WO2005103197A1 - Substance de stockage de lumière aluminate de strontium et son procédé de production - Google Patents

Substance de stockage de lumière aluminate de strontium et son procédé de production Download PDF

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Publication number
WO2005103197A1
WO2005103197A1 PCT/JP2005/007461 JP2005007461W WO2005103197A1 WO 2005103197 A1 WO2005103197 A1 WO 2005103197A1 JP 2005007461 W JP2005007461 W JP 2005007461W WO 2005103197 A1 WO2005103197 A1 WO 2005103197A1
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WIPO (PCT)
Prior art keywords
strontium
phosphorescent material
strontium aluminate
nitride
aluminum
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Application number
PCT/JP2005/007461
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English (en)
Japanese (ja)
Inventor
Hiromitsu Miyazaki
Norihiko Sanefuji
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Ishihara Sangyo Kaisha, Ltd
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Application filed by Ishihara Sangyo Kaisha, Ltd filed Critical Ishihara Sangyo Kaisha, Ltd
Publication of WO2005103197A1 publication Critical patent/WO2005103197A1/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
    • C09K11/77926—Aluminium Nitrides or Aluminium Oxynitrides

Definitions

  • the present invention relates to a strontium aluminate phosphorescent material having excellent afterglow characteristics and a method for producing the same.
  • phosphors those having a long afterglow time are known as luminous bodies, and are widely used in fields such as daily necessities, low-lighting night signboards, and clocks.
  • strontium aluminate (SrAl 2 O 3) activated with europium is a typical phosphorescent phosphor,
  • Patent Document 1 JP-A-7-11250 (pages 2-7)
  • the present inventors have conducted various studies to find a strontium aluminate-based phosphorescent material having even more excellent afterglow characteristics. It has been found that the phosphorescent material containing nitrogen has a structure in which the crystal lattice is smaller than that of ordinary stonium aluminate. In addition, it has been found that, in order to contain nitrogen in the composition, a method in which a metal nitride is contained in a mixture and heating and sintering is effective in addition to the solid phase synthesis method described above.
  • the present invention relates to a strontium aluminate phosphorescent material containing europium as an activator and dysprosium and Z or neodymium as a coactivator, wherein the composition contains at least 0.050 wt% of nitrogen.
  • This is a strontium aluminate phosphorescent material characterized by the following.
  • the host crystal is SrAl O
  • the strontium aluminate phosphorescent material of the present invention is excellent in phosphorescent properties (afterglow luminance, long afterglow time).
  • the production method of the present invention is characterized by using a metal nitride as a part of the raw material in the ordinary solid-phase synthesis method, and does not require a special apparatus. It is. Further, a phosphorescent material having sufficient afterglow characteristics can be obtained without using a flux, and a phosphorescent material having a small particle diameter can be obtained. This is a manufacturing method that can be used.
  • the present invention relates to europium as an activator, dysprosium as a co-activator and
  • nitrogen in the composition By including nitrogen in the composition, the luminous properties are significantly improved.
  • a more preferred content of nitrogen is at least 0.080 wt%.
  • the composition of strontium aluminate to be the host crystal includes SrAl O, Sr Al O, SrAl O, SrAl O and the like.
  • the (-211) plane spacing of SrAl O having a toughed tridymite structure is 0.3144 nm.
  • the (-211) plane spacing is in the range of 0.3120 to 0.3140 nm. It has a structure in which the crystal lattice shrinks, which is considered to have further improved the luminous storage characteristics of strontium aluminate.
  • the amount of europium contained as an activator and the amount of dysprosium and Z or neodymium contained as a coactivator are each preferably 0.002 to 20 mol% based on strontium. If the amount of the activator and co-activator is less than the above range, it is difficult to impart long afterglow, and if the amount is more than the above range, further improvement of long afterglow may be expected. No, it is rather difficult to maintain the crystal structure.
  • the present invention is a method for producing the above-mentioned strontium aluminate phosphorescent material, preferably a powder, comprising mixing a strontium compound, an aluminum compound, a europium compound, and a raw material containing a dysprosium compound and a Z or neodymium compound.
  • the metal nitride examples include metal nitrides such as strontium, aluminum, europium, dysprosium, neodymium, and gallium.
  • metal nitrides such as strontium, aluminum, europium, dysprosium, neodymium, and gallium.
  • it is a nitride of at least one metal selected from strontium, aluminum, europium, dysprosium, and neodymium. More preferably, it is nitrided.
  • Aluminum oxide is usually, the strontium aluminate-based phosphorescent powder is prepared by mixing strontium carbonate, aluminum oxide, sodium oxide europium, powders of sodium oxide disposable and Z or neodymium oxide, and a flux in a dry manner, followed by heating. Obtained by firing.
