WO2023074651A1 - 中空粒子、中空粒子の製造方法、樹脂組成物、及び成形体 - Google Patents

中空粒子、中空粒子の製造方法、樹脂組成物、及び成形体 Download PDF

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WO2023074651A1
WO2023074651A1 PCT/JP2022/039609 JP2022039609W WO2023074651A1 WO 2023074651 A1 WO2023074651 A1 WO 2023074651A1 JP 2022039609 W JP2022039609 W JP 2022039609W WO 2023074651 A1 WO2023074651 A1 WO 2023074651A1
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Prior art keywords
hollow particles
mass
hollow
resin
shell
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English (en)
French (fr)
Japanese (ja)
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左京 柳生
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Zeon Corp
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Zeon Corp
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Priority to US18/702,587 priority Critical patent/US20240416313A1/en
Priority to KR1020247012720A priority patent/KR20240088903A/ko
Priority to CN202280069995.XA priority patent/CN118119445A/zh
Priority to EP22886978.0A priority patent/EP4424726A4/en
Priority to JP2023556445A priority patent/JPWO2023074651A1/ja
Publication of WO2023074651A1 publication Critical patent/WO2023074651A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • 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
    • C08F2/34—Polymerisation in gaseous state
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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

Definitions

  • the present disclosure relates to hollow particles, hollow particle production methods, resin compositions, and molded articles.
  • Hollow particles have cavities inside the particles, so they are used by being added to resins, paints, various moldings, etc. for the purpose of weight reduction, heat insulation, low dielectric constant, etc.
  • Applications include automobiles, bicycles, aviation, electricity, electronics, architecture, home appliances, containers, stationery, tools, and footwear.
  • Patent Document 1 discloses hollow particles produced by emulsion polymerization using acrylic resin. There is a problem that the effects of low dielectric constant and low dielectric loss tangent cannot be sufficiently obtained. Therefore, in order to reduce the dielectric constant and dielectric loss tangent of hollow particles, hollow particles using styrene-based resins are manufactured.
  • the shell part contains an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c) having a specific structure. Hollow particles containing an aromatic polymer (P1) obtained by polymerizing a monomer composition containing.
  • thermosetting modified polyphenylene ether has attracted attention as an insulating resin with a low dielectric constant and dielectric loss tangent.
  • the resin film formed using the thermosetting modified polyphenylene ether contains the hollow particles described in Patent Document 2, the dielectric constant is lowered by the hollow particles as shown in Comparative Example 4 described later. And the effect of low dielectric loss tangent cannot be sufficiently obtained.
  • a resin film formed using a thermosetting resin is usually obtained by heating a coating film of a resin composition in which a thermosetting resin is dissolved in a solvent. It is presumed that the effect of lowering the dielectric constant and the dielectric loss tangent becomes insufficient as a result of the gas permeating the shell of the particle, entering the inside of the particle, and remaining even after heat curing. be done.
  • An object of the present disclosure is to provide hollow particles that have good dielectric properties and solvent resistance and that can reduce the dielectric constant and dielectric loss tangent of a resin molded product. It is an object of the present invention to provide a method for producing hollow particles, a resin composition containing the hollow particles, and a molded body of the resin composition containing the hollow particles.
  • the present inventor focused on the resin composition of the shell of the hollow particles and the permeability to toluene, made the shell contain a large amount of crosslinkable hydrocarbon monomer units, and further adjusted the method of forming the shell so that toluene
  • the hollow particles having a hard-to-penetrate shell have good dielectric properties and solvent resistance, and when a resin molded body is produced by adding them to a resin composition containing an organic solvent, the dielectric constant of the resin molded body is lowered. And it was found to be excellent in the effect of lowering the dielectric loss tangent.
  • the present disclosure provides a hollow particle comprising a shell containing a resin and a hollow portion surrounded by the shell and having a porosity of 50% or more,
  • the shell contains, as the resin, a polymer containing 70% by mass or more of a crosslinkable hydrocarbon monomer unit,
  • 0.1 mg of hollow particles are added to 4 mL of toluene, shaken for 10 minutes at a shaking speed of 100 rpm, and then left to stand for 48 hours. Hollow particles are provided in which the particles are less than 5% by weight.
  • the hollow particles of the present disclosure preferably have a dielectric loss tangent of 0.0010 or less at a frequency of 1 GHz.
  • the porosity is preferably 60% or more.
  • the hollow particles of the present disclosure preferably have a volume average particle diameter of 1.0 ⁇ m or more and 10.0 ⁇ m or less.
  • the present inventors found that when hollow particles are produced by a suspension polymerization method using a crosslinkable hydrocarbon monomer, by adding a specific reaction-accelerating additive liquid during the polymerization reaction, the dielectric properties and that hollow particles having good solvent resistance can be obtained.
  • the present disclosure provides a method for producing hollow particles having a shell containing a resin and a hollow portion surrounded by the shell and having a porosity of 50% or more, A step of preparing a mixed solution containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer and an aqueous medium; By suspending the mixed liquid, droplets of the monomer composition containing the polymerizable monomer, the hydrophobic solvent, and the polymerization initiator are dispersed in the aqueous medium.
  • a step of preparing By subjecting the suspension to a polymerization reaction, a precursor composition is prepared which includes precursor particles having a hollow portion surrounded by a resin-containing shell and encapsulating the hydrophobic solvent in the hollow portion. and The content of the crosslinkable hydrocarbon monomer is 70% by mass or more in 100% by mass of the polymerizable monomer contained in the mixed liquid,
  • the step of preparing the precursor composition after adding a reaction accelerating additive liquid during the polymerization reaction, the polymerization reaction is further performed, and the reaction accelerating additive liquid has a solubility in water at 20 ° C.
  • the amount of the non-reactive low-molecular-weight compound added is the amount of the polymerization It is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total mass of the reactive monomer and the hydrophobic solvent.
  • the amount of the low-molecular-weight compound added is preferably 1 to 3 parts by mass with respect to 100 parts by mass of the total mass of the polymerizable monomer and the hydrophobic solvent contained in the mixture.
  • the reaction acceleration it is preferable to add an additive solution for
  • the hydrophobic solvent is preferably a chain hydrocarbon-based solvent.
  • the polymerization initiator is preferably an organic peroxide.
  • the present disclosure provides a resin composition containing the hollow particles of the present disclosure and a matrix resin. Furthermore, the present disclosure provides a molded body of a resin composition containing the hollow particles of the present disclosure and a matrix resin.
  • hollow particles that have good dielectric properties and solvent resistance and that can reduce the dielectric constant and dielectric loss tangent of resin moldings.
  • a method for producing good hollow particles is provided.
  • a resin composition containing the hollow particles and a molded article of the resin composition containing the hollow particles are provided.
  • a polymerizable monomer is a compound having a functional group capable of addition polymerization (in the present disclosure, sometimes simply referred to as a polymerizable functional group).
  • a compound having an ethylenically unsaturated bond as a functional group capable of addition polymerization is generally used as the polymerizable monomer.
  • a polymerizable monomer having only one polymerizable functional group is referred to as a non-crosslinkable monomer, and a polymerizable monomer having two or more polymerizable functional groups is referred to as a crosslinkable monomer.
  • a crosslinkable monomer is a polymerizable monomer that forms a crosslinked bond in a resin by a polymerization reaction.
  • a hydrocarbon monomer is a polymerizable monomer composed of carbon and hydrogen.
  • a crosslinkable hydrocarbon monomer is a polymerizable monomer having two or more polymerizable functional groups and composed of carbon and hydrogen.
  • good dielectric properties mean low dielectric constant and low dielectric loss tangent, and the lower the dielectric constant and dielectric loss tangent, the better the dielectric properties.
  • the method for producing the hollow particles of the present disclosure and the hollow particles of the present disclosure will be described in detail in this order, and the resin composition and molded article containing the hollow particles of the present disclosure will also be described.
  • the method for producing hollow particles of the present disclosure includes a shell containing a resin and a hollow portion surrounded by the shell, and has a porosity of 50% or more. preparing a mixture containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer and an aqueous medium; By suspending the mixture, droplets of the monomer composition containing the polymerizable monomer, the hydrophobic solvent, and the polymerization initiator are dispersed in the aqueous medium.
  • a step of preparing By subjecting the suspension to a polymerization reaction, a precursor composition is prepared which includes precursor particles having a hollow portion surrounded by a resin-containing shell and encapsulating the hydrophobic solvent in the hollow portion. and The content of the crosslinkable hydrocarbon monomer is 70% by mass or more in 100% by mass of the polymerizable monomer contained in the mixed liquid,
  • the reaction accelerating additive liquid after adding a reaction accelerating additive liquid in the middle of the polymerization reaction, the polymerization reaction is further performed, and the reaction accelerating additive liquid has a solubility in water at 20 ° C. It is characterized by using a low-molecular-weight compound that is larger than the solvent and is 0.5 g/L to 1000 g/L.
  • the polymerizable monomer and the hydrophobic solvent are A suspension is prepared in which droplets having phase separation and a distribution structure in which the polymerizable monomer is unevenly distributed on the surface side and the hydrophobic solvent is unevenly distributed in the center are dispersed in an aqueous medium, and the suspension is It follows the basic technique of subjecting a liquid to a polymerization reaction to harden the surface of the droplets to form hollow particles having a hollow space filled with a hydrophobic solvent.
  • the ratio of the crosslinkable hydrocarbon monomer in the polymerizable monomer is increased, and the above-described specific reaction accelerating additive liquid is added during the polymerization reaction. By doing so, hollow particles having good dielectric properties and solvent resistance can be obtained.
  • the content of a crosslinkable hydrocarbon monomer such as divinylbenzene in 100% by mass of the polymerizable monomer contained in the suspension is 70% by mass or more, so that carbonization Since a shell with a high proportion of hydrogen is formed, it is possible to form a shell having a resin composition with a low dielectric constant and a low dielectric loss tangent compared to hollow particles or the like having an acrylic resin as the main component of the shell.
  • the shell is formed using a crosslinkable hydrocarbon monomer, when hollow particles are added to a resin composition containing an organic solvent to produce a resin molded body, the resin molded body is sufficiently formed.
  • a shell is formed by polymerization of a polymerizable monomer containing a large amount of a crosslinkable hydrocarbon monomer, and the specific Addition of the reaction-promoting additive liquid accelerates the polymerization reaction, allowing the polymerization reaction to proceed sufficiently.
  • the formed shell has a resin composition with good dielectric properties and a high crosslink density, so that hollow particles with excellent dielectric properties and solvent resistance can be obtained.
  • the specific reaction-promoting additive liquid added during the polymerization reaction enters the shell and swells the shell, thereby promoting the thermal movement of the shell, thereby promoting the polymerization reaction.
  • the method for producing hollow particles of the present disclosure includes a step of preparing a mixed solution, a step of preparing a suspension, and a step of subjecting the suspension to a polymerization reaction, and may further include steps other than these. Moreover, as long as it is technically possible, two or more of the above steps and other additional steps may be performed simultaneously as one step, or their order may be changed. For example, the preparation and suspension of the mixed solution may be performed simultaneously in one step, such as adding the materials for preparing the mixed solution while simultaneously suspending the mixture.
  • a preferred example of the method for producing hollow particles of the present disclosure includes a production method including the following steps.
