WO2010103773A1 - Particule composite et son procédé de fabrication - Google Patents

Particule composite et son procédé de fabrication Download PDF

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Publication number
WO2010103773A1
WO2010103773A1 PCT/JP2010/001574 JP2010001574W WO2010103773A1 WO 2010103773 A1 WO2010103773 A1 WO 2010103773A1 JP 2010001574 W JP2010001574 W JP 2010001574W WO 2010103773 A1 WO2010103773 A1 WO 2010103773A1
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Prior art keywords
particles
coating layer
phosphor
composite
composite particle
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PCT/JP2010/001574
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English (en)
Japanese (ja)
Inventor
鈴木真二
下山賢治
武居正史
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バンドー化学株式会社
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Priority to JP2010528622A priority Critical patent/JP4707200B2/ja
Publication of WO2010103773A1 publication Critical patent/WO2010103773A1/fr

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7729—Chalcogenides
    • C09K11/7731—Chalcogenides with alkaline earth metals

Definitions

  • the present invention relates to fluorescent composite particles and a method for producing the composite particles. More specifically, the present invention relates to composite particles used for imparting fluorescence to materials used for various display devices and light-emitting devices, and a method for producing the composite particles.
  • composite particles having fluorescence have been used in various display devices and light emitting devices such as light emitting diodes, cathode ray tubes, fluorescent lamps, plasma displays, field emission displays, fluorescent display tubes, cold cathode tubes, lasers, electroluminescence displays, and the like. It is used for the purpose of imparting fluorescence.
  • a film (phosphor film) containing phosphor particles as described above When a film (phosphor film) containing phosphor particles as described above is used in a device as described above, it is affected by the voltage, current or light source used as the excitation source of the phosphor particles, or the phosphor The phosphor particles may be deteriorated due to the influence of the heat accompanying the light emission of the particles themselves, the heat from the surroundings, moisture, oxygen, or the like, and the emission intensity may be lowered.
  • composite particles in which a coating layer containing a metal oxide is formed on at least a part of the surface of phosphor particles as a center are known.
  • a fluorescent film obtained by applying and heating a slurry in which composite particles are dispersed in a dispersion medium has been developed as a material imparted with a property (hereinafter referred to as “composite particle-containing material”) (for example, Patent Document 1).
  • This composite particle generally includes a dispersion treatment step in which a phosphor particle as a main component is dispersed in a dispersion medium, a dispersion treatment step for obtaining a paste, and an inorganic solution in the liquid, slurry, or paste obtained in this step. It is manufactured through a coating layer forming step in which a compound is added and a coating layer is formed by an alkoxide method or a sol-gel method (for example, Patent Documents 2 and 3).
  • phosphor particles having a particle size of less than a micron size have a large surface area and a high surface activity, so that aggregation easily occurs in the dispersion treatment step. A large shearing force is required to solve the aggregated state of the aggregated particles once aggregated. Further, even if the aggregated state of the aggregated particles is solved, reaggregation tends to occur.
  • Patent Document 4 intends to provide a coated illuminant that does not cause moisture degradation, has high luminance, and has a long light emission lifetime (see paragraph No. [0004] and the like in Patent Document 4).
  • Coating the phosphor with a coating material (II) obtaining a dispersion in which the coated phosphor is dispersed in a solvent; (III) separating the dispersion into a solid phase and a liquid phase.
  • a method of coating a light emitting body with a coating material by repeating steps (II) and (III) until the electric conductivity of the liquid phase becomes 100 ⁇ S / cm or less.
  • the present invention has been made in view of the above-described problems of the prior art, and provides composite particles having sufficient dispersibility in a dispersion medium, and thus sufficient dispersibility in a composite particle-containing material. Objective. Moreover, this invention aims at providing the manufacturing method of the composite particle which can obtain the composite particle of the above-mentioned this invention more reliably.
  • the present inventors have ensured sufficient dispersibility in the dispersion medium by sufficiently securing the bonding property between the phosphor particles of the composite particles and the coating layer.
  • the present inventors have found that it is extremely effective to make the composite particles satisfy the conditions represented by the following formula (1) at the same time.
  • the present invention Phosphor particles; Formed on at least a part of the surface of the phosphor particles, and a coating layer containing a metal oxide; Contains It has a configuration that satisfies the following formula (1): Provide composite particles. 0.53 ⁇ ( ⁇ / ⁇ 0 ) (1) [In the formula (1), ⁇ is a measured value of the bulk density of the composite particle based on the measurement method specified in JIS-R-1628, and ⁇ 0 is the true value of the composite particle based on the dry density measurement method by the constant volume expansion method. The measured density values are shown respectively. ]
  • the composite particles of the present invention have a configuration that simultaneously satisfies the condition represented by the formula (1), it is possible to sufficiently secure the bonding property between the phosphor particles and the coating layer. And the composite particle of this invention will have sufficient dispersibility in a dispersion medium and by extension sufficient dispersibility in a composite particle containing material.
  • the composite particles of the present invention are from the viewpoint that the metal oxide is chemically stable and it is difficult to form a composite compound with the phosphor particles, so that a coating can be formed without impairing the properties of the phosphor particles. It is valid.
  • the phosphor particles are not easily affected by heat, moisture, oxygen, or the like from the surroundings, are not easily deteriorated, and the light emission intensity is not easily lowered.
  • the value of ( ⁇ / ⁇ 0 ) shown in equation (1) is preferably as large as possible, but the theoretical upper limit is 1.0.
