WO2018124106A1 - Corps fluorescent présentant une accumulation de lumière ainsi que procédé de fabrication de celui-ci, et article luminescent à accumulation de lumière - Google Patents

Corps fluorescent présentant une accumulation de lumière ainsi que procédé de fabrication de celui-ci, et article luminescent à accumulation de lumière Download PDF

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WO2018124106A1
WO2018124106A1 PCT/JP2017/046734 JP2017046734W WO2018124106A1 WO 2018124106 A1 WO2018124106 A1 WO 2018124106A1 JP 2017046734 W JP2017046734 W JP 2017046734W WO 2018124106 A1 WO2018124106 A1 WO 2018124106A1
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phosphor
phosphorescence
raw material
light
bismuth
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PCT/JP2017/046734
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English (en)
Japanese (ja)
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哲男 土屋
裕子 鵜澤
巖 山口
智彦 中島
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国立研究開発法人産業技術総合研究所
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • 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
    • 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
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium

Definitions

  • the present invention relates to a phosphor having phosphorescence, a phosphorescent light-emitting product comprising the phosphor, and a method for producing the phosphor having phosphorescence.
  • LED lighting technology has been developed from the viewpoint of energy saving, but white light from LED lighting is different from conventional three-wavelength phosphors mixed with red, blue and green, and cerium-based fluorescence in which cerium is added to YAG.
  • the mainstream method is to excite the body with a blue LED light source in the wavelength region near 460 nm.
  • the pseudo white light is a combination of red and green emission colors, the whole is bluish and high color rendering cannot be realized.
  • it is possible to produce white light with high color rendering properties by using a method of illuminating a phosphor using a purple LED having a wavelength range of 450 to 460 nm and having a wavelength shorter than blue.
  • phosphorescent phosphors those that can emit light even after light excitation and have a long afterglow time are known as phosphorescent phosphors (phosphorescent materials).
  • phosphorescent materials phosphorescent materials
  • Such a phosphorescent phosphor is expected as a material for building a safe and secure society because it has a function as a guide sign or illumination even in the event of a disaster or power failure.
  • SrAl 2 O 4 is used as a mother crystal
  • europium is used as an activator
  • cerium, praseodymium, neodymium, samarium, terbium, dysprosium, holmium, erbium are used as coactivators.
  • An aluminate that emits green light and contains at least one element selected from the group consisting of thulium, ytterbium, and lutetium in a specific amount is known (Patent Document 1).
  • blue light having a wavelength range of 450 to 460 nm which is an excitation light source, has a health hazard. Therefore, there is a need for a phosphor that emits light with high brightness at a color temperature of 6500K to 10000K by excitation light in a wavelength range of 400 nm to 449 nm, which is relatively harmless.
  • YAG which is normally used for white LEDs, stops emitting light when the excitation light source is turned off, so it is indispensable to be a phosphorescent phosphor for safe and reliable evacuation guidance during power outages. It is.
  • the aluminate phosphor described in Patent Document 1 has low light absorption at a wavelength of less than 450 nm, and thus has insufficient light emission luminance and afterglow luminance.
  • the color temperature when emitted by excitation light with a wavelength of 420 nm is as high as 15000 K, and its application range is limited.
  • the phosphorescent phosphors described in Patent Documents 2 and 3 also have a low light absorption at a wavelength of less than 450 nm, a high color temperature, and are difficult to use for white LED illumination with excitation light in the wavelength range of 400 nm to 449 nm. is there.
  • An object of the present invention is to provide a phosphor having a phosphorescence that emits light at 10000 K and emits light even after excitation is stopped, a phosphorescent light-emitting product including the phosphor, and a method for producing the phosphor having the phosphorescence.
  • a phosphor having a specific composition formula emits light when excited by a light source having a wavelength range of 400 to 449 nm, and has a wavelength of 400 nm and It has been found that light is emitted at a color temperature of 6500 K to 10000 K with any one or more excitation lights of 420 nm and continues to be emitted even after excitation is stopped, and the present invention has been completed.
  • the phosphor having the phosphorescence of the present invention can eliminate the drawbacks related to the light absorption of the conventional phosphorescent phosphor with respect to the LED light source having a wavelength region of less than 450 nm, and the following composition formula (1a) or (1b): Sr (1-xyz) Mg x Al 2 O 4; Eu z (1a) Sr (1-xyz) Mg x Al 4 O 7; Eu z (1b) And a phosphor having a phosphorescence that emits light with excitation light in the wavelength region of 400 to 449 nm and is excited with one or more light sources of wavelengths 400 nm and 420 nm to emit light at a color temperature of 6500K to 10000K. It is.