  • a step of preparing (3) Polymerization step By subjecting the suspension to a polymerization reaction, a precursor composition comprising precursor particles having a hollow portion surrounded by a shell containing a resin and containing a hydrophobic solvent in the hollow portion preparing a product, (4) Solid-liquid separation step A step of solid-liquid separation of the precursor composition to obtain precursor particles containing a hydrophobic solvent in their hollow portions, and (5) Solvent removal step Obtained by the solid-liquid separation step a step of removing the hydrophobic solvent contained in the precursor particles to obtain hollow particles;
  • a hollow particle whose hollow portion is filled with a hydrophobic solvent is sometimes referred to as a "precursor particle", considering it as an intermediate of a hollow particle whose hollow portion is filled with a gas.
  • precursor composition means a composition comprising precursor particles.
  • FIG. 1 is a schematic diagram showing an example of the manufacturing method of the present disclosure.
  • (1) to (5) in FIG. 1 correspond to the above steps (1) to (5).
  • White arrows between each figure indicate the order of each step.
  • FIG. 1 is only a schematic diagram for explanation, and the manufacturing method of the present disclosure is not limited to the one shown in the diagram. Also, the structures, dimensions and shapes of the materials used in the manufacturing methods of the present disclosure are not limited to the structures, dimensions and shapes of the various materials in these figures.
  • (1) of FIG. 1 is a cross-sectional schematic diagram showing one embodiment of the liquid mixture in the liquid mixture preparation step. As shown in this figure, the mixture contains an aqueous medium 1 and a low-polarity material 2 dispersed in the aqueous medium 1 .
  • the low-polarity material 2 means a material that has low polarity and is difficult to mix with the aqueous medium 1 .
  • Low polarity material 2 in the present disclosure includes a polymerizable monomer, a hydrophobic solvent and a polymerization initiator.
  • (2) of FIG. 1 is a cross-sectional schematic diagram showing one embodiment of the suspension in the suspension step.
  • the suspension comprises an aqueous medium 1 and droplets 8 of a monomer composition dispersed in the aqueous medium 1 .
  • the droplet 8 of the monomer composition contains a polymerizable monomer, a hydrophobic solvent and a polymerization initiator, but the distribution within the droplet is non-uniform.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a precursor composition obtained by a polymerization step and containing precursor particles containing a hydrophobic solvent in their hollow portions.
  • the precursor composition includes an aqueous medium 1 and precursor particles 9 dispersed in the aqueous medium 1 and containing a hydrophobic solvent 4a in their hollow portions.
  • the shell 6 forming the outer surface of the precursor particle 9 is formed by polymerization of the polymerizable monomer in the droplet 8 of the monomer composition. Coalescence is included as a resin.
  • (4) of FIG. 1 is a cross-sectional schematic diagram showing one embodiment of the precursor particles after the solid-liquid separation step. (4) of FIG. 1 shows a state where the aqueous medium 1 is removed from the state of (3) of FIG. (5) of FIG. 1 is a schematic cross-sectional view showing one embodiment of the hollow particles after the solvent removal step. (5) of FIG.
  • This step is a step of preparing a mixed solution containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer, and an aqueous medium.
  • the mixed liquid may further contain other materials as long as the effects of the present disclosure are not impaired.
  • Materials for the mixed liquid are (A) polymerizable monomer, (B) hydrophobic solvent, (C) polymerization initiator, (D) dispersion stabilizer, (E) aqueous medium, and (F) other materials in that order. explain.
  • the polymerizable monomer in the mixed liquid contains at least a crosslinkable hydrocarbon monomer, and within a range that does not impair the effects of the present disclosure, a non-crosslinkable hydrocarbon monomer, and , may further contain a polymerizable monomer different from the hydrocarbon monomer.
  • Crosslinkable hydrocarbon monomers examples include aromatic divinyl monomers such as divinylbenzene, divinylbiphenyl and divinylnaphthalene; branched diolefins, and diene monomers such as alicyclic diolefins such as dicyclopentadiene, cyclopentadiene, and ethylidenetetracyclododecene;
  • Other crosslinkable macromers such as polybutadiene, polyisoprene, block copolymers of styrene and butadiene (SBS), and block copolymers of styrene and isoprene (SIS) can also be used.
  • crosslinkable hydrocarbon monomers may be used alone or in combination of two or more.
  • aromatic divinyl monomers are preferable, and divinylbenzene is more preferable, because the polymerization reaction is easily stabilized and hollow particles having excellent dielectric properties, solvent resistance, strength, heat resistance, etc. can be obtained.
  • the content of the crosslinkable hydrocarbon monomer in 100% by mass of the polymerizable monomer contained in the mixed liquid is 70% by mass or more, so that the crosslink density is high solvent resistance It is possible to form a shell having excellent dielectric properties, and to obtain hollow particles having good dielectric properties. Hollow particles having a shell with a high crosslink density also have the advantage of being excellent in strength, being less likely to be crushed, and being less likely to be deformed by heat or the like applied from the outside. Further, when the content of the crosslinkable hydrocarbon monomer is 70% by mass or more, phase separation between the components constituting the shell and the hydrophobic solvent is likely to occur in the droplets of the monomer composition. part is easily formed.
  • the content of the crosslinkable hydrocarbon monomer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • the upper limit of the content of the crosslinkable hydrocarbon monomer is not particularly limited, and may be, for example, 98% by mass or less, or 96% by mass or less.
  • Non-crosslinkable hydrocarbon monomers include aromatic monovinyl monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, p-methylstyrene, ethylvinylbenzene, ethylvinylbiphenyl, and ethylvinylnaphthalene; ethylene, Linear or branched monoolefins such as propylene and butylene; alicyclic monoolefins such as vinylcyclohexane, norbornene, tricyclododecene, and 1,4-methano-1,4,4a,9a-tetrahydrofluorene ; and the like.
  • aromatic monovinyl monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, p-methylstyrene, ethylvinylbenzene, ethylvinylbipheny
  • non-crosslinkable macromers can be used.
  • These non-crosslinkable hydrocarbon monomers may be used alone or in combination of two or more.
  • aromatic monovinyl monomers are preferred, and ethylvinylbenzene is particularly preferred, from the viewpoint of improving the dielectric properties of the hollow particles.
  • the content of the non-crosslinkable hydrocarbon monomer in 100% by mass of the polymerizable monomer contained in the mixed liquid is not particularly limited, but from the viewpoint of suppressing the deterioration of the solvent resistance of the hollow particles, the upper limit is is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and even more preferably 5% by mass or less, and the lower limit is not particularly limited, for example, 2% by mass or more. and may be 4% by mass or more.
  • the content of the hydrocarbon monomer which is the total content of the crosslinkable hydrocarbon monomer and the non-crosslinkable hydrocarbon monomer, is adjusted to the polymerizable amount contained in the mixed liquid.
  • 100% by mass of the monomer it is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and even more preferably 100% by mass.
  • the proportion of polymerizable monomers different from hydrocarbon monomers such as acrylic monomers increases, the obtained hollow particles tend to have higher dielectric constants and dielectric loss tangents. preferably has a high content of hydrocarbon monomers.
  • the polymerizable monomer in the mixed liquid may further contain a polymerizable monomer different from the hydrocarbon monomer as long as the effects of the present disclosure are not impaired.
  • the polymerizable monomer different from the hydrocarbon monomer may be a crosslinkable monomer or a non-crosslinkable monomer.
  • crosslinkable monomers different from hydrocarbon monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, tri Cyclodecane dimethanol di(meth)acrylate, 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaery
  • crosslinkable macromers such as vinyl-modified polyphenylene ether at both ends and polyphenylene ether methacrylic-modified at both ends can also be used.
  • non-crosslinkable monomers different from hydrocarbon monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate.
  • non-crosslinkable acrylic monomers such as (meth)acrylic acid; (meth)acrylamide, N-methylol Acrylamide-based monomers such as (meth)acrylamide and N-butoxymethyl (meth)acrylamide and derivatives thereof; Carboxylic acid vinyl ester monomers such as vinyl acetate; Vinyl halide monomers such as vinyl chloride; vinylidene halide monomer; vinylpyridine monomer;
  • non-crosslinkable macromers such as terminally (meth)acrylic-modified polystyrene and terminally (meth)acrylic-modified polymethyl methacrylate can also be used.
  • the content of the crosslinkable monomer which is the sum of the crosslinkable hydrocarbon monomer and the crosslinkable monomer different from the hydrocarbon monomer, is mixed.
  • 100% by mass of the polymerizable monomer contained in the liquid it is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and 95% by mass or more. is even more preferable.
  • the upper limit of the content of the crosslinkable monomer is not particularly limited, and may be, for example, 98% by mass or less, or 96% by mass or less.
  • the content of the polymerizable monomer in the mixed liquid is not particularly limited, but from the viewpoint of the balance between the porosity of the hollow particles, the particle size and the mechanical strength, the total mass of the components in the mixed liquid excluding the aqueous medium is 100. It is preferably 15 to 50% by mass, more preferably 20 to 40% by mass. Further, from the viewpoint of improving the mechanical strength of the hollow particles, the content of the polymerizable monomer with respect to 100% by mass of the total solid content excluding the hydrophobic solvent among the materials that become the oil phase in the mixed liquid is It is preferably 90% by mass or more, more preferably 95% by mass or more.
  • the solid content is all components except the solvent, and the liquid polymerizable monomer and the like are included in the solid content.
  • hydrophobic solvent used in the production method of the present disclosure is a non-polymerizable and sparingly water-soluble organic solvent. Hydrophobic solvents act as spacer materials that form cavities inside the particles.
  • a suspension is obtained in which droplets of the monomer composition containing the hydrophobic solvent are dispersed in the aqueous medium.
  • the hydrophobic solvent with low polarity tends to gather inside the droplets of the monomer composition.
  • the hydrophobic solvent is distributed inside and the other materials other than the hydrophobic solvent are distributed around the periphery according to their respective polarities. Then, in the polymerization step to be described later, an aqueous dispersion containing hollow particles encapsulating a hydrophobic solvent is obtained. That is, a hollow portion filled with the hydrophobic solvent is formed inside the obtained precursor particles by gathering the hydrophobic solvent inside the particles.
  • the hydrophobic solvent it is preferable to select an organic solvent that has a lower solubility in water at 20°C than the crosslinkable hydrocarbon monomer contained in the mixture.
  • the hydrophobic solvent with the highest solubility is more than the crosslinkable hydrocarbon monomer with the lowest solubility.
  • the organic solvent having a lower solubility in water at 20° C. than the crosslinkable hydrocarbon monomer can be appropriately selected from known organic solvents, and is not particularly limited.
  • a hydrocarbon solvent is preferably used. be able to.
  • Hydrocarbon-based solvents are also preferable in that they have a lower solubility in water at 20° C. than divinylbenzene, which is a crosslinkable hydrocarbon monomer preferably used in the present disclosure.
  • hydrocarbon solvents examples include linear hydrocarbon solvents such as pentane, hexane, heptane, octane, 2-methylbutane and 2-methylpentane; cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and cycloheptane; , aromatic hydrocarbon solvents such as toluene and xylene.
  • linear hydrocarbon solvents such as pentane, hexane, heptane, octane, 2-methylbutane and 2-methylpentane
  • cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and cycloheptane
  • aromatic hydrocarbon solvents such as toluene and xylene.
  • a hydrocarbon-based solvent is preferable, a chain hydrocarbon-based solvent having 5 to 8 carbon atoms is more preferable, and at least one selected from the group consisting of pentane, hexane, heptane and octane is more preferable.
