WO2023127624A1 - 中空粒子 - Google Patents

中空粒子 Download PDF

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Publication number
WO2023127624A1
WO2023127624A1 PCT/JP2022/047033 JP2022047033W WO2023127624A1 WO 2023127624 A1 WO2023127624 A1 WO 2023127624A1 JP 2022047033 W JP2022047033 W JP 2022047033W WO 2023127624 A1 WO2023127624 A1 WO 2023127624A1
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Prior art keywords
mass
hollow particles
parts
particles
hollow
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Ceased
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PCT/JP2022/047033
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English (en)
French (fr)
Japanese (ja)
Inventor
真司 渡邉
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Zeon Corp
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Zeon Corp
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Application filed by Zeon Corp filed Critical Zeon Corp
Priority to CN202280083252.8A priority Critical patent/CN118401569A/zh
Priority to EP22915848.0A priority patent/EP4458868A4/en
Priority to KR1020247020142A priority patent/KR20240123337A/ko
Priority to JP2023570895A priority patent/JPWO2023127624A1/ja
Priority to US18/720,891 priority patent/US20250059339A1/en
Publication of WO2023127624A1 publication Critical patent/WO2023127624A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • 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
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
    • 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
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/206—Hardening; drying
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2435/00—Characterised by the use 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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2435/02—Characterised by the use of homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • C08L2205/20—Hollow spheres

Definitions

  • the present disclosure relates to hollow particles.
  • 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.
  • the hollow particles are added during kneading with other materials and during molding after kneading. It is desirable to be able to maintain a high porosity.
  • Patent Document 1 as a method for obtaining hollow particles that have a high porosity and are not easily crushed, in a suspension polymerization method, the total content of a crosslinkable monomer is Using a polymerizable monomer having an amount of 80 to 98 parts by mass and a trifunctional or higher crosslinkable monomer content of 10 to 98 parts by mass, a hydrophobic solvent to be included in the particles during the production process, A method for producing hollow particles using a hydrocarbon solvent containing 50% by mass or more of a saturated hydrocarbon solvent is disclosed.
  • the thickness of the shell is 0.2 ⁇ m or more and 0.9 ⁇ m or less, and 70% by mass or more and 100% by mass or less of a crosslinkable monomer and 0
  • An object of the present disclosure is to provide hollow particles with excellent pressure resistance.
  • the conventional method had large variations in the test results, making it difficult to evaluate the difference in pressure resistance with high accuracy.
  • the present inventor completed a highly accurate press test method with little variation in test results, and furthermore, the void maintenance rate measured by the press test method was subjected to a process such as injection molding where external pressure is applied. It was found that it can be used as a guideline for the void maintenance rate of the hollow particles later.
  • the present inventors have found that by adjusting the composition of the polymerizable monomer used for forming the hollow particles, the type of hydrophobic solvent to be included in the particles during the production process, or the particle size of the hollow particles, etc., We succeeded in obtaining hollow particles with excellent pressure resistance, and found that the hollow particles can be differentiated from conventional hollow particles by the value of the residual void ratio measured by the newly completed high-precision press test method. rice field.
  • the present disclosure provides a hollow particle comprising a shell containing a resin and a hollow portion surrounded by the shell,
  • the porosity is 50% or more
  • Press test method A mixture obtained by melting and mixing 0.1 g of hollow particles and 0.9 g of polypropylene resin at 200° C. is placed in a mold for a hot press and heated at 200° C. for 15 minutes, then stirred, and then The mold filled with the mixture is placed in a heat press machine set at 80 ° C., the 80 ° C. cylinder is placed in the mold and allowed to stand, and when the surface temperature of the mold reaches 140 ° C., the pressure is 60 MPa.
  • the shell preferably contains, as the resin, a polymer containing 50 parts by mass or more of crosslinkable monomer units in 100 parts by mass of all monomer units.
  • the polymer contains, as the crosslinkable monomer unit, a trifunctional or higher crosslinkable monomer unit derived from a trifunctional or higher crosslinkable monomer, and It is preferable that the content of the trifunctional or higher crosslinkable monomer unit is 10 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the total monomer units of the combination.
  • the polymer comprises, as the crosslinkable monomer units, a bifunctional crosslinkable monomer unit derived from a bifunctional crosslinkable monomer and a trifunctional or higher crosslinkable monomer unit. It is preferable to contain a trifunctional or higher crosslinkable monomer unit derived from a monomer.
  • the content of the tri- or higher-functional crosslinkable monomer unit in the total 100 mass of the bi-functional and higher-functional cross-linkable monomer units is preferably 5 parts by mass or more and 40 parts by mass or less.
  • the shell contains a polymer containing acrylic monomer units and hydrocarbon monomer units as the resin, and the acrylic monomer units and the hydrocarbon monomer
  • the content of the hydrocarbon monomer unit is preferably 10 parts by mass or more and 80 parts by mass or less in a total of 100 parts by mass of the units.
  • the hollow particles of the present disclosure preferably have a volume average particle diameter of 5.0 ⁇ m or more and 40.0 ⁇ m or less.
  • the present disclosure as described above provides hollow particles whose porosity is less likely to decrease even through processes such as injection molding that apply external pressure.
  • 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
  • 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.
  • the hollow particles of the present disclosure are hollow particles comprising a shell containing a resin and a hollow portion surrounded by the shell, having a porosity of 50% or more, and having a void residual ratio measured according to the press test method described later. It is characterized by being 80% or more.
  • 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.
  • the hollow particles of the present disclosure preferably have a solid shell from the viewpoint of pressure 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 portion of the hollow particles of the present disclosure may be filled with gas such as air, may be in a vacuum or reduced pressure state, or may contain a solvent.
  • the press test method used in this disclosure is as follows. A mixture obtained by melting and mixing 0.1 g of hollow particles and 0.9 g of polypropylene resin at 200° C. is placed in a mold for a hot press and heated at 200° C. for 15 minutes, then stirred, and then The mold filled with the mixture is placed in a heat press machine set at 80 ° C., the 80 ° C. cylinder is placed in the mold and allowed to stand, and when the surface temperature of the mold reaches 140 ° C., the pressure is 60 MPa.
  • the void residual ratio of the hollow particles contained in the compact can be calculated by the following formula (A).
  • Formula (A): Void residual ratio (%) ⁇ (ca) / (cb) ⁇ ⁇ 100
  • a is the specific gravity of the molded body
  • b is the specific gravity of the molded body assuming that the voids are maintained (calculated value)
  • c is the specific gravity of the molded body that is assumed to have all the hollow particles crushed (calculated value ) respectively.