  • x, y, and z are 0 ⁇ x ⁇ 0.1, ⁇ 0.2 ⁇ y ⁇ 0.2, and 0.01 ⁇ z ⁇ 0.5, respectively. is there.
  • the phosphors having the phosphorescence include bismuth (Bi), dysprosium (Dy), samarium (Sm), lanthanum (La), praseodymium (Pr), terbium (Tb), holmium (Ho), thulium (Tm), lutetium ( From the viewpoint of controlling the phosphorescence time, it further contains at least one element selected from the group consisting of Lu), ytterbium (Yb), erbium (Er), gadolinium (Gd), neodymium (Nd) and cerium (Ce). ,preferable.
  • the phosphor having the light storage preferably has a fluorescence luminance of 2500 cd / m 2 or more due to excitation light of any one of wavelengths of 400 nm and 420 nm.
  • the present inventors added a bismuth (Bi) inorganic compound or a bismuth (Bi) organic compound to a raw material containing a strontium element, a raw material containing a magnesium element, a raw material containing a europium element, and alumina.
  • a method for producing a phosphor having phosphorescence including a step of obtaining a precursor material and a step of firing the precursor material in a range of 1300 ° C. to 1700 ° C., in particular, suitable for the phosphor having phosphorescence of the present invention.
  • the present invention was completed by finding that the production method can be obtained.
  • the phosphorescent light-emitting product of the present invention includes a phosphor having the phosphorescence of the present invention.
  • light is emitted by excitation light in the wavelength region of 400 to 449 nm, light is emitted at a color temperature of 6500 K to 10000 K by excitation light of any one of wavelengths 400 nm and 420 nm, and light is emitted even after excitation is stopped. It is possible to provide a phosphor having phosphorescence, a phosphorescent light-emitting product including the phosphor having phosphorescence, and a method for producing the phosphor having phosphorescence.
  • 6 is a spectrum showing emission characteristics when the phosphors of Example 2 and Comparative Examples 1 to 3 are irradiated with excitation light having a wavelength of 380 nm.
  • 6 is a spectrum showing emission characteristics when the phosphors of Example 2 and Comparative Examples 1 to 3 are irradiated with excitation light having a wavelength of 390 nm.
  • 6 is a spectrum showing emission characteristics when the phosphors of Example 2 and Comparative Examples 1 to 3 are irradiated with excitation light having a wavelength of 400 nm.
  • 6 is a spectrum showing emission characteristics when the phosphors of Example 2 and Comparative Examples 1 to 3 are irradiated with excitation light having a wavelength of 410 nm.
  • 6 is a spectrum showing emission characteristics when the phosphors of Example 2 and Comparative Examples 1 to 3 are irradiated with excitation light having a wavelength of 420 nm.
  • the phosphor having phosphorescence has the following composition formula (1a) or (1b): Sr (1-xyz) Mg x Al 2 O 4; Eu z (1a) Sr (1-xyz) Mg x Al 4 O 7; Eu z (1b) It is represented by This phosphor is an oxide-based phosphor and has high luminance.
  • the phosphor of this embodiment is also referred to as a “high brightness phosphor”.
  • x which is the composition ratio of Mg is 0 ⁇ x ⁇ 0.1, and more preferably 0.01 ⁇ from the viewpoint of obtaining excellent emission luminance and afterglow luminance.
  • Eu which is the composition ratio of Eu, is 0.01 ⁇ z ⁇ 0.5 from the viewpoint of good luminance, and preferably 0.03 ⁇ z ⁇ 0 from the viewpoint of excellent fluorescence intensity and low cost. .2.
  • Eu takes a bivalent (Eu 2+ ) and / or trivalent (Eu 3+ ) state in the phosphor depending on the synthesis conditions such as the mixing ratio of raw materials and the firing temperature.
  • a large amount of divalent Eu is contained.
  • Such a phosphor is preferably obtained by synthesis using bismuth oxide (Bi 2 O 3 ).
  • the bivalent Eu contained in the phosphor is preferably contained in an amount of 80% by mass or more, and more preferably 90% by mass or more with respect to 100% by mass of the total of divalent and trivalent Eu.
