WO1998006793A1 - Process for the preparaiton of aluminate-base phosphor - Google Patents
Process for the preparaiton of aluminate-base phosphor Download PDFInfo
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- WO1998006793A1 WO1998006793A1 PCT/JP1997/002739 JP9702739W WO9806793A1 WO 1998006793 A1 WO1998006793 A1 WO 1998006793A1 JP 9702739 W JP9702739 W JP 9702739W WO 9806793 A1 WO9806793 A1 WO 9806793A1
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- aluminate
- phosphor
- based phosphor
- alumina
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
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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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
Definitions
- the present invention relates to, for example, an aluminate-based phosphor used for a three-wavelength fluorescent lamp that emits blue, blue-green, or green light when excited by ultraviolet light, or a long-time excited by ultraviolet light or visible light.
- the present invention relates to a method for producing an aluminate-based phosphor having an afterglow characteristic, which is used as a phosphorescent material having an afterglow property.
- fluorescent lamps Since the production of fluorescent lamps began in 1938, improvements have been made in characteristics such as luminous brightness, luminous efficiency, color rendering, and lifespan. In recent years, fluorescent lamps that are close to natural light with improved color rendering properties, so-called “three-wavelength fluorescent lamps,” have been developed by concentrating fluorescence strongly around the wavelengths of 450 nm (blue), 540 nn (green), and 610 nm (red). Widely used.
- the three-wavelength fluorescent lamp includes, for example, a barium-magnesium-aluminum phosphor as a blue phosphor, a cerium-magnesium-aluminum phosphor as a green phosphor, and a yttrium oxide phosphor as a red phosphor.
- the body has been used.
- aluminate phosphors of blue or green phosphors magnesium (Mg), barium (Ba), and strontium (Sr) constituting an aluminate are added to an alumina powder.
- Calcium (C a), zinc (Z n) or cerium (C e) compound powder, and a small amount of europium (E u), manganese as an activator for producing luminescence (Mn> and terbium (Tb) are used.
- the mixed raw material is used.
- the mixed raw material is fired at a high temperature exceeding ⁇ , ⁇ and then pulverized. It is processed and used as a phosphor for lamps.
- the characteristics of the phosphor are influenced by the primary particle diameter of the phosphor particles, and it is well known that the larger the phosphor particles, the higher the light efficiency. It is necessary to have good applicability, and from that point, a phosphor having a primary particle diameter of 4 to 10 ⁇ is usually used as a phosphor for a three-wavelength fluorescent lamp. In the case of luminous phosphors, it is usually 20 ⁇ ! Phosphors with a primary particle size of 5050 ⁇ m are used. Further, it is well known that the emission characteristics of phosphors are greatly affected by trace impurities.
- high-purity alumina powder such as high-purity ⁇ -alumina or high-purity ⁇ -alumina is used as the main raw material for the aluminate serving as the base material of the aluminate phosphor. Since these high-purity alumina powders have a fine primary particle diameter, usually less than 1 m, and are highly agglomerated, the phosphor after firing forms hard aggregated particles.
- phosphors synthesized using these high-purity alumina powders are powders with a wide particle size distribution from submicron to about 100 ⁇ m.
- the aluminate-based phosphor uses a fine high-purity alumina raw material having a primary particle diameter of less than 1 ⁇ as the raw material alumina, and grows from submicron to approximately 200 / um fluorescent particles by high-temperature firing. Therefore, the phosphor particles after firing have a wide particle size distribution and are strongly aggregated, and need to be ground. In addition, it is essential to remove fine particles and coarse particles by classification. As a result, there have been major problems such as degradation of light emission characteristics due to destruction of primary particles and unevenness of crystallinity due to pulverization, and a low yield as phosphor particles.
- aluminate-based phosphors that are easy to be crushed, contain few particles, have excellent emission characteristics, and have a high product yield have not yet been obtained for both phosphors for three-wavelength fluorescent lamps and phosphorescent phosphors. Absent.
- An object of the present invention is to provide a method for producing an aluminate-based phosphor, which is easy to pulverize and has a small amount of fine particles, has excellent emission characteristics, and has a high product yield.
- a substantially crushed surface having a primary particle diameter of 0.3 / xm or more and 30 ⁇ or less is used as a raw material alumina in the synthesis of an aluminate-based phosphor. It uses ⁇ -alumina powder that does not have it.
- the aluminate-based phosphor has a general formula
- an aluminate-based phosphor has a general formula
- Tb terbium
- Mn manganese
- M 2 is at least one metal element selected from magnesium (Mg) and zinc (Zn),
- d is 0.9 to 1.1
- e is 0.9 to 1.1
- f is 5.5.
- an aluminate-based phosphor is represented by the following general formula:
- Ma is a group consisting of strontium (Sr), calcium (Ca), and barium (Ba); a compound consisting of at least one metal element selected from the group consisting of at least one metal element; h is 0.5 to 1.1
- Eu europium
- the aluminate-based phosphor is represented by the general formula
- M 3 strontium (S r), calcium (C a), barium ( ⁇ et compounds comprising at least one or more metal element selected consisting of B a), h is 1.1 to 0.5) a composite oxide represented by This is an aluminate phosphor having afterglow characteristics in which at least one metal element selected from lead (Pb), zinc (Zn) and bismuth (Bi) is added to a substrate.
- alumina as a raw material alumina, as an ⁇ -alumina powder having a primary particle diameter of 0.3 / tm or more and having substantially no fracture surface of 30 ⁇ or less, a method using an alumina purity of 99.9% by weight or more is used.
- the present invention is excellent in emission characteristics because of and less fine particles easily crushed, a method of manufacturing a product yield good aluminate-based phosphor, the raw material of the alpha - in the alumina - with the following particle size 0.3 im or Use ⁇ -alumina powder with substantially no crushed surface of 30 #m or less.
- ⁇ -anoremina powder for example, ⁇ -alumina sold by Sumitomo Chemical Co., Ltd. under the trade name of Advanced Alumina can be used (JP-A-6-191833, JP-A-6-191835). No., JP-A-6-191836).
- ⁇ -alumina powders having a primary particle size of 0.3 / ⁇ ID or more and having substantially no crushed surface of 30 ⁇ or less have almost no agglomerated particles and a sharp particle size distribution.
- the ⁇ -alumina particles form aluminate with magnesium ( ⁇ g), barium (Ba), strontium (Sr), calcium (Ca), zinc (Zn), and lead (Pb).
- Reaction with a compound such as bismuth (Bi) or cerium (Ce) resulted in the formation of aluminate-based phosphor particles having few fine particles and little aggregation.
- this ⁇ -alumina powder has almost no agglomerated particles. Since it does not have fine particles, it has good dispersibility, and magnesium (Mg), norium (Ba), strontium (Sr), calcium (Ca), sub-f & (Zn), lead (Pb ), Bismuth (Bi), or cerium (Ce) are mixed homogeneously with the compound powder, so it is considered that the phosphor will be less likely to generate fine particles.
- magnesium magnesium
- norium (Ba), strontium (Sr), calcium (Ca), sub-f & (Zn), lead (Pb ), Bismuth (Bi), or cerium (Ce) are mixed homogeneously with the compound powder, so it is considered that the phosphor will be less likely to generate fine particles.
- M g magnesium (M g) constituting the aluminate
- burrs ⁇ beam (B a), strontium (S r), calcium (Ca), nitrous f & (Zn), lead (P Reaction with compound powder such as b), bismuth (Bi) or cerium (Ce) becomes difficult.
- the alumina purity of ⁇ -alumina is 99.9% by weight or more.
- oxides, or hydroxides, carbonates, nitrates, halides and the like which can be decomposed at high temperatures to form oxides can be used.
- Aluminate-based phosphor becomes general formula aMiO ⁇ bMgO ⁇ c A 1 2 0 3 europium (Eu) to the double focus oxide substrate represented alone or europium (Eu) manganese (M n) activated
- Eu europium
- M n manganese
- aluminate-based phosphor is formula a (B a, S r) 0 - bMgO ⁇ c A 1 2 0 europium complex oxide substrate represented by 3 (Eu), or a europium (E u) Manganese
- a is in the range of 0.9 to 1, 7, b is 1.5 to 2.1, and c is 8.
- aluminate-based phosphor is formula a (B a, C a) 0 - europium (E u) to the composite oxide substrate represented by cA l 2 0 3, or europium (E u) and manganese (
- a is in the range of 1.0 to 1.5 and c is in the range of 6.
- europium complex oxide substrate aluminate-based phosphor represented by the general formula a S r O ⁇ c A 1 2 0 3 (Eu) is added compound as an activator, from a 3.9 4.1 and c are preferably in the range of 7.
- the aluminate-based phosphor is represented by d C e O, ⁇ eM 2 ⁇ ⁇ ⁇ ⁇ ⁇ in the general formula.
- d ranges from 0.9 to 1.1
- e ranges from 0.9 to 1.1
- f ranges from 5.5. Is preferred.
- Raw materials such as europium (Eu), manganese (Mn), and terbium (Tb) that act as activators for emitting light include oxides, hydroxides, carbonates, nitrates, and halides at high temperatures. Those which can be decomposed into oxides can be used.
- aluminate-based phosphor is formula a (B a, S r) europium complex oxide substrate represented by 0 ⁇ bMgO ⁇ c A 1 2 ⁇ 3 (Eu) alone or europium (In the case of an aluminate-based phosphor to which an activator consisting of Eu) and manganese (Mn) is added, the amount of europium (Eu) added is from 0.01 a to 0.15 a, and the amount of manganese (Mn) is 0.15 a.