  • the maximum filling rate of true spheres with the same particle size is theoretically 0.74, but the actual particles have a distribution in particle size and are not perfect spheres but an irregular shape. Since particles of the same material have the same surface potential, the repulsive force increases as the particles approach each other. For this reason, it is not easy to obtain the theoretical maximum filling rate.
  • the value is about .5.
  • the optimum particle size distribution is selected based on the concept of filling small particles into gaps between large particles and filling smaller particles into the gaps. To do. Such selection of the particle size distribution is generally performed by mixing particles having a particle size distribution peak in about two or three different sizes. If the optimum particle size distribution is selected and an ideal pressure that deforms the particles can be realized, the maximum filling rate can be 0.74 or more (for example, 1.0). Is very difficult.
  • the value of ( ⁇ / ⁇ 0 ) is 1.0 or less
  • the upper limit value of ( ⁇ / ⁇ 0 ) is more preferably 0.74 in order to prevent the above-described disadvantages, and further, 0. 66 (an embodiment of the present invention).
  • ⁇ represents a measurement value of the bulk density of the composite particles based on the measurement method defined in JIS-R-1628. Specifically, for example, the measurement can be performed manually using a tapping method.
  • “Bulk density” indicates the density when a measurement container having a certain volume is filled with composite particles and the inner volume is defined as the volume.
  • This volume includes the following five types of volumes. That is, (I) the volume of the composite particle itself, (II) the volume of the closed pores in the composite particle, (III) the volume of the space on the surface of the composite particle, (IV) the gap between the composite particle and the composite particle (V) is the volume of the gap between the composite particle and the measurement container.
  • ⁇ 0 represents a measured value of the true density of the composite particles based on a dry density measuring method by a constant volume expansion method. More preferably, in the present invention, ⁇ 0 represents a measured value of the true density of the composite particles measured with a dry automatic densimeter “Acupic 1330” manufactured by Shimadzu Corporation.
  • the “true density” indicates a density obtained by using only the volume occupied by the composite particle itself as a volume for density calculation. However, if there is a space (closed pore) that is not connected to the outside inside the composite particle (phosphor particle or coating layer), the measurement value is not available because the gas used for measurement cannot reach the internal space. May correspond to a so-called “apparent density”. Therefore, “true density” used in the present invention is a concept including “apparent density”.
  • the composite particle of this invention has the structure which satisfy
  • W ⁇ 0.14 (2) [Wherein, W is the half-width of three diffraction peaks whose peak intensity is 1st to 3rd among diffraction peaks obtained by powder X-ray diffraction spectrum measurement using CuK ⁇ characteristic X-rays. The arithmetic mean value of is shown. The unit is deg. ]
  • W shown in Formula (2) when W shown in Formula (2) is 0.14 or less, there is less disorder of the crystal lattice on the surface of the phosphor particles, and the coating layer can be formed without impairing the original properties of the phosphor particles. It is formed and preferable.
  • W shown in the formula (2) if W shown in the formula (2) is 0.085 or more, further 0.095 or more, the aggregation of the phosphor particles and It is preferable that the particles are not enlarged due to bonding or the like. From the viewpoint of obtaining the effect of the present invention more reliably, W is more preferably 0.10 or more.
  • the diffraction peak obtained by powder X-ray diffraction spectrum measurement using CuK ⁇ characteristic X-ray is preferably measured using a powder X-ray diffraction spectrum measurement device “ULTIMA-III” manufactured by Rigaku Corporation.
  • the peaks measured under the following conditions are shown. That is, X-ray tube (Cu, tube voltage: 40 kV, tube current: 40 mA), measurement conditions (measurement angle range of Bragg angle 2 ⁇ / degree: 10-90 degrees, sampling width: 0.01 degrees, scan speed: 4 Degree / minute, divergent slit: 1/2 degree, divergent longitudinal slit: 10 mm, scattering slit: 1/2 degree, light receiving slit: 0.3 mm).
  • the half width obtained using only one peak may lack accuracy
  • the half width is preferably obtained as an arithmetic average value of three diffraction peaks having high peak intensity.
  • the calculation may be performed by excluding the diffraction peak.
  • the metal oxide is preferably silica.
  • Such composite particles are effective from the viewpoint that silica can be formed by a relatively simple and inexpensive method with a relatively large amount of silica among metal oxides.
  • the phosphor particles are preferably phosphor particles containing sulfur atoms. If phosphor particles containing sulfur atoms are used, composite particles that can more reliably impart fluorescence to composite particle-containing materials can be obtained more reliably, and high luminous efficiency when excited by light in the ultraviolet to blue range It has the feature of showing.
  • the present invention also provides: A method for producing composite particles comprising: phosphor particles; and a coating layer formed on at least a part of the surface of the phosphor particles, A phosphor dispersion liquid preparation step of preparing a phosphor dispersion liquid including phosphor particles and an alkali catalyst; A coating component solution adjusting step for preparing a coating component solution in which a chemical species containing a metal that is a material of the coating layer is dissolved in a solvent; A coating layer forming step of adding the coating component solution to the phosphor dispersion to form a coating layer containing the metal oxide on the surface of the phosphor particles; Contains In the coating component solution preparing step, the amount of the chemical species including the metal in the coating layer forming step is 0.001% by mass or more in terms of the oxide of the metal with respect to the phosphor particles.
  • a method for producing composite particles is provided. 0.53 ⁇ ( ⁇ / ⁇ 0 ) (1) [In the formula (1), ⁇ represents a measured value of the bulk density of the composite particle based on the measurement method specified in JIS-R-1628, and ⁇ 0 represents a measured value of the true density of the composite particle.
