WO2023136283A1 - 被覆酸化アルミニウム粒子及びその製造方法、並びにその用途 - Google Patents

被覆酸化アルミニウム粒子及びその製造方法、並びにその用途 Download PDF

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WO2023136283A1
WO2023136283A1 PCT/JP2023/000578 JP2023000578W WO2023136283A1 WO 2023136283 A1 WO2023136283 A1 WO 2023136283A1 JP 2023000578 W JP2023000578 W JP 2023000578W WO 2023136283 A1 WO2023136283 A1 WO 2023136283A1
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aluminum oxide
oxide particles
antimony
component
tin
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French (fr)
Japanese (ja)
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祐樹 田中
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Ishihara Sangyo Kaisha Ltd
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Ishihara Sangyo Kaisha Ltd
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Priority to JP2023574060A priority Critical patent/JPWO2023136283A1/ja
Priority to EP23740291.2A priority patent/EP4464666A4/en
Priority to CN202380016515.8A priority patent/CN118524990A/zh
Publication of WO2023136283A1 publication Critical patent/WO2023136283A1/ja
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    • 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony

Definitions

  • the present invention relates to aluminum oxide particles coated with antimony-doped tin oxide, a method for producing the same, and a conductive material, solvent composition, resin composition, coating composition, and coating film containing the particles.
  • titanium dioxide particles have been classified from Group 3 (cannot be classified as to carcinogenicity to humans) to Group 2B (carcinogenicity to humans). There may be) has been reranked. As a result, there is a concern that conductive materials using titanium dioxide particles will not be certified by some environmental protection certification systems.
  • aluminum oxide particles can be mentioned as a candidate for a substitute material for titanium dioxide particles.
  • the surface of a substrate powder is coated with an oxide composed of elements of antimony and tin, and the content of antimony doped in tin oxide is calculated as antimony with respect to tin oxide. 8 to 25% by weight of white conductive powder is disclosed, and the examples are mixed such that Sb/SnO 2 is 0.14 (16.7% by weight in terms of oxide (Sb 2 O 3 /SnO 2 )).
  • the surface of the aluminum oxide particles is coated with a conductive layer of antimony-doped tin oxide.
  • the dopant element in the entire coating layer is 0.01 mol or more per 1 mol of tin. It is disclosed that it contains 0.60 mol or less, and in the example, the amount of dopant per 1 mol of Sn in the Al 2 O 3 base is 0.01 mol (1.0 mass in terms of oxide (Sb 2 O 3 /SnO 2 ) %).
  • oxide conversion means the content of the antimony component and the content of the tin component as Sb 2 O 3 (Sb 2 O 3 of the antimony component converted value) and the content as SnO 2 (also referred to as the SnO 2 conversion value of the tin component), and the ratio of the content of the antimony component to the content of the tin component is calculated as Sb to the content of SnO 2 2 O 3 content, that is, the content as Sb 2 O 3 divided by the content as SnO 2 , and the value is expressed in mass %.
  • the conductive materials produced by the above-described conventional techniques have not yet reached the desired level of conductivity, and further improvement in conductivity is required to replace the conductive materials made of titanium dioxide particles. It is Further, when used as a conductive white pigment or the like, it is necessary to further improve the conductivity while maintaining sufficient whiteness. Moreover, depending on the application, excellent crushability may be required.
  • the desired conductivity could not be obtained by applying the conductive treatment technology for titanium dioxide particles as it is to aluminum oxide particles. Therefore, the present inventors conducted extensive studies and found that by optimizing the antimony-doped tin oxide coating treatment in accordance with the properties of the aluminum oxide particles, it is possible to express the desired conductivity even if the aluminum oxide particles are used as the base material. He found the headline and completed the present invention.
  • the present invention includes the following inventions (1) to (19).
  • (1) Aluminum oxide particles have antimony-doped tin oxide on their surfaces, and the content of the antimony component is 26 mass in terms of oxide (Sb 2 O 3 /SnO 2 ) with respect to the content of the tin component. % or more and 45% by mass or less, coated aluminum oxide particles.
  • (2) Aluminum oxide particles have antimony-doped tin oxide on their surfaces, and the content of the antimony component is 30 mass in terms of oxide (Sb 2 O 3 /SnO 2 ) with respect to the content of the tin component. % or more and 45% by mass or less, coated aluminum oxide particles.