  • the divalent and trivalent Eu can be measured using X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure analysis (XAFS, X-ray Absorption Fine Structure).
  • the phosphor represented by the above composition formula (1a) and containing a large amount of divalent Eu is more preferable because it emits green light with higher luminance. Since red emission occurs when trivalent is present, Eu valence control is effective for high-intensity white light emission using the phosphor of the present embodiment that emits green light by excitation with a purple light source. Found by the inventors.
  • the composition ratio of Sr is 1-xyz from the viewpoint of having good fluorescence luminance and afterglow characteristics.
  • y is ⁇ 0.2 ⁇ y ⁇ 0.2, and is preferably ⁇ 0.05 ⁇ y ⁇ 0.1 from the viewpoint of more effectively and reliably introducing structural distortion due to defects and excess metal from the stoichiometric composition. More preferably, ⁇ 0.01 ⁇ y ⁇ 0.07, and further preferably 0 ⁇ y ⁇ 0.05.
  • 1-xyz is usually 0.2 ⁇ 1-xyz ⁇ 1.18, and from the viewpoint of long-term stability, 0.65 ⁇ 1-xyz ⁇ 1.05 is preferable, and 0.85 ⁇ 1-xyz ⁇ 1 is more preferable.
  • the phosphor having phosphorescence according to the present embodiment emits light at a color temperature of 6500K to 10,000K, preferably 7000K to 8500K, by excitation light having a wavelength of 400 nm or 420 nm.
  • a color temperature in this range is preferable from the viewpoint of increasing brightness.
  • the phosphor having phosphorescence according to the embodiment preferably emits light by being excited by a light source having a wavelength range of 400 to 449 nm, and has a color temperature of 6500 K to 10,000 K by excitation light having a wavelength of 400 nm or 420 nm.
  • the emission color of the excitation light by the excitation light of any one of the wavelengths of 400 nm and 420 nm and the white or green light emission of the phosphor of the present embodiment shows high luminance white light emission of 2500 cd / m 2 or more, It continues to emit light with high brightness even after excitation is stopped.
  • bismuth (Bi), dysprosium (Dy), samarium (Sm), and lanthanium (La) are used in terms of trap level formation for controlling the afterglow time after illumination stop.
  • Pr Praseodymium
  • Tb terbium
  • Ho holmium
  • Tm thulium
  • Tm thulium
  • Lu thulium
  • Lu thulium
  • Yb lutetium
  • Yb lutetium
  • Er gadolinium
  • Nd neodymium
  • Ce cerium
  • Dy dysprosium
  • composition formula (1a) or (1b) are represented by the following composition formula (2a) or (2b), respectively.
  • M is at least one element selected from the group consisting of Bi, Dy, Sm, La, Pr, Tb, Ho, Tm, Lu, Yb, Er, Gd, Nd, and Ce. Indicates.
  • a which is the composition ratio of M is not particularly limited, but is usually 0 ⁇ a ⁇ 0.15, preferably 0.005 ⁇ a ⁇ 0.13, and more preferably 0.01 ⁇ a ⁇ 0.1. 0.12. From the viewpoint of obtaining a high-luminance phosphor having a long afterglow time by controlling the trap level, it is preferable that a which is the composition ratio of M is 0.01 ⁇ a ⁇ 0.04.
  • the composition ratio a is preferably 0.04 ⁇ a ⁇ 0.15, and 0.045 ⁇ a ⁇ 0. 12 is more preferable, and 0.05 ⁇ a ⁇ 0.1 is still more preferable.
  • the phosphor having the phosphorescence represented by the composition formula (1a) or (1b) is a phosphor having the phosphorescence represented by the following composition formula (2c) or (2d).
  • z which is a composition ratio of Eu
  • z is 0.01 ⁇ z ⁇ 0.5 from the point of having good luminance, and from the viewpoint of further excellent fluorescence intensity and low cost.
  • Eu takes a bivalent (Eu 2+ ) and / or trivalent (Eu 3+ ) state in the phosphor depending on the synthesis conditions such as the mixing ratio of raw materials and the firing temperature.
  • Such a phosphor is preferably obtained by synthesis using bismuth oxide (Bi 2 O 3 ).
  • the bivalent Eu contained in the phosphor is preferably contained in an amount of 80% by mass or more, and more preferably 90% by mass or more with respect to 100% by mass of the total of divalent and trivalent Eu.
  • bivalent and trivalent Eu can be measured using X-ray photoelectron spectroscopy and X-ray absorption fine structure analysis as described above.