  • a hydrophobic solvent can be used individually or in combination of 2 or more types, respectively.
  • the boiling point of the hydrophobic solvent is preferably 130° C. or lower, more preferably 100° C. or lower, because it is easily removed in the solvent removal step described later.
  • the temperature is preferably 50° C. or higher, more preferably 60° C. or higher, because it is easy to heat.
  • the hydrophobic solvent is a mixed solvent containing a plurality of types of hydrophobic solvents and has a plurality of boiling points
  • the boiling point of the solvent with the highest boiling point among the solvents contained in the mixed solvent is the above upper limit value or less. It is preferable that the boiling point of the solvent with the lowest boiling point among the solvents contained in the mixed solvent is equal to or higher than the above lower limit.
  • the hydrophobic solvent used in the production method of the present disclosure preferably has a dielectric constant of 2.0 or less at 20°C.
  • the relative dielectric constant is one of the indices that indicate the degree of polarity of a compound.
  • the relative dielectric constant of the hydrophobic solvent is sufficiently low as 2.0 or less, it is considered that phase separation proceeds rapidly in the polymerizable monomer droplets, and voids are likely to be formed.
  • Examples of hydrophobic solvents having a dielectric constant of 2.0 or less at 20° C. are as follows. The value in parenthesis is the relative permittivity value. Pentane (1.8), Hexane (1.9), Heptane (1.9), Octane (1.9).
  • the porosity of the hollow particles can be adjusted by changing the amount of the hydrophobic solvent in the mixture.
  • the polymerization reaction proceeds in a state where the oil droplets containing the crosslinkable monomer and the like enclose the hydrophobic solvent. tends to be higher.
  • the content of the hydrophobic solvent in the mixed liquid is 50 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, so that the particle diameter of the hollow particles can be easily controlled. It is preferable because it is easy to increase the porosity while maintaining the strength of the hollow particles, and it is easy to reduce the amount of residual hydrophobic solvent in the particles.
  • the content of the hydrophobic solvent in the mixed liquid is more preferably 60 parts by mass or more and 400 parts by mass or less, and even more preferably 70 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. is.
  • the mixed liquid preferably contains an oil-soluble polymerization initiator as a polymerization initiator.
  • an emulsion polymerization method using a water-soluble polymerization initiator and a suspension polymerization method using an oil-soluble polymerization initiator.
  • Suspension polymerization can be carried out by using an agent.
  • the oil-soluble polymerization initiator is not particularly limited as long as it is lipophilic and has a solubility in water of 0.2% by mass or less.
  • organic peroxides such as noate, t-butylperoxydiethylacetate, t-butylperoxypivalate; 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, 2,2 azo compounds such as '-azobis(4-methoxy-2,4-dimethylvaleronitrile);
  • organic peroxide it is preferable to use an organic peroxide as the polymerization initiator. Since the organic peroxide easily promotes the polymerization reaction, it can improve the solvent resistance of the hollow particles, and since decomposition products are less likely to remain after the polymerization reaction, the deterioration of the dielectric properties of the hollow particles is suppressed.
  • Decomposition products of the polymerization initiator remaining in the shell increase the molecular motion of the shell. Therefore, if a large amount of the decomposition products remains, the dielectric loss tangent of the hollow particles may increase. Since decomposition products of organic peroxides are easily removed and hardly remain, the use of organic peroxides suppresses an increase in molecular motion of the shell, and as a result, an increase in dielectric loss tangent can be suppressed.
  • the content of the oil-soluble polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 100 parts by mass of the polymerizable monomer in the mixed liquid. is 1 to 5 parts by mass.
  • the content of the oil-soluble polymerization initiator is at least the above lower limit, the polymerization reaction can proceed sufficiently, and when it is at most the above upper limit, the oil-soluble polymerization initiator is less likely to remain after completion of the polymerization reaction. , there is little possibility that an unexpected side reaction will proceed.
  • the dispersion stabilizer is an agent that disperses droplets of the monomer composition in the aqueous medium in the suspension step.
  • examples of dispersion stabilizers include inorganic dispersion stabilizers, organic or inorganic water-soluble polymer stabilizers, and surfactants.
  • it is easy to control the particle size of the droplets in the suspension the particle size distribution of the obtained hollow particles can be narrowed, and the shell is suppressed from becoming too thin, and the strength of the hollow particles is improved. From the viewpoint of suppressing the decrease, it is preferable to use an inorganic dispersion stabilizer as the dispersion stabilizer.
  • inorganic dispersion stabilizers examples include sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate and magnesium carbonate; phosphates such as calcium phosphate; metals such as aluminum oxide and titanium oxide. oxides; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide and ferric hydroxide; and inorganic compounds such as silicon dioxide. These inorganic dispersion stabilizers can be used singly or in combination of two or more.
  • the poorly water-soluble inorganic dispersion stabilizer is preferably an inorganic compound having a solubility of 0.5 g or less in 100 g of water.
  • the sparingly water-soluble metal salt is preferably an inorganic metal salt having a solubility of 0.5 g or less in 100 g of water.
  • a poorly water-soluble inorganic dispersion stabilizer is dispersed in an aqueous medium in the form of colloidal particles, that is, a colloidal dispersion containing the poorly water-soluble inorganic dispersion stabilizer colloidal particles
  • a colloidal dispersion containing the poorly water-soluble inorganic dispersion stabilizer colloidal particles It is preferable to use in the state of
  • the sparingly water-soluble inorganic dispersion stabilizer in the form of a colloidal dispersion containing colloidal particles of the sparingly water-soluble inorganic dispersion stabilizer the particle size distribution of droplets of the monomer composition can be narrowed. In addition to this, washing can easily reduce the residual amount of the inorganic dispersion stabilizer in the obtained hollow particles.
  • the colloidal dispersion containing the sparingly water-soluble inorganic dispersion stabilizer colloidal particles includes, for example, at least one selected from alkali metal hydroxides and alkaline earth metal hydroxides, and a water-soluble polyvalent metal salt (hydroxide excluding alkaline earth metal salts) in an aqueous medium.
  • Alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.
  • Alkaline earth metal hydroxides include barium hydroxide and calcium hydroxide.
  • the water-soluble polyvalent metal salt may be any water-soluble polyvalent metal salt other than the compounds corresponding to the alkaline earth metal hydroxides. Examples include magnesium chloride, magnesium phosphate, magnesium sulfate, and the like.
  • magnesium metal salts such as calcium chloride, calcium nitrate, calcium acetate and calcium sulfate; aluminum metal salts such as aluminum chloride and aluminum sulfate; barium salts such as barium chloride, barium nitrate and barium acetate; zinc chloride and zinc nitrate , zinc salts such as zinc acetate; Among these, magnesium metal salt, calcium metal salt, and aluminum metal salt are preferred, magnesium metal salt is more preferred, and magnesium chloride is particularly preferred.
  • the water-soluble polyvalent metal salts can be used either singly or in combination of two or more.
  • the method of reacting at least one selected from the alkali metal hydroxides and alkaline earth metal hydroxides described above with the water-soluble polyvalent metal salt described above in an aqueous medium is not particularly limited.
  • a method of mixing at least one aqueous solution selected from alkali metal salts and alkaline earth metal hydroxides with an aqueous solution of a water-soluble polyvalent metal salt can be used.
  • hydroxide is added to the aqueous solution.
  • a method of mixing by gradually adding at least one aqueous solution selected from alkali metal salts and alkaline earth metal hydroxides is preferred.
  • Colloidal silica can also be used as a colloidal dispersion containing colloidal particles of a poorly water-soluble inorganic dispersion stabilizer.
  • Organic water-soluble polymer stabilizers include, for example, polyvinyl alcohol, polycarboxylic acids (polyacrylic acid, etc.), celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, etc.), polyvinylpyrrolidone, polyacrylimide, polyethylene oxide.
  • a surfactant is a compound having both a hydrophilic group and a hydrophobic group in one molecule, and includes known anionic surfactants, cationic surfactants, amphoteric surfactants and other ionic surfactants, and nonionic surfactants. activators and the like.
  • the content of the dispersion stabilizer is not particularly limited, but is preferably 0.5 to 15 parts by mass, more preferably 1 part by mass, with respect to 100 parts by mass of the total mass of the polymerizable monomer and the hydrophobic solvent. ⁇ 10 parts by mass.
  • the content of the dispersion stabilizer is at least the above lower limit, the droplets of the monomer composition can be sufficiently dispersed so as not to coalesce in the suspension.
  • the content of the dispersion stabilizer is equal to or less than the above upper limit, it is possible to prevent the viscosity of the suspension from increasing during granulation and avoid the problem of the suspension clogging the granulator. can.
  • the content of the dispersion stabilizer is usually 2 parts by mass or more and 15 parts by mass or less, preferably 3 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the aqueous medium.
  • the aqueous medium means a medium selected from the group consisting of water, hydrophilic solvents, and mixtures of water and hydrophilic solvents.
  • water it is preferable to use water as the aqueous medium in order to obtain the effect of promoting the polymerization reaction by the reaction-promoting additive liquid.
  • a mixture of water and a hydrophilic solvent it is important that the overall polarity of the mixture is not too low from the viewpoint of forming droplets of the monomer composition.
  • the mass ratio of water and hydrophilic solvent may be 99:1 to 50:50.
  • the hydrophilic solvent in the present disclosure is not particularly limited as long as it mixes well with water and does not cause phase separation.
  • hydrophilic solvents include alcohols such as methanol and ethanol; tetrahydrofuran (THF); dimethylsulfoxide (DMSO) and the like.
  • the hydrophilic solvent contained in the aqueous medium is preferably different from the reaction-accelerating additive liquid in order to sufficiently obtain the effect of accelerating the polymerization reaction by the reaction-accelerating additive liquid.
  • the mixed liquid may further contain other materials different from the materials (A) to (E) described above within a range that does not impair the effects of the present disclosure.
  • the liquid mixture may contain polar components as other materials. By including a polar component in the mixed liquid, the thickness of the shell of the obtained hollow particles can be appropriately adjusted.
  • polar component for example, an organic acid or a metal salt thereof can be preferably used.
  • organic acids include rosin acid and higher fatty acids.
  • Higher fatty acids include, for example, higher fatty acids having 10 to 25 carbon atoms that do not contain carbon atoms in the carboxyl group.
  • metals used in metal salts of organic acids include alkali metals such as Li, Na and K, and alkaline earth metals such as Mg and Ca. and K are more preferred.
  • the total content of the organic acid or its metal salt is preferably 0 with respect to a total of 100 parts by mass of the polymerizable monomer and the hydrophobic solvent in the mixed liquid. 001 parts by mass or more, more preferably 0.0015 parts by mass or more, and preferably 0.1 parts by mass or less, more preferably 0.05 parts by mass or less.
  • the content is at least the lower limit, it is easy to control the particle diameter and shell thickness of the hollow particles, and in particular, the volume average particle diameter of the hollow particles tends to fall within the preferred ranges described below.
  • the content is equal to or less than the upper limit, it is possible to suppress a decrease in the content of the polymerizable monomer, thereby suppressing a decrease in shell strength and solvent resistance.
  • a liquid mixture is obtained by mixing each of the above-mentioned materials and other materials as necessary and stirring them appropriately.
  • the dispersed state of these materials in the mixed liquid can be observed with the naked eye depending on the type of material.
  • the mixed solution may be obtained by simply mixing each of the above materials and, if necessary, other materials, and stirring them as appropriate.
