d90" refers to the volume-based cumulative 90% diameter of hollow silica particles determined by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII" manufactured by Microtrack-Bell Co., Ltd.). That is, d90 refers to the particle diameter at the point on the cumulative curve where the cumulative volume is 90% when the particle size distribution is measured by a laser diffraction/scattering method and a cumulative curve is calculated with the total volume of the hollow silica particles being 100%.
In the present disclosure, the d90 of the hollow silica particles is measured in a state including primary particles and secondary particles.
本開示において、「ｄ９０」は、レーザー回折式の粒度分布測定装置（例えば、マイクロトラック・ベル株式会社製「ＭＴ３３００ＥＸＩＩ」）により求められる中空シリカ粒子の体積基準累積９０％径である。すなわち、ｄ９０は、レーザー回折・散乱法によって粒度分布を測定し、中空シリカ粒子の全体積を１００％として累積カーブを求め、その累積カーブ上で累積体積が９０％となる点の粒子径である。
なお、本開示において、中空シリカ粒子のｄ９０は、一次粒子及び二次粒子を含む状態で測定する。 From the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate in the present composition 1, or from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant in the present composition 2, and from the viewpoint of improving the dielectric properties of the semi-cured product and the cured product, the d90 of the hollow silica particles is preferably 0.7 to 15.0 μm, more preferably 0.8 to 12.0 μm, even 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. Furthermore, by setting the d90 of the hollow silica particles to the above numerical range, the smoothness of the prepreg and the cured product can be improved, and the transmission loss in the circuit when an insulating layer is formed can be reduced.
In the present disclosure, "d90" refers to the volume-based cumulative 90% diameter of hollow silica particles determined by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII" manufactured by Microtrack-Bell Co., Ltd.). That is, d90 refers to the particle diameter at the point on the cumulative curve where the cumulative volume is 90% when the particle size distribution is measured by a laser diffraction/scattering method and a cumulative curve is calculated with the total volume of the hollow silica particles being 100%.
In the present disclosure, the d90 of the hollow silica particles is measured in a state including primary particles and secondary particles.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点、並びに半硬化物及び硬化物の誘電特性を向上する観点から、ｄ５０／ｄ１０は、６．０以下が好ましく、５．０以下がより好ましく、３．０以下が更に好ましく、２．５以下が特に好ましい。ｄ５０／ｄ１０の下限値は、特に限定されるものではなく、１．３とすることができる。
In the present composition 1, from the viewpoint of further reducing the relative dielectric constant and further improving adhesion to the substrate, or in the present composition 2, from the viewpoint of producing a prepreg and a cured product with a small variation in the relative dielectric constant, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, d50/d10 is preferably 6.0 or less, more preferably 5.0 or less, even more preferably 3.0 or less, and particularly preferably 2.5 or less. The lower limit of d50/d10 is not particularly limited, and can be 1.3.
半硬化物及び硬化物の平滑性を向上する観点から、中空シリカ粒子のコールターカウンター法により測定された１０μｍ以上の粒子割合は、５００質量ｐｐｍ以下が好ましく、２００質量ｐｐｍ以下がより好ましく、１００質量ｐｐｍ以下が更に好ましく、０質量ｐｐｍであってもよい。
From the viewpoint of improving the smoothness of the semi-cured product and the cured product, the proportion of hollow silica particles having a particle size of 10 μm or more as measured by the Coulter Counter method is preferably 500 ppm by mass or less, more preferably 200 ppm by mass or less, even more preferably 100 ppm by mass or less, and may be 0 ppm by mass.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点、並びに半硬化物及び硬化物の誘電特性を向上する観点から、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた中空シリカ粒子の密度は、０．３５～２．００ｇ／ｃｍ３が好ましく、０．３５～１．５０ｇ／ｃｍ３がより好ましく、０．４０～１．００ｇ／ｃｍ３が更に好ましい。
なお、本組成物が、２種以上の中空シリカ粒子を含む場合、中空シリカ粒子の密度は、各中空シリカ粒子の密度を加重平均することにより求める。
乾式ピクノメーターとしては、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡｃｃｕＰｙｃＩＩ １３４０又はこれと同等の装置を使用できる。 In the present composition 1, from the viewpoint of further reducing the relative dielectric constant and further improving the adhesion to the substrate, or in the present composition 2, from the viewpoint of producing a prepreg and a cured product having a small variation in the relative dielectric constant, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is preferably 0.35 to 2.00 g/ cm3 , more preferably 0.35 to 1.50 g/ cm3 , and even more preferably 0.40 to 1.00 g/ cm3 .
When the composition contains two or more types of hollow silica particles, the density of the hollow silica particles is determined by taking a weighted average of the densities of the individual hollow silica particles.
As the dry pycnometer, an AccuPycII 1340 manufactured by Micromeritics or an equivalent device can be used.
なお、本組成物が、２種以上の中空シリカ粒子を含む場合、中空シリカ粒子の密度は、各中空シリカ粒子の密度を加重平均することにより求める。
乾式ピクノメーターとしては、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡｃｃｕＰｙｃＩＩ １３４０又はこれと同等の装置を使用できる。 In the present composition 1, from the viewpoint of further reducing the relative dielectric constant and further improving the adhesion to the substrate, or in the present composition 2, from the viewpoint of producing a prepreg and a cured product having a small variation in the relative dielectric constant, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is preferably 0.35 to 2.00 g/ cm3 , more preferably 0.35 to 1.50 g/ cm3 , and even more preferably 0.40 to 1.00 g/ cm3 .
When the composition contains two or more types of hollow silica particles, the density of the hollow silica particles is determined by taking a weighted average of the densities of the individual hollow silica particles.
As the dry pycnometer, an AccuPycII 1340 manufactured by Micromeritics or an equivalent device can be used.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、半硬化物及び硬化物の誘電特性を向上する観点から、中空シリカ粒子のＢＥＴ比表面積は、１．０～１００．０ｍ２／ｇが好ましく、１．０～５０．０ｍ２／ｇがより好ましく、１．０～３０．０ｍ２／ｇが更に好ましい。
In the present composition 1, from the viewpoint of further reducing the relative dielectric constant and further improving the adhesion to the substrate, or in the present composition 2, from the viewpoint of improving the dielectric properties of the semi-cured product 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, and even more preferably 1.0 to 30.0 m 2 /g.
本組成物１において、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた中空シリカ粒子の密度をＡ（ｇ／ｃｍ３）、中空シリカ粒子のＢＥＴ比表面積をＢ１（ｍ２／ｇ）としたとき、Ａ×Ｂ１は、１．０～１２０．０ｍ２／ｃｍ３である。比誘電率をより低下させ、基材との密着性をより向上する観点から、Ａ×Ｂ１は、２．０～８０．０ｍ２／ｃｍ３が好ましく、２．５～４０．０ｍ２／ｃｍ３がより好ましく、３．０～２０．０ｍ２／ｃｍ３が更に好ましい。
本組成物２において、半硬化物及び硬化物の密着強度を向上する観点、及び比誘電率を低減させる観点から、Ａ×Ｂ１は、１．０～１２０．０ｍ２／ｃｍ３が好ましく、２．０～８０．０ｍ２／ｃｍ３がより好ましく、２．５～４０．０ｍ２／ｃｍ３が更に好ましく、３．０～２０．０ｍ２／ｃｍ３が特に好ましい。 In the present composition 1, when the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is A (g/cm 3 ) and the BET specific surface area of the hollow silica particles is B1 (m 2 /g), A×B1 is 1.0 to 120.0 m 2 /cm 3. From the viewpoint of further reducing the relative dielectric constant and further improving the adhesion to the substrate, A×B1 is preferably 2.0 to 80.0 m 2 /cm 3 , more preferably 2.5 to 40.0 m 2 /cm 3 , and even more preferably 3.0 to 20.0 m 2 /cm 3 .
In the present composition 2, from the viewpoint of improving the adhesion strength of the semi-cured product and the cured product, and from the viewpoint of reducing the relative dielectric constant, A×B1 is preferably 1.0 to 120.0 m 2 /cm 3 , more preferably 2.0 to 80.0 m 2 /cm 3 , even more preferably 2.5 to 40.0 m 2 /cm 3 , and particularly preferably 3.0 to 20.0 m 2 /cm 3 .
本組成物２において、半硬化物及び硬化物の密着強度を向上する観点、及び比誘電率を低減させる観点から、Ａ×Ｂ１は、１．０～１２０．０ｍ２／ｃｍ３が好ましく、２．０～８０．０ｍ２／ｃｍ３がより好ましく、２．５～４０．０ｍ２／ｃｍ３が更に好ましく、３．０～２０．０ｍ２／ｃｍ３が特に好ましい。 In the present composition 1, when the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is A (g/cm 3 ) and the BET specific surface area of the hollow silica particles is B1 (m 2 /g), A×B1 is 1.0 to 120.0 m 2 /cm 3. From the viewpoint of further reducing the relative dielectric constant and further improving the adhesion to the substrate, A×B1 is preferably 2.0 to 80.0 m 2 /cm 3 , more preferably 2.5 to 40.0 m 2 /cm 3 , and even more preferably 3.0 to 20.0 m 2 /cm 3 .
In the present composition 2, from the viewpoint of improving the adhesion strength of the semi-cured product and the cured product, and from the viewpoint of reducing the relative dielectric constant, A×B1 is preferably 1.0 to 120.0 m 2 /cm 3 , more preferably 2.0 to 80.0 m 2 /cm 3 , even more preferably 2.5 to 40.0 m 2 /cm 3 , and particularly preferably 3.0 to 20.0 m 2 /cm 3 .
本組成物１において、プリプレグ、硬化物等の比誘電率のばらつきを小さくする観点から、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた中空シリカ粒子及び樹脂の密度を、それぞれ、Ａ（ｇ／ｃｍ３）、及びＢ２（ｇ／ｃｍ３）としたとき、Ａ／Ｂ２が、０．３～１．５であることが好ましく、０．４～１．０であることがより好ましい。
本組成物２において、Ａ／Ｂ２は、０．３～１．５であり、硬化物等の比誘電率のばらつきをより小さくする観点から、０．４～１．０であることが好ましい。 In the present composition 1, from the viewpoint of reducing the variation in the dielectric constant of the prepreg, the cured product, etc., when the densities of the hollow silica particles and the resin determined by a constant volume expansion method using argon gas and a dry pycnometer are A (g/cm 3 ) and B2 (g/cm 3 ), respectively, A/B2 is preferably 0.3 to 1.5, and more preferably 0.4 to 1.0.
In the present composition 2, A/B2 is from 0.3 to 1.5, and from the viewpoint of further reducing the variation in the relative dielectric constant of the cured product, etc., it is preferably from 0.4 to 1.0.
本組成物２において、Ａ／Ｂ２は、０．３～１．５であり、硬化物等の比誘電率のばらつきをより小さくする観点から、０．４～１．０であることが好ましい。 In the present composition 1, from the viewpoint of reducing the variation in the dielectric constant of the prepreg, the cured product, etc., when the densities of the hollow silica particles and the resin determined by a constant volume expansion method using argon gas and a dry pycnometer are A (g/cm 3 ) and B2 (g/cm 3 ), respectively, A/B2 is preferably 0.3 to 1.5, and more preferably 0.4 to 1.0.
In the present composition 2, A/B2 is from 0.3 to 1.5, and from the viewpoint of further reducing the variation in the relative dielectric constant of the cured product, etc., it is preferably from 0.4 to 1.0.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点、並びに半硬化物及び硬化物の誘電特性を向上する観点から、中空シリカ粒子の空隙率は、３０～９０％が好ましく、４０～９０％がより好ましく、５０～８５％が更に好ましい。
本開示において、中空シリカ粒子の空隙率は、中空シリカ粒子の真密度により、中空シリカ粒子の密度を除し、１００倍することにより算出する。なお、中空シリカ粒子の真密度は、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡｃｃｕＰｙｃＩＩ １３４０又はこれと同等の装置により、Ｈｅガスを用いて測定する。 In the present composition 1, from the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate, or in the present composition 2, from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the porosity of the hollow silica particles is preferably 30 to 90%, more preferably 40 to 90%, and even more preferably 50 to 85%.
In the present disclosure, the porosity of hollow silica particles is calculated by dividing the density of hollow silica particles by the true density of hollow silica particles and multiplying the result by 100. The true density of hollow silica particles is measured using He gas with an AccuPycII 1340 manufactured by Micromeritics or an equivalent device.
本開示において、中空シリカ粒子の空隙率は、中空シリカ粒子の真密度により、中空シリカ粒子の密度を除し、１００倍することにより算出する。なお、中空シリカ粒子の真密度は、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡｃｃｕＰｙｃＩＩ １３４０又はこれと同等の装置により、Ｈｅガスを用いて測定する。 In the present composition 1, from the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate, or in the present composition 2, from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the porosity of the hollow silica particles is preferably 30 to 90%, more preferably 40 to 90%, and even more preferably 50 to 85%.
In the present disclosure, the porosity of hollow silica particles is calculated by dividing the density of hollow silica particles by the true density of hollow silica particles and multiplying the result by 100. The true density of hollow silica particles is measured using He gas with an AccuPycII 1340 manufactured by Micromeritics or an equivalent device.
中空シリカ粒子に含まれる個々の中空シリカ粒子の形状は、特に限定されるものではなく、球状であってもよく、非球状であってもよいが、低誘電正接の観点から、球状が好ましい。低誘電正接の観点から、球状中空シリカ粒子の真球度は、０．６０以上が好ましく、０．７５以上がより好ましく、０．９０以上が更に好ましく、０．９３以上が特に好ましく、１．００が最も好ましい。また、中空シリカ粒子は、低誘電正接の観点から、無孔質粒子が好ましい。
The shape of each hollow silica particle contained in the hollow silica particles is not particularly limited and may be spherical or non-spherical, but from the viewpoint of a low dielectric tangent, a spherical shape is preferred. From the viewpoint of a low dielectric tangent, the sphericity of the spherical hollow silica particles is preferably 0.60 or more, more preferably 0.75 or more, even more preferably 0.90 or more, particularly preferably 0.93 or more, and most preferably 1.00. From the viewpoint of a low dielectric tangent, the hollow silica particles are preferably non-porous particles.
絶縁層を形成したときの回路における伝送損失を低減させる観点から、中空シリカ粒子の誘電正接は、周波数１ＧＨｚにおいて、０．００４０以下が好ましく、０．００３０以下がより好ましく、０．００２０以下が更に好ましく、０．００１５以下が特に好ましく、０．００１２以下が最も好ましい。
From the viewpoint of reducing transmission loss in the circuit when an insulating layer is formed, the dielectric tangent of the hollow silica particles at a frequency of 1 GHz is preferably 0.0040 or less, more preferably 0.0030 or less, even more preferably 0.0020 or less, particularly preferably 0.0015 or less, and most preferably 0.0012 or less.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点、並びに半硬化物及び硬化物の誘電特性を向上する観点から、中空シリカ粒子の吸油量は、２０～５００ｍＬ／１００ｇが好ましく、２５～２００ｍＬ／１００ｇがより好ましく、３０～１５０ｍＬ／１００ｇが更に好ましく、３０～１００ｍＬ／１００ｇが特に好ましく、３０～８０ｍＬ／１００ｇが最も好ましい。
本開示において、「吸油量」は、ＪＩＳ Ｋ ５１０１－１３－１（２００４）（対応ＩＳＯ：ＩＳＯ ７８７－５ １９８０）に従って測定する。なお、本開示における吸油量は、ＪＩＳ Ｋ ５１０１－１３－１（２００４）に従って測定される値に、密度／真密度の値を乗じた値（すなわち、ＪＩＳ Ｋ ５１０１－１３－１（２００４）に従って測定される吸油量×（密度／真密度））とする。 In the present composition 1, from the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate, or in the present composition 2, from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the oil absorption of the hollow silica particles is preferably from 20 to 500 mL/100 g, more preferably from 25 to 200 mL/100 g, even more preferably from 30 to 150 mL/100 g, particularly preferably from 30 to 100 mL/100 g, and most preferably from 30 to 80 mL/100 g.
In the present disclosure, "oil absorption" is measured in accordance with JIS K 5101-13-1 (2004) (corresponding ISO: ISO 787-5 1980). Note 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., oil absorption measured in accordance with JIS K 5101-13-1 (2004) × (density/true density)).
