WO2014098163A1 - Procédé de production de particules de type noyau-enveloppe et procédé de production de particules creuses - Google Patents

Procédé de production de particules de type noyau-enveloppe et procédé de production de particules creuses Download PDF

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WO2014098163A1
WO2014098163A1 PCT/JP2013/083995 JP2013083995W WO2014098163A1 WO 2014098163 A1 WO2014098163 A1 WO 2014098163A1 JP 2013083995 W JP2013083995 W JP 2013083995W WO 2014098163 A1 WO2014098163 A1 WO 2014098163A1
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core
particles
shell
metal oxide
producing
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PCT/JP2013/083995
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Japanese (ja)
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雄一 ▲桑▼原
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旭硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the present invention relates to a method for producing core-shell particles and a method for producing hollow particles using the same.
  • Patent Document 1 discloses that a spherical polymer particle is uniformly dispersed in an alcohol solution or an alcohol / water mixed solution of titanium alkoxide and / or silicon alkoxide, and a titanium compound is formed on the surface of the spherical polymer particle by a hydrolysis reaction.
  • a method for producing core-shell type composite particles by providing a coating layer or a silicon compound coating layer is described.
  • a method is described in which the composite particles are heated to decompose the polymer as a core, thereby forming voids in the particles to produce hollow particles.
  • Patent Document 1 describes an example in which a hydrolysis reaction was performed with a core particle content of 1.5 to 20 g and a metal alkoxide content of 1 to 40 g per liter of the reaction mixture. Yes. From the viewpoint of production efficiency, it is preferable to increase the content of the core particles in the reaction solution.
  • the present invention has been made in view of the above circumstances, and is capable of stably producing a core-shell particle or hollow particle having a good shape even when the concentration of the reaction solution is high. It aims to provide a method.
  • the gist of the present invention is the following [1] to [13].
  • a method for producing core-shell particles comprising a step of subjecting the precursor to hydrolysis and dehydration condensation to form a coating layer made of the metal oxide on the surface of the core particles.
  • [11] A step of producing core-shell particles in which a coating layer made of a metal oxide is formed on the surface of the core particles by the production method according to any one of [1] to [10], Heating the core-shell particles to decompose and remove the core particles.
  • core-shell particles or hollow particles having a good shape can be stably produced even when the concentration of the reaction solution is high.
  • Example 1B It is an electron micrograph of the hollow particles obtained in Example 1B.
  • 2 is an electron micrograph of Example 2.
  • 4 is an electron micrograph of Example 3.
  • 6 is an electron micrograph of Example 4.
  • 6 is an electron micrograph of Example 5.
  • 6 is an electron micrograph of Example 6.
  • the core particles in the present invention are particles made of a polymer (polymer particles).
  • the polymer that forms the core particles is not particularly limited.
  • a known organic polymer can be suitably used in the core-shell particles used for the production of hollow particles.
  • the organic polymer is not particularly limited as long as core particles having a desired particle diameter can be obtained.
  • the organic polymer is preferably a homopolymer or copolymer of a monomer selected from the group consisting of (meth) acrylic monomers, styrene monomers, diene monomers, imide monomers, and amide monomers.
  • Acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Pentyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, ( (Meth) acrylic acid dodecyl, (meth) acrylic acid phenyl, (meth) acrylic acid methoxyethyl, (meth) acrylic acid ethoxyethyl, (meth) acrylic acid propoxyethyl, (meth) acrylic acid butoxyethyl, (meth) acrylic acid Ethoxy
  • Styrene monomers include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, fluorostyrene, chlorostyrene, bromostyrene, Examples thereof include dibromostyrene, chloromethylstyrene, nitrostyrene, acetylstyrene, methoxystyrene, ⁇ -methylstyrene, vinyltoluene, sodium p-styrenesulfonate, and the like.
  • diene monomer examples include butadiene, isoprene, cyclopentadiene, 1,3-pentadiene, dicyclopentadiene, and the like.
