WO2022163604A1 - 発光体、腕時計、及び発光体の製造方法 - Google Patents

発光体、腕時計、及び発光体の製造方法 Download PDF

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Publication number
WO2022163604A1
WO2022163604A1 PCT/JP2022/002516 JP2022002516W WO2022163604A1 WO 2022163604 A1 WO2022163604 A1 WO 2022163604A1 JP 2022002516 W JP2022002516 W JP 2022002516W WO 2022163604 A1 WO2022163604 A1 WO 2022163604A1
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Prior art keywords
ceramic composite
light
phase
less
phosphor
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PCT/JP2022/002516
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English (en)
French (fr)
Japanese (ja)
Inventor
敏郎 古滝
祥太 田中
拓人 佐々木
秀太 内海
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Adamant Namiki Precision Jewel Co Ltd
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Adamant Namiki Precision Jewel Co Ltd
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Priority to JP2022578385A priority Critical patent/JPWO2022163604A1/ja
Priority to CH000838/2023A priority patent/CH719632B1/fr
Publication of WO2022163604A1 publication Critical patent/WO2022163604A1/ja
Anticipated expiration legal-status Critical
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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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7715—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing cerium
    • C09K11/7721—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
    • C04B2235/764—Garnet structure A3B2(CO4)3
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/785—Submicron sized grains, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties

Definitions

  • the present invention relates to a luminous body, a wristwatch, and a method for manufacturing a luminous body.
  • Ultraviolet light (so-called black light) having an ultraviolet wavelength (315 nm or more and less than 380 nm) is used in entertainment environments such as downtown nightclubs, karaoke facilities, and concert venues.
  • Materials that change color when exposed to ultraviolet light in the black light wavelength range are in demand for decorative purposes.
  • An example of such materials is a ceramic composite (see, for example, Patent Document 1).
  • the phases constituting the matrix are the ⁇ -Al 2 O 3 phase and the YAG phase (Y 3 Al 5 O 12 phase), and the YAG phase is activated by Ce.
  • the YAG:Ce matrix phase acts as a uniform phosphor (cerium, an activating element that forms the luminescence center, is dispersed in the entire matrix phase at the atomic level. uniformly distributed). It is disclosed that the structure in which each phase is three-dimensionally and intricately intertwined makes it possible to achieve high brightness and effectively mix the transmitted light and the fluorescent light.
  • Patent Document 2 can be cited.
  • the ceramic composite for light conversion of Patent Document 2 at least two or more oxide phases selected from single metal oxides and composite metal oxides are continuously three-dimensionally intertwined with each other to solidify. consists of the body. Furthermore, at least one of the oxide phases in the solidified body is a Cr-activated Al 2 O 3 phase.
  • a light-emitting device comprising a light-emitting element, a coating layer containing at least Ce-activated phosphor powder having a garnet-type structure, and a light-converting ceramic composite.
  • the present invention has been devised in view of the conventional problems described above, and in particular provides a luminous body capable of changing color when ultraviolet light is incident, a manufacturing method thereof, and a wristwatch equipped with the luminous body.
  • the luminescent material of the present invention comprises a ceramic composite having at least two oxide phases of a Y 3 Al 5 O 12 phase and an Al 2 O 3 phase as a lamellar structure, and a phosphor. It is characterized by being composed
  • the wristwatch of the present invention is characterized by comprising the luminous body of the present invention.
  • the method for manufacturing a luminous body of the present invention includes a step of housing a plurality of dies each having a slit and arranged in parallel with each other in a crucible, and introducing a raw material containing at least aluminum oxide and yttrium oxide into the crucible. a step of heating the crucible to melt the raw material in the crucible to prepare a melt; a step of forming a melt pool in which the melt is stored above the slit through the slit; A ceramic composite is manufactured by a pulling step of bringing the crystal into contact and pulling the seed crystal at a pulling speed of 0.8 mm/hour or more and 400 mm/hour or less, and the ceramic composite is further provided with the phosphor.
  • the color changes and becomes visible before and after the entrance and exit of ultraviolet light having a wavelength band of black light, so that the decorativeness of the structure including the luminous body can be improved . Furthermore, by making the luminous body change color with black light in the dark, it is suitable as a production material or a decorative material for entertainment purposes.
  • the luminous body changes before and after the entrance and exit of ultraviolet light.
  • the color changes and becomes visible. Therefore, it is possible to expand the design of the wristwatch, change the impression of day and night, and improve the overall decorativeness regardless of the time.
