[go: up one dir, main page]

WO2025225398A1 - Composition de résine et ensemble de matériaux composites - Google Patents

Composition de résine et ensemble de matériaux composites

Info

Publication number
WO2025225398A1
WO2025225398A1 PCT/JP2025/014283 JP2025014283W WO2025225398A1 WO 2025225398 A1 WO2025225398 A1 WO 2025225398A1 JP 2025014283 W JP2025014283 W JP 2025014283W WO 2025225398 A1 WO2025225398 A1 WO 2025225398A1
Authority
WO
WIPO (PCT)
Prior art keywords
silica powder
treated silica
mass
resin composition
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/014283
Other languages
English (en)
Japanese (ja)
Inventor
拓人 岡部
宏幸 塩月
雄平 石垣
辰哉 中野
俊 大貫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denka Co Ltd
Original Assignee
Denka Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Denka Co Ltd filed Critical Denka Co Ltd
Publication of WO2025225398A1 publication Critical patent/WO2025225398A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene

Definitions

  • the present invention relates to a resin composition and a composite material set.
  • Patent Document 1 describes a post-curable resin composition containing an ethylene-olefin-polyene copolymer and an inorganic filler (see, for example, paragraph 0032 of Patent Document 1).
  • the dielectric loss tangent and dispersibility of the resin composition can be reliably evaluated by using the carbon content per unit area of the surface-treated silica powder as an index; that the dielectric loss tangent can be lowered by setting the upper limit of this index below a specified value, and that dispersibility can be improved by setting the lower limit of the index above a specified value, leading to the completion of the present invention.
  • the following resin composition and composite material set are provided.
  • An olefin-aromatic vinyl compound-aromatic polyene copolymer a surface-treated silica powder configured such that C and S satisfy the relationship 0.004 ⁇ C/S ⁇ 0.085, where C (mass%) is the carbon content measured according to the following procedure and S (m 2 /g) is the specific surface area measured by the BET single-point method using nitrogen gas adsorption; Resin composition. (procedure) 3 g of the surface-treated silica powder was added to 37 g of acetone and stirred for 30 minutes.
  • the slurry was then centrifuged at 3,500 rpm for 10 minutes to separate the surface-treated silica powder from the acetone, and the supernatant acetone was discarded. This acetone washing procedure was repeated twice, followed by drying at 120°C for 2 hours.
  • the carbon content (mass %) in 0.3 g of the washed surface-treated silica powder is measured using a carbon/sulfur simultaneous analyzer and quantified by a calibration curve method.
  • the resin composition according to 1. The resin composition, wherein the specific surface area of the surface-treated silica powder measured by the BET single-point method using nitrogen gas adsorption is 0.1 m 2 /g or more and 12.0 m 2 /g or less. 3. The resin composition according to 1.
  • the resin composition wherein the surface-treated silica powder has a D50 of 0.1 ⁇ m or more and 10 ⁇ m or less. 4.
  • the resin composition according to any one of 1. to 3. The resin composition has a number average molecular weight Mn of 500 or more and 100,000 or less of the olefin-aromatic vinyl compound-aromatic polyene copolymer. 5.
  • the resin composition has a water absorption rate of 1.0% or less of the olefin-aromatic vinyl compound-aromatic polyene copolymer.
  • a composite material set including a combination of raw material components used to produce a resin composition containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and silica powder, a resin varnish containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and a solvent; a surface-treated silica powder configured such that C and S satisfy the relationship 0.004 ⁇ C/S ⁇ 0.085, where C (mass%) is the carbon content measured according to the following procedure and S (m 2 /g) is the specific surface area measured by the BET single-point method using nitrogen gas adsorption; Composite materials set.
  • the present invention provides a resin composition and composite material set that has a low dielectric tangent and excellent dispersibility.
  • the resin composition of the present embodiment contains an olefin-aromatic vinyl compound-aromatic polyene copolymer and a surface-treated silica powder.
  • the surface-treated silica powder is configured so that C and S satisfy the relationship 0.004 ⁇ C/S ⁇ 0.085, where C (mass%) is the carbon content measured according to the following procedure and S (m 2 /g) is the specific surface area measured by the BET single-point method using nitrogen gas adsorption. (procedure) 3 g of the surface-treated silica powder was added to 37 g of acetone and stirred for 30 minutes.
  • the slurry was then centrifuged at 3,500 rpm for 10 minutes to separate the surface-treated silica powder from the acetone, and the supernatant acetone was discarded. This acetone washing procedure was repeated twice, followed by drying at 120°C for 2 hours.
  • the carbon content (mass %) in 0.3 g of the washed surface-treated silica powder is measured using a carbon/sulfur simultaneous analyzer and quantified by a calibration curve method.
  • a composite material set can be provided that includes a combination of raw material components used to produce a resin composition containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and silica powder.
  • the composite material set includes a resin varnish containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and a solvent, and a surface-treated silica powder.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer (hereinafter sometimes simply abbreviated as "copolymer”) is a copolymer comprising a structural unit A derived from an olefin monomer, a structural unit B derived from an aromatic vinyl compound monomer, and a structural unit C derived from an aromatic polyene monomer, and preferably satisfies all of the following conditions (1) to (4):
  • the number average molecular weight of the copolymer is 500 or more and 100,000 or less.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit in the copolymer is 0% by mass to 70% by mass.
  • the aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and/or vinylene groups in the molecule, and the content of vinyl groups and/or vinylene groups derived from aromatic polyene units in the copolymer is 1.5 or more and less than 20 per number average molecular weight.
  • the olefin is one or more olefins selected from olefins having from 2 to 20 carbon atoms, and the total amount of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units in the copolymer is 100 mass%.
  • the structural unit A can improve the low dielectric property and flexibility of the copolymer.
  • the structural unit B can improve the low dielectric property of the copolymer and the compatibility with other materials.
  • the structural unit C can improve the low dielectric property and crosslinkability of the copolymer. That is, a hydrocarbon copolymer having the above structural units A, B and C becomes a crosslinkable low dielectric resin, preferably a crosslinkable soft low dielectric resin.
  • a soft resin such as polybutadiene
  • the structural units A, B, and C it is possible to realize a copolymer that is a soft resin with crosslinkability and yet has low dielectric properties.
  • a resin composition containing such a copolymer can realize a high frequency resin material with reduced signal transmission loss in the high frequency range.
  • the following advantages can be obtained from the properties derived from the structural units of the copolymer.
  • the compatibility of the copolymer increases the solubility in solvents, allowing the resin composition to be used in the form of a resin varnish with excellent processability.
  • the compatibility of the copolymer also increases the compatibility with other resins, such as hard resins, allowing the resin composition to be used as a composite material containing other resins.
  • the crosslinking property of the copolymer makes it possible to realize a high frequency resin material having relatively high heat resistance.
  • the olefin monomer does not include unsaturated hydrocarbons containing aromatic groups, but is, for example, one or more selected from ⁇ -olefins having 2 to 20 carbon atoms and cyclic olefins having 5 to 20 carbon atoms. It is a compound composed of carbon and hydrogen and substantially free of oxygen, nitrogen, and halogens.