  • imide monomers include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 6-aminohexyl succinimide, 2-aminoethyl succinimide, and the like.
  • amide monomers examples include acrylamide derivatives such as acrylamide and N-methylacrylamide; allylamine derivatives such as N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide; acrylamide derivatives such as acrylamide and N-methylacrylamide Aminostyrenes such as N-aminostyrene;
  • polystyrene or polymethyl methacrylate as the polymer for forming the core particles from the viewpoint of availability.
  • Polymer core particles can be produced by a known method. For example, it can be produced by a method in which a monomer is polymerized by a known polymerization method such as emulsion polymerization, suspension polymerization, or dispersion polymerization to form a particulate polymer. Alternatively, the core particles can also be produced by a method in which a bulk polymer is produced by a known polymerization method and then pulverized to form particles.
  • a known polymerization method such as emulsion polymerization, suspension polymerization, or dispersion polymerization to form a particulate polymer.
  • the core particles can also be produced by a method in which a bulk polymer is produced by a known polymerization method and then pulverized to form particles.
  • the average particle diameter of the core particles is preferably 0.01 to 100 ⁇ m, more preferably 0.03 to 50 ⁇ m, and particularly preferably 0.1 to 5 ⁇ m.
  • the average particle diameter is not less than the lower limit of the above range, core-shell particles having good uniform dispersibility in the liquid can be easily obtained, and when the average particle diameter is not more than the upper limit, precipitation of particles in the liquid is difficult to occur. Easy dispersibility.
  • the particle diameter of the core particles affects the size of the pores of the hollow particles.
  • the average particle size of the core particles in the core-shell particles used for producing the hollow particles is preferably 0.01 to 100 ⁇ m, more preferably 0.03 to 50 ⁇ m, and particularly preferably 0.1 to 5 ⁇ m.
  • the average particle diameter of the core particle in this specification is a volume-based 50% median diameter of the particle diameter measured by the dynamic light scattering method.
  • the average particle diameter of the core-shell particles in this specification is an average value of the particle diameters of 10 particles randomly selected in an image obtained by observation with a microscope. As the microscope, a scanning electron microscope or a transmission electron microscope can be used.
  • the metal oxide precursor means a compound from which the target metal oxide is obtained by hydrolysis and dehydration condensation reaction.
  • the metal oxide in this invention should just be a thing which can be produced
  • One type of metal oxide may be used to form the coating layer, or two or more types of metal oxide may be used in combination to form the coating layer.
  • the reaction rate of hydrolysis is relatively fast, formation of a coating layer is likely to be poor when the concentration in the reaction solution is high, and titanium oxide is effective in applying the production method of the present invention. Is more preferable.
  • a known metal oxide precursor can be used. It is preferable to use a metal alkoxide in that it is easy to form a metal oxide from the precursor.
  • the number of carbon atoms of the alkoxy group in the metal alkoxide is preferably 1 to 6, and more preferably 1 to 4.
  • the titanium oxide precursor includes alkoxy titanium (titanium alkoxide), titanium chloride and the like, and alkoxy titanium is preferable.
  • the alkoxytitanium include tetraalkoxytitanium (tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, titanium dichloride diisopropoxide, and the like).
  • titanium chloride include titanium tetrachloride. Of these, tetraalkoxytitanium is preferred in that the metal oxide can be easily formed from the precursor.
  • the complexing agent in the present invention means a compound capable of coordinating with a metal oxide precursor.
  • Specific examples of the complexing agent include ⁇ -diketones such as acetylacetone, ethylenediamine, bipyridine, ethylenediaminetetraacetic acid, phenanthroline, porphyrin, crown ether and the like.
  • An organic solvent is used as a dispersion medium in the reaction solution.
  • the organic solvent include alcohols and glycol solvents. Of these, alcohol is preferred because it is inexpensive.