  • the coating layer forming step can be carried out by a so-called alkoxide method or sol-gel method, and the upper limit of the amount of the chemical species containing the metal is the amount of the chemical species containing the metal in the coating layer forming step, What is necessary is just about 60 mass% in the oxide conversion value of the said metal with respect to the said fluorescent substance particle.
  • the inventors have adjusted the addition amount of the chemical species including the metal in the coating component solution preparation step to the above range, and at least inactive the alkali coating layer forming step. It has been found that performing in a gas atmosphere is extremely effective for obtaining the above-described composite particles of the present invention more reliably.
  • the amount of the chemical species including the metal in the coating layer forming step is 0.001% by mass or more in terms of the oxide of the metal with respect to the phosphor particles” will be described.
  • the “metal oxide (metal oxide) equivalent value” means that the mass of a chemical species containing the metal is an oxide (metal oxide) containing a metal having the same chemical equivalent as the metal contained in the chemical species.
  • the mass of the obtained metal oxide is expressed as a ratio to the mass of the phosphor particles.
  • the phosphor particles are copper / aluminum-doped zinc sulfide particles and the metal is silicon (Si), silicon (such as tetraethoxysilane) used in the production of the composite particles of Example 1 described later
  • silicon such as tetraethoxysilane
  • the value expressed as a ratio is ⁇ (X 1 / Y) ⁇ 100 or (x 2 / Y) ⁇ 100 ⁇ .
  • the phosphor particles before composite (before forming the coating layer) alone by the dry density measurement method by the constant volume expansion method, respectively. This mass is determined.
  • the amount of the chemical species including the metal in the obtained mixed solution is the above-described amount.
  • the amount of the chemical species including the metal is determined, and the coating component solution is prepared.
  • the composite particles of the present invention described above can be obtained more reliably.
  • the porous coating layer has a relatively thin thickness, and the influence of the increase in specific surface area due to the porous structure is sufficiently increased.
  • a coating layer can be firmly formed on the surface of the phosphor particles in a suppressed state. Therefore, the composite particles obtained by the method for producing composite particles of the present invention can ensure sufficient dispersibility even with a small amount of dispersion medium, and can reduce the load on the dispersion treatment.
  • the amount of the chemical species containing metal is 0.001% by mass or more in terms of oxide of the metal with respect to the phosphor particles, the effect of preventing aggregation due to the coating of the composite particles is reliably obtained, and 0.001 If it is less than mass%, the coating amount is small and the effect of preventing the aggregation of the composite particles cannot be obtained with certainty.
  • the amount of the chemical species including the metal is approximately 60% by mass or less in terms of the oxide of the metal with respect to the phosphor particles, the fluorescence of the phosphor particles is surely imparted to the composite particles.
  • the mass fraction of the coating layer with respect to the phosphor particles becomes too large, and the fluorescence of the phosphor particles may not be reliably imparted to the composite particles. Furthermore, from the viewpoint of obtaining the effect of the present invention more reliably, the amount of the above-mentioned chemical species including the metal is 0.01 mass in terms of oxide of the metal with respect to the phosphor particles in the phosphor dispersion. % Or more and 40% by mass or less is more preferable.
  • inert gas refers to rare gas and nitrogen gas.
  • the “inert gas atmosphere” means an atmosphere (substantially containing oxygen) in which the concentration of oxygen in the inert gas atmosphere does not advance the oxidation state of the surface of the phosphor particles. No atmosphere).
  • the concentration of oxygen in the inert gas atmosphere is preferably 0.1% by volume or less, and more preferably 0.01% by volume or less. That is, the concentration of the inert gas is preferably 99.9% by volume or more, and more preferably 99.99% by volume or more.
  • this “inert gas atmosphere” can be performed using “inert gas atmosphere forming means” such as a dry room, a glove box, or a container such as a separable flask.
  • a container such as a separable flask
  • the “inert gas” may contain about 1 to 3% by volume of hydrogen gas. Since hydrogen gas has reducibility, it is more preferable because it can suppress oxidation when handling a phosphor that is easily oxidized (for example, a phosphor using divalent europium or divalent manganese as an activator).
  • composite particles of the present invention since at least the coating layer forming step is performed in an inert gas atmosphere, composite particles can be produced without impairing the fluorescence of the phosphor particles.
  • the detailed mechanism for obtaining such an effect has not been clearly elucidated.
  • the present inventors have carried out at least a coating layer forming step in an inert gas atmosphere, so that the surface of the phosphor particles forms a coating layer (a solution from which dissolved oxygen has been sufficiently removed). It is speculated that even when immersed, the change in crystallinity of the surface of the phosphor particles is prevented, and the fluorescence of the phosphor particles can be maintained.
  • the present inventors conventionally formed a coating layer on a phosphor particle in a liquid, the surface of the phosphor particle is immersed in a liquid (a liquid containing dissolved oxygen). It is presumed that the crystallinity of the phosphor changed and the fluorescence of the phosphor particles was sometimes impaired.
  • the phosphor particles having the coating layer are surface-treated using a dispersion liquid containing a coupling agent in a dispersion medium. It is preferable that the method further includes a surface treatment step. In addition, it is preferable to perform this surface treatment process also in inert gas atmosphere from a viewpoint of acquiring the effect of this invention more reliably.
  • the zeta potential and hydrophobicity of the surface of the composite particles are determined according to the type of dispersion medium in which the obtained composite particles are dispersed. It is possible to adjust the property or water repellency, and the dispersibility can be further improved, which is preferable.