  • the strontium compound, aluminum compound, europium compound and at least one compound of a dysprosium compound and a z or neodymium compound used as a raw material are used.
  • strontium aluminate obtained by heating and firing is included, the crystal lattice is reduced, and the luminous characteristics are further improved.
  • Strontium compounds that can be used as raw materials other than nitrides include strontium carbonate, strontium hydroxide, strontium chloride, strontium sulfate, strontium nitrate, strontium acetate, strontium oxalate, strontium citrate, strontium citrate, strontium oxide, Examples include strontium aluminate and strontium alkoxide, and it is preferable to use chemically stable strontium carbonate which has no deliquescence.
  • Aluminum compounds include aluminum oxide, aluminum hydroxide, aluminum hydroxide, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum oxalate, aluminum citrate, aluminum Examples thereof include strontium acid and aluminum alkoxide, and it is preferable to use chemically stable aluminum oxide which also has deliquescence.
  • europium compound include europium oxide, europium chloride, europium oxalate, europium sulfide, europium sulfate, europium nitrate, europium alkoxide, and the like.
  • dysprosium compound examples include dysprosium oxide, chlorprosium, oxalic acid dysprosium, sulfuric acid dysprosium, sulphate sprosm, sulphate disperse, nitric acid sprosium and dysprosium alkoxide.
  • neodymium compound examples include neodymium oxidized, neodymium eddy, neodymium oxalate, neodymium sulfide, neodymium sulfate, and neodymium nitrate.
  • each of the above-mentioned raw materials contains at least one metal nitride.
  • metal nitride for example, as an aluminum compound, aluminum oxide is used as a main component, and aluminum nitride is partially mixed and used.
  • the amount of the nitride used is preferably 0.05 to 10% by weight of nitrogen contained in the nitride based on the total amount of the raw materials.
  • the amount of nitride is less than the above range, it is difficult to further improve the luminous ability of the generated strontium aluminate. It is hard to hope for an improvement in sex.
  • the mixture is heated and fired in a non-oxidizing atmosphere to obtain a strontium aluminate-based phosphorescent powder activated by single-ported pium.
  • the atmosphere of the heating and firing is non-oxidizing, and examples thereof include an inert atmosphere such as nitrogen, argon, neon, and krypton, and a reducing atmosphere in which hydrogen, ammonia, and the like are mixed.
  • an inert atmosphere or a reducing atmosphere of 0: 1 to L: 0 in terms of hydrogen: nitrogen (molar ratio) is preferred, and more preferably 0.001: 0.9999 to 0.5: 0.5.
  • the caloric heat firing temperature may be 600 ° C to 1700 ° C, preferably 900 ° C to 1600 ° C. C, more preferably a temperature of 1100 ° C to 1500 ° C.
  • the production method of the present invention when a material containing a boron compound as a flux is further used as the raw material, particle growth is promoted during heating and firing, and the luminous characteristics of the resulting strontium aluminate are further improved.
  • the boron compound that can be used include boric acid and boron oxide.
  • the amount of the boron compound used as a flux is preferably at most 20% by weight, more preferably less than 10% by weight, based on the total amount of the raw materials. If the amount of the flux added is large, sintering proceeds to form aggregated particles, so that it is necessary to increase the load of pulverization, and the afterglow luminance is reduced by pulverization. It is desirable that the amount of the flux added is small.
  • the strontium aluminate phosphorescent material of the present invention obtained by heating and firing is used Depending on the purpose, the particle size can be adjusted by appropriately performing a pulverizing treatment by a known method.
  • general pulverization methods such as pin mill pulverization, ball mill pulverization, jet mill pulverization, and bantam mill pulverization can be employed.
  • a phosphorescent material is obtained by heating and firing a mixture of raw material powders without using a flux, particle growth during heating and firing is suppressed. Is also possible.
  • the fired product was pulverized in a mortar for 5 minutes to obtain a phosphorescent material (sample A) of the present invention.
  • Example B a phosphorescent material of the present invention.
  • Example 4 Except that the ratio was 96: 8, all treatments were performed in the same manner as in Example 1 to obtain the phosphorescent material of the present invention (Sample C).
  • Example 4 Except that the ratio was 96: 8, all treatments were performed in the same manner as in Example 1 to obtain the phosphorescent material of the present invention (Sample C).
  • Example D a phosphorescent material of the present invention.
  • Example E a phosphorescent material of the present invention.
  • Example F a phosphorescent material of the present invention
  • Example G a phosphorescent material of the present invention.
  • Example 1 was repeated except that 4.08 g of aluminum oxide and 0.0328 g of aluminum nitride were used instead of 4.04 g of aluminum oxide.
  • a material (sample I) was obtained.
  • the apparatus used was an inert gas carrier melting thermal conductivity measuring apparatus (Leco TC-436AR: manufactured by Leco).