  • An organic solvent may be used individually by 1 type, and may mix and use 2 or more types. Specific examples of the alcohol include saturated alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol.
  • the dispersion medium may contain water in addition to the organic solvent, but it is preferable that the content of water is small in that the reaction rate of hydrolysis and dehydration condensation reaction can be easily controlled. For example, the content of water is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably no water with respect to the total amount of the organic solvent and water.
  • the manufacturing method of the present embodiment includes a hydrolysis and dehydration condensation reaction of a metal oxide precursor in a reaction solution containing a dispersion medium, core particles, a metal oxide precursor, and a complexing agent. And forming a coating layer made of a metal oxide on the surface of the core particle. That is, the method for producing core-shell particles of the present embodiment includes a dispersion medium, core particles, a metal oxide precursor, and 0.01 to 0.25 mol of complexing agent with respect to 1 mol of the metal of the precursor.
  • the liquid temperature (reaction temperature) of the reaction solution is not particularly limited, and the reaction solution may be heated or cooled, or may be room temperature. For example, it can be in the range of 0 to 80 ° C. As the reaction temperature is higher, the reaction rate of hydrolysis and dehydration condensation reaction tends to increase. A temperature of 40 ° C. or lower is preferable because the reaction rate can be easily controlled, and a temperature of 0 ° C. or higher is preferable because the reaction solution is hardly frozen. 5 to 30 ° C. is more preferable. Room temperature is preferable in that heating or cooling equipment is unnecessary, and for example, 15 to 25 ° C is preferable.
  • the following method is mentioned as an example of the manufacturing method of a specific core-shell particle.
  • core particles are dispersed in a dispersion medium.
  • the complexing agent is mixed and dissolved.
  • a metal oxide precursor is added and mixed to prepare a reaction solution.
  • a metal chelate compound such as titanium acetylacetonate is obtained by mixing a metal oxide precursor and a complexing agent. Separately mix the dispersion medium and the core particles.
  • a liquid containing the metal chelate compound is added to and mixed with the mixed liquid of the dispersion medium and the core particles to prepare a reaction liquid.
  • the method (i) is preferable because the core-shell particles can be easily produced stably.
  • the order of adding the core particles, the complexing agent, and the optional components to the dispersion medium is arbitrary. Since the hydrolysis and dehydration condensation reaction may occur when the metal oxide precursor and the dispersion medium come into contact with each other, it is preferable to add the metal oxide precursor last.
  • the liquid temperature immediately before the addition of the metal oxide precursor is preferably a predetermined reaction temperature.
  • the core particles may be added in powder form, or may be added in the state of a dispersion (sol) in which the core particles are dispersed in an organic solvent.
  • the core particle content in the reaction solution is preferably 0.01 to 15.0 mass%, more preferably 0.05 to 5.0 mass%.
  • it is at least the lower limit of the above range, it is easy to synthesize core-shell particles with good productivity, and when it is at most the upper limit, aggregation of the particles can be easily suppressed and a core-shell particle dispersion with good uniform dispersibility can be easily obtained.
  • the content of the metal oxide precursor in the reaction solution is expressed as a value converted into the solid content mass of the metal oxide, it is 0.01 to 6.0 mass with respect to the total weight of the reaction solution (total solution weight). % Is preferable, and 0.03 to 2.0 mass% is more preferable.
  • the amount of the metal oxide precursor used is preferably set according to the thickness of the coating layer (shell) to be obtained.
  • the content of the metal oxide precursor in the reaction solution is preferably 0.03% by mass or more, more preferably 0.1% by mass or more in that the effect of applying the production method of the present invention is large. More preferred.
  • the addition amount of the complexing agent is too small, the effect of addition cannot be obtained, and if it is too large, formation failure of the coating layer tends to occur.
  • the content of the complexing agent in the reaction solution is 0.01 to 0.25 mol, preferably 0.03 to 0.20 mol, per mol of the precursor metal.