  • ⁇ -olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decane, 1-dodecane, 4-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene.
  • cyclic olefins having 5 to 20 carbon atoms include norbornene and cyclopentene.
  • Preferred olefins are a combination of ethylene and an ⁇ -olefin or cyclic olefin other than ethylene, or ethylene alone.
  • the content of ⁇ -olefin monomer units other than ethylene contained in the copolymer is 6% by mass or less, and most preferably 4% by mass or less, or the olefin is ethylene alone.
  • the peel strength with copper foil or copper wiring can be further increased, which is more preferable.
  • the glass transition temperature of the ethylene- ⁇ -olefin-aromatic vinyl compound-aromatic polyene sequence of the final cured product can be freely adjusted within the range of approximately -60°C to -10°C depending on the type and content of the ⁇ -olefin.
  • Aromatic vinyl compound monomers are aromatic vinyl compounds having 8 to 20 carbon atoms, such as styrene, paramethylstyrene, paraisobutylstyrene, various vinylnaphthalenes, and various vinylanthracenes.
  • the aromatic polyene monomer is a polyene having 5 to 20 carbon atoms and containing multiple vinyl and/or vinylene groups (preferably vinyl groups) in its molecule, preferably a polyene having 8 to 20 carbon atoms.
  • the aromatic polyene monomer is preferably a polyene having 8 to 20 carbon atoms and containing multiple vinyl groups in its molecule, more preferably various ortho-, meta-, and para-divinylbenzenes or mixtures thereof, divinylnaphthalene, divinylanthracene, p-2-propenylstyrene, p-3-butenylstyrene, and other compounds having an aromatic vinyl structure, substantially free of oxygen, nitrogen, and halogens, and composed of carbon and hydrogen.
  • Bifunctional aromatic vinyl compounds such as 1,2-bis(vinylphenyl)ethane (abbreviation: BVPE), as described in JP 2004-087639 A, can also be used.
  • BVPE 1,2-bis(vinylphenyl)ethane
  • various ortho-, meta-, and para-divinylbenzenes or mixtures thereof are preferred, with a mixture of meta- and para-divinylbenzene being most preferred.
  • these divinylbenzenes are referred to as divinylbenzenes.
  • divinylbenzenes When divinylbenzenes are used as aromatic polyenes, they are preferred because they have high curing efficiency and are easy to cure during curing treatment.
  • Each of the olefin, aromatic vinyl compound, and aromatic polyene monomers may independently contain another polar group, for example, an olefin containing an oxygen atom, a nitrogen atom, or the like, an aromatic vinyl compound containing an oxygen atom, a nitrogen atom, or the like, or an aromatic polyene containing an oxygen atom, a nitrogen atom, or the like.
  • the total mass of the polar group-containing monomers is preferably 10 mass% or less, more preferably 3 mass% or less, of the total mass of the composition, and most preferably no polar group-containing monomers are included.
  • the number average molecular weight of the copolymer is 500 to 100,000, preferably 5,000 to 100,000, more preferably 20,000 to 100,000, and even more preferably 30,000 to 100,000.
  • the number average molecular weight is 500 to 100,000, preferably 5,000 to 100,000, more preferably 20,000 to 100,000, and even more preferably 30,000 to 100,000.
  • the composition becomes less sticky in the uncured state even when other resins described below are added, and the thermoplasticity can be improved, and further, the final cured product can be easily imparted with good physical properties such as high strength at break and high elongation at break.
  • the number average molecular weight is less than 500, the mechanical properties of the composition in the uncured state are low and the adhesiveness is high, which may make it difficult to mold the composition as a thermoplastic resin. If the number average molecular weight is more than 100,000, the moldability may be reduced.
  • the number average molecular weight is determined as follows.
  • the molecular weight can be determined as a number average molecular weight (Mn) converted to standard polystyrene using GPC (gel permeation chromatography) under the following conditions.
  • GPC gel permeation chromatography
  • Detector RI detector
  • the content of aromatic vinyl compound monomer units contained in the copolymer is 0% by mass or more and 70% by mass or less, preferably 0% by mass or more and less than 70% by mass, more preferably 10% by mass or more and 60% by mass or less, and even more preferably 10% by mass or more and 55% by mass or less. If the content of aromatic vinyl compound monomer units is greater than 70% by mass, the glass transition temperature of the final cured product of the composition will be near room temperature, which may result in reduced toughness and elongation at low temperatures. If the content of aromatic vinyl compound monomer units is 10% by mass or more, the aromaticity of the copolymer is improved, improving compatibility with flame retardants and fillers, preventing bleed-out of flame retardants and allowing filler to be filled. Furthermore, if the content of aromatic vinyl compound monomer units is 10% by mass or more, a cured product of the composition with high peel strength from copper foil or copper wiring can be obtained.
  • the content of vinyl groups and/or vinylene groups derived from aromatic polyene units is 1.5 or more and less than 20, preferably 1.5 or more and less than 7, and more preferably 2 or more and less than 5, per number average molecular weight.
  • the content of vinyl groups and/or vinylene groups may be collectively referred to as the "vinyl group content.” If the vinyl group content is less than 1.5, the crosslinking efficiency is low, making it difficult to obtain a cured product with sufficient crosslink density. Increasing the vinyl group content makes it easier to improve the mechanical properties of the final cured product at room temperature and high temperatures.
  • the vinyl group content derived from aromatic polyene units (divinylbenzene units) per number average molecular weight in a copolymer can be obtained by comparing the number average molecular weight (Mn) calculated in terms of standard polystyrene determined by gel permeation chromatography (GPC) known to those skilled in the art with the vinyl group content and vinylene group content derived from aromatic polyene units obtained by 1 H-NMR measurement.
  • Mn number average molecular weight
  • the vinyl group content derived from aromatic polyene units (divinylbenzene units) in the copolymer is 0.095% by mass and the number average molecular weight calculated in terms of standard polystyrene by GPC measurement is 68,000, the molecular weight of the vinyl groups derived from aromatic polyene units in the number average molecular weight is the product of these values, 64.8, which is divided by the formula weight of the vinyl groups, 27, to obtain 2.4.
  • the vinyl group content derived from aromatic polyene units per number average molecular weight in this copolymer is 2.4.
  • the peak assignments obtained by 1 H-NMR measurement of copolymers are known in the literature.
  • a method for determining the composition of a copolymer by comparing peak areas obtained by 1 H-NMR measurement is known. Peak areas or their ratios in 13 C-NMR spectra measured in a known quantitative mode may also be used as an auxiliary method.
  • the content of divinylbenzene units in a copolymer is determined from the peak intensity (measured by 1 H-NMR measurement) of vinyl groups derived from divinylbenzene units. That is, the content of divinylbenzene units is determined from the content of vinyl groups derived from divinylbenzene units, assuming that one vinyl group is derived from one divinylbenzene unit in the copolymer.
  • the preferred olefin monomer unit content is 30% by mass or more, and particularly preferably 45% by mass or more.
  • the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100% by mass.
  • the olefin monomer unit content is 30% by mass or more, the toughness (elongation) of the final cured body is improved, and cracking during curing, a decrease in the impact resistance of the cured body, and cracking during heat cycle testing of the cured body do not occur.
  • the preferred olefin monomer unit content is 90% by mass or less.
  • suitable copolymers that do not contain aromatic vinyl compound monomer units include ethylene-divinylbenzene copolymer, ethylene-propylene-divinylbenzene copolymer, ethylene-1-butene-divinylbenzene copolymer, ethylene-1-hexene-divinylbenzene copolymer, and ethylene-1-octene-divinylbenzene copolymer.
