WO1999024528A1 - Phosphore, substance fluorescente produite a partir de phosphore et procedes de leur fabrication - Google Patents

Phosphore, substance fluorescente produite a partir de phosphore et procedes de leur fabrication Download PDF

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Publication number
WO1999024528A1
WO1999024528A1 PCT/JP1998/004054 JP9804054W WO9924528A1 WO 1999024528 A1 WO1999024528 A1 WO 1999024528A1 JP 9804054 W JP9804054 W JP 9804054W WO 9924528 A1 WO9924528 A1 WO 9924528A1
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WIPO (PCT)
Prior art keywords
phosphor
particle
length
particles
major axis
Prior art date
Application number
PCT/JP1998/004054
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English (en)
Japanese (ja)
Inventor
Shouzo Oshio
Teruaki Shigeta
Shigeru Horii
Tomizo Matsuoka
Koji Kitamura
Takeshi Nishiura
Original Assignee
Matsushita Electric Industrial Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP6463398A external-priority patent/JPH11199867A/ja
Application filed by Matsushita Electric Industrial Co., Ltd. filed Critical Matsushita Electric Industrial Co., Ltd.
Publication of WO1999024528A1 publication Critical patent/WO1999024528A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B11/00—Communication cables or conductors
    • H01B11/02—Cables with twisted pairs or quads
    • H01B11/06—Cables with twisted pairs or quads with means for reducing effects of electromagnetic or electrostatic disturbances, e.g. screens
    • H01B11/08—Screens specially adapted for reducing cross-talk

Definitions

  • the present invention relates to a lighting device such as a fluorescent lamp and a plasma display panel.
  • the present invention relates to a phosphor suitable for a light-emitting device such as a display device such as an electron tube (hereinafter abbreviated as a PDP) or an electron tube (hereinafter abbreviated as a CRT), and to a light-emitting device and a phosphor-containing material using the phosphor, as well as a method of manufacturing the phosphor.
  • a light-emitting device such as a display device such as an electron tube (hereinafter abbreviated as a PDP) or an electron tube (hereinafter abbreviated as a CRT)
  • PDP electron tube
  • CRT electron tube
  • various phosphors have been used for the light emitting device and the phosphor-containing material.
  • a phosphor that emits blue, green, and red light is used as the phosphor.
  • Europium-activated phosphors whose emission center is Eu 2+ such as BaMgA1 10O17: Eu 2+ or (Sr, Ba, Ca, g) 10 (P04) 6C 12: Eu 2+ in addition, a green phosphor as the C EMG a 1 n ⁇ 19: Tb 3+ and La P_ ⁇ 4: Ce 3+, Tb 3 + and (Ce, G d) Mg B s O 10: Tb 3+ , such as terbium-activated phosphor or a Ce to an emission center Tb 3+ ions (Mg, Z n) a 1 , ] O ⁇ 9: manganese activated phosphors with emission center Mn 2 +, such as Mn 2 + is, Further, as the red phosphor, Y 2 ⁇ 3: Eu 3 + and 3.
  • a non-localized luminescent center-type zinc sulfide phosphor is a non-localized luminescent center-type zinc sulfide phosphor using copper ions such as ZnS: Cu +, A13 + as an acceptor.
  • tiles and ash containing long afterglow phosphors are examples of phosphor-containing substances.
  • Solids such as dishes, adhesive tapes, seals, ropes, such as stationery, such as underlay or pencil, when describing the long afterglow phosphor-containing material as an example, to such long decay phosphor containing material,
  • An aluminum-containing oxide phosphor which is co-activated with Eu 2+ and Dy 3 + and Nd 3 + ions such as + is used.
  • the particle size of the phosphor is not uniform, and the maximum value of X is the particle length, where X is the distance from one point a on the particle surface to one point b on the particle surface different from a.
  • the major particle length of the phosphor particles with the longest major particle length is twice the major particle length of the phosphor particles with the shortest and major particle length.
  • large, medium, and small particles were composed of phosphor particles mixed randomly.
  • the average particle size of the phosphor for example, those in the range of 3 ⁇ m to 10 ⁇ are used for fluorescent lamps and PDPs, and those in the range of 1 ⁇ to 5 ⁇ are used for PDPs.
  • the phosphors containing aluminum used for long-afterglow phosphors have a range of 5 / m to 50 ⁇ .
  • the distance from one point a of the particle surface to one point b of the particle surface different from a is defined as X, and the maximum value of X is the particle major axis length.
  • the line connecting a to b is defined as the particle long axis, and the particle long axis
  • the c force and the distance from d to y are y
  • the minimum value of y is defined as the minor axis length of the particle.
  • B aM g A 1 Eu 2+
  • C eMg A InO Tb 3+
  • the particle length of the raw material particles used in the production is not uniform, and the particle length of the particle having the longest particle length is long. It was manufactured using phosphor raw material particles whose length was at least twice the particle major axis length of the particles having the shortest particle major axis length.
  • BaMgAl Conventionally o0 17:! Eu2 + in the method of manufacturing the blue phosphor, the phosphor raw material, barium carbonate (B ACOS) powder, basic magnesium carbonate (4MgC_ ⁇ 3 'Mg (OH) 2 ⁇ 3 ⁇ 2 ⁇ ) powder, Sani ⁇ Yu bite Piumu (Eu 2 0 3) powder, such as aluminum oxide (a 1 2 0 3) powder, powdered barium, magnesium, europium, aluminum raw material used I have been.
  • B ACOS barium carbonate
  • 4MgC_ ⁇ 3 'Mg (OH) 2 ⁇ 3 ⁇ 2 ⁇ ) powder 4MgC_ ⁇ 3 'Mg (OH) 2 ⁇ 3 ⁇ 2 ⁇ ) powder
  • Sani ⁇ Yu bite Piumu (Eu 2 0 3) powder such as aluminum oxide (a 1 2 0 3) powder, powdered barium, magnesium, europium, aluminum raw material used I have been.
  • the powder major axis of each of the powder particles constituting the powder is non-uniform, and the particles having the longest major axis length are used.
  • the length of the long axis of the particles was the shortest, and was twice or more the length of the long axis of the particles having the long axis of the particles.
  • each phosphor of aluminum oxide, barium carbonate, europium oxide and basic magnesium carbonate used in the conventional method for producing BaMg A 1, ⁇ ⁇ ⁇ : Eu 2 + blue phosphor Electron micrographs of the raw material powder are shown in FIGS. 10, 11, 12, and 13, respectively.
  • BaMg A 1 lOO ir: Eu 2 + blue phosphor has the particle major axis length of each powder particle which is non-uniform, and is composed of sodium, magnesium, europium, and aluminum.
  • Each raw material is weighed to a specified element ratio, mixed, and heated in a reducing atmosphere at a temperature in the range of 1400 ° C to 1900 ° C.
  • the longest particle length of the phosphor particles having the longest particle long axis length is twice the shortest particle length of the phosphor particles having the longest particle length.
  • Phosphor particles were used, in which large, medium and small particles were mixed randomly.
