WO2010070987A1 - Procédé de fabrication de microsphères creuses et procédé de fabrication de céramique moulée poreuse - Google Patents

Procédé de fabrication de microsphères creuses et procédé de fabrication de céramique moulée poreuse Download PDF

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WO2010070987A1
WO2010070987A1 PCT/JP2009/068869 JP2009068869W WO2010070987A1 WO 2010070987 A1 WO2010070987 A1 WO 2010070987A1 JP 2009068869 W JP2009068869 W JP 2009068869W WO 2010070987 A1 WO2010070987 A1 WO 2010070987A1
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solid material
thermally expandable
outer shell
microspheres
dispersion medium
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PCT/JP2009/068869
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Japanese (ja)
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江尻哲男
佐竹義克
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株式会社クレハ
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Priority to JP2010542918A priority Critical patent/JP5588880B2/ja
Priority to KR1020117016118A priority patent/KR101278410B1/ko
Priority to CN200980150780.5A priority patent/CN102256695B/zh
Publication of WO2010070987A1 publication Critical patent/WO2010070987A1/fr

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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
    • B01J13/18—In situ polymerisation with all reactants being present in the same 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
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/08—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons
    • C04B16/085—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons expanded in situ, i.e. during or after mixing the mortar, concrete or artificial stone ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0016—Granular materials, e.g. microballoons
    • C04B20/002—Hollow or porous granular materials
    • C04B20/0024—Hollow or porous granular materials expanded in situ, i.e. the material is expanded or made hollow after primary shaping of the mortar, concrete or artificial stone mixture
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
    • C04B38/062—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles the burned-out substance being formed in situ, e.g. by polymerisation of a prepolymer composition containing ceramic powder
    • C04B38/0625—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles the burned-out substance being formed in situ, e.g. by polymerisation of a prepolymer composition containing ceramic powder involving a foaming step of the burnable material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms

Definitions

  • the present invention relates to a method for producing hollow microspheres in which solid materials such as fine particles and fine fibers are firmly attached to the outer shell surface. Moreover, this invention relates to the manufacturing method of the porous ceramics molded object used as a porous formation agent of this hollow microsphere.
  • the thermally expandable microsphere has a microcapsule structure in which a foaming agent capable of gasification or gas generation is enclosed in an outer shell formed of a thermoplastic resin.
  • Thermally expandable microspheres are also referred to as thermally foamable microspheres or thermally expandable microcapsules.
  • the heat-expandable microsphere is heated to a temperature equal to or higher than the softening point of the thermoplastic resin forming the outer shell, the heat-expandable microsphere is thermally expanded by gasification of the foaming agent itself or pyrolysis gas of the foaming agent.
  • Hollow microspheres which are hollow body particles, are formed by thermal expansion of the thermally expandable microspheres.
  • Thermal expansion due to heating of thermally expandable microspheres is generally called heating foaming or foaming.
  • Thermally expandable microspheres form hollow microspheres as independent foam particles after foaming.
  • expandable polystyrene particles impregnated with a liquid foaming agent are filled into a mold and heated and foamed to form a foam molded body having a predetermined shape in which the foam particles are fused and integrated. It is formed and is not a thermally expandable microsphere.
  • Hollow microspheres are also called plastic balloons or plastic hollow beads. Thermally expandable microspheres can form hollow microspheres with a low specific gravity by thermal expansion. Therefore, the heat-expandable microsphere is added to various base materials such as ink, paint, and plastic for the purpose of weight reduction and designability.
  • thermally expandable microspheres As the application field of thermally expandable microspheres expands and higher performance is required in each application field, the required level for thermally expandable microspheres is also increasing.
  • One of the required properties for the thermally expandable microspheres is that there is little aggregation due to fusion between the foam particles during and after heat foaming, and furthermore, there is almost no aggregation.
  • Thermally expandable microspheres are not only foamed but are often blended in a foamed state as well as blended with substrates such as inks, paints and plastics.
  • Foam particles (hollow microspheres) in which thermally expandable microspheres are foamed are extremely lightweight. For example, when they are contained in a paint, the object to be coated can be reduced in weight. However, if the foam particles are aggregated, mixing with a substrate such as a paint becomes difficult, and further, the foam particles may be destroyed during the mixing.
  • a porous ceramic molded body is formed by molding a mixture containing a ceramic raw material and a porous forming agent into a molded body having a predetermined shape, Next, the molded body is manufactured by a method of firing.
  • thermally expandable microsphere foam particles (hollow microspheres) as a porous forming agent, it is possible to obtain a porous ceramic molded body having a desired porous structure corresponding to the size of the foam particles. it can.
  • the low specific gravity hollow microspheres that are the foam particles and the high specific gravity ceramic raw material that is the inorganic material are too difficult to uniformly disperse because the specific gravity difference is too large. Therefore, when hollow microspheres are used as the porous forming agent, it is difficult to obtain a porous ceramic molded body having a uniform porous structure.
  • the porous ceramic molded body is used for, for example, a diesel particulate filter (DPF) for reducing particulate matter contained in exhaust gas of a diesel engine, but the porous structure is not uniform. And sufficient performance as a filter cannot be demonstrated.
  • DPF diesel particulate filter
  • the amount of the dispersion stabilizer such as colloidal silica is increased, the amount of inorganic fine particles attached to the outer shell surface of the thermally expandable microsphere can be increased, and the specific gravity can be increased to some extent.
  • this method does not solve the problem of desorption of inorganic fine particles in the cleaning process and the subsequent processing process.