  • the present invention it is possible to provide composite particles having sufficient dispersibility in a dispersion medium (or solvent), and thus sufficient dispersibility in a composite particle-containing material. Further, according to the present invention, a method for producing composite particles that can more reliably obtain the composite particles of the present invention having sufficient dispersibility in the dispersion medium, and thus sufficient dispersibility in the composite particle-containing material. Can be provided.
  • the composite particles of the present embodiment mainly have a configuration including phosphor particles and a coating layer formed on at least a part of the surface of the phosphor particles and containing a metal oxide obtained by a metal alkoxide method. is doing. And the composite particle of this embodiment has the structure which satisfy
  • ⁇ is a measurement value of the bulk density of the composite particle based on the measurement method defined in JIS-R-1628
  • ⁇ 0 is the composite particle based on the dry density measurement method by the constant volume expansion method. Measured values of true density of each are shown.
  • the composite particles of the present embodiment have a configuration that simultaneously satisfies the condition represented by the formula (1), the bonding between the phosphor particles and the coating layer can be sufficiently ensured. Therefore, the composite particles of the present embodiment have sufficient dispersibility in the dispersion medium, and consequently sufficient dispersibility in the composite particle-containing material.
  • the dispersion medium include water, organic substances such as an organic dispersion medium, a polymer (polymer), and a binder.
  • the coating layer is porous, a large amount of solvent and resin are required because the specific surface area is large.
  • the coating layer is porous, the bulk density of the composite particles is smaller than the bulk density of the phosphor particles before coating, and the amount that can be dispersed in the dispersion medium is relatively small. I was sorry. For this reason, a large amount of dispersion medium is required to disperse in a large amount in the dispersion medium.
  • the composite particles of the present embodiment have a configuration that satisfies the condition represented by the formula (1), the thickness can be relatively reduced even with a porous coating layer. It is possible to adopt a configuration in which the coating layer can be firmly formed on the surface of the phosphor particles in a state where the influence of the increase in specific surface area due to the quality is sufficiently suppressed. Therefore, the composite particles of the present embodiment are excellent in the balance between the specific surface area and the density, and it is possible to ensure sufficient dispersibility even with a small amount of dispersion medium as compared with the conventional composite particles.
  • the present inventors have compared the particle size distribution of conventional composite particles by observation using a light scattering particle size distribution meter (light scattering particle size distribution meter “LB-550” manufactured by Horiba, Ltd.).
  • the particle size distribution of the composite particles of this embodiment is a plurality of types of dispersion media (water or ethanol). It has been confirmed that it is closer to the particle size distribution.
  • the present inventors have observed this using a light scattering type particle size distribution meter (light scattering type particle size distribution meter “LB-550” manufactured by HORIBA, Ltd.) as compared with conventional composite particles. It has been confirmed that the composite particles of the embodiment (specifically, composite particles of Example 1 described later) are well dispersed in a polymer (EC vehicle (ethylcellulose polymer) manufactured by Nisshin Kasei Co., Ltd.).
  • EC vehicle ethylcellulose polymer
  • the composite particle of the present embodiment has a configuration that further satisfies the condition of the following formula (2) described above in addition to the formula (1).
  • W ⁇ 0.14
  • W is a diffraction peak obtained by powder X-ray diffraction spectrum measurement using CuK ⁇ characteristic X-ray, and three diffraction peaks whose peak intensity is 1st to 3rd are shown. The arithmetic mean value of the half width is shown. The unit is deg.
  • phosphor particles constituting the composite particles of this embodiment.
  • Various phosphor particles can be used as the phosphor particles. From the viewpoint of reliably obtaining composite particles having fluorescence in the composite particle-containing material, excitation light in the ultraviolet to blue region can be used. It is preferable to use phosphor particles exhibiting high luminous efficiency. Examples of phosphor particles that exhibit high luminous efficiency with excitation light in the ultraviolet to blue region include Y 2 O 3 , Y 3 Al 5 O 12 , BaMgAl 10 O 17 , Zn 2 SiO 4 , Ba 2 SiO 4 , and Sr 2.
  • Oxides such as SiO 4 , Ca 2 SiO 4 , Ca 8 MgSi 4 0 16 , LaPO 4 , CaWO 4 , LaSi 3 N 5 , Ba 2 Si 5 N 8 , Ca 2 Si 5 N 8 , Sr 2 Si 5 N 8 , Nitrides such as CaAlSiN 3 and SrAlSiN 3 , SiAlON materials, SrSiON materials, BaSiON materials, CaAlSiON materials, LiSiAlON materials, MgAlSiON materials, CaAlSiON materials, SrAlSiON materials, BaAlSiON materials, ZnAlSiON materials Oxynitrides such as zinc sulfide (ZnS), calcium sulfide (CaS), strontium sulfide (Sr) ) Other such, SrGa 2 S 4, CaGa 2 S 4, BaGa 2 S 4, SrAl 2 S 4, CaAl 2 S 4, BaAl 2
  • SrGa 2 S 4 is more preferable to use phosphor particles composed of a compound containing a sulfur atom, such as Gd 2 O 2 S.
  • these phosphor particles do not need to be a single substance, and two or more kinds of phosphor particles may be mixed and used in order to adjust the emission color.
  • a part of elements such as Sr, Mg, Ca, Ba, and Zn constituting the phosphor particles are replaced with one or more different elements of, for example, Mg, Ca, Ba, Zn, and Sr. May be.
  • a part of elements such as Y and Al constituting the phosphor particles may be substituted with one or two or more different elements of, for example, Ga, Gd, and C. The part may be substituted with, for example, one or more different elements of Ge, Ti, and the like.