  • the content of the antimony-doped tin oxide is 10% by mass or more and 40% by mass or less in terms of oxide (total amount of Sb 2 O 3 and SnO 2 ) with respect to the amount of the aluminum oxide particles.
  • the content of sodium is 0.3% by mass or less in terms of oxide (Na 2 O) with respect to the amount of oxide in terms of all constituent components of the coated aluminum oxide particles, (1) to (3) Coated aluminum oxide particles according to any one of .
  • a coating film comprising the coating composition according to (11).
  • the antimony component is 26% by mass or more and 45% by mass or less with respect to the tin component in terms of oxide (Sb 2 O 3 /SnO 2 ).
  • a method for producing coated aluminum oxide particles comprising mixing a hydrochloric acid solution containing the antimony component and the tin component with an alkali, and then firing at a temperature of 400°C or higher and 800°C or lower.
  • the antimony component is 30% by mass or more and 45% by mass or less in terms of oxide (Sb 2 O 3 /SnO 2 ) with respect to the tin component.
  • a hydrochloric acid solution containing the antimony component and the tin component is mixed with an alkali to deposit the tin hydroxide containing the antimony component on the surface of the aluminum oxide particles.
  • a method for producing coated aluminum oxide particles by calcining at temperature to coat with antimony-doped tin oxide.
  • the total amount of the tin component and the antimony component contained in the hydrochloric acid solution is 10 mass in terms of oxide (total amount of Sb 2 O 3 and SnO 2 ) with respect to the amount of the aluminum oxide particles. % or more and 40% by mass or less, the method for producing coated aluminum oxide particles according to (13) or (14).
  • the method for producing coated aluminum oxide particles according to (13) or (14) Any one of (13) to (15), wherein the temperature of the dispersion is kept at 50° C. or more and 95° C. or less while the hydrochloric acid solution containing the tin component and the antimony component is mixed with the alkali.
  • the antimony-doped tin oxide-coated aluminum oxide particles of the present invention have sufficient electrical conductivity and can be suitably used as a substitute material for conductive titanium dioxide particles. Furthermore, it can also be used as a conductive white pigment by adjusting the whiteness. It is also possible to provide aluminum oxide particles coated with antimony-doped tin oxide, which are excellent in crushability.
  • aluminum oxide is used as the substrate.
  • the aluminum oxide referred to here is a compound represented by the chemical formula Al 2 O 3 and is also called alumina.
  • Aluminum oxide has crystal structures such as a trigonal system ( ⁇ -alumina) and a cubic system ( ⁇ -alumina), but any crystal structure may be used.
  • the aluminum oxide particles may contain various impurities that are unavoidable in manufacturing.
  • Impurities include, for example, iron, silicon, calcium, gallium, chromium, nickel, zinc, zirconium, magnesium, copper, sodium, and the like.
  • sodium reduces the electrical conductivity of the coated aluminum oxide particles of the present invention .
  • the content of impurities is measured by, for example, ICP emission spectrometry, atomic absorption spectrometry, or fluorescent X-ray analysis.
  • Aluminum oxide particles can be synthesized by a known method.
  • Various commercial products can also be used as the aluminum oxide particles.
  • Examples of commercially available products include SMM-22 (manufactured by Nippon Light Metal Co., Ltd.), AKP-15, AKP-20, AKP-30, AKP-50, AKP-53, AKP-700, AKP-3000, AL-41-01, AL-43A, AL-420A (above, manufactured by Sumitomo Chemical Co., Ltd.), APA-0.5, AHPA-0.5 (above, manufactured by SASOL), SAO-020A, SAO-020E, SAO-020N (above, manufactured by SINOCERA) and the like can be used.
  • the coated aluminum oxide particles of the present invention have a coating of antimony-doped tin oxide on the surface of the substrate aluminum oxide particles.
  • coating as used herein may be in a state in which the antimony-doped tin oxide particles cover the entire aluminum oxide particles in a layer, and a state in which a part of the coating is perforated, for example, the antimony-doped tin oxide may be present in the form of islands on the surface of the aluminum oxide particles, and the state of the coating is not particularly limited. A state in which the whole is covered in layers is desirable.
