WO2025053095A1 - 中空樹脂粒子、その製造方法、およびその用途 - Google Patents

中空樹脂粒子、その製造方法、およびその用途 Download PDF

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Publication number
WO2025053095A1
WO2025053095A1 PCT/JP2024/031382 JP2024031382W WO2025053095A1 WO 2025053095 A1 WO2025053095 A1 WO 2025053095A1 JP 2024031382 W JP2024031382 W JP 2024031382W WO 2025053095 A1 WO2025053095 A1 WO 2025053095A1
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weight
hollow resin
resin particles
parts
monomer
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English (en)
French (fr)
Japanese (ja)
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彩花 柴谷
晋弥 松野
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Sekisui Kasei Co Ltd
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Sekisui Kasei Co Ltd
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Priority to CN202480052849.5A priority Critical patent/CN121693525A/zh
Priority to JP2025544505A priority patent/JPWO2025053095A1/ja
Priority to KR1020267003137A priority patent/KR20260026590A/ko
Publication of WO2025053095A1 publication Critical patent/WO2025053095A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins

Definitions

  • the present invention relates to hollow resin particles, their production method, and their uses.
  • Hollow resin particles used in such applications are required to have high heat resistance so that the hollow resin particles do not undergo substantial change even when heated, for example, during molding of thermosetting resins containing the hollow resin particles or when soldering is used.
  • thermosetting resin or the like penetrates into the hollow resin particles during kneading in conventional hollow resin particles. This causes a problem in that the voids inside the hollow resin particles cannot be maintained, and the low dielectric properties expected of the resin composition are not expressed.
  • a porous hollow polymer particle obtained by suspension polymerization of a monomer mainly composed of an acrylic polyfunctional monomer such as trimethylolpropane tri(meth)acrylate and an acrylic monofunctional monomer such as methyl methacrylate together with a hydrophobic solvent has been reported (Patent Document 1).
  • acrylic resins generally have high relative dielectric constants and dielectric loss tangents, and insufficient heat resistance.
  • the porous hollow polymer particles described in Patent Document 1 are not suitable for the purpose of lowering the dielectric constant and dielectric loss tangent of the resin layer, or for the purpose of imparting high heat resistance to the resin layer.
  • the porous hollow polymer particles described in Patent Document 1 have a thin and porous shell surface, so that thermosetting resins and the like easily penetrate into the porous hollow polymer particles.
  • Patent Document 2 hollow resin particles obtained by suspension polymerization of divinylbenzene together with a hydrophobic solvent have been reported (Patent Document 2).
  • Patent Document 2 hollow resin particles with a composition containing a large amount of divinylbenzene have insufficient heat resistance.
  • the hollow resin particles described in Patent Document 2 have a high hollow ratio, so there is a possibility that the hollow resin particles will be crushed when mixed and kneaded with a thermosetting resin or the like, and the shell surface layer is thin, so that the thermosetting resin or the like can easily penetrate into the hollow resin particle.
  • hollow resin particles have been reported that are obtained by reacting an isocyanate compound with an active hydrogen compound, and the shell is formed of a polymer having urea bonds and/or urethane bonds (Patent Document 3).
  • hollow resin particles with a urethane composition have high values of dielectric constant and dielectric tangent, so the hollow resin particles described in Patent Document 3 are not suitable for the purpose of lowering the dielectric constant and dielectric tangent of the resin layer.
  • hollow resin particles with a urethane composition have insufficient heat resistance.
  • a method for producing hollow microparticles including step A of dispersing a solution containing a fluorine-substituted monomer and a non-polymerizable solvent in water to obtain a dispersion, step B of polymerizing the fluorine-substituted monomer to obtain phase-separated microparticles containing a fluorine-containing resin, and step C of removing the non-polymerizable solvent in the phase-separated microparticles to obtain hollow microparticles, and hollow microparticles obtained by said method have been reported (Patent Document 4).
  • fluorine-based resins have a high relative dielectric constant
  • the hollow microparticles described in Patent Document 4 are not suitable for the purpose of reducing the dielectric constant of a resin layer.
  • Hollow resin particles have been reported that have a shell portion and a hollow portion surrounded by the shell portion, the hollow portion being composed of a plurality of hollow regions or a porous structure, and the shell portion containing a polymer obtained, for example, by the reaction of polyphenylene ether with a monomer (B) (Patent Document 5).
  • Patent Document 5 the hollow resin particles described in Patent Document 5 have a thin shell surface layer, and thermosetting resins and the like easily penetrate into the interior of the hollow resin particles.