  • a colloidal dispersion obtained by dispersing a sparingly water-soluble inorganic dispersion stabilizer in the form of colloidal particles in an aqueous medium can be preferably used as the aqueous phase.
  • Suspension step is a step of preparing a suspension in which droplets of a monomer composition containing a hydrophobic solvent are dispersed in an aqueous medium by suspending the mixed solution described above.
  • a suspending method for forming droplets of the monomer composition is not particularly limited, and a known suspending method can be employed.
  • Dispersers used for preparing the suspension include, for example, a horizontal multi-stage such as Milder (: trade name) manufactured by Pacific Machinery Co., Ltd., Cavitron (: trade name) manufactured by Eurotech Co., Ltd.
  • in-line disperser such as in-line disperser, in-line disperser manufactured by IKA (for example, DISPAX-REACTOR (registered trademark) DRS (trade name), etc.); emulsification dispersion such as homomixer MARK II series manufactured by Primix Co., Ltd.
  • a commercially available stirring device such as a mixer can be used.
  • droplets of the monomer composition containing the lipophilic material and having a particle size of about 1 to 10 ⁇ m are uniformly dispersed in the aqueous medium.
  • Such droplets of the monomer composition are difficult to observe with the naked eye, and can be observed with a known observation instrument such as an optical microscope.
  • the hydrophobic solvent with low polarity tends to collect inside the droplets.
  • the resulting droplet has the hydrophobic solvent distributed inside and the material other than the hydrophobic solvent distributed around the periphery.
  • the droplets of the monomer composition dispersed in the aqueous medium are formed by surrounding the oil-soluble monomer composition with the dispersion stabilizer.
  • the droplets of the monomer composition contain an oil-soluble polymerization initiator, a polymerizable monomer and a hydrophobic solvent.
  • the droplets of the monomer composition are oil droplets, and the oil-soluble polymerization initiator generates polymerization initiation radicals inside the oil droplets. Therefore, precursor particles having a desired particle size can be produced without excessively growing fine oil droplets.
  • an oil-soluble polymerization initiator there is no opportunity for the polymerization initiator to come into contact with the polymerizable monomer dispersed in the aqueous medium. Therefore, by using an oil-soluble polymerization initiator, it is possible to suppress the by-production of excessive resin particles such as solid particles having a relatively small particle size in addition to the target resin particles having hollow portions.
  • the polymerization reaction is further carried out after adding the reaction accelerating additive liquid during the polymerization reaction.
  • the reaction-promoting additive liquid a low-molecular-weight compound having a solubility in water at 20° C. higher than that of the hydrophobic solvent and of 0.5 g/L to 1000 g/L is used.
  • the hydrophobic solvent contains a combination of two or more types, it is preferable to select the additive liquid for reaction acceleration so that the solubility is even greater than the hydrophobic solvent with the highest solubility.
  • the low-molecular-weight compound used as the reaction-promoting additive liquid is liquid at 0 to 30° C., and the upper limit of the molecular weight is preferably 200 or less, more preferably 100 or less, and the lower limit of the molecular weight is not particularly limited. Usually 50 or more.
  • the low-molecular-weight compound may be either a non-reactive low-molecular-weight compound or a reactive low-molecular-weight compound. , non-reactive low-molecular-weight compounds are preferred.
  • “reactive” means reacting with the polymerizable monomer in the mixed liquid
  • non-reactive means not reacting with the polymerizable monomer in the mixed liquid. In other words, reactivity means chemically reacting with the polymerizable monomer in the mixture to form a covalent bond.
  • the solubility of the non-reactive low-molecular-weight compound used as the additive liquid for accelerating the reaction in water at 20° C. should be greater than that of the hydrophobic solvent in the mixed liquid and 0.5 g/L to 1000 g/L. From the viewpoint of improving the solvent resistance of the particles, it is preferably 10 g/L or more, more preferably 30 g/L or more, still more preferably 40 g/L or more, still more preferably 50 g/L or more, and preferably 700 g /L or less, more preferably 500 g/L or less, still more preferably 300 g/L or less.
  • an organic solvent is preferably used because it easily enters the shell and facilitates the crosslinking reaction.
  • the organic solvent one that satisfies the above solubility can be appropriately selected from known organic solvents and used, and is not particularly limited.
  • the organic solvent used as the reaction accelerating additive include, for example, ketone solvents such as methyl ethyl ketone, acetone and 3-pentanone; ester solvents such as methyl acetate and ethyl acetate; ether solvents such as dimethyl ether and diethyl ether.
  • Solvent Alcohol-based solvents such as propanol, isopropanol and butanol can be used. These organic solvents can be used alone or in combination of two or more.
  • the organic solvent is preferably at least one selected from ketone-based solvents and ester-based solvents from the viewpoint of improving the solvent resistance of the hollow particles, and the group consisting of methyl ethyl ketone, 3-pentanone, methyl acetate and ethyl acetate. At least one selected from is more preferable.
  • the solubility in water at 20°C of the reactive low-molecular-weight compound used as the additive liquid for accelerating the reaction should be higher than that of the hydrophobic solvent in the mixed liquid and 0.5 g/L to 1000 g/L. preferably 100 g/L or less, more preferably 80 g/L or less, even more preferably 70 g/L or less, even more preferably 30 g/L or less, and particularly preferably 20 g/L or less is.
  • the lower limit of the solubility of the low-molecular-weight compound is not particularly limited, but is preferably 1.0 g/L or more, more preferably 2.0 g/L or more, from the viewpoint of improving the solvent resistance of the hollow particles. .
  • Polymerizable monomers containing heteroatoms are preferably used as the reactive low-molecular-weight compound used as the reaction-promoting additive liquid because they easily enter the shell and facilitate the cross-linking reaction.
  • the polymerizable monomer used as the reaction-promoting additive liquid may be a crosslinkable monomer or a non-crosslinkable monomer.
  • a crosslinkable monomer is preferable because it can suppress deterioration of the solvent resistance of the hollow particles.
  • the heteroatom-containing polymerizable monomer for example, a (meth)acrylic monomer having a (meth)acryloyl group as a polymerizable functional group and a polar group-containing monomer can be preferably used.
  • Examples of the (meth)acrylic monomer include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 5 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. , (meth)acrylamide, N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide and other (meth)acrylamides and their derivatives, (meth)acrylic acid nitrile, ethylene glycol di(meth)acrylate, diethylene glycol Di(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate and the like can be mentioned.
  • (meth)acrylic acid alkyl esters having an alkyl group having 1 to 5 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.
  • Preferred examples of the polar group-containing monomer include polymerizable monomers containing a polar group selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, an amino group, a polyoxyethylene group and an epoxy group. .
  • carboxyl group-containing monomers such as ethylenically unsaturated carboxylic acid monomers such as (meth)acrylic acid, crotonic acid, cinnamic acid, itaconic acid, fumaric acid, maleic acid and butentricarboxylic acid ; hydroxyl group-containing units such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate; monomer; sulfonic acid group-containing monomer such as styrenesulfonic acid; amino group-containing monomer such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate; methoxy polyoxyethylene group-containing monomers such as polyethylene glycol (meth)
  • heteroatom-containing polymerizable monomers may be used alone or in combination of two or more.
  • the polymerizable monomer containing the hetero atom among others, it is easy to promote the cross-linking reaction of the shell, and by suppressing the decrease in the cross-linking density of the shell due to the introduction of the polymerizable monomer, the hollow particle can be formed.
  • At least one selected from (meth)acrylic monomers having two or more polymerizable functional groups and polar group-containing monomers having two or more polymerizable functional groups from the viewpoint of suppressing deterioration of solvent resistance. is preferred, a (meth)acrylic monomer having two or more polymerizable functional groups is more preferred, and allyl (meth)acrylate is particularly preferred.
  • (meth)acrylic acid alkyl esters having an alkyl group having 1 to 5 carbon atoms, and the polar group ( A meth)acrylic monomer is preferable, and a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms and a (meth)acrylic monomer containing a hydroxyl group or an amino group are more preferable.
  • Methyl (meth)acrylate is particularly preferred as the (meth)acrylic acid alkyl ester having an alkyl group of 1 to 3 carbon atoms.
  • t-butylaminoethyl (meth)acrylate is particularly preferred.
  • reaction-promoting additive liquid a mixture of the non-reactive low-molecular-weight compound and the reactive low-molecular-weight compound may be used, or either the non-reactive low-molecular-weight compound or the reactive low-molecular-weight compound may be used. may be used only.
  • reaction-promoting additive liquids include ketone-based solvents, ester-based solvents, (meth)acrylic monomers having two or more polymerizable functional groups, and (meth)acryls having an alkyl group having 1 to 3 carbon atoms.
  • At least one selected from the group consisting of acid alkyl esters and (meth)acrylic monomers containing a hydroxyl group or an amino group can be preferably used, and methyl ethyl ketone, 3-pentanone, methyl acetate, ethyl acetate, allyl
  • At least one selected from the group consisting of (meth)acrylate, methyl (meth)acrylate and t-butylaminoethyl (meth)acrylate can be used more preferably.
  • the amount of the non-reactive low-molecular-weight compound added is 100 parts by mass of the total weight of the polymerizable monomer and the hydrophobic solvent contained in the mixed liquid.
  • the lower limit is preferably 1 part by mass or more, more preferably 2 parts by mass or more
  • the upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
  • the amount of the reactive low-molecular-weight compound added is The lower limit is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and the upper limit is preferably 3 parts by mass or less.
  • the amount of the reactive low-molecular-weight compound added as the reaction-promoting additive liquid is at least the above lower limit, the effect of promoting the cross-linking reaction of the shell increases, and the solvent resistance of the hollow particles can be improved.
  • the amount of the reactive low-molecular-weight compound added as the reaction-promoting additive liquid is equal to or less than the above upper limit, deterioration of the dielectric properties of the hollow particles can be suppressed.
  • the reactive low-molecular-weight compound usually contains a heteroatom and reacts with the polymerizable monomer in the shell to become a constituent component of the shell. , the deterioration of the dielectric properties can be suppressed by suppressing the increase in the amount of heteroatoms in the shell.
  • the addition amount of the reactive low-molecular-weight compound is set to the above upper limit or less, thereby suppressing a decrease in the cross-linking density of the shell and improving the solvent resistance. It is also preferable from the point of being able to suppress the deterioration of.
  • the additive liquid for accelerating the reaction is added. is preferable from the viewpoint of promoting the cross-linking reaction of the shell and improving the solvent resistance of the hollow particles.
  • the polymerization conversion rate refers to the mass of the solid content of the particles generated at the time of adding the reaction-accelerating additive liquid, and the unreacted polymerizable monomer at the time of adding the reaction-accelerating additive liquid. from the mass of the following formula (B).
  • the mass of the unreacted polymerizable monomer can be measured using gas chromatography (GC).
  • the precursor particles are formed by polymerization of the polymerizable monomer contained in the droplets of the monomer composition.
  • the provided shell contains the polymer of the polymerizable monomer as a resin.
  • a reactive low-molecular-weight compound is added as the reaction-promoting additive liquid, the precursor particles are formed by polymerization of the polymerizable monomer and the reactive low-molecular-weight compound contained in the droplets of the monomer composition.
  • the shell formed and provided by the precursor particles contains the polymer of the polymerizable monomer and the reactive low-molecular-weight compound as a resin.