  • Antimony-doped tin oxide is a solid solution of antimony inside the crystal of tin oxide, which can impart electrical conductivity to tin oxide.
  • the ratio of the content of the antimony component to the content of the tin component is represented by the ratio of the content of Sb 2 O 3 to the content of SnO 2 , that is, Sb 2 O 3 content as SnO 2 divided by the content as SnO 2 , and the value is expressed in % by mass. Therefore, the content of the antimony component in the above range is the Sb 2 O 3 equivalent amount of the antimony component contained in the antimony-doped tin oxide with respect to the SnO 2 equivalent amount of the tin component contained in the antimony-doped tin oxide coating the aluminum oxide particles. means the ratio (% by mass) of The reason why the content of the antimony component is set above is as follows.
  • the content of the antimony component is 26% by mass or more in terms of oxide with respect to the content of the tin component.
  • the upper limit of the content of the antimony component is not particularly limited from the viewpoint of conductivity, but even if it exceeds 45% by mass, no improvement in conductivity can be expected. A content of 45% by mass in terms of oxide with respect to the amount is sufficient.
  • the content of the antimony component should be 45% by mass or less in terms of oxide with respect to the content of the tin component from the viewpoint of whiteness. is preferred.
  • the content of the antimony component with respect to the content of the tin component is converted to the oxide standard (antimony component: Sb 2 O 3 , tin component: SnO 2 ), and the content of the antimony component is divided by the content of the tin component. calculated by The content of the antimony component with respect to the content of the tin component calculated in this manner is referred to as " oxide conversion ( Sb2O3 / SnO2 )" or " Sb2O3 / SnO2 " in the present application. sometimes.
  • the coating amount of antimony-doped tin oxide is equivalent to oxide conversion (Sb 2
  • the total amount of O 3 and SnO 2 ) is preferably 10% by mass or more and 40% by mass or less, more preferably 20% by mass or more and 35% by mass or less. If it is 10% by mass or more, the mass ratio of the antimony-doped tin oxide coating to the substrate particles made of aluminum oxide is sufficient, and if it is insufficient, the desired conductivity cannot be obtained. This is preferable in that it can be effectively avoided.
  • the coating amount of antimony-doped tin oxide is too large, an effective improvement in electrical conductivity cannot be expected, so the coating amount is preferably 40% by mass or less.
  • the above-mentioned “oxide conversion (total amount of Sb2O3 and SnO2 ) " may be expressed as " Sb2O3 + SnO2 " in the present application, and this is the content of the antimony component and the tin component . is converted into the content as Sb 2 O 3 and the content as SnO 2 , respectively, and the two are added. Therefore, the coating amount of antimony-doped tin oxide in the above range is the content of aluminum oxide (Al 2 O 3 ) particles in the coated aluminum oxide particles (that is, the content of the Al 2 O 3 component in the coated aluminum oxide particles). of the antimony component in terms of Sb 2 O 3 and the amount of tin component in terms of SnO 2 contained in the antimony-doped tin oxide coating the aluminum oxide particles.
  • the coating amount of antimony-doped tin oxide is obtained by converting the contents of the antimony component and the tin component contained in the coated aluminum oxide particles of the present invention into oxide standards (antimony component: Sb 2 O 3 , tin component: SnO 2 ). Then, it is calculated by dividing the sum of the content of the antimony component and the content of the tin component by the content of aluminum oxide.
  • the coating amount of antimony-doped tin oxide calculated in this manner is sometimes expressed as "(Sb 2 O 3 +SnO 2 )/Al 2 O 3 " in the present application.
  • the content of the sodium component is the oxide-equivalent amount of all constituent elements of the coated aluminum oxide particles (that is, the amount obtained by converting all the constituent elements to the content as oxides). is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.01% by mass or less in terms of oxide (Na 2 O). If the content of the sodium component is within the above range, it is possible to more effectively avoid the decrease in electrical conductivity due to the inclusion of the sodium component in the coated aluminum oxide particles. Therefore, the sodium component is preferably within the above range.
  • the pulverization time is defined as the time until the coated aluminum oxide particles are pulverized to a cumulative 50% diameter (D50) of 0.4 ⁇ m or less.