  • the method for producing a luminous body of the present invention it is possible to produce a luminous body having the above effects, and by optimizing the pull-up speed, the decrease in productivity of the ceramic composite and the variation in lamella size can be reduced. can be prevented. Furthermore, in the manufacturing apparatus using the EFG method, it becomes possible to easily control the temperature of the melt pool and to stably grow the crystal of the ceramic composite.
  • FIG. 1 is a schematic configuration diagram showing an apparatus for producing a ceramic composite by the EFG method according to the present invention
  • FIG. (a) It is a top view which shows typically an example of the die
  • FIG. 3 is a perspective view schematically showing the positional relationship between seed crystals and partition plates in the embodiment of the present invention.
  • (a) It is a front view which shows typically the positional relationship of a seed crystal and a partition plate in embodiment of this invention.
  • FIG. It is a top view which shows typically an example of the die
  • FIG. It is a front view of the same figure (a).
  • FIG. 3 is a perspective view schematically showing the positional relationship between seed crystal
  • FIG. 3 is a perspective view schematically showing a spreading step of the ceramic composite according to the embodiment of the present invention
  • 1 is a perspective view partially showing a plurality of ceramic composites according to an embodiment of the invention, obtained by an EFG method
  • FIG. 1 is a microscope observation image showing the surface of a ceramic composite according to an embodiment of the present invention, obtained by an EFG method.
  • FIG. 5 is a perspective view showing another form of the growth process of the ceramic composite according to the embodiment of the present invention obtained by the EFG method
  • 1 is a plan view showing an assembled state of a wristwatch part provided with phosphors according to an embodiment of the present invention
  • FIG. FIG. 10 is a perspective view showing an example of an index in the wristwatch component of FIG. 9;
  • FIG. 10 is a perspective view showing a dial in the wristwatch component of FIG. 9;
  • FIG. 10 is a perspective view showing a dial ring in the wristwatch component of FIG. 9;
  • (a) A cross-sectional view of the dial ring of FIG. 12 taken along the line aa.
  • FIG. 10 is a perspective view showing a bezel in the wristwatch component of FIG. 9;
  • (a) is a cross-sectional view of the bezel of FIG. 14 taken along line bb.
  • 11 is an explanatory diagram schematically showing an example of a propagation or reflection optical path of ultraviolet light when ultraviolet light is incident on the index in FIG. 10;
  • FIG. 10 is a perspective view showing a dial ring in the wristwatch component of FIG. 9;
  • (a) A cross-sectional view of the dial ring of FIG. 12 taken along the line aa.
  • It is a partial enlarged view within circle A
  • FIG. 1 to 8 are diagrams explaining a ceramic composite used in a light emitter according to an embodiment of the present invention and a method for manufacturing the same.
  • the same or equivalent constituent elements, members, and processes shown in each drawing are denoted by the same reference numerals, and duplication of description will be omitted as appropriate.
  • a ceramic composite manufacturing apparatus 1 is composed of a growth container 3 for growing a ceramic composite 2 and a lifting container 4 for pulling up the grown ceramic composite 2.
  • EFG Electrode-defined Film
  • the ceramic composite 2 is grown and manufactured by the growth method.
  • the growth container 3 includes a crucible 5 , a crucible drive section 6 , a heater 7 , an electrode 8 , a die 9 and a heat insulating material 10 .
  • the crucible 5 is made of molybdenum (Mo) or tungsten (W) and melts raw materials.
  • the crucible drive unit 6 rotates the crucible 5 around its vertical direction.
  • a heater 7 heats the crucible 5 .
  • the electrode 8 energizes the heater 7 .
  • the die 9 is installed in the crucible 5 and determines the liquid surface shape of the raw material melt (hereinafter simply referred to as "melt" as necessary) 21 when pulling up the ceramic composite 2 .
  • a thermal insulator 10 also surrounds the crucible 5 , the heater 7 and the die 9 .
  • the growth container 3 is provided with an atmosphere gas introduction port 11 and an exhaust port 12.
  • the atmosphere gas introduction port 11 is an introduction port for introducing an atmosphere gas such as argon gas into the growth vessel 3, and prevents the crucible 5, the heater 7 and the die 9 from being consumed by oxidation.
  • an exhaust port 12 is provided for exhausting the inside of the growth container 3 .
  • the pulling container 4 includes a shaft 13, a shaft drive unit 14, a gate valve 15, and a substrate inlet/outlet port 16, and pulls up a plurality of plate-shaped ceramic composites 2 grown from seed crystals 17.
  • Shaft 13 holds seed crystal 17 .
  • the shaft driving section 14 raises and lowers the shaft 13 toward the crucible 5 and rotates the shaft 13 about the elevation direction.
  • a gate valve 15 separates the growing vessel 3 and the raising vessel 4 .