  • the amount of inorganic fine particles attached to the outer shell surface of the thermally expandable microsphere is increased by such a method, the average particle size of the obtained thermally expandable microsphere is decreased and the particle size distribution is increased. Occurs.
  • Patent Document 2 discloses the presence of an organosilicon compound having a reactive group capable of polymerizing a polymerizable mixture containing a polymerizable monomer and a foaming agent in an aqueous dispersion medium.
  • a method for producing thermally expandable microspheres by suspension polymerization below has been proposed.
  • various solid fine particles such as colloidal silica can be attached to the outer shell surface of the thermally expandable microsphere by the action of the organosilicon compound. This method requires the use of an expensive organosilicon compound, and it is difficult to strongly adhere a large amount of solid fine particles with high specific gravity to the outer shell surface of the foam particles after foaming.
  • Patent Document 3 discloses thermally expandable microspheres and solid fine particles. And a method for producing thermally expandable microspheres in which solid fine particles are adhered to the surface of the outer shell.
  • solid fine particles cannot be firmly attached to the outer shell surface of the thermally expandable microsphere, and the solid fine particles easily fall off in the subsequent processing steps.
  • Patent Document 6 JP-A-3-273037
  • Patent Document 6 a wet cake of thermally expandable microspheres is mixed with a granular or fibrous solid, dried until the water content is less than 1% by weight, and then heated and foamed. Is disclosed.
  • the method disclosed in Patent Document 6 is difficult to suppress aggregation and premature foaming of thermally expandable microspheres in the drying process.
  • Patent Document 7 proposes a method of attaching colloidal calcium carbonate together with a surface treatment agent or a dispersant to the surface of foam particles of thermally expandable microspheres. According to the method disclosed in Patent Document 7, although it is possible to suppress the foam particles from being scattered in the air, it is difficult to firmly attach the solid fine particles to the outer shell surface of the foam particles. is there.
  • Patent Document 8 describes a mixture of a thermally expandable microsphere aqueous dispersion and inorganic fine particles, followed by solid-liquid separation to form a cake, or solid-liquid separation followed by drying to obtain a powder.
  • a method has been proposed in which a thermally expandable microsphere is heated and expanded. According to the method disclosed in Patent Document 8, although scattering of the foam particles can be prevented, it is difficult to suppress aggregation and early foaming of the thermally expandable microspheres.
  • Patent Document 9 JP-A-2006-137926 discloses drying a hydrous cake of thermally expandable microspheres having an acrylic polymer outer shell obtained by using dispersion stabilizer particles such as colloidal silica. There has been proposed a method for producing hollow microspheres that is heated and expanded. Since the method disclosed in Patent Document 9 does not require a drying step, it is possible to suppress fusion and early foaming between the hollow microspheres and to mix the hollow microspheres with solid fine particles. And solid fine particles can be obtained. However, in order to heat and foam the water-containing cake, it is necessary to heat it under mechanical shearing using a powder mixer, so that the thermally expandable microspheres and hollow microspheres are likely to be fused or damaged.
  • An object of the present invention is that organic or inorganic fine particles, fine fibers, etc. are not required without requiring complicated operations and the use of expensive compounds, and without causing fusion or premature foaming between thermally expandable microspheres.
  • Another object of the present invention is to provide a method for producing hollow microspheres in which the solid material is firmly attached to the outer shell surface.
  • Another object of the present invention is to provide use of a hollow microsphere as a porous forming agent. More specifically, another object of the present invention is to provide a method for producing a porous ceramic molded body using the hollow microspheres obtained by the above method as a porous forming agent.
  • the present inventors have made a method in which thermally expandable microspheres and a solid material are dispersed in a liquid dispersion medium to form a slurry, and heated steam is blown into the slurry. It was found that when the thermally expandable microspheres were heated and foamed (thermally expanded), the solid material adhered firmly to the outer shell surface softened during the heating and foaming.
  • Hollow microspheres with various functions can be obtained by selecting the amount and type of solid material.
  • hollow microspheres in which a solid material having a high specific gravity is attached to the outer shell surface can be suitably used as a porous forming agent of a raw material for producing a porous ceramic molded body because the entire particle has a high specific gravity. .
  • the following steps 1 and 2 (1) Thermal expansion that has a microcapsule structure in which a foaming agent capable of gasification or gas generation is enclosed in an outer shell formed of a thermoplastic resin, and that thermally expands by heating to form hollow microspheres. And (2) preparing a slurry by dispersing a solid material having an average particle size or an average major axis smaller than the average particle size of the expandable microsphere and the average particle size of the thermally expandable microsphere in a liquid dispersion medium; The thermally expandable microspheres are heated in the slurry to soften the outer shell, and thermally expanded by gasification of the foaming agent or gas generated from the foaming agent, thereby softening the outer shell surface. Forming a hollow microsphere having the solid material attached thereto in step 2; A method for producing hollow microspheres having a solid material attached to the outer shell surface is provided.
  • the ceramic raw material and the porous forming agent are mixed to prepare a mixture; the step a; the mixture is formed into a predetermined shaped body b; and the shaped body is cured or fired.
  • the method for producing a porous ceramic formed body comprising the step c) hollow microspheres obtained by the above production method and having a solid material attached to the surface of the outer shell are used as the porous forming agent.
  • a method for producing a porous ceramic molded body is provided.
  • the thermally expandable microspheres that are freely dispersed in the slurry are foamed, fusion between the thermally expandable microspheres during foaming hardly occurs, and hollow microspheres obtained after foaming It is difficult to cause mutual fusion.