  • Patent No. 4445495 International Publication No. 2022-092076 Patent No. 6924533 JP 2023-057052 A JP 2023-021971 A
  • the present invention has been made to solve the above-mentioned problems of the conventional art, and its main object is to provide hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, which inhibits the intrusion of thermosetting resins and the like into the interior of the particles, and which have excellent heat resistance and excellent dielectric properties. It also aims to provide a method for producing such hollow resin particles. It also aims to provide uses for such hollow resin particles.
  • the hollow resin particles according to an embodiment of the present invention are A hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion,
  • the shell portion contains a polymer (P) having an ether structure represented by formula (1),
  • the apparent density D1 (g/cm 3 ) and the loose bulk density D2 (g/cm 3 ) satisfy the formula (2).
  • the polymer (P) is a polymer obtained by reacting a composition containing a compound (A) having an ether structure and a radical reactive group represented by the above formula (1) and a monomer (M) that reacts with the compound (A),
  • the monomer (M) includes an aromatic crosslinkable monomer, At least one selected from the group consisting of (a) and (b) may be satisfied.
  • the composition further comprises a chain transfer agent (B).
  • the amount of the aromatic crosslinkable monomer is 1 part by weight or more and less than 32 parts by weight.
  • the monomer (M) may contain an aromatic monofunctional monomer.
  • the aromatic monofunctional monomer may be at least one selected from the group consisting of styrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, vinylnaphthalene, and acenaphthylene.
  • the compound (A) may be a polyphenylene ether having (meth)acryloyl groups at both ends.
  • the chain transfer agent (B) may be at least one selected from the group consisting of mercaptan compounds, styrene-based dimers, terpenes, halogenated hydrocarbons, and ⁇ -methylstyrene.
  • the compound (A) when the total amount of the compound (A) and the monomer (M) is 100 parts by weight, the compound (A) may be 5 parts by weight to 60 parts by weight.
  • the aromatic monofunctional monomer when the total amount of the compound (A) and the monomer (M) is 100 parts by weight, the aromatic monofunctional monomer may be 0 parts by weight to 80 parts by weight.
  • the aromatic crosslinkable monomer when the total amount of the compound (A) and the monomer (M) is 100 parts by weight, the aromatic crosslinkable monomer may be 10 parts by weight to 60 parts by weight.
  • the hollow portion may be composed of a plurality of hollow regions or a porous structure.
  • the hollow resin particles according to any one of [1] to [10] above may have a 5% thermal weight loss temperature of 300° C. or higher when heated at a rate of 10° C./min in a nitrogen atmosphere.
  • the hollow resin particle according to any one of [1] to [11] above may have a dielectric loss tangent of less than 0.0015 at a frequency of 10 GHz.
  • the hollow resin particle according to any one of the above [1] to [12] may be used in a resin composition for a semiconductor member.
  • the hollow resin particles according to any one of the above [1] to [12] may be used in a coating composition.
  • the hollow resin particle according to any one of the above [1] to [12] may be used in a heat insulating resin composition.
  • a resin composition for a semiconductor member according to an embodiment of the present invention contains the hollow resin particles according to any one of [1] to [15] above.
  • a coating composition according to an embodiment of the present invention contains the hollow resin particles according to any one of [1] to [15] above.
  • a heat insulating resin composition according to an embodiment of the present invention contains the hollow resin particles according to any one of [1] to [15] above.
  • a method for producing hollow resin particles includes the steps of: A method for producing hollow resin particles, comprising reacting a composition containing a compound (A) having an ether structure represented by formula (1) and a radical reactive group, and a monomer (M) reactive with the compound (A) in an aqueous medium in the presence of a non-reactive solvent,
  • the monomer (M) includes an aromatic crosslinkable monomer, At least one selected from the group consisting of (a) and (b) is satisfied.
  • the composition further comprises a chain transfer agent (B).
  • the amount of the aromatic crosslinkable monomer is 1 part by weight or more and less than 32 parts by weight.
  • the method for producing hollow resin particles according to the above item [19] satisfies the above item (a), and the aromatic crosslinkable monomer may be 10 parts by weight to 60 parts by weight when the total amount of the compound (A) and the monomer (M) is 100 parts by weight.
  • hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, which inhibits the intrusion of thermosetting resins and the like into the interior of the particles and has excellent heat resistance and excellent dielectric properties. It is also possible to provide a method for producing such hollow resin particles. Furthermore, it is also possible to provide uses for such hollow resin particles.
  • FIG. 4 is a schematic cross-sectional view illustrating the structure of a hollow portion.
  • FIG. 2 is a SEM photograph of the appearance of the particles (1) obtained in Example 1.
  • FIG. 2 is a SEM photograph of a cross section of a particle (1) obtained in Example 1.