  • the phosphor-containing substance includes a phosphor-containing liquid, a phosphor-containing paste, a light-emitting device using the phosphor, and a phosphor-containing solid.
  • Examples of the phosphor-containing liquid material include a phosphor suspension and a phosphor-containing paint in which a resin is dissolved in a mixture of a phosphor, a low-melting substance (for example, a low-melting glass), an organic solvent, or water.
  • Examples of the phosphor-containing paste include a phosphor paste obtained by mixing an organic solvent into which the luster is dissolved and a phosphor.
  • Light emitting devices using the phosphor include lighting devices such as fluorescent lamps, PDPs, and the like. There are display devices such as and CRT.
  • Examples of the phosphor solid include various structures containing the phosphor, such as solid objects such as tiles and ashtrays, adhesive tapes, stickers, ropes, stationery such as underlays and pencil cases, and the like.
  • a phosphor film in which the phosphor is formed into a film with a thickness of 10 On m to several cm is also included in the phosphor-containing material.
  • the phosphor-containing material may be a combination of a substance other than a phosphor, such as a solution of plastic, rubber, epoxy resin, timber, paper, fiber, soil, an organic solvent or water, or a phosphor. It is manufactured by arranging phosphor particles in a shape.
  • conventional phosphors have a non-uniform particle size, which means that phosphors containing phosphors of the desired particle size (solids such as tiles and ashtrays, adhesive tapes, seals, ropes, It is difficult to construct various structures such as stationery such as an underlay and a pencil case, a light emitting device, a fluorescent film, a phosphor suspension, and a phosphor paste).
  • the phosphor-containing material has an optimum particle size depending on its use, properties, and shape, it is difficult to construct a phosphor-containing material having the desired particle size using a conventional phosphor.
  • phosphors with a specific particle size must be sorted out by pre-work such as sieving, which is not only time-consuming, but also results in poor phosphor powder utilization efficiency. was there.
  • conventional phosphors have a large specific surface area due to non-uniform particle size, containing small particles, and non-spherical particle shapes.
  • a phosphor-containing material is formed, there is a problem that the phosphor deteriorates due to various damage factors. (Details will be described later).
  • the particle size is non-uniform, so there is a problem that the phosphor film formed by using the phosphor paste may have large uneven emission, and even with the phosphor-containing paint, there is a large uneven emission in the coated material after coating. There was a problem that occurred.
  • the phosphor-containing solid there is a problem that the internal strain of the solid is easily increased due to the non-uniform particle size, and the solid is fragile, vulnerable to external impact, and easily broken.
  • the phosphor particles have non-uniform particle sizes, and as a result, the phosphor powder has a large specific surface area. Since the light emitting device is configured using the light emitting device, various types of damage to the phosphor are large. When the light-emitting device is operated for a long time, there is a problem that the light-emitting intensity of the light-emitting device is reduced or the light emission color is changed due to the impact of an electron beam or an ultraviolet dion.
  • the phosphor is constantly irradiated with an electron beam during operation.
  • the phosphor surface is damaged by electron beam irradiation and accompanying heating, and is gradually deteriorated to deteriorate light emission performance.
  • the phosphor In fluorescent lamps and PDPs, the phosphor is hit by ions of rare gases such as Ar, Ne, and Xe during operation, or is exposed to ultraviolet light. For this reason, the surface of the phosphor is gradually deteriorated due to the damage due to the sputtering or the damage due to the irradiation of the ultraviolet rays, and the light emission performance is reduced.
  • Such damage caused by sputtering and ultraviolet irradiation is a problem that is more noticeable in phosphors having a large specific surface area, that is, phosphors having a small particle size.
  • Conventional phosphors have a non-uniform particle size and contain small particle size phosphors, especially fine particle phosphors that are extremely susceptible to damage. Is said to be strongly affected.
  • a particle size other than the desired particle size exists. Since the phosphor is manufactured using the phosphor containing particles, the phosphor having an undesired particle size is included in the phosphor-containing material. For this reason, a phosphor-containing material for a desired use cannot be produced, a phosphor-containing material having a desired property cannot be produced, or a phosphor-containing material having a desired shape cannot be produced. There were challenges.
  • the present invention has been made based on this finding, and has a particle size that is optimal for various phosphor-containing materials, and has a small percentage of various damages on the phosphor, and has a uniform particle size, particularly a spherical particle having a uniform size.
  • the present invention has been made to provide a phosphor having a particle shape and a method for producing the same.
  • phosphor-containing materials that do not cause various troubles such as the above uneven emission or damage due to external impact, as well as light-emitting devices such as fluorescent lamps, PDPs, and CRTs that do not degrade their fluorescent characteristics during the manufacturing process or during operation And a method for manufacturing the same.
  • the particle size of the phosphor is made uniform, and the distance from one point a of the particle surface to one point b of the particle surface different from a is determined.
  • the maximum value of X is defined as the major axis length of X
  • the longest particle The major axis length of the phosphor particles having the major axis length is 1 to 2 times, preferably 1 to 1 times the major axis length of the phosphor particles having the shortest major axis length. . Maintain phosphor particles within the range of up to 2 times.
  • the shape of the phosphor particles is spherical or substantially spherical, and the distance from one point a of the particle surface to one point of the particle surface different from a is X, and X
  • the maximum value is defined as the particle major axis length
  • the line segment connecting a and b at this time is defined as the particle major axis segment
  • the two points where the vertical bisector of the particle major axis intersects the particle surface are defined as , C and d
  • the distance from c to d is y
  • the minimum value of y is defined as the minor axis length of the particle, 0.5 ⁇ (particle minor axis length Z particle length axis length) ⁇ 1. Satisfy 0.
  • each of the phosphor particles constituting the phosphor particle group has a uniform particle major axis length, and the phosphor major particle having the longest particle major axis length has the largest particle major axis length.
  • Fluorescence mainly composed of phosphor particles having a length in the range of 1 to 2 times, preferably 1 to 1.2 times the particle long axis length of the phosphor particles having a short particle length and a particle long axis length. You may comprise a body combining two or more types.
  • the phosphor material is preferably an aluminum-containing oxide phosphor, and the main composition formula is (Ml-vEuv) (Mgl-wMnw) x A1yOz (where M is B a, S r, C a, and Mg represent alkaline earth elements, and v, w, x, y, and z are 0 ⁇ ⁇ 0.6, 0 ⁇ w ⁇ 0.
  • V is 0 ⁇ v ⁇ 0.6 and y and z are numbers that satisfy ly ⁇ 17 and 2 ⁇ z ⁇ 30.
  • ReNxA l yOz (where Re is Sc, Y, La , Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, a rare earth element group composed of at least one of the following elements, and N is Mg X, y, and z are 0.8 ⁇ x ⁇ l.2, 9 ⁇ y ⁇ 13, and 15 respectively.
  • Re Al y ⁇ z (where Re is Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho , Er, Tm, Yb, Lu, a rare earth element group composed of at least one or more elements, and y and z are each 0.3. A numerical value that satisfies 2 ⁇ z 5 is recommended.