  • D50 cumulative 50% diameter
  • the crushing time is preferably less than 20 minutes, more preferably within 15 minutes. If the crushing time is as described above, it can be said to have good crushability.
  • the proportion of particles larger than 1 ⁇ m is calculated from the particle size distribution obtained when the coated aluminum oxide particles of the present invention dispersed in a solvent are measured by a laser diffraction/scattering particle size distribution analyzer.
  • the crushing time was determined by weighing 5 g of coated aluminum oxide particles, 30 g of pure water, and 30 g of glass beads, placing them in a glass container, and crushing them with a disperser (paint shaker, manufactured by Red Devil). The time until the % diameter (D50) reaches 0.4 ⁇ m or less is measured.
  • a dispersion containing aluminum oxide particles and an aqueous dispersion medium is added with an antimony component of 26% by mass in terms of oxide (Sb 2 O 3 /SnO 2 ) with respect to the tin component.
  • the aqueous dispersion medium is mainly composed of water, that is, has a water content of 50% by mass or more.
  • the water content of the aqueous dispersion medium is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • components other than water include various organic solvents that dissolve in water (methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran, etc.).
  • the concentration of aluminum oxide particles in the aluminum oxide dispersion is preferably 10% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less.
  • a content of 10% by mass or more is preferable in that a decrease in the amount of coated aluminum oxide particles produced can be more effectively avoided.
  • the content is 40% by mass or less, it is possible to more effectively avoid the difficulty in forming an antimony-doped tin oxide coating on the surfaces of aluminum oxide particles due to the thickening of the dispersion. preferable.
  • a coating method a known method can be used. For example, at least one compound selected from zinc, silicon, titanium, aluminum, zirconium, tin and cerium is added to the aluminum oxide dispersion, and an acid and / Or you may add an alkali and coat an inorganic compound on the aluminum oxide particle surface.
  • a hydrochloric acid solution containing a tin component and an antimony component examples include tin halides such as tin chloride, tin oxide, tin hydroxide, tin sulfates, tin nitrate and other tin inorganic acid salts (stannous salts, stannic salts), and the like. These may be used alone or in combination of two or more. Above all, from the viewpoint of suppressing the content of sodium components in the coated aluminum oxide particles, use a sodium-free tin compound such as tin halide instead of a sodium-containing tin compound such as sodium stannate. is preferred.
  • Antimony components include antimony halides such as antimony chloride, antimony oxides, antimony hydroxides, and inorganic acid salts such as antimony sulfates. good. Above all, from the viewpoint of suppressing the content of sodium components in the coated aluminum oxide particles, use antimony compounds that do not contain sodium, such as antimony halides, instead of sodium-containing antimony compounds, such as sodium antimonate. is preferred.
  • the method of dissolving the tin component and the antimony component in the hydrochloric acid solution is not particularly limited.
  • the tin component and the antimony component may be dissolved in the hydrochloric acid solution at the same time, or the tin component dissolved in the hydrochloric acid solution and the antimony component dissolved in the hydrochloric acid solution may be separately prepared and mixed.
  • either the tin component or the antimony component may be dissolved in a hydrochloric acid solution and the other component may be dissolved.
  • the concentration of hydrochloric acid in the hydrochloric acid solution is not particularly limited.
  • the solution may be dissolved while being stirred using a known stirrer such as a blade stirrer, a disper, and a homomixer.
  • the tin component and the antimony component are 26% by mass or more and 45% by mass in terms of oxide (Sb 2 O 3 /SnO 2 ) with respect to the tin component. %, preferably 30% to 45% by mass, more preferably 30% to 40% by mass, even more preferably 30% to 35% by mass.
  • the content of the antimony component with respect to the tin component can be within the above range in terms of oxide (Sb 2 O 3 /SnO 2 ). , which can improve the electrical conductivity of the coated aluminum oxide particles and have appropriate whiteness.
  • a hydrochloric acid solution containing a tin component and an antimony component and an alkali are mixed with the aluminum oxide dispersion to precipitate tin hydroxide containing an antimony component on the surface of the aluminum oxide particles.