- b It is preferably in the following range.
- aluminate-based phosphor is formula a (B a, C a) 0 - cA l 2 O europium complex oxide substrate represented by a (E u) alone, or a europium (E u) manganese
- the amount of europium (Eu> 1) is 0.011 A, 0.15 a, manganese (M n) It is preferable that the amount of addition be in the range of 0.20 a or less.
- aluminate-based phosphor of the general formula a S r O ⁇ c A 1 2 0 europium (E u) to the composite oxide substrate represented by 3 is added, aluminate-based phosphor as an activator
- the amount of europium (Eu) added is preferably in the range of 0.02a to 0.06a.
- the composite oxide substrate aluminate-based phosphor is shown by the formula dC E_ ⁇ 1 5 ⁇ eM z O ⁇ ⁇ ⁇ 1 2 ⁇ 3 (T b) and ⁇ or manganese (M n)
- Tb aluminate-based phosphor to which an activator is added
- Mn manganese
- a flux to accelerate the reaction to the phosphor particles.
- the flux for example, boron oxide can be used.
- the aluminate-based phosphor according to the present invention obtained using ⁇ -alumina powder having a primary particle diameter of 0.3 ⁇ m or more and 30 ⁇ m or less and having substantially no crushed surface as a raw material, is easy to pulverize. In addition, it is very useful as a three-wavelength fluorescent lamp because it has good emission characteristics due to the small amount of fine particles and high product yield.
- any phosphor containing an aluminate in a mother crystal may be used.
- an aluminate-based phosphor having afterglow characteristics of several tens of minutes to several hours described in Japanese Patent No. 254 3825 and Japanese Patent Publication No. 7-112574 is exemplified.
- Aluminate-based phosphor having afterglow characteristics having afterglow characteristics, the formula hMhO ⁇ A 1 2 Oa [ ⁇ 3 strontium (S r), at least one selected from the group consisting of calcium (Ca), barium (B a) Compounds composed of the above metal elements, h is 0.5 to 1.1].
- europium complex oxide substrate phosphorescent aluminate clay based phosphor represented by formula h S rO 'A l 2 ⁇ 3 (Eu) is as an activator, was further added as dysprosium co activator
- h is preferably in the range of 0.9 to 1.1.
- europium (Eu) is a composite oxide substrate represented aluminate phosphor is by the formula h C a O ⁇ A 1 2 O a having afterglow characteristics, with further Neojiu arm co
- h is preferably in the range of 0.9 to 1.1.
- a europium complex oxide substrate phosphorescent aluminate-based phosphor is shown by the formula h S r O ⁇ A 1 2 0 3 (Eu) is an activator, further Jisupuroshiu
- the amount of europium (Eu) is preferably in the range of 0.1 to 0.1 lh, and the amount of dysprosium is preferably in the range of 0.02 to 0.2 h.
- the composite oxide substrate phosphorescent aluminate phosphor represented by the general formula hC aO ⁇ ⁇ 1 2 0 3 europium (Eu) is as an activator, is added as further Neojiumu is coactivator
- the addition amount of europium (Eu) is in the range of 0.01 h to 0.1 lh, and the addition amount of neodymium is in the range of 0.02 h to 0.2 h. It is not preferable to add an activator in a smaller amount or a larger amount than the above preferable range because the luminance is reduced.
- the product obtained by the above method is pulverized using a ball mill, a jet mill, or the like, and then washed, but classified if necessary.
- a flux can be added to promote the reaction to the phosphor particles.
- the flux for example, boron oxide can be used.
- the aluminate-based phosphor for a phosphorescent material according to the present invention obtained by using an ⁇ -alumina powder having a sub-particle diameter of 0.3 / 1 n or more and having substantially no crushed surface of 30 ⁇ m or less as a raw material, It is very useful as a phosphorescent material because it has excellent afterglow characteristics due to easy pulverization and few particles, and high product yield.
- FIG. 1 is a drawing showing the particle shape of ⁇ -alumina powder (AA2) by a scanning electron micrograph.
- FIG. 2 is a drawing showing the particle shape of the ct-alumina powder (A A3) by a scanning electron micrograph.
- FIG. 3 is a drawing showing the particle shape of ⁇ -alumina powder (AA5) by a scanning electron micrograph.
- FIG. 4 is a drawing showing the particle shape of ⁇ -alumina powder (AA10) by a scanning electron micrograph.
- FIG. 5 is a drawing showing the particle shape of ⁇ -alumina powder (R ⁇ -40) by a scanning electron micrograph.
- FIG. 6a and 6b are drawings showing the particle shape of the phosphor obtained by using a ⁇ 10 in a scanning electron micrograph, wherein FIG. 6a is 2,000 times and FIG. 6b is 5,000 times. .
- FIG. 7a and 7b are drawings showing the particle shape of the phosphor using RA-40 by a scanning electron micrograph.
- FIG. 7a is 2,000 times
- FIG. 7b is 5,000 times.
- the primary particle size of ⁇ -alumina powder was determined by selecting 80 to 100 particles from a SEM (scanning electron microscope, JEOL Ltd .: ⁇ -300) photograph of ⁇ -alumina powder. Image analysis was performed to determine the average value of the circle equivalent diameter.
- the equivalent circle diameter is a value converted into the diameter of a perfect circle having the same area.
- the average particle size (X50) and particle size distribution (X9 ⁇ 10) of the aluminate-based phosphor were measured using an S ⁇ laser micron sizer (manufactured by Seishin Enterprise) using the laser scattering method as the measurement principle. Measured.
- the particle shape of the aluminate phosphor was photographed using a scanning electron microscope (manufactured by JEOL Ltd .: T122OA).
- the afterglow intensity of the aluminate-based phosphor having the afterglow characteristic was measured by the following method.
- the sample container was filled with the phosphor powder (diameter: 38 mm, thickness: 5 mm), stored in a dark place for 16 hours, and irradiated with a fluorescent lamp placed at a height of 15 mm for the sample container for 10 minutes.
- the afterglow intensity after a lapse of a certain time after the irradiation was stopped was measured using a luminance meter (manufactured by Matsushita Electronics Industrial Lighting R & D Center: 5712) and a phototube (Hamamatsu Photonics: R847).
- the Hi-Alumina powder having a primary particle diameter of 0.3 ⁇ m or more and having substantially no crushed surface of 30 / i ⁇ or less used in this example includes “Advanced Advanced Rem Alumina powder having the physical properties shown in Tables 1 and 2 sold under the trade name of Na J was used.
- an alumina powder of RA-40 commercial product; manufactured by Iwatani Chemical Industry Co., Ltd. was used.
- the particle shapes of each ⁇ -alumina powder with a scanning electron microscope are shown in FIGS.
- the raw materials using AA10 or RA-40 were mixed sufficiently with ⁇ -alumina in a ball mill, fired at 1,300 in a reducing atmosphere for 3 hours, and the obtained oxide was pulverized. Further, this powder was fired in a reducing atmosphere at 1,300 ° C. for 3 hours to obtain a phosphor.
- composition formula of the obtained phosphor is as follows.
- the average particle size, particle size distribution, emission peak, and emission intensity of each phosphor are shown in Table 3 below.
- the emission intensity is a value calculated by assuming that the phosphor using RA-40 is 100%.
- Figures 6a and 6b are scanning electron micrographs of the phosphor using AA10, which are substitutes for the drawing of the particle shape.
- Figure 6a is 2,000 times
- Figure 6b is 5,000 times.
- Figures 7a and 7b are scanning electron micrographs of the phosphor using RA-40, which are substitutes for the drawing of the particle shape.
- Figure 7a is 2,000 (H &)
- Figure 7b is 5,000. It is twice.
- Example 3 phosphor (Ce 0 6S T bo 35) ⁇ ,., ⁇ creating a Mg O ⁇ 5.5A 1 2 0 3 ⁇ -alumina 27 1.98 g
- the raw materials using ⁇ 2, ⁇ 3, AA5 or RA-40 are mixed well with ⁇ -alumina in a ball mill, and calcined in a reducing atmosphere at 1,300 * t: for 2 hours.
- the obtained oxide was pulverized. Further, after baking this powder at 1,300 in a reducing atmosphere for 2 hours, the pulverization time was adjusted to adjust the average particle size X50 of the phosphor powder to about 8.5 ⁇ .
- the composition formula of the obtained phosphor is as follows.
- the emission intensity is a value calculated by assuming that the phosphor using R R-40 is 1 000.
- Table 4 below shows the properties of these phosphors.
- the aluminate-based phosphor according to the present invention has a sharp particle size distribution that is easier to pulverize as compared with a phosphor using conventionally used high-purity alumina RA-40 as a raw material.
- it is a very convenient aluminate-based phosphor that shows high emission intensity.
- composition formula of the obtained phosphor is as follows.
- Table 5 shows the characteristics of each phosphor such as average particle size, particle size distribution, and afterglow intensity. Note that the afterglow intensity is a value calculated by assuming that the phosphor using R-40 is 100%.
- the aluminate-based phosphor for a phosphorescent material according to the present invention is easier and more pulverizable than a phosphor using a high-purity alumina RA-40 used as a raw material.
- it has high afterglow intensity despite its small average particle size, and is an extremely excellent aluminate phosphor for phosphorescent materials.
- according to the present invention it is possible to obtain an aluminate-based phosphor that is easily crushed and has a small amount of fine particles, has excellent light emission characteristics, and has a high product yield.