  • the solid material is adhered to the outer shell surface that softens during heating and foaming, the foam of the thermally expandable microsphere is not inhibited, and the solid material is firmly attached to the softened outer shell surface. Can be attached to.
  • the amount and type of the solid material adhered to the outer shell surface can be arbitrarily controlled.
  • the high-specific gravity inorganic fine particles Using high-specific gravity inorganic fine particles as a solid material, and thermally expanding the thermally expandable microspheres while uniformly dispersing each component by stirring the slurry, the high-specific gravity inorganic fine particles firmly adhere to the outer shell surface.
  • hollow microspheres having a high specific gravity of the entire particle can be obtained.
  • Hollow microspheres with increased specific gravity can be mechanically and uniformly mixed with high specific gravity particles such as ceramic raw materials. Therefore, when a hollow microsphere having a solid material with a high specific gravity attached to the outer shell surface is used as a porous forming agent, a porous ceramic molded body having a uniform porous structure can be produced.
  • FIG. 1 is an explanatory diagram showing the thermal expansion of the thermally expandable microsphere.
  • FIG. 2 is an explanatory view showing a method for producing hollow microspheres in which a solid material adheres to the outer shell surface of the present invention.
  • the thermally expandable microsphere used in the present invention has a microcapsule structure in which a foaming agent capable of gasification or gas generation is enclosed in an outer shell formed of a thermoplastic resin, and is thermally expanded by heating. As long as it is a thermally expandable microsphere that forms a hollow microsphere, it may be obtained by any manufacturing method.
  • the thermally expandable microsphere 1 has a structure in which a foaming agent 3 is enclosed by an outer shell 2 made of a thermoplastic resin.
  • the thermally expandable microsphere 1 is heated to a temperature equal to or higher than the softening point of the thermoplastic resin constituting the outer shell 2, as shown in FIG. 1B, the foaming agent 3 is gasified or generated from the foaming agent.
  • a hollow microsphere 101 having a hollow 103 inside the expanded outer shell 102 is obtained by thermal expansion with gas.
  • thermally expandable microspheres can be produced by a method in which a polymerizable monomer mixture containing at least a foaming agent and a polymerizable monomer is subjected to suspension polymerization in an aqueous dispersion medium.
  • a polymer (thermoplastic resin) formed by polymerization of a polymerizable monomer forms an outer shell, and a thermally expandable microsphere having a structure in which a foaming agent is enclosed in the outer shell is generated.
  • the polymerizable monomer a radically polymerizable monomer is usually used.
  • the polymerizable monomer include nitrile monomers such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethoxyacrylonitrile, fumaronitrile; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid Carboxyl group-containing monomers such as citraconic acid; acrylic acid such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, ⁇ -carboxy acrylate Ester monomers: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl este
  • the thermally expandable microspheres are preferably those in which the polymer forming the outer shell is a thermoplastic resin and has gas barrier properties. From these viewpoints, vinylidene chloride (co) polymers and (meth) acrylonitrile (co) polymers are preferable, but not limited thereto.
  • the “(co) polymer” means a homopolymer and / or a copolymer.
  • the “(meth) acrylonitrile” means acrylonitrile and / or methacrylonitrile.
  • vinylidene chloride (co) polymer a (co) polymer obtained by using, as a polymerizable monomer, vinylidene chloride alone or a mixture of vinylidene chloride and a vinyl monomer copolymerizable therewith is used.
  • examples of the monomer copolymerizable with vinylidene chloride include acrylonitrile, methacrylonitrile, methacrylic acid ester, acrylic acid ester, styrene, and vinyl acetate.
  • the vinylidene chloride (co) polymer is selected from the group consisting of 30 to 100% by weight of vinylidene chloride as a polymerizable monomer, and acrylonitrile, methacrylonitrile, acrylate ester, methacrylate ester, styrene, and vinyl acetate.
  • a (co) polymer obtained using 0 to 70% by mass of the at least one monomer is preferred. If the copolymerization ratio of vinylidene chloride is less than 30% by mass, the gas barrier property becomes too low, which is not preferable.
  • Examples of the vinylidene chloride (co) polymer include 40 to 80% by mass of vinylidene chloride, 0 to 60% by mass of at least one monomer selected from the group consisting of acrylonitrile and methacrylonitrile, and acrylates and methacrylates.
  • a copolymer of 0 to 60% by mass of at least one monomer selected from the group consisting of By setting it as the copolymer of such a composition, design of foaming temperature is easy and it is easy to achieve a high foaming ratio.
  • the outer shell is preferably formed from a (meth) acrylonitrile (co) polymer.
  • the (meth) acrylonitrile (co) polymer is obtained by using (meth) acrylonitrile alone or (meth) acrylonitrile and a vinyl monomer copolymerizable therewith as the polymerizable monomer (co).
  • a polymer can be mentioned.
  • the vinyl monomer copolymerizable with (meth) acrylonitrile include vinylidene chloride, acrylic acid ester, methacrylic acid ester, styrene, and vinyl acetate.
  • the (meth) acrylonitrile (co) polymer includes, as a polymerizable monomer, at least one monomer selected from the group consisting of acrylonitrile and methacrylonitrile, 30 to 100% by mass, vinylidene chloride, and acrylate A (co) polymer obtained by using 0 to 70% by mass of at least one monomer selected from the group consisting of methacrylic acid ester, styrene, and vinyl acetate is preferred.