  • the substrate inlet/outlet 16 allows the seed crystal 17 to enter and exit.
  • the manufacturing apparatus 1 also has a control section (not shown), which controls the rotation of the crucible driving section 6 and the shaft driving section 14 .
  • the die 9 is made of molybdenum and has a number of partition plates 18 as shown in FIG. FIG. 2 shows a case where 30 partition plates 18 and 15 dies 9 are formed as an example of dies.
  • the partition plates 18 have the same flat plate shape and are arranged parallel to each other so as to form a minute gap (slit) 19 to form one die 9 .
  • the slit 19 is provided over substantially the entire width of the die 9 .
  • the plurality of dies 9 have the same shape and are arranged in parallel at predetermined intervals so that their longitudinal directions are parallel to each other, a plurality of slits 19 are provided.
  • the symbol t in FIGS. 2 and 3 refers to the thickness of the die 9.
  • FIG. Symbol D in FIG. 2 indicates the gap between each die 9 .
  • the symbol T in FIG. 3 indicates the thickness of the seed crystal 17 .
  • a slope 30 is formed on the upper part of each partition plate 18, and an acute-angled opening 20 is formed by arranging the slopes 30 facing each other.
  • the slits 19 also have the role of raising the melt 21 from the lower ends of the dies 9 to the openings 20 by capillary action.
  • the raw material charged into the crucible 5 is melted (raw material melt) as the temperature of the crucible 5 rises to become a melt 21 .
  • a part of this melt 21 enters the slit 19 of the die 9, rises in the slit 19 based on the capillary phenomenon as described above, is exposed from the opening 20, and reaches the raw material melt pool 22 at the opening 20. is formed (see FIG. 4(a)).
  • the ceramic composite 2 grows according to the shape of the melt surface formed in the raw material melt pool (hereinafter referred to as "melt pool” as necessary) 22 .
  • the shape of the melt surface is an elongated rectangle, a plate-shaped ceramic composite 2 is produced.
  • FIGS. 1 and 3 to 6 in this embodiment, a plate-shaped ceramic composite substrate is used as the seed crystal 17. As shown in FIG. Further, the seed crystal 17 is arranged so that the planar direction of the seed crystal 17 and the longitudinal direction of the die 9 are orthogonal to each other at an angle of 90°. Since the seed crystal 17 and the ceramic composite 2 are also perpendicular to each other at an angle of 90°, FIG. 1 shows the side of the ceramic composite 2 . 3 and 4 indicates the crystal plane of the seed crystal 17. As shown in FIG.
  • the contact area between the seed crystal 17 and the substrate holder (not shown) at the bottom of the shaft 13 is large, the seed crystal 17 will be deformed due to the stress due to the difference in thermal expansion coefficient, and in some cases it will break. Conversely, the seed crystal 17 may be loosely fixed due to the difference in thermal expansion coefficient. Therefore, it is preferable that the contact area between the seed crystal 17 and the substrate holder is small. Also, the seed crystal 17 must have a substrate shape that can be securely fixed to the substrate holder.
  • a notch portion 23 is provided in the upper portion of the seed crystal 17.
  • a U-shaped substrate holder can be inserted from below the cutouts 23 at two locations, and the seed crystal 17 can be securely held while reducing the contact area. Become.
  • granulated raw powder which is the raw material of the ceramic composite (for example, a powder containing 64.71% by weight of aluminum oxide, 35.02% by weight of yttrium oxide, 0.003% by weight of magnesium oxide, and 0.27% by weight of cerium oxide) is put into the crucible 5 in which the die 9 is housed to fill it with a predetermined amount.
  • the raw material powder may contain compounds and elements other than those described above, depending on the purity or composition of the ceramic composite to be produced.
  • the inside of the growth container 3 is replaced with argon gas to reduce the oxygen concentration to a predetermined value or less.
  • the heater 7 heats the crucible 5 to a predetermined temperature, and the raw material powder is melted in the crucible. Since the melting point of aluminum oxide is about 2050.degree. C. to 2072.degree.
  • the raw material powder After a while after heating, the raw material powder is melted, and the raw material melt 21 is prepared. Further, part of the melt 21 rises through the slit 19 of the die 9 by capillary action and reaches the surface of the die 9 , forming a melt reservoir 22 containing the melt 21 above the slit 19 .
  • the seed crystal 17 is lowered while being held at an angle perpendicular to the longitudinal direction of the melt pool 22 above the slit 19, so that the seed crystal 17 is melted in the melt pool 22. contact the liquid surface.
  • the seed crystal 17 is previously introduced into the pulling container 4 through the substrate inlet/outlet 16 .