本開示において、「吸油量」は、ＪＩＳ Ｋ ５１０１－１３－１（２００４）（対応ＩＳＯ：ＩＳＯ ７８７－５ １９８０）に従って測定する。なお、本開示における吸油量は、ＪＩＳ Ｋ ５１０１－１３－１（２００４）に従って測定される値に、密度／真密度の値を乗じた値（すなわち、ＪＩＳ Ｋ ５１０１－１３－１（２００４）に従って測定される吸油量×（密度／真密度））とする。 In the present composition 1, from the viewpoint of further reducing the dielectric constant and further improving the adhesion to the substrate, or in the present composition 2, from the viewpoint of producing a prepreg and a cured product having a small variation in the dielectric constant, and from the viewpoint of improving the dielectric properties of a semi-cured product and a cured product, the oil absorption of the hollow silica particles is preferably from 20 to 500 mL/100 g, more preferably from 25 to 200 mL/100 g, even more preferably from 30 to 150 mL/100 g, particularly preferably from 30 to 100 mL/100 g, and most preferably from 30 to 80 mL/100 g.
In the present disclosure, "oil absorption" is measured in accordance with JIS K 5101-13-1 (2004) (corresponding ISO: ISO 787-5 1980). Note 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., oil absorption measured in accordance with JIS K 5101-13-1 (2004) × (density/true density)).
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、又は本組成物２において、半硬化物及び硬化物の誘電特性を向上する観点から、中空シリカ粒子の水銀圧入法による２０％破壊圧力は、１２０ＭＰａ以上が好ましく、１５０ＭＰａ以上がより好ましく、２００ＭＰａ以上が更に好ましく、２５０ＭＰａ以上が特に好ましい。２０％破壊圧力の上限は、特に限定されるものではなく、例えば、６００ＭＰａ以下とすることができる。
本開示において、「２０％破壊圧力」とは、水銀圧入法によって測定される破壊圧力のことで、水銀圧入法で０～４００ＭＰaまで圧力をかけていった際、積算容量の最大値から２０％減少した容量を示す最小の圧力のことである。
中空シリカ粒子の水銀圧入法による２０％破壊圧力は、ＡＳＴＭ Ｄ ３１０２－７８に準拠して、水銀圧入ポロシメーター（例えば、MICROMERITICS INSTRUMENT社製のAutoPore IV 9500）を用いて測定する。 In the present composition 1, from the viewpoint of further reducing the relative dielectric constant and further improving the adhesion to the substrate, or in the present 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 as measured by mercury porosimetry is preferably 120 MPa or more, more preferably 150 MPa or more, even more 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, for example, 600 MPa or less.
In this disclosure, the "20% burst pressure" refers to the burst pressure measured by mercury porosimetry, and is the minimum pressure that indicates a 20% decrease in capacity from the maximum integrated capacity when pressure is applied from 0 to 400 MPa by mercury porosimetry.
The 20% collapse pressure of the hollow silica particles as measured by mercury intrusion porosimeter (for example, AutoPore IV 9500 manufactured by MICROMERITICS INSTRUMENT) is measured in accordance with ASTM D 3102-78.
本開示において、「２０％破壊圧力」とは、水銀圧入法によって測定される破壊圧力のことで、水銀圧入法で０～４００ＭＰaまで圧力をかけていった際、積算容量の最大値から２０％減少した容量を示す最小の圧力のことである。
中空シリカ粒子の水銀圧入法による２０％破壊圧力は、ＡＳＴＭ Ｄ ３１０２－７８に準拠して、水銀圧入ポロシメーター（例えば、MICROMERITICS INSTRUMENT社製のAutoPore IV 9500）を用いて測定する。 In the present composition 1, from the viewpoint of further reducing the relative dielectric constant and further improving the adhesion to the substrate, or in the present 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 as measured by mercury porosimetry is preferably 120 MPa or more, more preferably 150 MPa or more, even more 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, for example, 600 MPa or less.
In this disclosure, the "20% burst pressure" refers to the burst pressure measured by mercury porosimetry, and is the minimum pressure that indicates a 20% decrease in capacity from the maximum integrated capacity when pressure is applied from 0 to 400 MPa by mercury porosimetry.
The 20% collapse pressure of the hollow silica particles as measured by mercury intrusion porosimeter (for example, AutoPore IV 9500 manufactured by MICROMERITICS INSTRUMENT) is measured in accordance with ASTM D 3102-78.
半硬化物及び硬化物の曲げ強度を向上する観点から、中空シリカ粒子の帯電量は、０．００５μＣ／ｇ以上が好ましく、０．０１０μＣ／ｇ以上がより好ましく、０．０１５μＣ／ｇ以上が更に好ましく、０．０２０μＣ／ｇ以上が特に好ましい。帯電量の上限値は、特に限定されるものではなく、０．０８０μＣ／ｇ以下にできる。
本開示において、帯電量は、以下の方法により測定する。なお、測定装置としては、例えば、粉体摩擦帯電量測定装置 ＮＳ－Ｋ１００型（ナノシーズ社製）を使用できる。
中空シリカ粒子１０ｇをアルミ容器（内寸Φ４２ｍｍ、深さ７０ｍｍ）に入れ、試料回転用アームに固定して取り付ける。左右振り角は、左１５０度、右２１０度（左右振り速度は５４０ｄｅｇ／ｓ）として１２往復で１クールとする（中間の６往復終了時に２回転の粉払い落とし回転動作を加える）。３クールの摩擦攪拌を加えた後、帯電した中空シリカ粒子をファラデーケージに投入し、中空シリカ粒子の帯電量を測定し、質量当たりの帯電量に換算する（中空シリカ粒子の帯電量／中空シリカ粒子仕込み量１０ｇ）。 From the viewpoint of improving the bending 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, even more preferably 0.015 μC/g or more, and particularly preferably 0.020 μC/g or more. The upper limit of the charge amount is not particularly limited, and can be 0.080 μC/g or less.
In the present disclosure, the charge amount is measured by the following method. As a measuring device, for example, a powder triboelectric charge measuring device NS-K100 type (manufactured by Nano Seeds Corporation) can be used.
10 g of hollow silica particles are placed in an aluminum container (inner dimensions Φ42 mm, depth 70 mm) and fixed to a sample rotation arm. The left and right swing angles are 150 degrees left and 210 degrees right (swing speed is 540 deg/s), and 12 round trips are counted as one cycle (2 rotations of powder brushing off rotation are added at the end of the intermediate 6 round trips). After 3 cycles of friction stirring, the charged hollow silica particles are placed in a Faraday cage, the charge amount of the hollow silica particles is measured, and converted to the charge amount per mass (charge amount of hollow silica particles/10 g of hollow silica particles).
本開示において、帯電量は、以下の方法により測定する。なお、測定装置としては、例えば、粉体摩擦帯電量測定装置 ＮＳ－Ｋ１００型（ナノシーズ社製）を使用できる。
中空シリカ粒子１０ｇをアルミ容器（内寸Φ４２ｍｍ、深さ７０ｍｍ）に入れ、試料回転用アームに固定して取り付ける。左右振り角は、左１５０度、右２１０度（左右振り速度は５４０ｄｅｇ／ｓ）として１２往復で１クールとする（中間の６往復終了時に２回転の粉払い落とし回転動作を加える）。３クールの摩擦攪拌を加えた後、帯電した中空シリカ粒子をファラデーケージに投入し、中空シリカ粒子の帯電量を測定し、質量当たりの帯電量に換算する（中空シリカ粒子の帯電量／中空シリカ粒子仕込み量１０ｇ）。 From the viewpoint of improving the bending 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, even more preferably 0.015 μC/g or more, and particularly preferably 0.020 μC/g or more. The upper limit of the charge amount is not particularly limited, and can be 0.080 μC/g or less.
In the present disclosure, the charge amount is measured by the following method. As a measuring device, for example, a powder triboelectric charge measuring device NS-K100 type (manufactured by Nano Seeds Corporation) can be used.
10 g of hollow silica particles are placed in an aluminum container (inner dimensions Φ42 mm, depth 70 mm) and fixed to a sample rotation arm. The left and right swing angles are 150 degrees left and 210 degrees right (swing speed is 540 deg/s), and 12 round trips are counted as one cycle (2 rotations of powder brushing off rotation are added at the end of the intermediate 6 round trips). After 3 cycles of friction stirring, the charged hollow silica particles are placed in a Faraday cage, the charge amount of the hollow silica particles is measured, and converted to the charge amount per mass (charge amount of hollow silica particles/10 g of hollow silica particles).
個々の中空シリカ粒子はシランカップリング剤によって処理されていてもよい。中空シリカ粒子の表面がシランカップリング剤によって処理されていることで、表面のシラノール基の残存量が少なくなり、表面が疎水化され、水分吸着を抑えて誘電損失を向上できるとともに、本組成物において樹脂との親和性が向上し、分散性、及び樹脂製膜後の強度を向上できる。
シランカップリング剤の種類としては、アミノシラン系カップリング剤、メタクリルシラン系シランカップリング剤、エポキシシラン系カップリング剤、メルカプトシラン系カップリング剤、シラン系カップリング剤、オルガノシラザン化合物等が挙げられる。シランカップリング剤は１種類を用いてもよいし２種類以上を組み合わせて用いてもよい。
シランカップリング剤の付着量は、中空シリカ粒子１００質量部に対して、０．０１～５質量部が好ましく、０．０２～５質量部がより好ましく、０．１０～２質量部が更に好ましい。
中空シリカ粒子の表面がシランカップリング剤で処理されていることはＩＲによるシランカップリング剤の置換基によるピークの検出により確認できる。また、シランカップリング剤の付着量は、炭素量により測定できる。 Each hollow silica particle may be treated with a silane coupling agent. By treating the surface of the hollow silica particle with a silane coupling agent, the amount of remaining silanol groups on the surface is reduced, the surface is hydrophobicized, moisture adsorption is suppressed, and the dielectric loss is improved. In addition, the affinity with the resin in the composition is improved, and the dispersibility and strength after the resin film are improved.
Examples of the silane coupling agent include aminosilane coupling agents, methacrylsilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, etc. The silane coupling agents may be used alone or in combination of two or more.
The amount of the silane coupling agent attached is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 5 parts by mass, and even more preferably 0.10 to 2 parts by mass, based on 100 parts by mass of the hollow silica particles.
The fact that the surface of the hollow silica particles has been treated with a silane coupling agent can be confirmed by detecting a peak due to a substituent of the silane coupling agent by IR. The amount of the silane coupling agent attached can be measured by the amount of carbon.
シランカップリング剤の種類としては、アミノシラン系カップリング剤、メタクリルシラン系シランカップリング剤、エポキシシラン系カップリング剤、メルカプトシラン系カップリング剤、シラン系カップリング剤、オルガノシラザン化合物等が挙げられる。シランカップリング剤は１種類を用いてもよいし２種類以上を組み合わせて用いてもよい。
シランカップリング剤の付着量は、中空シリカ粒子１００質量部に対して、０．０１～５質量部が好ましく、０．０２～５質量部がより好ましく、０．１０～２質量部が更に好ましい。
中空シリカ粒子の表面がシランカップリング剤で処理されていることはＩＲによるシランカップリング剤の置換基によるピークの検出により確認できる。また、シランカップリング剤の付着量は、炭素量により測定できる。 Each hollow silica particle may be treated with a silane coupling agent. By treating the surface of the hollow silica particle with a silane coupling agent, the amount of remaining silanol groups on the surface is reduced, the surface is hydrophobicized, moisture adsorption is suppressed, and the dielectric loss is improved. In addition, the affinity with the resin in the composition is improved, and the dispersibility and strength after the resin film are improved.
Examples of the silane coupling agent include aminosilane coupling agents, methacrylsilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, etc. The silane coupling agents may be used alone or in combination of two or more.
The amount of the silane coupling agent attached is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 5 parts by mass, and even more preferably 0.10 to 2 parts by mass, based on 100 parts by mass of the hollow silica particles.
The fact that the surface of the hollow silica particles has been treated with a silane coupling agent can be confirmed by detecting a peak due to a substituent of the silane coupling agent by IR. The amount of the silane coupling agent attached can be measured by the amount of carbon.
中空シリカ粒子は、本開示の効果を妨げない範囲において、不純物元素を含んでいてもよい。不純物元素としては、例えば、Ａｌ、Ｆｅ、Ｔｉ等が挙げられる。
The hollow silica particles may contain impurity elements as long as the effects of the present disclosure are not hindered. Examples of impurity elements include Al, Fe, Ti, etc.
本組成物１において、比誘電率をより低下させ、基材との密着性をより向上する観点から、及び本組成物の吸水性を低減する観点から、又は本組成物２において、比誘電率のばらつきが小さいプリプレグ及び硬化物を作製する観点、半硬化物及び硬化物の誘電特性及び密着性を向上する観点、並びに本組成物の吸水性を低減する観点から、本組成物の総体積に対する中空シリカ粒子の含有量は、１０～７０体積％が好ましく、１５～６５体積％がより好ましく、１８～６０体積％が更に好ましい。
In the present composition 1, from the viewpoint of further reducing the relative dielectric constant and further improving adhesion to the substrate, and from the viewpoint of reducing the water absorption of the present composition, or in the present composition 2, from the viewpoint of producing a prepreg and a cured product with a small variation in the relative dielectric constant, from the viewpoint of improving the dielectric properties and adhesion of the semi-cured product and the cured product, and from the viewpoint of 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 volume %, more preferably 15 to 65 volume %, and even more preferably 18 to 60 volume %.
中空シリカ粒子は、市販されるものを使用してもよく、従来公知の方法により作製したものを使用してもよい。例えば、国際公開第２０１９／１３１６５８号、国際公開第２０２１／００６６９７号、国際公開第２０２１／１７２２９４号等に記載の方法により作製した中空シリカ粒子を使用できる。
The hollow silica particles may be commercially available or may be prepared by a conventional method. For example, hollow silica particles prepared by the methods described in WO 2019/131658, WO 2021/006697, WO 2021/172294, etc. may be used.
本組成物は、１種又は２種以上の溶剤を含んでもよい。溶剤としては、アセトン、メタノール、エタノール、ブタノール、２－プロパノール、２－メトキシエタノール、２－エトキシエタノール、トルエン、キシレン、メチルエチルケトン、Ｎ，Ｎ－ジメチルホルムアミド、メチルイソブチルケトン、Ｎ－メチル－２－ピロリドン、ｎ－ヘキサン、シクロヘキサン等が挙げられる。密着性等の観点から、溶剤は、トルエン、シクロヘキサノン、メチルエチルケトン、及びＮ－メチル－２－ピロリドンからなる群より選択される少なくとも１つを含むことが好ましい。本組成物の総質量に対する溶剤の含有率は、特に限定されず、例えば１０～６０質量％であってもよい。
The composition may contain one or more solvents. Examples of the solvent 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, and cyclohexane. From the viewpoint of adhesion, it is preferable that the solvent contains at least one selected from the group consisting of toluene, cyclohexanone, methyl ethyl ketone, and N-methyl-2-pyrrolidone. The content of the solvent relative to the total mass of the composition is not particularly limited, and may be, for example, 10 to 60% by mass.
中空シリカ粒子の凝集抑制等の観点から、溶剤の表面張力は、４０ｍＮ／ｍ以下が好ましく、３５ｍＮ／ｍ以下がより好ましく、３０ｍＮ／ｍ以下が更に好ましい。表面張力の下限は、特に限定されず、例えば５ｍＮ／ｍでもよい。
本開示において、「表面張力」は、表面張力計を用いて、２５℃の溶剤に対してウィルヘルミー法により測定する。 From the viewpoint of suppressing aggregation of the hollow silica particles, the surface tension of the solvent is preferably 40 mN/m or less, more preferably 35 mN/m or less, and even more preferably 30 mN/m or less. The lower limit of the surface tension is not particularly limited and may be, for example, 5 mN/m.
In this disclosure, "surface tension" is measured by the Wilhelmy method using a surface tensiometer for a solvent at 25°C.
本開示において、「表面張力」は、表面張力計を用いて、２５℃の溶剤に対してウィルヘルミー法により測定する。 From the viewpoint of suppressing aggregation of the hollow silica particles, the surface tension of the solvent is preferably 40 mN/m or less, more preferably 35 mN/m or less, and even more preferably 30 mN/m or less. The lower limit of the surface tension is not particularly limited and may be, for example, 5 mN/m.
In this disclosure, "surface tension" is measured by the Wilhelmy method using a surface tensiometer for a solvent at 25°C.
溶剤の粘度は、２５℃において、１０ｍＰａ・ｓ以下が好ましく、５ｍＰａ・ｓ以下がより好ましい。溶剤の粘度の下限は、特に限定されるものではなく、２ｍＰａ・ｓ以上にできる。
The viscosity of the solvent is preferably 10 mPa·s or less at 25°C, and more preferably 5 mPa·s or less. The lower limit of the viscosity of the solvent is not particularly limited, and can be 2 mPa·s or more.