  • the copolymerization ratio of (meth) acrylonitrile is less than 30% by mass, the solvent resistance and heat resistance are insufficient.
  • (Meth) acrylonitrile (co) polymer has a high proportion of (meth) acrylonitrile and a high foaming temperature (co) polymer, a small proportion of (meth) acrylonitrile and a low foaming temperature (co) heavy Can be divided into coalescence.
  • (co) polymer having a large proportion of (meth) acrylonitrile used as a polymerizable monomer, at least one monomer selected from the group consisting of acrylonitrile and methacrylonitrile, 80 to 100% by mass, and chloride (Co) polymers obtained by using 0 to 20% by mass of at least one monomer selected from the group consisting of vinylidene, acrylic acid ester, methacrylic acid ester, styrene, and vinyl acetate.
  • the (co) polymer having a small proportion of (meth) acrylonitrile used is at least one monomer selected from the group consisting of acrylonitrile and methacrylonitrile as a polymerizable monomer, but not less than 30% by mass and less than 80% by mass. , And at least one monomer selected from the group consisting of vinylidene chloride, acrylic acid ester, methacrylic acid ester, styrene, and vinyl acetate in excess of 20% by mass and 70% by mass or less. Coalescence is mentioned.
  • Examples of the (meth) acrylonitrile (co) polymer include at least one monomer selected from the group consisting of acrylonitrile and methacrylonitrile, 51 to 100% by mass, vinylidene chloride, 0 to 40% by mass, and acrylates and methacrylic esters. Preference is given to (co) polymers obtained using 0 to 48% by weight of at least one monomer selected from the group consisting of acid esters.
  • At least one monomer 30 selected from the group consisting of acrylonitrile and methacrylonitrile is used as the polymerizable monomer.
  • a (meth) acrylonitrile (co) polymer obtained using ⁇ 100% by mass and at least one monomer selected from the group consisting of acrylic acid ester and methacrylic acid ester is preferred.
  • polymers not containing vinylidene chloride include, as a polymerizable monomer, acrylonitrile 1 to 99% by mass, methacrylonitrile 1 to 99% by mass, and a group consisting of acrylic acid ester and methacrylic acid ester.
  • a copolymer obtained by using 0 to 70% by mass of at least one selected monomer is preferred.
  • (meth) acrylonitrile (co) polymer in the outer shell is used as the polymerizable monomer.
  • Copolymer obtained using 20 to 80% by mass of methacrylonitrile, 20 to 80% by mass of methacrylonitrile, and 0 to 20% by mass of at least one monomer selected from the group consisting of acrylic acid ester and methacrylic acid ester It is preferable that
  • a crosslinkable monomer can be used in combination with the polymerizable monomer in order to improve foaming characteristics, processing characteristics, solvent resistance, and heat resistance.
  • the crosslinkable monomer a compound having two or more carbon-carbon double bonds is usually used.
  • the crosslinkable monomer include divinylbenzene, divinylnaphthalene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, PEG # 200 di Bifunctional crosslinkable monomers such as (meth) acrylate, PEG # 400 di (me
  • the foaming agent a substance capable of gasification or gas generation by heating is used.
  • a compound that gasifies at a temperature below the softening point of the polymer (thermoplastic resin) forming the outer shell is preferable.
  • a low-boiling organic solvent is suitable.
  • Hydrocarbons such as trimethylpentane, n-hexane, isohexan
  • a foaming agent capable of generating a gas by heating is a compound that generates a gas by being thermally decomposed by heating, such as azodicarbonamide.
  • the content of the foaming agent enclosed in the heat-expandable microsphere is preferably 5 to 50% by mass, more preferably 7 to 40% by mass. It is preferable to adjust the usage ratio of the polymerizable monomer and the foaming agent so that the outer shell polymer and the foaming agent have the above ratio after the polymerization.
  • the polymerization initiator is preferably an oil-soluble polymerization initiator that is soluble in the polymerizable monomer.
  • the polymerization initiator include dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, and azo compound.
  • the polymerization initiator is usually contained in the monomer mixture. However, when it is necessary to suppress early polymerization, a part or all of the polymerization initiator is added to the aqueous dispersion medium during or after the granulation step. It may be added and transferred into droplets of the polymerizable mixture.
  • the polymerization initiator is usually used in a proportion of 0.0001 to 3% by mass based on the aqueous dispersion medium.
  • Suspension polymerization is usually performed in an aqueous dispersion medium containing a dispersion stabilizer.
  • the dispersion stabilizer include inorganic fine particles such as silica and magnesium hydroxide.
  • auxiliary stabilizers such as a condensation product of diethanolamine and an aliphatic dicarboxylic acid, polyvinyl pyrrolidone, polyethylene oxide, various emulsifiers and the like can be used.
  • the dispersion stabilizer is usually used at a ratio of 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
  • An aqueous dispersion medium containing a dispersion stabilizer is usually prepared by blending a dispersion stabilizer or an auxiliary stabilizer with deionized water.
  • the pH of the aqueous phase at the time of polymerization is appropriately determined depending on the type of dispersion stabilizer and auxiliary stabilizer used.
  • silica such as colloidal silica
  • polymerization is performed in an acidic environment.
  • an acid is added as necessary to adjust the pH of the system to 7 or less, preferably pH 6 or less, particularly preferably about pH 3 to 4.
  • the polymerization is carried out in an alkaline environment.
  • One preferred combination of dispersion stabilizers is a combination of colloidal silica and a condensation product.