  • the reaction solution prepared in this manner is stirred while maintaining a predetermined reaction temperature, and the precursor of the metal oxide is subjected to hydrolysis and dehydration condensation reaction, thereby forming the metal oxide on the surface of the core particle.
  • Core-shell particles with a coating layer formed are obtained.
  • the average particle diameter of the core-shell particles is preferably 0.01 to 200 ⁇ m, more preferably 0.03 to 100 ⁇ m, and particularly preferably 0.1 to 10 ⁇ m. When the average particle diameter is not less than the lower limit of the above range, uniformly dispersed core-shell particles can be obtained, and when the average particle diameter is not more than the upper limit, precipitation of particles can be prevented and a slurry having good dispersibility can be obtained.
  • the ratio of the average particle size of the core particles to the average particle size of the core-shell particles is preferably 0.50 to 0.99, and more preferably 0.77 to 0.97.
  • the ratio of the average particle diameter is not less than the lower limit of the above range, the effect of stabilizing the production of the core-shell particles due to the formation of the coating layer by electroadsorption to the core particles can be sufficiently obtained.
  • the function as the core-shell particle is sufficiently exhibited.
  • the mechanism by which the coating layer is formed on the surface of the core particle is considered as follows. That is, hydrolysis and dehydration condensation reaction of the metal oxide precursor occurs in the stirred reaction liquid. By this reaction, it is considered that the metal oxide precipitates in the form of fine particles, and the metal oxide particles move to the surface of the core particles and are adsorbed and deposited, whereby the coating layer grows. Normally, the core particles and the metal oxide particles each have a surface charge, and the metal oxide particles move to the surface of the core particles by electrophoresis (movement based on electrical interaction) and are adsorbed. It is thought. When the content of the metal oxide precursor in the reaction solution increases, the amount of metal oxide particles deposited per unit time in the reaction solution increases.
  • the complexing agent is coordinated to the metal of the precursor of the metal oxide, so that the hydrolysis and dehydration condensation reaction of the precursor is moderated.
  • the hydrolysis and dehydration condensation reaction of the precursor of the metal oxide becomes slow, and the precipitation rate of the metal oxide particles becomes slow, so that the aggregation of the metal oxide particles can be suppressed.
  • the complexing agent is contained in the reaction solution so that the molar ratio of the metal oxide precursor metal to the complexing agent is within a predetermined range.
  • the method for producing hollow particles of the present embodiment includes the steps of producing core-shell particles in which a coating layer made of a metal oxide is formed on the surface of the core particles, heating the core-shell particles, and And a step of decomposing and removing the particles. That is, the hollow particle production method of the present embodiment includes a dispersion medium, a core particle, a metal oxide precursor, and a predetermined amount of a complexing agent; the dispersion medium, the core particle, a metal oxide precursor; And a complexing agent is mixed; a coating layer made of a metal oxide is formed on the surface of the core particles; and the core particles are decomposed and removed.
  • the core-shell particles obtained by the above production method are heated in an atmosphere containing oxygen, such as air, so that the core particles made of the polymer are decomposed and gasified to be removed. Since the gasified polymer is scattered through the shell of the core-shell particles, hollow particles having pores inside are obtained.
  • the method for heating the core-shell particles is not particularly limited. For example, a method in which dried particles obtained by drying core-shell particles are heated in a heating furnace, and a coating solution in which core-shell particles are dispersed in an organic solvent such as alcohol is applied on a heat-resistant substrate, and then heated in a heating furnace. Methods and the like.
  • the heating temperature for heating the core-shell particles may be higher than the decomposition temperature of the polymer forming the core particles.
  • the heating temperature (the highest temperature in the heating step) is preferably 100 ° C. or higher, more preferably 300 ° C. or higher, and further preferably 400 ° C. or higher.