  • the content of the hydrocarbon monomer in the total amount of 100% by mass of the polymerizable monomer forming the shell and the reactive low-molecular-weight compound is preferably It is 90% by mass or more, more preferably 91% by mass or more, and still more preferably 94% by mass or more.
  • the polymerization system is not particularly limited, and for example, a batch system (batch system), a semi-continuous system, a continuous system, or the like can be employed.
  • the polymerization temperature is preferably 40-90°C, more preferably 50-80°C.
  • the rate of temperature rise when raising the temperature to the polymerization temperature is preferably 10 to 60°C/h, more preferably 15 to 55°C/h.
  • the reaction time for polymerization is preferably 1 to 48 hours, more preferably 4 to 36 hours.
  • the timing of adding the reaction-accelerating additive solution is preferably adjusted appropriately so that the polymerization conversion rate of the polymerizable monomers in the mixed solution is within the preferred range described above.
  • the polymerization reaction may be carried out for about 25 hours.
  • the shell portion of the droplet of the monomer composition containing the hydrophobic solvent inside is polymerized. A hollow is formed.
  • This step is a step of obtaining a solid content containing precursor particles by performing solid-liquid separation on the precursor composition containing precursor particles obtained by the polymerization step described above.
  • a method for solid-liquid separation of the precursor composition is not particularly limited, and a known method can be used.
  • the solid-liquid separation method include centrifugation, filtration, static separation, etc. Among them, centrifugation or filtration can be employed. may be adopted.
  • an optional step such as a pre-drying step may be carried out before carrying out the below-described solvent removal step.
  • the pre-drying step include a step of pre-drying the solid content obtained after the solid-liquid separation step using a drying device such as a dryer or a drying device such as a hand dryer.
  • Solvent removal step is a step of removing the hydrophobic solvent included in the precursor particles obtained by the solid-liquid separation step. For example, by removing the hydrophobic solvent contained in the precursor particles in air, the hydrophobic solvent inside the precursor particles is replaced with air, and hollow particles filled with gas are obtained.
  • in air in this step means an environment where there is no liquid component outside the precursor particles, and a very small amount of hydrophobic solvent outside the precursor particles that does not affect the removal of the solvent. means an environment where there is only a liquid fraction of “In air” can be rephrased as a state in which the precursor particles are not present in the slurry, and can be rephrased as a state in which the precursor particles are present in the dry powder. That is, in this step, it is important to remove the hydrophobic solvent in an environment where the precursor particles are in direct contact with the external gas.
  • a method for removing the hydrophobic solvent in the precursor particles in air is not particularly limited, and a known method can be adopted. Examples of the method include a vacuum drying method, a heat drying method, a flash drying method, or a combination of these methods.
  • the heating temperature must be higher than the boiling point of the hydrophobic solvent and lower than the maximum temperature at which the shell structure of the precursor particles does not collapse. Therefore, depending on the composition of the shell in the precursor particles and the type of hydrophobic solvent, the heating temperature may be, for example, 50 to 200°C, 70 to 200°C, or 100 to 200°C. Due to the drying operation in air, the hydrophobic solvent inside the precursor particles is replaced by the external gas, resulting in hollow particles in which the hollow portion is filled with gas.
  • the drying atmosphere is not particularly limited, and can be appropriately selected depending on the use of the hollow particles. Air, oxygen, nitrogen, argon, etc. can be considered as the dry atmosphere, for example. Further, hollow particles whose insides are temporarily vacuumed can also be obtained by once filling the insides of the hollow particles with gas and then drying them under reduced pressure.
  • the hydrophobic solvent may be removed in the slurry containing the precursor particles and the aqueous medium without solid-liquid separation of the slurry-like precursor composition obtained in the polymerization step.
  • the hydrophobic solvent contained in the precursor particles is removed by bubbling an inert gas through the precursor composition at a temperature equal to or higher than the boiling point of the hydrophobic solvent minus 35°C. be able to.
  • the hydrophobic solvent is a mixed solvent containing a plurality of types of hydrophobic solvents and has a plurality of boiling points
  • the boiling point of the hydrophobic solvent in the solvent removal step is the boiling point of the solvent contained in the mixed solvent.
  • the boiling point is the boiling point of the solvent with the highest boiling point, that is, the highest boiling point among a plurality of boiling points.
  • the temperature at which the inert gas is bubbled through the precursor composition is preferably at least the temperature obtained by subtracting 30°C from the boiling point of the hydrophobic solvent in order to reduce the residual amount of the hydrophobic solvent in the hollow particles.
  • the temperature is preferably equal to or higher than the temperature minus 20°C.
  • the temperature during bubbling is usually a temperature equal to or higher than the polymerization temperature in the polymerization step. Although not particularly limited, the temperature during bubbling may be 50° C. or higher and 100° C. or lower.
  • the bubbling inert gas is not particularly limited, but examples thereof include nitrogen and argon.
  • the bubbling conditions are appropriately adjusted according to the type and amount of the hydrophobic solvent so that the hydrophobic solvent contained in the precursor particles can be removed, and are not particularly limited. /min, and may be bubbled for 1 to 10 hours.
  • a water-based slurry in which the inert gas is included in the precursor particles is obtained.
  • the hollow particles obtained by solid-liquid separation of this slurry are dried to remove the aqueous medium remaining in the hollow particles, thereby obtaining the hollow particles in which the hollow portion is filled with gas.
  • a slurry containing an aqueous medium after removing the hydrophobic solvent contained in the precursor particles, solid-liquid separation is performed, and the aqueous medium in the precursor particles is removed in the air, so that the hollow part is gas.
  • the former method has the advantage that the hollow particles are less likely to be crushed in the process of removing the hydrophobic solvent, and the latter method involves bubbling with an inert gas. There is an advantage that the remaining hydrophobic solvent is reduced.
  • the hydrophobic solvent contained in the precursor particles is removed without solid-liquid separation of the slurry-like precursor composition obtained in the polymerization step.
  • a predetermined pressure high pressure, normal pressure or reduced pressure
  • a method of evaporating the hydrophobic solvent contained in the precursor particles from the precursor composition under a predetermined pressure (under high pressure, a method of introducing an inert gas such as nitrogen, argon, or helium or water vapor into the precursor composition under normal pressure or reduced pressure to evaporate it.
  • (6-a) washing step and (6-b) particle interior replacement step may be added.
  • (6-a) Washing step an acid or alkali is added to remove the dispersion stabilizer remaining in the precursor composition containing the precursor particles before the solvent removal step. It is a process to do.
  • the dispersion stabilizer used is an acid-soluble inorganic dispersion stabilizer, it is preferable to wash by adding an acid to the precursor composition containing the precursor particles.
  • is an inorganic compound that is soluble in alkali it is preferable to add an alkali to the precursor composition containing the precursor particles for washing.
  • the acid is added to the precursor composition containing the precursor particles, and the pH is adjusted to preferably 6.5 or less, more preferably 6.5. It is preferable to adjust as follows.
  • inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as formic acid and acetic acid can be used. , in particular sulfuric acid, is preferred.
  • the particle interior replacement step is a step of replacing the gas or liquid inside the hollow particles with another gas or liquid.
  • the environment inside the hollow particles can be changed, molecules can be selectively confined inside the hollow particles, and the chemical structure inside the hollow particles can be modified according to the application.
  • the hollow particle of the present disclosure is a hollow particle that includes a resin-containing shell and a hollow portion surrounded by the shell, and has a porosity of 50% or more,
  • the shell contains, as the resin, a polymer containing 70% by mass or more of a crosslinkable hydrocarbon monomer unit, In an environment of 25 ° C., 0.1 mg of hollow particles are added to 4 mL of toluene, shaken for 10 minutes at a shaking speed of 100 rpm, and then left to stand for 48 hours. Less than 5% by weight of particles.
  • the hollow particles of the present disclosure have less than 5% by mass of hollow particles precipitated in toluene in the above immersion test, and therefore have excellent solvent resistance.
  • the hollow particles that precipitate in toluene in the immersion test should be less than 5% by mass, preferably less than 3% by mass, and more preferably less than 1% by mass.
  • the hollow particles of the present disclosure are particles comprising a resin-containing shell (outer shell) and a hollow portion surrounded by the shell.
  • the hollow portion is a hollow space clearly distinguished from the shell of the hollow particle formed by resin material.
  • the shell of the hollow particle may have a porous structure, in which case the hollow portion has a size that can be clearly distinguished from a large number of minute spaces uniformly distributed within the porous structure. have.
  • Hollow particles of the present disclosure preferably have a solid shell from the standpoint of dielectric properties and solvent resistance.
  • the hollow portion of the hollow particles can be confirmed, for example, by SEM observation of the cross section of the particles or by TEM observation of the particles as they are.
  • the hollow particles of the present disclosure are preferably filled with a gas such as air in order to exhibit excellent dielectric properties.
  • Hollow particles obtained using hydrocarbon-based resins such as styrene-based resins have low dielectric constants and dielectric loss tangents of the resins themselves that make up the shell. Expected as an additive.
  • hydrocarbon-based resins such as styrene-based resins
  • the effect of lowering the dielectric constant and the dielectric loss tangent is inadequate.
  • the organic solvent in the resin composition permeates into the hollow particles, and the organic solvent remains in the hollow particles even in the resin molding, reducing the proportion of gas in the hollow portions.
  • the shell has a resin composition with a low dielectric constant and dielectric loss tangent, and has excellent solvent resistance. , the dielectric constant and dielectric loss tangent of the resin molding can be sufficiently lowered.
  • the shell contains a polymer containing 70% by mass or more of structural units derived from a crosslinkable hydrocarbon monomer such as divinylbenzene, and the proportion of hydrocarbon in the shell is high. Therefore, it has a resin composition with a low relative dielectric constant and a low dielectric loss tangent compared to hollow particles or the like having an acrylic resin as the main component of the shell.
  • the shell of the hollow particles of the present disclosure contains a large number of crosslinkable monomer units, the covalent bond network is densely spread. It is presumed that the shell has a structure with a high cross-linking density that makes it difficult for toluene to permeate, resulting in excellent solvent resistance.
  • the hollow particles of the present disclosure are excellent in dielectric properties and solvent resistance, when a resin molding is produced by adding the hollow particles of the present disclosure to a resin composition containing an organic solvent, the hollow particles In addition to its excellent dielectric properties, the organic solvent in the resin composition does not easily penetrate into the hollow particles, and the proportion of the gas in the hollow particles is maintained even in the resin molded body. It is excellent in the effect of lowering the dielectric constant and the dielectric loss tangent.
  • hollow particles of the present disclosure preferably have 5 or less hollow particles out of 100 hollow particles that have continuous pores or shell defects in SEM observation.
  • hollow particles include those in which the shell does not have a communicating hole through which the hollow portion and the outer space of the particle communicate, and those in which the shell has one or two or more communicating holes, and the hollow portion communicates with the outside of the particle through the communicating hole.
  • the diameter of the communicating pores is usually about 10 to 500 nm.
  • the communicating pores may impart beneficial functions to the hollow particles, they also reduce the strength of the hollow particles and make them susceptible to crushing because they are portions where the shell is missing. Hollow particles may also have crack-like shell defects that are extremely large relative to the size of the particles.
  • a crack having a length of 1 ⁇ m or more generally significantly deteriorates the strength of the hollow particle and is recognized as a shell defect.
  • the number of hollow particles having continuous pores or shell defects is 5 or less out of 100 hollow particles. be able to.