  • these phosphor particles are made of copper, silver, gold, aluminum, manganese, europium, terbium, cerium, praseodymium, scandium, thulium, ytterbium, yttrium, lanthanum, neodymium for the purpose of increasing the color and brightness.
  • Various activators and / or coactivators such as samarium, gadolinium, dysprosium, holmium, erbium, lutetium, boron, chlorine, bromine, and other halogens and lanthanoids may be added (doped). Any one or more of these activators and / or coactivators can be used.
  • zinc sulfide doped with copper and aluminum and SrGa 2 S 4 doped with europium exhibit yellow-green light emission and can be used for white LEDs.
  • Examples of the shape of the phosphor particles include various shapes such as a needle shape, a rod shape, a plate shape, a scale shape, a spherical shape, a granular shape, an elliptical shape, and a cubic shape, and can be applied in the present invention. From the viewpoint of enhancing, it is preferably a rod shape, a spherical shape, a granular shape, an elliptical shape, or a cubic shape, and more preferably a spherical shape or a granular shape.
  • the volume average particle size measured using a Beckman Coulter Coulter Counter is 0.01 to 100 ⁇ m. It is sufficient that the thickness is 0.1 to 50 ⁇ m.
  • the diffraction peak when the condition of the formula (2) described above is given is the (111) plane.
  • a diffraction peak attributed to (28.53 degrees), (220) plane (47.45 degrees), and (311) plane (56.31 degrees) is preferable.
  • Such composite particles have sufficient crystallinity and are effective from the viewpoint of more reliably imparting fluorescence to the composite particle-containing material.
  • europium activated SrGa 2 S 4 diffraction peaks attributed to the (422) plane (24.10 degrees), the (062) plane (29.97 degrees), and the (444) plane (38.42 degrees).
  • the coating layer in this embodiment is a layer containing a metal oxide. Even when the coating layer has a porous structure, the coating layer is placed on the surface of the phosphor particles while sufficiently suppressing the influence of an increase in specific surface area by reducing the thickness and making it porous. From the viewpoint of forming a strong film, the coating layer preferably contains a metal oxide as a main component, and the coating layer is more preferably made of a metal oxide. As a result, the composite particles of the present embodiment can ensure sufficient dispersibility even with a small amount of dispersion medium compared to conventional composite particles, while maintaining the fluorescence more reliably.
  • the metal oxide may be any material that has a certain degree of transparency to light in the wavelength range to be used so as not to impair the fluorescence of the composite particle-containing material using the composite particles of the present embodiment.
  • a metal oxide such as silica, titania, ceria, yttria, alumina, magnesia, zirconia is preferable. Silica or alumina is more preferable, and silica is further preferable.
  • many of such oxides can have various crystal forms, and can take an amorphous form in addition to several crystal forms having different structures. From the viewpoint of refractive index, dielectric constant, mechanical characteristics, chemical characteristics, and the like, an oxide having a desired crystal form can be used.
  • the coating layer may be composed of one layer or may be composed of two or more layers. When the coating layer is composed of two or more layers, each layer may contain the same metal oxide or different metal oxides.
  • the method for producing composite particles of the present embodiment mainly includes a phosphor dispersion liquid preparation step and a coating layer formation step. More specifically, the composite particle manufacturing method of the present embodiment includes (a) a phosphor dispersion liquid preparation step, (b) a coating component solution preparation step, (c) a dissolved oxygen purge step, and (d) a metal. A coating layer forming step by an alkoxide method; and (e) a composite particle extraction step.
  • the amount of chemical species including silicon in the coating component solution preparation step is adjusted to the above-described range, and at least the coating layer forming step is performed as an inert gas. Perform under atmosphere. This makes it possible to more reliably obtain the composite particles of the present embodiment that simultaneously satisfy the condition of the formula (1) described above in the method for producing composite particles of the present embodiment.
  • each process of the manufacturing method of the composite particle of this embodiment is demonstrated.
  • the phosphor dispersion preparation step is a step of preparing a phosphor dispersion by dispersing phosphor particles in a dispersion medium and an alkali catalyst (base).
  • the dispersion medium used in this step is not particularly limited as long as the phosphor particles do not dissolve and are suitable for the metal alkoxide method described in (b) coating component solution preparation step described later. Water and / or alcohol may be mentioned.
  • the metal alkoxide method is described in detail in documents such as T. Sugimoto (Ed.), Fine Particles, Marcel Dekker (New York), 2000, etc., and these can be used in this embodiment.
  • the alkali catalyst used in this step is not particularly limited as long as it has an OH group and raises the pH of the reaction solvent.
  • ammonia, sodium hydroxide, potassium hydroxide is mentioned.
  • produces ammonia by hydrolysis like sodium carbonate, potassium carbonate, and urea, and raises the pH of a liquid may be sufficient.
  • this step the hydroxyl group is bonded to the surface of the metal fine particles.
  • This can be confirmed by powder X-ray diffraction spectrum measurement using CuK ⁇ characteristic X-rays.
  • the present inventors have contributed to improving the bond between the surface of the phosphor particles and the coating layer formed on the surface of the phosphor particles in the coating layer forming step described later, in which the hydroxyl group bonded to the surface of the phosphor particles is described later. I guess that.
  • this coating component solution preparation step may also be performed in the inert gas atmosphere described above.
  • the phosphor particles are agitated using an ultrasonic homogenizer, a ball mill, or the like to unaggregate the phosphor particles in advance. Further, when holding the phosphor dispersion liquid, it is preferable to stir the phosphor particles using an ultrasonic homogenizer, a ball mill or the like.
