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WO2005044946A1 - Phosphore d'emission de phosphorescence et procede de production de ce phosphore - Google Patents

Phosphore d'emission de phosphorescence et procede de production de ce phosphore Download PDF

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Publication number
WO2005044946A1
WO2005044946A1 PCT/JP2004/016401 JP2004016401W WO2005044946A1 WO 2005044946 A1 WO2005044946 A1 WO 2005044946A1 JP 2004016401 W JP2004016401 W JP 2004016401W WO 2005044946 A1 WO2005044946 A1 WO 2005044946A1
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WIPO (PCT)
Prior art keywords
dysprosium
compound
ratio
amount
palladium
Prior art date
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PCT/JP2004/016401
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English (en)
Japanese (ja)
Inventor
Yoneichi Hirata
Tomoya Sakaguchi
Nobuyoshi Takeuchi
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Nemoto & Co., Ltd.
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Publication of WO2005044946A1 publication Critical patent/WO2005044946A1/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
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7792—Aluminates

Definitions

  • the present invention relates to a phosphorescent phosphor, particularly to a phosphorescent phosphor having a long-term afterglow characteristic.
  • the afterglow time of a phosphor is extremely short, and the luminescence is rapidly attenuated when an external stimulus is stopped. Afterglows can be observed with the naked eye for several tens of minutes (even for several hours). These phosphorescent phosphors are distinguished from ordinary phosphors by phosphorescent phosphors.
  • Examples of the phosphorescent phosphors include phosphors such as CaS: Bi (purple blue light emission), CaSrS: Bi (blue light emission), ZnS: Cu (green light emission), and ZnCdS: Cu (yellow-orange light emission). Any of these sulfide phosphors are chemically unstable, have poor light resistance, and are not suitable for use in luminous watches. However, there were many practical problems, such as the afterglow time for which the time was recognizable to the naked eye was about 30 minutes to 2 hours.
  • the applicant of the present invention has a long-lasting property that is much longer than commercially available sulfide-based phosphors, is chemically stable, and has excellent light resistance over a long period of time.
  • Power group power A phosphorescent phosphor in which at least one or more selected metal element power compound is used as a mother crystal was invented and a patent was obtained (for example, Japanese Patent No. 2543825).
  • the phosphorescent phosphor has a much longer afterglow characteristic than the conventional phosphorescent phosphor, and furthermore is a phosphorescent phosphor-based phosphor. Therefore, it has become possible to provide a long afterglow phosphorescent phosphor that is chemically stable and has excellent light resistance and is applicable to various uses.
  • the present invention has been made in view of such circumstances, and after a long period of time after excitation, a luminous phosphor having excellent afterglow luminance characteristics compared to conventional strontium aluminate phosphorescent phosphors of the same type. It is intended to provide a body and a method for producing the same.
  • the present inventor has proposed that, in the strontium aluminate-based phosphorescent phosphor described in the above-mentioned Patent Publication, the activator Yuguchi Pium (Eu) and the coactivator Dysprosium (Dy) were used.
  • Eu activator Yuguchi Pium
  • Dysprosium Dy
  • Sr strontium
  • Ba barium
  • Ca calcium
  • A1 aluminum
  • the phosphorescent phosphor according to the first invention of the present invention is a compound represented by MAIO,
  • palladium (Eu) is added as an activator and dysprosium (Dy) is added as a coactivator.
  • the amount of spiked porridge (Eu) added is 0.5% or more and 2% or less in terms of mol%, based on the total number of moles of the metal element represented by M and the number of moles of euphyllium (Eu) and dysprosium (Dy).
  • the molar amount of dysperm shim (Dy) is 1 and Dy / Eu ⁇ 20 in molar ratio with respect to palladium (Eu), and the addition of pium (Eu) and dysprosium (Dy). total ⁇ is a mole 0/0 1. 5% or less than 42% relative to the total number of moles of metallic element and Yu port Piumu (Eu) and dysprosium (Dy) expressed by M, aluminum (A1) Of the metal element represented by M and the total number of moles of palladium (Eu) and dysprosium (Dy) 3.0 or less, and the ratio of barium to M is 0.015 ⁇ Ba / (Sr + Ba) ⁇ 0.35 in molar ratio.
  • Yu port Piumu as an activating agent (Eu)
  • Yu port Piumu as an activating agent (Eu)
  • Dyprosium Dye
  • M molecular weight
  • DyZEu molar 0/0 0
  • DyZEu molar ratio of 1
  • DyZEu the total amount of palladium (Eu) and dysprosium (Dy) in the mouth to the total number of moles of the metal element represented by M and the total number of moles of pium (Eu) and dysprosium (Dy) in the mouth.