  • FIG. 2 is a SEM photograph of the appearance of particles (2) obtained in Example 2.
  • FIG. 2 is a SEM photograph of a cross section of a particle (2) obtained in Example 2.
  • FIG. 2 is a SEM photograph of the appearance of particles (3) obtained in Example 3.
  • FIG. 2 is a SEM photograph of a cross section of a particle (3) obtained in Example 3.
  • FIG. 1 is a SEM photograph of the appearance of particles (4) obtained in Example 4.
  • FIG. 2 is a SEM photograph of a cross section of particle (4) obtained in Example 4.
  • FIG. 1 is a SEM photograph of the appearance of particles (5) obtained in Example 5.
  • FIG. 1 is a SEM photograph of a cross section of a particle (5) obtained in Example 5.
  • FIG. 1 is a SEM photograph of the appearance of particles (6) obtained in Example 6.
  • FIG. 1 is a SEM photograph of a cross section of a particle (6) obtained in Example 6.
  • FIG. 1 is a SEM photograph of the appearance of particles (7) obtained in Example 7.
  • FIG. 1 is a SEM photograph of a cross section of a particle (7) obtained in Example 7.
  • FIG. 1 is a SEM photograph of the appearance of particles (8) obtained in Example 8.
  • FIG. 1 is a SEM photograph of a cross section of a particle (8) obtained in Example 8.
  • FIG. 1 is a SEM photograph of a cross section of a particle (8) obtained in Example 8.
  • FIG. 1 is a SEM photograph of the appearance of particles (9) obtained in Example 9.
  • FIG. 1 is a SEM photograph of a cross section of a particle (9) obtained in Example 9.
  • FIG. 1 is a SEM photograph of the appearance of particles (10) obtained in Example 10.
  • FIG. 1 is a SEM photograph of a cross section of a particle (10) obtained in Example 10.
  • FIG. 1 is a SEM photograph of the appearance of particles (11) obtained in Example 11.
  • FIG. 1 is a SEM photograph of a cross section of a particle (11) obtained in Example 11.
  • FIG. 1 is a SEM photograph of the appearance of particles (12) obtained in Example 12.
  • FIG. 1 is a SEM photograph of a cross section of a particle (12) obtained in Example 12.
  • FIG. 1 is a SEM photograph of the appearance of particles (13) obtained in Example 13.
  • FIG. 1 is a SEM photograph of a cross section of a particle (13) obtained in Example 13.
  • FIG. 2 is a SEM photograph of the appearance of particles (14) obtained in Comparative Example 1.
  • FIG. 2 is a SEM photograph of a cross section of a particle (14) obtained in Comparative Example 1.
  • FIG. 2 is a SEM photograph of the appearance of particles (15) obtained in Comparative Example 2.
  • (meth)acrylic means “acrylic and/or methacrylic
  • the term “(meth)acrylate” means “acrylate and/or methacrylate
  • the term “(meth)allyl” means “allyl and/or methallyl”
  • the term “(meth)acryloyl” means “acryloyl and/or methacryloyl”.
  • the hollow resin particles according to an embodiment of the present invention are hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, and the apparent density D1 (g/cm 3 ) and the loose bulk density D2 (g/cm 3 ) satisfy the following formula (2). D1-D2 ⁇ 0.70...(2)
  • “hollow” means that the inside is filled with a substance other than resin, such as gas or liquid, and preferably filled with gas, which can better demonstrate the effects of the present invention.
  • the hollow portion may be composed of one hollow region, or may be composed of multiple hollow regions or a porous structure.
  • the hollow portion is preferably composed of a porous structure.
  • FIG. 1(a) is a schematic cross-sectional view of a hollow resin particle whose hollow portion is composed of one hollow region.
  • FIG. 1(b) is a schematic cross-sectional view of a hollow resin particle whose hollow portion is composed of multiple hollow regions.
  • FIG. 1(c) is a schematic cross-sectional view of a hollow resin particle whose hollow portion is composed of a porous structure.
  • the hollow portion has multiple independent holes.
  • the hollow portion has interconnected holes like a three-dimensional network structure.
  • the hollow portion may be composed of one hollow region (interconnected holes) or may be composed of a mixture of multiple independent holes and one or more interconnected holes.
  • the apparent density D1 and loose bulk density D2 of the hollow resin particles satisfy the relationship of formula (2) above, when the hollow resin particles are kneaded with a thermosetting resin or the like to form a resin composition, the penetration of resin into the particles can be suppressed and voids inside the particles can be maintained.
  • the lower limit of the difference between the apparent density D1 and the loose bulk density D2, represented by D1-D2, is, for example, 0 or more.