  • the specific gravity of the molded article (a in the above formula (A)) can be measured by a water substitution method in accordance with JIS K 7112.
  • the specific gravity (b in the above formula (A)) of the compact assuming that the voids are maintained can be calculated by the following formula (B).
  • Formula (B): b 1/ ⁇ ( PA / PG )+( RA / RG ) ⁇
  • PA is the amount of hollow particles added
  • PG is the specific gravity of the hollow particles
  • RA is the amount of polypropylene resin added
  • RG is the specific gravity of the polypropylene resin.
  • the specific gravity of the compact (c in the above formula (A)) assuming that all the hollow particles have been crushed can be calculated by the following formula (C).
  • Formula (C): c [R G ⁇ R A + ⁇ D 0 ⁇ P A ⁇ (1 ⁇ P V /100) ⁇ ]/ ⁇ R A +P A ⁇ (1 ⁇ P V /100) ⁇
  • RA is the added amount of the polypropylene resin
  • RG is the specific gravity of the polypropylene resin
  • D0 is the true density of the hollow particles
  • PA is the added amount of the hollow particles
  • PV is the porosity of the hollow particles. (%) respectively.
  • the void residual ratio measured according to the above press test method is as high as the hollow particles have excellent pressure resistance. That's it.
  • the procedure of the press test method performed in Examples described later can be mentioned.
  • polypropylene resin used in the press test a polypropylene resin having an MFR (melt flow rate) at 230°C of 10 to 30 g/min, preferably 15 to 25 g/min can be used.
  • MFR melt flow rate
  • Commercially available products of such polypropylene resin include, for example, Novatec PP, grade: MA1B (MFR at 230° C. is 21 g/min) manufactured by Japan Polypropylene Corporation.
  • the hollow particles of the present disclosure are hollow particles having a high porosity of 50% or more, yet have a void residual rate of 80% or more measured according to the above press test method, and have excellent pressure resistance. Since conventional hollow particles have insufficient pressure resistance, it has been difficult to achieve a void residual rate of 80% or more in the above press test method in which pressure is applied at 60 MPa. In order to obtain hollow particles with a void residual ratio of 80% or more in the above press test method, for example, the strength of the shell is improved by adjusting the composition of the polymerizable monomer used for forming the shell of the hollow particle. Furthermore, it is effective to improve the uniformity of the shell in terms of shell composition, thickness, etc.
  • Hollow particles of the present disclosure are, for example, preparing a mixture containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer and an aqueous medium; By suspending the mixture, a suspension is prepared in which droplets of a monomer composition containing the polymerizable monomer, the hydrophobic solvent and the polymerization initiator are dispersed in the aqueous medium. and 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. It can be obtained by the method for producing hollow particles of the present disclosure, comprising the steps of:
  • 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 polymerizable monomer and the hydrophobicity of the droplets of the monomer composition dispersed in the suspension are When the solvent is sufficiently phase-separated and the suspension is subjected to the polymerization reaction, the polymerization reaction of the polymerizable monomer proceeds uniformly, forming a shell with excellent uniformity in composition and thickness.
  • 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 by 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.
  • Suspension step Suspension in which droplets of a monomer composition containing a polymerizable monomer, a hydrophobic solvent and a polymerization initiator are dispersed in an aqueous medium by suspending the mixture.
  • a step of preparing (3) Polymerization step By subjecting the suspension to a polymerization reaction, a precursor composition containing precursor particles having a hollow portion surrounded by a resin-containing shell 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;
  • hollow particles whose hollow portions are filled with a hydrophobic solvent are sometimes referred to as "precursor particles", considering them as intermediates of hollow particles whose hollow portions are 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 process. 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 droplets 8 of the monomer composition contain a polymerizable monomer, a hydrophobic solvent and a polymerization initiator, but the distribution within the droplets 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 schematic cross-sectional view 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.
  • the materials of the mixed solution are described in order of (A) polymerizable monomer, (B) hydrophobic solvent, (C) polymerization initiator, (D) dispersion stabilizer, and (E) aqueous medium.
  • (A) Polymerizable monomer As the polymerizable monomer, known polymerizable monomers that have been conventionally used for producing hollow particles can be used, and are not particularly limited. It is preferred to include When the polymerizable monomer contains a crosslinkable monomer, the crosslink density of the shell can be increased, so that a shell with excellent strength is easily formed, the hollow particles are easily spherical, and the particles are formed from the shell. Clearly distinct hollows are likely to be formed.
  • the polymerizable monomer is preferably a polymerizable monomer having a (meth)acryloyl group or a vinyl group as the polymerizable functional group.
  • Acrylic monomers containing acryloyl groups are more preferred.
  • the stable polymerization reaction means that the reactivity of the polymerization reaction is good and the polymerization reaction proceeds uniformly.
  • the polymerizable monomer contains an acrylic monomer and a hydrocarbon monomer because the polymerization reaction is easily stabilized and the pressure resistance of the hollow particles can be improved.
  • the reaction rate of the hydrocarbon monomer is increased, and as a result, the reactivity of the entire polymerizable monomer is improved, resulting in a stable polymerization reaction. presumed to be easy.
  • the polymerizable monomer contains an acrylic monomer and a hydrocarbon monomer, the compatibility with the hydrophobic solvent becomes appropriate, so that when the suspension is subjected to the polymerization reaction, It is presumed that the pressure resistance of the hollow particles is improved because the polymerization reaction of the polymerizable monomers tends to proceed uniformly, and the shells formed tend to be excellent in uniformity in composition, thickness, and the like.
  • the hydrocarbon monomer preferably has a vinyl group as the polymerizable functional group because the polymerization reaction is easily stabilized.
  • a polymerizable monomer having a (meth)acryloyl group as a polymerizable functional group is referred to as an acrylic monomer
  • a crosslinkable monomer having a (meth)acryloyl group as a polymerizable functional group is called a crosslinkable acrylic monomer
  • a non-crosslinkable monomer having a (meth)acryloyl group as a polymerizable functional group is called a noncrosslinkable acrylic monomer.
  • At least one polymerizable functional group may be a (meth)acryloyl group, but all polymerizable functional groups are preferably (meth)acryloyl groups.
  • a polymerizable monomer composed of carbon and hydrogen is referred to as a hydrocarbon monomer
  • a crosslinkable monomer composed of carbon and hydrogen is referred to as a crosslinkable hydrocarbon monomer
  • carbon and hydrogen A non-crosslinking monomer consisting of is called a non-crosslinking hydrocarbon monomer.
  • crosslinkable acrylic monomer and a crosslinkable hydrocarbon monomer are preferable as the crosslinkable monomer used in the production method of the present disclosure.