本組成物の総質量に対する溶剤の含有率は、特に限定されるものではなく、例えば、１０質量％～９０質量％にできる。
The content of the solvent relative to the total mass of the composition is not particularly limited, and can be, for example, 10% by mass to 90% by mass.
本組成物は、重合開始剤を１種又は２種以上含有してもよい。重合開始剤としては、α，α’－ビス（ｔ－ブチルパーオキシ－ｍ－イソプロピル）ベンゼン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）－３－ヘキシン、過酸化ベンゾイル、３，３’，５，５’－テトラメチル－１，４－ジフェノキノン、クロラニル、２，４，６－トリ－ｔ－ブチルフェノキシル、ｔ－ブチルペルオキシイソプロピルモノカーボネート、アゾビスイソブチロニトリル等が挙げられる。樹脂１００質量部に対する重合開始剤の含有量は、０．１～５質量部が好ましい。
The composition may contain one or more polymerization initiators. Examples of polymerization initiators include α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, and azobisisobutyronitrile. The content of the polymerization initiator per 100 parts by mass of resin is preferably 0.1 to 5 parts by mass.
本組成物は、重合促進剤を１種又は２種以上含有してもよい。重合促進剤としては、トリアリルイソシアヌレート等のトリアルケニルイソシアヌレート化合物、分子中にアクリロイル基又はメタクリロイル基を２個以上有する多官能アクリル系化合物、分子中にビニル基を２個以上有する多官能ビニル化合物、分子中にビニルベンジル基を有するスチレン等のビニルベンジル化合物等が挙げられる。樹脂１００質量部に対する重合促進剤の含有量は、１０～１００質量部が好ましい。
The composition may contain one or more polymerization accelerators. Examples of polymerization accelerators include trialkenyl isocyanurate compounds such as triallyl isocyanurate, 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, and vinylbenzyl compounds such as styrene having a vinylbenzyl group in the molecule. The content of the polymerization accelerator per 100 parts by mass of the resin is preferably 10 to 100 parts by mass.
本組成物は、可塑剤を１種又は２種以上含有してもよい。可塑剤としては、ブタジエン・スチレンコポリマー等が挙げられる。樹脂１００質量部に対する可塑剤の含有量は、１０～５０質量部が好ましく、２０～４０質量部がより好ましい。
The composition may contain one or more plasticizers. Examples of plasticizers include butadiene-styrene copolymers. The content of the plasticizer per 100 parts by mass of resin is preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass.
本組成物は、上記成分以外にも、その効果を損なわない範囲で、界面活性剤、チキソ性付与剤、ｐＨ調整剤、ｐＨ緩衝剤、粘度調節剤、消泡剤、シランカップリング剤、脱水剤、可塑剤、耐候剤、酸化防止剤、熱安定剤、滑剤、帯電防止剤、増白剤、着色剤、導電材、離型剤、表面処理剤、難燃剤、各種有機又は無機フィラー等の他の成分を更に含んでいてもよい。
In addition to the above components, the composition may further contain other components such as surfactants, thixotropy imparting agents, pH adjusters, pH buffers, viscosity regulators, defoamers, silane coupling agents, dehydrating agents, plasticizers, weather resistance agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brightening agents, colorants, conductive materials, release agents, surface treatment agents, flame retardants, and various organic or inorganic fillers, to the extent that the effects of the composition are not impaired.
本組成物は、パソコン、ノートパソコン、デジタルカメラ等の電子機器や、スマートフォン、ゲーム機等の通信機器等に用いられる電子基板の作製に用いられる樹脂組成物として好適に使用できる。また、本発明の樹脂組成物は、低誘電率化、低伝送損失化、低吸湿化、剥離強度向上のために、プリプレグ、金属箔張積層板、プリント配線板、樹脂シート、接着層、接着フィルム、ソルダーレジスト、バンプリフロー用樹脂組成物、再配線絶縁層、ダイボンド材、封止材、アンダーフィル、モールドアンダーフィル及び積層インダクタ等への応用も期待される。
This composition can be suitably used as a resin composition for producing electronic substrates for use in electronic devices such as personal computers, notebook computers, and digital cameras, and communication devices such as smartphones and game consoles. The resin composition of the present invention is also expected to be applied to prepregs, metal foil-clad laminates, printed wiring boards, resin sheets, adhesive layers, adhesive films, solder resists, resin compositions for bump reflow, rewiring insulating layers, die bond materials, encapsulants, underfills, mold underfills, and laminated inductors, etc., in order to reduce dielectric constant, transmission loss, moisture absorption, and improve peel strength.
本開示のプリプレグは、本組成物又はその半硬化物と、繊維質基材と、を含む。繊維質基材としては、ガラスクロス、アラミドクロス、ポリエステルクロス、ガラス不織布、アラミド不織布、ポリエステル不織布、パルプ紙等が挙げられる。繊維質基材としては、ガラス成分を含むものが好ましい。繊維質基材の厚さは、特に限定されるものではなく、１２μｍ～１０００μｍとできる。なお、本組成物については上記したため、ここでは記載を省略する。
The prepreg of the present disclosure includes the present composition or a semi-cured product thereof, and a fibrous substrate. Examples of the fibrous substrate include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, and pulp paper. The fibrous substrate preferably contains a glass component. The thickness of the fibrous substrate is not particularly limited, and can be 12 μm to 1000 μm. Note that the present composition has been described above, so a description thereof will be omitted here.
本開示のプリプレグは、繊維質基材に、本組成物を塗布又は含浸させることにより製造できる。本組成物の塗布又は含浸後に、樹脂組成物を加熱し、半硬化させてもよい。
The prepreg of the present disclosure can be produced by applying or impregnating the present composition to a fibrous substrate. After applying or impregnating the present composition, the resin composition may be heated and semi-cured.
本開示の樹脂付き金属基材は、本組成物若しくはその半硬化物又は上記プリプレグと、金属基材層と、を含む。金属基材層は、本組成物若しくはその半硬化物又は上記プリプレグの一方の表面に設けられてもよく、両面に設けられてもよい。
金属基材層の種類は特に限定されるものではなく、金属基材層を構成する金属としては、銅、銅合金、ステンレス鋼、ニッケル、ニッケル合金（４２合金も含む。）、アルミニウム、アルミニウム合金、チタン、チタン合金等が挙げられる。金属基材層は、金属箔であるのが好ましく、圧延銅箔、電解銅箔等の銅箔であるのがより好ましい。金属箔の表面は、防錆処理（クロメート等の酸化物皮膜等）されていてもよく、粗化処理されていてもよい。金属箔として、キャリア銅箔（厚さ：１０～３５μｍ）と、剥離層を介してキャリア銅箔表面に積層された極薄銅箔（厚さ：２～５μｍ）とからなるキャリア付金属箔を使用してもよい。金属基材層の表面は、シランカップリング剤により処理されていてもよい。この場合、金属基材層の表面の全体がシランカップリング剤により処理されていてもよく、金属基材層の表面の一部がシランカップリング剤により処理されていてもよい。シランカップリング剤としては、上記したものを使用できる。 The resin-coated metal substrate of the present disclosure includes the present composition or a semi-cured product thereof, or the prepreg, and a metal substrate layer. The metal substrate layer may be provided on one surface or both surfaces of the present composition or a semi-cured product thereof, or the prepreg.
The type of the metal substrate layer is not particularly limited, and examples of metals constituting the metal substrate layer include copper, copper alloys, stainless steel, nickel, nickel alloys (including alloy 42), aluminum, aluminum alloys, titanium, and titanium alloys. The metal substrate layer is preferably a metal foil, and more preferably a copper foil such as rolled copper foil or electrolytic copper foil. The surface of the metal foil may be rust-proofed (oxide film such as chromate) or may be roughened. As the metal foil, a carrier-attached metal foil consisting of a carrier copper foil (thickness: 10 to 35 μm) and an ultra-thin copper foil (thickness: 2 to 5 μm) laminated on the carrier copper foil surface via a peeling layer may be used. The surface of the metal substrate layer may be treated with a silane coupling agent. In this case, the entire surface of the metal substrate layer may be treated with a silane coupling agent, or a part of the surface of the metal substrate layer may be treated with a silane coupling agent. As the silane coupling agent, the above-mentioned ones can be used.
金属基材層の種類は特に限定されるものではなく、金属基材層を構成する金属としては、銅、銅合金、ステンレス鋼、ニッケル、ニッケル合金（４２合金も含む。）、アルミニウム、アルミニウム合金、チタン、チタン合金等が挙げられる。金属基材層は、金属箔であるのが好ましく、圧延銅箔、電解銅箔等の銅箔であるのがより好ましい。金属箔の表面は、防錆処理（クロメート等の酸化物皮膜等）されていてもよく、粗化処理されていてもよい。金属箔として、キャリア銅箔（厚さ：１０～３５μｍ）と、剥離層を介してキャリア銅箔表面に積層された極薄銅箔（厚さ：２～５μｍ）とからなるキャリア付金属箔を使用してもよい。金属基材層の表面は、シランカップリング剤により処理されていてもよい。この場合、金属基材層の表面の全体がシランカップリング剤により処理されていてもよく、金属基材層の表面の一部がシランカップリング剤により処理されていてもよい。シランカップリング剤としては、上記したものを使用できる。 The resin-coated metal substrate of the present disclosure includes the present composition or a semi-cured product thereof, or the prepreg, and a metal substrate layer. The metal substrate layer may be provided on one surface or both surfaces of the present composition or a semi-cured product thereof, or the prepreg.
The type of the metal substrate layer is not particularly limited, and examples of metals constituting the metal substrate layer include copper, copper alloys, stainless steel, nickel, nickel alloys (including alloy 42), aluminum, aluminum alloys, titanium, and titanium alloys. The metal substrate layer is preferably a metal foil, and more preferably a copper foil such as rolled copper foil or electrolytic copper foil. The surface of the metal foil may be rust-proofed (oxide film such as chromate) or may be roughened. As the metal foil, a carrier-attached metal foil consisting of a carrier copper foil (thickness: 10 to 35 μm) and an ultra-thin copper foil (thickness: 2 to 5 μm) laminated on the carrier copper foil surface via a peeling layer may be used. The surface of the metal substrate layer may be treated with a silane coupling agent. In this case, the entire surface of the metal substrate layer may be treated with a silane coupling agent, or a part of the surface of the metal substrate layer may be treated with a silane coupling agent. As the silane coupling agent, the above-mentioned ones can be used.
金属基材層の厚さは１～４０μｍが好ましく、２～２０μｍがより好ましい。樹脂付き金属基材をプリント配線板として使用した場合の伝送損失を低減できる観点から、金属基材層の最大高さ粗さ（Ｒｚ）は、６μｍ以下が好ましく、４μｍ以下がより好ましい。
The thickness of the metal substrate layer is preferably 1 to 40 μm, more preferably 2 to 20 μm. From the viewpoint of reducing transmission loss when the resin-coated metal substrate is used 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.
一実施形態において、本開示の樹脂付き金属基材は、金属基材層の表面に、本組成物を塗布することにより製造できる。本組成物の塗布後に、樹脂組成物を加熱し、半硬化させてもよい。
他の実施形態において、本開示の樹脂付き金属基材は、金属基材層とプリプレグとを積層することにより製造できる。金属基材層とプリプレグとの積層方法としては、これらを熱圧着する方法等が挙げられる。 In one embodiment, the resin-attached metal substrate of the present disclosure can be produced by applying the present composition to the surface of a metal substrate layer. After applying the present composition, the resin composition may be heated to be semi-cured.
In another embodiment, the resin-coated metal substrate of the present disclosure can be produced by laminating a metal substrate layer and a prepreg. Examples of a method for laminating the metal substrate layer and the prepreg include a method of thermocompression bonding them.
他の実施形態において、本開示の樹脂付き金属基材は、金属基材層とプリプレグとを積層することにより製造できる。金属基材層とプリプレグとの積層方法としては、これらを熱圧着する方法等が挙げられる。 In one embodiment, the resin-attached metal substrate of the present disclosure can be produced by applying the present composition to the surface of a metal substrate layer. After applying the present composition, the resin composition may be heated to be semi-cured.
In another embodiment, the resin-coated metal substrate of the present disclosure can be produced by laminating a metal substrate layer and a prepreg. Examples of a method for laminating the metal substrate layer and the prepreg include a method of thermocompression bonding them.
本開示の配線板は、本組成物の硬化物と、金属配線とを含む。金属配線としては、上記した金属基材層をエッチング等することにより製造したものを使用できる。
The wiring board of the present disclosure includes a cured product of the present composition and metal wiring. The metal wiring can be produced by etching the above-mentioned metal substrate layer, etc.
本開示の配線板は、上記樹脂付き金属基材が備える金属基材層をエッチングする方法、本組成物の硬化物表面に電解めっき法（セミアディティブ法（ＳＡＰ法）、モディファイドセミアディティブ法（ＭＳＡＰ法）等）によってパターン回路に形成する方法等により製造できる。
The wiring board of the present disclosure can be manufactured by a method of etching the metal substrate layer of the resin-coated metal substrate, or by a method of forming a pattern circuit on the cured surface of the present composition by electrolytic plating (semi-additive method (SAP method), modified semi-additive method (MSAP method), etc.).
次に本開示の実施形態を実施例により具体的に説明するが、本開示の実施形態はこれらの実施例に限定されるものではない。以下の例において、「粒子」は、特に特定がない場合、中空シリカ粒子、中空粒子及び／又は中実粒子を表す。
Next, the embodiments of the present disclosure will be specifically explained using examples, but the embodiments of the present disclosure are not limited to these examples. In the following examples, "particles" refers to hollow silica particles, hollow particles, and/or solid particles, unless otherwise specified.
［評価方法］
（樹脂組成物の粘度の測定）
樹脂組成物の粘度は、以下のようにして測定した。
２５℃において、回転式レオメータ（アントンパール（Ａｎｔｏｎ ｐａａｒ）社製、モジュラーレオメーター ＰｈｙｓｉｃａＭＣＲ－３０１）を用いて、せん断速度１ｒｐｍで３０秒測定し、得られた３０秒時点での粘度を測定した。 [Evaluation method]
(Measurement of Viscosity of Resin Composition)
The viscosity of the resin composition was measured as follows.
At 25° C., using a rotational rheometer (modular rheometer Physica MCR-301, manufactured by Anton Paar), measurements were performed at a shear rate of 1 rpm for 30 seconds, and the viscosity obtained at the 30 second point was measured.
（樹脂組成物の粘度の測定）
樹脂組成物の粘度は、以下のようにして測定した。
２５℃において、回転式レオメータ（アントンパール（Ａｎｔｏｎ ｐａａｒ）社製、モジュラーレオメーター ＰｈｙｓｉｃａＭＣＲ－３０１）を用いて、せん断速度１ｒｐｍで３０秒測定し、得られた３０秒時点での粘度を測定した。 [Evaluation method]
(Measurement of Viscosity of Resin Composition)
The viscosity of the resin composition was measured as follows.
At 25° C., using a rotational rheometer (modular rheometer Physica MCR-301, manufactured by Anton Paar), measurements were performed at a shear rate of 1 rpm for 30 seconds, and the viscosity obtained at the 30 second point was measured.
（粒子の密度の測定方法）
各例で用いた粒子を２３０℃で減圧乾燥して水分を完全に除去し、試料とした。この試料について、乾式ピクノメーター（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡｃｃｕＰｙｃＩＩ １３４０）を用いて密度を測定した。測定条件は下記の通りである。
（測定条件）
・試料セル：１０ｃｍ３セル
・試料重量：１．０ｇ
・測定ガス：アルゴンガス
・パージ回数：１０回
・パージ処理充填圧力：１３５ｋＰａｇ
・サイクル回数：１０回
・サイクル充填圧力：１３５ｋＰａｇ
・圧力平衡を終了するレート：０．０５ｋＰａｇ／分 (Method of Measuring Particle Density)
The particles used in each example were dried under reduced pressure at 230° C. to completely remove moisture, and used as a sample. The density of this sample was measured using a dry pycnometer (AccuPycII 1340 manufactured by Micromeritics). The measurement conditions were as follows.