- This aluminate-based phosphor is industrially extremely useful as a three-wavelength fluorescent lamp and an aluminate-based phosphor for a phosphorescent material.
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Abstract
Description
明 細 書 Specification
アルミン酸塩系蛍光体の製造方法 Method for producing aluminate phosphor
技術分野 Technical field
本発明は、 例えば、 紫外線で励起されて青色、 青緑色或いは緑色発光を示す 3 波長形蛍光ランプ等に使用されるアルミン酸塩系蛍光体、 又は、 紫外線、 可視光 で励起されて長時間の残光性を示す蓄光材等に使用される残光特性を有するアル ミン酸塩系蛍光体の製造方法に関する。 The present invention relates to, for example, an aluminate-based phosphor used for a three-wavelength fluorescent lamp that emits blue, blue-green, or green light when excited by ultraviolet light, or a long-time excited by ultraviolet light or visible light. The present invention relates to a method for producing an aluminate-based phosphor having an afterglow characteristic, which is used as a phosphorescent material having an afterglow property.
背景技術 Background art
蛍光ランプは 1938年に製造開始されて以来、発光輝度、発光効率、演色性、寿命な どの特性向上がはかられてきた。 近年、 450nm (青）、 540nn (緑）、 610nm (赤）の各々 の波長付近に強く蛍光を集中させることにより、 演色性を改良した自然光に近い 蛍光ランプ、 所謂 「3波長形蛍光ランプ」 が広く使用されている。 Since the production of fluorescent lamps began in 1938, improvements have been made in characteristics such as luminous brightness, luminous efficiency, color rendering, and lifespan. In recent years, fluorescent lamps that are close to natural light with improved color rendering properties, so-called “three-wavelength fluorescent lamps,” have been developed by concentrating fluorescence strongly around the wavelengths of 450 nm (blue), 540 nn (green), and 610 nm (red). Widely used.
この 3波長形蛍光ランプには、 例えば、 青色蛍光体としてはバリウム一マグネ シゥム—アルミネィ ト蛍光体が、 緑色蛍光体としてはセリゥム—マグネシウム一 アルミネィト蛍光体が、 また赤色蛍光体としては酸化ィットリゥム蛍光体が使用 されてきた。 The three-wavelength fluorescent lamp includes, for example, a barium-magnesium-aluminum phosphor as a blue phosphor, a cerium-magnesium-aluminum phosphor as a green phosphor, and a yttrium oxide phosphor as a red phosphor. The body has been used.
例えば、 青色蛍光体又は緑色蛍光体のアルミン酸塩系蛍光体の製造には、 アル ミナ粉末に、 アルミン酸塩を構成するマグネシウム（M g )、 バリウム（B a )、 ス トロンチウム（S r )、 カルシウム（C a )、 亜鉛（Z n )或いはセリウム（C e )の化 合物粉末を混合し、 更に、 発光を生じさせるための付活剤として少量のユーロピ ゥム（E u )、 マンガン（M n〉やテルビウム（T b )が 1種以上添加混合された原料 が用いられる。 これら混合原料は、 ι, οοοΐを越える高温にて焼成された後粉砕さ れ、 更に分級、 洗浄等の処理が行われ、 ランプ用蛍光体として用いられる。 For example, for the production of aluminate phosphors of blue or green phosphors, magnesium (Mg), barium (Ba), and strontium (Sr) constituting an aluminate are added to an alumina powder. , Calcium (C a), zinc (Z n) or cerium (C e) compound powder, and a small amount of europium (E u), manganese as an activator for producing luminescence (Mn> and terbium (Tb) are used. The mixed raw material is used. The mixed raw material is fired at a high temperature exceeding ι, οοοΐ and then pulverized. It is processed and used as a phosphor for lamps.
一方、 夜間表示や夜光時計用として、 放射性物質を蛍光体に添加した自発光性 夜光塗料が利用されてきた。 最近に至っては放射性物質を用いない長時間の残光 性を有する蓄光性蛍光体の応用が広く検討されている。 蓄光性蛍光体としては、 例えばユーロピウム付活ストロンチウムアルミネィトが主として検討されている (特許第 2 5 4 3 8 2 5号公報)。 On the other hand, self-luminous luminous paints, in which a radioactive substance is added to a phosphor, have been used for nighttime display and luminous clocks. Recently, the application of phosphorescent phosphors having long-term persistence without using radioactive substances has been widely studied. For example, europium-activated strontium aluminate has been mainly studied as a phosphorescent phosphor (Japanese Patent No. 2543838).
発明の開示 蛍光体の特性は、 蛍光体粒子の一次粒子径に影饗を受け、 ^光効率は蛍光体粒 子が大きいほうが高いことはよく知られているが、 一方、 実用蛍光体は発光特性 に加え塗布性にも便れていることが必要であり、 その点から 3波長形蛍光ランプ 用蛍光体では、 通常 4〜10 μ ι»の一次粒子径の蛍光体が使用されている。 また、 蓄 光性蛍光体では、 通常 20 μ ι！〜 50 μ mの一次粒子径の蛍光体が使用されている。 更に、 蛍光体の発光特性は微量不純物に大きく影響を受けることはよく知られ ている。 そのため、 アルミン酸塩系蛍光体の基体となるアルミネイトには、 高純 度に精製した高純度 α—アルミナ或いは髙純度 γ—アルミナ等の高純度アルミナ 粉末が主原料として用いられる。 これら高純度アルミナ粉末は、 一次粒子径が微 細で通常 1 m未満であり凝集が強いため、 焼成後の蛍光体は堅い凝集粒子を形成 する。 Disclosure of the invention The characteristics of the phosphor are influenced by the primary particle diameter of the phosphor particles, and it is well known that the larger the phosphor particles, the higher the light efficiency. It is necessary to have good applicability, and from that point, a phosphor having a primary particle diameter of 4 to 10 μιη is usually used as a phosphor for a three-wavelength fluorescent lamp. In the case of luminous phosphors, it is usually 20 μι! Phosphors with a primary particle size of 5050 μm are used. Further, it is well known that the emission characteristics of phosphors are greatly affected by trace impurities. For this reason, high-purity alumina powder such as high-purity α-alumina or high-purity γ-alumina is used as the main raw material for the aluminate serving as the base material of the aluminate phosphor. Since these high-purity alumina powders have a fine primary particle diameter, usually less than 1 m, and are highly agglomerated, the phosphor after firing forms hard aggregated particles.
—方、 これらの堅い凝集粒子を粉砕することにより低減することも出来るが、 凝集粒子の残留や粉砕に伴う微粒子の生成により粉砕後の粒度分布は広いものと なる。 そのためこれらの高純度アルミナ粉末を用いて合成された蛍光体は、 サブ ミクロンから約 100 μ mの広い粒度分布からなる粉末となる。 On the other hand, the reduction can be achieved by pulverizing these hard agglomerated particles, but the particle size distribution after the pulverization becomes wider due to the remaining of the agglomerated particles and the generation of fine particles accompanying the pulverization. Therefore, phosphors synthesized using these high-purity alumina powders are powders with a wide particle size distribution from submicron to about 100 μm.
即ち、 アルミン酸塩系蛍光体は、 原料アルミナとして一次粒子径が 1 μ η未満の 微細な高純度アルミナ原料を用い、 高温焼成によりサブミクロンから約 200 /u mの 蛍光体粒子に成長する。 そのため、 焼成後の蛍光体粒子は粒度分布が広く且つ強 く凝集しており粉碎する必要がある。 加えて分級により微粒子及び粗大粒子を除 去することが必須である。 その結果、 粉砕による一次粒子の破壊や結晶性の不均 —化を原因とする発光特性の低下、 更には蛍光体粒子としての歩留りが低い等大 きな問題があった。 That is, the aluminate-based phosphor uses a fine high-purity alumina raw material having a primary particle diameter of less than 1 μη as the raw material alumina, and grows from submicron to approximately 200 / um fluorescent particles by high-temperature firing. Therefore, the phosphor particles after firing have a wide particle size distribution and are strongly aggregated, and need to be ground. In addition, it is essential to remove fine particles and coarse particles by classification. As a result, there have been major problems such as degradation of light emission characteristics due to destruction of primary particles and unevenness of crystallinity due to pulverization, and a low yield as phosphor particles.
従って、 これまで粉碎が容易で且つ微粒子が少なく発光特性に傻れ、 製品歩留 りが高いアルミン酸塩系蛍光体は 3波長形蛍光ランプ用蛍光体及び蓄光性蛍光体 では共に未だ得られていない。 Therefore, to date, aluminate-based phosphors that are easy to be crushed, contain few particles, have excellent emission characteristics, and have a high product yield have not yet been obtained for both phosphors for three-wavelength fluorescent lamps and phosphorescent phosphors. Absent.
かかる事情のもとで、 本発明らは鋭意検討を重ねた結果、 青色蛍光体、 青緑蛍 光体或いは緑色蛍光体として、 3波長形蛍光ランプ等に適するアルミン酸塩蛍光 体及び蓄光材等に適するアルミン酸塩蛍光体の製造方法を見い出し、 本発明を完 成するに至った。 本発明は、 粉砕が容易で且つ微粒子が少ないため発光特性に優れ、 製品歩留り が高いことを特徴とするアルミン酸塩系蛍光体の製造方法を得ることを目的とす る。 Under these circumstances, the present inventors have conducted intensive studies and found that as a blue phosphor, a blue-green phosphor, or a green phosphor, an aluminate phosphor and a phosphorescent material suitable for a three-wavelength fluorescent lamp and the like. The present inventors have found a method for producing an aluminate phosphor suitable for the present invention, and have completed the present invention. An object of the present invention is to provide a method for producing an aluminate-based phosphor, which is easy to pulverize and has a small amount of fine particles, has excellent emission characteristics, and has a high product yield.