  • the composition ratio of Sr is 1-yz from the viewpoint of good fluorescence luminance and afterglow characteristics.
  • y is ⁇ 0.2 ⁇ y ⁇ 0.2, and is preferably ⁇ 0.05 ⁇ y ⁇ 0.15 from the viewpoint of more effectively and reliably introducing structural distortion due to defects and excess metal from the stoichiometric composition. More preferably, 0 ⁇ y ⁇ 0.12 from the viewpoint that defects can be suitably introduced from the stoichiometric composition, and more preferably 0.05 ⁇ from the point that a phosphor emitting green light with high luminance can be obtained. y ⁇ 0.12.
  • M is at least one element selected from the group consisting of Bi, Dy, Sm, La, Pr, Tb, Ho, Tm, Lu, Yb, Er, Gd, Nd, and Ce. Indicates.
  • it is Dy from the viewpoint of obtaining a high-luminance phosphor.
  • a which is the composition ratio of M is not particularly limited, but is usually 0 ⁇ a ⁇ 0.15, preferably 0.005 ⁇ a ⁇ 0.13, and more preferably 0.01 ⁇ a ⁇ 0.1. From the point of obtaining a phosphor that emits green light with high brightness, it is more preferably 0.01 ⁇ a ⁇ 0.07.
  • the fluorescence brightness of the phosphor having phosphorescence of the present embodiment is not particularly limited depending on the application, but is preferably 2500 cd / m 2 or more as the fluorescence brightness by excitation light of any one of wavelengths 400 nm and 420 nm. , more preferably 3000 cd / m 2 or more, since it can be used as a white phosphor having a high brightness, still more preferably 4000 cd / m 2 or more, still more not less 4100cd / m 2 or more preferably, more preferably more is at 4500 cd / m 2 or more, most preferably 5000 cd / m 2 or more.
  • the upper limit is not particularly limited, but is usually 25000 cd / m 2 in order to avoid eye damage when viewed directly.
  • the afterglow brightness of the phosphor having phosphorescence of the present embodiment excited by any one or more light sources having wavelengths of 400 nm and 420 nm and 10 minutes after the excitation stop is not particularly limited depending on the application.
  • the luminance is visible to about 0.3 mcd / m 2, so the afterglow luminance is preferably at least 0.3 mcd / m 2 or more, more preferably 3 mcd / m 2 or more, further preferably 10mcd / m 2 or more, and still more preferably at 15mcd / m 2 or more.
  • the afterglow intensity is more preferably 20 mcd / m 2 or more, since it can be used as a guide sign or illumination having excellent afterglow brightness even in the event of a disaster, power failure or after extinguishing.
  • it is 30 mcd / m 2 or more.
  • the phosphor having the phosphorescence represented by the composition formula Sr 0.90 Mg 0.04 Al 2 O 4; Eu 0.04 Dy 0.02 is combined with the green emission of the phosphor obtained by exciting with a violet light source. It is preferable because it emits white light with luminance and continues to emit light with moderate luminance even after excitation is stopped.
  • the phosphor having phosphorescence represented by the composition formula Sr 0.90 Mg 0.04 Al 2 O 4; Eu 0.04 Dy 0.02 includes a raw material containing a strontium element, a raw material containing a magnesium element, a raw material containing a europium element, alumina, It is obtained from a raw material containing a bismuth (Bi) inorganic compound and / or a bismuth (Bi) organic compound. Preferably, these raw materials are mixed and further synthesized.
  • the phosphor having phosphorescence is a phosphor obtained by using at least one selected from the group consisting of a bismuth (Bi) inorganic compound and a bismuth (Bi) organic compound. It is more preferable because white and green light emission of the color and phosphor emits white light with high brightness and continues to emit light with appropriate brightness even after excitation is stopped.
  • the bismuth (Bi) inorganic compound is not particularly limited, and examples thereof include bismuth oxide, bismuth hydroxide, and bismuth carbonate.
  • bismuth (Bi) oxide that is, bismuth oxide
  • the bismuth (Bi) organic compound is not particularly limited, and examples thereof include bismuth acetate, bismuth 2-ethylhexanoate, bismuth naphthenate, and acetylacetonate bismuth.