  • the addition amount of the zipper opening seam that contributes to the afterglow luminance characteristic is increased compared to the addition amount of the europium pium that contributes to the fluorescent luminance characteristic, and optimization is difficult. Due to the force, even after a long time of about 10 to 12 hours after excitation, the phosphor has excellent afterglow luminance characteristics as compared with the conventional phosphorescent phosphor.
  • the ratio of aluminum (A1) is 2.05 or more in terms of molar ratio to the total number of moles of the metal element represented by M, the pium (Eu), and the dies (Dy).
  • the ratio is set to 0 or less, the ratio of the aluminum is increased from 2.0, which is the stoichiometric ratio, to 2.05 or more, so that the crystal structure is distorted and traps are easily formed. Even after a long period of time, it has better afterglow luminance characteristics than conventional phosphorescent phosphors.
  • the phosphor has more excellent afterglow luminance characteristics than the conventional phosphorescent phosphor.
  • the added amount of dysprosium as a co-activator in the molar ratio of dysprosium as a coactivator with respect to the amount of palladium in Eu ie, in the case of DyZEu ⁇ l, the amount of added dysprosium contributing to the afterglow luminance characteristics Therefore, afterglow luminance characteristics cannot be obtained as desired.
  • the molar ratio of dysprosium added to the amount of added casket to palladium in the mouth exceeds 20, that is, in the case of DyZEu, the dysprosium ratio increases, the base color becomes white, the excitation efficiency decreases, and light emission occurs.
  • the amount of syrup added to palladium as an activator depends on the amount of metal element represented by M and the amount of pium
  • DyZEu ⁇ 20 and the total force of the added amounts of palladium (Eu) and dysprosium (Dy) in the mouth and the total number of moles of the metal element represented by M and pium (Eu) and dysprosium (Dy) in the mouth By being 1.5% or more and 42% or less in terms of mol%, the phosphorescent light has excellent afterglow brightness characteristics compared to conventional phosphorescent phosphors even after a long time of about 10 to 12 hours after excitation. A phosphor is obtained.
  • the ratio of aluminum (A1) is less than 2.05 in molar ratio with respect to the total number of moles of the metal element represented by M, the pium (Eu) and the shim (Dy), ie,
  • A1Z (M + Eu + Dy) ⁇ 2.05 this is almost equal to or less than the stoichiometric ratio of 2.0, so the afterglow luminance characteristic is the same as that of the conventional phosphorescent fluorescent light. Equal to or lower than the body.
  • the molar ratio exceeds 3.0, that is, 3.0 ⁇ A1Z (M + Eu + Dy)
  • the ratio of by-products increases and the luminance decreases, which is not preferable. .
  • the ratio of aluminum (A1) was set to a molar ratio of 2.05 or more to 3.0 or less with respect to the total number of moles of the metal element represented by M, the europium (Eu), and the dysprosium (Dy).
  • M the total number of moles of the metal element represented by M
  • Eu europium
  • Dy dysprosium
  • the ratio of barium to M in terms of molar ratio, 0.01 ⁇ Ba / (Sr + Ba) ⁇ 0.35, makes the conventional storage possible even after a long time of about 10 to 12 hours after excitation. A luminous phosphor having better afterglow luminance characteristics than the luminous phosphor can be obtained.
  • the amount of dysprosium that contributes to the afterglow luminance characteristics is increased compared to the amount of europium that contributes to the fluorescent luminance characteristics, and optimization is achieved.
  • the ratio of aluminum from the stoichiometric ratio of 2.0 to 2.05 or more, distortion occurs in the crystal structure, and furthermore, part of strontium is replaced by barium.
  • an appropriate strain is generated in the crystal, so that even after a long time of about 10 to 12 hours after excitation, excellent afterglow luminance characteristics can be obtained as compared with the conventional phosphorescent phosphor.
  • the phosphorescent phosphor according to the second invention of the present invention is a compound represented by MAIO,
  • the molar amount of dysprosium (Dy) added to palladium (Eu) is 1 and the molar ratio of DyZEu is less than 20, and the amount of added potassium sulphate of palladium (Eu) and dysprosium (Dy) is relatively small. total is less 42% 1.5% or more by mole 0/0 to the total mole number of the metal elements and Yu port Piumu (Eu) and dysprosium (Dy) expressed by M, the ratio of aluminum (A1) is The molar ratio of the metal element represented by M to the total number of moles of europium (Eu) and dysprosium (Dy) is 2.05 or more. 3. is 0 or less, the ratio of calcium to M is characterized in that a 0. 005 ⁇ Ca / (Sr + Ca) ⁇ 0. 15 in molar ratio.