即ち、 本発明に係るアルミン酸塩系蛍光体の製造方法では、 アルミン酸塩系蛍 光体の合成にあたり、 原料アルミナとして一次粒子径が 0.3 /xm以上で 30 μιη以下の 実質的に破砕面を有しない α—アルミナ粉末を用いるものである。 That is, in the method for producing an aluminate-based phosphor according to the present invention, a substantially crushed surface having a primary particle diameter of 0.3 / xm or more and 30 μιη or less is used as a raw material alumina in the synthesis of an aluminate-based phosphor. It uses α-alumina powder that does not have it.
本発明の 1つの態様によれば、 アルミン酸塩系蛍光体が、 一般式 According to one embodiment of the present invention, the aluminate-based phosphor has a general formula
aM.O · bMgO · c A 12 O 3 aM.ObMgOc A 1 2 O 3
で示される複合酸化物基体にユーロピウム（Eu)単独、 又はユーロピウム（E u) とマンガン (Mn)からなる付活剤が添加された化合物であり、 Is a compound in which europium (Eu) alone or an activator consisting of europium (Eu) and manganese (Mn) is added to a composite oxide substrate represented by
がバリゥム（B a)、 ストロンチウム（S r)及びカルシウム（C a)からなる群 から選ばれる少なくとも 1種の金属元素であり、 Is at least one metal element selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca);
aが 0.5から 4.5、 bが 0から 4、 cが 0.5から 20の範囲にあるものである。 また、 本発明の別の態様によれば、 アルミン酸塩系蛍光体が一般式 a is in the range of 0.5 to 4.5, b is in the range of 0 to 4, and c is in the range of 0.5 to 20. Further, according to another aspect of the present invention, an aluminate-based phosphor has a general formula
d C e 01 5 · eM20 · f A 1 d C e 0 1 5eM 2 0fA 1
で示される複合酸化物基体にテルビウム（Tb)及び/ ^又はマンガン (Mn)からな る付活剤が添加された化合物であり、 Is a compound in which an activator composed of terbium (Tb) and / or manganese (Mn) is added to a composite oxide substrate represented by
M2がマグネシウム（Mg)、 亜铅（Z n)から選ばれる少なくとも 1種の金属元素 であり、 M 2 is at least one metal element selected from magnesium (Mg) and zinc (Zn),
dが 0.9から 1.1、 eが 0.9から 1.1、 f が 5.5であるものである。 d is 0.9 to 1.1, e is 0.9 to 1.1, and f is 5.5.
更に、 本発明の別の態様によれば、 アルミン酸塩系蛍光体が、 一般式 Further, according to another aspect of the present invention, an aluminate-based phosphor is represented by the following general formula:
(Maはストロンチウム（S r )、 カルシウム（C a)、 バリウム（B a )からなる群力、 ら選ばれる少なくとも 1つ以上の金属元素からなる化合物、 hは 0.5から 1.1) で示される複合酸化物基体に、 付活剤としてのユーロピウム（Eu)が M:tで表す金 属元素に対するモル％で 0.002%以上 20%以下添加され、 更に、 共付活剤として、 ランタン（L a)、 セリウム（C e)、 プラセオジム（P r)、 ネオジゥム（Nd)、 サ マリゥム（Sm)、 ガドリニウム（G d)、 テルビウム（Tb)、 ジスプロシウム（D y)、 ホルミウム（Ho)、 エルビウム（E r)、 ツリウム（Tm)、 イッテルビウム (Yb)、 ルテチウム（Lu〉、 マンガン（Mn)、 スズ（Sn)、 ビスマス（B i)、 ス カンジゥム（S c)からなる群の少なくとも 1つ以上の元素が M3で表す金属元素に 対するモル％で 0.002%以上 20%以下添加された残光特性を有するアルミン酸塩系 蛍光体である。 (Ma is a group consisting of strontium (Sr), calcium (Ca), and barium (Ba); a compound consisting of at least one metal element selected from the group consisting of at least one metal element; h is 0.5 to 1.1) To the oxide substrate, europium (Eu) as an activator is added in an amount of 0.002% or more and 20% or less in terms of mol% based on a metal element represented by M: t . Further, lanthanum (La), Cerium (C e), Praseodymium (P r), Neodymium (Nd), Samarium (Sm), Gadolinium (G d), Terbium (Tb), Dysprosium (D y), Holmium (Ho), Erbium (E r) , Thulium (Tm), Ytterbium (Yb), lutetium (Lu>, manganese (Mn), tin (Sn), bismuth (B i), at least one or more elements of the group consisting of scan Kanjiumu (S c) is against the metal elements expressed by M 3 It is an aluminate-based phosphor with afterglow properties added in an amount of 0.002% to 20% in mol%.
また、 より具体的には、 アルミン酸塩系蛍光体が、 一般式 More specifically, the aluminate-based phosphor is represented by the general formula
hMsO · A 1203 hMsOA 1 2 0 3
(M3はストロンチウム（S r)、 カルシウム（C a)、 バリウム（B a )からなる鮮力 ら選ばれる少なくとも 1つ以上の金属元素からなる化合物、 hは 0.5から 1.1) で示される複合酸化物基体に、 更に鉛（Pb)、 亜鉛（Zn)及びビスマス（B i)か ら選ばれる少なくとも 1種の金属元素が添加された残光特性を有するアルミン酸 塩蛍光体である。 (M 3 strontium (S r), calcium (C a), barium (鮮力et compounds comprising at least one or more metal element selected consisting of B a), h is 1.1 to 0.5) a composite oxide represented by This is an aluminate phosphor having afterglow characteristics in which at least one metal element selected from lead (Pb), zinc (Zn) and bismuth (Bi) is added to a substrate.
例えば、 原料アルミナとして一次粒子径が 0.3/tm以上で 30μη以下の実質的に破 砗面を有しない α—アルミナ粉末としては、 アルミナ純度が 99.9重量％以上のも のを用いる方法である。 For example, as a raw material alumina, as an α-alumina powder having a primary particle diameter of 0.3 / tm or more and having substantially no fracture surface of 30 μη or less, a method using an alumina purity of 99.9% by weight or more is used.
本発明は粉砕が容易で且つ微粒子が少ないため発光特性に優れ、 製品歩留りが よいアルミン酸塩系蛍光体の製造方法に関するもので、 原料の α—アルミナには —次粒子径が 0.3 im以上で 30 # m以下の実質的に破砕面を有しない α—アルミナ粉 末を用いる。 この α—ァノレミナ粉末には、 例えば、 住友化学工業株式会社からァ ドバンストアルミナの商品名で販売されている α—アルミナを用いることが出来 る（特開平 6— 191833号、 特開平 6— 191835号、 特開平 6— 1 91 8 36号） 。 The present invention is excellent in emission characteristics because of and less fine particles easily crushed, a method of manufacturing a product yield good aluminate-based phosphor, the raw material of the alpha - in the alumina - with the following particle size 0.3 im or Use α-alumina powder with substantially no crushed surface of 30 #m or less. As the α-anoremina powder, for example, α-alumina sold by Sumitomo Chemical Co., Ltd. under the trade name of Advanced Alumina can be used (JP-A-6-191833, JP-A-6-191835). No., JP-A-6-191836).
これら一次粒子径が 0.3/ί ID以上で 30μιη以下の実質的に破砕面を有しない α—ァ ルミナ粉末は凝集粒子がほとんど無く、 粒度分布がシャープである。 驚くことに この α—アルミナ粒子は、 これと共にアルミン酸塩を構成するマグネシウム（Μ g)、 バリウム（B a)、 ストロンチウム（S r)、 カルシウム（Ca)、 亜鉛（Zn)、 鉛（Pb)、 ビスマス（B i)、 或いはセリゥム（C e)等の化合物と反応して、 微粒 子が少なく、 且つ凝集が少ないアルミン酸塩系蛍光体粒子になることを見い出し た。 These α-alumina powders having a primary particle size of 0.3 / ίID or more and having substantially no crushed surface of 30 μιη or less have almost no agglomerated particles and a sharp particle size distribution. Surprisingly, the α-alumina particles form aluminate with magnesium (構成 g), barium (Ba), strontium (Sr), calcium (Ca), zinc (Zn), and lead (Pb). Reaction with a compound such as bismuth (Bi) or cerium (Ce) resulted in the formation of aluminate-based phosphor particles having few fine particles and little aggregation.
この理由は明確ではないが、 この α—アルミナ粉末は凝集粒子がほとんど無く 微粒子を有しないため分散性に便れ、 アルミン酸塩を構成するマグネシウム（M g)、 ノ リウム（B a)、 ストロンチウム（S r)、 カルシウム（Ca)、 亜 f&(Zn)、 鉛（Pb)、 ビスマス（B i)、 或いはセリウム（C e)等の化合物粉末と均質に混合 されるため微粒子の生成が少ない蛍光体になると考えられる。 The reason for this is not clear, but this α-alumina powder has almost no agglomerated particles. Since it does not have fine particles, it has good dispersibility, and magnesium (Mg), norium (Ba), strontium (Sr), calcium (Ca), sub-f & (Zn), lead (Pb ), Bismuth (Bi), or cerium (Ce) are mixed homogeneously with the compound powder, so it is considered that the phosphor will be less likely to generate fine particles.