  • the phosphorescent phosphors have the following composition formula (3a) to (3d): Sr (1-xyz) Mg x Al 2 O 4; Eu z M a Bi b ⁇ (3a) Sr (1-xyz) Mg x Al 4 O 7; Eu z M a Bi b ⁇ (3b) Sr (1-yz) Al 2 O 4; Eu z M a Bi b ⁇ (3c) Sr (1-yz) Al 4 O 7; Eu z M a Bi b ⁇ (3d) It is represented by
  • composition formulas (3a) and (3b) x, y, z and a are as defined above.
  • M is obtained by removing Bi from M in the composition formulas (2a) and (2b).
  • composition formulas (3c) and (3d) y, z, and a are synonymous with the composition formulas (2c) and (2d).
  • M is obtained by removing Bi from M in the composition formulas (2c) and (2d).
  • Bi which is the composition ratio of Bi, is 0 ⁇ b ⁇ 0.15, preferably 0.01 ⁇ b ⁇ 0.12, and preferably 0.02 ⁇ b ⁇ 0. 11, more preferably 0.04 ⁇ b ⁇ 0.06 from the viewpoint of high fluorescence intensity, good color temperature, and low cost.
  • the method for producing a phosphor having phosphorescence includes a raw material containing a strontium element, a raw material containing a magnesium element, a raw material containing a europium element, alumina (aluminum oxide), bismuth (Bi) inorganic compound, and The method includes a step of obtaining a precursor raw material (mixture) by adding at least one selected from the group consisting of bismuth (Bi) organic compounds, and a step of firing the precursor raw material in the range of 1300 ° C. to 1700 ° C.
  • the method for producing a phosphor having phosphorescence if necessary, at least one selected from the group consisting of dysprosium, samarium, lanthanium, praseodymium, terbium, holmium, thulium, lutetium, ytterbium, erbium, gadolinium, neodymium and cerium.
  • the precursor raw material may be obtained by further mixing raw materials containing these elements.
  • the phosphor having phosphorescence according to this embodiment is not particularly limited, but can be manufactured by dry mixing without using a solvent described later, wet mixing using a solvent, or the like.
  • inorganic compounds and metal organic compounds can be used as precursors (precursors) as the respective raw materials.
  • precursors precursors
  • a metal carbonate, a metal oxide, a metal hydroxide, and / or a metal hydroxide are mentioned, for example, 1 type is used individually or in combination of 2 or more types.
  • a precursor raw material that is a raw material of a phosphor having phosphorescence can be obtained by mixing the inorganic compound with a material that has been uniformly and nanosized with an appropriate mortar or planetary ball mill.
  • a phosphor having phosphorescence that emits light even after excitation is stopped is preferably obtained.
  • the contents of the bismuth (Bi) inorganic compound and the bismuth (Bi) organic compound in the precursor raw material are not particularly limited as long as the effects of the present invention are exhibited, but with respect to 100% by mass of the total raw material in the precursor raw material (mixture)
  • the content is preferably 0.1 to 15% by mass, more preferably 1 to 13% by mass, and still more preferably 4 to 10% by mass.
  • the bismuth (Bi) inorganic compound and the bismuth (Bi) organic compound the above-described inorganic compounds and organic compounds can be used.
  • the precursor raw material (mixture) is fired in the range of 1300 ° C. to 1700 ° C., preferably in the range of 1300 to 1450 ° C. preferable.
  • the content of bismuth oxide (Bi 2 O 3 ) in the precursor raw material is not particularly limited as long as the effect of the present invention is exhibited, but with respect to 100% by mass of the total raw material in the precursor raw material (mixture).
  • the content is preferably 0.1 to 15% by mass, more preferably 1 to 13% by mass, and still more preferably 4 to 10% by mass.
  • boron compounds such as boron oxide (B 2 O 3 ), boron hydroxide, boron nitride and the like as a flux emits light with high brightness by excitation light in the wavelength region of 400 to 449 nm. It is preferable because a phosphor can be suitably obtained.
  • the boron compound since a phosphor with particularly high brightness can be obtained, it is more preferable to mix boron oxide as a flux.
  • the mixing ratio of the boron compound is not particularly limited as long as the effect of the present invention is exhibited, but the boron compound is 0.01 to 15% by mass of the boron raw material with respect to 100% by mass of the total amount of the raw material (mixture).
  • the boron compound is preferably mixed so as to be 0.1 to 10% by mass, more preferably the boron compound is further mixed so as to be 0.5 to 5% by mass. Even more preferably, the boron compound is mixed so as to be ⁇ 3 mass%.