  • Yu port Piumu as an activating agent (Eu), relative to the total mole number of the metal elements and Yu port Piumu (E u) and dysprosium (Dy) expressed by M, a molar 0/0 0
  • Dysprosium (Dy) as a co-activator in a molar ratio of 1 to Dyzeu (Eu) to DyZEu ⁇ 20 and add Dyzeu ⁇ 20 as a co-activator, and add Dyzeu ⁇ 20 to Dyprosium (Eu) and Dysprosium (Dy). Is added to the total number of moles of the metal element represented by M, the palladium (Eu) and dysprosium (Dy).
  • the amount of added disp-seam which contributes to the afterglow luminance characteristics, is increased compared to the amount of palladium-pium, which contributes to the fluorescent luminance characteristics. Due to the weakness, even after a long time of about 10 to 12 hours after the excitation, the phosphor has excellent afterglow luminance characteristics as compared with the conventional phosphorescent phosphor.
  • the ratio of aluminum (A1) is 2.05 or more in terms of molar ratio to the total number of moles of the metal element represented by M, the pium (Eu), and the dies (Dy).
  • the ratio is set to 0 or less, the ratio of the aluminum is increased from 2.0, which is the stoichiometric ratio, to 2.05 or more, so that the crystal structure is distorted and traps are easily formed. Even after a long period of time, it has better afterglow luminance characteristics than conventional phosphorescent phosphors.
  • the phosphor has more excellent afterglow luminance characteristics than the conventional phosphorescent phosphor.
  • DyZEu ⁇ l the added amount of dysprosium as a coactivator in the molar ratio of the added amount of dysprosium to the palladium of Yuguchi, that is, in the case of DyZEu ⁇ l, Therefore, afterglow luminance characteristics cannot be obtained as desired.
  • the molar ratio of dysprosium added to the amount of added casket to palladium in the mouth exceeds 20, that is, in the case of DyZEu, the dysprosium ratio increases, the base color becomes white, the excitation efficiency decreases, and light emission occurs.
  • luminous dysprosium (DyAlO) or the like is produced as a by-product, the luminance is greatly reduced as a whole.
  • the amount of sulfur added to palladium as an activator is 0.5% or more and 2% or more in terms of mol% based on the total number of moles of the metal element represented by M and the number of mols of palladium (Eu) and dysprosium (Dy).
  • the amount of dysprosium added as a co-activator is as follows: the molar ratio of dysprosium to euphyllium is 1 and DyZEu ⁇ 20, and the amounts of euprosium (Eu) and dysprosium (Dy) added.
  • the total force of the metal element expressed by M and the molar percentage of the total number of moles of palladium (Eu) and dysprosium (Dy) in the mouth are 1.5% or more and 42% or less. Even after a long period of time, a phosphorescent phosphor having excellent afterglow luminance characteristics compared to conventional phosphorescent phosphors can be obtained.
  • the ratio of aluminum (A1) is less than 2.05 in molar ratio with respect to the total number of moles of the metal element represented by M, the pium (Eu), and the shim (Dy).
  • A1Z (M + Eu + Dy) ⁇ 2.05
  • this is almost equal to or less than the stoichiometric ratio of 2.0.
  • the molar ratio exceeds 3.0, that is, when 3.0 ⁇ A1Z (M + Eu + Dy)
  • the proportion of by-products increases and the luminance decreases, which is not preferable. .
  • the ratio of aluminum (A1) was set to a molar ratio of 2.05 or more to 3.0 or less with respect to the total number of moles of the metal element represented by M, the palladium (Eu) and the dysprosium (Dy).
  • M the metal element represented by M
  • Eu palladium
  • Dy dysprosium
  • the ratio of calcium is less than 0.005 in molar ratio to M, that is, CaZ (Sr
  • the amount of dysprosium that contributes to the afterglow luminance characteristics is increased compared to the amount of palladium that contributes to the fluorescent luminance characteristics, and optimization is achieved.
  • the ratio of aluminum from the stoichiometric ratio of 2.0 to 2.05 or more the crystal structure is distorted, and a part of strontium is replaced with calcium.
  • an appropriate strain is generated in the crystal, so that even after a long time of about 10 to 12 hours from the excitation, it is possible to obtain excellent afterglow luminance characteristics compared to the conventional phosphorescent phosphor.
  • the phosphorescent phosphor according to the third invention of the present invention is a compound represented by MAIO,
  • the amount of dysprosium (Dy) added is 1 ⁇ DyZEu ⁇ 20 in terms of molar ratio with respect to palladium (Eu) in the mouth, and pium (Eu) in the mouth and dysprosium (Dy) are used.