  • the ratio of the total amount of the tin component and the antimony component contained in the hydrochloric acid solution is the ratio of the aluminum oxide (Al 2 O 3 ) component of the aluminum oxide particles to the oxide conversion (the ratio of Sb 2 O 3 and SnO 2 total amount) is preferably 10% by mass or more and 40% by mass or less, more preferably 20% by mass or more and 35% by mass or less.
  • the coating amount of antimony-doped tin oxide on the aluminum oxide particles can be within the above range.
  • the above-mentioned “oxide conversion (total amount of Sb2O3 and SnO2 ) " may be expressed as " Sb2O3 + SnO2 " in the present application, and this is the content of the antimony component and the tin component . is converted into the content as Sb 2 O 3 and the content as SnO 2 , respectively, and the two are added.
  • the ratio of the total amount of the tin component and the antimony component contained in the hydrochloric acid solution within the above range is the amount of aluminum oxide (Al 2 O 3 ) particles contained in the aluminum oxide dispersion in the hydrochloric acid solution. It means the ratio (% by mass) of the sum (total) of the Sb 2 O 3 equivalent amount of the antimony component and the SnO 2 equivalent amount of the tin component.
  • the total amount of the tin component and the antimony component contained in the hydrochloric acid solution is obtained by converting the contents of the antimony component and the tin component into oxide standards (antimony component: Sb 2 O 3 , tin component: SnO 2 ), It is calculated by dividing the sum (total) of the content of the antimony component and the content of the tin component by the amount of aluminum oxide (Al 2 O 3 ) particles contained in the aluminum oxide dispersion.
  • the total amount of the tin component and the antimony component contained in the hydrochloric acid solution calculated in this manner may be expressed as "(Sb 2 O 3 +SnO 2 )/Al 2 O 3 " in the present application.
  • the aluminum oxide particles are referred to as “antimony-containing tin hydroxide-coated aluminum oxide particles”
  • the coated aluminum oxide particles obtained by sintering the particles are also suppressed from agglomerating, and the crushing time to a desired particle size can be shortened.
  • the aluminum oxide dispersion is preferably heated to a liquid temperature of 50° C. or higher and 95° C. or lower. °C or higher and 95 °C or lower, and more preferably 60 °C or higher and 95 °C or lower.
  • the aluminum oxide dispersion liquid may be heated to a liquid temperature of 50° C. or higher and 90° C. or lower, 55° C. or higher and 90° C. or lower, or 60° C. or higher and 90° C. or lower.
  • the temperature of the aluminum oxide dispersion is in the range of 50° C. or higher and 95° C.
  • the pH is preferably maintained at 4 or more and 10 or less, more preferably 5 or more and 9 or less. It is more preferable to keep it at 6 or more and 8 or less. With such a pH range, aggregation of the aluminum oxide particles as the base material can be suppressed, so that a uniform antimony-doped tin oxide coating can be formed on the aluminum oxide particle surfaces, and the conductivity can be more effectively improved. can be made
  • the dispersion of antimony-containing tin hydroxide-coated aluminum oxide particles thus obtained may be subjected to an aging treatment, if necessary.
  • the conditions for the aging treatment are not particularly limited, but the temperature conditions are preferably 50° C. or higher and 95° C. or lower. Moreover, you may heat to 60 degreeC or more and 80 degrees C or less.
  • the aging time is preferably 10 minutes or more and 120 minutes or less. Further, it is preferable to keep the pH at 2 or more and 8 or less, more preferably 2 or more and 5 or less during the aging treatment. By setting the pH within the above range, the content of the sodium component in the coated aluminum oxide particles can be suppressed.
  • the pH of the dispersion of antimony-containing tin hydroxide-coated aluminum oxide particles may be adjusted using a known pH adjuster or the like.
  • aging may be performed while stirring using a known stirrer such as a blade stirrer, disper, homomixer, and the like.
  • the dispersion of antimony-containing tin hydroxide-coated aluminum oxide particles may be subjected to solid-liquid separation, if necessary.
  • a known filtration method can be used for solid-liquid separation.
  • pressure filtration devices such as rotary presses and filter presses that are usually used industrially, and vacuum filtration devices such as Nutsche and Moore filters can be used. can be done. Centrifugation or the like can also be used.
  • the solid content may be washed by a known method using pure water or the like.
  • the drying temperature and drying time can be appropriately set.