  • the illustration of the melt 21 and the melt pool 22 is omitted in order to prioritize visibility of the slit 19 and the opening 20.
  • FIG. 3 and 4 are diagrams showing the positional relationship between the seed crystal 17 and the partition plate 18.
  • FIG. As described above, by making the planar direction of seed crystal 17 orthogonal to the longitudinal direction of partition plate 18, the contact area between seed crystal 17 and melt 21 can be reduced. Therefore, the contact portion of the seed crystal 17 conforms to the melt 21, and crystal defects are less likely to occur in the ceramic composite 2 to be grown.
  • FIG. 4(b) is a diagram showing how a portion of the seed crystal 17 is melted.
  • the substrate holder is pulled up at a predetermined pulling speed to start pulling up the seed crystal 17 .
  • the shaft 13 raises the substrate holder and the seed crystal 17 at a predetermined pulling speed.
  • FIG. 5 is a schematic diagram showing how the width of the ceramic composite 2 is increased by the spreading process.
  • a straight body portion 26 having a flat plate shape and having a constant width approximately equal to the full width of the die 9 as shown in FIG.
  • a plate-shaped ceramic composite 2 is obtained by pulling it up to a predetermined length (straight body length) at a speed.
  • the temperature is controlled using the heater 7 or the like so that the interfacial temperature of the melt 21 in the melt pool 22 formed above the slit 19 is constant.
  • the ceramic composite 2 grows as the melt 21 rising to the melt pool 22 contacts the seed crystal 17 and is cooled while being pulled up. Therefore, by controlling the temperature of the melt pool 22 to be constant, the crystal growth conditions can be maintained at the same level during the growth period of the ceramic composite 2, and a uniform lamellar structure can be obtained over the entire area of the ceramic composite 2. can be formed.
  • the pulling speed of the seed crystal 17 in the pulling process is preferably in the range of 0.8 mm/hour or more and 400 mm/hour or less.
  • the pulling rate of the seed crystal 17 is optimized, and it is possible to prevent a decrease in productivity of the ceramic composite 2 and variations in lamella size.
  • the pulling speed is set to 400 mm/hour or less, the temperature of the melt pool 22 can be easily controlled, and the crystal of the ceramic composite 2 can be stably grown.
  • the size of the lamellar structure will vary greatly with respect to the error in the pulling speed, making it difficult to control the size of the lamellar structure. Therefore, the emission intensity of the emitted light from the grown ceramic composite 2 is lowered. Moreover, since the growth rate is slow, the productivity is lowered, which is not preferable.
  • the pulling speed exceeds 400 mm/hour, it becomes difficult to control the temperature of the melt pool 22, so it becomes difficult to control the size of the lamella structure.
  • the pulling speed is too high, the melt 21 in the melt pool 22 is likely to separate from the seed crystal 17 and the straight body portion 26, thereby interrupting the growth of the ceramic composite 2, which is not preferable.
  • FIG. 6 shows the appearance of the obtained flat plate-shaped ceramic composite 2 .
  • the straight body length is not particularly limited, it is preferably 10 mm or more and 1500 mm or less.
  • the full width of the die 9 and the width of the seed crystal 17 may be the same, and the ceramic composite 2 may be grown with the same width as the full width of the seed crystal 17.
  • the melt 21 and the melt pool 22 are omitted in order to prioritize the visibility of the slit 19 .
  • the manufacturing apparatus 1 By using the manufacturing apparatus 1, the seed crystal 17, and the die 9 as described above, it is possible to simultaneously manufacture a plurality of ceramic composites 2 from a common seed crystal 17. Therefore, it is possible to reduce the manufacturing cost of the ceramic composite 2 per sheet.
  • a plurality of ceramic composites 2 are grown. Therefore, by uniformly cooling and standing to cool the plurality of ceramic composites 2, a uniform lamellar structure without variation can be obtained.
  • the manufacturing apparatus 1 is provided with a crucible driving section 6 that rotates a crucible 5 in which a die 9 is installed, and a control section (not shown) that controls the rotation.
  • a shaft driving section 14 for rotating the shaft 13 and a control section (not shown) for controlling the rotation thereof are provided. That is, the positioning of the seed crystal 17 with respect to the die 9 is adjusted by rotating the shaft 13 or the crucible 5 by the controller.
  • the precise positioning of the seed crystal 17 and the die 9 can also be achieved by using the die 9 in which a part of the slope 30 of each partition plate 18 is notched.