一方、 30/i iDを越える場合はアルミン酸塩を構成するマグネシウム（Mg)、 バリ ゥム（B a)、 ストロンチウム（S r)、 カルシウム（Ca)、 亜 f&(Zn)、 鉛（P b)、 ビスマス（B i)、 或いはセリウム（C e)等の化合物粉末との反応が困難とな る。 更に、 輝度等の発光性を高めるためには α—アルミナのアルミナ純度が 99.9 重量％以上であることが好ましい。 On the other hand, 30 / i of magnesium (M g) constituting the aluminate If exceeding iD, burrs © beam (B a), strontium (S r), calcium (Ca), nitrous f & (Zn), lead (P Reaction with compound powder such as b), bismuth (Bi) or cerium (Ce) becomes difficult. Further, in order to enhance the light emission such as luminance, it is preferable that the alumina purity of α-alumina is 99.9% by weight or more.
アルミン酸塩を構成するマグネシウム（Mg)、 バリウム（B a)、 ストロンチウ ム（S r)、 カルシウム（C a)、 亜鉛（Zn)、 鉛（Pb)、 ビスマス（B i )、 或いは セリウム（C e)の化合物粉末としては酸化物、 或いは水酸化物、 炭酸塩、 硝酸 塩、 ハロゲン化物など高温で分解して酸化物になりうるものが使用出来る。 Magnesium (Mg), barium (Ba), strontium (Sr), calcium (Ca), zinc (Zn), lead (Pb), bismuth (Bi), or cerium (C) As the compound powder of e), oxides, or hydroxides, carbonates, nitrates, halides and the like which can be decomposed at high temperatures to form oxides can be used.
アルミン酸塩系蛍光体が、 一般式 aMiO · bMgO · c A 1203で示される複 合酸化物基体にユーロピウム（Eu)単独、 又はユーロピウム（Eu)とマンガン（M n)からなる付活剤が添加された化合物の場合、 aが 0.5から 4.5、 bが 0から 4、 cが 0.5から 20の範囲になるように混合される。 Aluminate-based phosphor becomes general formula aMiO · bMgO · c A 1 2 0 3 europium (Eu) to the double focus oxide substrate represented alone or europium (Eu) manganese (M n) activated In the case of the compound to which the agent is added, the components are mixed so that a is in the range of 0.5 to 4.5, b is in the range of 0 to 4, and c is in the range of 0.5 to 20.
例えば、 アルミン酸塩系蛍光体が一般式 a (B a, S r)0 - bMgO · c A 1 203で示される複合酸化物基体にユーロピウム（Eu) 、 又はユーロピウム（E u)とマンガン (Mn)からなる付活剤が添加された化合物の場合、 aが 0.9から 1, 7、 bが 1.5から 2.1、 cが 8の範囲にあることが好ましい。 For example, aluminate-based phosphor is formula a (B a, S r) 0 - bMgO · c A 1 2 0 europium complex oxide substrate represented by 3 (Eu), or a europium (E u) Manganese In the case of a compound to which an activator of (Mn) is added, it is preferable that a is in the range of 0.9 to 1, 7, b is 1.5 to 2.1, and c is 8.
また例えば、 アルミン酸塩系蛍光体が一般式 a (B a， C a)0 - cA l 203で 示される複合酸化物基体にユーロピウム（E u) 、 又はユーロピウム（E u)と マンガン（Mn)からなる付活剤が添加された化合物の場合、 aが 1.0から 1.5、 c が 6の範囲にあることが好ましい。 Further, for example, aluminate-based phosphor is formula a (B a, C a) 0 - europium (E u) to the composite oxide substrate represented by cA l 2 0 3, or europium (E u) and manganese ( In the case of a compound to which an activator comprising Mn) is added, it is preferable that a is in the range of 1.0 to 1.5 and c is in the range of 6.
更に例えば、 アルミン酸 系蛍光体が一般式 a S r O · c A 1203で示される 複合酸化物基体にユーロピウム（Eu)が付活剤として添加された化合物の場合、 aが 3.9から 4.1、 cが 7の範囲にあることが好ましい。 Furthermore, for example, when europium complex oxide substrate aluminate-based phosphor represented by the general formula a S r O · c A 1 2 0 3 (Eu) is added compound as an activator, from a 3.9 4.1 and c are preferably in the range of 7.
一方、 アルミン酸塩系蛍光体が一般式で d C e O, · eM2〇 · ίΑ Ι ^で示 される複合酸化物基体にテルビウム（Tb)及ぴノ又はマンガン（Mn)からなる付 活剤が添加された化合物の場合、 dが 0.9から 1.1、 eが 0.9から 1.1、 f が 5.5の範 囲にあることが好ましい。 On the other hand, the aluminate-based phosphor is represented by d C e O, · eM 2 〇 · ίΑ Ι ^ in the general formula. In the case of a compound in which an activator made of terbium (Tb) and / or manganese (Mn) is added to the composite oxide substrate to be used, d ranges from 0.9 to 1.1, e ranges from 0.9 to 1.1, and f ranges from 5.5. Is preferred.
発光を生じさせるための付活剤となるユーロピウム（Eu)、 マンガン（Mn)、 テルビウム（Tb)等の原料としては、 酸化物、 或いは水酸化物、 炭酸塩、 硝酸 塩、 ハロゲン化物など高温で分解し酸化物になりうるものが使用出来る。 Raw materials such as europium (Eu), manganese (Mn), and terbium (Tb) that act as activators for emitting light include oxides, hydroxides, carbonates, nitrates, and halides at high temperatures. Those which can be decomposed into oxides can be used.
添加量としては、 例えば、 アルミン酸塩系蛍光体が一般式 a (B a， S r )0 · bMgO · c A 12〇3で示される複合酸化物基体にユーロピウム（Eu)単独又は ユーロピウム（E u)とマンガン（Mn)からなる付活剤が添加されたアルミン酸塩 系蛍光体の場合、 ユーロピウム（Eu)の添加量が 0.01 aから 0.15 a、 マンガン（M n)の添加量が 0.15b以下の範囲にあることが好ましい。 The amount, for example, aluminate-based phosphor is formula a (B a, S r) europium complex oxide substrate represented by 0 · bMgO · c A 1 2 〇 3 (Eu) alone or europium ( In the case of an aluminate-based phosphor to which an activator consisting of Eu) and manganese (Mn) is added, the amount of europium (Eu) added is from 0.01 a to 0.15 a, and the amount of manganese (Mn) is 0.15 a. b It is preferably in the following range.
例えば、 アルミン酸塩系蛍光体が一般式 a (B a， C a)0 - cA l 2Oaで示さ れる複合酸化物基体にユーロピウム（E u)単独、 又はユーロピウム（E u)とマン ガン (M n )からなる付活剤が添加されたアルミン酸塩系蛍光体の場合、 ユーロピ ゥム（E u〉の 1]量が 0· 01 a力、ら 0.15 a、 マンガン（M n )の添加量が 0· 20 a以下 の範囲にあることが好ましい。 For example, aluminate-based phosphor is formula a (B a, C a) 0 - cA l 2 O europium complex oxide substrate represented by a (E u) alone, or a europium (E u) manganese In the case of an aluminate-based phosphor to which an activator composed of (M n ) is added, the amount of europium (Eu> 1) is 0.011 A, 0.15 a, manganese (M n) It is preferable that the amount of addition be in the range of 0.20 a or less.
例えば、 アルミン酸塩系蛍光体が一般式 a S r O · c A 1203で示される複合 酸化物基体にユーロピウム（E u)が付活剤として添加されたアルミン酸塩系蛍光 体の場合、 ユーロピウム（Eu)の添加量が 0.02aから 0.06aの範囲にあることが 好ましい。 For example, aluminate-based phosphor of the general formula a S r O · c A 1 2 0 europium (E u) to the composite oxide substrate represented by 3 is added, aluminate-based phosphor as an activator In this case, the amount of europium (Eu) added is preferably in the range of 0.02a to 0.06a.
例えば、 アルミン酸塩系蛍光体が一般式 dC e〇1 5 · eMzO · ί Α 12〇3で示 される複合酸化物基体にテルビゥム（T b )及び Ζ又はマンガン（M n )からなる付 活剤が添加されたアルミン酸塩系蛍光体の場合、 テルビウム（T b)の添加量が 0. 3d力 ら 0.5d、 マンガン（Mn)の添加量が 0.15 e以下の範囲にあることが好まし い。 For example, from Terubiumu the composite oxide substrate aluminate-based phosphor is shown by the formula dC E_〇 1 5 · eM z O · ί Α 1 2 〇 3 (T b) and Ζ or manganese (M n) In the case of an aluminate-based phosphor to which an activator is added, the amount of terbium (Tb) should be within 0.3d to 0.5d, and the amount of manganese (Mn) should be within 0.15e. Is preferred.
これら原料をボールミル、 V型混合機等を用い混合した後、 1， 100から 1,800 にて数時間焼成する。 更に前記方法にて得られた生成物をボールミル、 ジェット ミル等を用い解碎した後、 洗浄するが、 必要に応じて分級する。 After mixing these raw materials using a ball mill, V-type mixer, etc., they are fired at 1,100 to 1,800 for several hours. Further, the product obtained by the above method is pulverized using a ball mill, a jet mill, or the like, and then washed, but classified if necessary.