  • examples of olefin-aromatic vinyl compound-aromatic polyene copolymers containing aromatic vinyl compound monomer units include ethylene-styrene-divinylbenzene copolymer, ethylene-propylene-styrene-divinylbenzene copolymer, ethylene-1-hexene-styrene-divinylbenzene copolymer, and ethylene-1-octene-styrene-divinylbenzene copolymer.
  • the upper limit of the water absorption rate of the copolymer is, for example, 1.0% or less, preferably 0.5% or less, and more preferably 0.1% or less.
  • the lower limit of the water absorption rate of the copolymer is not particularly limited, but may be equal to or higher than the measurement limit.
  • the water absorption rate of the copolymer can be determined by immersing the copolymer in water at 25° C. in the atmosphere for 24 hours and measuring the change in weight before and after immersion in water.
  • the copolymer can be produced, for example, by the production methods described in International Publication No. 00/37517, Japanese Patent Application Laid-Open No. 2009-161743, Japanese Patent Application Laid-Open No. 2010-280771, Japanese Patent Application Laid-Open No. 2009-161743, Japanese Patent Application Laid-Open No. 2010-280771, etc.
  • the lower limit of the C/S ratio in the surface-treated silica powder is 0.004 or more, preferably 0.005 or more, and more preferably 0.006 or more, thereby improving the dispersibility of the resin composition.
  • the upper limit of the C/S is 0.085 or less, preferably 0.080 or less, and more preferably 0.075 or less, thereby making it possible to reduce the dielectric loss tangent of the resin composition.
  • the dielectric loss tangent of the resin composition under conditions of 40 GHz, 25°C and 50% RH can be measured according to the procedure described in the Examples below, and is, for example, 0.005 or less, preferably 0.003 or less, and more preferably 0.0015 or less.
  • the carbon content (C) of the surface-treated silica powder is determined according to the following procedure B. (Procedure B) 3 g of the surface-treated silica powder was added to 37 g of acetone and stirred for 30 minutes. The slurry was then centrifuged at 3,500 rpm for 10 minutes to separate the surface-treated silica powder from the acetone, and the supernatant acetone solution was discarded. This acetone washing procedure was repeated twice, and the mixture was then dried at 120°C for 2 hours. The carbon content (mass %) in 0.3 g of the washed surface-treated silica powder is measured using a carbon/sulfur simultaneous analyzer and quantified by the calibration curve method.
  • the lower limit of the specific surface area (S) of the surface-treated silica powder measured by the BET single-point method using nitrogen gas adsorption is, for example, 1.0 m 2 /g or more, preferably 2.5 m 2 /g or more, and more preferably 2.9 m 2 /g or more, which allows the amount added to the resin to be increased and the thermal expansion coefficient of the resin composition to be suppressed.
  • the upper limit of the specific surface area (S) of the surface-treated silica powder is, for example, 12.0 m 2 /g or less, preferably 8.5 m 2 /g or less, and more preferably 7.0 m 2 /g or less, which can suppress the aggregation of the filler.
  • the BET single-point method using nitrogen gas adsorption can be performed using a specific surface area measuring device (for example, manufactured by Yuasa Ionics Co., Ltd., device name: MONOSORB) using nitrogen gas as the adsorption gas and helium gas as the carrier gas, after drying and degassing 1 g of sample at 300°C for 15 minutes.
  • a specific surface area measuring device for example, manufactured by Yuasa Ionics Co., Ltd., device name: MONOSORB
  • D50 is the particle size at which the cumulative value from the small particle size side reaches 50%.
  • the lower limit of D50 is, for example, 0.1 ⁇ m or more, preferably 0.2 ⁇ m or more, and more preferably 0.3 ⁇ m or more, which can improve the fillability into the resin.
  • the upper limit of D50 is, for example, 10 ⁇ m or less, preferably 9 ⁇ m or less, and more preferably 8 ⁇ m or less, which can reduce the amount of coarse particles and make it possible to further reduce the sheet thickness when the resin composition is molded into a sheet.
  • the lower limit of the average sphericity of the surface-treated silica powder is, for example, 0.80 or more, preferably 0.85 or more, and more preferably 0.90 or more, thereby further improving the flowability of the resin composition.
  • the upper limit of the average sphericity of the surface-treated silica powder is not particularly limited, but may be, for example, 1.00 or less.
  • the C/S ratio can be controlled by appropriately selecting, for example, the method for preparing the raw silica powder or the method for surface treatment of the raw silica powder.
  • factors for achieving the desired C/S ratio include appropriately adjusting the specific surface area of the raw silica powder, adjusting the amount of silane coupling agent added per specific surface area depending on the type of silane coupling agent, and performing a heat treatment before silane treatment.
  • the surface-treated silica powder may be any powder containing silica (SiO 2 ) as a main component.
  • the term "main component" means that the silica powder contains, for example, 50% or more, preferably 80% or more, and more preferably 90% or more, of silica (SiO 2 ), calculated by mass, based on the total amount of the silica powder.
  • the surface-treated silica powder may be amorphous, crystalline, or both.
  • the surface-treated silica powder preferably has an amorphous ratio of 95% or more, and more preferably 97% or more, as measured by the method described below.
  • the amorphous ratio is determined by X-ray diffraction analysis using a powder X-ray diffractometer (e.g., RIGAKU Corporation's "Model MiniFlex") at a 2 ⁇ range of 26° to 27.5° with CuK ⁇ radiation, and the intensity ratio of specific diffraction peaks is used to determine the amorphous ratio.
  • a powder X-ray diffractometer e.g., RIGAKU Corporation's "Model MiniFlex”
  • crystalline silica exhibits a main peak at 26.7°, while amorphous silica exhibits no peak.
  • the silane coupling agent can be, for example, a silane compound containing one or more functional groups selected from the group consisting of epoxy groups, methacrylic groups, acrylic groups, amino groups, vinyl groups, alkyl groups, phenyl groups, mercapto groups, styryl groups, acid anhydride groups, ureido groups, isocyanurate groups, and isocyanate groups, preferably epoxy groups, methacrylic groups, acrylic groups, amino groups, vinyl groups, alkyl groups, and phenyl groups.
  • the silane compound has one or more hydrolyzable groups in addition to functional groups in the molecule.
  • the hydrolyzable group for example, an alkoxy group such as a methoxy group or an ethoxy group is used.
  • the alkoxy groups are hydrolyzed to generate silanol groups, which chemically react with OH groups (reactive sites) present on the surface of the silica particles, thereby chemically bonding the silane coupling agent to the surface of the silica particles.
  • the surface-treated silica powder has a silane coupling agent chemically and/or physically bonded to the surface of the silica particles.
  • silane compounds having an epoxy group examples include 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.
  • silane compounds having a methacryl group examples include 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
  • silane compounds having an acrylic group examples include 3-acryloxypropyltrimethoxysilane.
  • silane compounds having an amino group include N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride.
  • silane compounds having a vinyl group examples include vinyltrimethoxysilane, 7-octenyltrimethoxysilane, and vinyltriethoxysilane.
  • Examples of silane compounds having an alkyl group include hexyltrimethoxysilane, octyltriethoxysilane, and decyltrimethoxysilane.
  • Examples of silane compounds having a phenyl group include phenyltrimethoxysilane and trimethoxy(2-phenylethyl)silane.
  • the content of the surface-treated silica powder is, for example, 1 to 90 mass%, preferably 10 to 80 mass%, and more preferably 20 to 70 mass%, based on 100 mass% of the total content of the surface-treated silica powder and the copolymer.