  • the samples A to I obtained in Examples 1 to 8 and Comparative Example 1 were subjected to powder X-ray diffraction analysis using an X-ray diffraction analyzer (RI NT1000: manufactured by Rigaku Corporation). Although the sample also has a stuffed 'tridymite structure, the spacing between the (—211) planes was in the range of 0.3120 nm to 0.3140 nm in the samples A to H of the present invention. In Comparative Sample I, it was 0.3144 nm. Table 1 summarizes the measurement results.
  • the sample was irradiated with light for 3 minutes at an illuminance of 200 lux, then the light irradiation was stopped, and the luminance 10 minutes later was measured using a photosensor.
  • the afterglow luminance of Comparative Sample I was 100
  • the afterglow luminance of Samples A to H of the present invention was 280 or more. Table 1 summarizes the measurement results.
  • the europium of the present invention when co-activated with a disposable system, the europium of the present invention is used.
  • the strontium aluminate activated by the above has a stuffed 'tridymite structure in which the lattice is shrunk, and the amount of residual nitrogen increases with the increase in the amount of nitride used. And increased brightness and long afterglow.
  • Al nitride 0.0984 g
  • Al nitride 0.0984 g
  • the amount of nitride (aluminum nitride) is 0.34% by weight of the total amount of nitrogen in the nitride, and the ratio of aluminum oxide to aluminum nitride is expressed as a molar ratio.
  • Al O: A1N 97: 6. Then the resulting mixture
  • the fired product was pulverized in a mortar for 5 minutes to obtain a phosphorescent material of the present invention (Sample J).
  • Example 9 In treatment line 9, the same treatment as in Example 9 was carried out except that 3.08 g of Soni-Dai Anorinium and 0.00884 g of Sani-Dani Anorinium were replaced by 4.08 g of Sani-Dani Aluminum. Thus, a phosphorescent material (sample K) of a comparative sample was obtained.
  • Example 9 With respect to the samples J and K obtained in Example 9 and Comparative Example 2, the measurement of the spacing between the (211) planes and the measurement of the afterglow luminance were performed by the methods described above. The measurement results are summarized in Table 2. The afterglow luminance is expressed as a relative intensity with the value of sample K being 100.
  • the strontium aluminate activated with europium of the present invention has a stuffed 'tridymite structure in which the lattice is shrunk, and due to this, the luminous properties are reduced. It has been shown that it has improved and has high luminance and long afterglow.
  • Dy O dysprosium oxide
  • aluminum oxide a-Al ⁇
  • the compounding amount of nitride is an amount containing 0.22% by weight of nitrogen in the nitride based on the total amount of the raw materials, and the compounding ratio of aluminum oxide and aluminum nitride is expressed as a molar ratio of Al 2 O 3.
  • N 98: 4.
  • Boric acid has a molar ratio of 0.08 to strontium carbonate.
  • the fired product was ground in a mortar for 5 minutes to obtain a phosphorescent material of the present invention (Sample L).
  • Example 1 use 4.00 g of Sani-Dani Anorinium and 0.0656 g of Honey-Dan Ano-Remini.
  • a phosphorescent material (sample N) as a comparative sample was obtained in the same manner as in Example 10, except for using 4.08 g of aluminum oxide.
  • the mixing ratio of the raw material powder was determined in Example 1.
  • the distance between planes and the afterglow luminance were measured.
  • Table 3 shows the measurement results.
  • the afterglow luminance is expressed as a relative intensity with the value of sample N being 100.
  • the strontium aluminate activated with europium of the present invention has a stuffed 'tridymite structure with a reduced lattice even when boric acid is added as a flux and when co-activated with dysprosium. As a result, it has been found that the light storage characteristics are improved, and high luminance and long afterglow are exhibited.
  • the specific surface area was measured using a specific surface area measuring device (MS-18: manufactured by Quantum Chrome Co., Ltd.), and a scanning electron microscope (S 3200N : Manufactured by Hitachi, Ltd.).
  • MS-18 manufactured by Quantum Chrome Co., Ltd.
  • S 3200N Manufactured by Hitachi, Ltd.
  • the specific surface area was about 1.0 m 2 Zg in both Examples and Comparative Examples, whereas it was about 0.3 m 2 Zg when using a flux.
  • the samples prepared without using the flux had narrow particle size distributions, and all had an average particle diameter of about 1.0 m.
  • a flux when a flux is used, large particles of about 10 m are mainly used for industrial applications.
  • the strontium aluminate phosphorescent powder of the present invention has much higher luminance and long persistence, and thus has been widely used in the fields of conventional household goods, weakly illuminated night signboards, and clocks. Can be used. Furthermore, when a flux is not added, fine particles with a uniform particle size can be obtained, so that it is expected to obtain a coating film which is easy to apply and has excellent smoothness.
  • FIG. 1 is a scanning electron micrograph (3000 times magnification) showing the particle shape of sample M.
  • FIG. 2 is a scanning electron micrograph ( ⁇ 3000) showing the particle shape of sample N.