(Measurement condition)
Sample cell: 10 cm3 cell Sample weight: 1.0 g
Measurement gas: Argon gas Purge times: 10 times Purge processing filling pressure: 135 kPag
Number of cycles: 10 Cycle filling pressure: 135 kPag
Rate to end pressure equilibration: 0.05 kPag/min
各例で用いた粒子を２３０℃で減圧乾燥して水分を完全に除去し、試料とした。この試料について、乾式ピクノメーター（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡｃｃｕＰｙｃＩＩ １３４０）を用いて密度を測定した。測定条件は下記の通りである。
（測定条件）
・試料セル：１０ｃｍ３セル
・試料重量：１．０ｇ
・測定ガス：アルゴンガス
・パージ回数：１０回
・パージ処理充填圧力：１３５ｋＰａｇ
・サイクル回数：１０回
・サイクル充填圧力：１３５ｋＰａｇ
・圧力平衡を終了するレート：０．０５ｋＰａｇ／分 (Method of Measuring Particle Density)
The particles used in each example were dried under reduced pressure at 230° C. to completely remove moisture, and used as a sample. The density of this sample was measured using a dry pycnometer (AccuPycII 1340 manufactured by Micromeritics). The measurement conditions were as follows.
(Measurement condition)
Sample cell: 10 cm3 cell Sample weight: 1.0 g
Measurement gas: Argon gas Purge times: 10 times Purge processing filling pressure: 135 kPag
Number of cycles: 10 Cycle filling pressure: 135 kPag
Rate to end pressure equilibration: 0.05 kPag/min
（粒子のＢＥＴ比表面積の測定方法）
各例で用いた粒子を２３０℃で減圧乾燥して水分を完全に除去し、試料とした。この試料について、マイクロメリティック社製の自動比表面積・細孔分布測定装置「トライスターＩＩ」にて、窒素ガスを用いて多点ＢＥＴ法により比表面積を求めた。 (Method of measuring BET specific surface area of particles)
The particles used in each example were dried under reduced pressure at 230° C. to completely remove moisture, and used as a sample. The specific surface area of this sample was determined by the multipoint BET method using nitrogen gas with an automatic specific surface area/pore distribution measuring device "Tristar II" manufactured by Micromeritics.
各例で用いた粒子を２３０℃で減圧乾燥して水分を完全に除去し、試料とした。この試料について、マイクロメリティック社製の自動比表面積・細孔分布測定装置「トライスターＩＩ」にて、窒素ガスを用いて多点ＢＥＴ法により比表面積を求めた。 (Method of measuring BET specific surface area of particles)
The particles used in each example were dried under reduced pressure at 230° C. to completely remove moisture, and used as a sample. The specific surface area of this sample was determined by the multipoint BET method using nitrogen gas with an automatic specific surface area/pore distribution measuring device "Tristar II" manufactured by Micromeritics.
（粒子のｄ５０の測定方法）
各例で用いた粒子のｄ５０は、レーザー回折・散乱法により、粒度分布測定装置（マイクロトラック・ベル社製、ＭＴ３３００ＥＸＩＩ）を用いて測定した。具体的には、超音波照射を１２０秒間行うことで二次粒子を分散させてから測定を行い、得られた粒子の大きさの累積分布が５０％になる値をｄ５０とした。 (Method of measuring d50 of particles)
The d50 of the particles used in each example was measured by a laser diffraction/scattering method using a particle size distribution analyzer (MT3300EXII, manufactured by Microtrac-Bell). Specifically, the secondary particles were dispersed by irradiating with ultrasonic waves for 120 seconds, and then the measurement was performed. The value at which the cumulative distribution of the particle sizes obtained was 50% was taken as d50.
各例で用いた粒子のｄ５０は、レーザー回折・散乱法により、粒度分布測定装置（マイクロトラック・ベル社製、ＭＴ３３００ＥＸＩＩ）を用いて測定した。具体的には、超音波照射を１２０秒間行うことで二次粒子を分散させてから測定を行い、得られた粒子の大きさの累積分布が５０％になる値をｄ５０とした。 (Method of measuring d50 of particles)
The d50 of the particles used in each example was measured by a laser diffraction/scattering method using a particle size distribution analyzer (MT3300EXII, manufactured by Microtrac-Bell). Specifically, the secondary particles were dispersed by irradiating with ultrasonic waves for 120 seconds, and then the measurement was performed. The value at which the cumulative distribution of the particle sizes obtained was 50% was taken as d50.
（粒子の平均一次粒子径の測定方法）
各例で用いた粒子の平均一次粒子径は、ＳＥＭ観察によりその粒子径（直径、球状でない場合は長辺と短辺の平均値）を直接観察することによって求めた。具体的には、ＳＥＭ画像より１００個の粒子の一次粒子の大きさを測定し、それらを平均して得られた一次粒子の大きさの累積分布が５０％になる値を、全体の一次粒子の平均一次粒子径と推定した。 (Method of measuring average primary particle size of particles)
The average primary particle size of the particles used in each example was determined by directly observing the particle size (diameter, or the average of the long and short sides if the particle is not spherical) using SEM observation. Specifically, the primary particle sizes of 100 particles were measured using SEM images, and the value at which the cumulative distribution of the primary particle sizes obtained by averaging these was 50% was estimated to be the average primary particle size of all the primary particles.
各例で用いた粒子の平均一次粒子径は、ＳＥＭ観察によりその粒子径（直径、球状でない場合は長辺と短辺の平均値）を直接観察することによって求めた。具体的には、ＳＥＭ画像より１００個の粒子の一次粒子の大きさを測定し、それらを平均して得られた一次粒子の大きさの累積分布が５０％になる値を、全体の一次粒子の平均一次粒子径と推定した。 (Method of measuring average primary particle size of particles)
The average primary particle size of the particles used in each example was determined by directly observing the particle size (diameter, or the average of the long and short sides if the particle is not spherical) using SEM observation. Specifically, the primary particle sizes of 100 particles were measured using SEM images, and the value at which the cumulative distribution of the primary particle sizes obtained by averaging these was 50% was estimated to be the average primary particle size of all the primary particles.
（粒子の真球度の測定方法）
粒子の真球度は、走査型電子顕微鏡（ＳＥＭ）により写真撮影して得られる写真投影図における任意の１００個の粒子について、それぞれの最大径（ＤＬ）と、これと直交する短径（ＤＳ）とを測定し、最大径（ＤＬ）に対する最小径（ＤＳ）の比（ＤＳ／ＤＬ）を算出し、その平均を算出することにより求めた。 (Method of measuring particle sphericity)
The sphericity of the particles was determined by measuring the maximum diameter (DL) and the minor diameter (DS) perpendicular to the maximum diameter (DL) of any 100 particles in a photographic projection obtained by photographing with a scanning electron microscope (SEM), calculating the ratio (DS/DL) of the minimum diameter (DS) to the maximum diameter (DL), and calculating the average.
粒子の真球度は、走査型電子顕微鏡（ＳＥＭ）により写真撮影して得られる写真投影図における任意の１００個の粒子について、それぞれの最大径（ＤＬ）と、これと直交する短径（ＤＳ）とを測定し、最大径（ＤＬ）に対する最小径（ＤＳ）の比（ＤＳ／ＤＬ）を算出し、その平均を算出することにより求めた。 (Method of measuring particle sphericity)
The sphericity of the particles was determined by measuring the maximum diameter (DL) and the minor diameter (DS) perpendicular to the maximum diameter (DL) of any 100 particles in a photographic projection obtained by photographing with a scanning electron microscope (SEM), calculating the ratio (DS/DL) of the minimum diameter (DS) to the maximum diameter (DL), and calculating the average.
（粒子の誘電正接の測定方法）
粒子の周波数１ＧＨｚにおける誘電正接は、キーコム株式会社製「ベクトルネットワークアナライザ Ｅ５０６３Ａ」）を用い、摂動方式共振器法にて測定した。 (Method of measuring dielectric tangent of particles)
The dielectric loss tangent of the particles at a frequency of 1 GHz was measured by a perturbation resonator method using a vector network analyzer E5063A manufactured by Keycom Corporation.
粒子の周波数１ＧＨｚにおける誘電正接は、キーコム株式会社製「ベクトルネットワークアナライザ Ｅ５０６３Ａ」）を用い、摂動方式共振器法にて測定した。 (Method of measuring dielectric tangent of particles)
The dielectric loss tangent of the particles at a frequency of 1 GHz was measured by a perturbation resonator method using a vector network analyzer E5063A manufactured by Keycom Corporation.
（粒子の空隙率の測定方法）
粒子の空隙率は、粒子の真密度により、粒子の密度を除し、１００倍することにより算出した。粒子の真密度は、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡｃｃｕＰｙｃＩＩ １３４０により測定した。 (Method of measuring particle porosity)
The porosity of the particles was calculated by dividing the density of the particles by the true density of the particles and multiplying the result by 100. The true density of the particles was measured using an AccuPycII 1340 manufactured by Micromeritics.
粒子の空隙率は、粒子の真密度により、粒子の密度を除し、１００倍することにより算出した。粒子の真密度は、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡｃｃｕＰｙｃＩＩ １３４０により測定した。 (Method of measuring particle porosity)
The porosity of the particles was calculated by dividing the density of the particles by the true density of the particles and multiplying the result by 100. The true density of the particles was measured using an AccuPycII 1340 manufactured by Micromeritics.
（粒子の吸油量の測定方法）
粒子の吸油量は、ＪＩＳ Ｋ ５１０１－１３－１（２００４）に従って測定した。 (Method of measuring oil absorption of particles)
The oil absorption of the particles was measured in accordance with JIS K 5101-13-1 (2004).
粒子の吸油量は、ＪＩＳ Ｋ ５１０１－１３－１（２００４）に従って測定した。 (Method of measuring oil absorption of particles)
The oil absorption of the particles was measured in accordance with JIS K 5101-13-1 (2004).
（樹脂の密度の測定方法）
各例で用いた樹脂の密度は、下記のように測定した。
－ポリフェニレンエーテル含有樹脂の密度測定－
ポリフェニレンエーテルの５９質量部、ブタジエン・スチレンランダムコポリマーの１６質量部、トリアリルイソシアヌレートの２５質量部、α，α’－ジ（t－ブチルペルオキシ）ジイソプロピルベンゼンの１質量部、トルエンの６０質量部をポリビンに入れ、プラネタリーディスパで混練して樹脂を得た。得られた樹脂を１２０℃で真空乾燥し、溶剤を除いた後、２００℃の窒素オーブンで硬化させたのち、カッターミルを用いて粉砕し、Ａｒピクノメーターで密度を測定したところ、密度は１．１ｇ／ｃｍ３であった。 (Method of measuring resin density)
The density of the resin used in each example was measured as follows.
- Density measurement of polyphenylene ether-containing resin -
59 parts by mass of polyphenylene ether, 16 parts by mass of butadiene-styrene random copolymer, 25 parts by mass of triallyl isocyanurate, 1 part by mass of α,α'-di(t-butylperoxy)diisopropylbenzene, and 60 parts by mass of toluene were placed in a polyvinyl bottle and kneaded with a planetary disperser to obtain a resin. The resin obtained was vacuum dried at 120°C to remove the solvent, and then cured in a nitrogen oven at 200°C. It was then pulverized using a cutter mill, and the density was measured with an Ar pycnometer, which gave a density of 1.1 g/ cm3 .
各例で用いた樹脂の密度は、下記のように測定した。
－ポリフェニレンエーテル含有樹脂の密度測定－
ポリフェニレンエーテルの５９質量部、ブタジエン・スチレンランダムコポリマーの１６質量部、トリアリルイソシアヌレートの２５質量部、α，α’－ジ（t－ブチルペルオキシ）ジイソプロピルベンゼンの１質量部、トルエンの６０質量部をポリビンに入れ、プラネタリーディスパで混練して樹脂を得た。得られた樹脂を１２０℃で真空乾燥し、溶剤を除いた後、２００℃の窒素オーブンで硬化させたのち、カッターミルを用いて粉砕し、Ａｒピクノメーターで密度を測定したところ、密度は１．１ｇ／ｃｍ３であった。 (Method of measuring resin density)
The density of the resin used in each example was measured as follows.
- Density measurement of polyphenylene ether-containing resin -
59 parts by mass of polyphenylene ether, 16 parts by mass of butadiene-styrene random copolymer, 25 parts by mass of triallyl isocyanurate, 1 part by mass of α,α'-di(t-butylperoxy)diisopropylbenzene, and 60 parts by mass of toluene were placed in a polyvinyl bottle and kneaded with a planetary disperser to obtain a resin. The resin obtained was vacuum dried at 120°C to remove the solvent, and then cured in a nitrogen oven at 200°C. It was then pulverized using a cutter mill, and the density was measured with an Ar pycnometer, which gave a density of 1.1 g/ cm3 .
－ポリイミド樹脂の密度測定－
ポリイミド樹脂（荒川化学工業製、ＰＩＡＤ３００、固形分３０％）を１５０℃で真空乾燥し、溶剤を除いた後、カッターミルを用いて粉砕し、Ａｒピクノメーターで密度を測定したところ、密度は１．５ｇ／ｃｍ３であった。 - Measurement of density of polyimide resin -
A polyimide resin (Arakawa Chemical Industries, Ltd., PIAD300, solid content 30%) was vacuum dried at 150°C to remove the solvent, and then pulverized using a cutter mill. The density was measured using an Ar pycnometer and found to be 1.5 g/ cm3 .
ポリイミド樹脂（荒川化学工業製、ＰＩＡＤ３００、固形分３０％）を１５０℃で真空乾燥し、溶剤を除いた後、カッターミルを用いて粉砕し、Ａｒピクノメーターで密度を測定したところ、密度は１．５ｇ／ｃｍ３であった。 - Measurement of density of polyimide resin -
A polyimide resin (Arakawa Chemical Industries, Ltd., PIAD300, solid content 30%) was vacuum dried at 150°C to remove the solvent, and then pulverized using a cutter mill. The density was measured using an Ar pycnometer and found to be 1.5 g/ cm3 .
≪例１－１～１～７≫
以下の例１－１～１－７中、例１～５は第１の実施形態における実施例であり、例６～７は第１の実施形態における比較例である。 <Example 1-1 to 1-7>
Among the following Examples 1-1 to 1-7, Examples 1 to 5 are examples of the first embodiment, and Examples 6 and 7 are comparative examples of the first embodiment.
以下の例１－１～１－７中、例１～５は第１の実施形態における実施例であり、例６～７は第１の実施形態における比較例である。 <Example 1-1 to 1-7>
Among the following Examples 1-1 to 1-7, Examples 1 to 5 are examples of the first embodiment, and Examples 6 and 7 are comparative examples of the first embodiment.
１．樹脂組成物を製造するための各成分の準備
［熱硬化性樹脂］
・ポリフェニレンエーテル：ポリフェニレンエーテルの末端水酸基をメタクリル基で変性した変性ポリフェニレンエーテル、ＳＡＢＩＣ社製、Ｎｏｒｙｌ ＳＡ９０００、Ｍｗ１７００、１分子あたりの官能基数２個 1. Preparation of each component for producing a resin composition [thermosetting resin]
Polyphenylene ether: Modified polyphenylene ether in which the terminal hydroxyl groups of polyphenylene ether are modified with methacrylic groups, manufactured by SABIC, Noryl SA9000, Mw 1700, two functional groups per molecule
［熱硬化性樹脂］
・ポリフェニレンエーテル：ポリフェニレンエーテルの末端水酸基をメタクリル基で変性した変性ポリフェニレンエーテル、ＳＡＢＩＣ社製、Ｎｏｒｙｌ ＳＡ９０００、Ｍｗ１７００、１分子あたりの官能基数２個 1. Preparation of each component for producing a resin composition [thermosetting resin]
Polyphenylene ether: Modified polyphenylene ether in which the terminal hydroxyl groups of polyphenylene ether are modified with methacrylic groups, manufactured by SABIC, Noryl SA9000, Mw 1700, two functional groups per molecule
＜中空シリカ粒子Ａ１＞
中空シリカ粒子Ａ１は以下のようにして作製した。 <Hollow Silica Particles A1>
The hollow silica particles A1 were prepared as follows.
中空シリカ粒子Ａ１は以下のようにして作製した。 <Hollow Silica Particles A1>
The hollow silica particles A1 were prepared as follows.