  • An example of a method for producing the surface-treated silica powder is as follows: heat-treating the prepared silica powder; The method includes a step of bringing the heat-treated silica powder into contact with a silane coupling agent to carry out a silane coupling treatment in which the silane coupling agent reacts with the surfaces of the silica particles, thereby obtaining a surface-treated silica powder.
  • a surface-treated silica powder with excellent low dielectric properties can be realized by two-stage surface treatment, namely, heat treatment and silane coupling treatment.
  • raw silica powder produced by a dry method is subjected to coarse powder classification and then to fine powder classification, thereby obtaining the silica powder.
  • the classification treatment can be carried out by mixing or classifying appropriate amounts of silica powders having different particle size compositions.Industrially, classification using a classifier such as a sieve or a precision air classifier is desirable, and the classification operation is preferably a dry method.By dry classifying raw silica powder produced by a dry method, aggregation of the silica powder can be suppressed compared to raw silica powder produced by a wet method and/or wet classification, and handleability can be improved.
  • the obtained silica powder is preferably stored in a moisture-proof bag.
  • the raw silica powder can be produced by any method, including: powder made by crushing silica stone, silica sand, quartz, etc. and putting it into a flame or high-temperature plasma to form spheroids; powder synthesized by gas-phase hydrolysis of silicon tetrachloride and then calcining or flame spraying this material; powder synthesized in the gas or liquid phase from metallic silicon or alkoxysilane as the starting material and then calcining or flame spraying this material to form spheroids; and powder synthesized in the gas or liquid phase from metallic silicon or alkoxysilane as the starting material and then calcining or flame spraying this material to form spheroids.
  • the prepared silica powder is subjected to a heat treatment under the following conditions.
  • the heat treatment is carried out at a temperature of 500 to 1100°C for a predetermined time (e.g., about 1 to 52 hours) such that the heating temperature (°C) x heating time (h) is 1000 to 26400 (°C ⁇ h), preferably 1800 to 17600 (°C ⁇ h) (e.g., about 2 to 35 hours) using hot air or an electric furnace.
  • the heating temperature is 500 to 1100°C, the specific surface area and average particle size do not change before and after heating. Therefore, it is desirable to carry out the classification step before heating, and then adjust the specific surface area and average particle size to the desired values before carrying out the heat treatment.
  • the silica powder After the heat treatment, the silica powder is allowed to cool naturally in the electric furnace, and then recovered at 110°C to 300°C.
  • the recovered silica powder may be further cooled to 25°C in an environment with a humidity of 40% RH or less, stored at 15 to 25°C, and then recovered and stored in a moisture-proof aluminum bag.
  • the heat-treated silica powder is subjected to a silane coupling treatment using a silane coupling agent.
  • a method for surface treatment with a silane coupling agent well-known techniques such as a dry method or a wet method can be used, but it is preferable to use a dry method.
  • the dry method is not particularly limited as long as it is a method of contacting a silane coupling agent with spherical silica powder in a solid state, and any known method can be used, including, for example, a stirring method that applies shear force, a mixing method using a ball mill, a mixer, etc.
  • the solid state refers to a state in which the raw silica powder is not dispersed in a dispersion medium.
  • an acidic substance or an alkaline substance may be present.
  • the silane coupling agent treatment is carried out, for example, by adding a silane coupling agent to the heat-treated silica powder under atmospheric pressure, at a temperature of 0 to 120°C, and at a humidity of 10 to 90%, and mixing them for 10 minutes to 10 hours using the above-mentioned mixing method. If necessary, after mixing, the mixture may be allowed to stand under the same environmental conditions for 0 to 10 days. Thereafter, if necessary, the silica powder treated with the coupling agent may be further subjected to a drying treatment at 100 to 300° C. for 1 to 10 hours.
  • the resin composition of the present embodiment may contain other resins in addition to the copolymer described above, as necessary, as long as the effects of the present invention are not impaired.
  • the other resins are preferably one or more selected from hydrocarbon elastomers, polyphenylene ethers, and aromatic polyene resins. Of these, polyphenylene ethers or hydrocarbon elastomers are more preferred. Of the hydrocarbon elastomers, conjugated diene polymers are preferred. Of the conjugated diene polymers, 1,2-polybutadiene is preferred.
  • the use of one or more resins selected from the group consisting of hydrocarbon elastomers, polyphenylene ethers, and aromatic polyene resins has the effect of reducing the amount of monomer used, and for example, making it possible to obtain a suitable cured product of the present invention without using any monomer.
  • the amount of other resins may be preferably 1 to 500 parts by mass, more preferably 1 to 300 parts by mass, in total, per 100 parts by mass of the copolymer.
  • the resin composition of the present embodiment may contain a curing agent for the copolymer and/or other resins as needed, as long as the effects of the present invention are not impaired.
  • the curing agent may be a known curing agent that can be used for the polymerization or curing of conventional aromatic polyenes or aromatic vinyl compounds. Examples of such curing agents include radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators, but radical polymerization initiators are preferred. Preferred are organic peroxides and azo polymerization initiators, which can be freely selected depending on the application and conditions. Also, known photopolymerization initiators that use light, ultraviolet light, or radiation can be used as curing agents.
  • curing agents that use photopolymerization initiators include photoradical polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators. Such photopolymerization initiators are available, for example, from Tokyo Chemical Industry Co., Ltd. Furthermore, curing can also be achieved by radiation or electron beams themselves. Furthermore, crosslinking and curing can also be achieved by thermal polymerization of the raw materials contained therein without using a curing agent. There are no particular restrictions on the amount of curing agent used, but generally, 0.01 to 10 parts by mass per 100 parts by mass of the composition (preferably excluding the curing agent and solvent) is preferred.
  • the curing treatment is carried out at an appropriate temperature and time, taking into account its half-life.
  • the conditions are optional depending on the curing agent, but generally, a temperature range of approximately 50°C to 180°C is appropriate.
  • the resin composition of this embodiment may contain a monomer, if necessary, as long as it does not impair the effects of the present invention.
  • the amount of the monomer is optional, but is preferably 300 parts by mass or less per 100 parts by mass of the copolymer.
  • the composition may be substantially free of a monomer. If a monomer is contained, the amount is preferably 1 part by mass or more, more preferably 5 parts by mass or more.
  • the monomer amount is 300 parts by mass or less, the uncured composition does not become viscous, making it easy to mold and process as a thermoplastic resin. Furthermore, when the content of volatile monomers is below a certain level, odor in the uncured state is not a problem.
  • Monomers suitable for use in the composition of the present invention preferably have a molecular weight of less than 1,000, more preferably less than 500.
  • Monomers that can be suitably used in the composition of the present invention are aromatic vinyl compound monomers, aromatic polyene monomers, and/or polar monomers.
  • the monomers are preferably monomers that can be polymerized with a radical polymerization initiator, and more preferably one or more monomers from the group consisting of aromatic vinyl compounds and aromatic polyenes. Also suitable for use is BVPE (1,2-bis(vinylphenyl)ethane), as described in JP-A-2003-212941.