  • the particle long axis length of the particles is uniform, and the particle length axis of the particles having the longest particle length and the particle long axis length of the main particles is large.
  • Length force The shortest particle among the main particles, the particle of the particle having the particle long axis length in the range of 1 to 2 times the particle long axis length ⁇ , preferably 1 to 1.2 times
  • the phosphor is manufactured by using the phosphor raw material in the range (1).
  • a phosphor mainly composed of spherical or substantially spherical particles that satisfies 0.5 ⁇ (particle minor axis length / particle major axis length) ⁇ 1.0, 0.5 ⁇ (Shorter length of particle / Length of major axis of particle)
  • a phosphor is produced using a phosphor material mainly having a spherical or substantially spherical particle shape that satisfies 0.
  • the phosphor may be manufactured using a mixed phosphor material obtained by combining two or more kinds of phosphor materials having the same major axis length of the particles.
  • the phosphor to be produced is preferably an aluminum-containing oxide phosphor.
  • the particle long axis length of the particles is uniform, and the particle long axis length of the particle having the longest particle long axis length is the shortest particle long axis length.
  • the phosphor raw material containing acid aluminum having a uniform particle major axis length is used in the range of 140 ° C. or more and 1900 ° C. or less, preferably 150 ° C. or more and 1 ° C. or more. It is preferable to heat at a temperature in the range of 800 ° C. or less.
  • the heating may include heating in a reducing atmosphere.
  • the phosphor-containing material of the present invention includes phosphor-containing materials (solids such as tiles and ashtrays, various structures such as stationery such as adhesive tapes, stickers, ropes, underlays and pencil cases, light emitting devices, The phosphor film, the phosphor suspension, and the phosphor paste are also included in the above.)
  • the phosphor having the longest particle major axis length and the phosphor having the shortest particle major axis length The phosphor is configured so that the phosphor particles in the range of 1 to 2 times, preferably 1 to 1.2 times the particle major axis length of the particles contain the main phosphor.
  • the phosphor may have a spherical or substantially spherical particle shape that satisfies 0.5 ⁇ (particle short axis length / particle long axis length) ⁇ 1.0. Further, in the method for producing a phosphor-containing material of the present invention, the phosphor particles having the longest particle major axis length have a particle major axis length of the fluorescent substance having the shortest particle major axis length.
  • a phosphor mainly composed of phosphor particles in the range of 1 to 2 times, preferably 1 to 1.2 times the major axis length of the body particles, more preferably, 0.5, (Shorter particle length Z Particle major axis length)
  • the phosphor-containing material is manufactured using a phosphor having a spherical or substantially spherical particle shape satisfying ⁇ 1.0.
  • FIG. 1 is a view showing a phosphor particle group of the present invention and a phosphor raw material particle group according to the production method.
  • FIG. 2 is a view showing a phosphor particle group of the present invention and a phosphor raw material particle group according to the production method.
  • FIG. 3 is a view showing a phosphor particle group of the present invention and a phosphor raw material particle group according to the production method.
  • FIG. 4 is an electron micrograph of an aluminum oxide phosphor raw material powder according to the phosphor production method of the present invention.
  • FIG. 5 is an electron micrograph of a raw material powder of silicone resin fine particle phosphor according to the method for producing a phosphor of the present invention.
  • FIG. 6 is an electron micrograph of a silicon dioxide phosphor raw material powder according to the phosphor production method of the present invention.
  • FIG. 7 is a flowchart showing a method for producing an aluminum-containing phosphor according to the method for producing a phosphor of the present invention.
  • FIG. 8 is a schematic diagram showing the phosphor-containing material of the present invention.
  • FIG. 9 is a schematic view showing a light emitting device according to the phosphor-containing material of the present invention.
  • FIG. 10 is an electron micrograph of an aluminum oxide phosphor raw material powder according to a conventional phosphor production method.
  • FIG. 11 is an electron micrograph of a barium carbonate phosphor raw material powder according to a conventional phosphor production method.
  • FIG. 12 is an electron micrograph of a europium oxide phosphor raw material powder according to a conventional phosphor production method.
  • FIG. 13 is an electron micrograph of a basic magnesium carbonate phosphor raw material powder according to a conventional phosphor production method.
  • FIG. 14 is an electron micrograph of the BaO.9EuO.lMgA110.17 europium activated phosphor of Example 1 according to the present invention.
  • Figure 1 5 is an electron micrograph of a conventional B a O. 9 E u O. 1 M g A 1 1 0 ⁇ 1 7 europium-activated phosphor.
  • FIG. 16 shows the relationship between the sintering temperature and the luminance according to the method for producing a phosphor of Example 1.
  • FIG. 17 is an electron micrograph of the phosphor after firing at 180 ° C. according to the method for producing the phosphor of Example 1.
  • FIG. 18 shows the relationship between the heat treatment temperature in air and the luminance of the phosphor of Example 1.
  • FIG. 19 shows the relationship between the atmospheric heat treatment temperature of the phosphor of Example 1 and the chromaticity coordinate y value.
  • FIG. 20 shows the relationship between the ion bombardment time applied to the phosphor of Example 1 and the chromaticity coordinate y value.
  • FIG. 21 shows the relationship between the UV irradiation time applied to the phosphor of Example 1 and the chromaticity coordinate y value.
  • FIG. 22 shows the relationship between the lighting time of the fluorescent lamp of the first embodiment and the chromaticity coordinate y value.
  • FIG. 23 shows the relationship between the particle size uniformity index and the luminance maintenance ratio of the phosphor of Example 1.
  • FIG. 24 shows the relationship between the average particle sphericity and the luminance retention rate according to the phosphor of Example 1.
  • FIG. 25 shows BaO.9EuO.1MgA1! Of Example 1. ⁇ 17 europium activated phosphor emission spectrum.
  • FIG. 26 is an electron micrograph of a conventional phosphor.
  • FIG. 1 is a diagram illustrating a phosphor particle group of a phosphor according to an embodiment of the present invention.
  • the phosphor is composed of phosphor particles having a uniform particle major axis length xmax (m) of each particle.
  • the length of the major axis of the phosphor particles having the longest major axis length is 1 to 2 times that of the phosphor particles having the shortest major axis length.
  • the phosphor is configured by limiting the particle size distribution of each phosphor so as to fall within the range up to, and preferably within the range of 1 to 1.2 times.
  • FIG. 1 shows the case of a phosphor having an elliptical particle shape.
  • the force can be similarly applied to other particle shapes such as a disk shape and a hexagonal plate shape.
  • FIG. 2 is also a diagram illustrating a phosphor particle group of the phosphor according to the present invention.
  • the distance from one point a (m) on the particle surface to one point b (m) on the particle surface different from a (m) is x (m)
  • the maximum value of X (m) is the particle length.