  • the content of boron oxide in the precursor raw material (mixture) is not particularly limited as long as the effect of the present invention is exhibited, but is 0.01 to 15 with respect to 100% by mass of the total raw material in the precursor raw material (mixture). Preferably, it is 0.1% by mass, more preferably 0.1-10% by mass, still more preferably 0.5-5% by mass, and even more preferably 1-3% by mass.
  • aluminum oxide examples include ⁇ -alumina, ⁇ -alumina, and aluminum hydroxide oxide. Of these, firing with ⁇ -alumina ( ⁇ -aluminum oxide) as a raw material is particularly preferable because a phosphor with relatively high luminance and longer persistence can be obtained. Aluminum oxide is used alone or in combination of two or more.
  • metal organic compound examples include metal organic acid salt, ⁇ -diketonate, metal alkoxide, metal acetate, metal 2-ethylhexanoate, metal acetylacetonate, and metal naphthenate. Any metal organic compound that can be dissolved in a solvent can be used without particular limitation.
  • a metal organic compound is used individually by 1 type or in combination of 2 or more types.
  • the solvent is not particularly limited as long as it dissolves the metal organic compound, but methanol, ethanol, propanol, butanol, hexanol, heptanol, ethyl acetate, butyl acetate, toluene, xylene, benzene, acetylacetonate, ethylene glycol, and At least one selected from the group consisting of water is preferred.
  • a compound containing a metal that cannot be dissolved in a solvent for example, a solid material such as a metal oleate or a metal stearate can also be used as a precursor.
  • the manufacturing method of the present embodiment may include a step of drying the precursor raw material.
  • the manufacturing method of the present embodiment includes a step of removing the solvent and organic components at a temperature of 500 ° C. or lower after the mixing step. May be.
  • the step of firing the obtained precursor raw material at 1200 ° C. or higher, preferably 1200 ° C. or higher and 1800 ° C. or lower, more preferably 1300 ° C. or higher and 1700 ° C. or lower from the viewpoint of high crystallinity and Eu valence control.
  • a high-intensity phosphor having phosphorescence can be obtained.
  • Eu 2+ can be generated by using a reducing gas as the atmosphere for firing.
  • a mixed gas in which 4% or less of H 2 (hydrogen) gas is mixed in Ar (argon) gas and / or N 2 (nitrogen) gas is suitable.
  • bismuth may be removed from the body to be fired by firing.
  • the fired body In the firing in which the temperature is changed in multiple stages after completion of the firing process, the fired body (phosphor) is molded into an appropriate shape after any firing process, preferably after the last firing process. As a result, a sintered molded body (luminescent phosphorescent product) can be obtained. Further, the obtained sintered molded body can be appropriately pulverized to obtain a high-intensity phosphor having a pulverized light storage.
  • the high-intensity phosphor having a fine powdery phosphorescence is applied to various object surfaces together with a solid binder or a liquid medium, or mixed with plastics, rubber, vinyl chloride, synthetic resin or glass, A phosphorescent molded body of each color, preferably a red phosphorescent molded body or a fluorescent film can also be used.
  • light is emitted by being excited by a light source having a wavelength range of 400 to 449 nm that is relatively less harmful to health, and a color temperature of 6500K to 10000K is generated by one or more excitation lights having wavelengths of 400 nm and 420 nm.
  • Lights on. Preferably, it emits light when excited by a light source in the wavelength region of 400 to 449 nm, emits light at a color temperature of 6500 K to 10,000 K by any one or more excitation light of wavelengths 400 nm and 420 nm, and any of wavelengths 400 nm and 420 nm.
  • One or more excitation lights emit light with a high luminance of 2500 cd / m 2 or more.
  • the luminance is relatively high, and a high-intensity phosphor having a phosphorescence having a long afterglow phosphorescence property, a phosphorescent light-emitting product comprising the high-luminance phosphor having the phosphorescence, And the manufacturing method of the high-intensity fluorescent substance which has phosphorescence can be provided.
  • the phosphor of the present embodiment can realize high color rendering properties with high luminance as compared with a phosphor obtained by adding cerium to YAG used in a conventional LED that requires an excitation light source of 460 nm, and has a wide range of applications. Can be used.
  • the phosphor having phosphorescence can be suitably applied to energy-saving LED lighting technology, and emits light even at the time of a power failure. Therefore, it is possible to maintain a function as a guidance sign or illumination even at the time of a disaster, power failure, or light extinction.