  • crosslinkable acrylic monomers include allyl (meth)acrylate, vinyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, 2-hydroxy -3-(meth)acryloyloxypropyl (meth)acrylate, tricyclodecanedimethanol di(meth)acrylate and other bifunctional crosslinkable acrylic monomers; and trimethylolpropane tri(meth)acrylate, ditrimethylol Trifunctionals such as propane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaery
  • crosslinkable macromer such as polyphenylene ether having both ends (meth)acryl-modified
  • crosslinkable hydrocarbon monomers include aromatic divinyl monomers such as divinylbenzene, divinylbiphenyl, and divinylnaphthalene; linear monomers such as butadiene, isoprene, 2,3-dimethylbutadiene, pentadiene, and hexadiene or branched diolefins, and diene-based monomers such as alicyclic diolefins such as dicyclopentadiene, cyclopentadiene, and ethylidenetetracyclododecene; are mentioned.
  • 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 monomers include crosslinkable allyl monomers such as diallyl phthalate, and crosslinkable macromers such as polyphenylene ether having both ends vinyl-modified. These crosslinkable monomers may be used alone or in combination of two or more.
  • the crosslinkable monomer preferably contains a trifunctional or higher crosslinkable monomer having three or more polymerizable functional groups.
  • the tri- or more functional cross-linkable monomer the above-mentioned tri- or more functional cross-linkable acrylic monomer is preferable.
  • Propane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol poly(meth)acrylate are preferred, pentaerythritol tetra(meth)acrylate, and trimethylolpropane tri( meth)acrylates are more preferred.
  • the crosslinkable monomer is a bifunctional crosslinkable monomer having only two polymerizable functional groups and a polymerizable functional group. It is more preferable to contain a trifunctional or higher crosslinkable monomer having 3 or more.
  • the bifunctional crosslinkable monomer is preferably at least one selected from the group consisting of the above bifunctional crosslinkable acrylic monomers and the above bifunctional crosslinkable hydrocarbon monomers.
  • the bifunctional crosslinkable acrylic monomers ethylene glycol di(meth)acrylate and pentaerythritol di(meth)acrylate are preferable, and ethylene glycol di(meth)acrylate is more preferable.
  • Divinylbenzene is particularly preferred as the bifunctional crosslinkable hydrocarbon monomer.
  • the content of the crosslinkable monomer is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and still more preferably 70 parts by mass in 100 parts by mass of the polymerizable monomer. It is at least 80 parts by mass, more preferably at least 80 parts by mass.
  • the content of the crosslinkable monomer is at least the above lower limit, hollow portions are likely to be formed in the particles, the particles are likely to be spherical, and the crosslink density of the shell can be increased.
  • solvent resistance, strength, heat resistance, etc. can be improved.
  • the polymerizable monomer may contain a non-crosslinkable monomer, in which case the content of the crosslinkable monomer is the polymerizable monomer For example, it may be 95 parts by mass or less, or may be 90 parts by mass or less in 100 parts by mass.
  • the content of the crosslinkable monomer is the total content of the bifunctional crosslinkable monomer and the trifunctional or higher crosslinkable monomer.
  • the content of the trifunctional or higher crosslinkable monomer is adjusted to the polymerizable monomer from the viewpoint of improving the pressure resistance of the hollow particles.
  • the lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more
  • the upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably It is 30 parts by mass or less.
  • the crosslinkable monomer contains a bifunctional crosslinkable monomer and a trifunctional or higher crosslinkable monomer
  • the bifunctional crosslinkable monomer and The content of the trifunctional crosslinkable monomer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, as a lower limit with respect to the total mass of 100 parts by mass of the trifunctional or higher crosslinkable monomers, It is more preferably 20 parts by mass or more, and the upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.
  • the polymerizable monomer may contain a non-crosslinkable monomer as long as the effects of the present disclosure are not impaired.
  • non-crosslinkable monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate.
  • non-crosslinkable acrylic monomers aromatic monovinyl monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, p-methylstyrene, ethylvinylbenzene, ethylvinylbiphenyl, ethylvinylnaphthalene, and ethylene, propylene , linear or branched monoolefins such as butylene, and alicyclic monoolefins such as vinylcyclohexane, norbornene, tricyclododecene, and 1,4-methano-1,4,4a,9a-tetrahydrofluorene.
  • aromatic monovinyl monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, p-methylstyrene, ethylvinylbenzene, ethylvinylbiphenyl, ethy
  • Carboxylic acid vinyl ester monomers such as vinyl acetate; Halogenated aromatic vinyl monomers such as halogenated styrene; Halogenation such as vinyl chloride vinyl monomers; vinylidene halide monomers such as vinylidene chloride; vinylpyridine monomers;
  • non-crosslinkable macromers such as terminally (meth)acrylic-modified polystyrene and terminally (meth)acrylic-modified polymethyl methacrylate can also be used. These non-crosslinkable monomers can be used alone or in combination of two or more.
  • (meth)acrylic acid alkyl esters and aromatic monovinyl monomers are preferable from the viewpoints of easily stabilizing the polymerization reaction and suppressing a decrease in the pressure resistance of the hollow particles.
  • Monovinyl monomers are more preferred.
  • Butyl acrylate and methyl methacrylate are particularly preferred as (meth)acrylic acid alkyl esters.
  • Ethylvinylbenzene is particularly preferred as the aromatic monovinyl monomer.
  • the content of the acrylic monomer is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, based on 100 parts by mass of the polymerizable monomer.
  • the content of the acrylic monomer and the hydrocarbon monomer in 100 parts by mass of the polymerizable monomer is It is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, still more preferably 98 parts by mass or more, and even more preferably 99 parts by mass or more.
  • the polymerizable monomer contains an acrylic monomer and a hydrocarbon monomer
  • the content of the hydrocarbon monomer is, as a lower limit, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and as an upper limit, preferably 90 parts by mass parts or less, more preferably 80 parts 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.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less.
  • 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 preferably 95% by mass or more, more preferably 97% 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 precursor 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 can be appropriately selected from known hydrophobic solvents, and is not particularly limited. Examples include esters such as ethyl acetate and butyl acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate. and hydrocarbon solvents, among which hydrocarbon solvents are preferred. Examples of hydrocarbon solvents include linear hydrocarbon solvents such as pentane, hexane, heptane, octane, 2-methylbutane and 2-methylpentane, and cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and cycloheptane. and aromatic hydrocarbons such as benzene, toluene and xylene. These hydrophobic solvents can be used alone or in combination of two or more.