更に蛍光体粒子への反応を促進するためフラックスを添加することも可能であ る。 フラックスとしては、 例えば酸化ホウ素が使用出来る。 ' 一次粒子径が 0.3 μ m以上で 30 μ m以下の実質的に破砕面を有しない α—アルミナ 粉末を原料に用いて得られた本発明によるアルミン酸塩系蛍光体は、 粉砕が容易 で且つ微粒子が少ないため発光特性に便れ、 製品歩留りが高いため 3波長形蛍光 ランプとして極めて有用である。 It is also possible to add a flux to accelerate the reaction to the phosphor particles. You. As the flux, for example, boron oxide can be used. '' The aluminate-based phosphor according to the present invention, obtained using α-alumina powder having a primary particle diameter of 0.3 μm or more and 30 μm or less and having substantially no crushed surface as a raw material, is easy to pulverize. In addition, it is very useful as a three-wavelength fluorescent lamp because it has good emission characteristics due to the small amount of fine particles and high product yield.
また、 本発明で製造される具体的な残光特性を有するアルミン酸塩系蛍光体と しては、 アルミン酸塩を母結晶に含む蛍光体であればよい。 例えば特許第 254 3825号公報及び特顔平 7— 1 12574号公報に記載された数 10分〜数時 間の残光特性を有するアルミン酸塩系蛍光体が例示される。 Further, as the aluminate-based phosphor having specific afterglow characteristics produced in the present invention, any phosphor containing an aluminate in a mother crystal may be used. For example, an aluminate-based phosphor having afterglow characteristics of several tens of minutes to several hours described in Japanese Patent No. 254 3825 and Japanese Patent Publication No. 7-112574 is exemplified.
残光特性を有するアルミン酸塩系蛍光体が、 一般式 hMhO · A 12Oa [Μ3は ストロンチウム（S r)、 カルシウム（Ca)、 バリウム（B a)からなる群から選ば れる少なくとも 1つ以上の金属元素からなる化合物、 hは 0.5から 1.1] で示され る複合酸化物基体に、 ユーロピウム（Eu)が付活剤として、 更にランタン（L a)、 セリウム（Ce)、 ブラセォジゥム（P r)、 ネオジゥム（Nd)、 サマリウム (Sm)、 ガドリニウム（Gd)テルビウム（Tb)、 ジスプロシウム（Dy)、 ホルミ ゥム（Ho)、 エルビウム（E r)、 ツリウム（Tm)、 イッテルビウム（Yb)、 ルテ チウム（Lu)、 マンガン（Mn)、 スズ（Sn)、 ビスマス（B i)、 スカンジウム（S c)からなる群の少なくとも 1つ以上の元素が共付活剤として添加された化合物の 場合、 添加量は M3で表す金属元素に対するモル％で 0.002%以上 20%以下である ことが好ましい。 Aluminate-based phosphor having afterglow characteristics, the formula hMhO · A 1 2 Oa [Μ 3 strontium (S r), at least one selected from the group consisting of calcium (Ca), barium (B a) Compounds composed of the above metal elements, h is 0.5 to 1.1]. A complex oxide substrate represented by the following formula: Europium (Eu) is used as an activator, and lanthanum (La), cerium (Ce), brassodim (Pr ), Neodymium (Nd), samarium (Sm), gadolinium (Gd) terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lute Addition if the compound contains at least one element selected from the group consisting of titanium (Lu), manganese (Mn), tin (Sn), bismuth (Bi), and scandium (Sc) as a co-activator the amount in mol% relative to the metal element expressed by M 3 0.002% It is preferably not more than the upper 20%.
例えば、 蓄光性アルミン酸埴系蛍光体が一般式 h S rO ' A l 2〇3で示される 複合酸化物基体にユーロピウム（Eu)が付活剤として、 更にジスプロシウム共付 活剤として添加された化合物の場合、 hが 0.9から 1.1の範囲にあることが好まし い。 更に、 残光特性を有するアルミン酸塩系蛍光体が一般式 h C a O · A 12Oa で示される複合酸化物基体にユーロピウム（Eu)が付活剤として、 更にネオジゥ ムが共付活剤として添加された化合物の場合、 hが 0.9から 1.1の範囲にあること が好ましい。 For example, europium complex oxide substrate phosphorescent aluminate clay based phosphor represented by formula h S rO 'A l 2 〇 3 (Eu) is as an activator, was further added as dysprosium co activator For compounds, h is preferably in the range of 0.9 to 1.1. Furthermore, as an activator europium (Eu) is a composite oxide substrate represented aluminate phosphor is by the formula h C a O · A 1 2 O a having afterglow characteristics, with further Neojiu arm co In the case of a compound added as an activator, h is preferably in the range of 0.9 to 1.1.
更に、 例えば、 蓄光性アルミン酸塩系蛍光体が一般式 h S r O · A 1203で示 される複合酸化物基体にユーロピウム（Eu)が付活剤として、 更にジスプロシゥ ムが共付活剤として添加された化合物の場合、 ユーロピウム（E u)の添加量が 0. Olhから 0. lh、 ジスプロシウムの添加量が 0.02hから 0.2hの範囲にあることが 好ましい。 例えば、 蓄光性アルミン酸塩系蛍光体が一般式 hC aO · Λ 1203で 示される複合酸化物基体にユーロピウム（Eu)が付活剤として、 更にネオジゥム が共付活剤として添加された化合物の場合、 ユーロピウム（E u)の添加量が 0.01 hから 0. lh、 ネオジゥムの添加惫が 0.02hから 0.2hの範囲にあることが好まし い。 これら好ましい範囲より少量或いは多量の付活剤添加は輝度を低下させるた め好ましくない。 Furthermore, for example, as a europium complex oxide substrate phosphorescent aluminate-based phosphor is shown by the formula h S r O · A 1 2 0 3 (Eu) is an activator, further Jisupuroshiu In the case of a compound to which europium (Eu) is added as a co-activator, the amount of europium (Eu) is preferably in the range of 0.1 to 0.1 lh, and the amount of dysprosium is preferably in the range of 0.02 to 0.2 h. For example, the composite oxide substrate phosphorescent aluminate phosphor represented by the general formula hC aO · Λ 1 2 0 3 europium (Eu) is as an activator, is added as further Neojiumu is coactivator In the case of a compound, it is preferable that the addition amount of europium (Eu) is in the range of 0.01 h to 0.1 lh, and the addition amount of neodymium is in the range of 0.02 h to 0.2 h. It is not preferable to add an activator in a smaller amount or a larger amount than the above preferable range because the luminance is reduced.
また、 共付活剤としてランタン（L a)、 セリウム（Ce)、 プラセォジゥム（P r)、 ネオジゥム（Nd)、 サマリウム（Sm)、 ガドリニウム（Gd)、 テルビウム (Tb)、 ジスプロシウム（Dy)、 ホルミウム（Ho)、 エルビウム（E r)、 ッリウ ム（Tm)、 イッテルビウム（Yb)、 ルテチウム（Lu)、 マンガン（Mn)、 スズ（S n)、 ビスマス（B i)、 スカンジウム（S c)からなる群の少なくとも 1種の金属元 素を一般式 hM30 · A 12 03 で示される複合酸化物基体において 0.001 hから 0. lh添加することが出来る。 In addition, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), Erbium (Er), Gallium (Tm), Ytterbium (Yb), Lutetium (Lu), Manganese (Mn), Tin (Sn), Bismuth (Bi), Scandium (Sc) group of at least one metal elemental general formula hM 3 0 · a 1 2 0 in the composite oxide substrate represented by 3 can be 0. lh added from 0.001 h.
これら原料をボールミル、 V型混合機等を用い混合した後、 1，100から 1,800 にて数時間焼成する。 更に前記方法にて得られた生成物をボールミル、 ジェット ミル等を用い解碎した後、 洗浄するが、 必要に応じて分級する。 After mixing these materials using a ball mill, V-type mixer, etc., they are fired at 1,100 to 1,800 for several hours. Further, the product obtained by the above method is pulverized using a ball mill, a jet mill, or the like, and then washed, but classified if necessary.
更に蛍光体粒子への反応を促進するためフラックスを添加することも可能であ る。 フラックスとしては、 例えば酸化ホウ素が使用出来る。 Further, a flux can be added to promote the reaction to the phosphor particles. As the flux, for example, boron oxide can be used.
—次粒子径が 0.3/1 n以上で 30 μ m以下の実質的に破砕面を有しない α—アルミナ 粉末を原料に用いて得られた本発明による蓄光材用アルミン酸塩系蛍光体は、 粉 砕が容易で且つ微粒子が少ないため残光特性に優れ、 製品歩留りが高いため蓄光 材として極めて有用である。 The aluminate-based phosphor for a phosphorescent material according to the present invention obtained by using an α-alumina powder having a sub-particle diameter of 0.3 / 1 n or more and having substantially no crushed surface of 30 μm or less as a raw material, It is very useful as a phosphorescent material because it has excellent afterglow characteristics due to easy pulverization and few particles, and high product yield.
図面の簡単な説明 BRIEF DESCRIPTION OF THE FIGURES
図 1は α—アルミナ粉末（ A A 2 )の走査型電子顕微鏡写真による粒子形状を示 す図面である。 FIG. 1 is a drawing showing the particle shape of α-alumina powder (AA2) by a scanning electron micrograph.
図 2は ct—アルミナ粉末（ A Λ 3 )の走査型電子顕微鏡写真による粒子形状を示 す図面である。 図 3は α—アルミナ粉末（ A A 5 )の走査型電子顕微鏡写真による粒子形状を示 す図面である。 Figure 2 is a drawing showing the particle shape of the ct-alumina powder (A A3) by a scanning electron micrograph. FIG. 3 is a drawing showing the particle shape of α-alumina powder (AA5) by a scanning electron micrograph.