  • the shape and size of the ceramic composite 2 in the plane direction are not limited, but from the viewpoint of preventing deterioration of the workability of the ceramic composite 2, a rectangular shape with a width of 0.5 mm or more and 300 mm or less and a length of 10 mm or more and 1500 mm or less is preferred. desirable. If the width is less than 0.5 mm, the productivity of the ceramic composite 2 will deteriorate. On the other hand, if the width exceeds 300 mm, the temperature uniformity at the tip of the die 9 (die top) is deteriorated, and unevenness in thickness tends to occur, making it difficult to grow the ceramic composite 2 . Moreover, the length is desirably 10 mm or more and 1500 mm or less from the viewpoint of preventing deterioration of the workability of the ceramic composite 2 .
  • the ceramic composite 2 of this embodiment is manufactured using the EFG method, it is possible to easily obtain a large-area ceramic composite 2 by increasing the width of the die 9 and the length to be lifted.
  • the average value of the lamellar spacing is in the range of 0.5 ⁇ m to 20 ⁇ m and has a fine structure, light is easily scattered at the interface between the Y 3 Al 5 O 12 phase and the Al 2 O 3 phase, and the surface area is large. The light is scattered evenly over the entire surface of the ceramic composite 2, and uniform reflected light can be obtained inside the ceramic composite 2.
  • the thickness of the ceramic composite 2 is not limited, it is preferably in the range of 0.2 mm or more and 5.0 mm or less.
  • the thickness of the ceramic composite 2 is less than 0.2 mm, it becomes difficult to control the crystal growth in the EFG method, and the influence of thickness due to manufacturing errors and the influence of thickness unevenness in the plane increase. It becomes difficult to obtain reflected light uniformly over the entire surface of the body 2 .
  • the thermal conductivity of the Y 3 Al 5 O 12 phase contained in the ceramic composite 2 is only about 1/4 that of the Al 2 O 3 phase. A temperature difference is more likely to occur inside. Therefore, when the thickness of the ceramic composite 2 exceeds 5.0 mm, the temperature difference between the outer side and the inner side in the thickness direction tends to occur during pulling by the EFG method, and colony structures are likely to occur, resulting in uniformity of the lamellar spacing. is not preferred because it impairs Moreover, the interfacial density between the Y 3 Al 5 O 12 phase and the Al 2 O 3 phase becomes non-uniform, which is not preferable.
  • 7 and 9 to 16 are diagrams for explaining the light emitter according to the embodiment of the present invention.
  • a luminous body according to an embodiment of the present invention is composed of a ceramic composite having at least two oxide phases of a Y 3 Al 5 O 12 phase and an Al 2 O 3 phase as a lamellar structure, and a phosphor.
  • FIG. 7 is a microscopic image showing the surface of the ceramic composite 2 obtained by the EFG method described above.
  • the Y 3 Al 5 O 12 phase as the first phase and the Al 2 O 3 phase as the second phase are present as a eutectic, It has a lamellar structure in which the first phase and the second phase are sterically entangled with each other.
  • the region shown in dark color is the Y 3 Al 5 O 12 phase
  • the region shown in light color is the Al 2 O 3 phase.
  • the first phase and the second phase have few island-like independent separations, and have regions that are continuous in the three-dimensional direction.
  • the phosphor is provided inside a recess separately formed on the surface of the ceramic composite 2 or on the surface of the ceramic composite. Further, the ultraviolet light incident on the light emitter first enters only the ceramic composite, is reflected by the ceramic composite, and is emitted while being scattered.
  • a portion of the ultraviolet light not reflected by the ceramic composite is transmitted through the ceramic composite and is incident on the phosphor.
  • the ultraviolet light is incident on the phosphor, the light of the appearance color of the phosphor is emitted while being scattered from the phosphor.
  • the ultraviolet light in the present invention refers to so-called black light having a wavelength of 315 nm or more and less than 380 nm.
  • the Y 3 Al 5 O 12 phase may also be activated with Ce.
  • Ce By activating Ce, it becomes possible to use a ceramic composite with a yellow exterior color that has already been put into practical use on the market.
  • the Ce content in the Y 3 Al 5 O 12 phase is preferably in the range of 0.01 mol % or more and 5.0 mol % or less. If it is less than 0.01 mol %, the luminous intensity of the ceramic composite becomes weak and unsuitable for use as a luminous body. On the other hand, if it exceeds 5.0 mol %, other compounds than desired are produced and do not contribute to emission of emitted light.
  • the Y 3 Al 5 O 12 phase By activating the Y 3 Al 5 O 12 phase with Ce and partially substituting Y in the Y 3 Al 5 O 12 phase with Ce, the Y 3 Al 5 O 12 phase functions as a phosphor material.
  • the Ce content is adjusted within the range of 0.01 mol % or more and 5.0 mol % or less.