  • the coating component solution preparation step is a step of preparing a coating component solution in which a chemical species containing a metal that is a material of the coating layer is dissolved in a solvent.
  • the amount of the chemical species including the metal in the mixture in the coating layer forming step described later is the oxide equivalent value of the metal with respect to the phosphor particles.
  • the addition amount of the chemical species including the metal is adjusted in advance so that it is 0.001% by mass or more (and about 60% by mass or less), preferably 0.01% by mass or more and 40% by mass or less.
  • the chemical species including the metal used in this step varies depending on the type of metal oxide constituting the coating layer.
  • examples include tetramethoxysilane, tetraethoxysilane, tetra-i-propoxysilane, and tetra-n-propoxysilane containing silicon, which is a metal
  • titania is used for the coating layer.
  • examples thereof include tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-propoxy titanium, and the like containing titanium which is a metal.
  • examples include tetramethoxyzirconium, tetraethoxyzirconium, tetra-i-propoxyzirconium, tetra-n-propoxyzirconium and the like containing zirconium which is a metal, and yttria is used for the coating layer. Include triethoxy yttrium, tri-i-propoxy yttrium, and tri-n-butoxy yttrium containing metal yttrium. When ceria is used for the coating layer, tri-i-propoxy containing cerium metal Examples include cerium.
  • examples include trimethoxyaluminum containing metal aluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-i-propoxyaluminum, etc.
  • metal Examples include magnesium containing dimethoxymagnesium, diethoxymagnesium, di-n-propoxymagnesium, and di-i-propoxymagnesium.
  • the solvent used for preparing the coating component solution in this step is not particularly limited as long as the chemical species containing the metal dissolves and the phosphor particles do not dissolve.
  • the chemical species containing the metal dissolves and the phosphor particles do not dissolve.
  • water and / or Or alcohol is mentioned.
  • the alcohol include ethanol, methanol, isopropyl alcohol and the like.
  • the chemical species including the metal is difficult to dissolve, for example, tetrahydrofuran, dimethylformaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, or the like may be used.
  • stirring may be performed while irradiating the coating component solution with ultrasonic waves using an ultrasonic homogenizer or the like.
  • the dissolved oxygen purging step is obtained through the dissolved oxygen in the phosphor dispersion obtained through the phosphor dispersion preparing step (a) and the coating component solution preparing step (b).
  • the dissolved oxygen in the coating component solution is purged with an inert gas.
  • This purging can be performed by bubbling a rare gas or nitrogen gas in the phosphor dispersion and the coating component solution by a conventionally known method.
  • the phosphor dispersion liquid or the coating component solution may be bubbled with an inert gas for about 30 minutes.
  • (D) Coating layer forming step the coating component solution obtained through the coating component solution preparation step (b) is added to the phosphor dispersion obtained through the phosphor dispersion preparation step (a). In this step, a coating layer containing a metal oxide is formed on the surface of the phosphor particles.
  • This coating layer forming step is performed in an inert gas atmosphere having a dissolved oxygen concentration of preferably 1 mg / L or less.
  • stirring is performed while irradiating the reaction mixture with ultrasonic waves using an ultrasonic homogenizer or the like. It is preferable to do.
  • an additive may be further added to promote the formation of the coating layer or to further suppress the aggregation of the phosphor particles or the composite particles.
  • various surfactants anionic, cationic, nonionic
  • various surfactants anionic, cationic, nonionic and the like can be used.
  • the reaction temperature in the reaction mixture is preferably 5 to 80 ° C., more preferably 10 to 40 ° C. If the temperature is low, the reaction rate is too slow, and if the temperature is high, problems such as solvent volatilization and alkali catalyst (particularly ammonia) evaporation tend to occur. Since the solubility of oxygen in water decreases with an increase in water temperature, a low temperature is not preferable from this point.
  • the composite particle extraction step is a step of extracting composite particles from the reaction mixture after the coating layer forming step by a solid-liquid separation method.
  • This solid-liquid separation can be performed by a conventionally known method by decanting, centrifuging, suction filtration, dialysis, ultrafiltration, or the like for the reaction mixture containing the composite particles after the coating layer forming step.
  • the obtained solid component is dried in, for example, an electric furnace to obtain the composite particles of the present invention.
  • the obtained solid component may be fired, for example, in an electric furnace.
  • the extracted composite particles in order to remove unreacted alkoxide and alkali catalyst.
  • the cleaning of the composite particles is preferably performed repeatedly using water and / or alcohol. Ultrafiltration may be used for washing the composite particles.
  • the composite particles of the present embodiment are obtained by the above steps (a) to (e).
  • the phosphor particles having the coating layer may further include a surface treatment step (f) in which a surface treatment is performed using a dispersion liquid containing a coupling agent in a dispersion medium.
  • a surface treatment step in which a surface treatment is performed using a dispersion liquid containing a coupling agent in a dispersion medium.
  • this surface treatment process also in inert gas atmosphere from a viewpoint of acquiring the effect of this invention more reliably.
  • the zeta potential and hydrophobicity of the surface of the composite particles are determined according to the type of dispersion medium in which the obtained composite particles are dispersed.
  • the surface treatment as described above can be performed by a conventionally known method, and the degree of the surface treatment may be controlled by the amount of the coupling agent used.
  • a metal oxide such as silica
  • amino such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, etc.
  • a coupling agent having a group may be used.
  • a metal oxide such as silica which is hydrophilic, to hydrophobic, for example, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, trifluoropropyltrimethoxy Silane or the like may be used.