  • the upper limit of the heating temperature is not particularly limited, but is preferably less than the melting point of the metal oxide to be formed (for example, the melting point of titanium oxide is 1870 ° C.) in that the phenomenon that the shell melts and the internal vacancies disappear hardly occurs. More preferably, the melting point is 200 ° C. or more lower than the melting point. That is, the upper limit of the heating temperature is preferably 1870 ° C.
  • the heating time is not particularly limited as long as the polymer forming the core particles is sufficiently decomposed and removed.
  • the time from the start of temperature increase to the start of temperature decrease is preferably 1 minute to 100 hours, and more preferably 3 minutes to 50 hours.
  • the heating rate when heating the core-shell particles is preferably 30 to 3,000 ° C./hour, more preferably 100 to 1,000 ° C./hour.
  • the average particle size of the hollow particles is preferably 0.01 to 200 ⁇ m, more preferably 0.03 to 100 ⁇ m, and particularly preferably 0.1 to 10 ⁇ m. If the average particle diameter is not less than the lower limit of the above range, hollow particles having good uniform dispersibility in the liquid can be easily obtained, and if it is not more than the upper limit, precipitation of particles in the liquid is difficult to occur and good. Easy dispersibility.
  • the ratio of the average pore diameter (inner diameter) when the average particle diameter (outer diameter) of hollow particles is 1 (hereinafter also referred to as the ratio of inner diameter average / outer diameter average) is 0.50 to 0.99 is preferable, and 0.77 to 0.97 is more preferable.
  • the average particle diameter of the hollow particles in the present specification is an average value of the particle diameters (outer diameters) of 10 particles randomly selected in an image obtained by observation with a microscope.
  • the average value of the pore diameter (inner diameter) of the hollow particles in the present specification is the average value of the diameter (inner diameter) of ten randomly selected holes in the image obtained by observation with a transmission microscope. is there.
  • core-shell particles having a good shape can be stably obtained, hollow particles having a good shape can be stably produced by using this. be able to.
  • the hollow particles obtained by the production method of the present invention can be suitably used for, for example, a low reflection material, a heat insulating material, a light scattering material, a drug delivery and the like.
  • hollow particles made of titanium oxide are suitable for light scattering materials and the like because they have a large refractive index difference between the internal pores and the shell.
  • the core-shell particles obtained by the production method of the present invention produce hollow particles. In addition to the use as an intermediate for the purpose, for example, it can be suitably used for a matte material or the like.
  • the room temperature is 15 ° C.
  • the following method was used for the measurement.
  • [Measurement method of average particle diameter of core particles] The particle size distribution was measured using a dynamic light scattering nanotrack particle size analyzer (manufactured by Nikkiso Co., Ltd., product name: UPA-EX150 type), and the volume-based 50% median diameter was determined to obtain the average particle size.
  • [Measurement method of average particle diameter of hollow particles] The average particle size of the hollow particles is measured randomly by observing the hollow particles obtained by removing the core particles of the core-shell particles by the method of each example with a scanning electron microscope on the glass substrate.
  • the average value of the 10 particles selected in the above was determined and used as the average particle size.
  • the inner diameter of the hollow particles was measured randomly by observing the hollow particles obtained by removing the core particles of the core-shell particles by the method of each example with a transmission electron microscope on the glass substrate, and measuring the diameter (inner diameter) of the pores.
  • the average value of 10 selected particles was obtained and used as the inner diameter of the hollow particles (the diameter of the pores).
  • Preparation Example 1 Preparation of core particles
  • a solution obtained by adding 0.75 g of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) to 49.24 ml of distilled water was heated to 70 ° C. in a thermostatic bath, and then 2,2′-azobis (2- 0.012 g of methylpropionamidine) dihydrochloride (AIBA) was added. While maintaining this at 70 ° C., the mixture was stirred for 8 hours to cause a polymerization reaction, thereby obtaining a dispersion in which core particles (polystyrene particles) made of polystyrene were dispersed in water.