  • the drying temperature is preferably 30° C. or higher and 120° C. or lower, and the drying time is preferably 0.5 hours or longer and 10 hours or shorter.
  • a heating device such as a dryer, an oven, or an electric furnace can be used.
  • the firing temperature in the firing step is 400° C. or higher and 800° C. or lower, preferably 450° C. or higher and 750° C. or lower, and more preferably 500° C. or higher and 700° C. or lower. By setting the temperature within the above range, antimony-doped tin oxide-coated aluminum oxide particles having a desired particle size can be obtained.
  • the firing time is not particularly limited, but is preferably 30 minutes or more and 10 hours or less, more preferably 1 hour or more and 4 hours or less.
  • the firing atmosphere in the firing step is not particularly limited, but it is industrially preferable to perform firing in an air atmosphere.
  • coated aluminum oxide particles produced by the above method may be appropriately adjusted in particle size using a known crusher, classifier, or the like.
  • the organic compound coating it is preferable to add the organic compound to the powder of the coated aluminum oxide particles for coating, and it is more preferable to include a heating step.
  • the conditions of the heating step can be appropriately set.
  • the heating temperature is preferably 50° C. or higher and 200° C. or lower, and the heating time is preferably 10 minutes or longer and 120 minutes or shorter.
  • the coated aluminum oxide particles of the present invention can be used as a conductive material by utilizing their conductive properties, and their volume resistivity is preferably 50 ⁇ cm or less, more preferably 30 ⁇ cm or less. is more preferable, and 15 ⁇ cm or less is even more preferable. If the volume resistivity is as described above, it can be used as a conductive material.
  • the volume resistivity can be calculated from a volume resistance value measured using a known measuring device. As the measuring device, for example, a digital multimeter (manufactured by Yokogawa Instrument Co., Ltd.) can be used.
  • coated aluminum oxide particles of the present invention can also be used as a white conductive material by utilizing the conductivity and whiteness.
  • the coated aluminum oxide particles of the present invention may be used in combination with other coloring agents and conductive agents.
  • a known mixer can be used for the mixing step when producing the above solvent composition. Moreover, you may deaerate as needed in the case of said mixing.
  • the mixer include a twin-screw mixer, three-roll mixer, sand mill, planetary mixer, etc., which are commonly used industrially, and for laboratory scale, stirrers, hybrid mixers, homogenizers, paint shakers, etc. are used. be able to. At that time, if necessary, pulverizing media containing glass, alumina, zirconia, zirconium silicate, or the like may be used.
  • the coated aluminum oxide particles of the present invention can be mixed with a resin to form a resin composition.
  • Resins used in the resin composition include thermoplastic resins, thermosetting resins, thermoplastic elastomers, and the like.
  • a thermoplastic resin (1) general-purpose plastic resins (e.g., (a) polyolefin resins (polyethylene, polypropylene, etc.), (b) polyvinyl chloride resins, (c) acrylonitrile-butadiene-styrene resins, (d) polystyrene resins, (e) methacrylic resins, ( f) polyvinylidene chloride resin, etc.), (2) engineering plastic resin (for example, (a) polycarbonate resin, (b) polyethylene terephthalate resin, (c) polyamide resin, (d) polyacetal resin, (e) modified polyphenylene ether, (f) fluororesin, etc.), (3) super engineering plastic resins (for example, (a) polyphenylene
  • the coated aluminum oxide particles of the present invention and the conductive material containing the same can be mixed with a coating resin to form a coating composition.
  • the paint resin is not particularly limited as long as it is commonly used for paint applications. , polyolefin resin, polyurethane resin, acrylic urethane resin, epoxy resin, modified epoxy resin, silicone resin, acrylic silicone resin, fluorine resin, ethylene vinyl acetate copolymer, acrylic-styrene copolymer, amino resin, methacrylic resin, polycarbonate resin , polyvinyl chloride resin, etc., can be used.
  • the coating composition of the present invention can contain various additives, solvents, etc., if necessary.
  • Additives include various commonly used dispersants, emulsifiers, antifreeze agents, pH adjusters, thickeners, antifoaming agents, film-forming aids, and the like.