  • the difference may be 0 or more and 0.60 or less, 0 or more and 0.50 or less, or 0 or more and 0.45 or less.
  • the volume average particle diameter of the hollow resin particles according to the embodiment of the present invention is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.2 ⁇ m to 50.0 ⁇ m, even more preferably 0.3 ⁇ m to 30.0 ⁇ m, and particularly preferably 0.4 ⁇ m to 20.0 ⁇ m. If the volume average particle diameter of the hollow resin particles according to the embodiment of the present invention is within the above range, the effects of the present invention can be more effectively achieved. If the volume average particle diameter of the hollow resin particles according to the embodiment of the present invention is too small outside the above range, the thickness of the shell portion becomes relatively thin, so that the hollow resin particles may not have sufficient strength.
  • thermosetting resin or the like may penetrate into the hollow resin particles. If the average particle diameter of the hollow resin particles according to the embodiment of the present invention is too large outside the above range, phase separation between the polymer and the solvent produced by polymerization of the monomer component during suspension polymerization may be difficult to occur, which may make it difficult to form the shell portion.
  • the hollow resin particles according to an embodiment of the present invention preferably have a 5% thermal weight loss temperature of 300°C or higher, more preferably 320°C or higher, even more preferably 340°C or higher, and particularly preferably 360°C or higher, when heated in a nitrogen atmosphere at a rate of 10°C/min.
  • the upper limit of the above 5% thermal weight loss temperature is preferably 500°C or lower. If the hollow resin particles according to an embodiment of the present invention have a 5% thermal weight loss temperature of 10°C/min or higher, when heated in a nitrogen atmosphere at a rate of 10°C/min, within the above range, the hollow resin particles according to an embodiment of the present invention can exhibit excellent heat resistance.
  • the 5% thermal weight loss temperature of the hollow resin particles according to the embodiment of the present invention when heated at 10°C/min in a nitrogen atmosphere, is too small and falls outside the above range, for example, when the hollow resin particles are kneaded with a thermosetting resin to form a resin composition, the particles may be deformed by heating for the curing reaction, and the hollow portion may be lost, which may reduce the dielectric properties that should be expressed in the resin composition by the hollow resin particles, such as the effect of lowering the dielectric constant and the effect of lowering the dielectric tangent.
  • the shell portion contains a polymer (P) having an ether structure represented by formula (1).
  • P polymer having an ether structure represented by formula (1).
  • the polymer (P) may be of only one type or of two or more types.
  • the content of polymer (P) in the shell portion is preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, and particularly preferably 90% by weight to 100% by weight, in order to further exert the effects of the present invention.
  • the shell portion may contain any other appropriate components as long as they do not impair the effects of the present invention.
  • any suitable polymer can be adopted within the scope of not impairing the effects of the present invention.
  • such a polymer (P) can be a polymer obtained by reacting a compound (A) having an ether structure represented by formula (1) and a radical reactive group with a monomer (M) that reacts with the compound (A), preferably a polymer obtained by reacting a compound (A), a monomer (M) that reacts with the compound (A), and a chain transfer agent (B).
  • the monomer (M) preferably contains an aromatic crosslinkable monomer.
  • the polymer (P) is, for example, a polymer obtained by the reaction of a composition containing a compound (A) and a monomer (M) that reacts with the compound (A), where the monomer (M) contains an aromatic crosslinkable monomer, and the polymer (P) preferably satisfies at least one selected from the group consisting of the following (a) and (b):
  • the composition further comprises a chain transfer agent (B).
  • B chain transfer agent
  • the amount of the aromatic crosslinkable monomer is 1 part by weight or more and less than 32 parts by weight.
  • the compound (A) having an ether structure and a radical reactive group represented by formula (1) may be of only one type, or of two or more types.
  • the monomer (M) that reacts with the compound (A) may be of only one type, or of two or more types.
  • the ratio of compound (A) to monomer (M) is preferably (5 parts by weight to 80 parts by weight):(95 parts by weight to 20 parts by weight) in terms of parts by weight (compound (A) to monomer (M)), more preferably (10 parts by weight to 80 parts by weight):(90 parts by weight to 20 parts by weight), more preferably (20 parts by weight to 70 parts by weight):(80 parts by weight to 30 parts by weight), even more preferably (25 parts by weight to 60 parts by weight):(75 parts by weight to 40 parts by weight), and particularly preferably (30 parts by weight to 50 parts by weight):(70 parts by weight to 50 parts by weight). If the content of compound (A) is too small outside the above range, the heat resistance may be insufficient.
  • the content of compound (A) is too high and outside the above range, it may be difficult to form the shell portion and the hollow portion surrounded by the shell portion.