  • the ratio of A1 is expressed by the total number of moles of the metal element represented by M and the moles of palladium (Eu) and dysprosium (Dy).
  • the ratio of barium to M is 0.011 ⁇ Ba / (Sr + Ba + Ca) ⁇ 0.3 in molar ratio, and the ratio of calcium to M is The molar ratio is 0.005 ⁇ Ca / (Sr + Ba + Ca) ⁇ 0.1.
  • Yu port Piumu as an activating agent (Eu), relative to the total mole number of the metal elements and Yu port Piumu (E u) and dysprosium (Dy) expressed by M, a molar 0/0 0
  • Dysprosium (Dy) as a co-activator in a molar ratio of 1 to Dyzeu (Eu) to DyZEu ⁇ 20 and add Dyzeu ⁇ 20 as a co-activator, and add Dyzeu ⁇ 20 to Dyprosium (Eu) and Dysprosium (Dy). Is added to the total number of moles of the metal element represented by M, the palladium (Eu) and dysprosium (Dy).
  • the amount of added disp-seam which contributes to the afterglow luminance characteristics, is increased compared to the amount of palladium-pium, which contributes to the fluorescent luminance characteristics. Due to the weakness, even after a long time of about 10 to 12 hours after the excitation, the phosphor has excellent afterglow luminance characteristics as compared with the conventional phosphorescent phosphor.
  • the ratio of aluminum (A1) is 2.05 or more in a molar ratio to the total number of moles of the metal element represented by M, the pium (Eu), and the shim (Dy).
  • the ratio is set to 0 or less, the ratio of the aluminum is increased from 2.0, which is the stoichiometric ratio, to 2.05 or more, so that the crystal structure is distorted and traps are easily formed. Even after a long period of time, it has better afterglow luminance characteristics than conventional phosphorescent phosphors.
  • the molar ratio of barium to M is 0.01 ⁇ Ba / (Sr + Ba + Ca) ⁇ 0.3, and the calcium ratio to M is 0.005 ⁇ Ca / (Sr + (Ba + Ca) ⁇ 0.1, by replacing a part of strontium with barium and calcium, an appropriate strain is generated in the crystal. It has better afterglow luminance characteristics than the luminescent phosphor.
  • DyZEu ⁇ l the added amount of dysprosium as a coactivator in the molar ratio of the added amount of dysprosium to the palladium of Yuguchi, that is, in the case of DyZEu ⁇ l, Therefore, afterglow luminance characteristics cannot be obtained as desired.
  • the molar ratio of dysprosium added to the amount of added casket to palladium in the mouth exceeds 20, that is, in the case of DyZEu, the dysprosium ratio increases, the base color becomes white, the excitation efficiency decreases, and light emission occurs.
  • luminous dysprosium (DyAlO) or the like is produced as a by-product, the luminance is greatly reduced as a whole.
  • the metal element expressed by the total force M of the added amount of the casket added to the palladium and dysprosium of Yu and the metal When the mole 0/0 1. less than 5% mouth Piumu and (Eu) to moles total of dysprosium (Dy), luminance characteristics for the amount of the activator and co-activator is too small is reduced and also 42% When it exceeds, the amount of strontium is relatively reduced, and the afterglow luminance characteristic is deteriorated.
  • the amount of sulfur added to palladium as an activator is 0.5% or more and 2% or more in terms of mol% based on the total number of moles of the metal element represented by M and the number of mols of palladium (Eu) and dysprosium (Dy).
  • the amount of dysprosium added as a co-activator is as follows: the molar ratio of dysprosium to euphyllium is 1 and DyZEu ⁇ 20, and the amounts of euprosium (Eu) and dysprosium (Dy) added.
  • the total force of the metal element expressed by M and the molar percentage of the total number of moles of palladium (Eu) and dysprosium (Dy) in the mouth are 1.5% or more and 42% or less. Even after a long period of time, a phosphorescent phosphor having excellent afterglow luminance characteristics compared to conventional phosphorescent phosphors can be obtained.
  • the ratio of aluminum (A1) is less than 2.05 in molar ratio with respect to the total number of moles of the metal element represented by M, the pium (Eu) and the shim (Dy).
  • A1Z (M + Eu + Dy) ⁇ 2.05
  • this is almost equal to or less than the stoichiometric ratio of 2.0, so the afterglow luminance characteristic is the same as that of the conventional phosphorescent fluorescent light.
  • the molar ratio exceeds 3.0, that is, 3.0 ⁇ A1Z (M + Eu + Dy)
  • the ratio of by-products increases and the luminance decreases, which is not preferable. .