  • a condensation product of diethanolamine and an aliphatic dicarboxylic acid is preferable, and a condensation product of diethanolamine and adipic acid or a condensation product of diethanolamine and itaconic acid is particularly preferable.
  • the acid value of the condensation product is preferably 60 or more and less than 95, and more preferably 65 to 90.
  • an inorganic salt such as sodium chloride or sodium sulfate is added, it becomes easier to obtain thermally expandable microspheres having a more uniform particle shape.
  • sodium chloride is usually preferably used.
  • the amount of colloidal silica used varies depending on the particle size, but is usually in the range of 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, with respect to 100 parts by mass of the polymerizable monomer.
  • the condensation product is usually used at a ratio of 0.05 to 2 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
  • the inorganic salt is used in a ratio of 0 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
  • At least one compound selected from the group consisting of alkali metal nitrite, stannous chloride, stannic chloride, water-soluble ascorbic acid, and boric acid can be present in the aqueous dispersion medium.
  • alkali metal nitrite, stannous chloride, stannic chloride, water-soluble ascorbic acid, and boric acid can be present in the aqueous dispersion medium.
  • alkali metal nitrites sodium nitrite and potassium nitrite are preferable in terms of availability and price.
  • ascorbic acids include ascorbic acid, metal salts of ascorbic acid, esters of ascorbic acid, and the like. Among these, water-soluble ones are preferably used. Water-soluble ascorbic acids mean those having a solubility in water at 23 ° C. of 1 g / 100 cm 3 or more, and ascorbic acid and alkali metal salts thereof are preferred. Among these, L-ascorbic acid (vitamin C), sodium ascorbate, and potassium ascorbate are preferable.
  • the polymerization aid is usually used in a proportion of 0.001 to 2 parts by mass, preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of the polymerizable monomer.
  • the order of adding each component to the aqueous dispersion medium is arbitrary, but usually an aqueous dispersion containing a dispersion stabilizer by adding water and a dispersion stabilizer, and if necessary, a stabilizer or a polymerization assistant.
  • a dispersion stabilizer by adding water and a dispersion stabilizer, and if necessary, a stabilizer or a polymerization assistant.
  • the medium On the other hand, the polymerizable monomer and the foaming agent may be separately added to the aqueous dispersion medium and integrated in the aqueous dispersion medium to form a polymerizable monomer mixture (oil-based mixture). Both are mixed in advance and then added to the aqueous dispersion medium.
  • the polymerization initiator can be used by adding it to the polymerizable monomer in advance, but when it is necessary to avoid early polymerization, for example, a mixture of the polymerizable monomer and the foaming agent is dispersed in water.
  • the polymerization initiator may be added to the medium while stirring, and may be integrated in the aqueous dispersion medium.
  • the polymerization mixture and the aqueous dispersion medium may be mixed in a separate container, stirred and mixed with a stirrer or disperser having high shearing force, and then charged into a polymerization can.
  • a polymerizable monomer mixture droplet is formed in the aqueous dispersion medium by stirring and mixing the polymerizable monomer mixture and the aqueous dispersion medium. It is preferable that the average particle size of the liquid droplets is approximately the same as the average particle size of the target thermally expandable microsphere.
  • the suspension polymerization is usually carried out by degassing the inside of the reaction vessel or replacing it with an inert gas and raising the temperature to 30 to 100 ° C.
  • the aqueous phase is removed by, for example, filtration, centrifugation, and sedimentation.
  • the thermally expandable microspheres are dried after being filtered and washed.
  • the thermally expandable microsphere is dried at a relatively low temperature such that the foaming agent is not gasified.
  • the average particle size of the thermally expandable microspheres of the present invention is usually in the range of 0.5 to 150 ⁇ m, preferably 1 to 130 ⁇ m, more preferably 3 to 100 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
  • the content of the blowing agent in the thermally expandable microsphere of the present invention is usually 5 to 50% by mass, preferably 7 to 40% by mass.
  • the foaming temperature of the thermally expandable microsphere varies depending on the type and thickness of the thermoplastic resin (polymer) constituting the outer shell.
  • the production method of the present invention is a method for producing hollow microspheres including the following steps 1 and 2, in which a solid material adheres to the outer shell surface.
  • FIG. 2A a slurry in which the thermally expandable microspheres 1 and the solid material 23 are dispersed in a liquid dispersion medium 22 is charged in a container 21.
  • a slurry in which the thermally expandable microspheres 1 and the solid material 23 are dispersed in a liquid dispersion medium 22 is charged in a container 21.
  • the thermally expandable microspheres are heated and foamed by heating means such as blowing heated steam into the slurry, as shown in FIG. 2 (b), a foam (hollow microsphere) 101 is generated, A large number of solid materials 23 adhere to the surface.
  • the solid material used in Step 1 is a fine solid material that is solid at normal temperature (25 ⁇ 15 ° C.) and has an average particle diameter or an average major axis smaller than the average particle diameter of the thermally expandable microsphere.
  • the shape of the solid material is not particularly limited, and may be granular, spherical, cubic, spindle, rod, plate, needle, fiber, or the like.
  • the material of the solid material may be inorganic or organic.