  • the axis length Xm ax (m), and the line connecting a (m) to b (m) at this time is defined as the particle long axis, and the particle long axis length Xm a X (m) of each particle is uniform
  • the two points where the perpendicular bisector of the particle major axis intersects the particle surface are c (m) and d (m), respectively, and c (m) to d
  • the distance to (m) is defined as y (m)
  • the minimum value of y (m) is defined as the particle minor axis length Ymin (m)
  • the phosphor is configured so as to satisfy (Ymin (m)) Z major axis length (Xmax (m))) ⁇ 1.0.
  • the phosphor is composed of particles having a uniform particle diameter and a spherical or substantially spherical particle shape.
  • the length of the major axis of each phosphor particle and the ratio of the minor axis length to the major axis length of each phosphor particle are limited.
  • FIG. 3 also shows an example of a phosphor particle group of the phosphor according to the present invention.
  • the first phosphor particle group, the second phosphor particle group, and the third phosphor particle group are phosphor particles described with reference to FIG. 1 or FIG. 2, each having a different average particle diameter. Group. That is, FIG. 3 shows that the phosphor according to the present invention is composed of a plurality of phosphor particle groups having a uniform particle diameter.
  • all of the phosphors of the first phosphor particle group, the second phosphor particle group, and the third phosphor particle group are 0.5 ⁇ (particle short axis length Z particle length
  • the present invention can be similarly applied to other particle shapes.
  • the phosphor materials of the first phosphor particle group, the second phosphor particle group, and the third phosphor particle group are not limited, but all are the same phosphor material. The same can be applied to the case where all the phosphor materials are different.
  • the average particle size of the first phosphor is set to be larger than the average particle size of the second phosphor, and the average particle size of the second phosphor is set to be larger than that of the third phosphor. It is feasible to make it much larger than the particle size. In this case, even if the first phosphor, the second phosphor, and the third phosphor are mixed, each phosphor can be easily separated.
  • Table 1 is a table summarizing the composition formulas of representative phosphors according to the present invention, each of which is composed of phosphor particles having a uniform particle major axis length. ⁇ table 1 ⁇
  • M is an alkaline earth metal group composed of Ba, Sr and C Mg.
  • Re is a rare earth element group composed of at least one or more of a, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y ⁇ LL ⁇ on Sc, Y .
  • N is composed of at least one element among Mg, Zn, and Mn.
  • Table 1 shows that one of the phosphors according to the present invention has a composition formula of (Ml—vEuv) (Mg 1 -wMn w) x A 1 y ⁇ z (where M is Ba, Sr, Ca, M Indicate the group of alkaline earth elements composed of g, and v, w, x, y, and z are 0 ⁇ v ⁇ 0.6, 0 ⁇ w ⁇ 0.6, 0.8 ⁇ x ⁇ 1.
  • a numerical value that satisfies 2, 8 ⁇ y ⁇ 12, 14 ⁇ z ⁇ 20) is an aluminum-containing oxide phosphor mainly composed of: (Ml—vMnv) Al yOz Composition formula (where M is an alkaline earth element group composed of Ba, Sr, Ca, and Mg.
  • V,, and z are 0 ⁇ v ⁇ 0.6, 8 ⁇ y ⁇ 18, 13 ⁇ z ⁇ 28.
  • M represents an alkaline earth element group composed of Ba, Sr, Ca, and Mg
  • v, y, and z are each 0 ⁇ v 0.6, 1 ⁇ y ⁇ 17, 2 ⁇ z ⁇ 30.
  • This is an aluminum-containing oxide phosphor mainly composed of), and another is a composition formula of ReNxAl yOz ( However, 6 is 3.
  • N represents a group of elements composed of at least one of Mg, Zn, and Mn, and x, y, and z each represent 0.8 ⁇ x ⁇ l.2, 9 ⁇ y ⁇ 13, 15 ⁇ z23.
  • y, z is People, 0. 3 ⁇ y ⁇ 2, 2 ⁇ z ⁇ 5.
  • Table 1 shows that, as the phosphor according to the present invention composed of phosphor particles having a uniform particle major axis length of each particle, the above-mentioned (Ml) containing Dy 3+ ions or Nd 3+ ions as impurities.
  • a 1 y O z composition formula (where M indicates an alkaline earth element group composed of Ba, Sr, Ca, and Mg. V, y, and z are each 0 The values satisfy v ⁇ 0.6, 1 ⁇ y ⁇ 17, 2 ⁇ z ⁇ 30.) It also indicates that there is an aluminum-containing oxide phosphor mainly composed of).
  • the phosphor of the present invention is composed of phosphor particles having a uniform particle major axis length of each particle, and the phosphor major particle having the longest particle major axis length has the shortest particle major axis length. Since the particle size distribution of each phosphor is limited so as to be within the range of 1 to 2 times the particle long axis length of the phosphor particles having the particle long axis length, various phosphor-containing substances ( Solids such as tiles and ashtrays, adhesive tapes, stickers, ropes, various structures such as stationery such as underlays and pencil cases, light-emitting devices, phosphor films, phosphor suspensions, and phosphor pastes). A phosphor having an optimum particle size can be provided.
  • a phosphor that has a small specific surface area and a low rate of being subjected to various impacts, and does not deteriorate in light emission characteristics during manufacture or operation of a light emitting device such as a fluorescent lamp, PDP, and CRT.
  • FIGS. 1, 2, and 3 described in the first embodiment are also diagrams showing phosphor raw material particles used in the production of the phosphor according to the phosphor production method of the present invention.
  • FIG. 1 is a view showing a phosphor raw material particle group used in the production of a phosphor according to the phosphor production method of the present invention.
  • the phosphor raw material is composed of phosphor raw material particles having a uniform particle major axis length X max (m) of each particle. That is, the particle length of the phosphor raw material particles having the longest particle long axis length is from 1 to 2 times the particle long axis length of the phosphor material particles having the shortest particle long axis length.
  • the phosphor raw material is configured by limiting the particle size of the phosphor raw material so as to be within the range of up to twice. Note that all the phosphor raw materials used in the production of the phosphor have the above-described phosphor raw material particles having the longest particle long axis length having the shortest particle long axis length. It is not necessary to use a phosphor material whose particle size is limited so that it is within the range of 1 to 2 times the major axis length of the phosphor material particles. It is sufficient that at least one of the plurality of types of phosphor raw materials used is a phosphor raw material having a limited particle size. In the production method of the present invention, as shown in FIG.
  • FIG. 2 is a view showing a phosphor raw material particle group used in the production of a phosphor according to the phosphor production method of the present invention.
  • the maximum value of X (m) is defined as xma x (m), the length of particle long axis, and b (m) from a (m) at this time.
  • the minimum value of y (m) is defined as the particle minor axis length ym in (m), and the particle shape is 0.5 ⁇ (particle minor axis length / particle major axis length) ⁇ 1
  • the phosphor material is configured so as to satisfy 0.0. That is, the particle major axis length and the particle minor axis length are limited so that the particle shape of the phosphor raw material having a uniform particle diameter is spherical or substantially spherical.
  • FIG. 3 is a view showing a phosphor raw material particle group used in producing a phosphor according to the production method of the present invention.