  • the content of compound (A) may be 5 parts by weight to 60 parts by weight, or 10 parts by weight to 50 parts by weight.
  • any suitable compound may be used as long as it has the ether structure represented by formula (1) and a radical reactive group, without impairing the effects of the present invention.
  • a preferable example of such a compound (A) is polyphenylene ether.
  • polyphenylene ethers examples include the NORYL (registered trademark) series (NORYL (registered trademark) SA9000, etc.) (manufactured by SABIC), the Iupiace (registered trademark) series (manufactured by Mitsubishi Chemical Corporation), the ZYLON (registered trademark) series (manufactured by Asahi Kasei Corporation), and the OPE-2St series (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
  • the compound (A) may be a polyphenylene ether having (meth)acryloyl groups at both ends.
  • the polyphenylene ether is an oligomer, and that the number average molecular weight Mn is 500 to 3500.
  • Examples of the monomer (M) include crosslinkable monomers and monofunctional monomers. In terms of being able to more effectively exert the effects of the present invention, a monomer that reacts with the terminal group of the compound (A) is preferred.
  • crosslinkable monomers examples include polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerin tri(meth)acrylate; polyfunctional acrylamide derivatives such as N,N'-methylene bis(meth)acrylamide and N,N'-ethylene bis(meth)acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; and aromatic crosslinkable monomers such as divinylbenzene, divinylnaphthalene, and diallyl phthalate. As described above, aromatic crosslinkable monomers are preferred, and divinylbenzene is more preferred, in terms of being able to more effectively exhibit the effects of the present invention.
  • the crosslinkable monomer may be of one type only, or of two or more types.
  • monofunctional monomers examples include alkyl (meth)acrylic acid esters having 1 to 16 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; aromatic monofunctional monomers, such as styrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene; dicarboxylic acid ester monomers, such as dimethylmaleate, diethylfumarate, dimethylfumarate, and diethylfumarate; maleic anhydride; N-vinylcarbazole; and (meth)acrylonitrile.
  • alkyl (meth)acrylic acid esters having 1 to 16 carbon atoms such as methyl (meth)acrylate,
  • aromatic monofunctional monomers are preferred, and styrene and ethylvinylbenzene are more preferred.
  • the monofunctional monomer may be one type only, or two or more types.
  • the monomer (M) preferably includes an aromatic monofunctional monomer. That is, the monomer (M) preferably includes an aromatic crosslinkable monomer and an aromatic monofunctional monomer.
  • the aromatic monofunctional monomer is, for example, at least one selected from the group consisting of styrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, vinylnaphthalene, and acenaphthylene, and is preferably styrene or ethylvinylbenzene.
  • the monomer (M) preferably includes styrene, and more preferably includes divinylbenzene, ethylvinylbenzene, and styrene.
  • the amount of the aromatic monofunctional monomer is preferably 0 to 80 parts by weight, more preferably 1 to 80 parts by weight, even more preferably 10 to 80 parts by weight, still more preferably 10 to 70 parts by weight, even more preferably 20 to 60 parts by weight, and particularly preferably 30 to 50 parts by weight.
  • the amount of the aromatic crosslinkable monomer is preferably 1 to 60 parts by weight, more preferably 1 to 50 parts by weight, even more preferably 1 to 32 parts by weight, even more preferably 10 to 32 parts by weight, and particularly preferably 10 to 25 parts by weight.
  • the polymer (P) satisfies the above (a).
  • the chain transfer agent (B) may be at least one selected from the group consisting of mercaptan compounds, styrene-based dimers, terpenes, halogenated hydrocarbons, and ⁇ -methylstyrene.
  • Examples of the mercaptan compounds include n-octyl mercaptan (1-octanethiol), n-dodecyl mercaptan (1-dodecanethiol), tert-dodecyl mercaptan, 2-hydroxyethyl mercaptan, n-octadecyl mercaptan (stearyl mercaptan), alkylenedithiols, and thiocyanuric acid, with n-octyl mercaptan and n-dodecyl mercaptan being preferred.
  • Examples of the styrene-based dimer include ⁇ -methylstyrene dimer, etc.
  • Examples of the terpene include ⁇ -terpinene and dipentene, etc.
  • Examples of the halogenated hydrocarbon include halogenated hydrocarbons.
  • chain transfer agents mercaptan, ⁇ -methylstyrene, and styrene-based dimers are preferred, mercaptan and ⁇ -methylstyrene are more preferred, and mercaptan is even more preferred.
  • These chain transfer agents may be used alone or in combination of two or more.
  • the polymer (P) is a polymer obtained by a reaction using a chain transfer agent (B)
  • a shell portion and a hollow portion surrounded by the shell portion can be formed regardless of the type and composition of the compound (A) and the monomer (M).