  • the lamellar structure contains interfaces between the Y 3 Al 5 O 12 phase and the Al 2 O 3 phase at a density of 30/mm or more and 800/mm or less. Since the lamellar structure has interfaces between the Y 3 Al 5 O 12 phase and the Al 2 O 3 phase at a density of 30 pieces / mm or more and 800 pieces / mm or less, the Y 3 Al 5 O 12 phase and Al 2 O Light is easily scattered at the interface of the three phases, and even with a large area, light can be uniformly scattered over the entire surface to obtain uniform emitted light.
  • the number of interfaces is less than 30/mm, the density of the lamellar structure is insufficient, and the Y 3 Al 5 O 12 phase and the Al 2 O 3 phase are formed during the transmission of the ultraviolet light through the ceramic composite 2.
  • the number of times that the light enters the interface decreases, and the light is not sufficiently scattered, resulting in a decrease in the efficiency of wavelength conversion and color mixing.
  • the number of interfaces exceeds 800/mm, the size of the Y 3 Al 5 O 12 phase becomes small and becomes several times the wavelength of ultraviolet light.
  • the average value of the lamellar spacing in the Y 3 Al 5 O 12 phase is 0.5 ⁇ m or more and 20 ⁇ m or less. is preferred.
  • the lamellar spacing of the Y 3 Al 5 O 12 phase indicates the width of the Y 3 Al 5 O 12 phase sandwiched between the Al 2 O 3 phases, and the continuous Y 3 Al 5 O 12 phase in the longitudinal direction. indicates the width across the
  • a ceramic composite with a lamellar spacing of less than 0.5 ⁇ m requires a very high pull-up speed, making it difficult to fabricate.
  • the lamellar spacing is more than 20 ⁇ m, the lamellar structure is insufficiently dense, and the Y 3 Al 5 O 12 phase and the Al 2 O 3 phase are formed while the ultraviolet light is transmitted through the ceramic composite 2. The number of incidents on the interface is reduced and the light is not sufficiently scattered.
  • the lamellar size in the Y 3 Al 5 O 12 phase is desirably 1.0 ⁇ m or more and 40 ⁇ m or less. The reason is that the light can be scattered more uniformly inside the ceramic composite 2 .
  • the ceramic composite 2 contains MgO in the range of 10 mol-ppm or more and 500 mol-ppm or less. By containing MgO in this range, it becomes possible to scatter light more uniformly inside the ceramic composite 2 .
  • the amount of Mo or W contained in the ceramic composite is preferably in the range of 1 mol-ppm or more and 30000 mol-ppm or less.
  • the content of Mo or W should be less than 1 mol.ppm. is very difficult.
  • the content of Mo or W exceeds 30000 mol ⁇ ppm, the crystallinity of the Y 3 Al 5 O 12 phase and the Al 2 O 3 phase deteriorates, which is not preferable.
  • the ceramic composite 2 When a material other than Mo or W is used for the crucible 5, the amount of the material of the crucible 5 that melts into the melt 21 increases due to its low melting point, and the content of elements derived from the crucible 5 contained in the ceramic composite 2 is reduced. Unfavorable because it increases. Moreover, using a material other than Mo or W having a high melting point as a material for the crucible 5 is not preferable because of problems such as reactivity with the raw material melt 21 and formability of the crucible 5 . Therefore, in order to produce the ceramic composite 2 using the EFG method and refine the lamellar structure of the Y 3 Al 5 O 12 phase and the Al 2 O 3 phase, the ceramic composite 2 should contain Mo or W in the above range. It is important that the
  • the thickness of the ceramic composite 2 is preferably in the range of 0.2 mm or more and 5.0 mm or less as described above. The reason for this is that, in addition to the above effects in terms of manufacturing, the thickness can be set to be optimum for the color change of the appearance color of the light emitter. When the thickness exceeds 5.0 mm, even if the light emitted from the ceramic composite 2 is mixed with the light emitted from the phosphor, the emitted light from the ceramic composite 2 is superior, and the color change in the appearance of the light emitter is reduced. Resulting in.
  • the thickness is less than 0.2 mm, in addition to the above-mentioned adverse effects, the thickness is too thin, so when used for decoration, it is necessary to form a light emitter by stacking a plurality of ceramic composites 2, resulting in a decrease in the productivity of the light emitter. I don't like it because I invited him.
  • Examples of phosphors include phosphors that emit any of blue light, green light, red light, yellow light, yellow-green light, orange light, and white light.
  • a phosphor that emits blue light it has a blue appearance color, an emission peak at a wavelength of 446 nm to 450 nm, and a composition of (Sr, Ca) 5 (PO 4 ) 3 Cl:Eu, BaMgAl 10 O 17 . :Eu or ZnS:AgCl phosphors.