  • solvents include water solvents, alcohols (methanol, butanol, ethylene glycol, etc.), esters (ethyl acetate, etc.), ethers, ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (toluene, xylene, mineral spirits, etc.), Non-aqueous solvents such as aliphatic hydrocarbons, or mixed solvents thereof may be used.
  • concentration of coated aluminum oxide particles in such a coating composition can be set appropriately.
  • the same method as the mixing step in preparing the solvent composition can be used.
  • Example 1 200 g of aluminum oxide particles (manufactured by Sumitomo Chemical Co., Ltd., AKP-30) were dispersed in 1 L of pure water using a stirrer to obtain an aluminum oxide dispersion having a pH of 7 to 8. This dispersion was heated to 70° C. while stirring with a stirrer. The liquid temperature of the aluminum oxide dispersion was maintained until the aging process was completed. Also, 20.7 g of antimony trichloride was dissolved in 118 g of 35% by mass hydrochloric acid, and 138.3 g of a 50% by mass aqueous solution of tin tetrachloride was mixed to obtain a hydrochloric acid solution.
  • aluminum oxide particles manufactured by Sumitomo Chemical Co., Ltd., AKP-30
  • Example 2 In Example 1, the Sb 2 O 3 /SnO 2 in the hydrochloric acid solution was changed to 33.3% by mass, and the (Sb 2 O 3 + SnO 2 )/Al 2 O 3 was changed to 33.3% by mass. Sample 2 was obtained in the same manner as in Example 1. For Sample 2, the cumulative frequency of particles with a particle diameter of more than 1 ⁇ m was calculated and found to be 13.8%.
  • Example 3 In Example 1, except that Sb 2 O 3 /SnO 2 in the hydrochloric acid solution was changed to 35.0% by mass and (Sb 2 O 3 + SnO 2 )/Al 2 O 3 was changed to 33.0% by mass. Sample 3 was obtained in the same manner as in Example 1. For sample 3, the cumulative frequency of particles with a particle diameter of more than 1 ⁇ m was calculated and found to be 20.1%.
  • Example 4 In Example 1, except that Sb 2 O 3 /SnO 2 in the hydrochloric acid solution was changed to 40.0% by mass and (Sb 2 O 3 + SnO 2 )/Al 2 O 3 was changed to 28.0% by mass. Sample 4 was obtained in the same manner as in Example 1. For Sample 4, the cumulative frequency of particles with a particle diameter of more than 1 ⁇ m was calculated and found to be 19.8%.
  • Example 5 In Example 1, the Sb 2 O 3 /SnO 2 in the hydrochloric acid solution was changed to 29.7% by mass, and the (Sb 2 O 3 + SnO 2 )/Al 2 O 3 was changed to 19.5% by mass. Sample 5 was obtained in the same manner as in Example 1. For sample 5, the cumulative frequency of particles with a particle diameter of more than 1 ⁇ m was calculated and found to be 16.3%.
  • Example 6 Sample 6 was obtained in the same manner as in Example 1, except that the pH was changed to 5 in the aging step. For Sample 6, the cumulative frequency of particles with a particle diameter of more than 1 ⁇ m was calculated and found to be 15.5%.
  • Example 7 Sample 7 was obtained in the same manner as in Example 1, except that the pH was changed to 6 in the aging step. For Sample 7, the cumulative frequency of particles with a particle diameter of more than 1 ⁇ m was calculated and found to be 16.2%.
  • Example 8 Sample 8 was obtained in the same manner as in Example 1, except that the pH was changed to 7 in the aging step. For Sample 8, the cumulative frequency of particles with a particle diameter of more than 1 ⁇ m was calculated and found to be 15.8%.
  • Example 9 Sample 9 was obtained in the same manner as in Example 1, except that the temperature of the aluminum oxide dispersion was changed to 90° C. and maintained until the aging step was completed.
  • ⁇ Comparative Example 1> 300 g of aluminum oxide particles (manufactured by Sumitomo Chemical Co., Ltd., AKP-30) were dispersed in 2 L of pure water using a stirrer to obtain a dispersion having a pH of 8. This aluminum oxide dispersion was heated to 70° C. while stirring with a stirrer. Next, 18.1 g of antimony trichloride was dissolved in 779.8 g of 2.4N hydrochloric acid, and 160.5 g of tin tetrachloride pentahydrate was dissolved therein to obtain a hydrochloric acid solution. In the hydrochloric acid solution, Sb 2 O 3 /SnO 2 16.7% by mass.