  • the amount of aromatic vinyl compound is preferably 50 to 250 parts by mass, and more preferably 80 to 200 parts by mass, per 100 parts by mass of copolymer.
  • the amount of aromatic polyene is preferably 1 to 30 parts by mass, per 100 parts by mass of copolymer.
  • the mass ratio of aromatic vinyl compound to aromatic polyene is preferably 70-99:1-30, and more preferably 85-95:5-15, per 100 parts by mass of the total of aromatic vinyl compound and aromatic polyene.
  • polar monomer can be used to impart adhesion to other materials required for the insulating material and to impart or adjust the mechanical properties of the cured product.
  • the polar monomer include various maleimides, bismaleimides, maleic anhydride, glycidyl (meth)acrylate, triallyl isocyanurate, tri(meth)acrylic isocyanurate, and trimethylolpropane tri(meth)acrylate.
  • Maleimides and bismaleimides that can be used in the present invention are described, for example, in International Publication No. 2016/114287 and Japanese Patent Application Laid-Open No. 2008-291227, and are available commercially from Daiwa Chemical Industry Co., Ltd.
  • maleimide group-containing compounds may be used as polyaminobismaleimide compounds from the perspectives of solubility in organic solvents, high-frequency characteristics, high adhesion to conductors, and prepreg moldability.
  • Polyaminobismaleimide compounds can be obtained, for example, by subjecting a compound having two maleimide groups at its terminals to a Michael addition reaction with an aromatic diamine compound having two primary amino groups in its molecule.
  • a polar monomer with a multifunctional group e.g., difunctional or higher
  • a multifunctional group e.g., difunctional or higher
  • bismaleimides e.g., bismaleimides
  • triallyl isocyanurate TAIC
  • trimethylolpropane tri(meth)acrylate e.g., bismaleimides, triallyl isocyanurate (TAIC), or trimethylolpropane tri(meth)acrylate.
  • the amount of polar monomer that may be contained in the composition may be in the range of 0.1 to 30 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the copolymer. Using 30 parts by weight or less results in a low dielectric constant and dielectric dissipation factor for the resulting cured product.
  • the resin composition of the present embodiment may contain a solvent as needed.
  • the solvent is used to adjust the viscosity and fluidity of the composition.
  • Volatile solvents are preferred, such as cyclohexane, toluene, ethylbenzene, acetone, and isopropanol.
  • the amount used is preferably 10 parts by mass or less per 100 parts by mass of the copolymer of the present invention. From the viewpoint of moldability and handling of the composition as a thermoplastic resin before curing, and from the viewpoint of removal during and after curing, it is more preferable to use substantially no solvent.
  • Substantially no solvent preferably means 5 parts by mass or less, more preferably 1 part by mass or less, and most preferably 0 parts by mass. Particularly when used as a varnish, it is preferable to add an appropriate solvent to the composition of the present invention.
  • the solvent is used to adjust the viscosity and fluidity of the composition as a varnish.
  • a solvent with a high boiling point at atmospheric pressure i.e., low volatility, results in a uniform thickness of the applied film; therefore, a solvent with a boiling point above a certain level is preferred.
  • a preferred boiling point is 100°C or higher at atmospheric pressure, more preferably 110°C or higher and 300°C or lower.
  • Suitable solvents for such varnishes include cyclohexane, toluene, xylene, mesitylene, tetralin, acetone, ethylbenzene, limonene, mixed alkanes, mixed aromatic solvents, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc.
  • the amount used is preferably in the range of 10 to 2,000 parts by mass, more preferably 5 to 500 parts by mass, and even more preferably 10 to 300 parts by mass, per 100 parts by mass of the composition of the present invention.
  • the resin composition of the present embodiment may contain additives other than the above-mentioned components as needed, as long as the effects of the present invention are not impaired.
  • Other additives may include fillers other than the surface-treated silica powder, antioxidants, weathering agents, light stabilizers, lubricants, compatibilizers, antistatic agents, flame retardants, surface modifiers, heat stabilizers, ultraviolet absorbers, antiaging agents, lubricants, colorants, pigments, and the like. These may be contained alone or in any combination of two or more.
  • the other fillers include known inorganic or organic fillers other than the surface-treated silica powder.
  • a known surface modifier such as a silane coupling agent.
  • the type and amount of the other filler can be appropriately selected depending on the purpose.
  • examples of inorganic fillers include boron nitride (BN), etc.
  • examples of organic fillers include high molecular weight polyethylene and ultra-high molecular weight polyethylene, etc.
  • the resin composition of this embodiment can be made into a product form such as a "thermoplastic composition,” "semi-cured state (such as a B-stage sheet),” or “varnish” by appropriately adjusting the blending ratios of the copolymer, surface-treated silica powder, and these, as well as, if necessary, the blending ratios of other resins, monomers, solvents, and other additives.
  • a thermoplastic composition such as a B-stage sheet
  • varnish by appropriately adjusting the blending ratios of the copolymer, surface-treated silica powder, and these, as well as, if necessary, the blending ratios of other resins, monomers, solvents, and other additives.
  • the resin composition of this embodiment uses a copolymer having a molecular weight above a certain range, and when it also contains the specified other resin, it can exhibit the properties of a thermoplastic resin. Therefore, it can be molded into shapes such as sheets, tubes, strips, pellets, etc. in a substantially uncured state by a known molding method for thermoplastic resins under conditions that do not cause crosslinking. The molded product may then be crosslinked (cured).
  • a preferred embodiment of the present composition is as follows.
  • the composition contains a certain proportion or more of one or more resins selected from the hydrocarbon elastomer, polyphenylene ether, olefin-aromatic vinyl compound-aromatic polyene copolymer oligomer, or aromatic polyene resin as the other resin, excluding the resin that is liquid at room temperature
  • the composition can be easily molded as a thermoplastic resin in its uncured state.
  • the hydrocarbon elastomer (excluding liquid resins) and/or polyphenylene ether can be added in an amount of 30 to 200 parts by mass per 100 parts by mass of the copolymer.
  • the amount of the added resin is preferably 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass, per 100 parts by mass of the copolymer.
  • the amount of the monomer used in the present thermoplastic composition may be preferably 10 parts by mass or less per 100 parts by mass of the copolymer.
  • the number-average molecular weight of the copolymer used is 500 to 100,000, preferably 20,000 to 100,000, and more preferably 30,000 to 100,000.
  • thermoplastic composition described above may be molded into various shapes such as a sheet in advance by utilizing its thermoplasticity at a temperature below the action temperature of the curing agent, and may be combined with a semiconductor element, wiring, or substrate and laminated therewith, as necessary, and then heated to cure and bond.
  • the thermoplastic composition of the present invention containing the surface-treated silica is molded into a molded product (either an uncured or semi-cured molded product) in advance, which has the advantage of making it easier to suppress increases in the dielectric constant and dielectric loss tangent associated with water absorption (water adsorption) of the silica.
  • molded products are preferably in the form of sheets or pellets.
  • compositions of the present invention may be provided as a sheet obtained by molding the composition, heated and melted at a temperature below the curing agent's working temperature or decomposition temperature, using a known method. Forming into a sheet may be achieved by T-die extrusion, two-roll extrusion, or extrusion lamination onto a substrate film. In this case, the composition's composition, copolymer/monomer mass ratio, or solvent, other resin, and flame retardant are selected and adjusted so that the composition melts at the curing agent's working temperature or below its decomposition temperature and becomes solid at around room temperature.