  • a phosphor that emits green light it has a green appearance color, an emission peak at a wavelength of 505 nm to 525 nm, and a composition of (BaMg 2 Al 16 O 27 :Eu, Mn), ZnO:Zn, or Zn 2 SiO 4 :Mn phosphor.
  • a phosphor that emits red light As a phosphor that emits red light, it has a red appearance color, has an emission peak at a wavelength of 617 nm to 658 nm, and has a composition of Y 2 O 2 S:Eu, 0.5 MgF 2 .3.5 MgO.GeO 2 . :Mn or Y(P,V,B)O 4 :Eu.
  • a phosphor that emits yellow light includes a phosphor having a yellow appearance, an emission peak at a wavelength of 562 nm, and a composition of Y 3 Al 5 O 12 :Ce.
  • Examples of phosphors that emit yellow-green light include phosphors that have a yellow-green appearance color, an emission peak at a wavelength of 527 nm to 528 nm, and a composition of ZnS:CuCl.
  • a phosphor that emits orange light includes a phosphor that has an orange appearance, an emission peak at a wavelength of 585 nm, and a composition of ZnS:Mn.
  • a phosphor that has a white appearance color and emits white light can also be used.
  • the index 32 is configured by forming a recess on the surface of the ceramic composite 2 having a substantially rectangular outer shape and providing a phosphor 31 having a desired appearance color in the recess.
  • a substantially rectangular portion indicated by a dashed line in FIG. 10 is the phosphor 31 .
  • the dial 33 is configured by providing a phosphor 31 on the back surface of the ceramic composite 2 having a disk-shaped outer shape.
  • an insertion hole is formed for a shaft that rotatably supports the long hand, short hand, and second hand of the wristwatch.
  • a concave portion is formed over the entire circumference on the bottom side surface of the ceramic composite body 2 having a ring-shaped outer shape.
  • a phosphor 31 having a desired external color is provided in the recess. 12 or 14, the phosphor 31 is a substantially circumferential portion indicated by a dashed line.
  • Fig. 9 shows a wristwatch part in which the parts shown in Figs. 10 to 15 are assembled.
  • the concave portions formed in the index 32, the dial ring 34, and the bezel 35 may be formed by a dicer, a scriber, or the like.
  • the external shapes of the indexes, dial, dial ring, and bezel are not limited to the shapes shown in FIGS. 9 to 15.
  • the concave portion may be formed at one or a plurality of positions, or the dial may be provided with a concave portion in a portion of the back surface and the fluorescent substance may be provided in the concave portion.
  • the luminous body according to the present invention is configured such that the ceramic composite 2 is on the front side in appearance.
  • the index 32 in FIG. 10 uses the exposed surface side of the phosphor 31 (the lower surface in FIG. 10) as the fixed surface on the face of the dial 33 .
  • the dial 33 of FIG. 11 has the side of the ceramic composite 2 that is viewed by the wristwatch user.
  • the dial ring 34 in FIGS. 12 and 13 and the bezel 35 in FIGS. 14 and 15 have the side of the ceramic composite 2 that is viewed by the watch user.
  • ultraviolet light 36 incident from outside the light emitter does not directly enter the phosphor 31, only the ceramic composite 2.
  • ultraviolet light (black light) 36 is incident only on the ceramic composite 2 of the light emitter, the incident ultraviolet light 36 is sequentially scattered along the optical path (double-dot chain line) inside the ceramic composite 2. It is reflected and emitted to the outside of the ceramic composite 2 .
  • Drawer number 37 indicates a part of the optical path of the light reflected by the ceramic composite and emitted to the outside of the ceramic composite 2 .
  • the light 37 reflected from the ceramic composite is the appearance color of the ceramic composite 2 .
  • part of the ultraviolet light 36 that has not been reflected inside the ceramic composite 2 propagates along the optical path and passes through the ceramic composite 2 .
  • Part of the ultraviolet light 36 that has passed through the ceramic composite 2 is further incident on the phosphor 31 , and the incident ultraviolet light 36 causes the phosphor 31 to emit light of the appearance color of the phosphor 31 while being scattered.
  • a part of the optical path of the light of the appearance color of the phosphor 31 is indicated by drawer number 38 .
  • the light 37 reflected and emitted from the ceramic composite 2 and the light 38 emitted from the phosphor 31 are mixed and visually observed. Therefore, the color of the light-emitting body changes before and after the ultraviolet light 36 enters and exits, making it visible and improving the decorativeness.