（エマルションの作製）
純水１２５０ｇにＥＯ－ＰＯ－ＥＯブロックコポリマー（ＡＤＥＫＡ社製、プルロニック（登録商標）Ｆ６８）を４ｇ添加し溶解するまで撹拌し、水溶液を得た。この水溶液にソルビタン酸モノオレート（三洋化成工業社製、イオネット（登録商標）Ｓ－８０）４ｇを溶解したｎ－デカン４２ｇを加え、ＩＫＡ社製ホモジナイザーを使って液全体が均一になるまで撹拌し、粗エマルションを作製した。
この粗エマルションを、高圧乳化機（エスエムテー社製、ＬＡＢ１０００）を使い、圧力５０ｂａｒで乳化を行い、エマルション径が１μｍのエマルションを作製した。 (Preparation of emulsion)
4 g of EO-PO-EO block copolymer (Pluronic (registered trademark) F68, manufactured by ADEKA Corporation) 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 acid monooleate (IONET (registered trademark) S-80, manufactured by Sanyo Chemical Industries, Ltd.) was dissolved was added to this aqueous solution, and the whole solution was stirred using an IKA homogenizer until it became uniform to prepare a crude emulsion.
This crude emulsion was emulsified at a pressure of 50 bar using a high-pressure emulsifier (LAB1000, manufactured by SMT Corporation) to produce an emulsion with an emulsion diameter of 1 μm.
純水１２５０ｇにＥＯ－ＰＯ－ＥＯブロックコポリマー（ＡＤＥＫＡ社製、プルロニック（登録商標）Ｆ６８）を４ｇ添加し溶解するまで撹拌し、水溶液を得た。この水溶液にソルビタン酸モノオレート（三洋化成工業社製、イオネット（登録商標）Ｓ－８０）４ｇを溶解したｎ－デカン４２ｇを加え、ＩＫＡ社製ホモジナイザーを使って液全体が均一になるまで撹拌し、粗エマルションを作製した。
この粗エマルションを、高圧乳化機（エスエムテー社製、ＬＡＢ１０００）を使い、圧力５０ｂａｒで乳化を行い、エマルション径が１μｍのエマルションを作製した。 (Preparation of emulsion)
4 g of EO-PO-EO block copolymer (Pluronic (registered trademark) F68, manufactured by ADEKA Corporation) 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 acid monooleate (IONET (registered trademark) S-80, manufactured by Sanyo Chemical Industries, Ltd.) was dissolved was added to this aqueous solution, and the whole solution was stirred using an IKA homogenizer until it became uniform to prepare a crude emulsion.
This crude emulsion was emulsified at a pressure of 50 bar using a high-pressure emulsifier (LAB1000, manufactured by SMT Corporation) to produce an emulsion with an emulsion diameter of 1 μm.
（エージング）
得られたエマルションを４０℃で１２時間静置した。 (aging)
The resulting emulsion was allowed to stand at 40° C. for 12 hours.
得られたエマルションを４０℃で１２時間静置した。 (aging)
The resulting emulsion was allowed to stand at 40° C. for 12 hours.
（１段目シェル層形成）
静置後、エマルション１３００ｇに、ｐＨが２となるよう、希釈したケイ酸ナトリウム水溶液（ＳｉＯ２濃度１０．４質量％、Ｎａ２Ｏ濃度３．６質量％）２３ｇ及び２Ｍ塩酸を加え、３０℃で保持しながら撹拌し、混合液を得た。
次いで、混合液を撹拌しながら１Ｍ水酸化ナトリウム水溶液をｐＨが６となるようゆっくり滴下し、オイルコア－シリカシェル粒子分散液を得た。得られたオイルコア－シリカシェル粒子分散液を保持し、熟成させた。 (First shell layer formation)
After standing, 23 g of a diluted sodium silicate aqueous solution ( SiO2 concentration 10.4 mass%, Na2O concentration 3.6 mass%) and 2 M hydrochloric acid were added to 1,300 g of the emulsion so that the pH was 2, and the mixture was stirred while maintaining the temperature at 30° C. to obtain a mixed liquid.
Next, while stirring the mixture, a 1M aqueous solution of sodium hydroxide was slowly added dropwise so that the pH of the mixture became 6, thereby obtaining an oil core-silica shell particle dispersion. The obtained oil core-silica shell particle dispersion was retained and aged.
静置後、エマルション１３００ｇに、ｐＨが２となるよう、希釈したケイ酸ナトリウム水溶液（ＳｉＯ２濃度１０．４質量％、Ｎａ２Ｏ濃度３．６質量％）２３ｇ及び２Ｍ塩酸を加え、３０℃で保持しながら撹拌し、混合液を得た。
次いで、混合液を撹拌しながら１Ｍ水酸化ナトリウム水溶液をｐＨが６となるようゆっくり滴下し、オイルコア－シリカシェル粒子分散液を得た。得られたオイルコア－シリカシェル粒子分散液を保持し、熟成させた。 (First shell layer formation)
After standing, 23 g of a diluted sodium silicate aqueous solution ( SiO2 concentration 10.4 mass%, Na2O concentration 3.6 mass%) and 2 M hydrochloric acid were added to 1,300 g of the emulsion so that the pH was 2, and the mixture was stirred while maintaining the temperature at 30° C. to obtain a mixed liquid.
Next, while stirring the mixture, a 1M aqueous solution of sodium hydroxide was slowly added dropwise so that the pH of the mixture became 6, thereby obtaining an oil core-silica shell particle dispersion. The obtained oil core-silica shell particle dispersion was retained and aged.
（２段目シェル層形成）
オイルコア－シリカシェル粒子分散液を７０℃に加熱し、撹拌しながら１Ｍ水酸化ナトリウム水溶液をゆっくり添加し、ｐＨを９とした。
次に、希釈したケイ酸ナトリウム水溶液（ＳｉＯ２濃度１０．４質量％、Ｎａ２Ｏ濃度３．６質量％）３３０ｇを、ｐＨ９になるように０．５Ｍ塩酸とともに徐々に添加した。
この懸濁液を８０℃で１日間保持した後、室温（２５℃）まで冷却し、中空シリカ前駆体分散液を得た。 (Second shell layer formation)
The oil core-silica shell particle dispersion was heated to 70° C., and a 1M aqueous solution of sodium hydroxide was slowly added thereto with stirring to adjust the pH to 9.
Next, 330 g of a diluted aqueous sodium silicate solution ( SiO2 concentration 10.4% by mass, Na2O concentration 3.6% by mass) was gradually added together with 0.5 M hydrochloric acid to adjust the pH to 9.
This suspension was kept at 80° C. for 1 day and then cooled to room temperature (25° C.) to obtain a hollow silica precursor dispersion.
オイルコア－シリカシェル粒子分散液を７０℃に加熱し、撹拌しながら１Ｍ水酸化ナトリウム水溶液をゆっくり添加し、ｐＨを９とした。
次に、希釈したケイ酸ナトリウム水溶液（ＳｉＯ２濃度１０．４質量％、Ｎａ２Ｏ濃度３．６質量％）３３０ｇを、ｐＨ９になるように０．５Ｍ塩酸とともに徐々に添加した。
この懸濁液を８０℃で１日間保持した後、室温（２５℃）まで冷却し、中空シリカ前駆体分散液を得た。 (Second shell layer formation)
The oil core-silica shell particle dispersion was heated to 70° C., and a 1M aqueous solution of sodium hydroxide was slowly added thereto with stirring to adjust the pH to 9.
Next, 330 g of a diluted aqueous sodium silicate solution ( SiO2 concentration 10.4% by mass, Na2O concentration 3.6% by mass) was gradually added together with 0.5 M hydrochloric acid to adjust the pH to 9.
This suspension was kept at 80° C. for 1 day and then cooled to room temperature (25° C.) to obtain a hollow silica precursor dispersion.
（ろ過、洗浄、乾燥、焼成）
中空シリカ前駆体分散液全量を、２Ｍ塩酸でｐＨ２まで中和後、定量ろ紙５Ｃを用いてろ過を行った。その後、８０℃のイオン交換水３５０ｍｌを加えて再度加圧濾過し、中空シリカケーキを洗浄した。
ろ過後のケーキを、窒素雰囲気下で、１００℃で１時間、続けて４００℃で２時間乾燥し（昇温時間１０℃／ｍｉｎ）、有機分を除去することで中空シリカ前駆体を得た。
得られた中空シリカ前駆体を、１０００℃で１時間焼成（昇温時間１０℃／ｍｉｎ）することでシェルの焼き締めを行い、中空シリカ焼成粒子を得た。 (Filtering, washing, drying, firing)
The entire 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 80° C. ion-exchanged water was added and pressure filtered again to wash the hollow silica cake.
The cake after filtration was dried in a nitrogen atmosphere at 100° C. for 1 hour and then at 400° C. for 2 hours (heating rate: 10° C./min) to remove the organic matter, thereby obtaining a hollow silica precursor.
The obtained hollow silica precursor was baked at 1000° C. for 1 hour (heating rate: 10° C./min) to bake and tighten the shell, thereby obtaining baked hollow silica particles.
中空シリカ前駆体分散液全量を、２Ｍ塩酸でｐＨ２まで中和後、定量ろ紙５Ｃを用いてろ過を行った。その後、８０℃のイオン交換水３５０ｍｌを加えて再度加圧濾過し、中空シリカケーキを洗浄した。
ろ過後のケーキを、窒素雰囲気下で、１００℃で１時間、続けて４００℃で２時間乾燥し（昇温時間１０℃／ｍｉｎ）、有機分を除去することで中空シリカ前駆体を得た。
得られた中空シリカ前駆体を、１０００℃で１時間焼成（昇温時間１０℃／ｍｉｎ）することでシェルの焼き締めを行い、中空シリカ焼成粒子を得た。 (Filtering, washing, drying, firing)
The entire 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 80° C. ion-exchanged water was added and pressure filtered again to wash the hollow silica cake.
The cake after filtration was dried in a nitrogen atmosphere at 100° C. for 1 hour and then at 400° C. for 2 hours (heating rate: 10° C./min) to remove the organic matter, thereby obtaining a hollow silica precursor.
The obtained hollow silica precursor was baked at 1000° C. for 1 hour (heating rate: 10° C./min) to bake and tighten the shell, thereby obtaining baked hollow silica particles.
（表面処理）
２００ｍｌガラスビーカーに、中空シリカ焼成粒子１０ｇ、イソプロパノール１５０ｍｌ、ビニルトリメトキシシラン０．１ｇを添加し、１００℃で１時間還流した。その後、疎水性ＰＴＦＥメンブレンフィルターを用いて減圧濾過し、イソプロパノール２０ｍｌで洗浄後、１５０℃に温度調整した真空乾燥機で２時間真空乾燥し、表面処理された中空シリカ粒子Ａ１を得た。
１段目シェル層及び２段目シェル層の総質量に対するナトリウムの含有率は、５００質量ｐｐｍであった。 (surface treatment)
10 g of hollow calcined silica particles, 150 ml of isopropanol, and 0.1 g of vinyltrimethoxysilane were added to a 200 ml glass beaker and refluxed for 1 hour at 100° C. Thereafter, the mixture was filtered under reduced pressure using a hydrophobic PTFE membrane filter, washed with 20 ml of isopropanol, and then vacuum-dried for 2 hours in a vacuum dryer adjusted to a temperature of 150° C. to obtain surface-treated hollow silica particles A1.
The sodium content relative to the total mass of the first shell layer and the second shell layer was 500 ppm by mass.
２００ｍｌガラスビーカーに、中空シリカ焼成粒子１０ｇ、イソプロパノール１５０ｍｌ、ビニルトリメトキシシラン０．１ｇを添加し、１００℃で１時間還流した。その後、疎水性ＰＴＦＥメンブレンフィルターを用いて減圧濾過し、イソプロパノール２０ｍｌで洗浄後、１５０℃に温度調整した真空乾燥機で２時間真空乾燥し、表面処理された中空シリカ粒子Ａ１を得た。
１段目シェル層及び２段目シェル層の総質量に対するナトリウムの含有率は、５００質量ｐｐｍであった。 (surface treatment)
10 g of hollow calcined silica particles, 150 ml of isopropanol, and 0.1 g of vinyltrimethoxysilane were added to a 200 ml glass beaker and refluxed for 1 hour at 100° C. Thereafter, the mixture was filtered under reduced pressure using a hydrophobic PTFE membrane filter, washed with 20 ml of isopropanol, and then vacuum-dried for 2 hours in a vacuum dryer adjusted to a temperature of 150° C. to obtain surface-treated hollow silica particles A1.
The sodium content relative to the total mass of the first shell layer and the second shell layer was 500 ppm by mass.
＜中空シリカ粒子Ａ２＞
ＥＯ－ＰＯ－ＥＯブロックコポリマーの使用量を２ｇに、ソルビタン酸モノオレートの使用量を２ｇに変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ２を得た。 <Hollow Silica Particles A2>
Hollow silica particles A2 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 2 g and the amount of sorbitan acid monooleate used was changed to 2 g.
ＥＯ－ＰＯ－ＥＯブロックコポリマーの使用量を２ｇに、ソルビタン酸モノオレートの使用量を２ｇに変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ２を得た。 <Hollow Silica Particles A2>
Hollow silica particles A2 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 2 g and the amount of sorbitan acid monooleate used was changed to 2 g.
＜中空シリカ粒子Ａ３＞
ＥＯ－ＰＯ－ＥＯブロックコポリマーの使用量を１０ｇに変更し、ソルビタン酸モノオレートを使用せず、乳化における圧力を１００ｂａｒに変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ３を得た。 <Hollow Silica Particles A3>
Hollow silica particles A3 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 10 g, sorbitan acid monooleate was not used, and the pressure in emulsification was changed to 100 bar.
ＥＯ－ＰＯ－ＥＯブロックコポリマーの使用量を１０ｇに変更し、ソルビタン酸モノオレートを使用せず、乳化における圧力を１００ｂａｒに変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ３を得た。 <Hollow Silica Particles A3>
Hollow silica particles A3 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 10 g, sorbitan acid monooleate was not used, and the pressure in emulsification was changed to 100 bar.
＜中空シリカ粒子Ａ４＞
中空シリカ前駆体の焼成条件を、１１００℃で１時間（昇温時間１０℃／ｍｉｎ）に変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ４を得た。 <Hollow Silica Particles A4>
Hollow silica particles A4 were obtained in the same manner as hollow silica particles A1, except that the hollow silica precursor was calcined at 1,100° C. for 1 hour (temperature increase rate: 10° C./min).
中空シリカ前駆体の焼成条件を、１１００℃で１時間（昇温時間１０℃／ｍｉｎ）に変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ４を得た。 <Hollow Silica Particles A4>
Hollow silica particles A4 were obtained in the same manner as hollow silica particles A1, except that the hollow silica precursor was calcined at 1,100° C. for 1 hour (temperature increase rate: 10° C./min).
＜中空シリカ粒子Ａ５＞
中空シリカ前駆体の焼成条件を、８００℃で１時間（昇温時間１０℃／ｍｉｎ）に変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ５を得た。 <Hollow Silica Particles A5>
Hollow silica particles A5 were obtained in the same manner as hollow silica particles A1, except that the calcination conditions of the hollow silica precursor were changed to 800° C. for 1 hour (heating time: 10° C./min).
中空シリカ前駆体の焼成条件を、８００℃で１時間（昇温時間１０℃／ｍｉｎ）に変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ５を得た。 <Hollow Silica Particles A5>
Hollow silica particles A5 were obtained in the same manner as hollow silica particles A1, except that the calcination conditions of the hollow silica precursor were changed to 800° C. for 1 hour (heating time: 10° C./min).
＜中空粒子Ｂ１＞
シリカ系中空微粒子分散ゾル（触媒化成工業（株）製、スルーリア（登録商標）１４２０、平均一次粒子径６０ｎｍ、濃度２０．５質量％、分散媒：イソプロパノール）を、１２０℃で２時間真空引きし、溶剤を乾固し、中空粒子Ｂ１を得た。 <Hollow Particles B1>
A silica-based hollow fine particle dispersion sol (Catalysts and Chemical Industries Co., Ltd., Sururia (registered trademark) 1420, average primary particle diameter 60 nm, concentration 20.5 mass%, dispersion medium: isopropanol) was subjected to vacuum drawing at 120° C. for 2 hours to dry out the solvent, thereby obtaining hollow particles B1.
シリカ系中空微粒子分散ゾル（触媒化成工業（株）製、スルーリア（登録商標）１４２０、平均一次粒子径６０ｎｍ、濃度２０．５質量％、分散媒：イソプロパノール）を、１２０℃で２時間真空引きし、溶剤を乾固し、中空粒子Ｂ１を得た。 <Hollow Particles B1>
A silica-based hollow fine particle dispersion sol (Catalysts and Chemical Industries Co., Ltd., Sururia (registered trademark) 1420, average primary particle diameter 60 nm, concentration 20.5 mass%, dispersion medium: isopropanol) was subjected to vacuum drawing at 120° C. for 2 hours to dry out the solvent, thereby obtaining hollow particles B1.