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

Abstract

En ce qui concerne les substances de stockage de lumière aluminate de strontium, il existe une demande d’amélioration de l’incandescence résiduelle, de sa manipulation, etc. afin de développer et d’étendre ses applications. En particulier, il existe une demande d’amélioration de la luminosité d’incandescence résiduelle et de la durée d’incandescence résiduelle, de pulvérisabilité facile, etc. On fournit une substance de stockage de lumière aluminate de strontium, qui comprend de l’europium comme activateur et du dysprosium et/ou du néodymium comme co-activateur, et caractérisé par la présence de nitrogène en quantité au moins égale à 0.050 wt.%, en se basant sur la composition de la substance. En outre, on fournit une substance de stockage de lumière aluminate de strontium caractérisée par son cristal à matrice qui a une structure tridymite remplie représentée par la formule SrAl2O4 dont l’espacement de plan (-211) est compris entre 0.3120 et 0.3140 nm.
PCT/JP2005/007461 2004-04-20 2005-04-19 Substance de stockage de lumière aluminate de strontium et son procédé de production WO2005103197A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2093273A1 (fr) * 2006-11-20 2009-08-26 Sichuan Sunfor Light Co., Ltd. Phosphores d'accumulation de lumière à longue émission rémanente coactivés à multiples éléments résistants à l'eau
WO2011078941A1 (fr) * 2009-12-21 2011-06-30 Sabic Innovative Plastics Ip B.V. Phosphores persistants à base de pyrosilicate d'oxynitrure

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0711250A (ja) * 1993-04-28 1995-01-13 Nemoto Tokushu Kagaku Kk 蓄光性蛍光体
JP2002249768A (ja) * 2000-12-22 2002-09-06 Toshiba Corp アルミン酸塩蛍光体，その製造方法および発光デバイス

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0711250A (ja) * 1993-04-28 1995-01-13 Nemoto Tokushu Kagaku Kk 蓄光性蛍光体
JP2002249768A (ja) * 2000-12-22 2002-09-06 Toshiba Corp アルミン酸塩蛍光体，その製造方法および発光デバイス

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2093273A1 (fr) * 2006-11-20 2009-08-26 Sichuan Sunfor Light Co., Ltd. Phosphores d'accumulation de lumière à longue émission rémanente coactivés à multiples éléments résistants à l'eau
EP2093273A4 (fr) * 2006-11-20 2009-12-16 Sichuan Sunfor Light Co Ltd Phosphores d'accumulation de lumière à longue émission rémanente coactivés à multiples éléments résistants à l'eau
WO2011078941A1 (fr) * 2009-12-21 2011-06-30 Sabic Innovative Plastics Ip B.V. Phosphores persistants à base de pyrosilicate d'oxynitrure
US8178002B2 (en) 2009-12-21 2012-05-15 Sabic Innovative Plastics Ip B.V. Oxy-nitride pyrosilicate based persistent phosphors

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