  • FIG. 3 shows, as an example, a case of a mixed phosphor material in which three kinds of phosphor particle groups are mixed, and the mixed phosphor material is mixed with a first fluorescent material having an average particle size s 1 and a uniform particle size.
  • the phosphor raw material as shown in FIGS. 1 and 2 is, for example, sold under the trade name of Sumikoundum (Advanced Alumina) manufactured by Sumitomo Chemical Co., Ltd.
  • Aluminum oxide powder Figure 4 shows an electron micrograph
  • Toshiba Silicone Co., Ltd. under the trade name Tospearl and fine particles of silicone resin
  • Figure 5 shows an electron micrograph
  • Ube Silicon dioxide powder sold by Nitto Kasei Co., Ltd. under the trade name of High Pressure
  • FIG. 7 is a flowchart showing a method for producing an aluminum-containing oxide phosphor according to the present invention.
  • FIG. 7 shows that the method for producing an aluminum-containing oxide phosphor according to the present invention is performed at a temperature in the range of 140 ° C. or more and 1900 ° C. or less, preferably 1550 ° C. This indicates that the method includes a heating step of heating at a temperature in the range of 180 ° C. or less.
  • FIG. 7 also shows that the method for producing an aluminum-containing oxidized phosphor according to the present invention includes a heating step of heating in a reducing atmosphere.
  • the method for producing a phosphor of the present invention uses a phosphor raw material in which each particle has a uniform particle major axis length, and the phosphor particles having the longest particle major axis length have the smallest particle major axis length.
  • Phosphor whose particle size distribution is limited so as to be within the range of 1 to 2 times, preferably 1 to 1.2 times the particle long axis length of the phosphor particles having a long axis length Since the phosphor is manufactured using the raw material, it is possible to manufacture a phosphor having a particle size optimal for various phosphor-containing materials and various light emitting devices.
  • a phosphor material having a uniform particle major axis length of each particle used, but also a phosphor material having a spherical or substantially spherical particle shape is produced.
  • Manufacture phosphors of uniform particle size with particle shape It can also be made.
  • the method for producing an aluminum-containing oxide phosphor according to the present invention is described below.
  • 1 4 0 0 ° C over 1 9 0 0 D C following range temperature ⁇ preferably 1 5 5 0 ° temperature pressurized heat heating process and reduction in the 1 8 0 0 ° C or less the range of C
  • the method may include a heating step of heating in an atmosphere, for example, a method of manufacturing a phosphor including a heating step in which the heating temperature is divided into several sections, and a fluorescent method including a heating step in which the heating atmosphere is divided into several sections.
  • Other phosphor production methods such as a method for producing a phosphor, a method for producing a phosphor to which a phosphor grinding step and a phosphor washing step are added, can be similarly performed.
  • the above heating temperature is not less than 140 ° C and not more than 190 ° C Must be set within the range.
  • FIG. 8 is a diagram showing a phosphor-containing material of the present invention.
  • phosphor 1 has a function of emitting fluorescence, and includes at least the phosphor having a uniform particle diameter described in the first embodiment.
  • the substance 2 is a solid or liquid or a liquid substance or a paste-like substance, and plays a role of dispersing or holding the phosphor 1.
  • the substance 2 corresponds to a body, an organic solvent in which a resin is dissolved, or a liquid substance in which a liquid substance is mixed with the above solid substance such as paint or paste.
  • Phosphor 1 emits fluorescence when irradiated with ultraviolet rays, electron beams, X-rays, or infrared rays, or when excited by an external stimulus such as application of an electric field, pressurization, or heating. Irradiation with ultraviolet rays, electron beams, X-rays, etc.) excites the phosphor contained in the phosphor-containing material, causing the phosphor-containing material to emit fluorescence.
  • the phosphor-containing material of the present invention contains a phosphor in which the major axis length of each particle is uniform, only a phosphor having a particle size that is optimal for the desired use, properties, and shape of the phosphor-containing material Can be provided.
  • the particle size of the phosphor of the phosphor-containing material is uniform, it is possible to reduce the unevenness of light emission of the fluorescent film. It is possible to provide a phosphor-containing coating that can be reduced, and a phosphor-containing solid that is resistant to external impact.
  • Examples of the phosphor-containing material according to the present invention include solid materials such as tiles and ashtrays, adhesive tapes, seals, ropes, stationery such as underlays and pencil cases, phosphor-containing paints, light-emitting devices described in Embodiment 4, There are a wide range of products such as membranes, phosphor suspensions, and phosphor bases, but other phosphor-containing materials can also be used.
  • the particle major axis length is uniform. Since the phosphor-containing material is manufactured using a phosphor, the phosphor-containing material having a phosphor having a uniform particle major axis length can be manufactured.
  • FIG. 9 is a schematic view showing a light emitting device of the present invention.
  • phosphor 1 has a function of emitting fluorescence 3, and includes at least the phosphor having a uniform particle diameter described in the first embodiment.
  • the excitation source 4 has a role of emitting an excitation beam 5 such as an ultraviolet ray, an electron beam, or an X-ray, and represents a radiation source such as an ultraviolet light source, an electron source, or an X-ray source.
  • the phosphor 1 Since the phosphor 1 has a function of emitting fluorescence when irradiated with the excitation ray 5, when the phosphor 1 is irradiated with the excitation ray 5 (ultraviolet ray, electron beam, X-ray, etc.), the phosphor 1 is excited to emit fluorescence. Starts firing 3.
  • the light emitting device is configured using a phosphor having a uniform particle size, that is, a small particle that is easily damaged, in particular, a phosphor that does not include a fine particle phosphor that is extremely easily damaged, Percentage of various types of damage to the phosphor during the manufacturing process of the light-emitting device or during operation of the light-emitting device (for example, phosphor during the manufacturing process Damage due to oxidation during the heating process, or fluorescent light during the operation of the light-emitting device It is possible to reduce the amount of damage to the body caused by electron beams, ultraviolet rays, and ion bombardment, and to reduce the problem that the fluorescence characteristics (e.g., emission intensity and emission color) of the light-emitting device change over time.
  • a phosphor having a uniform particle size that is, a small particle that is easily damaged, in particular, a phosphor that does not include a fine particle phosphor that is extremely easily damaged
  • a phosphor having a particle shape close to a spherical shape and a uniform particle size that is, a specific surface area can be further reduced than the above, and various kinds of damage ratios which the phosphor suffers during the manufacturing and operation of the light emitting device) Fluorescent material)
  • the problem that the light emitting characteristics of the light emitting device deteriorate during manufacturing or change during operation can be further reduced.
  • the light emitting device includes a fluorescent lamp, a PDP, and a CRT, but other light emitting devices can be similarly implemented.
  • Example 1 of the phosphor according to the present invention and the method for producing the same wherein the main peak wavelength of light emission is around 450 nm, the average particle size is 5 ⁇ m, and a particle a different from a from one point a of the particle surface
  • the particle length axis length of each phosphor particle constituting the phosphor particle group is uniform and the longest length
  • the length of the major axis of the phosphor particles having the major axis length is the shortest, and ranges from 1 to 1.2 times the major axis length of the phosphor particles having the major axis length.