＜中空粒子Ｂ２＞
グラスバブルスｉＭ１６Ｋ（メジアン径１７μｍのガラスバルーン、３Ｍ社）をそのまま用いた。 <Hollow Particles B2>
Glass Bubbles iM16K (glass balloons with a median diameter of 17 μm, 3M Company) were used as is.
グラスバブルスｉＭ１６Ｋ（メジアン径１７μｍのガラスバルーン、３Ｍ社）をそのまま用いた。 <Hollow Particles B2>
Glass Bubbles iM16K (glass balloons with a median diameter of 17 μm, 3M Company) were used as is.
[例１－１]
ポリフェニレンエーテル樹脂の５９質量部、ブタジエン・スチレンランダムコポリマーの１６質量部、トリアリルイソシアヌレートの２５質量部、α，α’－ジ（t－ブチルペルオキシ）ジイソプロピルベンゼンの１質量部、中空シリカ粒子Ａ１を全体の２０体積％となる質量部、トルエンの８０質量部をポリビンに入れ、プラネタリーディスパで混練して樹脂組成物を得た。
樹脂組成物を、ＩＰＣスペック２１１６のガラスクロスに含浸塗工し、１６０℃で４分間加熱乾燥してプリプレグを得た。
プリプレグを３枚重ね、上下にロープロファイル銅箔（厚さ：１８μｍ、Ｒｚ：３．５μｍ、三井金属社製、３ＥＣ－Ｍ３－Ｖ－１８）を積層し、２３０℃、圧力３０ｋｇ／ｃｍ２で１２０分間加熱成形し、樹脂付き金属基材を得た。 [Example 1-1]
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'-di(t-butylperoxy)diisopropylbenzene, parts by mass of hollow silica particles A1 accounting for 20% by volume of the total, and 80 parts by mass of toluene were placed in a polyvinyl chloride bottle and kneaded using a planetary dispenser to obtain a resin composition.
The resin composition was applied to a glass cloth of IPC spec 2116 by impregnation, and then heated and dried at 160° C. for 4 minutes to obtain a prepreg.
Three sheets of prepreg were stacked, low-profile copper foil (thickness: 18 μm, Rz: 3.5 μm, Mitsui Kinzoku Co., Ltd., 3EC-M3-V-18) was laminated on the top and bottom, and the resulting mixture was heated and molded at 230° C. and a pressure of 30 kg/cm 2 for 120 minutes to obtain a metal substrate with resin.
ポリフェニレンエーテル樹脂の５９質量部、ブタジエン・スチレンランダムコポリマーの１６質量部、トリアリルイソシアヌレートの２５質量部、α，α’－ジ（t－ブチルペルオキシ）ジイソプロピルベンゼンの１質量部、中空シリカ粒子Ａ１を全体の２０体積％となる質量部、トルエンの８０質量部をポリビンに入れ、プラネタリーディスパで混練して樹脂組成物を得た。
樹脂組成物を、ＩＰＣスペック２１１６のガラスクロスに含浸塗工し、１６０℃で４分間加熱乾燥してプリプレグを得た。
プリプレグを３枚重ね、上下にロープロファイル銅箔（厚さ：１８μｍ、Ｒｚ：３．５μｍ、三井金属社製、３ＥＣ－Ｍ３－Ｖ－１８）を積層し、２３０℃、圧力３０ｋｇ／ｃｍ２で１２０分間加熱成形し、樹脂付き金属基材を得た。 [Example 1-1]
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'-di(t-butylperoxy)diisopropylbenzene, parts by mass of hollow silica particles A1 accounting for 20% by volume of the total, and 80 parts by mass of toluene were placed in a polyvinyl chloride bottle and kneaded using a planetary dispenser to obtain a resin composition.
The resin composition was applied to a glass cloth of IPC spec 2116 by impregnation, and then heated and dried at 160° C. for 4 minutes to obtain a prepreg.
Three sheets of prepreg were stacked, low-profile copper foil (thickness: 18 μm, Rz: 3.5 μm, Mitsui Kinzoku Co., Ltd., 3EC-M3-V-18) was laminated on the top and bottom, and the resulting mixture was heated and molded at 230° C. and a pressure of 30 kg/cm 2 for 120 minutes to obtain a metal substrate with resin.
［例１－２～１－７］
中空シリカ粒子Ａ１を、表１に記載の中空シリカ粒子又は中空粒子に変更した以外は、例１－１と同様にして、樹脂組成物、プリプレグ及び樹脂付き金属基材を製造した。 [Examples 1-2 to 1-7]
Except for changing the hollow silica particles A1 to the hollow silica particles or hollow particles shown in Table 1, a resin composition, a prepreg, and a resin-coated metal substrate were produced in the same manner as in Example 1-1.
中空シリカ粒子Ａ１を、表１に記載の中空シリカ粒子又は中空粒子に変更した以外は、例１－１と同様にして、樹脂組成物、プリプレグ及び樹脂付き金属基材を製造した。 [Examples 1-2 to 1-7]
Except for changing the hollow silica particles A1 to the hollow silica particles or hollow particles shown in Table 1, a resin composition, a prepreg, and a resin-coated metal substrate were produced in the same manner as in Example 1-1.
＜剥離強度の測定＞
例１－１～１－７において製造した樹脂付き金属基材を用いて、ＩＰＣ－ＴＭ６５０－２．４．８に準拠し、プリプレグの硬化物と銅箔との間の剥離強度を測定した。測定結果を表１にまとめた。 <Measurement of Peel Strength>
The resin-coated metal substrates produced in Examples 1-1 to 1-7 were used to measure the peel strength between the cured prepreg and the copper foil in accordance with IPC-TM650-2.4.8. The measurement results are summarized in Table 1.
例１－１～１－７において製造した樹脂付き金属基材を用いて、ＩＰＣ－ＴＭ６５０－２．４．８に準拠し、プリプレグの硬化物と銅箔との間の剥離強度を測定した。測定結果を表１にまとめた。 <Measurement of Peel Strength>
The resin-coated metal substrates produced in Examples 1-1 to 1-7 were used to measure the peel strength between the cured prepreg and the copper foil in accordance with IPC-TM650-2.4.8. The measurement results are summarized in Table 1.
＜比誘電率及び誘電正接の測定＞
例１－１～１－７において製造した樹脂付き金属基材を、エッチング液（サンハヤト社製、Ｈ－１０００Ａ、塩化第二鉄水溶液）に浸漬し、片面の銅箔を完全に除去した後、オーブンにて１００℃で１０分乾燥した。得られたプレス済プリプレグを用いて、縦スプリットポスト誘電体共振器（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製）にて、比誘電率と誘電正接（測定周波数：１０ＧＨｚ）とを測定した。結果を表１に示す。 <Measurement of relative dielectric constant and dielectric loss tangent>
The resin-coated metal substrates produced in Examples 1-1 to 1-7 were immersed in an etching solution (H-1000A, ferric chloride aqueous solution, manufactured by Sanhayato Corporation) to completely remove the copper foil on one side, and then dried in an oven at 100°C for 10 minutes. The obtained pressed prepregs were used to measure the relative dielectric constant and dielectric loss tangent (measurement frequency: 10 GHz) using a vertical split post dielectric resonator (manufactured by Agilent Technologies). The results are shown in Table 1.
例１－１～１－７において製造した樹脂付き金属基材を、エッチング液（サンハヤト社製、Ｈ－１０００Ａ、塩化第二鉄水溶液）に浸漬し、片面の銅箔を完全に除去した後、オーブンにて１００℃で１０分乾燥した。得られたプレス済プリプレグを用いて、縦スプリットポスト誘電体共振器（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製）にて、比誘電率と誘電正接（測定周波数：１０ＧＨｚ）とを測定した。結果を表１に示す。 <Measurement of relative dielectric constant and dielectric loss tangent>
The resin-coated metal substrates produced in Examples 1-1 to 1-7 were immersed in an etching solution (H-1000A, ferric chloride aqueous solution, manufactured by Sanhayato Corporation) to completely remove the copper foil on one side, and then dried in an oven at 100°C for 10 minutes. The obtained pressed prepregs were used to measure the relative dielectric constant and dielectric loss tangent (measurement frequency: 10 GHz) using a vertical split post dielectric resonator (manufactured by Agilent Technologies). The results are shown in Table 1.
表１に示されるように、本組成物を用いて得られた硬化物は、低比誘電率であり、また、基材との密着性に優れている。
As shown in Table 1, the cured product obtained using this composition has a low dielectric constant and excellent adhesion to the substrate.
≪例２－１～２－６及び例３－１～３－６≫
以下の例２－１～２－７及び例３－１～３－６中、例２－１～２－４及び例３－１～３－４は第２の実施形態における実施例であり、例２－５～２－６及び例３－５～３－６は第２の実施形態における比較例である。 <Examples 2-1 to 2-6 and Examples 3-1 to 3-6>
Among the following Examples 2-1 to 2-7 and Examples 3-1 to 3-6, Examples 2-1 to 2-4 and Examples 3-1 to 3-4 are Examples in the second embodiment, and Examples 2-5 to 2-6 and Examples 3-5 to 3-6 are Comparative Examples in the second embodiment.
以下の例２－１～２－７及び例３－１～３－６中、例２－１～２－４及び例３－１～３－４は第２の実施形態における実施例であり、例２－５～２－６及び例３－５～３－６は第２の実施形態における比較例である。 <Examples 2-1 to 2-6 and Examples 3-1 to 3-6>
Among the following Examples 2-1 to 2-7 and Examples 3-1 to 3-6, Examples 2-1 to 2-4 and Examples 3-1 to 3-4 are Examples in the second embodiment, and Examples 2-5 to 2-6 and Examples 3-5 to 3-6 are Comparative Examples in the second embodiment.
１．樹脂組成物を製造するための各成分の準備
＜熱硬化性樹脂＞
・ポリフェニレンエーテル：ポリフェニレンエーテルの末端水酸基をメタクリル基で変性した変性ポリフェニレンエーテル、ＳＡＢＩＣ社製、Ｎｏｒｙｌ ＳＡ９０００、Ｍｗ１７００、１分子あたりの官能基数２個
・ポリイミド樹脂：荒川化学社製、ＰＩＡＤ３００、固形分濃度３０質量％ 1. Preparation of each component for producing a resin composition <Thermosetting resin>
Polyphenylene ether: Modified polyphenylene ether in which the terminal hydroxyl groups of polyphenylene ether are modified with methacrylic groups, manufactured by SABIC Corporation, Noryl SA9000, Mw 1700, number of functional groups per molecule: 2 Polyimide resin: Manufactured by Arakawa Chemical Industries, Ltd., PIAD300, solid content concentration 30% by mass
＜熱硬化性樹脂＞
・ポリフェニレンエーテル：ポリフェニレンエーテルの末端水酸基をメタクリル基で変性した変性ポリフェニレンエーテル、ＳＡＢＩＣ社製、Ｎｏｒｙｌ ＳＡ９０００、Ｍｗ１７００、１分子あたりの官能基数２個
・ポリイミド樹脂：荒川化学社製、ＰＩＡＤ３００、固形分濃度３０質量％ 1. Preparation of each component for producing a resin composition <Thermosetting resin>
Polyphenylene ether: Modified polyphenylene ether in which the terminal hydroxyl groups of polyphenylene ether are modified with methacrylic groups, manufactured by SABIC Corporation, Noryl SA9000, Mw 1700, number of functional groups per molecule: 2 Polyimide resin: Manufactured by Arakawa Chemical Industries, Ltd., PIAD300, solid content concentration 30% by mass
＜中空シリカ粒子Ａ１＞
中空シリカ粒子Ａ１は以下のようにして作製した。 <Hollow Silica Particles A1>
The hollow silica particles A1 were prepared as follows.
中空シリカ粒子Ａ１は以下のようにして作製した。 <Hollow Silica Particles A1>
The hollow silica particles A1 were prepared as follows.
（エマルションの作製）
純水１２５０ｇにＥＯ－ＰＯ－ＥＯブロックコポリマー（ＡＤＥＫＡ社製、プルロニック（登録商標）Ｆ６８）を４ｇ添加し溶解するまで撹拌し、水溶液を得た。この水溶液にソルビタン酸モノオレート（三洋化成工業社製、イオネット（登録商標）Ｓ－８０）４ｇを溶解したｎ－デカン４２ｇを加え、ＩＫＡ社製ホモジナイザーを使って液全体が均一になるまで撹拌し、粗エマルションを作製した。
この粗エマルションを、高圧乳化機（エスエムテー社製、ＬＡＢ１０００）を使い、圧力５０ｂａｒで乳化を行い、エマルション径が１μｍのエマルションを作製した。 (Preparation of emulsion)
4 g of EO-PO-EO block copolymer (Pluronic (registered trademark) F68, manufactured by ADEKA Corporation) 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 acid monooleate (IONET (registered trademark) S-80, manufactured by Sanyo Chemical Industries, Ltd.) was dissolved was added to this aqueous solution, and the whole solution was stirred using an IKA homogenizer until it became uniform to prepare a crude emulsion.
This crude emulsion was emulsified at a pressure of 50 bar using a high-pressure emulsifier (LAB1000, manufactured by SMT Corporation) to produce an emulsion with an emulsion diameter of 1 μm.
純水１２５０ｇにＥＯ－ＰＯ－ＥＯブロックコポリマー（ＡＤＥＫＡ社製、プルロニック（登録商標）Ｆ６８）を４ｇ添加し溶解するまで撹拌し、水溶液を得た。この水溶液にソルビタン酸モノオレート（三洋化成工業社製、イオネット（登録商標）Ｓ－８０）４ｇを溶解したｎ－デカン４２ｇを加え、ＩＫＡ社製ホモジナイザーを使って液全体が均一になるまで撹拌し、粗エマルションを作製した。
この粗エマルションを、高圧乳化機（エスエムテー社製、ＬＡＢ１０００）を使い、圧力５０ｂａｒで乳化を行い、エマルション径が１μｍのエマルションを作製した。 (Preparation of emulsion)
4 g of EO-PO-EO block copolymer (Pluronic (registered trademark) F68, manufactured by ADEKA Corporation) 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 acid monooleate (IONET (registered trademark) S-80, manufactured by Sanyo Chemical Industries, Ltd.) was dissolved was added to this aqueous solution, and the whole solution was stirred using an IKA homogenizer until it became uniform to prepare a crude emulsion.
This crude emulsion was emulsified at a pressure of 50 bar using a high-pressure emulsifier (LAB1000, manufactured by SMT Corporation) to produce an emulsion with an emulsion diameter of 1 μm.
（エージング）
得られたエマルションを４０℃で１２時間静置した。 (aging)
The resulting emulsion was allowed to stand at 40° C. for 12 hours.
得られたエマルションを４０℃で１２時間静置した。 (aging)
The resulting emulsion was allowed to stand at 40° C. for 12 hours.
（１段目シェル層形成）
静置後、エマルション１３００ｇに、ｐＨが２となるよう、希釈したケイ酸ナトリウム水溶液（ＳｉＯ２濃度１０．４質量％、Ｎａ２Ｏ濃度３．６質量％）２３ｇ及び２Ｍ塩酸を加え、３０℃で保持しながら撹拌し、混合液を得た。
次いで、混合液を撹拌しながら１Ｍ水酸化ナトリウム水溶液をｐＨが６となるようゆっくり滴下し、オイルコア－シリカシェル粒子分散液を得た。得られたオイルコア－シリカシェル粒子分散液を保持し、熟成させた。 (First shell layer formation)
After standing, 23 g of a diluted sodium silicate aqueous solution ( SiO2 concentration 10.4 mass%, Na2O concentration 3.6 mass%) and 2 M hydrochloric acid were added to 1,300 g of the emulsion so that the pH was 2, and the mixture was stirred while maintaining the temperature at 30° C. to obtain a mixed liquid.
Next, while stirring the mixture, a 1M aqueous solution of sodium hydroxide was slowly added dropwise so that the pH of the mixture became 6, thereby obtaining an oil core-silica shell particle dispersion. The obtained oil core-silica shell particle dispersion was retained and aged.