  • the sheet is substantially uncured.
  • the sheet is finally treated at a temperature and time above the curing agent's working temperature or decomposition temperature to achieve complete curing.
  • This method is a common technique used for ethylene-vinyl acetate resin-based crosslinked sealant sheets for solar cells (photovoltaic power generation devices).
  • the composition of the present invention can also be formed into a molded article, such as a sheet or tube, in a partially crosslinked state, for example, by reacting a portion of the curing agent contained therein and semi-curing it (so-called B-stage state).
  • B-stage state a portion of the curing agent contained therein and semi-curing it
  • the composition can be semi-cured and the melt viscosity and fluidity can be controlled to achieve a B-stage state.
  • the curable resin or composition can be molded into an easily handled B-stage sheet by a first curing step (partial curing), which can then be laminated and pressure-bonded to an electronic device or substrate, and then subjected to a second curing step (complete curing) to form the final shape.
  • the composition composition i.e., the copolymer/monomer mass ratio
  • a solvent, other resins, and a flame retardant can be added.
  • the composition containing a curing agent such as a peroxide can be partially cured to form a sheet (B-stage state), and after molding and assembling the device, the composition can be fully cured by heating under pressure.
  • Known methods can be used to partially cure the composition.
  • one method involves using a combination of peroxides with different decomposition temperatures, treating for a predetermined period of time at a temperature at which only one of the peroxides is substantially active, obtaining a semi-hardened sheet, and finally treating for a sufficient period of time at a temperature at which all of the hardeners are active to completely harden the sheet.
  • the molded article may be a sheet.
  • the sheet may be uncured (semi-cured) to the extent that it can maintain its sheet shape, or may be fully cured.
  • the degree of curing of the composition can be quantitatively measured by known dynamic mechanical analysis (DMA).
  • the composition of the present invention can also be made into a viscous liquid varnish by adjusting its composition and blending ratio.
  • a varnish can be obtained by using a sufficient amount of solvent and/or an appropriate amount of liquid monomer.
  • an appropriate solvent is used to adjust the viscosity and fluidity of the composition as a varnish.
  • a solvent with a high boiling point at atmospheric pressure i.e., low volatility, contributes to a uniform thickness of the applied film, so a solvent with a boiling point above a certain level is preferred.
  • a preferred boiling point is approximately 110°C or higher and 300°C or lower at atmospheric pressure.
  • solvents suitable for such varnishes include toluene, xylene, mesitylene, ethylbenzene, limonene, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether.
  • the amount of the solvent used is preferably in the range of 10 to 2,000 parts by mass per 100 parts by mass of the composition of the present invention.
  • the varnish can be applied to or impregnated into a substrate, and the solvent can be removed by drying or other methods to produce an uncured or semi-cured molded product.
  • This molded product generally has the form of a sheet, film, or tape.
  • the resulting uncured or semi-cured molded product can then be cured under specified conditions, such as by heating or pressing.
  • the composition can be cured by a known method, taking into consideration the curing conditions (temperature, time, pressure) of the curing agent contained therein.
  • the curing conditions can be determined by taking into consideration the half-life temperature and the like disclosed for each peroxide.
  • the composition of the present invention can be used as a base material or substrate for single-layer or multi-layer printed circuit boards, flexible printed circuit boards, so-called single-layer or multi-layer CCL (copper clad laminate), single-layer or multi-layer FCCL (flexible copper clad laminate) boards, etc. It can also be used as various insulating materials for wiring, preferably for high-frequency signal wiring, such as coverlays, solder resists, build-up materials, interlayer insulating agents, bonding sheets, interlayer adhesives, and bump sheets for flip-chip bonders.
  • Uncured or partially cured sheets of the composition of the present invention can be suitably used as high-frequency electrical insulating materials. For example, they can be used as build-up films, bonding sheets, coverlay sheets, bump sheets for flip-chip bonders, or insulating or adhesive layers for substrates.
  • the composition of the present invention can be used as a replacement for conventionally used epoxy resin or silicone resin sheets.
  • the composition of the present invention can form a cured insulating layer or cured matrix phase with a low dielectric constant and low dielectric loss by undergoing a curing treatment.
  • the sheet thickness is generally 1 to 300 ⁇ m.
  • the sheet may contain woven or nonwoven fabrics such as glass cloth or ceramic fibers.
  • the sheet may be impregnated or may be multilayered with these.
  • flexible, bendable wiring insulated partially or completely with the sheet can be used as an antenna cable for mobile phones and the like, replacing conventional coaxial cables.
  • the sheet of the present invention or a B-stage sheet (coverlay sheet) can be used to cover wiring using a substrate of LCP (liquid crystal polymer), PPE sheet, fluorine-based resin, or polyimide resin, followed by curing and adhering to the substrate, and used as an insulating material.
  • Multilayer wiring boards in which the cured product obtained using the composition of the present invention serves as an insulating layer can be wiring boards with low dielectric loss and excellent high-frequency characteristics.
  • advantages include heat resistance sufficient to withstand soldering, and a certain degree of flexibility, elongation, and impact resistance sufficient to withstand stress due to heat cycles or differential thermal expansion.
  • wiring boards can be produced by laminating and pressing a core material, such as glass or quartz cloth, nonwoven fabric, film material, ceramic substrate, glass substrate, general-purpose resin plate (e.g., epoxy), or general-purpose laminate, with an insulating layer-attached conductor foil made of the cured product.
  • a core material such as glass or quartz cloth, nonwoven fabric, film material, ceramic substrate, glass substrate, general-purpose resin plate (e.g., epoxy), or general-purpose laminate
  • an insulating layer-attached conductor foil made of the cured product.
  • an insulating layer can be formed by applying a slurry or solution containing the composition to the core material, drying, and curing. The thickness of the insulating layer is generally 1 to 300 ⁇ m.
  • Such multilayer wiring boards can also be used in a multilayered or integrated configuration.
  • the cured product obtained by curing the varnish-like composition of the present invention can be suitably used as an electrical insulating material, as described above, and in particular can be used as a potting material, surface coating agent, coverlay, solder resist, buildup material, underfill material, filling insulating agent, interlayer insulating agent, or interlayer adhesive, or as a cured product for printed circuit boards, flexible printed circuit boards, CCL (copper clad laminate) substrates, FCCL (flexible copper clad laminate) substrates, or as a buildup film, bonding sheet, coverlay sheet, or cured product for a bump sheet for a flip chip bonder, as an electrical insulating material, in particular an electrical insulating material for high frequencies.
  • the present invention can provide an electrical insulating material comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer, having a storage modulus at 250°C of 10 MPa or more and 10 GPa or less, a dielectric constant at 23°C, 10 GHz or 25 GHz to 40 GHz of 2.0 or more and 3.5 or less, and a dielectric dissipation factor of 1.2 ⁇ 10 or less.