  • the content of the crosslinkable hydrocarbon monomer unit in the polymer contained in the shell may be 70% by mass or more, but the dielectric properties and solvent resistance of the hollow particles are improved. from the point of view that the content is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • the upper limit of the content of the crosslinkable hydrocarbon monomer units is not particularly limited, and may be, for example, 98% by mass or less, or 96% by mass or less.
  • the content of the hydrocarbon monomer unit in the polymer contained in the shell is preferably 90% by mass or more, more preferably It is 91% by mass or more, more preferably 94% by mass or more.
  • the upper limit of the content of hydrocarbon monomer units is not particularly limited, and may be, for example, 98% by mass or less, or 96% by mass or less.
  • the content of the crosslinkable monomer unit in the polymer contained in the shell is preferably 70% by mass or more, more preferably 70% by mass or more, from the viewpoint of improving the solvent resistance of the hollow particles. is 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
  • the upper limit of the content of the crosslinkable monomer unit is not particularly limited, and may be, for example, 98% by mass or less, or 96% by mass or less.
  • the hollow particles of the present disclosure preferably have a dielectric constant of 1.50 or less, more preferably 1.45 or less, and even more preferably 1.40 or less at a frequency of 1 GHz.
  • the lower limit of the dielectric constant at a frequency of 1 GHz of the hollow particles of the present disclosure is not particularly limited, but is usually 1.00 or more.
  • the hollow particles of the present disclosure preferably have a dielectric loss tangent at a frequency of 1 GHz of 0.0010 (1.0 ⁇ 10 ⁇ 3 ) or less, more preferably 9.5 ⁇ 10 ⁇ 4 or less, and even more preferably 9.0. ⁇ 10 ⁇ 4 or less, more preferably 8.5 ⁇ 10 ⁇ 4 or less.
  • the lower limit of the dielectric loss tangent at a frequency of 1 GHz of the hollow particles of the present disclosure is not particularly limited, and may be, for example, 1.0 ⁇ 10 ⁇ 5 or more.
  • the dielectric constant and dielectric loss tangent of the hollow particles are measured using a perturbation-type measuring device at a measurement frequency of 1 GHz.
  • the hollow particles of the present disclosure have a porosity of 50% or more, preferably 60% or more, more preferably 65% or more, and even more preferably 70% or more.
  • the porosity is equal to or higher than the above lower limit, the hollow particles are excellent in dielectric properties, lightness, heat insulation, and the like.
  • the upper limit of the porosity of the hollow particles is not particularly limited, but it is preferably 90% or less from the viewpoint of suppressing a decrease in the strength of the hollow particles, making them difficult to crush, and suppressing a decrease in solvent resistance. It is more preferably 85% or less, still more preferably 80% or less, and even more preferably 75% or less.
  • the porosity of the hollow particles is calculated from the apparent density D1 and the true density D0 of the hollow particles.
  • the method for measuring the apparent density D1 of hollow particles is as follows. First, a measuring flask with a volume of 100 cm 3 is filled with about 30 cm 3 of hollow particles, and the mass of the filled hollow particles is accurately weighed. The volumetric flask filled with hollow particles is then filled precisely to the mark with isopropanol, taking care not to introduce air bubbles. Accurately weigh the mass of isopropanol added to the volumetric flask, and calculate the apparent density D 1 (g/cm 3 ) of the hollow particles based on the following formula (I).
  • Apparent density D 1 [mass of hollow particles]/(100-[mass of isopropanol]/[specific gravity of isopropanol at measurement temperature])
  • the apparent density D1 corresponds to the specific gravity of the entire hollow particle when the hollow portion is regarded as part of the hollow particle.
  • the method for measuring the true density D0 of the hollow particles is as follows. After pre-pulverizing the hollow particles, about 10 g of pulverized pieces of the hollow particles are filled into a volumetric flask having a capacity of 100 cm 3 , and the mass of the filled pulverized pieces is accurately weighed. After that, isopropanol is added to the volumetric flask in the same manner as the above apparent density measurement, the mass of isopropanol is accurately weighed, and the true density D 0 (g/cm 3 ) of the hollow particles is calculated based on the following formula (II). do.
  • True density D 0 [mass of pulverized pieces of hollow particles]/(100-[mass of isopropanol]/[specific gravity of isopropanol at measurement temperature])
  • the true density D0 corresponds to the specific gravity of only the shell portion of the hollow particles. As is clear from the above measurement method, the hollow portion is not considered part of the hollow particle when calculating the true density D0 .
  • the porosity (%) of the hollow particles is calculated by the following formula (III) from the apparent density D1 and the true density D0 of the hollow particles.
  • Formula (III) Porosity (%) 100 - (apparent density D 1 / true density D 0 ) x 100
  • the lower limit of the volume average particle diameter is preferably 1.0 ⁇ m or more, more preferably 1.5 ⁇ m or more, and even more preferably 2.0 ⁇ m or more.
  • the upper limit of the volume average particle diameter of the hollow particles is preferably 10.0 ⁇ m or less, more preferably 8.0 ⁇ m or less, and even more preferably 6.0 ⁇ m or less.
  • the volume average particle diameter of the hollow particles is equal to or less than the above upper limit, variations in shell thickness are suppressed, a uniform shell is easily formed, and the hollow particles are less likely to be crushed, resulting in high mechanical strength.
  • the hollow particles having a volume average particle diameter within the above range have sufficiently small particle diameters, they are suitably used as a substrate material for electronic circuit boards and the like, and can be added to thin and small substrates.
  • the shape of the hollow particles of the present disclosure is not particularly limited as long as a hollow portion is formed inside, and examples thereof include spherical, ellipsoidal, irregular shapes, and the like. Among these, a spherical shape is preferable from the viewpoint of ease of production.
  • the hollow particles of the present disclosure may have one or more hollow portions. Those having only one portion are preferred.
  • the shell provided in the hollow particles of the present disclosure, and the partition wall that partitions adjacent hollow portions in the case of having two or more hollow portions may be porous, but have dielectric properties and solvent resistance. From the point of view of improvement, it is preferable to be dense.
  • the hollow particles of the present disclosure may have an average circularity of 0.950 to 0.995.
  • An example of the image of the shape of the hollow particles of the present disclosure is a bag made of a thin film and inflated with gas, the cross-sectional view of which is shown as the hollow particles 10 in (5) of FIG. 1 .
  • a thin film is provided on the outside and the inside is filled with gas.
  • the particle shape can be confirmed by, for example, SEM or TEM.
  • the particle size distribution (volume average particle size (Dv)/number average particle size (Dn)) of the hollow particles may be, for example, 1.1 or more and 2.5 or less. When the particle size distribution is 2.5 or less, particles with little variation in compressive strength characteristics and heat resistance among particles can be obtained. Moreover, when the particle size distribution is 2.5 or less, for example, when manufacturing a sheet-like resin molding, a product having a uniform thickness can be manufactured.
  • the volume average particle diameter (Dv) and number average particle diameter (Dn) of the hollow particles are obtained, for example, by measuring the particle diameter of the hollow particles with a particle size distribution analyzer and calculating the number average and volume average, respectively. The values can be the number average particle size (Dn) and the volume average particle size (Dv) of the particles.
  • the particle size distribution is obtained by dividing the volume average particle size by the number average particle size.
  • hollow particles of the present disclosure include, for example, low dielectric materials used in various fields such as automobiles, electricity, electronics, construction, aviation, space, members such as heat insulating materials, sound insulating materials and light reflecting materials, food containers , sports shoes, footwear such as sandals, home appliance parts, bicycle parts, stationery, tools, filaments for 3D printers, etc.
  • the hollow particles of the present disclosure are excellent in dielectric properties and solvent resistance, and thus are suitably used as an additive for achieving low dielectric constant or low transmission loss in the field of electricity or electronics.
  • the hollow particles of the present disclosure are suitably used as an electronic circuit board material. It is possible to reduce the transmission rate and reduce the transmission loss of the electronic circuit board.
  • the hollow particles of the present disclosure can also be used as interlayer insulating materials, dry film resists, solder resists, bonding wires, magnet wires, semiconductor sealing materials, epoxy sealing materials, mold underfills, underfills, die bond pastes, It is also suitably used as an additive in semiconductor materials such as buffer coating materials, copper-clad laminates, flexible substrates, high-frequency device modules, antenna modules, and in-vehicle radars.
  • semiconductor materials such as interlayer insulation materials, solder resists, magnet wires, epoxy sealing materials, underfills, buffer coating materials, copper-clad laminates, flexible substrates, high-frequency device modules, antenna modules, and in-vehicle radars are particularly useful. preferred.
  • the hollow particles of the present disclosure have a high porosity, are resistant to crushing, and have excellent heat resistance, they satisfy the heat insulating properties and cushioning properties (cushion properties) required for undercoat materials, and can be used immediately for thermal paper applications. It also satisfies the required heat resistance.
  • the hollow particles of the present disclosure are also useful as plastic pigments with excellent gloss, hiding power, and the like.
  • the hollow particles of the present disclosure can enclose useful ingredients such as fragrances, chemicals, agricultural chemicals, and ink ingredients inside by means of immersion treatment, reduced pressure or pressure immersion treatment, etc., so that various It can be used for various purposes.
  • the resin composition of the present disclosure contains the hollow particles of the present disclosure and a matrix resin. Since the hollow particles of the present disclosure have excellent solvent resistance, if the resin composition of the present disclosure further contains an organic solvent, when the resin composition of the present disclosure is formed into a molded body, the hollow particles of the present disclosure It is preferable from the viewpoint of excellent effects of low dielectric constant and low dielectric loss tangent.
  • the matrix resin used in the liquid resin composition of the present disclosure is not particularly limited. can be done.
  • a matrix resin that is dispersed or dissolved in an organic solvent is preferable, and a thermosetting resin is particularly preferable, because the hollow particles of the present disclosure are likely to exhibit the effects of low dielectric constant and low dielectric loss tangent.
  • the matrix resin contained in the resin composition of the present disclosure may be an unreacted monomer, prepolymer or macromonomer, may be a polymer, or may be a cured resin such as polyamic acid.
  • binder may be a precursor of The matrix resin contained in the resin composition of the present disclosure functions as a binder (binding agent) by, for example, heating, light irradiation, or curing using a curing agent, polymerization initiator, catalyst, or the like.
  • thermosetting resin a known one can be used and is not particularly limited, but examples include phenolic resins, melamine-based resins, urea-based resins, unsaturated polyester-based resins, epoxy-based resins, polyurethane-based resins, Silicon-based resin, alkyd-based resin, thermosetting modified polyphenylene ether-based resin, thermosetting polyimide-based resin, benzoxazine-based resin, allyl-based resin, aniline-based resin, maleimide-based resin, bismaleimide triazine-based resin, liquid crystalline polyester resins, vinyl ester resins, unsaturated polyester resins, cyanate ester resins, polyetherimide resins, and precursors of these resins before curing.
  • phenolic resins melamine-based resins, urea-based resins, unsaturated polyester-based resins, epoxy-based resins, polyurethane-based resins, Silicon-based resin, alkyd-based resin, thermosetting modified polyphenylene
  • thermosetting resins can be used alone or in combination of two or more.
  • the thermosetting resin is preferably used together with a curing agent such as amines, acid anhydrides, imidazoles, or the like, or a curing catalyst, depending on the type of resin.