  • Example 2 ⁇ Comparative Example 2>
  • the Sb 2 O 3 /SnO 2 in the hydrochloric acid solution was changed to 20.0% by mass, and the (Sb 2 O 3 + SnO 2 )/Al 2 O 3 was changed to 24.0% by mass.
  • Sample 12 of Comparative Example 2 was obtained in the same manner as in Example 1.
  • Example 3 ⁇ Comparative Example 3> In Example 1, except that Sb 2 O 3 /SnO 2 in the hydrochloric acid solution was changed to 50.0% by mass and (Sb 2 O 3 + SnO 2 )/Al 2 O 3 was changed to 30.0% by mass. Sample 13 of Comparative Example 3 was obtained in the same manner as in Example 1.
  • the content of the antimony component with respect to the content of the tin component in samples 1 to 13 (Sb 2 O 3 /SnO 2 ), the total amount of the content of the tin component and the content of the antimony component with respect to the aluminum oxide particles ((Sb 2 O 3 +SnO 2 )/Al 2 O 3 ), the analytical value of the sodium component content (Na 2 O), and the volume resistivity are shown in Table 1.
  • each value of Sb 2 O 3 /SnO 2 (% by mass) and (Sb 2 O 3 +SnO 2 )/Al 2 O 3 (% by mass) described in Table 1 was obtained from Sample 1, which is the final product. It should be noted that this is an analytical value of 13 and not the expressed value in hydrochloric acid solution.
  • samples 1 to 10 produced with Sb 2 O 3 /SnO 2 of 26% by mass or more and 45% by mass or less have a volume resistivity of 50 ⁇ cm or less and have sufficient conductivity. I understand.
  • the same sample has an L value of 60 or more and a b value of 0.3 or less, indicating sufficient whiteness.
  • the volume resistivity is greater than 50 ⁇ cm, indicating insufficient conductivity.
  • the Sb 2 O 3 /SnO 2 content exceeds 45% by mass (Sample 13)
  • the b value exceeds 0.3, indicating insufficient whiteness.
  • D50 cumulative 50% diameter

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PCT/JP2023/000578 2022-01-13 2023-01-12 被覆酸化アルミニウム粒子及びその製造方法、並びにその用途 Ceased WO2023136283A1 (ja)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61286221A (ja) * 1985-06-07 1986-12-16 Ishihara Sangyo Kaisha Ltd 白色導電性粉末の製造方法
JPH09249820A (ja) * 1996-03-15 1997-09-22 Titan Kogyo Kk 白色導電性粉末及びその製造方法
JP2000082326A (ja) * 1998-09-04 2000-03-21 Toyota Central Res & Dev Lab Inc 酸化錫被覆無機粉末の製造方法
JP2014175174A (ja) * 2013-03-08 2014-09-22 Mitsui Mining & Smelting Co Ltd 導電性粒子
WO2015060232A1 (ja) * 2013-10-25 2015-04-30 三井金属鉱業株式会社 導電性粒子及びその製造方法
JP2015090825A (ja) * 2013-11-07 2015-05-11 三井金属鉱業株式会社 導電性粒子及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61286221A (ja) * 1985-06-07 1986-12-16 Ishihara Sangyo Kaisha Ltd 白色導電性粉末の製造方法
JPH09249820A (ja) * 1996-03-15 1997-09-22 Titan Kogyo Kk 白色導電性粉末及びその製造方法
JP2000082326A (ja) * 1998-09-04 2000-03-21 Toyota Central Res & Dev Lab Inc 酸化錫被覆無機粉末の製造方法
JP2014175174A (ja) * 2013-03-08 2014-09-22 Mitsui Mining & Smelting Co Ltd 導電性粒子
WO2015060232A1 (ja) * 2013-10-25 2015-04-30 三井金属鉱業株式会社 導電性粒子及びその製造方法
JP2015090825A (ja) * 2013-11-07 2015-05-11 三井金属鉱業株式会社 導電性粒子及びその製造方法

Non-Patent Citations (1)

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Title
See also references of EP4464666A4 *

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