  • the uncured or semi-cured thermoplastic composition of the present invention can be bonded to a metal foil, particularly a copper foil for wiring, by heat and pressure treatment, without the need for adhesive coating or adhesive treatment, to obtain a laminate.
  • the term "metal foil” refers to a concept that includes metal wiring.
  • olefin-aromatic vinyl compound-aromatic polyene copolymer preferably a copolymer containing 10% by mass or more of an aromatic vinyl compound, and/or when the olefin is ethylene alone, or when the mass ratio of olefin monomer components other than ethylene to the ethylene monomer component contained in the olefin is 1/7 or less, a peel strength of 1 N/mm or more can be obtained as measured in accordance with Japanese Industrial Standards (JIS) C6481:1996. It is even more preferable to obtain a peel strength of 1.3 N/mm or more.
  • JIS Japanese Industrial Standards
  • the olefin is ethylene alone, or the ratio of olefin monomer components other than ethylene to the ethylene monomer component contained in the olefin is 1/10 or less, and most preferably, the content of ⁇ -olefin monomer units other than ethylene contained in the copolymer is 4% by mass or less, or when the olefin is ethylene alone, the peel strength can be further improved.
  • adhesive treatment deteriorates the dielectric properties of laminates such as copper-clad laminate sheets. Therefore, even without such treatment, it is preferable to provide a peel strength of 1 N/mm or more as measured according to Japanese Industrial Standards (JIS) C6481:1996.
  • the uncured or semi-cured thermoplastic composition of the present invention can be bonded to metal foils, such as copper foils for wiring, by curing treatments such as heat and pressure treatments, without the need for adhesive coating or adhesive treatment.
  • metal foils such as copper foils for wiring
  • curing treatments such as heat and pressure treatments
  • this does not preclude the use of other adhesive-imparting measures (such as adhesive coating or adhesive treatments) to impart adhesion to metal foils or other components, including the addition of the "surface modifier.”
  • the composition of the present invention for example, the curable composition, has the properties of a thermoplastic resin.
  • the cured product obtained by curing the curable composition has excellent low dielectric properties, a high storage modulus at high temperatures, and a small coefficient of thermal expansion (CTE), making it particularly suitable for use in various electronic substrates.
  • CTE coefficient of thermal expansion
  • the composition of copolymer P1 was such that the ethylene content was 78% by mass, the 1-hexene content was 0% by mass, the styrene content was 20% by mass, and the divinylbenzene content was 2% by mass.
  • the number average molecular weight Mn of the copolymer P1 was 7,500.
  • the water absorption rate in copolymer P1 was less than 0.1%.
  • Divinylbenzene (meta-para mixed product, divinylbenzene purity 81%) manufactured by Nippon Steel Chemical & Material Co., Ltd. was used.
  • the curing agent used was Perbutyl P (1,4-bis[(t-butylperoxy)isopropyl]benzene) manufactured by NOF Corporation or Percumyl D (dicumyl peroxide) manufactured by NOF Corporation.
  • the content of vinyl group units derived from ethylene, hexene, styrene, and divinylbenzene in the olefin-aromatic vinyl compound-aromatic polyene copolymer was determined from the peak area intensity assigned to each by 1H -NMR.
  • the sample was dissolved in 1,1,2,2-dTetrachloroethane, and the measurement was carried out at 80 to 130°C.
  • the molecular weight was determined as a number average molecular weight (Mn) converted to standard polystyrene using GPC (gel permeation chromatography) under the following conditions: Column: Four columns of TSKgel GMHXL TSKgel ⁇ 7.8 ⁇ 300 mm (manufactured by Tosoh Corporation) connected in series are used. Column temperature: 40°C Solvent: THF Liquid flow rate: 1.0 ml/min. Detector: RI detector
  • Silica powders having the specific surface areas shown in Table 1 were prepared.
  • the prepared silica powder was filled into an alumina crucible and heat-treated in air in an electric furnace at 1000°C for 4 hours. After the heat treatment, it was cooled to 200°C in the furnace and then cooled to room temperature in a desiccator (23°C, 10% RH), and the heat-treated silica powder was recovered.
  • Surface-treated silica powder 4 was obtained in the same manner as surface-treated silica powder 1, except that a silica powder having a specific surface area shown in Table 1 was used and 0.1 parts by mass of vinylsilane was added to 100 parts by mass of the heat-treated silica powder.
  • Surface-treated silica powder 5 was obtained in the same manner as surface-treated silica powder 1, except that a silica powder having a specific surface area shown in Table 1 was used and 1.2 parts by mass of phenylsilane (KBM-103 manufactured by Shin-Etsu Silicones Co., Ltd.) was added instead of vinylsilane per 100 parts by mass of the heat-treated silica powder.
  • Surface-treated silica powder 6 was obtained in the same manner as surface-treated silica powder 1, except that a silica powder having a specific surface area shown in Table 1 was used and 0.1 parts by mass of vinylsilane was added to 100 parts by mass of the heat-treated silica powder.
  • Surface-treated silica powder 7 was obtained in the same manner as surface-treated silica powder 1, except that a silica powder having a specific surface area shown in Table 1 was used and 1.5 parts by mass of methacrylsilane was added to 100 parts by mass of the heat-treated silica powder.
  • the resulting surface-treated silica powders 1 to 7 were stored in aluminum packs until immediately before various evaluations.
  • the specific surface area of the silica powder was measured by the BET single-point method using nitrogen gas adsorption. Specifically, a specific surface area measuring device (manufactured by Anton Paar, device name: NOVA 800 BET) was used, and nitrogen gas was transported by a vacuum pump. 0.1 to 5.0 g of the sample was dried and degassed at 300°C for 30 minutes before measurement.
  • the volume frequency particle size distribution of silica powder was determined by a wet laser diffraction scattering method using a particle size distribution analyzer (Coulter, LS13 320). A 0.2% aqueous solution of sodium hexametaphosphate was used as the solvent, and the powder was pre-dispersed for 120 seconds or more using a homogenizer at 500 W output. The PIDS (Polarization Intensity Differential Scattering) concentration was adjusted to 45-55% for measurement. The refractive index of water was set to 1.33, and the refractive index of the powder was determined taking into account the refractive index of the powder material. For example, amorphous silica was measured at a refractive index of 1.50. Based on the volume frequency particle size distribution thus obtained, the particle size (D x ) at which the cumulative value from the small particle size side was X% was calculated.
  • the resulting resin composition was evaluated for the following items.
  • the resulting resin composition was stirred using a THINKY MIXER (Thinky Corporation) and then poured onto a PTFE sheet mounted on a silicone rubber mold (frame thickness: 0.5 mm or 1.0 mm) placed on a glass plate. The mixture was then vacuum dried at 80°C for 10 hours at 20 Torr. After completion of the drying process, the silicone rubber mold was replaced with a SUS mold (frame thickness: 0.2 mm). The mixture was sandwiched between PTFE sheets and heated at 200°C for 2 hours under 10 MPa pressure using a heating press to obtain a sheet-like cured product.
  • a 30 mm x 40 mm x 0.2 mm sample was cut from the resulting sheet-like cured product and its dielectric loss tangent at 40 GHz was measured.
  • a 40 GHz split cylinder resonator (EM Lab) was used as the measurement device, and the measurement temperature was 25°C and humidity was 50% RH.
  • the sheet-like cured product prepared in the above ⁇ Measurement of dielectric tangent> was attached to a cross-section processing device (ion milling device (e.g., Hitachi High-Tech Corporation, product name "IM4000PLUS”)) and subjected to broad ion beam processing (accelerating voltage: 4 kV, processing time: 5 hours) to prepare a cross-section sample.
  • the cross-section sample was fixed to an observation sample stage of a scanning electron microscope (hereinafter referred to as "SEM") and introduced into a field emission SEM (e.g., JEOL Ltd., product name "JSM-70001F”) for SEM observation (accelerating voltage: 5 kV).
  • SEM scanning electron microscope