  • BaO.9 E mainly composed of phosphor particles inside and having a particle shape satisfying 0.5 ⁇ (particle short axis length / particle long axis length) ⁇ 1.0 uO.lMg A 1 10-17 Europium-activated phosphor will be described.
  • This phosphor is used for three-wavelength fluorescent lamps and PDPs, and emits blue light.
  • the particles mainly consist of particles with a uniform particle size in the range of 1 to 1.2 times the particle major axis length of the particles, and the particle shape is 0.5 ⁇ (particle minor axis length 25.50 g of approximately spherical aluminum oxide (average particle size: 4.6 ⁇ , purity: 99.9%) satisfying ⁇ 1.0.
  • substantially spherical aluminum oxide was obtained from Sumitomo Chemical Co., Ltd. under the trade name "Advanced Alumina (Sumicorundum) IV-5" ( Figure 4 shows an electron micrograph). .
  • fluoride such as A 1 F 3, MgF 2, Ba F 2, EuF 3 as the reaction accelerator was used.
  • Figure 10 is an electron micrograph of the aluminum oxide material, also, for reference Figures 11, 12, and 13 show electron micrographs of barium carbonate raw material, europium oxide raw material, and basic magnesium carbonate raw material.
  • the conventional Ba 0.9 EuO. LMg A 1 io 0 17 europium-activated fluorescence is used.
  • the barium carbonate raw material (Fig. 11), the europium oxide raw material (Fig. 12), and the basic magnesium carbonate raw material (Fig. 13) used in the body production method were used.
  • the mixed powder is fired in a reducing atmosphere at 1600 ° C (in a mixed gas atmosphere of nitrogen and hydrogen) using an atmosphere furnace, and BaO.9Eu 0.1 lMg A 11 (3 to 17 europium activated phosphor was synthesized.
  • Figure 14 is an electron micrograph of the thus according to the present invention synthesized by B a0.9 EuO. 1 Mg A 1 1Q ⁇ 17 europium-activated phosphor.
  • Um in a conventional B a0.9 E u0 lMg A 1 10 O An electron micrograph of the 17 europium activated phosphor was shown.
  • the conventional B a0.9 E u0.1 Mg A 1 1 () 0 17 europium-activated phosphor, a mixed particle size, the longest record, particles
  • the longest particle length of the particles having the longest axis length was at least twice as long as the longest particle length of the particles having the longest particle length, and the particle shape was plate-shaped.
  • the Ba 0.9 EuO.1Mg A 1 Ow europium activated phosphor of the present invention has a uniform particle size, and the particle having the longest particle long axis has a particle long axis length of: Particles that are within the range of 1 to 1.2 times the particle long axis length of the particles having the shortest particle long axis length are mainly used, and the particle shape is 0.5 ⁇ ( Particle minor axis length Z Particle major axis length) It is a substantially spherical shape satisfying 0.
  • the particle shape of the europium-activated phosphor is the particle shape of the aluminum oxide powder used as the phosphor raw material when the above reaction accelerator is not used. Determined by shape and particle size. That is, the longest particle length of the particles having the longest longest particle length is the shortest! /, And the length of the longest particle length of the particle having the longest particle length is 1 to 1.2 times the length of the longest particle.
  • Substantially spherical aluminum oxide that satisfies 0.5 ⁇ (particle minor axis length / particle major axis length) ⁇ 1.0 with particles mainly within the range (average particle size 4 . 6 / zm) of the case of the embodiment 1 was used as a phosphor raw material, B AO.9EuO after synthesis.
  • LMG a 1 10 ⁇ 17 Yuropi ⁇ beam-activated phosphors, the longest particle major axis length
  • the particles having a length of 1 to 1.2 times the particle length of the particles having the shortest particle length
  • the phosphor was a substantially spherical phosphor having a particle shape satisfying 0.5 ⁇ (particle minor axis length / particle major axis length) 0, and the average particle diameter was 5.0 inches.
  • the particle shape and particle size of the BaO.9EuO.lMgAl ⁇ C? Europium-activated phosphor were determined by the particle shape and particle size of the aluminum oxide powder as the phosphor raw material.
  • the reason is that, because aluminum oxide is a chemically stable material, the particles are used as a nucleus to react with other phosphor raw materials (ie, barium carbonate, europium oxide, basic magnesium carbonate). It is considered that the reaction occurred and the phosphor was generated.
  • B aO.9EuO. LMg A 1 1 () is a scatter diagram showing the relationship ⁇ 17 and Brightness of europium-activated phosphor and firing temperature.
  • Figure 16 shows, for comparison, a conventional BaO.9 EuO.lMg A 1 ⁇ C? Particle size is non-uniform, the particle shape is plate-like, and the average particle size is 5 ⁇ m.
  • the brightness level of the europium-activated phosphor is shown by a dotted line.
  • B aO.9 E uO by using the manufacturing method of the present invention.
  • LMg A 1 10 The brightness of the 7 europium activated phosphor was found to increase as the firing temperature was increased.
  • BaO.9EuO.1 BaO.9EuO.1
  • Mg A 1 1 () ⁇ 17 luminance europium-activated phosphor is rapidly increased with increasing firing temperature in the firing temperature range up to 1400 ° C, 1400 ° C in a conventional B a 0.9 E uO.
  • LMg A 1 ,. 0 17 exceed 85 percent europium-activated phosphor luminance level of 75% to reach 1550 ° C of, 1700 ° C in a conventional B a 0.9 E u 0.1
  • the firing temperature in order to produce a BaO.9 EuO.lMg A1OW europium-activated phosphor with high brightness and uniform particle size, the firing temperature must be between 1400 ° C and 1900 ° C. Preferably, it is necessary to set the temperature to 1550 ° C or higher and 1800 ° C or lower.
  • Table 2 a firing atmosphere as air and reducing atmosphere (a mixed gas Kiri ⁇ gas of nitrogen and hydrogen), 1 600 ° was synthesized at a sintering temperature of C B aO.9EuO. LMg A 1 10 O i 7 activated phosphor europium It is a comparative table which compared the brightness of a body relatively. [Table 2]
  • Table 2 shows that the luminance can be significantly improved by setting the firing atmosphere to a reducing atmosphere.
  • Europium ion is a divalent and trivalent ion, and although its stable valence is trivalent, BaO.9EuO.lMg A11 () ⁇ 17 in europium-activated phosphor If it is not europium ions, blue emission color cannot be obtained.
  • Divalent europium ions are produced when BaO.9 EuO.lMg A11 () ⁇ 17 europium activated phosphor material is heated in a reducing atmosphere, while BaO.9EuO.
  • terbium ions capable of taking trivalent and tetravalent valences and manganese ions capable of taking divalent and tetravalent valences also undergo the same valence change as europium ions, so that trivalent terbium ions or Even in the method for producing a phosphor having divalent manganese ions, a high-luminance phosphor can be obtained by setting the atmosphere for heating the phosphor raw material to a reducing atmosphere.