  • AIBA 2,2′-azobis (2- 0.012 g of methylpropionamidine) dihydrochloride
  • the dispersion was centrifuged at a rotational speed of 10,000 rpm for 30 minutes using a centrifuge (manufactured by KOKUSAN, product name: H-2000B, the same applies hereinafter) to obtain a precipitate of polystyrene particles.
  • the precipitate was diluted with ethanol (manufactured by Kanto Chemical Co., Ltd., the same shall apply hereinafter) so that the solid content concentration was 1.5% by mass.
  • This was repeated three times to obtain a polystyrene particle sol dispersed in an ethanol solvent.
  • the content of polystyrene particles in the obtained polystyrene particle sol was 1.5% by mass, and the average particle diameter of the polystyrene particles in the polystyrene particle sol was 0.24 ⁇ m.
  • Example 1A Production of core-shell particles
  • tetraisopropoxy titanium manufactured by Kanto Chemical Co., Inc., the same applies hereinafter
  • acetylacetone is used as the complexing agent.
  • 0.0075 g of acetylacetone manufactured by Junsei Co., Ltd. was added to 7.78 g of ethanol at room temperature.
  • reaction solution (total amount: 10 g), which was stirred at room temperature (15 ° C.) for 30 minutes.
  • the content of polystyrene particles in the reaction solution is 0.3% by mass
  • the content of tetraisopropoxytitanium is a value converted to the solid content mass of titanium oxide and is 0.59% by mass with respect to the total weight of the reaction solution. It is.
  • the content of acetylacetone is 0.1 mol with respect to 1 mol of titanium of tetraisopropoxytitanium.
  • a core-shell particle sol in which core-shell particles in which a coating layer made of titanium oxide was formed on the surface of polystyrene particles (core particles) was dispersed in ethanol was obtained.
  • the content of the core-shell particles in the obtained core-shell particle sol was 0.89% by mass.
  • the average particle diameter of the obtained core-shell particles was 0.25 ⁇ m, and the ratio of the average particle diameter of the core particles to the average particle diameter of the core-shell particles (core particle diameter / core-shell particle diameter) was 0.97.
  • the main production conditions of this example and the physical property values of the product are shown in the “Example 1B” column of Table 1 below.
  • Example 1B Production of hollow particles
  • Example 2 2.71 g of the core-shell particle sol obtained in Example 1A was added to 17.29 g of ethanol and stirred at room temperature for 10 minutes to prepare a coating solution. About 3 g of the coating solution was dropped onto soda lime glass (Asahi Glass Co., Ltd., the same applies hereinafter) having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm, and a spin coater (Mikasa 1H-360S, the same applies hereinafter). A coating film was formed by spin coating under the conditions of 500 rpm and 20 seconds. The coating film was heated from 60 ° C. to 600 ° C.
  • FIG. 1 is an electron micrograph of the obtained hollow particles observed with a scanning electron microscope.
  • Example 1C Production of core-shell particles, production of hollow particles
  • Core shell particles were prepared as in Example 1A. However, 7.79 g of ethanol and 0.0038 g of acetylacetone were used.
  • Example 1D Production of core-shell particles, production of hollow particles
  • Example Core shell particles were prepared as in Example 1A. However, 0.0150 g of acetylacetone was used. The content of acetylacetone in the reaction solution is 0.2 mol with respect to 1 mol of titanium of tetraisopropoxytitanium. In this way, a core-shell particle sol was obtained.
  • the production conditions and physical property values of the products are shown in Table 1 below. Further, hollow particles were produced in the same manner as in Example 1B.
  • Example 2 This example is a comparative example in which core-shell particles were produced in Example 1A without containing a complexing agent in the reaction solution.
  • 2.0 g of the polystyrene particle sol obtained in Preparation Example 1 was added to 7.79 g of ethanol at room temperature, 0.21 g of tetraisopropoxy titanium was further added, and the mixture was stirred at room temperature (15 ° C.) for 30 minutes.
  • the main production conditions of this example and the physical properties of the product are shown in Table 1 below.