静置後、エマルション１３００ｇに、ｐＨが２となるよう、希釈したケイ酸ナトリウム水溶液（ＳｉＯ２濃度１０．４質量％、Ｎａ２Ｏ濃度３．６質量％）２３ｇ及び２Ｍ塩酸を加え、３０℃で保持しながら撹拌し、混合液を得た。
次いで、混合液を撹拌しながら１Ｍ水酸化ナトリウム水溶液をｐＨが６となるようゆっくり滴下し、オイルコア－シリカシェル粒子分散液を得た。得られたオイルコア－シリカシェル粒子分散液を保持し、熟成させた。 (First shell layer formation)
After standing, 23 g of a diluted sodium silicate aqueous solution ( SiO2 concentration 10.4 mass%, Na2O concentration 3.6 mass%) and 2 M hydrochloric acid were added to 1,300 g of the emulsion so that the pH was 2, and the mixture was stirred while maintaining the temperature at 30° C. to obtain a mixed liquid.
Next, while stirring the mixture, a 1M aqueous solution of sodium hydroxide was slowly added dropwise so that the pH of the mixture became 6, thereby obtaining an oil core-silica shell particle dispersion. The obtained oil core-silica shell particle dispersion was retained and aged.
（２段目シェル層形成）
オイルコア－シリカシェル粒子分散液を７０℃に加熱し、撹拌しながら１Ｍ水酸化ナトリウム水溶液をゆっくり添加し、ｐＨを９とした。
次に、希釈したケイ酸ナトリウム水溶液（ＳｉＯ２濃度１０．４質量％、Ｎａ２Ｏ濃度３．６質量％）３３０ｇを、ｐＨ９になるように０．５Ｍ塩酸とともに徐々に添加した。
この懸濁液を８０℃で１日間保持した後、室温まで冷却し、中空シリカ前駆体分散液を得た。 (Second shell layer formation)
The oil core-silica shell particle dispersion was heated to 70° C., and a 1M aqueous solution of sodium hydroxide was slowly added thereto with stirring to adjust the pH to 9.
Next, 330 g of a diluted aqueous sodium silicate solution ( SiO2 concentration 10.4% by mass, Na2O concentration 3.6% by mass) was gradually added together with 0.5 M hydrochloric acid to adjust the pH to 9.
This suspension was kept at 80° C. for 1 day and then cooled to room temperature to obtain a hollow silica precursor dispersion.
オイルコア－シリカシェル粒子分散液を７０℃に加熱し、撹拌しながら１Ｍ水酸化ナトリウム水溶液をゆっくり添加し、ｐＨを９とした。
次に、希釈したケイ酸ナトリウム水溶液（ＳｉＯ２濃度１０．４質量％、Ｎａ２Ｏ濃度３．６質量％）３３０ｇを、ｐＨ９になるように０．５Ｍ塩酸とともに徐々に添加した。
この懸濁液を８０℃で１日間保持した後、室温まで冷却し、中空シリカ前駆体分散液を得た。 (Second shell layer formation)
The oil core-silica shell particle dispersion was heated to 70° C., and a 1M aqueous solution of sodium hydroxide was slowly added thereto with stirring to adjust the pH to 9.
Next, 330 g of a diluted aqueous sodium silicate solution ( SiO2 concentration 10.4% by mass, Na2O concentration 3.6% by mass) was gradually added together with 0.5 M hydrochloric acid to adjust the pH to 9.
This suspension was kept at 80° C. for 1 day and then cooled to room temperature to obtain a hollow silica precursor dispersion.
（ろ過、洗浄、乾燥、焼成）
中空シリカ前駆体分散液全量を、２Ｍ塩酸でｐＨ２まで中和後、定量ろ紙５Ｃを用いてろ過を行った。その後、８０℃のイオン交換水３５０ｍｌを加えて再度加圧濾過し、中空シリカケーキを洗浄した。
ろ過後のケーキを、窒素雰囲気下で、１００℃で１時間、続けて４００℃で２時間乾燥し（昇温時間１０℃／ｍｉｎ）、有機分を除去することで中空シリカ前駆体を得た。
得られた中空シリカ前駆体を、１０００℃で１時間焼成（昇温時間１０℃／ｍｉｎ）することでシェルの焼き締めを行い、中空シリカ焼成粒子を得た。 (Filtering, washing, drying, firing)
The entire 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 80° C. ion-exchanged water was added and pressure filtered again to wash the hollow silica cake.
The cake after filtration was dried in a nitrogen atmosphere at 100° C. for 1 hour and then at 400° C. for 2 hours (heating rate: 10° C./min) to remove the organic matter, thereby obtaining a hollow silica precursor.
The obtained hollow silica precursor was baked at 1000° C. for 1 hour (heating rate: 10° C./min) to bake and tighten the shell, thereby obtaining baked hollow silica particles.
中空シリカ前駆体分散液全量を、２Ｍ塩酸でｐＨ２まで中和後、定量ろ紙５Ｃを用いてろ過を行った。その後、８０℃のイオン交換水３５０ｍｌを加えて再度加圧濾過し、中空シリカケーキを洗浄した。
ろ過後のケーキを、窒素雰囲気下で、１００℃で１時間、続けて４００℃で２時間乾燥し（昇温時間１０℃／ｍｉｎ）、有機分を除去することで中空シリカ前駆体を得た。
得られた中空シリカ前駆体を、１０００℃で１時間焼成（昇温時間１０℃／ｍｉｎ）することでシェルの焼き締めを行い、中空シリカ焼成粒子を得た。 (Filtering, washing, drying, firing)
The entire 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 80° C. ion-exchanged water was added and pressure filtered again to wash the hollow silica cake.
The cake after filtration was dried in a nitrogen atmosphere at 100° C. for 1 hour and then at 400° C. for 2 hours (heating rate: 10° C./min) to remove the organic matter, thereby obtaining a hollow silica precursor.
The obtained hollow silica precursor was baked at 1000° C. for 1 hour (heating rate: 10° C./min) to bake and tighten the shell, thereby obtaining baked hollow silica particles.
（表面処理）
２００ｍｌガラスビーカーに、中空シリカ焼成粒子１０ｇ、イソプロパノール１５０ｍｌ、ビニルトリメトキシシラン０．１ｇを添加し、１００℃で１時間還流した。その後、疎水性ＰＴＦＥメンブレンフィルターを用いて減圧濾過し、イソプロパノール２０ｍｌで洗浄後、１５０℃に温度調整した真空乾燥機で２時間真空乾燥し、表面処理された中空シリカ粒子Ａ１を得た。
１段目シェル層及び２段目シェル層の総質量に対するナトリウムの含有率は、５００質量ｐｐｍであった。 (surface treatment)
10 g of hollow calcined silica particles, 150 ml of isopropanol, and 0.1 g of vinyltrimethoxysilane were added to a 200 ml glass beaker and refluxed for 1 hour at 100° C. Thereafter, the mixture was filtered under reduced pressure using a hydrophobic PTFE membrane filter, washed with 20 ml of isopropanol, and then vacuum-dried for 2 hours in a vacuum dryer adjusted to a temperature of 150° C. to obtain surface-treated hollow silica particles A1.
The sodium content relative to the total mass of the first shell layer and the second shell layer was 500 ppm by mass.
２００ｍｌガラスビーカーに、中空シリカ焼成粒子１０ｇ、イソプロパノール１５０ｍｌ、ビニルトリメトキシシラン０．１ｇを添加し、１００℃で１時間還流した。その後、疎水性ＰＴＦＥメンブレンフィルターを用いて減圧濾過し、イソプロパノール２０ｍｌで洗浄後、１５０℃に温度調整した真空乾燥機で２時間真空乾燥し、表面処理された中空シリカ粒子Ａ１を得た。
１段目シェル層及び２段目シェル層の総質量に対するナトリウムの含有率は、５００質量ｐｐｍであった。 (surface treatment)
10 g of hollow calcined silica particles, 150 ml of isopropanol, and 0.1 g of vinyltrimethoxysilane were added to a 200 ml glass beaker and refluxed for 1 hour at 100° C. Thereafter, the mixture was filtered under reduced pressure using a hydrophobic PTFE membrane filter, washed with 20 ml of isopropanol, and then vacuum-dried for 2 hours in a vacuum dryer adjusted to a temperature of 150° C. to obtain surface-treated hollow silica particles A1.
The sodium content relative to the total mass of the first shell layer and the second shell layer was 500 ppm by mass.
＜中空シリカ粒子Ａ２＞
ＥＯ－ＰＯ－ＥＯブロックコポリマーの使用量を２ｇに、ソルビタン酸モノオレートの使用量を２ｇに変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ２を得た。 <Hollow Silica Particles A2>
Hollow silica particles A2 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 2 g and the amount of sorbitan acid monooleate used was changed to 2 g.
ＥＯ－ＰＯ－ＥＯブロックコポリマーの使用量を２ｇに、ソルビタン酸モノオレートの使用量を２ｇに変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ２を得た。 <Hollow Silica Particles A2>
Hollow silica particles A2 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 2 g and the amount of sorbitan acid monooleate used was changed to 2 g.
＜中空シリカ粒子Ａ３＞
ＥＯ－ＰＯ－ＥＯブロックコポリマーの使用量を１０ｇに変更し、ソルビタン酸モノオレートを使用せず、乳化における圧力を１００ｂａｒに変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ３を得た。
１段目シェル層及び２段目シェル層の総質量に対するナトリウムの含有率は、１２００質量ｐｐｍであった。 <Hollow Silica Particles A3>
Hollow silica particles A3 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 10 g, sorbitan acid monooleate was not used, and the pressure in emulsification was changed to 100 bar.
The sodium content relative to the total mass of the first shell layer and the second shell layer was 1,200 ppm by mass.
ＥＯ－ＰＯ－ＥＯブロックコポリマーの使用量を１０ｇに変更し、ソルビタン酸モノオレートを使用せず、乳化における圧力を１００ｂａｒに変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ３を得た。
１段目シェル層及び２段目シェル層の総質量に対するナトリウムの含有率は、１２００質量ｐｐｍであった。 <Hollow Silica Particles A3>
Hollow silica particles A3 were obtained in the same manner as hollow silica particles A1, except that the amount of EO-PO-EO block copolymer used was changed to 10 g, sorbitan acid monooleate was not used, and the pressure in emulsification was changed to 100 bar.
The sodium content relative to the total mass of the first shell layer and the second shell layer was 1,200 ppm by mass.
＜中空シリカ粒子Ａ５＞
中空シリカ前駆体の焼成条件を、８００℃で１時間（昇温時間１０℃／ｍｉｎ）に変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ５を得た。 <Hollow Silica Particles A5>
Hollow silica particles A5 were obtained in the same manner as hollow silica particles A1, except that the calcination conditions of the hollow silica precursor were changed to 800° C. for 1 hour (heating time: 10° C./min).
中空シリカ前駆体の焼成条件を、８００℃で１時間（昇温時間１０℃／ｍｉｎ）に変更した以外は、中空シリカ粒子Ａ１と同様にして、中空シリカ粒子Ａ５を得た。 <Hollow Silica Particles A5>
Hollow silica particles A5 were obtained in the same manner as hollow silica particles A1, except that the calcination conditions of the hollow silica precursor were changed to 800° C. for 1 hour (heating time: 10° C./min).
＜中実粒子Ｃ１＞
ＳＯ－Ｃ２（メジアン径（ｄ５０）０．６μｍの中実シリカ粒子、アドマテックス社）をそのまま用いた。 <Solid particle C1>
SO-C2 (solid silica particles with a median diameter (d50) of 0.6 μm, Admatechs Co., Ltd.) was used as is.
ＳＯ－Ｃ２（メジアン径（ｄ５０）０．６μｍの中実シリカ粒子、アドマテックス社）をそのまま用いた。 <Solid particle C1>
SO-C2 (solid silica particles with a median diameter (d50) of 0.6 μm, Admatechs Co., Ltd.) was used as is.
＜中空粒子Ｃ２＞
Ｓ２２（メジアン径（ｄ５０）１７μｍのガラスバルーン、３Ｍ社）をそのまま用いた。 <Hollow Particles C2>
S22 (glass balloons with a median diameter (d50) of 17 μm, manufactured by 3M) was used as is.
Ｓ２２（メジアン径（ｄ５０）１７μｍのガラスバルーン、３Ｍ社）をそのまま用いた。 <Hollow Particles C2>
S22 (glass balloons with a median diameter (d50) of 17 μm, manufactured by 3M) was used as is.
[例２－１]
ポリフェニレンエーテル樹脂の５９質量部、ブタジエン・スチレンランダムコポリマーの１６質量部、トリアリルイソシアヌレートの２５質量部、α，α’－ジ（t－ブチルペルオキシ）ジイソプロピルベンゼンの１質量部、中空シリカ粒子Ａ１を全体の２０体積％となる質量部、トルエンの８０質量部をポリビンに入れ、プラネタリーディスパで混練して樹脂組成物を得た。
樹脂組成物を２５℃、相対湿度５０％の環境に１２時間静置した。
静置後、樹脂組成物を、ＩＰＣスペック２１１６のガラスクロスに含浸塗工し、１６０℃で４分間加熱乾燥してプリプレグを得た。
プリプレグを３枚重ね、上下にロープロファイル銅箔（厚さ：１８μｍ、Ｒｚ：３．５μｍ、三井金属社製、３ＥＣ－Ｍ３－Ｖ－１８）を積層し、２３０℃、圧力３０ｋｇ／ｃｍ２で１２０分間加熱成形し、樹脂付き金属基材を得た。
なお、使用した中空シリカ粒子の密度をＡ（ｇ／ｃｍ３）、樹脂の密度をＢ２（ｇ／ｃｍ３）としたとき、Ａ／Ｂ２を算出し、表２に示した。以降の例においても同様に算出し、表２にまとめた。なお、例２－５～２－６及び例３－５～３－６においては、中空シリカ粒子の密度ではなく、中実粒子、又は中空粒子の密度をＡとした。 [Example 2-1]
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'-di(t-butylperoxy)diisopropylbenzene, parts by mass of hollow silica particles A1 accounting for 20% by volume of the total, and 80 parts by mass of toluene were placed in a polyvinyl chloride bottle and kneaded using a planetary dispenser to obtain a resin composition.
The resin composition was allowed to stand in an environment of 25° C. and a relative humidity of 50% for 12 hours.
After standing, the resin composition was applied to impregnate a glass cloth of IPC spec 2116, and then heated and dried at 160° C. for 4 minutes to obtain a prepreg.
Three sheets of prepreg were stacked, low-profile copper foil (thickness: 18 μm, Rz: 3.5 μm, Mitsui Kinzoku Co., Ltd., 3EC-M3-V-18) was laminated on the top and bottom, and the resulting mixture was heated and molded at 230° C. and a pressure of 30 kg/cm 2 for 120 minutes to obtain a metal substrate with resin.
When the density of the hollow silica particles used is A (g/cm 3 ) and the density of the resin is B2 (g/cm 3 ), A/B2 was calculated and shown in Table 2. In the subsequent examples, similar calculations were performed and the results are summarized in Table 2. In Examples 2-5 to 2-6 and Examples 3-5 to 3-6, A was used as the density of the solid particles or hollow particles, not the density of the hollow silica particles.
ポリフェニレンエーテル樹脂の５９質量部、ブタジエン・スチレンランダムコポリマーの１６質量部、トリアリルイソシアヌレートの２５質量部、α，α’－ジ（t－ブチルペルオキシ）ジイソプロピルベンゼンの１質量部、中空シリカ粒子Ａ１を全体の２０体積％となる質量部、トルエンの８０質量部をポリビンに入れ、プラネタリーディスパで混練して樹脂組成物を得た。
樹脂組成物を２５℃、相対湿度５０％の環境に１２時間静置した。
静置後、樹脂組成物を、ＩＰＣスペック２１１６のガラスクロスに含浸塗工し、１６０℃で４分間加熱乾燥してプリプレグを得た。
プリプレグを３枚重ね、上下にロープロファイル銅箔（厚さ：１８μｍ、Ｒｚ：３．５μｍ、三井金属社製、３ＥＣ－Ｍ３－Ｖ－１８）を積層し、２３０℃、圧力３０ｋｇ／ｃｍ２で１２０分間加熱成形し、樹脂付き金属基材を得た。
なお、使用した中空シリカ粒子の密度をＡ（ｇ／ｃｍ３）、樹脂の密度をＢ２（ｇ／ｃｍ３）としたとき、Ａ／Ｂ２を算出し、表２に示した。以降の例においても同様に算出し、表２にまとめた。なお、例２－５～２－６及び例３－５～３－６においては、中空シリカ粒子の密度ではなく、中実粒子、又は中空粒子の密度をＡとした。 [Example 2-1]
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'-di(t-butylperoxy)diisopropylbenzene, parts by mass of hollow silica particles A1 accounting for 20% by volume of the total, and 80 parts by mass of toluene were placed in a polyvinyl chloride bottle and kneaded using a planetary dispenser to obtain a resin composition.