  • Table 3 shows BaO.9 EuO.lMg A1 10 ⁇ ⁇ ⁇ 17 with europium according to the present invention.
  • the relative bulk density of the active phosphor (average particle size 5. 5. ⁇ , see Fig. 14) and the conventional BaO.9EuO.1 Mg A 1 europium activated phosphor (average particle size 6.4 ⁇ , see Fig. 15) It is a value comparison table. [Table 3]
  • B aO.9 E uO of the present invention LMg A 1 1 () ⁇ 17 bulk density of europium-activated phosphor is a conventional B aO.9EuO. LMgAl!. ⁇ 17 and 167% of the bulk density of the europium-Katsuhotaru the light B aO.9 E uO of the present invention.
  • Toward LMG A 1 10 ⁇ 17 europium-activated phosphor, despite having an average particle size less Large size and bulk density. Note that the phosphor having a high bulk density has an effect of reducing the amount of solvent used when producing the phosphor suspension and the phosphor paste, as described in the problem to be solved by the invention.
  • the present invention (the phosphor, 0.456 mg)
  • FIG. 15 is a comparison table of relative values of specific surface area of FIG. Table 4 shows that the specific surface area of the BaO.9EuO.1 MgA1O! 7 europium-activated phosphor of the present invention is the same as that of the conventional BaO.9Eu0.1Mg A11 ( ) 0 17 europium-activated phosphor.
  • the phosphor particles having a small specific surface area have an effect of reducing various damage rates of the phosphor as described in the problem to be solved by the invention.
  • FIG. 4 is a comparison diagram comparing y values on a degree coordinate.
  • LMgAl 10 ⁇ 17 europium-activated phosphor is a phosphor having a uniform particle size without the extreme degradation Chasse have microparticles Te cowpea to oxidation Since the specific surface area is smaller than that of the conventional phosphor, damage to the phosphor due to oxidation can be reduced, and such an effect is considered to have appeared.
  • FIG. 20 shows the results obtained by using a discharge device to obtain the Ba 0.9Eu0.
  • LMgAl 10 7 europium-activated phosphor (average particle size: 5. ⁇ , see FIG. 14) and the conventional Ba0.9Eu0. 1 10 ⁇ 17 Europium-activated phosphor (average particle size: 6.4 ⁇ , see Fig. 15) is bombarded with Ar ions having a certain impact strength, and its emission color changes (in CIE chromaticity coordinates).
  • FIG. 21 shows that the combination of an ion lamp and an interference filter combined with the B a 0.9 E u0. lMg A 1 C?
  • a 10 O 17 europium activated phosphor average particle size of 6.4 ⁇ , see Fig. 15
  • a single blue fluorescent lamp was fabricated, and the emission color changes with lighting time.
  • the BaO.9EuO.1MgA1 europium-activated phosphor of the present invention has a smaller specific surface area than conventional phosphors, and reduces damage to the phosphor due to ion bombardment or ultraviolet irradiation. It is considered that such an effect appeared in a fluorescent lamp using this, since it has an effect.
  • FIG. 23 shows BaO.9 EuO.lMg A 1. ⁇ This is a graph showing the relationship between the uniformity of the phosphor particle size and the rate of decrease in luminance after heating in the air for the europium-activated phosphor.
  • the longest particle length of the phosphor particles having the longest long axis length is X1
  • the longest particle length of the phosphor particles having the shortest long particle length is X1 Is defined as X s
  • A x lZx s is defined as the particle size uniformity index.
  • Fig. 23 demonstrates that the smaller the particle size uniformity index A is close to 1, that is, the more uniform the phosphor particle size, the more difficult it is for the luminance to be reduced by heat treatment in the atmosphere.
  • the particle size uniformity index A is preferably within the range of, and within this range, it is possible to secure a luminance maintenance ratio of 85% or more, exceeding the luminance maintenance ratio (84.6%) of the conventional phosphor. Is shown. Further, the particle size uniformity index A is preferably in the range of 1 ⁇ A ⁇ 1.2, and it is shown that a brightness maintenance ratio of 90% or more can be ensured within this range.
  • the particle size uniformity index A was calculated by measuring the major axis length of a phosphor particle with an electron micrograph. The reason that the more uniform the phosphor particle size is, the harder it is for the brightness to decrease due to the heat treatment in the atmosphere is because, as described above, the specific surface area is smaller than that of the conventional phosphor due to the absence of fine particles.
  • Fig. 24 shows the average particle sphericity of the phosphor particle shape and the air temperature at 600 ° C for 1 hour for BaO.9EuO.lMg A11 ( ) 0 17 europium-activated phosphor. It is a graph which investigated the relationship with the luminance reduction ratio after medium heating.
  • the average value of the above is defined as the average particle sphericity S (where S is a value satisfying S ⁇ 1), and the luminance before heat treatment ( 254 nm UV
  • the percentage of decrease in luminance after heat treatment in the air at 600 ° C for 1 hour with respect to the luminance when irradiated with light is defined as the luminance maintenance ratio (unit:%), the average particle sphericity S of the phosphor particle shape, and the heating in the air.
  • the relationship with the later luminance reduction ratio was examined.
  • the average particle sphericity S should be in the range of 0.5 ⁇ S1, and within this range, it exceeds the brightness maintenance rate of the conventional phosphor (84.6%). This indicates that a luminance maintenance ratio of not less than% can be secured.
  • the average particle sphericity S was determined by measuring the major axis length and minor axis length of each phosphor particle in an electron micrograph of the phosphor particles, calculating the average value, and determining the numerical value.
  • FIG. 25 shows the emission spectrum (measured by irradiating ultraviolet light of 254 nm) of the Ba 0.9 Eu0.1mMAlAlO ⁇ europium-activated phosphor of Example 1 synthesized for reference.
  • Figure 25 is, BaO.9Eu0.1 Mg A 1 1 () 0 17 europium activated phosphor of Example 1, indicating a blue phosphor having an emission peak at 450 nm.
  • BaO.9EuO.lMgAloC 7 europium-activated phosphor was described as an example of a phosphor having a uniform particle size.
  • the same effect can be obtained by using a material, and a phosphor having a uniform particle size or preferably a phosphor having a spherical particle shape has the same effect as in the first embodiment and the same effect can be obtained.
  • the particle size of the phosphor may be other than 5 ⁇ .
  • Example 1 as an embodiment of a method for producing a phosphor having a uniform particle size, BaO.9EuO. LMgA 1 1 ⁇ ) ⁇ 17 has been described a method for manufacturing a europium-activated phosphor, the present invention Is related to a method for producing a phosphor having a uniform particle size. The same applies to a method for producing a phosphor other than the O 7 europium activated phosphor.