  • the phase separation between the polymerizable monomer and the hydrophobic solvent is likely to occur in the droplets of the monomer composition. It is preferable to select an organic solvent that has a lower solubility in water than the organic monomer. Moreover, when the polymerizable monomer contains an acrylic monomer and a hydrocarbon monomer, it is preferable to use a chain hydrocarbon solvent as the hydrophobic solvent.
  • a chain hydrocarbon solvent a chain hydrocarbon solvent having 5 to 8 carbon atoms is preferred, and at least one selected from the group consisting of pentane, hexane, heptane and octane is more preferred.
  • the polymerizable monomer contains an acrylic monomer and does not contain a hydrocarbon monomer
  • a hydrocarbon solvent having 4 to 7 carbon atoms as the hydrophobic solvent.
  • a hydrocarbon-based solvent having 5 to 7 carbon atoms it is more preferable to use a hydrocarbon-based solvent having 5 to 7 carbon atoms.
  • the hydrocarbon-based solvent may be either an aromatic hydrocarbon or an aliphatic hydrocarbon, preferably an aliphatic hydrocarbon, more preferably a cyclic hydrocarbon-based solvent, At least one selected from the group consisting of cyclohexane, cycloheptane and methylcyclohexane is more preferred.
  • the pressure resistance of the hollow particles can be easily improved.
  • a combination of a polymerizable monomer containing an acrylic monomer and a hydrocarbon monomer and the above-described preferred hydrophobic solvent is used, the uniformity of the shell is improved, and the pressure resistance of the hollow particles is reduced. It is preferable because it improves the properties.
  • 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 2.5 or less at 20° C., more preferably 2.0 or less.
  • the relative dielectric constant is one of the indices that indicate the degree of polarity of a compound.
  • phase separation proceeds rapidly in droplets of the monomer composition, and hollow portions 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), Cyclohexane (2.0).
  • 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 polymerizable 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 70 parts by mass or more and 300 parts by mass or less, and even more preferably 90 parts by mass or more and 200 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, Azo compounds such as 2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) and the like can be mentioned.
  • the content of the 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. 1 to 5 parts by mass.
  • the content of the polymerization initiator is at least the above lower limit value, the polymerization reaction can proceed sufficiently, and when it is at most the above upper limit value, there is little possibility that the oil-soluble polymerization initiator will remain after the polymerization reaction is completed. There is also little possibility that undesired side reactions 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 resulting hollow particles can be narrowed, and the strength of the hollow particles is improved by suppressing the shell from becoming too thin. 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.
  • water-insoluble inorganic dispersion stabilizers are preferred, and water-insoluble metal salts such as the above-mentioned sulfates, carbonates, phosphates, and metal hydroxides are more preferred. is more preferred, and magnesium hydroxide is particularly preferred.
  • poor water solubility means that the solubility in 100 g of water is preferably 0.5 g or less.
  • the poorly water-soluble inorganic dispersion stabilizer is dispersed in an aqueous medium in the form of colloidal particles, that is, the colloidal dispersion containing the poorly water-soluble inorganic dispersion stabilizer colloidal particles. It is preferable to use it in the state As a result, the particle size distribution of the droplets of the monomer composition can be narrowed, and the residual amount of the inorganic dispersion stabilizer in the resulting hollow particles can be easily reduced by washing.
  • 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.
  • 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 examples include polyvinyl alcohol, polycarboxylic acids (polyacrylic acid, etc.), celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, etc.), polyvinylpyrrolidone, polyacrylimide, polyethylene oxide. , poly(hydroxystearic acid-g-methyl methacrylate-co-methacrylic acid) copolymer and the like.
  • inorganic water-soluble polymer compounds include sodium tripolyphosphate.
  • 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 to 10 parts by mass, with respect to 100 parts by mass of the total mass of the polymerizable monomer and the hydrophobic solvent. is.
  • 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 preferably 0.5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect 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.
  • 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. Examples of hydrophilic solvents include alcohols such as methanol and ethanol; tetrahydrofuran (THF); dimethylsulfoxide (DMSO) and the like.
  • the content of the aqueous medium is not particularly limited, but from the viewpoint of keeping the particle diameter and porosity of the hollow particles within the preferable ranges described later, the lower limit is is preferably 200 parts by mass or more, more preferably 400 parts by mass or more, still more preferably 600 parts by mass or more, and the upper limit is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less.
  • 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.
  • a mixed solution can be obtained by mixing each of the above materials and, if necessary, other materials, and appropriately stirring the mixture.
  • the oil phase containing lipophilic materials such as (A) the polymerizable monomer, (B) the hydrophobic solvent and (C) the polymerization initiator, (D) the dispersion stabilizer and (E)
  • the particles are dispersed with a particle size of about several millimeters.
  • the mixed solution preparation step 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.
  • the 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 above-mentioned mixture.
  • a suspending method for forming droplets of the monomer composition is not particularly limited, and a known suspending method can be employed.
  • Dispersers used in preparing the suspension include, for example, Milder (: product name) manufactured by Pacific Machinery Co., Ltd., Cavitron (: product name) manufactured by Eurotech Co., Ltd., and Inline manufactured by IKA. Horizontal or vertical in-line dispersers such as dispersers (eg, DISPAX-REACTOR (registered trademark) DRS (: product name)); emulsifying dispersers such as homomixer MARK II series manufactured by Primix Corporation;
  • droplets of the monomer composition containing the lipophilic material and having a particle size of about 5 to 40 ⁇ 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 suspension obtained by the suspension step described above is subjected to a polymerization reaction to have a hollow portion surrounded by a shell containing a resin, and a hydrophobic solvent in the hollow portion.
  • the precursor particles are formed by polymerizing the polymerizable monomers contained in the droplets of the monomer composition, and the shells of the precursor particles contain the polymer of the polymerizable monomers as a resin.
  • the polymerization system there is no particular limitation on the polymerization system, 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 polymerization reaction time is preferably 1 to 48 hours, more preferably 4 to 36 hours.
  • a polymerizable monomer may be further added during the polymerization reaction of the polymerizable monomer in the suspension to carry out the polymerization reaction.
  • the pressure resistance of the hollow particles can be improved by carrying out the polymerization reaction in two stages in the polymerization process.
  • 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.
  • Solid-liquid separation methods include, for example, centrifugation, filtration, static separation, etc. Among these, 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 solvent removal step described below. Examples of 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.
  • 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, the heating temperature may be, for example, 50 to 200°C, 70 to 200°C, or 100 to 200°C, depending on the composition of the shell in the precursor particles and the type of hydrophobic solvent. 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 slurry of hollow particles containing an inert gas 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 method for obtaining hollow particles in which the hollow portions are filled with gas by removing the hydrophobic solvent in the precursor particles in the air after solid-liquid separation of the slurry-like precursor composition In 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 remaining in the hollow particles is removed in the air, so that the hollow parts are gaseous.