  • the polymer (P) is a polymer obtained by a reaction using a chain transfer agent (B)
  • hollow resin particles By using such hollow resin particles, it is possible to express excellent dielectric properties in the resin composition.
  • Hollow resin particles with excellent dielectric properties are, for example, hollow resin particles that have a low dielectric constant and a low dielectric tangent.
  • the content of the chain transfer agent (B) is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, even more preferably 0.1 to 3 parts by weight, and particularly preferably 0.1 to 1 part by weight, when the total amount of the compound (A) and the monomer (M) is 100 parts by weight.
  • the polymer (P) satisfies the above (b).
  • the aromatic crosslinkable monomer is 1 part by weight or more and less than 32 parts by weight, thereby further improving the dielectric properties of the hollow resin particles.
  • Such hollow resin particles have, for example, an excellent low dielectric constant and low dielectric tangent.
  • the aromatic crosslinkable monomer is preferably 10 parts by weight to less than 32 parts by weight, and more preferably 10 parts by weight to 25 parts by weight.
  • the polymer (P) satisfies the above (a) and (b).
  • the polymer (P) satisfies the above (a) and (b)
  • the monomer (M) includes an aromatic crosslinkable monomer and an aromatic monofunctional monomer.
  • the aromatic monofunctional monomer preferably includes styrene.
  • the amount of styrene is preferably 1 to 70 parts by weight, more preferably 10 to 70 parts by weight, even more preferably 20 to 70 parts by weight, and particularly preferably 30 to 70 parts by weight.
  • reaction of the above composition can be carried out by any appropriate reaction as long as it does not impair the effects of the present invention.
  • the reaction of compound (A), monomer (M), and chain transfer agent (B) can be carried out by subjecting compound (A) and monomer (M) to a suspension polymerization reaction in the presence of chain transfer agent (B).
  • an oil phase is added to an aqueous phase and suspended to carry out the polymerization reaction.
  • the aqueous phase or oil phase may contain any appropriate solvent as long as it does not impair the effects of the present invention. Examples of such solvents include aqueous media and non-reactive solvents as described below.
  • the solvent may be of only one type, or of two or more types.
  • any suitable additive (C) that does not fall under any of compound (A), monomer (M), and chain transfer agent (B) may be used within a range that does not impair the effects of the present invention.
  • the additive (C) may be of only one type, or of two or more types.
  • the additive (C) does not include solvents such as aqueous media and non-reactive solvents, as described below, and dispersion stabilizers.
  • the content of additive (C) is preferably 1 to 40 parts by weight, more preferably 1 to 30 parts by weight, even more preferably 1 to 20 parts by weight, and particularly preferably 1 to 10 parts by weight, when the total amount of compound (A) and monomer (M) is 100 parts by weight.
  • any suitable additive (C) that does not fall under any of the compound (A), the monomer (M), and the chain transfer agent (B) may be used as long as it does not impair the effects of the present invention.
  • additives (C) include non-crosslinkable polymers, polymerization initiators, surfactants, and other compounds.
  • phase separation between the polymer (P) and the solvent that is produced as the reaction proceeds can be promoted, facilitating shell formation.
  • the non-crosslinkable polymer may be, for example, at least one selected from the group consisting of polyolefins, styrene-based polymers, (meth)acrylic acid-based polymers, styrene-(meth)acrylic acid-based polymers, and hydrocarbon-based resins.
  • polyolefins examples include polyethylene, polypropylene, and poly- ⁇ -olefins. From the viewpoint of solubility in the monomer components including compound (A) and monomer (M), it is preferable to use side-chain crystalline polyolefins using long-chain ⁇ -olefins as raw materials, and low-molecular-weight polyolefins and olefin oligomers produced with metallocene catalysts.
  • styrene-based polymers include polystyrene, styrene-acrylonitrile copolymers, and acrylonitrile-butadiene-styrene copolymers.
  • Examples of (meth)acrylic acid-based polymers include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and polypropyl (meth)acrylate.
  • styrene-(meth)acrylic acid polymers examples include styrene-methyl (meth)acrylate copolymers, styrene-ethyl (meth)acrylate copolymers, styrene-butyl (meth)acrylate copolymers, and styrene-propyl (meth)acrylate copolymers.
  • R 3 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 8 carbon atoms, particularly preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.
  • R 5 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 8 carbon atoms, particularly preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.
  • m is preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 40, and particularly preferably 1 to 30.
  • b is preferably 0 to 100, more preferably 0 to 50, even more preferably 0 to 10, particularly preferably 0 to 5, and most preferably 0 or 1.