  • the ratio of aluminum (A1) was set to a molar ratio of 2.05 or more to 3.0 or less with respect to the total number of moles of the metal element represented by M, the europium (Eu), and the dysprosium (Dy).
  • M the total number of moles of the metal element represented by M
  • Eu europium
  • Dy dysprosium
  • the ratio of barium is less than 0.01 in terms of a molar ratio to M, that is, BaZ (Sr + Ba + Ca) ⁇ 0.01, the ratio of norium is too small, so There is no effect due to little distortion.
  • the molar ratio to M exceeds 0.3, that is, when 0.3 ⁇ BaZ (Sr + Ba + Ca), the ratio of strontium is relatively reduced, and the overall luminance is reduced. It is not preferable because.
  • the molar ratio of calcium to M is less than 0.005, that is, when CaZ (Sr + Ba + Ca) ⁇ 0.005, the calcium ratio is too small, so Slight distortion is hard to occur and has no effect.
  • the molar ratio to M exceeds 0.1, that is, when it is 0.1 and CaZ (Sr + Ba + Ca) is used, calcium aluminate (CaAl 2 O 3) etc.
  • the ratio force of barium to M is 0.011 ⁇ Ba / (Sr + Ba + Ca) ⁇ 0.3 in molar ratio, and the ratio of calcium to M is 0.005 ⁇ Ca / Since (Sr + Ba + Ca) ⁇ 0.1, even after a long time of about 10-12 hours after excitation, the phosphorescent light has better afterglow luminance characteristics than the conventional phosphorescent phosphor. A luminescent phosphor is obtained.
  • the amount of dysprosium that contributes to the afterglow luminance characteristics is increased as compared with the amount of europium that contributes to the fluorescent luminance characteristics, and optimization is achieved.
  • the ratio of aluminum from 2.0, which is the stoichiometric ratio, to 2.05 or more, the crystal structure is distorted, and furthermore, a part of strontium is replaced by barium and calcium. Since an appropriate strain is generated in the crystal, even after a long time of about 10 to 12 hours after the excitation, excellent afterglow luminance characteristics can be obtained as compared with the conventional phosphorescent phosphor.
  • the method for producing the alkaline earth metal aluminate phosphorescent phosphor according to the fourth aspect of the present invention comprises an aluminum (A1) compound, a strontium (Sr) compound, a barium compound (Ba), It is characterized in that a pium (Eu) compound and a dysprosium (Dy) compound are mixed so that each element has the following molar ratio, fired in a reducing atmosphere, and then cooled and pulverized.
  • an alkaline earth metal aluminate phosphorescent phosphor having excellent afterglow luminance characteristics as compared with the conventional phosphorescent phosphor can be manufactured.
  • the method for producing an alkaline earth metal aluminate phosphorescent phosphor according to the fifth invention of the present invention is a method for producing an aluminum (A1) compound, a strontium (Sr) compound, a calcium compound (Ca), It is characterized in that an orifice (Eu) compound and a dysprosium (Dy) compound are mixed so that each element has the following molar ratio, fired in a reducing atmosphere, and then cooled and pulverized.
  • the phosphorescent phosphor is superior to the conventional phosphorescent phosphor.
  • An alkaline earth metal aluminate phosphorescent phosphor having afterglow luminance characteristics can be manufactured.
  • the method for producing an alkaline earth metal aluminate phosphorescent phosphor comprises: an aluminum (A1) compound, a strontium (Sr) compound, and a barium (Ba) compound.
  • a calcium compound (Ca), a palladium (Eu) compound, and a dysprosium (Dy) compound were mixed at the following molar ratios, calcined in a reducing atmosphere, and then cooled and pulverized. It is characterized by:
  • the phosphorescent phosphor is superior to the conventional phosphorescent phosphor.
  • An alkaline earth metal aluminate phosphorescent phosphor having afterglow luminance characteristics can be manufactured.
  • the method for producing an alkaline earth metal aluminate luminous phosphor according to the seventh invention of the present invention includes the alkaline earth metal aluminate luminous phosphor according to the fourth, fifth, or sixth invention.
  • the method for producing a phosphor is characterized in that a boron compound is added as a flux to the raw material and the mixture is fired. Then, by adding a boron compound as a flux to the raw material and firing the mixture, an alkaline earth metal element aluminate phosphorescent phosphor excellent at a low firing temperature can be manufactured.
  • a boron compound for example, boric acid (HBO) is preferable.
  • the amount of the boron compound to be added is preferably about 0.01 to 10%, more preferably about 0.5 to 3%, based on the total mass of the raw materials.