図 4は α—アルミナ粉末（ A A 10 )の走査型電子顕微鏡写真による粒子形状を 示す図面である。 FIG. 4 is a drawing showing the particle shape of α-alumina powder (AA10) by a scanning electron micrograph.
図 5は α—アルミナ粉末（R Λ -40 )の走査型電子顕微鏡写真による粒子形状 を示す図面である。 FIG. 5 is a drawing showing the particle shape of α-alumina powder (RΛ-40) by a scanning electron micrograph.
図 6 a及び図 6 bは ΑΛ 10を用いた蛍光体の走査型電子顕微鏡写真による粒 子形状を示す図面であり、 図 6 aは 2, 000倍、 図 6 bは 5, 000倍である。 6a and 6b are drawings showing the particle shape of the phosphor obtained by using a ΑΛ10 in a scanning electron micrograph, wherein FIG. 6a is 2,000 times and FIG. 6b is 5,000 times. .
図 7 a及び図 7 bは RA— 40を用いた蛍光体の走査型電子顕微鏡写真による 粒子形状を示す図面であり、 図 7 aは 2,000倍、 図 7 bは 5, 000倍である。 7a and 7b are drawings showing the particle shape of the phosphor using RA-40 by a scanning electron micrograph. FIG. 7a is 2,000 times, and FIG. 7b is 5,000 times.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
次に実施例により本発明を更に詳しく説明するが、 本発明はこれらの実施例に 限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例 1. 各種特性評価方法 Example 1. Various characteristic evaluation methods
1. α_アルミナ粉末の特性評価方法 1. Characteristic evaluation method of α_alumina powder
(1) α—アルミナ粉末の一次粒子径は、 α—アルミナ粉末の SEM (走査型電子顕 微鏡、 日本電子株式会社製： Τ- 300)写真から 80ないし 100個の粒子を選 び出して画像解析を行い、 円相当径の平均値を求めた。 円相当径とは、 面積が等 しい真円の直径に換算した値である。 (1) The primary particle size of α-alumina powder was determined by selecting 80 to 100 particles from a SEM (scanning electron microscope, JEOL Ltd .: Τ-300) photograph of α-alumina powder. Image analysis was performed to determine the average value of the circle equivalent diameter. The equivalent circle diameter is a value converted into the diameter of a perfect circle having the same area.
(2) α—アルミナ粉末の平均粒子径（D 50)及ぴ粒度分布（D 9 OZD 10)は、 レーザー散乱法を測定原理とするマスタ一サイザ一（マルバーン社製）を用いて測 定した。 (2) The average particle size (D50) and particle size distribution (D9OZD10) of α-alumina powder were measured using a master sizer (Malvern) using a laser scattering method as a measurement principle. .
( 3 ) α—アルミナ粉末の比表面積は Β Ε Τ法で測定した。 (3) The specific surface area of α -alumina powder was measured by the Β Ε method.
(4 ) α—アルミナ粉末の純度分析は発光分析装置（島津製作所製 CQM- 75) を用いて行った。 (4) The purity analysis of α -alumina powder was performed using an emission spectrometer (CQM-75 manufactured by Shimadzu Corporation).
2. アルミン酸塩系蛍光体の特性評価方法 2. Method for evaluating characteristics of aluminate phosphor
(1)アルミン酸塩系蛍光体の平均粒子径（X 50)及び粒度分布（X 9 ΟΖΧ 10) は、 レーザー散乱法を測定原理とする S Κレーザーミクロンサイザ一（セィシン企 業製）を用いて測定した。 (2)アルミン酸塩系蛍光体の粒子形状は走査型電子顕微鏡（日本電子株式会社製： T一 2 2 OA)を用いて撮影した。 (1) The average particle size (X50) and particle size distribution (X9ΟΖΧ10) of the aluminate-based phosphor were measured using an SΚ laser micron sizer (manufactured by Seishin Enterprise) using the laser scattering method as the measurement principle. Measured. (2) The particle shape of the aluminate phosphor was photographed using a scanning electron microscope (manufactured by JEOL Ltd .: T122OA).
(3)アルミン酸塩系蛍光体の発光強度は蛍光分光光度計（ォプトリサーチ社製）を 用いて測定した。 (3) The emission intensity of the aluminate-based phosphor was measured using a fluorescence spectrophotometer (made by Opto Research).
(4)残光特性を有するアルミン酸塩系蛍光体の残光強度は以下の方法により実施 した。 蛍光体粉末を試料容器に充填し（直径 38 mm， 厚さ 5mm)、 1 6時間暗 所に保管した後、 試料容器の 1 5 Omm高さに設置した蛍光灯を 1 0分間照射し た。 照射停止した後一定時間経過した時の残光強度を輝度計（松下電子工業照明 R &Dセンター製： 5 7 1 2型)及び光電管（浜松ホトニクス製： R 84 7型）を用い て測定した。 (4) The afterglow intensity of the aluminate-based phosphor having the afterglow characteristic was measured by the following method. The sample container was filled with the phosphor powder (diameter: 38 mm, thickness: 5 mm), stored in a dark place for 16 hours, and irradiated with a fluorescent lamp placed at a height of 15 mm for the sample container for 10 minutes. The afterglow intensity after a lapse of a certain time after the irradiation was stopped was measured using a luminance meter (manufactured by Matsushita Electronics Industrial Lighting R & D Center: 5712) and a phototube (Hamamatsu Photonics: R847).
本実施例で用いた一次粒子径が 0.3 μ m以上で 30/i Β以下の実質的に破砕面を有し ないひ一アルミナ粉末には、 住友化学工業株式会社から 「アドバンス トア ^レミ ナ J の商品名で販売されている前記表 1及び表 2に示す物性のアルミナ粉末を用 いた。 尚、 比較例としては、 RA— 40 (市販品；岩谷化学工業株式会社製）のァ ルミナ粉末を用いた。 各々の α—アルミナ粉末の走査型電子顕微鏡での粒子形状 を図 1〜図 5の図面代用写真に示す。 The Hi-Alumina powder having a primary particle diameter of 0.3 μm or more and having substantially no crushed surface of 30 / iΒ or less used in this example includes “Advanced Advanced Rem Alumina powder having the physical properties shown in Tables 1 and 2 sold under the trade name of Na J was used. As a comparative example, an alumina powder of RA-40 (commercial product; manufactured by Iwatani Chemical Industry Co., Ltd.) was used. The particle shapes of each α-alumina powder with a scanning electron microscope are shown in FIGS.
実施例 2. 蛍光体（B a0 eoE u o ,o)0 - gO · 5A 12〇3の作成 Example 2. Preparation of phosphor (B a 0 eoE uo, o) 0-gO · 5A 1 2 〇 3
α一アルミナ 2 4 7. 2 5 g α-alumina 2 4 7.25 g
炭酸バリウム 88.79 g Barium carbonate 88.79 g
塩基性炭酸マグネシウム 4 3. 5 3 g Basic magnesium carbonate 43.5 3 g
酸化ユーロピウム 8. 8 0 g Europium oxide 8.80 g
フッ化アルミニウム 1 2. 6 0 g Aluminum fluoride 1.2.6 g
α—アルミナに各々 AA 10或いは RA— 40を用いた前記原料をボールミル にて十分に混合し、 還元性雰囲気中 1，300 で 3時間焼成した後、 得られた酸化物 を粉砕した。 更にこの粉末を還元性雰囲気中 1,300¾で 3時間焼成し蛍光体を得 た。 The raw materials using AA10 or RA-40 were mixed sufficiently with α-alumina in a ball mill, fired at 1,300 in a reducing atmosphere for 3 hours, and the obtained oxide was pulverized. Further, this powder was fired in a reducing atmosphere at 1,300 ° C. for 3 hours to obtain a phosphor.
得られた蛍光体の組成式は次の通りであり、 各蛍光体の平均粒子径， 粒度分 布， 発光ピーク， 発光強度は次の表 3に示す。 尚、 発光強度は R A— 40を用い た蛍光体を 100%として計算した値である。 The composition formula of the obtained phosphor is as follows. The average particle size, particle size distribution, emission peak, and emission intensity of each phosphor are shown in Table 3 below. The emission intensity is a value calculated by assuming that the phosphor using RA-40 is 100%.
(B a uo. 10)O · MgO · 5 A 1203 (B a uo. 10 ) OMgO5 A 1 2 0 3
表 3 Table 3
また、 図 6 a及び図 6 bは AA 10を用いた蛍光体の走査型電子顕微鏡写真で の粒子形状の図面代用写真であり、 図 6 aは 2,000倍、 図 6 bは 5, 000倍である。 図 7 a及び図 7 bは RA— 40を用いた蛍光体の走査型電子顕微鏡写真での粒子 形状の図面代用写真であり、 図 7 aは 2,00(H&、 図 7 bは 5, 000倍である。 Figures 6a and 6b are scanning electron micrographs of the phosphor using AA10, which are substitutes for the drawing of the particle shape.Figure 6a is 2,000 times, and Figure 6b is 5,000 times. is there. Figures 7a and 7b are scanning electron micrographs of the phosphor using RA-40, which are substitutes for the drawing of the particle shape.Figure 7a is 2,000 (H &), and Figure 7b is 5,000. It is twice.