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une composition de résine selon la présente invention comprend : un copolymère de polyène aromatique-composé vinylique aromatique-oléfine ; et une poudre de silice traitée en surface formée de sorte que C et S satisfassent à 0,004 ≤ C/S ≤ 0,085, où C (% en masse) est la teneur en carbone telle que mesurée selon une procédure prédéterminée, et S (m2/g) est la surface spécifique telle que mesurée par une méthode BET à point unique à l'aide d'une adsorption d'azote gazeux.
PCT/JP2025/014283 2024-04-25 2025-04-10 Composition de résine et ensemble de matériaux composites Pending WO2025225398A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024071590A JP2025167197A (ja) 2024-04-25 2024-04-25 樹脂組成物および複合材料セット
JP2024-071590 2024-04-25

Publications (1)

Publication Number Publication Date
WO2025225398A1 true WO2025225398A1 (fr) 2025-10-30

Family

ID=97489976

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/014283 Pending WO2025225398A1 (fr) 2024-04-25 2025-04-10 Composition de résine et ensemble de matériaux composites

Country Status (2)

Country Link
JP (1) JP2025167197A (fr)
WO (1) WO2025225398A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002146233A (ja) * 2000-11-07 2002-05-22 Denki Kagaku Kogyo Kk 表面処理された微細球状シリカ粉末および樹脂組成物
JP2016141790A (ja) * 2015-02-05 2016-08-08 信越化学工業株式会社 Ｅｐｄｍ組成物
JP2020111474A (ja) * 2019-01-08 2020-07-27 株式会社アドマテックス シリカ粒子材料及びシリカ粒子材料分散液
WO2021112088A1 (fr) * 2019-12-03 2021-06-10 デンカ株式会社 Composition durcissable et corps durci associé
JP2021178770A (ja) * 2020-04-24 2021-11-18 デンカ株式会社 球状シリカ粉末
WO2022054885A1 (fr) * 2020-09-11 2022-03-17 デンカ株式会社 Composition et son produit durci
JP2022085610A (ja) * 2020-11-27 2022-06-08 デンカ株式会社 組成物及びその硬化物
JP2023165263A (ja) * 2022-05-02 2023-11-15 味の素株式会社 樹脂組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002146233A (ja) * 2000-11-07 2002-05-22 Denki Kagaku Kogyo Kk 表面処理された微細球状シリカ粉末および樹脂組成物
JP2016141790A (ja) * 2015-02-05 2016-08-08 信越化学工業株式会社 Ｅｐｄｍ組成物
JP2020111474A (ja) * 2019-01-08 2020-07-27 株式会社アドマテックス シリカ粒子材料及びシリカ粒子材料分散液
WO2021112088A1 (fr) * 2019-12-03 2021-06-10 デンカ株式会社 Composition durcissable et corps durci associé
JP2021178770A (ja) * 2020-04-24 2021-11-18 デンカ株式会社 球状シリカ粉末
WO2022054885A1 (fr) * 2020-09-11 2022-03-17 デンカ株式会社 Composition et son produit durci
JP2022085610A (ja) * 2020-11-27 2022-06-08 デンカ株式会社 組成物及びその硬化物
JP2023165263A (ja) * 2022-05-02 2023-11-15 味の素株式会社 樹脂組成物

Also Published As

Publication number Publication date
JP2025167197A (ja) 2025-11-07

Similar Documents

Publication Publication Date Title
JP7654738B2 (ja) 硬化性組成物及びその硬化体
JP7428815B2 (ja) 組成物及びその硬化体
JP7570901B2 (ja) 組成物及びその硬化物
CN101570640B (zh) 含有薄层石英玻璃布的预浸料、及使用其的布线板
CN101692756A (zh) 低热膨胀性低介质损耗的预浸料及其应用品
CN1597770A (zh) 树脂组合物、使用其的预浸渍体、层压板及多层印刷线路板
CN105051111A (zh) 树脂组合物以及采用其得到的粘接膜、覆盖膜、层间粘接剂
JP7286569B2 (ja) 熱硬化性樹脂組成物、熱硬化性接着剤、熱硬化性樹脂フィルム並びに前記熱硬化性樹脂組成物を用いた積層板、プリプレグ、及び回路基板
CN1944557A (zh) 稳定性优良的低介质损耗正切树脂清漆及采用该清漆的布线板材料
CN113004462B (zh) 热固性树脂组合物及其应用
WO2025225398A1 (fr) Composition de résine et ensemble de matériaux composites
WO2025225399A1 (fr) Composition de résine et ensemble de matériaux composites
JP7330638B2 (ja) 熱硬化性樹脂組成物及びその使用
TW202438597A (zh) 樹脂組成物、樹脂膜、印刷線路板及半導體封裝體
TW202315912A (zh) 樹脂薄片、積層板、覆金屬積層板、印刷線路板及半導體封裝體
TWI868058B (zh) 熱硬化性樹脂組成物之用途
TW202304717A (zh) 樹脂薄片及印刷配線板的製造方法
JP7638410B2 (ja) 絶縁層を含む多層構造体
JP7298468B2 (ja) 熱硬化性樹脂組成物及びその使用
JP2023035743A (ja) 誘電体層、配線板
WO2024106433A1 (fr) Structure multicouche comprenant une couche adhésive isolante, et article durci de celle-ci
CN119487090A (zh) 阻燃树脂组合物及由其制造的制品
WO2025126968A1 (fr) Composition liquide, stratifié utilisant ladite composition liquide, et procédé de production de préimprégné
CN114456502A (zh) 基于三元乙丙橡胶-聚苯醚树脂的组合物、半固化片及制备方法、积层板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25793723

Country of ref document: EP

Kind code of ref document: A1