  • Example 1 Phosphor dispersion preparation step and dissolved oxygen purge step First, copper / aluminum-doped zinc sulfide particles (SPD-500A-M manufactured by Toshiba Corporation, average particle size: 11.7 ⁇ m) 20 g as phosphor particles Is mixed with 100 ml of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 5 ml of ion-exchanged water to form a dispersion, and nitrogen gas (made by Umemoto Sangyo Co., Ltd., purity: 99.99%) was bubbled (purged) for 30 minutes, 7 ml of 28% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and further bubbled (purged) with nitrogen gas for 5 minutes. Thereby, a phosphor dispersion liquid was prepared.
  • SPD-500A-M copper / aluminum-doped zinc sulfide particles manufactured by Toshiba Corporation, average particle size: 11.7 ⁇ m
  • the half-value width of the phosphor particles was confirmed by powder X-ray diffraction spectrum measurement using CuK ⁇ characteristic X-rays. More specifically, the measurement was performed under the following measurement conditions using a powder X-ray diffraction spectrum measurement apparatus “ULTIMA-III” manufactured by Rigaku Corporation. That is, X-ray tube (Cu, tube voltage: 40 kV, tube current: 40 mA), measurement conditions (measurement angle range of Bragg angle 2 ⁇ / degree: 10-90 degrees, sampling width: 0.01 degrees, scan speed: 4 Degree / minute, divergent slit: 1/2 degree, divergent longitudinal slit: 10 mm, scattering slit: 1/2 degree, light receiving slit: 0.3 mm).
  • the phosphor particle size is a value measured using a Coulter counter manufactured by Beckman Coulter.
  • the amount of tetraethoxysilane added was adjusted such that tetraethoxysilane was contained in an amount of 0.1% by mass in terms of silicon dioxide with respect to the phosphor particles in the reaction mixture in the coating layer forming step described later.
  • the “silicon dioxide equivalent value” means that the mass of tetraethoxysilane is converted to the mass of silicon dioxide (SiO 2 ) containing silicon having the same chemical equivalent as that of silicon contained in the silicon dioxide, and the obtained silicon dioxide This is a value expressing the mass of (SiO 2 ) as a ratio to the mass of the phosphor particles.
  • Coating layer forming step The phosphor dispersion obtained by carrying out the preparation and dissolved oxygen purge as described above and the coating component solution are mixed with stirring to form a reaction mixture, and in a nitrogen stream The reaction was performed for 4 hours. At this time, the reaction mixture was not particularly heated or cooled, but the temperature of the reaction mixture was in the range of 18-22 ° C.
  • composite particles were obtained in which a coating layer containing a metal oxide (silica) as a main component was formed on the surface of phosphor particles (copper / aluminum-doped zinc sulfide particles).
  • Example 2 5 g of composite particles (precipitate) obtained in the same manner as in Example 1 were dispersed in 20 ml of ion-exchanged water adjusted to pH 4 with acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.). Stir the resulting dispersion in a glass sample bottle with a magnetic stirrer, add 0.5 g of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone), and stir vigorously for 1 hour. While mixing. The temperature of the dispersion at this time was 18 to 22 ° C.
  • the dispersion was centrifuged at 3000 rpm for 10 minutes using an 8420 type centrifuge manufactured by Kubota Shoji Co., Ltd., and the supernatant obtained by removing the supernatant was treated with methanol (Wako Pure Chemical Industries, Ltd.). The product was added to 20 ml and sufficiently suspended, and then centrifuged again.
  • the precipitate after this operation was vacuum-dried for about 15 hours in a vacuum container using a diaphragm-type vacuum pump, and dried at 80 ° C. and 6 hours using an electric oven.
  • a coating layer containing a metal oxide (silica) as a main component was formed on the surface of phosphor particles (copper / aluminum-doped zinc sulfide particles), and composite particles having amino groups introduced on the surface were obtained. The presence of this amino group was confirmed by the following method.
  • the composite particles were removed from the thermostatic bath, and the supernatant was collected by centrifugation.
  • the recovered supernatant solution was confirmed for the presence of an amino group by confirming the expression of a peak at 425 nm using a self-recording spectrophotometer U-3500 manufactured by Hitachi, Ltd.
  • Example 3 Composite particles having a coating layer were obtained in the same manner as in Example 1 except that europium activated SrGa 2 S 4 (Mitsui Metal Mining Co., Ltd.) was used as the phosphor particles. The full width at half maximum of the phosphor particles was confirmed from the peaks on the (422) plane, (062) plane, and (444) plane, which are peaks attributed to SrGa 2 S 4 (JCPDS no. 25-0895).
  • SrGa 2 S 4 Mitsubishi Metal Mining Co., Ltd.
  • Example 4 The same phosphor as in Example 3, except that the amount of tetraethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.) used in the coating component solution preparation step and dissolved oxygen purge step was changed to 2 g. Thus, composite particles having a coating layer were obtained.
  • tetraethoxysilane manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 1 The “dissolved oxygen purging step” in Example 1 was not performed, and the others were the same as in Example 1. “(1) Phosphor dispersion preparation step”, “(2) Coating component solution preparation step”, “(3) The composite particles of Comparative Example 1 were obtained by performing the “coating layer forming step” and the “(4) composite particle extraction step”.
  • the volume average particle diameter of the composite particles was measured with a Coulter counter manufactured by Beckman Coulter. About 0.1 g of the sample (composite particles) obtained in Examples 1 to 4 and Comparative Example 1 or the sample (particles) of Comparative Example 2 was dispersed in about 100 mL of ion-exchanged water and sufficiently stirred. The volume average particle diameter was measured.