  • an observation sample fired on glass was prepared in the same manner as in Example 1B.
  • FIG. 2 is an electron micrograph obtained by observing the observation sample thus obtained with a scanning electron microscope.
  • Examples 3 to 6 A core-shell particle sol was obtained in the same manner as in Example 1A except that the composition of the reaction solution was changed as shown in Table 1. Table 1 below shows main production conditions and physical properties of the products in each example. Using the sol obtained after stirring for 30 minutes, an observation sample fired on glass was prepared in the same manner as in Example 1B. 3 to 6 are electron micrographs obtained by observing the observation sample thus obtained with a scanning electron microscope. [Example 7: Production of core-shell particles, production of hollow particles] (Example) Core shell particles were prepared as in Example 1A. However, 0.0115 g of 2,2′-bipyridine (manufactured by Nacalai Tesque) was used as a complexing agent.
  • 2,2′-bipyridine manufactured by Nacalai Tesque
  • the content of 2,2′-bipyridine in the reaction solution is 0.1 mol with respect to 1 mol of titanium of tetraisopropoxytitanium.
  • a core-shell particle sol was obtained.
  • the average particle diameter of the obtained core-shell particles was 0.25 ⁇ m, and the ratio of the average particle diameter of the core particles to the average particle diameter of the core-shell particles (core particle diameter / core-shell particle diameter) was 0.97.
  • hollow particles were produced in the same manner as in Example 1B.
  • the average particle diameter of the obtained hollow particles was 0.25 ⁇ m, and the ratio of inner diameter average / outer diameter average of the hollow particles was 0.97.
  • Example 8 Production of core-shell particles, production of hollow particles
  • Core shell particles were prepared as in Example 1A.
  • polystyrene particles having an average particle diameter of 1 ⁇ m were used as core particles (the content of polystyrene particles in the polystyrene particle sol was 1.5% by mass, and the polystyrene particle sol used was 2.0 g).
  • the content of acetylacetone in the reaction solution is 0.1 mol with respect to 1 mol of titanium of tetraisopropoxytitanium. In this way, a core-shell particle sol was obtained.
  • the average particle diameter of the obtained core-shell particles was 1.03 ⁇ m, and the ratio of the average particle diameter of the core particles to the average particle diameter of the core-shell particles (core particle diameter / core-shell particle diameter) was 0.97. Further, hollow particles were produced in the same manner as in Example 1B. The average particle diameter of the obtained hollow particles was 1.03 ⁇ m, and the ratio of the inner diameter average / outer diameter average of the hollow particles was 0.97.
  • the hollow particles obtained by the production method of the present invention can be suitably used for, for example, a low reflection material, a heat insulating material, a light scattering material, a drug delivery and the like.
  • the core-shell particle obtained by the manufacturing method of this invention can be used suitably for a mat

Abstract

La présente invention concerne des procédés avec lesquels des particules de type noyau-enveloppe et des particules creuses de forme satisfaisante peuvent être produites de façon stable même dans des cas dans lesquels la concentration de solution de réaction est élevée. Un procédé de production de particules de type noyau-enveloppe comprend une étape dans laquelle, dans une solution de réaction comprenant un milieu de dispersion, les particules de noyau, un précurseur d'oxyde métallique, et de 0,01 à 0,25 mole d'un agent complexant pour 1 mole de métal dans le précurseur, le précurseur est soumis à une réaction d'hydrolyse et de condensation par déshydratation pour former, sur les surfaces des particules de noyau, une couche de revêtement comprenant de l'oxyde métallique. Un procédé de production de particules creuses comprend une étape dans laquelle les particules de type noyau-enveloppe sont chauffées pour décomposer et éliminer les particules de noyau.
PCT/JP2013/083995 2012-12-21 2013-12-18 Procédé de production de particules de type noyau-enveloppe et procédé de production de particules creuses WO2014098163A1 (fr)

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