  • 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 residual amount of the 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 under 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. , particularly sulfuric acid, are 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 particles of the present disclosure contain the above polymerizable monomer polymer as a main component of the shell, and the polymer forms the skeleton of the shell of the hollow particles.
  • the polymer contained in the shell preferably contains a crosslinkable monomer unit in order to improve pressure resistance.
  • the content of the crosslinkable monomer units in 100 parts by mass of the total monomer units of the polymer is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and still more preferably 70 parts by mass or more, Even more preferably, it is 80 parts by mass or more.
  • the polymer may contain a non-crosslinkable monomer unit within a range that does not impair the effects of the present disclosure. In that case, the content of the crosslinkable monomer unit is For example, it may be 95 parts by mass or less, or may be 90 parts by mass or less in 100 parts by mass of the total monomer units.
  • the polymer contained in the shell contains trifunctional or higher crosslinkable monomer units.
  • the content of trifunctional or higher crosslinkable monomer units is preferably 10 parts by mass or more, more preferably 20 parts by mass or more as a lower limit,
  • the upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
  • the polymer contained in the shell preferably contains a bifunctional crosslinkable monomer unit and a trifunctional or higher crosslinkable monomer unit.
  • the polymer contains a bifunctional crosslinkable monomer unit and a trifunctional or higher crosslinkable monomer unit
  • the bifunctional crosslinkable monomer unit and the trifunctional or higher crosslinkable monomer unit of the total 100 parts by mass the content of trifunctional or higher crosslinkable monomer units is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more, while preferably is 50 parts by mass or less, more preferably 40 parts by mass or less.
  • a crosslinkable monomer unit derived from a bifunctional crosslinkable monomer may be referred to as a "bifunctional crosslinkable monomer unit".
  • a crosslinkable monomeric unit derived from a polymer may be referred to as a "trifunctional or higher crosslinkable monomeric unit”.
  • the polymer contained in the shell preferably contains an acrylic monomer unit because the uniformity of the shell is likely to be improved.
  • the content of acrylic monomer units is not particularly limited, but is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, based on 100% by mass of the total monomer units.
  • the uniformity of the shell is likely to be improved, and the pressure resistance is improved. Therefore, the polymer contained in the shell contains an acrylic monomer unit and a hydrocarbon monomer unit. is preferred.
  • the total content of acrylic monomer units and hydrocarbon monomer units in 100 parts by mass of the total monomer units of the polymer is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and still more preferably is 98 parts by mass or more, more preferably 99 parts by mass or more.
  • the acrylic monomer unit and the hydrocarbon monomer In a total of 100 parts by mass of the units, the content of the hydrocarbon monomer unit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, and the upper limit is is preferably 90 parts by mass or less, more preferably 80 parts by mass or less.
  • the content of the polymer of the polymerizable monomer is preferably 96% by mass or more, more preferably 97% by mass or more, based on 100% by mass of the total solid content of the shell.
  • the content of the polymer is preferably 4% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the total solid content of the shell. is.
  • Components other than the polymer contained in the hollow particles of the present disclosure include, for example, a polymerizable monomer that remains unreacted, a polymer that is different from the polymer of the polymerizable monomer, and a polymer that initiates polymerization.
  • Examples include decomposition products of agents, low-molecular-weight compounds contained as impurities in raw materials of polymerizable monomers, and the like. Those with low boiling points (eg, boiling points of 200° C. or lower) are usually removed during the manufacturing process of hollow particles, but those with high boiling points (eg, boiling points of 250° C. or higher) may remain without being removed.
  • the hollow particles of the present disclosure have a porosity of 50% or more, preferably 60% or more, more preferably 65% or more.
  • the porosity is at least the above lower limit, the hollow particles are also excellent in lightness, heat insulation, dielectric properties, and the like.
  • the upper limit of the porosity of the hollow particles is not particularly limited, it is preferably 90% or less, more preferably 85% or less, and still more preferably 80% or less from the viewpoint of suppressing a decrease in pressure resistance of the hollow particles.
  • 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 with 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.
  • Formula (II): 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 volume average particle diameter of the hollow particles of the present disclosure is preferably 5.0 ⁇ m or more, more preferably 6.0 ⁇ m or more, still more preferably 7.0 ⁇ m or more as a lower limit, and preferably 40.0 ⁇ m as an upper limit. Below, more preferably 30.0 ⁇ m or less, still more preferably 20.0 ⁇ m or less.
  • the volume average particle diameter of the hollow particles is at least the above lower limit, it is easy to achieve both a high porosity and excellent pressure resistance, and the cohesion between the hollow particles becomes small, so that excellent dispersibility can be exhibited. can be done.
  • the volume average particle diameter of the hollow particles is equal to or less than the above upper limit, the uniformity of the shell is likely to be improved, so that hollow particles having excellent pressure resistance are likely to be obtained.
  • the particle size of the hollow particles of the present disclosure can be adjusted, for example, by adjusting the content of the dispersion stabilizer with respect to the total mass of the polymerizable monomer and the hydrophobic solvent.
  • the thickness of the shell of the hollow particles of the present disclosure is not particularly limited, but from the viewpoint of improving pressure resistance, it is preferably 0.30 ⁇ m or more, more preferably 0.40 ⁇ m or more, still more preferably 0.50 ⁇ m or more, and more preferably 0.50 ⁇ m or more. More preferably, it is 0.60 ⁇ m or more, and from the viewpoint of increasing the porosity, it is preferably 3.00 ⁇ m or less, more preferably 2.00 ⁇ m or less, and still more preferably 1.50 ⁇ m or less.
  • the thickness of the shell of the hollow particles is obtained by calculating the inner diameter r of the hollow particles by the following formula (1) using the volume average particle diameter R and the porosity of the hollow particles, and calculating the inner diameter r and the volume average It is a value calculated by the following formula (2) using the particle size R.
  • Formula (1): 4/3 ⁇ (R/2) 3 ⁇ (porosity/100) 4/3 ⁇ (r/2) 3
  • Shell thickness (R-r)/2
  • the porosity in said Formula (1) is a numerical value represented by percentage.
  • 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 having little variation in compressive strength characteristics and heat resistance among particles can be obtained. In addition, when the particle size distribution is 2.5 or less, for example, when manufacturing a sheet-like compact to which the hollow particles of the present disclosure are added, 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.
  • 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 manufacture, pressure resistance, and the like.
  • the hollow particles of the present disclosure may have one or more hollow parts, but from the viewpoint of maintaining a good balance between high porosity and mechanical strength, those having only one hollow part preferable.