  • the amount of the boron compound to be added exceeds 10% of the total mass of the raw material, the fired product is hard and sintered, so that pulverization becomes difficult, and the reduction in luminance due to the pulverization decreases. Get offended. Therefore, the amount of the boron compound to be added is preferably 0.01% to 10% based on the total mass of the raw materials.
  • the alkaline earth metal aluminate phosphorescent phosphor according to the fourth, fifth, or sixth invention is provided. According to the manufacturing method, an alkaline earth metal element aluminate phosphorescent phosphor which is excellent even at a low firing temperature can be manufactured.
  • FIG. 1 is a view showing a particle size distribution of sample 1 (3).
  • FIG. 2 is an X-ray powder diffraction pattern of Sample 2- (9).
  • FIG. 3 is an X-ray powder diffraction pattern of Sample 3- (6). BEST MODE FOR CARRYING OUT THE INVENTION
  • strontium (Sr), barium (Ba) and barium (Ca) as raw materials of metal elements represented by M, such as strontium carbonate (SrCO) and barium carbonate (Ba).
  • Dysprosium oxide (Dy 2 O 3) is added as a raw material. At this time, the added calorie of pium (Eu)
  • the amount is 2% 0.5% by molar 0/0 to moles total of metal elements and Yu port Piumu dysprosium expressed by M, ⁇ Ka ⁇ of dysprosium (Dy) are, Yu port Piumu (Eu) in a molar ratio of more than 1 to 20 or less, and the total amount of palladium (Eu) and dysprosium (Dy) added to the metal element represented by M, palladium (Eu) and dysprosium (Eu) mole 0/0 1. 5% or less than 42% relative to the total number of moles of dy).
  • a raw material of aluminum (A1) for example, alumina (Al 2 O 3) is converted to strontium, norium, calcium,
  • the molar ratio of aluminum to the sum of the number of moles of palladium and dysprosium is 2.05 or more and 2.7 or less.
  • boric acid HBO
  • HBO boric acid
  • the mixture is calcined in a reducing atmosphere, for example, a mixed gas stream of nitrogen and hydrogen at a calcining temperature of about 1300 ° C to 1500 ° C for about 1 hour to 6 hours, and then to room temperature for about 1 hour to 6 hours. Cool over time.
  • the obtained fired product is pulverized and sieved to obtain a phosphorescent phosphor having a predetermined particle size.
  • the added amount of palladium (Eu) as an activator to be added refers to the amount of each of the metal element M, the activator palladium (Eu) and the co-activator dysprosium (Dy). It is expressed in mol% based on the total number of moles of the element.
  • the metal element represented by M is strontium and norium
  • the molar ratio of barium to the total number of moles of strontium and barium is 0.1
  • Yu port Piumu 1 mole 0/0 added, to 2 mol 0/0 ⁇ Ka ⁇ dysprosium is strontium element is 0.873 mol
  • the compound of each element is blended so that the dysprosium element becomes 0.02 mol. This makes it possible to determine the amount of pium Stood 1% mole 0/0, the molar ratio of barium to the total mole number of strontium and barium will be 0.1.
  • the firing temperature using the boron compound as the flux is sufficiently higher than the temperature required for the reaction, for example, about 1450 ° C.
  • the obtained fired product is weakly agglomerated, and crushing is facilitated, so that a decrease in luminance due to crushing can be reduced.
  • the metal element represented by M in the present invention is substantially a strontium and barium, a strontium and calcium, or a strontium, barium and calcium and a trace amount of another element in addition to these elements as long as they are also composed of power. Is included in the scope of the present invention.
  • strontium carbonate (SrCO) 128.88 g (0.873) was used as a raw material for strontium (Sr).
  • DyO dysprosium oxide
  • This mixture is calcined in a reducing atmosphere in a gas stream of 97% nitrogen-3% hydrogen at a calcining temperature of 1350 ° C for 4 hours, and then cooled to room temperature in about 1 hour.
  • the obtained fired product was pulverized, sieved and passed through a # 250 mesh to obtain a phosphorescent phosphor sample 11 (3).
  • strontium was 0.783 mol
  • barium was 0.097 mol
  • the molar ratio of strontium to 0.97 mol of the total number of mols of strontium and barium was 0.9. The molar ratio is 0.1.
  • Patent Document 1 Sample 2- (1), the metal elements expressed by M and only strike strontium, 1 mol ⁇ Yu port Piumu 0/0 the dysprosium ⁇ 1 molar 0/0, Arumi - ⁇ beam molar ratio AlZ a (Sr + Eu + Dy), the stoichiometric ratio 2.0, other manufacturing conditions, process the sample 1
  • a sample identical to that of (3) was prepared in the same manner as Comparative Example 1.