実施例 3. 蛍光体（Ce0 6S T b o 35)θ, .,■ Mg O · 5.5A 1203の作成 α—アルミナ 27 1. 98 g Example 3. phosphor (Ce 0 6S T bo 35) θ,., ■ creating a Mg O · 5.5A 1 2 0 3 α-alumina 27 1.98 g
酸化セリウム 5 5. 9 3 g Cerium oxide 5 5.93 g
塩基性炭酸マグネシウム 4 3. 5 3 g Basic magnesium carbonate 43.5 3 g
酸化テルビウム 3 1.4 8 g Terbium oxide 3 1.4 8 g
フッ化アルミニウム 1 3. 8 6 g Aluminum fluoride 1.3.8 g
ホウ酸 3. 1 1 g Boric acid 3.1 g
α—アルミナに各々 ΑΛ 2， ΛΑ 3, A A 5或いは R A— 4 0を用いた前記原 料をボールミルにて十分に混合し、 還元性雰囲気中 1， 300*t:で 2時間焼成した後、 得られた酸化物を粉砕した。 更にこの粉末を還元性雰囲気中 1,300 で 2時間焼成 した後、 粉砕時間を調整し蛍光体粉末の平均粒子径 X 50を約 8. 5 μ ΐηに揃え た。 The raw materials using ΑΛ2, ΛΑ3, AA5 or RA-40 are mixed well with α-alumina in a ball mill, and calcined in a reducing atmosphere at 1,300 * t: for 2 hours. The obtained oxide was pulverized. Further, after baking this powder at 1,300 in a reducing atmosphere for 2 hours, the pulverization time was adjusted to adjust the average particle size X50 of the phosphor powder to about 8.5 μΐη .
得られた蛍光体の組成式は次の通りである。 尚、 発光強度は R Α— 4 0を用い た蛍光体を 1 000 として計算した値である。 また、 これら蛍光体の特性を次の 表 4に示す。 The composition formula of the obtained phosphor is as follows. The emission intensity is a value calculated by assuming that the phosphor using R R-40 is 1 000. Table 4 below shows the properties of these phosphors.
(C eo. T b )Oi · Mg O · 5.5A 1 203 (C eo.T b) OiMg O5.5A 1 2 0 3
表 4 Table 4
前記結果の通り、 本発明によるアルミン酸塩系蛍光体は、 従来から用いられて いた高純度アルミナ R A— 40を原料に用いた蛍光体に比較し粉砕が容易で且つ シャープな粒度分布を有する。 しかも高い発光強度を示し、 極めて便れたアルミ ン酸塩系蛍光体である。 As described above, the aluminate-based phosphor according to the present invention has a sharp particle size distribution that is easier to pulverize as compared with a phosphor using conventionally used high-purity alumina RA-40 as a raw material. In addition, it is a very convenient aluminate-based phosphor that shows high emission intensity.
実施例 4. 蓄光性蛍光体（S r。 9., E u。《? D y »。 )0 · A 1 20:,の作成 a—アルミナ 98. 9 g (...?. S r 9, E u "D y») Example 4 phosphorescent phosphors 0 · A 1 2 0:, creating a- alumina 98. 9 g
炭酸ストロンチウム 2 74. 59 g 酸化ユーロピウム 7.04 g Strontium carbonate 2 74.59 g Europium oxide 7.04 g
酸化ジスプロシウム 1 8.05 g Dysprosium oxide 1 8.05 g
フッ化ァノレミニゥム 1 6.92 g Fluorinated Minimum 1 6.92 g
ホウ酸 4.67 g Boric acid 4.67 g
a—アルミナに各々 AA 2, ΑΑ 1 0或いは RA— 40を用いた前記原料をボ ールミルにて十分に混合し、 還元性雰囲気中 1,300 で 3時間焼成した後、 得られ た酸化物を粉砕した。 The above-mentioned raw materials using AA2, ΑΑ10 or RA-40 in a-alumina were sufficiently mixed by a ball mill, fired at 1,300 in a reducing atmosphere for 3 hours, and the obtained oxide was pulverized. .
得られた蛍光体の組成式は次の通りであり、 各蛍光体の平均粒子径， 粒度分 布， 残光強度等の特性を次の表 5に示す。 尚残光強度は R Α— 40を用いた蛍光 体を 100%として計算した値である。 The composition formula of the obtained phosphor is as follows. Table 5 shows the characteristics of each phosphor such as average particle size, particle size distribution, and afterglow intensity. Note that the afterglow intensity is a value calculated by assuming that the phosphor using R-40 is 100%.
(S r E u o.。2 D y o.。 )0 · A 12 O 3 (SrEuo..2Dyo ..) 0 · A12O3
表 5 Table 5
前記結果の通り、 本発明による蓄光材用アルミン酸塩系蛍光体は、 従来から用 いられていた高純度アルミナ R A— 40を原料に用いた蛍光体に比較し粉砕が容 易で且つシャープな粒度分布を有する。 しかも、 平均粒子径が小さいにもかかわ らず高い残光強度を示し、 極めて優れた蓄光材用アルミン酸塩系蛍光体である。 以上説明した通り、 本発明によれば、 粉碎が容易で且つ微粒子が少ないため発 光特性に優れ、 製品歩留りが高いアルミン酸塩系蛍光体を得ることが出来る。 こ のアルミン酸塩系蛍光体は 3波長形蛍光ランプ及び蓄光材用アルミン酸塩系蛍光 体として工業上極めて有用なものである。 As described above, the aluminate-based phosphor for a phosphorescent material according to the present invention is easier and more pulverizable than a phosphor using a high-purity alumina RA-40 used as a raw material. Has a particle size distribution. In addition, it has high afterglow intensity despite its small average particle size, and is an extremely excellent aluminate phosphor for phosphorescent materials. As described above, according to the present invention, it is possible to obtain an aluminate-based phosphor that is easily crushed and has a small amount of fine particles, has excellent light emission characteristics, and has a high product yield. This aluminate-based phosphor is industrially extremely useful as a three-wavelength fluorescent lamp and an aluminate-based phosphor for a phosphorescent material.
Claims
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8/224661 | 1996-08-08 | ||
| JP22466196A JP3599913B2 (en) | 1996-08-08 | 1996-08-08 | Method for producing aluminate phosphor for phosphorescent material |
| JP8/224662 | 1996-08-08 | ||
| JP22466296A JP3599914B2 (en) | 1996-08-08 | 1996-08-08 | Method for producing aluminate-based phosphor |
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| WO1998006793A1 true WO1998006793A1 (en) | 1998-02-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP1997/002739 Ceased WO1998006793A1 (en) | 1996-08-08 | 1997-08-07 | Process for the preparaiton of aluminate-base phosphor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1073089A1 (en) * | 1999-07-26 | 2001-01-31 | General Electric Company | Mn2+ activated green emitting SrAl12O19 luminescent material |
| EP1142976A3 (en) * | 2000-04-06 | 2003-07-23 | Sumitomo Chemical Company, Limited | Vacuum ultraviolet ray-excited light-emitting phosphor |
| EP1167489A3 (en) * | 2000-06-27 | 2003-09-17 | Sumitomo Chemical Company, Limited | Method for producing aluminate fluorescent substance, a fluorescent and a device containing a fluorescent substance |
| EP1220332A3 (en) * | 2000-12-22 | 2005-10-12 | Sanken Electric Co., Ltd. | A light permeable fluorescent cover for light emitting diode |
| WO2022168705A1 (en) * | 2021-02-05 | 2022-08-11 | 住友化学株式会社 | Phosphor and method for producing phosphor |
| WO2022168704A1 (en) * | 2021-02-05 | 2022-08-11 | 住友化学株式会社 | Phosphor production method and phosphor |
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| JPH05194946A (en) * | 1992-01-23 | 1993-08-03 | Toshiba Corp | Stimulable phosphor and fluorescent lamp prepared therefrom |
| JPH05230454A (en) * | 1992-02-21 | 1993-09-07 | Matsushita Electron Corp | Aluminate phosphor and fluorescent lamp made by using same |
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| JPH05194946A (en) * | 1992-01-23 | 1993-08-03 | Toshiba Corp | Stimulable phosphor and fluorescent lamp prepared therefrom |
| JPH05230454A (en) * | 1992-02-21 | 1993-09-07 | Matsushita Electron Corp | Aluminate phosphor and fluorescent lamp made by using same |
| JPH06191835A (en) * | 1992-06-02 | 1994-07-12 | Sumitomo Chem Co Ltd | Production of alpha-alumina |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1073089A1 (en) * | 1999-07-26 | 2001-01-31 | General Electric Company | Mn2+ activated green emitting SrAl12O19 luminescent material |
| EP1142976A3 (en) * | 2000-04-06 | 2003-07-23 | Sumitomo Chemical Company, Limited | Vacuum ultraviolet ray-excited light-emitting phosphor |
| EP1167489A3 (en) * | 2000-06-27 | 2003-09-17 | Sumitomo Chemical Company, Limited | Method for producing aluminate fluorescent substance, a fluorescent and a device containing a fluorescent substance |
| EP1220332A3 (en) * | 2000-12-22 | 2005-10-12 | Sanken Electric Co., Ltd. | A light permeable fluorescent cover for light emitting diode |
| WO2022168705A1 (en) * | 2021-02-05 | 2022-08-11 | 住友化学株式会社 | Phosphor and method for producing phosphor |
| WO2022168704A1 (en) * | 2021-02-05 | 2022-08-11 | 住友化学株式会社 | Phosphor production method and phosphor |
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