  • the proportion of particles having only one or two hollow portions is preferably 90% by mass or more, more preferably 95% by mass or more.
  • the proportion of particles having only one hollow portion is preferably 90% by mass or more, more preferably 95% by mass or more.
  • the shell provided in the hollow particle of the present disclosure and the partition walls separating adjacent hollow portions when the hollow particles have two or more hollow portions may be porous, but from the viewpoint of improving pressure resistance, , preferably solid.
  • 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 hollow particles 10 in FIG. 1(5).
  • 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 hollow particles of the present disclosure preferably have a small percentage of particles with a degree of circularity of 0.85 or less.
  • Particles with a circularity of 0.85 or less are typically particles with deformation such as dents or cracks, and are sometimes referred to as "irregularly shaped particles" in the present disclosure.
  • Such irregular-shaped particles are inferior to spherical particles in pressure resistance due to the fact that external pressure is likely to be applied locally.
  • irregularly shaped particles tend to agglomerate when dispersed in a binder resin as compared to spherical particles, resulting in poor dispersibility.
  • the hollow particles of the present disclosure may contain, as an impurity, a small amount of particles with a low degree of circularity in which particle cracking, deformation, etc. have occurred, but the degree of circularity is 0.85 or less in 100% by mass of the hollow particles of the present disclosure.
  • Circularity is defined as the value obtained by dividing the diameter of a circle having the same area as the projected image of the particle (equivalent circle diameter) by the diameter of the circle having the same perimeter as the projected image of the particle (equivalent perimeter diameter). be done. If the particle is a perfect sphere, the circularity is 1, and the more complicated the surface shape of the particle, the smaller the circularity. In the present disclosure, circularity is measured using a flow particle image measurement device with an image resolution of 0.185 ⁇ m/pixel.
  • IF-3200 (trade name) manufactured by Jusco International Co., Ltd.
  • IF-3200 trade name
  • a mixture of 0.10 to 0.12 g of hollow particles in an aqueous solution (concentration of 0.3%) of sodium linear alkylbenzene sulfonate is dispersed with an ultrasonic cleaner for 5 minutes.
  • the average circularity is the average circularity of 1000 to 3000 arbitrarily selected particles.
  • the hollow particles of the present disclosure preferably have a thermal decomposition initiation temperature of 150 to 400°C, more preferably 200 to 350°C. Hollow particles having a thermal decomposition initiation temperature within the above range are excellent in heat resistance.
  • the thermal decomposition start temperature of the hollow particles is the temperature at which the weight is reduced by 5%, under the conditions of an air atmosphere, an air flow rate of 230 mL / min, and a heating rate of 10 ° C. / min. can be measured by
  • the hollow particles of the present disclosure have excellent pressure resistance, they are not easily crushed during kneading with other materials and during molding after kneading. Since it has excellent effects as a material, etc., it is suitable as an additive for molded articles, and for example, it is suitably used as an additive for molded articles made of resin. In addition, the hollow particles of the present disclosure are not easily crushed even through processes such as kneading and injection molding that apply external pressure, and the porosity is difficult to decrease. It is preferably used.
  • the molded article containing the hollow particles of the present disclosure includes resins such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, epoxy resins, acrylonitrile-butadiene-styrene (ABS) resins, acrylonitrile-styrene (AS) resins, Poly(meth)acrylate, polycarbonate, polyamide, polyimide, polyphenylene ether, polyphenylene sulfide, polyester, polytetrafluoroethylene, maleimide resin, bismaleimide triazine resin, liquid crystalline polyester resin, phenol resin, vinyl ester resin, unsaturated polyester resin, Thermoplastic resins such as cyanate ester resins, polyether ketone ketone resins, polyetherimide resins, polyphenylene oxide resins, melamine resins, urea resins, silicon resins, alkyd resins, benzoxazine resins, allyl resins, aniline
  • the molded article containing the hollow particles of the present disclosure may contain a thermoplastic elastomer as the resin.
  • thermoplastic elastomer thermoplastic elastic polymers conventionally used as molding resins can be used. Examples include urethane-based elastomers, styrene-based elastomers, olefin-based elastomers, amide-based elastomers and ester-based elastomers.
  • thermoplastic elastomer generally exhibits rubber elasticity at room temperature (25° C.) and has the property of being plasticized and moldable at high temperatures.
  • the molded body containing the hollow particles of the present disclosure is not limited to a resin molded body, and may be, for example, a rubber molded body, or may contain a mixture of resin and rubber.
  • Molded articles containing hollow particles of the present disclosure include, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber.
  • the molded article containing the hollow particles of the present disclosure may further contain organic or inorganic fibers such as carbon fibers, glass fibers, aramid fibers, and polyethylene fibers.
  • the hollow particles of the present disclosure are molded bodies formed using thermoplastic or thermosetting resins or rubber, and thermoplastic or thermosetting resins, or materials containing rubber and fibers.
  • the resin molded article or rubber molded article containing the hollow particles of the present disclosure can also be contained as a filler in a molded article formed by Applications of the resin molded article or rubber molded article containing the hollow particles of the present disclosure include, for example, light reflecting materials, heat insulating materials, and sound insulating materials used in various fields such as automobiles, electricity, electronics, construction, aviation, and space. Materials and members such as low dielectric materials, food containers, sports shoes, footwear such as sandals, home appliance parts, bicycle parts, stationery, tools, filaments for 3D printers, and the like.
  • the hollow particles of the present disclosure are excellent in dielectric properties, they are also useful as an additive to insulating resin sheets used for manufacturing electronic components such as printed wiring boards.
  • the insulating resin sheet containing the hollow particles of the present disclosure is prepared by mixing the above-described thermoplastic resin, thermosetting resin, thermoplastic elastomer, or mixture thereof with the hollow particles of the present disclosure. , the composition can be coated and dried on one or both sides of a sheet-like substrate, extruded, or formed into a sheet by transfer or the like.
  • the resin or elastomer contained in the insulating resin sheet has adhesive properties
  • the insulating resin sheet can be used as an adhesive sheet, specifically, for example, as a bonding sheet.
  • a bonding sheet is an insulating adhesive layer-forming material used for bonding a conductor layer and an organic insulating layer when manufacturing a multilayer printed wiring board.
  • 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 hollow particles of the present disclosure are also suitable for use as a rust inhibitor.
  • the hollow particles of the present disclosure are also useful as an additive that reduces electrical conductivity. It can be used as a paint (paint base, lubricating paint, etc.).
  • the hollow particles added to the antirust paint can contain an antirust additive.