  • inorganic solid materials include natural products such as silica, limestone, quartz, apatite, magnetite, zeolite, clay (montmorillonite, hectorite, saponite, vermiculite, talc, mica, mica, etc.); metal carbonates such as calcium carbonate
  • Metal sulfates such as barium sulfate, aluminum sulfate, cobalt sulfate, copper sulfate, nickel sulfate
  • metals such as titanium oxide, zinc oxide, aluminum oxide, tin oxide, vanadium oxide, indium oxide, chromium oxide, tungsten oxide, iron oxide Oxides;
  • Metal hydroxides such as aluminum hydroxide and magnesium hydroxide;
  • Metal sulfides such as copper sulfide and lead sulfide;
  • Metal borates such as aluminum borate and zinc borate;
  • colloidal inorganic solid materials include colloidal silica, colloidal calcium carbonate, magnesium hydroxide colloid, and calcium phosphate colloid.
  • needle-like or fibrous inorganic solid material include glass fiber, carbon fiber, alumina fiber, potassium titanate whisker, aluminum borate whisker, and wollastonite.
  • organic solid material examples include fine particles of organic resin such as polystyrene beads, polymethyl methacrylate beads, and polytetrafluoroethylene beads, cotton fibers, and polyamide fibers.
  • the organic resin fine particles include organic resin fine particles introduced with a crosslinked structure, organic resin fine particles introduced with a functional group or a polar group, and the like.
  • solid materials can be used alone or in combination of two or more.
  • the solid material may be subjected to a surface treatment such as a hydrophobic treatment.
  • a surface treatment such as a hydrophobic treatment.
  • the specific gravity can be controlled, heat insulation, slip, sound insulation, conductivity, magnetism, piezoelectricity, bactericidal, ultraviolet absorption, etc. Can be added.
  • the average particle diameter or average long diameter of the inorganic and / or organic solid material is preferably sufficiently smaller than the average particle diameter of the thermally expandable microsphere, and is usually 10 ⁇ m or less, preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less. Particularly preferably, it is 0.1 ⁇ m or less.
  • the lower limit of the average particle diameter or the average major axis is about 0.001 ⁇ m from the viewpoints of effects and handleability.
  • the average particle diameter of the solid material is an average diameter or an average major axis of primary particles measured by an observation counting method using an electron microscope or an optical microscope.
  • the solid material has an average particle size of 3 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.1 ⁇ m or less, and a specific gravity (true specific gravity) of 1.5 to 6.0 g / cm 3 , preferably 2.0 to 6.
  • a specific gravity true specific gravity
  • the specific gravity of the hollow microsphere can be increased.
  • examples of such inorganic substances include calcium carbonate (for example, heavy calcium carbonate having a specific gravity of about 2.70 g / cm 3 , light and colloidal calcium carbonate having a specific gravity of about 2.60 g / cm 3 ), crystalline silica, and the like.
  • the content (adhesion amount) of the solid material can be appropriately determined according to the desired function and the type of the solid material, but usually 1 to 99.9 masses based on the total amount of the hollow microspheres to which the solid material is adhered. %, Preferably 10 to 99.5% by mass, more preferably 15 to 99.3% by mass, particularly preferably 20 to 99.0% by mass. However, the amount of dispersion stabilizer (for example, inorganic fine particles such as silica and magnesium hydroxide) used for controlling the particle size of the thermally expandable microsphere is excluded from these.
  • dispersion stabilizer for example, inorganic fine particles such as silica and magnesium hydroxide
  • the amount of the solid material attached to the outer shell surface of the hollow microsphere can be generally calculated based on the mass difference between the hollow microspheres obtained in the presence and absence of the solid material.
  • the amount of solid material deposited can be calculated by burning the hollow microsphere with the solid material adhered to the outer shell surface and measuring the amount of ash after combustion. .
  • step 1 the thermally expandable microsphere and a solid material having an average particle diameter or an average major axis smaller than the average particle diameter of the thermally expandable microsphere are dispersed in a liquid dispersion medium to prepare a slurry.
  • liquid dispersion medium a medium that does not dissolve the thermoplastic resin that forms the outer shell of the thermally expandable microsphere or has a low solubility is preferable.
  • the liquid dispersion medium is preferably a medium that does not decompose or has a low degree of decomposition of the thermoplastic resin that forms the outer shell of the thermally expandable microsphere.
  • liquid dispersion medium examples include water; organic solvents such as isopropyl alcohol, ethylene glycol, glycerin, phthalate ester, silicone oil, and paraffin oil; mixed solvents such as water / ethylene glycol mixed solution and water / glycerin mixed solution; Etc.
  • organic solvents such as isopropyl alcohol, ethylene glycol, glycerin, phthalate ester, silicone oil, and paraffin oil
  • mixed solvents such as water / ethylene glycol mixed solution and water / glycerin mixed solution
  • Etc Among these, water and an aqueous dispersion medium such as a mixed solvent containing water are preferable, and water is particularly preferable.
  • a surfactant or a dispersion stabilizer may be added to the liquid dispersion medium.
  • the concentration of the heat-expandable microspheres in the liquid dispersion medium is usually 0.1 to 10% by mass, preferably 0.1 to 8% by mass, more preferably 0.2 to 7% by mass, and particularly preferably 0.8. It is within the range of 3 to 5% by mass. If this concentration is too high, the thermal expansion of the thermally expandable microspheres tends to cause thermal fusion between the foams, or the amount of solid material added must be reduced. If this concentration is too low, the production efficiency decreases.
  • the heat-expandable microspheres are formed by suspension polymerization of a polymerizable monomer mixture containing a polymerizable monomer and a foaming agent in an aqueous dispersion medium
  • a slurry in which the thermally expandable microspheres and the solid material are dispersed in the aqueous dispersion medium can be prepared.
  • the solid material may be added in several batches before and after suspension polymerization, before suspension polymerization and during suspension polymerization.