  • KAYAMER registered trademark
  • PM-21 manufactured by Nippon Kayaku Co., Ltd.
  • any suitable dispersion stabilizer (D) that does not fall under either compound (A) or monomer (M) may be used as long as it does not impair the effects of the present invention.
  • the dispersion stabilizer (D) may be of only one type, or of two or more types.
  • the amount of the dispersion stabilizer (D) is preferably 0.5 to 10 parts by weight per 100 parts by weight of the aqueous medium.
  • the amount of the dispersion stabilizer (D) may be one type or two or more types.
  • Dielectric constant and dielectric loss tangent of hollow resin particles In electronic devices, one of the applications of hollow resin particles, the transmission loss caused by radio waves transmitted for communication being converted into heat in a dielectric is expressed as the product of the frequency, the square root of the relative dielectric constant, and the dielectric loss tangent. In other words, since the transmitted signal is more likely to be converted into heat in proportion to the frequency, the higher the frequency band, the lower the dielectric properties required for communication component (semiconductor component) materials in order to suppress transmission loss.
  • the dielectric constant of the hollow resin particles according to an embodiment of the present invention is preferably 1.0 to 2.5, more preferably 1.0 to 2.3, and even more preferably 1.0 to 2.0, at a measurement frequency of 10 GHz.
  • the dielectric loss tangent of the hollow resin particles according to the embodiment of the present invention is preferably 0 to 0.005, more preferably 0 to 0.0045, even more preferably 0 to 0.004, even more preferably 0 to 0.003, even more preferably 0 to 0.002, and particularly preferably 0 to 0.0015, at a measurement frequency of 10 GHz. If the relative dielectric constant and dielectric loss tangent of the hollow resin particles according to the embodiment of the present invention are within the above ranges, the effects of the present invention can be more effectively achieved.
  • the hollow resin particles according to the embodiment of the present invention preferably have a relative dielectric constant of less than 2.0 and a dielectric loss tangent of less than 0.004 at a measurement frequency of 10 GHz, and even more preferably have a relative dielectric constant of less than 2.0 and a dielectric loss tangent of less than 0.0015 at a measurement frequency of 10 GHz.
  • the hollow resin particles according to an embodiment of the present invention have a dielectric constant greater than 2.5 and a dielectric loss tangent greater than 0.005
  • the resin composition will not have a sufficient effect of lowering the dielectric constant, and there is a risk of transmission loss occurring and an increase in the amount of heat generated by the component when used in the high frequency band.
  • the hollow resin particles have a dielectric constant greater than 2.0 and a dielectric loss tangent greater than 0.004 the above-mentioned inconveniences are more likely to occur.
  • the values of the dielectric constant and dielectric tangent of the hollow resin particles according to the embodiments of the present invention are not limited to the above.
  • the values of the dielectric constant and dielectric tangent are not limited to the above.
  • hollow resin particles according to the embodiment of the present invention can be used in various applications. In that the effects of the present invention can be more effectively utilized, the hollow resin particles according to the embodiment of the present invention are suitable for semiconductor members, and can be typically used in resin compositions for semiconductor members. In addition, the hollow resin particles according to the embodiment of the present invention can be used in applications such as paint compositions, cosmetics, paper coating compositions, heat insulating resin compositions, light diffusing resin compositions, and light diffusing films, in addition to the above-mentioned applications for resin compositions for semiconductor members.
  • the hollow resin particles according to the embodiment of the present invention can achieve a low dielectric constant and a low dielectric loss tangent and exhibit excellent heat resistance, and therefore can be suitably used in a resin composition for a semiconductor member.
  • the resin composition for semiconductor components according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.
  • Semiconductor components refer to components that constitute semiconductors, such as semiconductor packages and semiconductor modules.
  • resin compositions for semiconductor components refer to resin compositions used in semiconductor components.
  • a semiconductor package is made up of an IC chip as an essential component and at least one material selected from the group consisting of mold resin, underfill material, mold underfill material, die bond material, prepreg for semiconductor package substrates, metal-clad laminate for semiconductor package substrates, and build-up material for printed circuit boards for semiconductor packages.
  • a semiconductor module is comprised of a semiconductor package as an essential component and at least one member selected from prepregs for printed circuit boards, metal-clad laminates for printed circuit boards, build-up materials for printed circuit boards, solder resist materials, coverlay films, electromagnetic shielding films, and adhesive sheets for printed circuit boards.
  • the hollow resin particles according to the embodiment of the present invention can impart an excellent appearance to a coating film containing the hollow resin particles, and therefore can be suitably used in a coating composition.
  • the coating composition according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.
  • the coating composition according to an embodiment of the present invention preferably contains at least one selected from a binder resin and a UV-curable resin.