  • the color visually observed before the incidence of ultraviolet light is the appearance color of the ceramic composite 2 arranged on the front side.
  • the mixed color light is visually observed. Therefore, by varying the wavelength band of the mixed color light with respect to the appearance color of the ceramic composite 2, the color change can be recognized. It becomes possible.
  • the color of the light-emitting body changes before and after the ultraviolet light enters and exits, making the light-emitting body visible. improvement can be achieved. Furthermore, by making the luminous body change color with black light in the dark, it is suitable as a production material or a decorative material for entertainment purposes.
  • the ultraviolet light incident only on the ceramic composite it is possible to make the appearance color of the light emitter only the appearance color of the ceramic composite, and it is possible to reliably cause a color change when the ultraviolet light is incident. . Further, according to the method for manufacturing a luminous body according to the present invention, it is possible to manufacture a luminous body having these effects.
  • the luminous body for example, the movement frame, the hour index 32, the dial 33, the dial ring 34
  • the exterior parts such as the case and the bezel 35
  • the light emitter changes color and becomes visible. Therefore, it is possible to expand the design of the wristwatch, change the impression of day and night, and improve the overall decorativeness regardless of the time.
  • a ceramic composite provided in the luminous body of this example was manufactured through each manufacturing process of the above embodiment using the manufacturing apparatus according to the EFG method shown in FIGS.
  • explanations that overlap with the above embodiment will be omitted or simplified, and the same drawer numbers will be used.
  • the crucible 5 is made of Mo, and raw material powder (powder containing 64.71% by weight of aluminum oxide, 35.02% by weight of yttrium oxide, 0.003% by weight of magnesium oxide, and 0.27% by weight of cerium oxide) is poured into the crucible 5 in which the die 9 is accommodated.
  • a melt 21 and a melt pool 22 were prepared by throwing in and heating.
  • a ceramic composite seed crystal 17 was brought into contact with the melt pool 22 and pulled up at a pulling speed of 50 mm/hour to produce a ceramic composite 2 .
  • the planar shape of the ceramic composite 2 pulled up was a square with a width of 45 mm and a length of 300 mm.
  • the observed image of FIG. 7 was obtained.
  • the Y 3 Al 5 O 12 phase of the ceramic composite 2 is activated with Ce, the Ce content is 0.5 mol%, the average lamellar spacing in the Y 3 Al 5 O 12 phase is 3 ⁇ m, and the Y 3 Al 5
  • the interface between the O 12 phase and the Al 2 O 3 phase was included at a density of 330/mm, and the lamellar size in the Y 3 Al 5 O 12 phase was 3 ⁇ m.
  • the ceramic composite 2 was molded to a thickness of 2.5 mm, and a recess was provided with a dicer. .
  • Various phosphors that emit blue light, green light, red light, yellow-green light, orange light, and white light were used for the phosphor 31 .
  • black light having a wavelength of 365 nm or more and 375 nm or less was incident on the obtained sample, and the color change operation was confirmed.
  • the appearance color of the light emitter before the incidence of black light the appearance color of the ceramic composite 2 was visually confirmed as it was, and the appearance color was yellow.

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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Compositions Of Oxide Ceramics (AREA)
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JP2011216543A (ja) * 2010-03-31 2011-10-27 Ube Industries Ltd 発光ダイオード、それに用いられる発光ダイオード用基板及びその製造方法
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JP2018203909A (ja) * 2017-06-06 2018-12-27 パナソニック株式会社 波長変換蛍光体
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08253389A (ja) * 1995-01-19 1996-10-01 Ube Ind Ltd セラミックス複合材料
JP2001156336A (ja) * 1999-11-30 2001-06-08 Nichia Chem Ind Ltd 発光ダイオード
JP2004168996A (ja) * 2002-09-24 2004-06-17 General Electric Co <Ge> 蛍光体ブレンド及び液晶ディスプレイ用バックライト光源
JP2005298284A (ja) * 2004-04-13 2005-10-27 Nec Tokin Corp 装飾材料
JP2006169422A (ja) * 2004-12-17 2006-06-29 Ube Ind Ltd 光変換用セラミック複合体およびそれを用いた発光装置
JP2011216543A (ja) * 2010-03-31 2011-10-27 Ube Industries Ltd 発光ダイオード、それに用いられる発光ダイオード用基板及びその製造方法
CN102173825A (zh) * 2011-01-28 2011-09-07 中国科学院上海光学精密机械研究所 用于钇铝石榴石基荧光透明陶瓷的烧结助剂及其使用方法
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JP2019056038A (ja) * 2017-09-20 2019-04-11 アダマンド並木精密宝石株式会社 発光体及び発光体の製造方法

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