  • the solid material is a dispersion stabilizer such as colloidal silica, it is usually added during suspension polymerization or after suspension polymerization.
  • a liquid dispersion medium such as water may be added, or a part of the aqueous dispersion medium may be removed by filtration or tilting.
  • the heat-expandable microsphere When the heat-expandable microsphere is formed by suspension polymerization of a polymerizable monomer mixture containing a polymerizable monomer and a foaming agent in an aqueous dispersion medium, the heat recovered from the aqueous dispersion medium
  • the expandable microspheres can be dispersed with a solid material in a liquid dispersion medium to prepare a slurry.
  • the thermally expandable microspheres are heated in the slurry to soften the outer shell, and thermally expanded by the gasification of the foaming agent or the gas generated from the foaming agent, thereby softening the outer shell. Hollow microspheres with solid material attached to the surface are formed.
  • the slurry is charged into a container (tank, polymerization can, etc.) equipped with a stirring device, stirred, and thermally expanded microsphere. It is preferable that the solid material is uniformly dispersed in the slurry.
  • the thermal expansion of the thermally expandable microsphere is also preferably performed while stirring the slurry.
  • the heating and foaming means there are a method of heating the slurry, a method of blowing heated steam into the slurry, a dielectric heating method and the like.
  • a liquid that evaporates at a relatively low temperature such as an aqueous dispersion medium
  • the method of blowing heated steam into the slurry is particularly preferable because the thermally expandable microsphere can be heated and foamed in a very short time.
  • the temperature of the heated steam is usually 100 to 200 ° C., preferably 110 to 190 ° C., more preferably 120 to 180 ° C., although it depends on the foaming temperature of the thermally expandable microsphere.
  • the pressure at which heated steam is blown is usually in the range of 0.1 to 1.56 MPa, preferably 0.14 to 1.26 MPa, more preferably 0.2 to 1.0 MPa.
  • hollow microspheres in which the solid material is firmly attached to the outer shell surface are collected by a method of filtering the slurry and washing the foam particles.
  • the outer shell made of a thermoplastic resin is softened at the time of heating and foaming, and the solid material adheres to the surface of the softened outer shell. There is nothing to do.
  • the average particle size of the hollow microspheres of the present invention is preferably in the range of 2 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, particularly preferably 10 to 60 ⁇ m. If the average particle size of the hollow microspheres is too small, when the hollow microspheres are used as a porous forming agent, formation of a porous structure tends to be insufficient. On the other hand, if the average particle size of the hollow microspheres is too large, the hollow microspheres may be hollow when kneaded with a raw material constituting a porous molded body such as a porous ceramic molded body and / or when a mixture obtained by kneading is molded. Microspheres are liable to collapse, and as a result, the formation of a porous structure may be insufficient.
  • the hollow microsphere of the present invention has a solid material attached to the outer shell surface thereof, mutual fusion is prevented, and scattering from the air during the handling is suppressed.
  • Various functions can be imparted to the hollow microsphere by adjusting the type and amount of the solid material to be attached to the outer shell surface.
  • the hollow microsphere of the present invention can increase the specific gravity (apparent specific gravity) of the entire particle by attaching a solid material having a high specific gravity to the outer shell surface. Uniform mixing is facilitated.
  • the hollow microsphere having a high specific gravity is suitable as a porous forming agent used in the production process of a porous ceramic molded body, for example.
  • a porous ceramic molded body using a porous forming agent can be produced, for example, by a production method disclosed in Japanese Patent Application Laid-Open No. 2007-39333 (Patent Document 1).
  • a process a for mixing a ceramic raw material and a porous forming agent to prepare a mixture a process b for forming the mixture into a molded body having a predetermined shape; and a process c for firing the molded body.
  • a process a for producing a porous ceramic formed body hollow microspheres obtained by the above production method and having a solid material attached to the outer shell surface are used as the porous forming agent.
  • Ceramic raw materials include ceramic mixtures such as talc, kaolin, aluminum oxide, aluminum hydroxide, and silica, silicon carbide, and metal silicon.
  • the use ratio of the hollow microsphere having a solid material attached to the outer shell surface can be appropriately determined according to the desired porous structure.
  • the firing temperature is about 1400 to 2000 ° C.
  • Ceramics In general, the group of substances called ceramics is extremely wide and has various characteristics. Types of ceramics include ceramics, glass, cement, gypsum, enamel, fine ceramics (new ceramics) and the like.
  • the hollow microsphere of the present invention is also used as a porous forming agent for lightweight cellular concrete (ALC), for example.
  • ALC containing the porous forming agent includes closed cells inside, and exhibits excellent properties such as relatively high strength while being very lightweight.
  • ALC is widely used as a building material for walls and floors of buildings because it is lightweight, relatively strong, and excellent in fire resistance, heat insulation, and workability.
  • siliceous raw materials such as silica and calcareous raw materials such as cement and lime are generally used as main raw materials, and gypsum and process repetition raw materials are used as auxiliary raw materials.
  • Water and a porous molding agent are added to these raw material fine powders to form a slurry, which is then placed in a mold and semi-cured.
  • ALC can be obtained by subjecting the semi-cured product to high-temperature and high-pressure steam curing with an autoclave.
  • the step of producing ALC as a porous ceramic molded body includes a step of preparing a mixture by mixing a ceramic raw material and a porous forming agent; a step b of molding the mixture into a molded body having a predetermined shape. And a step c of curing the shaped body.
  • curing may be performed instead of firing.
  • the hollow microsphere of the present invention is used as a porous forming agent such as ALC.