  • the particle size distribution of Sample 11 (3) was measured by a laser diffraction type particle size distribution analyzer (SALD-2100, Shimadzu Corporation). This is shown in Figure 1.
  • the metal elements represented by M are strontium and barium, and aluminum Ratio is 2.3 and the molar ratio of dysprosium to europium is fixed at 2, the amount of europium added is 0.5 mol% or more and 2 mol% or less. It can be seen that excellent afterglow luminance characteristics are obtained.
  • Samples 11 (7) to 11 (16) are the same as Samples 11 (1) to 11 (6). It was excited under the same illuminance conditions (D65 standard light source Z4001xZ20 minutes) and the afterglow luminance characteristics were examined. The results are shown in Table 4 together with Comparative Example 1 and Sample 1- (3) as relative luminance when the afterglow luminance of Comparative Example 1 is 1.
  • the afterglow luminance is about 6.5 times or more as compared with the comparative example.
  • sample 1- (16) that is, when the molar ratio of dysprosium is 30 (that is, in this case, 30 mol% in the added amount of dysprosium), for example, by-products such as dysprosium aluminate (DvAlO)
  • DvAlO dysprosium aluminate
  • dysprosium-added kafun is not preferable in terms of economy because dysprosium itself is expensive, and if the added amount of dysprosium is too large, the brightness may be reduced due to concentration quenching.
  • the metal elements represented by M are strontium and barium
  • the ratio of aluminum is 2.3
  • the amount of pium added to the mouth is 1 mol%
  • dysprosium with respect to the mouth of pium is considered. It can be seen that a phosphorescent phosphor having excellent afterglow luminance characteristics as compared with the conventional example can be obtained in a molar ratio of more than 1 and not more than 20. It was also confirmed that the same results were obtained when the amount of pulping pulp of Yuguchi pium was 0.5% and 2%.
  • M is strontium (Sr) and barium (Ba)
  • DyO dysprosium oxide
  • Dy 2.1) and boric acid (HBO) as a boron (B) compound as a flux.
  • the molar ratio of aluminum that is, AlZ (Sr + Ba + Eu + Dy) was set to 2.0 as shown in Table 5 and to 2 .
  • 05 Ryara Phosphorescent phosphors varied in the range of 3.1 were prepared, and Sample 2— (1) to Sample 2— (3), Sample 2— (4) or Sample 2— (10) As obtained.
  • sample 2- (9) (the molar ratio of aluminum was 3.0), powder X-ray diffraction analysis was performed using a Cu bulb to obtain a diffraction pattern. This is shown in FIG.
  • Samples 2- (1) to 2- (10) were excited under the same illuminance conditions (D65 standard light source Z4001xZ20 minutes) as Sample 11 (1) of Experimental Example 1, and the afterglow luminance characteristics Investigated.
  • the results were compared with Sample 11 (3), which was the same conditions except that the molar ratio of aluminum was 2.3. Both are shown in Table 6 as relative luminance when the afterglow luminance of Comparative Example 1 was set to 1.
  • M is strontium (Sr) and barium
  • strontium carbonate (SrCO 2) (0.996) was used as a raw material of strontium (Sr).
  • Dy dysprosium oxide
  • This mixture is calcined in a reducing atmosphere in a gas stream of 97% nitrogen-3% hydrogen at a calcining temperature of 1350 ° C for 4 hours, and then cooled to room temperature in about 1 hour.
  • the obtained fired product was pulverized, sieved, and passed through # 250 mesh to obtain a phosphorescent phosphor sample 3- (2).
  • This sample 3- (2) has 0.9603 mol of strontium and 0.0097 mol of norium, and the molar ratio of strontium to 0.97 mol of the total number of mols of strontium and barium is 0.99.
  • the molar ratio of lithium is 0.01.
  • DyO dysprosium oxide
  • This mixture is calcined in a reducing atmosphere in a gas stream of 97% nitrogen-3% hydrogen at a calcining temperature of 1350 ° C for 4 hours, and then cooled to room temperature in about 1 hour.
  • the obtained fired product was pulverized, sieved, and passed through a # 250 mesh to obtain a phosphorescent phosphor sample 4 (3).
  • This sample 4 (3) had 0.9603 mol of strontium and 0.0097 mol of calcium, and the molar ratio of strontium to 0.97 mol of the total number of mols of strontium and calcium was 0.99, and the molar ratio of calcium was 0.999 mol It will be 0.01.
  • the amount of added syrup of eutronic pium is 1 mol% and the amount of added dysprosium is 2 mol% based on the total of strontium, calcium, euproium and dysprosium.