  • the binder resin may be of only one type or of two or more types.
  • the UV-curable resin may be of only one type or of two or more types.
  • binder resin Any suitable binder resin may be used as long as it does not impair the effects of the present invention.
  • binder resins include resins that are soluble in organic solvents or water, and emulsion-type water-based resins that can be dispersed in water.
  • binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.
  • any suitable UV-curable resin may be used as long as it does not impair the effects of the present invention.
  • examples of such UV-curable resins include polyfunctional (meth)acrylate resins and polyfunctional urethane acrylate resins. Polyfunctional (meth)acrylate resins are preferred, and polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule are more preferred.
  • polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate.
  • the content ratio may be any appropriate content ratio depending on the purpose.
  • the hollow resin particles according to an embodiment of the present invention are preferably 5% by weight to 50% by weight, more preferably 10% by weight to 50% by weight, and even more preferably 20% by weight to 40% by weight, based on the total amount of the binder resin (in solids content in the case of an emulsion-type aqueous resin) and at least one selected from a UV-curable resin, and the hollow resin particles according to an embodiment of the present invention.
  • a photopolymerization initiator is preferably used in combination. Any appropriate photopolymerization initiator may be used as long as it does not impair the effects of the present invention. Examples of such photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (described in JP-A No.
  • 2,3-dialkyldione compounds 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, onium salts, borate salts, active halogen compounds, and ⁇ -acyloxime esters.
  • the coating composition according to the embodiment of the present invention may contain a solvent.
  • the solvent may be of only one type, or of two or more types.
  • the content ratio of the solvent may be any appropriate content ratio depending on the purpose.
  • any suitable solvent may be used as long as it does not impair the effects of the present invention.
  • a solvent is preferably one that can dissolve or disperse the binder resin or UV-curable resin.
  • solvents include, for example, hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and ether solvents such as dioxane, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether.
  • solvents include, for example, water and alcohols.
  • the coating composition according to the embodiment of the present invention may be diluted to adjust the viscosity as necessary.
  • Any appropriate diluent may be used depending on the purpose. Examples of such diluents include the solvents mentioned above.
  • the diluent may be one type only, or two or more types.
  • the coating composition according to the embodiment of the present invention may contain other components, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, and a dye, as necessary.
  • a coating surface conditioner such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, and a dye, as necessary.
  • any appropriate coating method may be used depending on the purpose.
  • coating methods include spray coating, roll coating, brush coating, coating reverse roll coating, gravure coating, die coating, comma coating, and spray coating.
  • any appropriate formation method may be adopted as the formation method depending on the purpose.
  • a formation method includes a method in which a coating film is formed by applying the composition to any coating surface of a substrate, drying the coating film, and then curing the coating film as necessary to form a coating film.
  • substrates include metal, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetyl cellulose), etc.).
  • the hollow resin particles according to the embodiment of the present invention can impart excellent heat insulation to a coating film containing the hollow resin particles, and therefore can be suitably used in a heat insulating resin composition.
  • the coating film containing the hollow resin particles according to the embodiment of the present invention can exhibit excellent reflectance in the wavelength range from ultraviolet light to near infrared light.
  • the heat insulating resin composition according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.
  • the heat insulating resin composition according to an embodiment of the present invention preferably contains at least one selected from a binder resin and a UV-curable resin.
  • the above-mentioned explanation of the coating composition may be applied to the binder resin and the UV-curable resin.
  • the heat insulating resin composition according to an embodiment of the present invention may contain other components, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, a body pigment, a color pigment, a metal pigment, a mica powder pigment, and a dye, as necessary.
  • a coating surface conditioner such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, a body pigment, a color pigment, a metal pigment, a mica powder pigment, and a dye, as necessary.
  • the light diffusion film according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.
  • Any appropriate polymerization time may be used as long as it is suitable for suspension polymerization and does not impair the effects of the present invention.
  • Such a polymerization time is preferably 1 hour to 48 hours.

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WO2012050138A1 (ja) * 2010-10-13 2012-04-19 旭化成ケミカルズ株式会社 ポリフェニレンエーテル粉体及びポリフェニレンエーテル樹脂組成物
WO2022131127A1 (ja) * 2020-12-17 2022-06-23 積水化成品工業株式会社 中空樹脂粒子、その製造方法、およびその用途

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012050138A1 (ja) * 2010-10-13 2012-04-19 旭化成ケミカルズ株式会社 ポリフェニレンエーテル粉体及びポリフェニレンエーテル樹脂組成物
WO2022131127A1 (ja) * 2020-12-17 2022-06-23 積水化成品工業株式会社 中空樹脂粒子、その製造方法、およびその用途

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