  • Foaming magnification 0.7 g of thermally expandable microspheres was placed in a gear-type oven and heated at a predetermined foaming temperature for 2 minutes for foaming (thermal expansion). The resulting hollow microspheres were placed in a graduated cylinder and the volume was measured. The volume of the hollow microsphere was divided by the volume of the unexpanded thermally expandable microsphere to calculate the expansion ratio. At this time, the foaming temperature was increased from 70 ° C. in increments of 5 ° C. and foamed at each temperature. The expansion ratio at a temperature at which the maximum expansion ratio was obtained under these conditions was defined as the maximum expansion ratio.
  • the specific gravity of the thermally expandable microsphere and the hollow microsphere means the specific gravity of the whole particle, and was measured by a measuring method using a specific gravity bottle defined in JIS Z 8807.
  • ⁇ Quantity of foaming agent The amount and ratio of the remaining foaming agent contained in the hollow microsphere (dried sample) that has been stored in a desiccator for one day after air drying and dried are measured by the following procedure.
  • the cup was covered with an upper lid made of aluminum, subjected to heat treatment at 200 ° C. for 10 minutes to vaporize the foaming agent, and then subjected to the heat treatment (hereinafter referred to as “foaming agent”).
  • Foaming agent The “removed sample”) was weighed.
  • Ws (g) Wb (g) -Wa (g)
  • Preparation Example 1 (1) Preparation of aqueous dispersion medium 22 g of colloidal silica having a solid content of 40% by mass was added to 770 g of deionized water and dispersed therein. Next, 0.8 g of diethanolamine-adipic acid condensate and 0.13 g of sodium nitrite were added to the dispersion and dissolved. Furthermore, hydrochloric acid was added to the dispersion to prepare an aqueous dispersion medium having a pH of 3.5.
  • Thermally expandable microspheres have an average particle size of 14 ⁇ m, a maximum expansion ratio of 50 times at a foaming temperature of 130 ° C., and a specific gravity of 0. 0.02 g / cm 3 .
  • This thermally expandable microsphere contained 3.3% by mass of colloidal silica used as a dispersion stabilizer.
  • Example 1 Deionized water was added to the thermally expandable microsphere obtained in Preparation Example 1 to prepare 500 g of an aqueous slurry having a concentration of 1% by mass of the thermally expandable microsphere. After adding 40 g of colloidal calcium carbonate (average particle diameter 50 nm) to this aqueous slurry, it was charged into a polymerization can equipped with a stirrer having a capacity of 1.5 liters. While stirring the aqueous slurry, steam heated to a temperature of 150 ° C. was blown in at a pressure of 0.48 MPa to heat and expand the thermally expandable microspheres. Foam particles (hollow microspheres) were dispersed in the aqueous slurry after foaming without forming aggregates.
  • colloidal calcium carbonate average particle diameter 50 nm
  • the foam particles in the aqueous slurry were filtered and washed with water. Further, washing with water and filtration were repeated twice, followed by drying to collect foam particles (hollow microspheres).
  • the foam particles had an average particle size of 50 ⁇ m and a specific gravity of 0.095 g / cm 3 .
  • the total content of inorganic substances contained in the foam particles was 80% by mass.
  • the hollow microspheres obtained in this way were those whose scattering properties in air were remarkably suppressed and excellent in mixing properties with inorganic substances having a high specific gravity.
  • Example 2 Foam particles (hollow microspheres) were produced in the same manner as in Example 1 except that 100 g of colloidal silica (solid content 40% by mass, average particle size 12 nm) was used instead of 40 g of colloidal calcium carbonate.
  • the foam particles had an average particle size of 53 ⁇ m and a specific gravity of 0.10 g / cm 3 .
  • the total content of inorganic substances contained in the foam particles was 85% by mass.
  • the hollow microspheres obtained in this way were those whose scattering properties in air were remarkably suppressed and excellent in mixing properties with inorganic substances having a high specific gravity.
  • the hollow microsphere having a solid material adhered to the outer shell surface of the present invention can be used in a wide range of technical fields for the purpose of reducing the weight, making it porous, and imparting various functions to plastics, paints, and various materials.
  • the hollow microsphere having a high specific gravity can also be used as a porous forming agent for a porous ceramic molded body.

Abstract

L'invention porte sur un procédé de fabrication de microsphères creuses qui comprend : une étape (1) dans laquelle des microsphères thermo-expansibles à la chaleur ayant une structure microcapsulaire qui comprend une coquille formée à partir d'une résine thermoplastique, et, encapsulés dans celle-ci, un agent gonflant capable de gazéifier ou de générer un gaz et une matière solide ayant un diamètre moyen de particule ou une longueur moyenne de plus grand axe inférieur au diamètre moyen de particule des microsphères thermo-expansibles, sont dispersées dans un milieu de dispersion liquide afin de préparer une bouillie ; et une étape (2) dans laquelle les microsphères thermo-expansibles sont chauffées dans la bouillie pour ramollir et provoquer l’extension thermique des coquilles de celles-ci, formant ainsi des microsphères creuses avec la matière solide qui adhère à la surface des coquilles ramollies.
PCT/JP2009/068869 2008-12-18 2009-11-05 Procédé de fabrication de microsphères creuses et procédé de fabrication de céramique moulée poreuse WO2010070987A1 (fr)

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KR1020117016118A KR101278410B1 (ko) 2008-12-18 2009-11-05 중공 마이크로스피어의 제조 방법 및 다공질 세라믹 성형체의 제조 방법
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