  • Example 1 (1) Mixed Solution Preparation Step First, the following materials were mixed to form an oil phase. Ethylene glycol dimethacrylate 25 parts Trimethylolpropane trimethacrylate 30 parts Divinylbenzene 26 parts Ethylvinylbenzene 19 parts 2,2'-azobis (2,4-dimethylvaleronitrile) (oil-soluble polymerization initiator) 3 parts Hydrophobic solvent: Hexane 100 parts
  • a stirring tank at room temperature, an aqueous solution prepared by dissolving 17.1 parts of magnesium chloride (water-soluble polyvalent metal salt) in 494 parts of ion-exchanged water, sodium hydroxide ( An aqueous solution of 12.1 parts of alkali metal hydroxide) was gradually added with stirring to prepare a magnesium hydroxide colloid (poorly water-soluble metal hydroxide colloid) dispersion (4 parts of magnesium hydroxide). , as the aqueous phase. A mixture was prepared by mixing the obtained
  • Solvent removal step The precursor particles obtained in the solid-liquid separation step are heat-treated in a vacuum dryer at 200 ° C. under nitrogen atmosphere for 12 hours to remove the hydrophobicity contained in the particles. After removing the solvent, hollow particles of Example 1 were obtained. 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, the hollow particles of Example 2 were obtained in the same procedure as in Example 1, except that the amount of hexane added was changed as shown in Table 1 in the above "(1) mixed solution preparation step". rice field.
  • Example 3-4 In Example 1, the same procedure as in Example 1 was performed except that the type and amount of the polymerizable monomer added were changed as shown in Table 1 in the above "(1) mixed liquid preparation step”. 3-4 hollow particles were obtained.
  • Example 5 In Example 1, in the above “(1) Mixed solution preparation step", the amount of magnesium chloride and sodium hydroxide added was adjusted to 10 parts of magnesium hydroxide in the aqueous phase (magnesium hydroxide colloidal dispersion). Hollow particles of Example 5 were obtained in the same procedure as in Example 1, except that the procedure was changed.
  • Example 6 In Example 1, the same procedure as in Example 1 was performed, except that the total amount of ion-exchanged water in the aqueous phase was changed to 780 parts in the above "(1) mixed solution preparation step". Hollow particles of Example 6 were obtained.
  • Example 7-8 In Example 1, in the above "(1) mixture preparation step", the type and amount of the polymerizable monomer and the type and amount of the hydrophobic solvent were changed as shown in Table 1. Hollow particles of Examples 7 and 8 were obtained in the same procedure as in Example 1.
  • the above mixture is stirred and suspended at a rotation speed of 15,000 rpm with an in-line emulsifying disperser (manufactured by Taihei Kiko Co., Ltd., product name: Milder), and a polymerizable monomer containing a hydrophobic solvent is suspended.
  • a suspension of body droplets in water was prepared.
  • the suspension was stirred for 4 hours at a temperature of 65° C. in a nitrogen atmosphere to carry out a polymerization reaction, thereby obtaining a precursor composition containing precursor particles encapsulating a hydrophobic solvent.
  • the precursor composition was bubbled with 2 L/min of nitrogen for 4 hours at a temperature of 75° C.
  • Example 2 In Example 1, the above “(1) mixture preparation step” was changed as follows, the polymerization reaction time was changed to 4 hours in the above "(3) polymerization step", and the above “(5) solvent Hollow particles of Comparative Example 2 were obtained in the same procedure as in Example 1, except that the heat treatment time in the removal step was changed to 6 hours.
  • the mixture preparation step was performed as follows. First, a mixture obtained by mixing the following materials was used as an oil phase.
  • Ethylene glycol dimethacrylate 100 parts Polar resin (MMA / AA / EA copolymer) 2 parts 2,2'-azobis (2,4-dimethylvaleronitrile) (oil-soluble polymerization initiator) 3 parts Hydrophobic solvent: Cyclohexane 207
  • an aqueous solution of 7.8 parts of magnesium chloride (water-soluble polyvalent metal salt) dissolved in 225 parts of ion-exchanged water, 55 parts of ion-exchanged water and sodium hydroxide (hydroxide Alkali metal) 5.5 parts dissolved in the aqueous solution is gradually added with stirring to prepare a magnesium hydroxide colloid (poorly water-soluble metal hydroxide colloid) dispersion (4 parts of magnesium hydroxide). phased.
  • a mixture was prepared by mixing the obtained aqueous phase and oil phase.
  • Comparative Example 3 In Comparative Example 2, in the above "(1) mixed liquid preparation step", the amount of cyclohexane added was changed to 187 parts, and the total amount of ion-exchanged water in the aqueous phase was changed to 615 parts. , in the same procedure as in Comparative Example 2, to obtain hollow particles of Comparative Example 3.
  • the polar resin (MMA/AA/EA copolymer) used in Comparative Examples 2 and 3 was synthesized by the following procedure. 200 parts of toluene was introduced into the reaction vessel, and the inside of the reaction vessel was sufficiently replaced with nitrogen while stirring the toluene. AA) 0.3 parts, ethyl acrylate (EA) 3.5 parts, and t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perbutyl O) 2.8 parts mixed solution was added dropwise into the reaction vessel over a period of 2 hours. Furthermore, the polymerization was completed by keeping the toluene reflux for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polar resin (MMA/AA/EA copolymer, number average molecular weight 10000). .
  • volume average Particle Size of Hollow Particles The volume average particle size of hollow particles was measured using a particle size distribution analyzer (manufactured by Beckman Coulter, product name: Multisizer 4e). The measurement conditions were as follows: aperture diameter: 50 ⁇ m, dispersion medium: Isoton II (product name), concentration: 10%, number of measured particles: 100,000. Specifically, 0.2 g of a particle sample was placed in a beaker, and an aqueous surfactant solution (manufactured by Fuji Film Co., Ltd., product name: Drywell) was added therein as a dispersant.
  • aqueous surfactant solution manufactured by Fuji Film Co., Ltd., product name: Drywell
  • Density and porosity of hollow particles 2-1. Measurement of Apparent Density of Hollow Particles First, about 30 cm 3 of hollow particles were filled into a volumetric flask with a capacity of 100 cm 3 , and the mass of the filled hollow particles was accurately weighed. Next, the hollow particle-filled volumetric flask was filled with isopropanol exactly to the marked line, taking care not to introduce air bubbles. The mass of isopropanol added to the volumetric flask was accurately weighed, and the apparent density D 1 (g/cm 3 ) of the hollow particles was calculated based on the above formula (I).
  • Shell thickness of hollow particles Calculate the inner diameter r of the hollow particles from the above formula (1) using the volume average particle diameter R and the porosity of the hollow particles, and use the inner diameter r and the volume average particle diameter R to calculate the above formula ( 2), the shell thickness of the hollow particles was calculated.