  • Dispersibility evaluation test in dispersion medium Dispersibility was evaluated by a sedimentation test. About 0.2 g of the sample was added to about 30 mL of ion-exchanged water, and well dispersed using an ultrasonic homogenizer. And it transferred to the graduated cylinder of equal magnitude
  • the particle size distribution of the composite particles constitutes this. It is closer to the particle size distribution (d 0 ) of the primary particles. Further, the composite particles of Examples 1 to 4 also had good dispersibility in ethyl cellulose polymers.
  • Example 2 it was confirmed that the zeta potential can be converted from minus to plus by introducing an amino group on the surface of the composite particle. Thereby, for example, dispersibility in a dispersion medium containing a polyacrylic resin is improved.
  • the composite particles obtained by the present invention have the characteristics that when mixed with a solvent such as water or polymer, they are easy to disperse with little aggregation and do not impair the properties of the phosphor particles constituting the composite particles. . Therefore, the composite particles of the present invention are suitable for various display devices and light emitting devices such as light emitting diodes, cathode ray tubes, fluorescent lamps, plasma displays, field emission displays, fluorescent display tubes, cold cathode tubes, lasers, electroluminescent displays and the like. Can be used. Moreover, the manufacturing method of the composite particle obtained by this invention can be utilized in order to manufacture said composite particle suitably.

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne une particule composite présentant des propriétés de dispersion adéquates dans un milieu de dispersion, et un procédé de fabrication des particules composites permettant d'obtenir avec plus de fiabilité cette particule composite. La particule composite comprend une particule de phosphore et une couche de revêtement qui est formée sur au moins une partie de la surface de la particule de phosphore mentionnée ci-dessus et comprend un oxyde métallique, et remplit les conditions d'une formule (1). (1) 0,53 ≦ (ρ／ρ0) Dans la formule (1), ρ indique la valeur de mesure de la masse volumique apparente de la particule composite mentionnée ci-dessus d'après le procédé de mesure prescrit dans la norme JIS-R-1628, et ρ0 indique la valeur de mesure de la masse volumique vraie de la particule composite mentionnée ci-dessus d'après un procédé de mesure de la masse volumique sèche employant une technique de déplacement de gaz.
PCT/JP2010/001574 2009-03-12 2010-03-05 Particule composite et son procédé de fabrication WO2010103773A1 (fr)

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Cited By (5)

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JP2011231266A (ja) * 2010-04-30 2011-11-17 Sumitomo Metal Mining Co Ltd 耐湿性に優れた被覆膜付き酸化物蛍光体粒子の製造方法
JP2012007082A (ja) * 2010-06-25 2012-01-12 Sumitomo Metal Mining Co Ltd 耐湿性に優れた被覆膜付き硫化物蛍光体粒子の製造方法
WO2019107080A1 (fr) * 2017-11-30 2019-06-06 デクセリアルズ株式会社 Phosphore revêtu, procédé pour le produire, feuille de phosphore, et dispositif électroluminescent
US11312900B2 (en) 2019-02-08 2022-04-26 Nichia Corporation Method for producing nitride fluorescent material, and nitride fluorescent material
US11613696B2 (en) 2017-11-30 2023-03-28 Dexerials Corporation Coated phosphor, method for producing same, phosphor sheet, and light-emitting device

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JP6122747B2 (ja) * 2013-09-25 2017-04-26 三井金属鉱業株式会社 蛍光体
JP6489543B2 (ja) * 2014-05-28 2019-03-27 シャープ株式会社 波長変換部材、発光装置、および波長変換部材の製造方法

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JP2006124680A (ja) * 2004-09-29 2006-05-18 Toda Kogyo Corp 改質蛍光体粒子粉末、該改質蛍光体粒子粉末の製造法及び該改質蛍光体粒子粉末を用いたｅｌ素子
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JPS575785A (en) * 1980-06-13 1982-01-12 Toshiba Corp Fluorescent material
JP2000144128A (ja) * 1998-04-23 2000-05-26 Konica Corp 輝尽性蛍光体及びその製造方法並びに放射線像変換パネル及びその製造方法
JP2006124680A (ja) * 2004-09-29 2006-05-18 Toda Kogyo Corp 改質蛍光体粒子粉末、該改質蛍光体粒子粉末の製造法及び該改質蛍光体粒子粉末を用いたｅｌ素子
JP2006152032A (ja) * 2004-11-25 2006-06-15 Matsushita Electric Works Ltd 蛍光体ナノ粒子の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011231266A (ja) * 2010-04-30 2011-11-17 Sumitomo Metal Mining Co Ltd 耐湿性に優れた被覆膜付き酸化物蛍光体粒子の製造方法
JP2012007082A (ja) * 2010-06-25 2012-01-12 Sumitomo Metal Mining Co Ltd 耐湿性に優れた被覆膜付き硫化物蛍光体粒子の製造方法
WO2019107080A1 (fr) * 2017-11-30 2019-06-06 デクセリアルズ株式会社 Phosphore revêtu, procédé pour le produire, feuille de phosphore, et dispositif électroluminescent
US11613696B2 (en) 2017-11-30 2023-03-28 Dexerials Corporation Coated phosphor, method for producing same, phosphor sheet, and light-emitting device
US11795390B2 (en) 2017-11-30 2023-10-24 Dexerials Corporation Coated phosphor method for producing same, phosphor sheet, and light-emitting device
US11312900B2 (en) 2019-02-08 2022-04-26 Nichia Corporation Method for producing nitride fluorescent material, and nitride fluorescent material

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