  • Curing agents (radical initiators) for thermosetting modified polyphenylene ethers include, for example, 2,5-dimethyl-2,5-di-tert-butylperoxy-hexane, di-tert-butyl peroxide, dicumyl peroxide, organic peroxides such as oxides, benzoyl peroxide, 1,3-di(2-tert-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di-tert-butylperoxy-hexyne can be preferably used.
  • room temperature curable resins include adhesives such as epoxy adhesives, silicone adhesives, and acrylic adhesives, which can be cured at room temperature with the addition of a catalyst.
  • thermoplastic resins examples include polyolefin-based resins, polyamide-based resins, polycarbonate-based resins, polyphenylene sulfide-based resins, polyetheretherketone-based resins, polystyrene-based resins, polyphenylene oxide-based resins, liquid crystalline polymer (LCP), and the like. mentioned. These matrix resins can be used alone or in combination of two or more.
  • epoxy resins thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicon resins, and benzoxazine resins are used as matrix resins.
  • melamine-based resins, urea-based resins, allyl-based resins, phenol-based resins, unsaturated polyester-based resins, polyurethane-based resins, aniline-based resins, and other insulating resins are preferably used.
  • resins, modified polyphenylene ether-based resins, silicon-based resins, benzoxazine-based resins, melamine-based resins, and the like are preferably used. These insulating resins can be used alone or in combination of two or more.
  • the resin composition of the present disclosure includes a toluene-soluble matrix resin and toluene as an organic solvent.
  • a resin composition is preferred.
  • toluene-soluble matrix resins include thermosetting modified polyphenylene ether resins and thermosetting epoxy resins.
  • the content of the matrix resin is not particularly limited, it is preferably 50 to 95% by mass or less based on 100% by mass of the total solid content of the resin composition of the present disclosure.
  • the content of the matrix resin is at least the above lower limit, the moldability of the resin composition when used as a resin molding is excellent, and the resulting resin molding is excellent in mechanical strength.
  • the content of the matrix resin is equal to or less than the above upper limit, the hollow particles of the present disclosure can be sufficiently contained, so that the hollow particles of the present disclosure can achieve effects such as a low dielectric constant and a low dielectric loss tangent. can be fully demonstrated.
  • the matrix resin is a resin or the like used together with an additive for curing the resin such as a curing agent and a curing catalyst
  • the content of the matrix resin includes the content of the additive. shall be included.
  • the content of the hollow particles of the present disclosure is not particularly limited, it is preferably 5 to 50 mass% of the total solid content of 100 mass% of the resin composition of the present disclosure.
  • the content of the hollow particles is equal to or higher than the lower limit, the effects of the hollow particles of the present disclosure, such as low dielectric constant and low dielectric loss tangent, can be sufficiently exhibited.
  • the content of the hollow particles is equal to or less than the above upper limit, the matrix resin can be sufficiently contained, so that moldability and mechanical strength can be improved.
  • the resin composition of the present disclosure preferably contains an organic solvent in a state before forming a molded body, because the effects of low dielectric constant and low dielectric loss tangent due to the hollow particles of the present disclosure are easily exhibited. It is preferable to contain at least toluene as an organic solvent.
  • the resin composition of the present disclosure may contain an organic solvent other than toluene, and may contain an organic solvent appropriately selected according to the type of matrix resin. Among them, the hollow particles of the present disclosure are likely to exhibit a low dielectric constant and a low dielectric loss tangent effect, so the organic solvent contained in the resin composition of the present disclosure contains at least toluene and is an aromatic hydrocarbon. It is preferably composed of a system solvent, and particularly preferably composed of toluene. When the resin composition of the present disclosure contains an organic solvent, the content of the organic solvent is not particularly limited. It may be parts by mass.
  • the resin composition of the present disclosure contains, in addition to the hollow particles and matrix resin of the present disclosure, an ultraviolet absorber, a colorant, a heat stabilizer, a filler, a flame retardant, etc., if necessary, within a range that does not impair the effects of the present disclosure. may further contain additives.
  • the resin composition of the present disclosure may further contain organic or inorganic fibers such as carbon fibers, glass fibers, aramid fibers, and polyethylene fibers when formed into molded articles.
  • Examples of the method for producing the resin composition of the present disclosure include a method including a step of mixing the hollow particles obtained by the production method of the present disclosure with a matrix resin.
  • the liquid resin composition of the present disclosure is obtained, for example, by mixing the hollow particles of the present disclosure, a matrix resin, and an organic solvent and additives that are added as necessary.
  • the resin composition of the present disclosure may be used as a molded article.
  • the molded body of the resin composition of the present disclosure may be a molded body obtained by solidifying the liquid resin composition into a desired shape, or alternatively, the hollow particles of the present disclosure and the thermoplastic resin
  • the resin composition may be heated to melt the thermoplastic resin, melt-kneaded, and molded to form a molded article.
  • the matrix resin is a solidified material.
  • the matrix resin, which is a solidified product is a resin that has been solidified with or without undergoing a chemical reaction. Examples thereof include resins that have been cured by a curing reaction, resins that have been solidified by drying, and thermoplastic resins that have been solidified by cooling.
  • a molded article obtained using the resin composition described above contains, as a matrix resin, a cured product of a resin cured using a curing agent, a polymerization initiator, a catalyst, or the like, if necessary.
  • the matrix resin may contain a curing agent or the like.
  • a molded body obtained by melt-kneading the hollow particles of the present disclosure and a thermoplastic resin and molding the mixture contains, as a matrix resin, a solidified product obtained by cooling and solidifying the thermoplastic resin.
  • thermoplastic resin used in molding a known thermoplastic resin can be used, and is not particularly limited.
  • polypropylene polyolefins such as polyethylene; polyamides such as PA6, PA66, PA12; polyimide, polyamideimide, polyetherimide, polyetherketoneketone, polyvinyl chloride, polystyrene, poly(meth)acrylate, polycarbonate, polyvinylidene fluoride, acrylonitrile-butadiene - styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), polyphenylene ether, polyphenylene sulfide, polyester, polytetrafluoroethylene, thermoplastic elastomers, and the like.
  • thermoplastic resins can be used alone or in combination of two or more.
  • a resin molded article which is a molded article of the resin composition of the present disclosure, has excellent dielectric properties by containing the hollow particles of the present disclosure.
  • the resin molding of the present disclosure preferably has a dielectric constant of 2.50 or less, more preferably 2.40 or less, and even more preferably 2.30 or less at a frequency of 1 GHz.
  • the lower limit of the dielectric constant at a frequency of 1 GHz of the resin molding of the present disclosure is not particularly limited, but is usually 1.00 or more.
  • the resin molding of the present disclosure preferably has a dielectric loss tangent at a frequency of 1 GHz of 0.010 (1.0 ⁇ 10 ⁇ 2 ) or less, more preferably 5.0 ⁇ 10 ⁇ 3 or less, still more preferably 4.0 ⁇ 10 ⁇ 3 or less. 5 ⁇ 10 ⁇ 3 or less.
  • the lower limit of the dielectric loss tangent at a frequency of 1 GHz of the resin molding of the present disclosure is not particularly limited, and may be, for example, 1.0 ⁇ 10 ⁇ 5 or more.
  • the dielectric constant and dielectric loss tangent of the resin molding are measured using a perturbation-type measuring device at a measurement frequency of 1 GHz in accordance with JIS C 2565.
  • Examples of the method of forming the liquid resin composition of the present disclosure into a molded product include a method of applying the liquid resin composition of the present disclosure to a support, drying if necessary, and then curing by heating. can be done.
  • Examples of the material of the support include resins such as polyethylene terephthalate and polyethylene naphthalate; and metals such as copper, aluminum, nickel, chromium, gold and silver.
  • a method for applying the liquid resin composition a known method can be used, and examples thereof include dip coating, roll coating, curtain coating, die coating, slit coating, gravure coating and the like. When the resin composition contains an organic solvent, it is preferable to dry the resin composition after the application.
  • the drying temperature is preferably a temperature at which the resin composition is not cured from the viewpoint of removing the organic solvent while leaving the resin composition in an uncured or semi-cured state. °C or lower, preferably 30 °C or higher and 150 °C or lower.
  • the drying time is usually 30 seconds or more and 1 hour or less, preferably 1 minute or more and 30 minutes or less.
  • the heating temperature for curing the resin composition is appropriately adjusted according to the type of the curable resin, and is not particularly limited. 400° C. or lower, preferably 70° C. or higher and 300° C. or lower, more preferably 100° C. or higher and 200° C. or lower.
  • the curing time is 5 minutes or more and 5 hours or less, preferably 30 minutes or more and 3 hours or less.
  • the heating method is not particularly limited, and may be performed using, for example, an electric oven.
  • melt-kneading the hollow particles of the present disclosure and a resin composition containing a thermoplastic resin to form a molded body for example, after melt-kneading a pellet-shaped resin composition, extrusion molding, injection molding, press molding , a method of molding into a desired shape by a known molding method such as compression molding.
  • the temperature during melt-kneading is not particularly limited as long as it is a temperature at which the thermoplastic resin to be used can be melted.
  • Kneading can be performed by a known method, and is not particularly limited, but can be performed using a kneading device such as a single-screw kneader or a twin-screw kneader.
  • a kneading device such as a single-screw kneader or a twin-screw kneader.
  • the shape of the resin molded article of the present disclosure is not particularly limited, and can be various shapes that can be molded using the resin composition of the present disclosure. and any other shape such as various three-dimensional shapes.
  • the fibers in the resin molding may be in the form of a non-woven fabric.
  • the resin molding may be a molding of a resin composition in which the hollow particles of the present disclosure are added to the fiber-reinforced plastic containing the resin and fibers as described above.
  • Examples of applications of the resin composition of the present disclosure and molded articles thereof include, among the applications of the hollow particles of the present disclosure described above, applications in which the resin composition can be used.
  • Example 1 (1) Mixed Solution Preparation Step First, the following materials were mixed to form an oil phase.
  • DVB960 trade name, Nippon Steel Chemical & Material Co., Ltd., divinylbenzene 96%, ethylvinylbenzene 4%) 38.7 parts t-butyl peroxydiethyl acetate (oil-soluble polymerization initiator, Kayaku Nourion Co., Ltd., commercial Name: Trigonox 27) 0.89 parts Rosin acid (softening point 150 ° C.
  • Solvent removal step The precursor particles obtained in the solid-liquid separation step are heat-treated in a vacuum dryer under vacuum conditions of 200°C for 6 hours to remove the hydrophobic solvent contained in the particles. was removed to obtain hollow particles of Example 1. The obtained hollow particles were confirmed to be spherical and to have a hollow portion from the results of scanning electron microscope observation and porosity values.
  • Example 2 In Example 1, except that 5 parts of ethyl acetate (solubility in water at 20 ° C.: 83 g / L) was added in place of 5 parts of MEK as the additive solution for accelerating the reaction in the above "(3) Polymerization step". Hollow particles of Example 2 were produced in the same manner as in Example 1.
  • Example 3 In Example 1, the procedure was the same as in Example 1, except that the addition amount of MEK added as the reaction accelerating additive liquid was changed from 5 parts to 2 parts in the above "(3) Polymerization step”. 3 hollow particles were produced.
  • Example 4 In Example 1, in the above “(3) Polymerization step", the timing of adding the reaction accelerating additive liquid was changed from 1 hour after reaching 80 ° C. to 8 hours after reaching 80 ° C. Example Hollow particles of Example 4 were produced in the same manner as in Example 1.