  • the phosphor having phosphorescence according to the present embodiment can be used as a phosphor for an excellent white light-emitting lighting device that contributes to a safe and secure society. Is possible.
  • the phosphor having phosphorescence of the present embodiment is applied to the surface of various articles, or mixed with plastics, rubber, vinyl chloride, synthetic resin, glass, etc. By doing so, it can be used for road signs, visual indications, ornaments, leisure goods, watches, OA equipment, educational equipment, safety signs, building materials, and the like. Moreover, it can be used as a fluorescent lamp with excellent afterglow by using the phosphor having phosphorescence of this embodiment as a fluorescent film of a fluorescent lamp.
  • ⁇ Test method> Measurement of fluorescence intensity (luminance, cd / m 2 ) and afterglow intensity (luminance, mcd / m 2 )
  • the fluorescence intensity of the obtained sample was measured by a light source (product name “MAX” -302 "), and was measured with a luminance meter (product name” SR-UA1 ") manufactured by Topcon Corporation.
  • a light source product name “MAX” -302”
  • Afterglow intensity first, after being left for 1 hour in a dark place, after being excited for 1 minute at wavelengths of 400 nm and 420 nm using a light source (product name “MAX-302”) manufactured by Asahi Spectroscopy Co., Ltd. Excitation was stopped.
  • the afterglow luminance after 10 minutes was measured with a luminance meter (product name “SR-UA1”) manufactured by Topcon Corporation.
  • the illuminance of the 400 nm excitation light source was 350 lux, and the illuminance of the 420 nm excitation light source was 120 lux.
  • the illuminance was measured with a digital illuminometer LX-105 manufactured by Custom Co., Ltd.
  • ⁇ Raw material> The following raw materials (reagents) were used for the synthesis of phosphors having phosphorescence.
  • Strontium carbonate manufactured by Rare Metallic Co., Ltd., purity: 99.9%
  • ⁇ -aluminum oxide manufactured by Rare Metallic Co., Ltd., purity: 99.9%
  • Magnesium oxide Rare Metallic Co., Ltd., purity: 99.99%)
  • Europium oxide manufactured by Rare Metallic Co., Ltd., purity: 99.99%)
  • Dysprosium oxide Rare Metallic Co., Ltd., purity: 99.9%
  • Bismuth oxide manufactured by Wako Pure Chemical Industries, Ltd., purity: 99.99%)
  • Boron oxide manufactured by Kojundo Chemical Laboratory Co., Ltd., purity: 99.9%
  • Example 1 Sr 0.9 Mg 0.04 Al 2 O 4; Eu 0.04 Dy 0.02 Bi 0.03
  • the above raw materials were weighed so as to obtain a precursor raw material powder by mixing for 2 hours using an automatic mortar (Bi mixing) The amount is 4.8% by mass of Bi raw material with respect to 100% by mass of all raw materials (mixture)).
  • the obtained powder was packed in an alumina firing board and fired in an argon-hydrogen mixed gas (argon amount: 3%) at 1400 ° C. for 3 hours. After firing, it was pulverized in a mortar to obtain a phosphor powder sample. The sample was measured for fluorescence intensity and afterglow intensity. The results are shown in Tables 1 and 2.
  • Example 2 Sr 0.9 Mg 0.04 Al 2 O 4; Eu 0.04 Dy 0.02 Bi 0.05
  • the above raw materials were weighed so that the Bi raw material was 7.8% based on 100% by mass of the total raw material (mixture).
  • a sample was prepared in the same manner as in Example 1 except that it was (mass%). The sample was measured for fluorescence intensity and afterglow intensity. The results are shown in Tables 1 and 2.
  • the divalent Eu contained in the phosphor powder sample was 90% by mass with respect to 100% by mass of the total of divalent and trivalent Eu.
  • Example 3 Sr 0.9 Mg 0.04 Al 2 O 4; Eu 0.04 Dy 0.02 Bi 0.07
  • the above raw materials were weighed so that the Bi raw material was 10.6 Bi based on 100% by mass of the total raw material (mixture).
  • a sample was prepared in the same manner as in Example 1 except that it was (mass%). The sample was measured for fluorescence intensity and afterglow intensity. The results are shown in Tables 1 and 2.
  • Example 4 Sr 0.9 Mg 0.04 Al 2 O 4; Eu 0.04 Dy 0.02 Bi 0.10 Each of the above raw materials was weighed (Bi mixed amount was 100% by mass of all raw materials (mixtures), Bi raw material 14.5 A sample was prepared in the same manner as in Example 1 except that it was (mass%). The sample was measured for fluorescence intensity and afterglow intensity. The results are shown in Table 1.