  • the ratio, DyZEu is 2.
  • the molar ratio of aluminum, that is, AlZ (Sr + Ca + Eu + Dy) is determined to be 2.3, which exceeds the stoichiometric ratio of 2.0.
  • Sample 4 (1) (having a calcium ratio of 0.002) had an afterglow luminance characteristic less than three times that of Comparative Example 1 after 10 hours, and Sample 4 (7) (having a calcium ratio of 10%).
  • the ratio of strontium may be relatively reduced, and the afterglow brightness is sharply reduced.
  • the metal element represented by M is strontium and calcium
  • the ratio of calcium to M that is, CaZ (Sr + Ca) is 0.005 or more and 0.15 or less
  • excellent afterglow luminance characteristics are obtained. It can be seen that the phosphor has a phosphorescent property.
  • strontium carbonate (SrCO 2) 127.45 g (0.863) was used as a raw material for strontium (Sr).
  • barium carbonate (BaCO 3) as a raw material for barium (Ba)
  • DyO dysprosium oxide
  • the added amount of caloric power of palladium based on the total amount of strontium, normium, calcium, palladium and dysprosium is Si mol%, and the added amount of dysprosium added with dysprosium is 2 mol%.
  • Ie, Dy / Eu is 2.
  • the molar ratio of aluminum, that is, AlZ (Sr + Ba + Ca + Eu + Dy) is 2.3, which exceeds the stoichiometric ratio of 2.0.
  • the metal element represented by M is strontium, norium and calcium
  • the ratio of barium to M that is, BaZ (Sr + Ba + Ca) is 0.01 or more.
  • the ratio of calcium to M that is, CaZ (Sr + Ba + Ca) is 0.01 or more and 0.1 or less, it is understood that the phosphorescent phosphor has excellent afterglow luminance characteristics.
  • the invention can be used, for example, for luminous watches.

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

Abstract

Cette invention se rapporte à un phosphore d'émission de phosphorescence qui, à l'expiration d'une période prolongée après l'excitation, possède une propriété de luminescence résiduelle supérieure à celle des phosphores d'émission de phosphorescence à base d'aluminate de strontium du même type, ce phosphore d'émission de phosphorescence satisfaisant aux relations de proportion suivantes : 0,005 ≤ Eu/(Sr+Ba+Eu+Dy) ≤ 0,02 ; 1 < Dy/Eu ≤ 20 ; 0,015 ≤ (Eu+Dy)/(Sr+Ba+Eu+Dy) ≤ 0,42 ; 0,01 ≤ Ba/(Sr+Ba) ≤ 0,35 ; et 2,05 ≤ Al/(Sr+Ba+Eu+Dy) ≤ 3,0.
PCT/JP2004/016401 2003-11-06 2004-11-05 Phosphore d'emission de phosphorescence et procede de production de ce phosphore WO2005044946A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007033576A1 (fr) * 2005-09-23 2007-03-29 Dalian Luminglight Science And Technology Co., Ltd. Matériau luminescent à longue rémanence et son procédé de préparation
US8404153B2 (en) 2010-12-17 2013-03-26 General Electric Company White persistent phosphor blend or layered structure
US8506843B2 (en) 2010-12-17 2013-08-13 General Electric Company White emitting persistent phosphor

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1190520A (en) * 1967-11-22 1970-05-06 Philips Electronic Associated Luminescent Materials
JPH0711250A (ja) * 1993-04-28 1995-01-13 Nemoto Tokushu Kagaku Kk 蓄光性蛍光体
JPH08127772A (ja) * 1994-11-01 1996-05-21 Nemoto Tokushu Kagaku Kk 蓄光性蛍光体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1190520A (en) * 1967-11-22 1970-05-06 Philips Electronic Associated Luminescent Materials
JPH0711250A (ja) * 1993-04-28 1995-01-13 Nemoto Tokushu Kagaku Kk 蓄光性蛍光体
JPH08127772A (ja) * 1994-11-01 1996-05-21 Nemoto Tokushu Kagaku Kk 蓄光性蛍光体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007033576A1 (fr) * 2005-09-23 2007-03-29 Dalian Luminglight Science And Technology Co., Ltd. Matériau luminescent à longue rémanence et son procédé de préparation
US7686979B2 (en) 2005-09-23 2010-03-30 Dalian Luminglight Science And Technology Co., Ltd. Long afterglow luminescent material and its manufacturing method
US8404153B2 (en) 2010-12-17 2013-03-26 General Electric Company White persistent phosphor blend or layered structure
US8506843B2 (en) 2010-12-17 2013-08-13 General Electric Company White emitting persistent phosphor

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