  • Example 5 In Example 1, the amount of DVB960 added was changed from 38.7 parts to 36.7 parts in the above "(1) mixture preparation step”, and further, the above “(3) polymerization step” was changed to 5 parts of MEK. Hollow particles of Example 5 were produced in the same manner as in Example 1, except that 2 parts of allyl methacrylate (AMA) (solubility in water at 20° C.: 2.2 g/L) was added instead.
  • AMA allyl methacrylate
  • Example 6 Hollow particles of Example 6 were produced in the same procedure as in Example 1, except that the amount of MEK added was changed from 5 parts to 10 parts in the above "(3) Polymerization step".
  • Example 7 In Example 1, the amount of DVB960 added was changed from 38.7 parts to 49.6 parts in the above "(1) mixture preparation step", and the amount of polymerization initiator added and the amount of heptane added were adjusted according to Table 2. Hollow particles of Example 7 were produced in the same procedure as in Example 1, except that the procedure was changed.
  • Example 8 In Example 1, the amount of DVB960 added was changed from 38.7 parts to 33.0 parts in the above "(1) mixture preparation step", and the amount of polymerization initiator added and the amount of heptane added were adjusted according to Table 2. Hollow particles of Example 8 were produced in the same procedure as in Example 1, except that the procedure was changed.
  • Example 9 In Example 1, in the above "(1) mixture preparation step", the amount of DVB960 added was changed from 38.7 parts to 37.7 parts, and 1.0 part of styrene was added. Hollow particles of Example 9 were produced in the same procedure as above.
  • Example 10 In Example 1, in the above "(1) mixture preparation step", the amount of DVB960 added was changed from 38.7 parts to 32.7 parts, and 6.0 parts of styrene was added. Hollow particles of Example 10 were produced in the same procedure as above.
  • Example 11 In Example 1, in the above "(1) mixture preparation step", the amount of DVB960 added was changed from 38.7 parts to 28.7 parts, and 10.0 parts of styrene was added. Hollow particles of Example 11 were produced in the same procedure as above.
  • Example 12 In Example 1, in the above “(3) polymerization step", 5 parts of 3-pentanone (solubility in water at 20 ° C.: 47 g / L) was added instead of 5 parts of MEK as the additive liquid for accelerating the reaction. Hollow particles of Example 12 were produced in the same manner as in Example 1.
  • Example 13 Example 1 except that 5 parts of methyl acetate (solubility in water at 20 ° C.: 250 g / L) was added in place of 5 parts of MEK as the additive liquid for accelerating the reaction in the above "(3) Polymerization step". Hollow particles of Example 13 were produced in the same manner as in Example 1.
  • Example 14 In Example 1, the amount of DVB960 added was changed from 38.7 parts to 36.7 parts in the above "(1) mixture preparation step”, and the reaction acceleration additive solution was added in the above "(3) polymerization step”. Hollow particles of Example 14 were produced in the same manner as in Example 1, except that 2 parts of methyl methacrylate (solubility in water at 20°C: 15.9 g/L) was added instead of 5 parts of MEK.
  • Example 15 In Example 1, the amount of DVB960 added was changed from 38.7 parts to 36.7 parts in the above "(1) mixture preparation step”, and the reaction acceleration additive solution was added in the above "(3) polymerization step”. Hollow particles of Example 15 were produced in the same manner as in Example 1, except that 2 parts of t-butylaminoethyl methacrylate (solubility in water at 20°C: 18 g/L) was added instead of 5 parts of MEK. .
  • Example 2 In Example 1, in the above "(3) Polymerization step", the timing of adding the reaction accelerating additive liquid was changed from 1 hour after reaching 80 ° C. to before the temperature was raised. Hollow particles of Comparative Example 2 were produced according to the procedure.
  • Example 3 In Example 1, in the above "(1) mixture preparation step", the amount of DVB960 added was changed from 38.7 parts to 33.7 parts, the amount of the polymerization initiator added was changed according to Table 3, and further, The same procedure as in Example 1 except that 5 parts of styrene (St) (solubility in water at 20 ° C.: 0.3 g / L) was added instead of 5 parts of MEK in the above "(3) polymerization step". Hollow particles of Comparative Example 3 were produced.
  • St styrene
  • Comparative Example 4 Hollow particles of Comparative Example 4 were produced in the same manner as in Example 1 of Patent Document 2 above. That is, 1.15 parts of styrene, DVB810 (: trade name, Nippon Steel Chemical & Material Co., Ltd., divinylbenzene 81%, ethylvinylbenzene 19%) 1.85 parts, heptane 2.4 parts, HS Crysta 4100 (: product name, side chain crystalline polyolefin, manufactured by Toyokuni Oil Co., Ltd.) 0.3 parts, Blemmer 50PEP-300 (: trade name, polyethylene glycol propylene glycol monomethacrylate, manufactured by NOF Corporation) 0.3 parts, perroyl L (: (trade name, polymerization initiator, manufactured by NOF Corporation) were mixed to prepare an oil phase.
  • styrene, DVB810 trade name, Nippon Steel Chemical & Material Co., Ltd., divinylbenzene 81%, ethylvinyl
  • volume average particle size (Dv) and number average particle size (Dn), and calculation of particle size distribution (Dv/Dp) Using a particle size distribution analyzer (manufactured by Beckman Coulter, trade name: Multisizer 4e) The volume average particle size (Dv) and number average particle size (Dn) of the hollow particles were measured to calculate the particle size distribution (Dv/Dn).
  • the measurement conditions were as follows: aperture diameter: 50 ⁇ m, dispersion medium: Isoton II (trade name), concentration: 10%, number of measured particles: 100,000.
  • a particle sample was placed in a beaker, and an aqueous surfactant solution (manufactured by Fuji Film Co., Ltd., trade name: Drywell) was added therein as a dispersant.
  • an aqueous surfactant solution manufactured by Fuji Film Co., Ltd., trade name: Drywell
  • 2 ml of a dispersing medium was further added thereto to wet the particles, and then 10 ml of a dispersing medium was added, dispersed for 1 minute with an ultrasonic disperser, and then measured with the particle size distribution analyzer.
  • Immersion test (toluene solvent resistance) Add 0.1 mg of the hollow particles to 4 mL of toluene in an environment of 25° C., shake for 10 minutes at a shaking speed of 100 rpm using a shaker, and allow to stand for 48 hours. and evaluated according to the following evaluation criteria.
  • the hollow particles precipitated in toluene were separated by a centrifugal separator, dried, and the mass of the hollow particles precipitated in toluene was measured.
  • the ratio of the precipitated hollow particles was obtained by calculating the ratio of the mass of the hollow particles precipitated in toluene to the mass of the entire hollow particles immersed in toluene.
  • An aluminum foil was pasted on a glass plate without wrinkles, and the obtained resin composition was coated on the aluminum foil with a bar coater No. 1. 75 to form a coating film.
  • the coating film was cured under a nitrogen atmosphere by heating at 80° C. for 1 hour, 120° C. for 30 minutes, and 160° C. for 1 hour in order to form a PPE film containing hollow particles on an aluminum foil.
  • the laminate of the film and aluminum foil was immersed in a 1N hydrochloric acid aqueous solution overnight to remove the aluminum foil and obtain only the film.
  • the resulting film was washed with deionized water and dried to obtain a PPE film containing hollow particles.
  • the hollow particles obtained in Comparative Examples 1 to 3 had a porosity of 50% or more, and the shell contained a polymer containing 70% by mass or more of crosslinkable hydrocarbon monomer units. Hollow particles that precipitated in toluene were 5% by mass or more. Therefore, although the hollow particles obtained in Comparative Examples 1 to 3 had low relative dielectric constant and dielectric loss tangent, they were inferior in the effect of lowering the dielectric constant and dielectric loss tangent of the PPE film. In Comparative Examples 1 to 3, toluene in the resin composition permeated into the hollow particles in the process of producing the PPE film, and toluene remained in the hollow particles in the resulting PPE film.
  • Comparative Example 1 it is presumed that a low dielectric constant and a low dielectric loss tangent could not be achieved.
  • Comparative Example 2 since the additive liquid for accelerating the reaction was added before the polymerization reaction, the effect of promoting the cross-linking reaction of the shell by the additive liquid for accelerating the reaction was not exerted, so a shell excellent in solvent resistance was formed. presumed not to have been.
  • Comparative Example 3 in the polymerization step, styrene was added in place of the reaction-promoting additive liquid, but styrene had a low solubility in water and could not enter into the shell. was not obtained, and it is presumed that a shell having excellent solvent resistance was not formed.
  • Comparative Example 4 corresponds to Example 1 of Patent Document 2, and the obtained hollow particles have a porosity of less than 50%, and the shell contains 70 crosslinkable hydrocarbon monomer units in the polymer. % by mass, and 5% by mass or more of the hollow particles precipitated in toluene in the above immersion test.
  • the hollow particles obtained in Comparative Example 4 had high relative dielectric constant and dielectric loss tangent, poor solvent resistance, and poor effects of reducing the dielectric constant and dielectric loss tangent of the PPE film. It is presumed that the hollow particles obtained in Comparative Example 4 had high relative permittivity and dielectric loss tangent due to their low porosity, and poor solvent resistance due to their insufficient shell crosslink density. be. In Comparative Example 4, the dielectric properties of the hollow particles themselves were inferior, and the solvent resistance of the hollow particles was insufficient. It is presumed that toluene remained in the hollow particles in the obtained PPE film, so that the PPE film was not sufficiently lowered in dielectric constant and dielectric loss tangent.
  • the hollow particles obtained in each example had a porosity of 50% or more, and the shell contained a polymer containing 70% by mass or more of crosslinkable hydrocarbon monomer units.
  • the amount of hollow particles that precipitated in toluene was less than 5% by mass, the dielectric constant and dielectric loss tangent were low, and the effect of reducing the dielectric constant and dielectric loss tangent of the PPE film was also excellent.
  • the content of the crosslinkable hydrocarbon monomer was set to 70% by mass or more in 100% by mass of the polymerizable monomer contained in the mixed solution, and the additive liquid for accelerating the reaction was added during the polymerization reaction. As a result, hollow particles having excellent dielectric properties and solvent resistance could be obtained.
  • the content of the hydrocarbon monomer in the polymerizable monomer was sufficiently high, so that the formed shell had a resin composition with excellent dielectric properties, and the polymerizable monomer contained
  • the content of the crosslinkable monomer in is sufficiently high, and the crosslink reaction of the shell is accelerated by the addition of the reaction-promoting additive liquid, resulting in the formation of a shell with a high crosslink density.
  • the hollow particles themselves had excellent dielectric properties, and the hollow particles had excellent solvent resistance. Since little or no toluene remained in the hollow particles in the obtained PPE film, it is presumed that the effect of lowering the dielectric constant and the dielectric loss tangent of the PPE film was excellent.

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EP22886978.0A EP4424726A4 (en) 2021-10-29 2022-10-25 HOLLOW PARTICLE, HOLLOW PARTICLE PRODUCTION PROCESS, RESIN COMPOSITION AND MOLDED BODY
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WO2024095851A1 (ja) * 2022-10-31 2024-05-10 日本ゼオン株式会社 中空粒子、中空粒子の製造方法、樹脂組成物及び樹脂構造体
WO2025062901A1 (ja) * 2023-09-19 2025-03-27 積水化成品工業株式会社 中空樹脂粒子、その用途、およびその製造方法

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