  • Example 5 Sr 0.75 Mg 0.04 Al 4 O 7; Eu 0.2 Dy 0.01
  • boron oxide was added in a boron raw material of 0.73 to 100% by mass of the total raw material (mixture). It added to this raw material so that it might become the mass%, and it mixed for 2 hours using the automatic mortar, and obtained the powder of the precursor raw material.
  • the obtained powder was packed in an alumina firing board and fired in an argon-hydrogen mixed gas (argon amount: 3%) at 1400 ° C. for 3 hours. After firing, it was pulverized in a mortar to obtain a phosphor powder sample. The sample was measured for fluorescence intensity and afterglow intensity. The results are shown in Table 5.
  • Example 6 A sample was prepared in the same manner as in Example 5, except that the above raw materials were weighed so as to have a composition ratio of Sr 0.75 Mg 0.04 Al 4 O 7; Eu 0.14 Dy 0.01 . The sample was measured for fluorescence intensity and afterglow intensity. The results are shown in Table 5.
  • Example 7 A sample was prepared in the same manner as in Example 5 except that the above raw materials were weighed so that the composition ratio was Sr 0.84 Al 2 O 4; Eu 0.05 Dy 0.05 . The sample was measured for fluorescence intensity and afterglow intensity. The results are shown in Table 6. The divalent Eu contained in the phosphor powder sample was 85% by mass with respect to 100% by mass of the total of divalent and trivalent Eu.
  • Example 8 A sample was prepared in the same manner as in Example 5 except that the above raw materials were weighed so as to have a composition ratio of Sr 0.90 Al 2 O 4; Eu 0.04 Dy 0.02 . The sample was measured for fluorescence intensity and afterglow intensity. The results are shown in Table 6.
  • Comparative Example 1 As Comparative Example 1, the color temperature and the light emission characteristics of a powder sample of a phosphorescent phosphor having a composition of SrAl 2 O 4 : EuDy (manufactured by Nemoto Lumi Material Co., Ltd., product name “GLL300M”) were measured. The results are shown in Tables 3 and 4 and FIGS. The divalent Eu contained in the phosphor powder sample was 75% by mass with respect to 100% by mass of the total of divalent and trivalent Eu.
  • Comparative Example 2 As Comparative Example 2, the emission characteristics of YAG (cerium phosphor) powder used in a commercially available LED were measured in the same manner as in Example 1. The results are shown in FIGS.
  • Comparative Example 3 As Comparative Example 3, the light emission characteristics of a phosphor sample having a composition of SrAl 2 O 4 : EuDy (manufactured by Nemoto Lumi Material Co., Ltd., product name “GLL300FF”) were measured. The results are shown in FIGS.
  • phosphors having phosphorescence according to this embodiment include conventional YAG cerium phosphors, Comparative Example 2 and commercially available phosphorescent materials (Comparative Examples 1 and 3). It can be seen that the brightness is higher than that of ().
  • the phosphor having phosphorescence of the present invention is, for example, a proof using LED such as a lighting device for road signs, safety signs and visual indications, ornaments, leisure goods, watches, OA equipment, educational equipment and building materials. Widely applicable to technology.

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Abstract

Le corps fluorescent présentant une accumulation de lumière de l'invention, est représenté par Ｓｒ(1-x-y-z)ＭｇxＡｌ2Ｏ4;Ｅｕz・・・（１ａ）, ou Ｓｒ(1-x-y-z)ＭｇxＡｌ4Ｏ7;Ｅｕz・・・（１ｂ）(dans les formules (1a) et (1b), x, y et z sont chacun tels que ０≦ｘ≦０,１, －０,２≦ｙ＜０,２ et ０,０１≦ｚ≦０,５), génère une lumière sous l'effet d'une lumière d'excitation de région de longueur d'onde comprise entre 400 et 449nm, et génère une lumière de température de couleur comprise entre 6500K et 10000K sous l'effet d'une lumière d'excitation ou plus de longueur d'onde de 400nm et 420nm.
PCT/JP2017/046734 2016-12-28 2017-12-26 Corps fluorescent présentant une accumulation de lumière ainsi que procédé de fabrication de celui-ci, et article luminescent à accumulation de lumière WO2018124106A1 (fr)

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