The resin composition was allowed to stand in an environment of 25° C. and a relative humidity of 50% for 12 hours.
After standing, the resin composition was applied to impregnate a glass cloth of IPC spec 2116, and then heated and dried at 160° C. for 4 minutes to obtain a prepreg.
Three sheets of prepreg were stacked, low-profile copper foil (thickness: 18 μm, Rz: 3.5 μm, Mitsui Kinzoku Co., Ltd., 3EC-M3-V-18) was laminated on the top and bottom, and the resulting mixture was heated and molded at 230° C. and a pressure of 30 kg/cm 2 for 120 minutes to obtain a metal substrate with resin.
When the density of the hollow silica particles used is A (g/cm 3 ) and the density of the resin is B2 (g/cm 3 ), A/B2 was calculated and shown in Table 2. In the subsequent examples, similar calculations were performed and the results are summarized in Table 2. In Examples 2-5 to 2-6 and Examples 3-5 to 3-6, A was used as the density of the solid particles or hollow particles, not the density of the hollow silica particles.
[例２－２～２－６]
中空シリカ粒子Ａ１を、表２に記載の中空シリカ粒子、中実粒子又は中空粒子に変更した以外は、例２－１と同様にして、樹脂組成物、プリプレグ及び樹脂付き金属基材を製造した。 [Examples 2-2 to 2-6]
Except for changing the hollow silica particles A1 to the hollow silica particles, solid particles or hollow particles shown in Table 2, a resin composition, a prepreg and a resin-coated metal substrate were produced in the same manner as in Example 2-1.
中空シリカ粒子Ａ１を、表２に記載の中空シリカ粒子、中実粒子又は中空粒子に変更した以外は、例２－１と同様にして、樹脂組成物、プリプレグ及び樹脂付き金属基材を製造した。 [Examples 2-2 to 2-6]
Except for changing the hollow silica particles A1 to the hollow silica particles, solid particles or hollow particles shown in Table 2, a resin composition, a prepreg and a resin-coated metal substrate were produced in the same manner as in Example 2-1.
[例３－１]
ポリイミド樹脂（荒川化学工業製、ＰＩＡＤ３００、固形分３０％）の５０質量部、中空シリカ粒子Ａ－１を全体の２０体積％となる質量部、シクロヘキサノン２０質量部をポリビンに入れ、Φ２０ｍｍのアルミナボールを入れて３０ｒｐｍで１２時間混合し、アルミナボールを除いて樹脂組成物を得た。
樹脂組成物を２５℃、相対湿度５０％の環境に１２時間静置した。
静置後、樹脂組成物を、ＩＰＣスペック２１１６のガラスクロスに含浸塗工し、１６０℃で４分間加熱乾燥してプリプレグを得た。
プリプレグを３枚重ね、上下にロープロファイル銅箔（厚さ：１８μｍ、Ｒｚ：３．５μｍ、三井金属社製、３ＥＣ－Ｍ３－Ｖ－１８）を積層し１８０℃、圧力３０ｋｇ／ｃｍ２で１２０分間加熱成形し、樹脂付き金属基材を得た。 [Example 3-1]
50 parts by mass of polyimide resin (manufactured by Arakawa Chemical Industries, Ltd., PIAD300, solid content 30%), 20 parts by mass of hollow silica particles A-1 corresponding to 20 volume % of the total, and 20 parts by mass of cyclohexanone were placed in a polyvinyl bottle, and alumina balls having a diameter of 20 mm were added and mixed at 30 rpm for 12 hours. The alumina balls were then removed to obtain a resin composition.
The resin composition was allowed to stand in an environment of 25° C. and a relative humidity of 50% for 12 hours.
After standing, the resin composition was applied to impregnate a glass cloth of IPC spec 2116, and then heated and dried at 160° C. for 4 minutes to obtain a prepreg.
Three sheets of prepreg were stacked, low-profile copper foil (thickness: 18 μm, Rz: 3.5 μm, Mitsui Kinzoku Co., Ltd., 3EC-M3-V-18) was laminated on top and bottom, and the resulting mixture was heated and molded at 180° C. and a pressure of 30 kg/cm 2 for 120 minutes to obtain a metal substrate with resin.
ポリイミド樹脂（荒川化学工業製、ＰＩＡＤ３００、固形分３０％）の５０質量部、中空シリカ粒子Ａ－１を全体の２０体積％となる質量部、シクロヘキサノン２０質量部をポリビンに入れ、Φ２０ｍｍのアルミナボールを入れて３０ｒｐｍで１２時間混合し、アルミナボールを除いて樹脂組成物を得た。
樹脂組成物を２５℃、相対湿度５０％の環境に１２時間静置した。
静置後、樹脂組成物を、ＩＰＣスペック２１１６のガラスクロスに含浸塗工し、１６０℃で４分間加熱乾燥してプリプレグを得た。
プリプレグを３枚重ね、上下にロープロファイル銅箔（厚さ：１８μｍ、Ｒｚ：３．５μｍ、三井金属社製、３ＥＣ－Ｍ３－Ｖ－１８）を積層し１８０℃、圧力３０ｋｇ／ｃｍ２で１２０分間加熱成形し、樹脂付き金属基材を得た。 [Example 3-1]
50 parts by mass of polyimide resin (manufactured by Arakawa Chemical Industries, Ltd., PIAD300, solid content 30%), 20 parts by mass of hollow silica particles A-1 corresponding to 20 volume % of the total, and 20 parts by mass of cyclohexanone were placed in a polyvinyl bottle, and alumina balls having a diameter of 20 mm were added and mixed at 30 rpm for 12 hours. The alumina balls were then removed to obtain a resin composition.
The resin composition was allowed to stand in an environment of 25° C. and a relative humidity of 50% for 12 hours.
After standing, the resin composition was applied to impregnate a glass cloth of IPC spec 2116, and then heated and dried at 160° C. for 4 minutes to obtain a prepreg.
Three sheets of prepreg were stacked, low-profile copper foil (thickness: 18 μm, Rz: 3.5 μm, Mitsui Kinzoku Co., Ltd., 3EC-M3-V-18) was laminated on top and bottom, and the resulting mixture was heated and molded at 180° C. and a pressure of 30 kg/cm 2 for 120 minutes to obtain a metal substrate with resin.
[例３－２～３－６]
中空シリカ粒子Ａ１を、表２に記載の中空シリカ粒子、中実粒子又は中空粒子に変更した以外は、例３－１と同様にして、樹脂組成物、プリプレグ及び樹脂付き金属基材を製造した。 [Examples 3-2 to 3-6]
Except for changing the hollow silica particles A1 to the hollow silica particles, solid particles or hollow particles shown in Table 2, a resin composition, a prepreg and a resin-coated metal substrate were produced in the same manner as in Example 3-1.
中空シリカ粒子Ａ１を、表２に記載の中空シリカ粒子、中実粒子又は中空粒子に変更した以外は、例３－１と同様にして、樹脂組成物、プリプレグ及び樹脂付き金属基材を製造した。 [Examples 3-2 to 3-6]
Except for changing the hollow silica particles A1 to the hollow silica particles, solid particles or hollow particles shown in Table 2, a resin composition, a prepreg and a resin-coated metal substrate were produced in the same manner as in Example 3-1.
＜比誘電率の標準偏差の測定＞
例２－１～２－６及び例３－１～３－６の樹脂付き金属基材から、銅箔をエッチングし、十分に蒸留水で洗浄した後、１００℃のオーブンで１０分乾燥し、プレス済プリプレグを得た。得られたプレス済プリプレグの比誘電率を、キーコム株式会社製「ベクトルネットワークアナライザ Ｅ５０６３Ａ」を用い、摂動方式共振器法にて測定した。
具体的には、図１に示すプレス済プリプレグの短辺方向の中央部Ｘで、長辺方向の全長をＬとしたとき、１／４Ｌ、２／４Ｌ、３／４Ｌの３点の比誘電率を測定し、比誘電率の標準偏差を求めた。測定結果を表２にまとめた。なお、図１において、プリプレグを符号１０で示す。 <Measurement of standard deviation of dielectric constant>
The copper foil was etched from the resin-coated metal substrates of Examples 2-1 to 2-6 and Examples 3-1 to 3-6, thoroughly washed with distilled water, and then dried for 10 minutes in an oven at 100° C. to obtain pressed prepregs. The relative dielectric constant of the pressed prepregs obtained was measured by a perturbation resonator method using a "Vector Network Analyzer E5063A" manufactured by Keycom Corporation.
Specifically, the dielectric constants were measured at three points, 1/4L, 2/4L, and 3/4L, at the center X in the short side direction of the pressed prepreg shown in Figure 1, where L is the total length in the long side direction, and the standard deviation of the dielectric constants was calculated. The measurement results are summarized in Table 2. In Figure 1, the prepreg is indicated by the reference symbol 10.
例２－１～２－６及び例３－１～３－６の樹脂付き金属基材から、銅箔をエッチングし、十分に蒸留水で洗浄した後、１００℃のオーブンで１０分乾燥し、プレス済プリプレグを得た。得られたプレス済プリプレグの比誘電率を、キーコム株式会社製「ベクトルネットワークアナライザ Ｅ５０６３Ａ」を用い、摂動方式共振器法にて測定した。
具体的には、図１に示すプレス済プリプレグの短辺方向の中央部Ｘで、長辺方向の全長をＬとしたとき、１／４Ｌ、２／４Ｌ、３／４Ｌの３点の比誘電率を測定し、比誘電率の標準偏差を求めた。測定結果を表２にまとめた。なお、図１において、プリプレグを符号１０で示す。 <Measurement of standard deviation of dielectric constant>
The copper foil was etched from the resin-coated metal substrates of Examples 2-1 to 2-6 and Examples 3-1 to 3-6, thoroughly washed with distilled water, and then dried for 10 minutes in an oven at 100° C. to obtain pressed prepregs. The relative dielectric constant of the pressed prepregs obtained was measured by a perturbation resonator method using a "Vector Network Analyzer E5063A" manufactured by Keycom Corporation.
Specifically, the dielectric constants were measured at three points, 1/4L, 2/4L, and 3/4L, at the center X in the short side direction of the pressed prepreg shown in Figure 1, where L is the total length in the long side direction, and the standard deviation of the dielectric constants was calculated. The measurement results are summarized in Table 2. In Figure 1, the prepreg is indicated by the reference symbol 10.
表２に示されるように、本組成物を用いて得られた硬化物は、比誘電率の標準偏差が低く抑えられている。
As shown in Table 2, the standard deviation of the dielectric constant of the cured product obtained using this composition is kept low.
１０：プレス済プリプレグ、Ｘ：プレス済プリプレグの短辺方向の中央部、Ｌ：プレス済プリプレグの長辺方向の全長
10: Pressed prepreg, X: Center of the pressed prepreg in the short side direction, L: Total length of the pressed prepreg in the long side direction
２０２２年１２月５日に出願された日本国特許出願第２０２２－１９４２０９号及び日本国特許出願第２０２２－１９４２１０号の開示は、その全体が参照により本明細書に取り込まれる。本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
The disclosures of Japanese Patent Application Nos. 2022-194209 and 2022-194210, filed on December 5, 2022, are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.
Claims (14)
- 樹脂及び中空シリカ粒子を含む樹脂組成物であって、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた前記中空シリカ粒子の密度をＡ（ｇ／ｃｍ３）、前記中空シリカ粒子のＢＥＴ比表面積をＢ１（ｍ２／ｇ）としたとき、Ａ×Ｂ１が、１．０～１２０．０ｍ２／ｃｍ３である、樹脂組成物。 A resin composition comprising a resin and hollow silica particles, wherein when the density of the hollow silica particles determined by a constant volume expansion method using argon gas and a dry pycnometer is A (g/cm 3 ) and the BET specific surface area of the hollow silica particles is B1 (m 2 /g), A×B1 is 1.0 to 120.0 m 2 /cm 3 .
- 樹脂及び中空シリカ粒子を含む樹脂組成物であって、アルゴンガス及び乾式ピクノメーターを用いた定容積膨張法により求めた前記中空シリカ粒子の密度及び前記樹脂の密度を、それぞれ、Ａ（ｇ／ｃｍ３）、及びＢ２（ｇ／ｃｍ３）としたとき、Ａ／Ｂ２が、０．３～１．５である、樹脂組成物。 A resin composition comprising a resin and hollow silica particles, wherein when the density of the hollow silica particles and the density of the resin determined by a constant volume expansion method using argon gas and a dry pycnometer are A (g/cm 3 ) and B2 (g/cm 3 ), respectively, A/B2 is 0.3 to 1.5.
- 前記中空シリカ粒子の密度が、０．３５～２．００ｇ／ｃｍ３である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the hollow silica particles have a density of 0.35 to 2.00 g/ cm3 .
- 前記中空シリカ粒子のＢＥＴ比表面積が、１．０～１００．０ｍ２／ｇである、請求項１又は２に記載の樹脂組成物。 3. The resin composition according to claim 1, wherein the hollow silica particles have a BET specific surface area of 1.0 to 100.0 m 2 /g.
- 前記中空シリカ粒子のメジアン径（ｄ５０）が０．１～１０．０μｍである、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the median diameter (d50) of the hollow silica particles is 0.1 to 10.0 μm.
- 前記樹脂が、エポキシ樹脂、ポリイミド樹脂、ポリフェニレンエーテル樹脂、ジビニルベンゼン骨格を含む樹脂、及びピリミジン骨格を含む樹脂から選択される少なくとも１つを含む、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the resin comprises 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.
- 樹脂組成物の総体積に対する前記中空シリカ粒子の含有量が１０～７０体積％である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the content of the hollow silica particles relative to the total volume of the resin composition is 10 to 70 volume %.
- 請求項１又は２に記載の樹脂組成物又はその半硬化物と、繊維質基材と、を含むプリプレグ。 A prepreg comprising the resin composition or a semi-cured product thereof according to claim 1 or 2, and a fibrous base material.
- 前記繊維質基材が、ガラス成分を含む、請求項８に記載のプリプレグ。 The prepreg according to claim 8, wherein the fibrous base material contains a glass component.
- 請求項１若しくは２に記載の樹脂組成物又はその半硬化物と、金属基材層と、を含む樹脂付き金属基材。 A resin-coated metal substrate comprising the resin composition or semi-cured product thereof according to claim 1 or 2, and a metal substrate layer.
- 請求項９に記載のプリプレグと、金属基材層と、を含む樹脂付き金属基材。 A resin-coated metal substrate comprising the prepreg according to claim 9 and a metal substrate layer.
- 前記金属基材層が、銅箔である、請求項１０に記載の樹脂付き金属基材。 The resin-coated metal substrate according to claim 10, wherein the metal substrate layer is copper foil.
- 前記金属基材層が、銅箔である、請求項１１に記載の樹脂付き金属基材。 The resin-coated metal substrate according to claim 11, wherein the metal substrate layer is copper foil.
- 請求項１又は２に記載の樹脂組成物の硬化物と、金属配線と、を含む配線板。 A wiring board comprising a cured product of the resin composition according to claim 1 or 2 and metal wiring.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-194209 | 2022-12-05 | ||
| JP2022194209 | 2022-12-05 | ||
| JP2022-194210 | 2022-12-05 | ||
| JP2022194210 | 2022-12-05 |
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| WO2024122433A1 true WO2024122433A1 (en) | 2024-06-13 |
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| PCT/JP2023/042806 WO2024122433A1 (en) | 2022-12-05 | 2023-11-29 | Resin composition, prepreg, metal substrate provided with resin, and wiring board |
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| WO (1) | WO2024122433A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021172294A1 (en) * | 2020-02-27 | 2021-09-02 | Ａｇｃ株式会社 | Hollow silica particles and method for producing same |
| WO2023140378A1 (en) * | 2022-01-21 | 2023-07-27 | 花王株式会社 | Method for producing hollow silica particles |
| WO2023218948A1 (en) * | 2022-05-09 | 2023-11-16 | Ａｇｃ株式会社 | Silica particle dispersion liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021172294A1 (en) * | 2020-02-27 | 2021-09-02 | Ａｇｃ株式会社 | Hollow silica particles and method for producing same |
| WO2021172293A1 (en) * | 2020-02-27 | 2021-09-02 | Ａｇｃ株式会社 | Hollow silica particles and method for manufacturing hollow silica particles |
| WO2023140378A1 (en) * | 2022-01-21 | 2023-07-27 | 花王株式会社 | Method for producing hollow silica particles |
| WO2023218948A1 (en) * | 2022-05-09 | 2023-11-16 | Ａｇｃ株式会社 | Silica particle dispersion liquid |
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