  • the mold filled with the stirred mixture was placed in a hot press (manufactured by AS ONE, model number: H300-15) set at 80°C, and a cylinder at 80°C was placed in the mold and allowed to stand.
  • a press pressure of 60 MPa (cylinder pressure of the press machine was 4 MPa) was applied to obtain a disk-shaped compact with a diameter of 14 mm and a thickness of 8 mm.
  • the obtained disk-shaped molded body was taken out from the mold and pressed at a pressure of 1 MPa or less using a press machine at 200° C. to form a sheet having a thickness of 0.3 mm to obtain a sheet-shaped molded body.
  • the void residual ratio of the hollow particles contained in the obtained sheet-like compact was calculated by the following formula (A), and was defined as the void residual ratio after the press test.
  • Formula (A): Void residual rate (%) ⁇ (ca) / (cb) ⁇ ⁇ 100
  • a is the specific gravity of the molded body
  • b is the specific gravity of the molded body assuming that the voids are maintained (calculated value)
  • c is the specific gravity of the molded body that is assumed to have all the hollow particles crushed (calculated value ) respectively.
  • the specific gravity (a in the above formula (A)) of the sheet-like molded body used for calculating the residual void ratio was measured by the water substitution method according to JIS K 7112.
  • the specific gravity (b in the above formula (A)) of the molded body assuming that the voids were maintained was calculated by the following formula (B).
  • Formula (B): b 1/ ⁇ ( PA / PG )+( RA / RG ) ⁇
  • PA is the amount of hollow particles added
  • PG is the specific gravity of the hollow particles (apparent density D 1 )
  • RA is the amount of polypropylene resin added
  • RG is the specific gravity of the polypropylene resin.
  • the specific gravity (c in the above formula (A)) of the compact assuming that all the hollow particles were crushed was calculated by the following formula (C).
  • Formula (C): c [R G ⁇ R A + ⁇ D 0 ⁇ P A ⁇ (1 ⁇ P V /100) ⁇ ]/ ⁇ R A +P A ⁇ (1 ⁇ P V /100) ⁇
  • RA is the added amount of the polypropylene resin
  • RG is the specific gravity of the polypropylene resin
  • D0 is the true density D0 of the hollow particles
  • PA is the added amount of the hollow particles
  • PV is the amount of the hollow particles.
  • Void residual ratio after injection molding 10 parts of hollow particles and 90 parts of polypropylene resin (manufactured by Nippon Polypro Co., Ltd., product name: Novatec PP, grade: MA1B (MFR at 230 ° C.: 21 g / min)) are mixed in a blender. Then, the mixture was kneaded under the following kneading conditions using a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., product name: TEM-35B), extruded, and pelletized to obtain pellets of the resin composition.
  • a twin-screw kneader manufactured by Toshiba Machine Co., Ltd., product name: TEM-35B
  • the obtained pellets of the resin composition are dried by heating at 80° C. for 6 hours, and then molded to a size of 80 mm ⁇ 10 mm ⁇ thickness 4 mm using an injection molding machine under the following molding conditions. got a body ⁇ Molding conditions> Cylinder temperature: 200°C Mold temperature: 70°C Injection pressure: 70MPa Holding pressure: 30MPa
  • the residual void ratio of the hollow particles contained in the molding obtained by injection molding was calculated by the above formula (A).
  • the specific gravity (a in the above formula (A)) of the molding obtained by injection molding was measured by the water substitution method in accordance with JIS K 7112.
  • the specific gravity of the molded body assuming that the voids were maintained (b in the above formula (A)) and the specific gravity of the molded body assuming that all the hollow particles were crushed (c in the above formula (A)) are The same values as those used to calculate the post-test void residual ratio were used.
  • Table 1 shows the amount of each material added (parts by mass) and the results of each measurement or evaluation.
  • the variation coefficient of the residual void ratio after the press test was 0.006 or less. This indicates that the press test method is a highly accurate test method.
  • the hollow particles obtained in Comparative Examples 1 to 3 had a low void retention rate after the press test, were inferior in pressure resistance, and had a low void retention rate after injection molding.
  • Comparative Examples 1 and 2 due to the composition of the polymerizable monomers used, a shell with excellent strength was not formed, and the thickness of the shell was thin. .
  • Comparative Example 3 the same polymerizable monomer as in Comparative Example 2 was used and the shell thickness was set to the same extent as in the Examples. was inferior. From this, it can be seen that in order to sufficiently improve the pressure resistance of the hollow particles, it is necessary to adjust not only the shell thickness but also the composition of the polymerizable monomers used for forming the shell.
  • the hollow particles obtained in each example are spherical particles having a hollow portion, and while having a high porosity of 50% or more, the void retention rate after the press test is as high as 80% or more. It had excellent elasticity and a high void retention rate after injection molding.
  • the composition of the polymerizable monomer used for forming the shell by adjusting the composition of the polymerizable monomer used for forming the shell, the type of hydrophobic solvent to be included in the particles during the production process, the particle diameter of the hollow particles, etc., hollow particles with excellent pressure resistance were obtained. presumed to have been obtained.
  • the hollow particles obtained in Examples 1 to 6 had a high residual void ratio after the press test and a high residual void ratio after injection molding, and were particularly excellent in pressure resistance.
  • Examples 1 to 6 a combination of an acrylic monomer and a hydrocarbon monomer was used as the polymerizable monomer, and a chain hydrocarbon solvent was used as the hydrophobic solvent, thereby improving the uniformity of the shell. As a result, it is presumed that pressure resistance was improved.
  • the proportion of particles with a circularity of 0.85 or less was 10% by mass or less, The proportion of particles having only one or two hollow portions was 90% by mass or more.

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WO2025094928A1 (ja) * 2023-10-31 2025-05-08 日本ゼオン株式会社 中空粒子、中空粒子の製造方法、塗料組成物、及び塗装物品
JP7784595B1 (ja) * 2024-09-10 2025-12-11 積水化成品工業株式会社 中空樹脂粒子、その製造方法、およびその用途

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WO2021112110A1 (ja) 2019-12-06 2021-06-10 日本ゼオン株式会社 中空粒子、樹脂組成物及び成形体
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WO2025094928A1 (ja) * 2023-10-31 2025-05-08 日本ゼオン株式会社 中空粒子、中空粒子の製造方法、塗料組成物、及び塗装物品
JP7784595B1 (ja) * 2024-09-10 2025-12-11 積水化成品工業株式会社 中空樹脂粒子、その製造方法、およびその用途

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