  • Example 1 as an example of a method for producing an aluminum-containing oxide phosphor having a uniform particle size, a Ba 0.9 EuO.lMg A 1 10 ⁇ 17 europium activated phosphor having a limited heating temperature range was used. having described the manufacturing method, the present invention is aluminum having a uniform particle size with a limited pressure heat temperature range -. There is also a method of manufacturing ⁇ beam containing oxide phosphor, B aO.9 E uO lMg a 1 10 ⁇ "Europium-activated phosphor can be carried out in the same manner as the method for producing an aluminum-containing oxide phosphor other than the phosphor. If the method for producing an aluminum-containing oxide phosphor is the same as that of Example 1, the same effect is obtained. The effect is also obtained.
  • Example 1 as an example of a light emitting device using a phosphor having a uniform particle size, a blue color using a BaO.9Eu0.1MgAl 10 to 17 europium activated phosphor having a uniform particle size was used.
  • a monochromatic fluorescent lamp has been described, the same applies to, for example, a lighting device other than a three-wavelength fluorescent lamp or a fluorescent lamp, or a light emitting device other than a lighting device, such as a display device such as a plasma display. Work The same effect can be obtained with the use.
  • B a 0.9 EuO described in Example 1.
  • LMgAl 10 ⁇ 17 europium-activated phosphor i.e., particle length of particles having a longest particle major axis length Particles mainly consisting of particles whose axis length is within the range of 1 to 1.2 times the particle long axis length of the particles having the shortest particle length and the particle long axis length, and 0.5 ⁇ (particle short axis length ⁇ particle long axis length) Phosphor with an approximately spherical shape that satisfies 1.0 and an average particle size of 5 ⁇
  • Figure 14 shows an electron micrograph. A description will be given of a phosphor suspension using. First, a method of manufacturing a phosphor suspension will be described.
  • the low melting glass, ethyl cellulose, and butyl acetate as the components were weighed so that the weight ratio became 100: 1: 5: 100. After that, they were put into a 1-liter beaker.
  • the phosphor according to the present invention containing a phosphor having a uniform particle size by thoroughly stirring the solution mixture put in the beaker with a metal spoon to completely dissolve ethyl cellulose in butyl acetate. A suspension was prepared.
  • the conventional phosphor suspension By adjusting the mixing ratio of butyl acetate, the conventional phosphor suspension When the viscosity was made the same as that of the phosphor suspension according to the present invention, the amount used was 40% smaller than that of the phosphor suspension according to the present invention. This indicates that the production method according to the present invention can reduce the amount of the solvent used for producing the phosphor suspension.
  • the glass substrate 400m1 After placing the phosphor suspension 400m1 in a beaker and stirring thoroughly, immediately put a glass substrate perpendicular to the liquid surface of the phosphor suspension, so that almost the entire surface of the glass substrate is immersed in the phosphor suspension, Immediately, the glass substrate was pulled up from the phosphor suspension liquid surface while maintaining the direction perpendicular to the phosphor suspension liquid surface, and the phosphor suspension was attached to the glass substrate. Thereafter, the glass substrate to which the phosphor suspension was attached was suspended in the air, and the butyl acetate contained in the phosphor suspension was naturally dried.
  • the glass substrate with the phosphor attached was heated at 600 ° C in the air using an electric furnace. Heating causes the combustion of gaseous cellulose and gas evaporation, and the melting point of the low-melting glass melts.
  • a phosphor film consisting of a phosphor and a trace amount of a low-melting glass component was successfully fabricated.
  • the fluorescent film is irradiated with ultraviolet light having a wavelength of 254 nm to emit light directly through the fluorescent film.
  • the average luminance within a 3 mm diameter circle was measured with a luminance meter.
  • the luminance was measured at 10 points, and the luminance unevenness of both phosphor films was compared and evaluated.
  • Table 5 summarizes the results of comparative evaluation of the luminance unevenness of the fluorescent film. [Table 5]
  • the present invention using a D phosphor [: 3 ⁇ 4, the phosphor is measured at a fluorescent film measurement point
  • the fluorescent film is used for the relative luminance of the fluorescent film
  • Table 5 shows that the brightness unevenness of the phosphor film could be reduced by producing the phosphor film using the phosphor suspension containing the phosphor according to the present invention. It is considered that the reason for this is that, since a phosphor having a uniform particle size was used for the phosphor suspension, the thickness distribution of the applied phosphor film became uniform, and the luminance distribution became uniform.
  • Example 2 as an example of a phosphor-containing material using a phosphor having a uniform grain size, B have a uniform particle size aO.9 E uO. IMg A 1 10 O 17 Yuropi ⁇ beam activated
  • the phosphor suspension using a phosphor has been described.
  • a terbium-activated phosphor represented by a composition formula of Ce 1 -xTb xMg A 1 nC 9
  • a phosphor-containing material using other phosphor materials if the phosphor suspension uses a phosphor having a uniform particle size, the same effect can be obtained and the same effect can be obtained.
  • a liquid or paste-like phosphor-containing substance other than the phosphor suspension described in Embodiment 2 such as a phosphor paste or a phosphor-containing paint, has the same function and the same effect.
  • Example 2 as an example of a method for manufacturing a phosphor-containing material using a phosphor having a uniform particle size, a phosphor, low-melting glass, ethyl cellulose, and butynole acetate were used.
  • Example 3 of the phosphor-containing substance according to the present invention B a 0.9Eu0.1MgAl described in Example 1.
  • ⁇ 17 europium activated phosphor ie, the longest particle length of the phosphor particles having the longest longest particle length is one of the longest particle length of the phosphor particles having the shortest longest particle length
  • a phosphor having an average particle diameter of about 5 ⁇ m is shown in Fig. 14.
  • An electron micrograph is shown in Fig. 14.)
  • BaO.9EuO.1MgA1 of Example 1 weighed so as to have a weight ratio of 100: 30: 30: 10: 5: 5: 5.
  • MgO average particle size 2 ⁇ , purity 99.9%
  • the mixed powder is charged into a mold and press-molded at a pressure of 400 kgf / cm2 to form a container-shaped press.
  • a molded product was obtained.
  • the shape of the press-formed product was a square ashtray having a length of 90 mm, a width of 60 mm, a height of 2 Omm, and a thickness of 8 mm.
  • form 1 hour sintered press molded article in a mixed gas of nitrogen and hydrogen in 1000 ° C, of Example 1 according to the present invention B aO.9 E uO. LMg A 1 10 ⁇ 17 Yuropi ⁇ beam activated
  • a sintered body container containing the phosphor was produced.
  • Table 6 shows that the bottom of the rectangular ashtray-shaped container was 10 cm from the height of 50 cm for 10 sintered bodies of the phosphor-containing material according to the present invention and 20 sintered bodies manufactured using the conventional phosphor.
  • the table below summarizes the results of examining the percentage of breakage by dropping naturally on a concrete surface so as to receive an impact. [Table 6]
  • Table 6 shows that the ratio of breakage of the sintered body container of the phosphor-containing material according to the present invention is lower than that of the conventional sintered body container. This indicates that the impact resistance is high. It also shows that the method for producing a phosphor-containing material of the present invention using a phosphor having a uniform particle diameter produces a sintered body container having high impact resistance.
  • the reason why the sintered body container of the phosphor-containing material according to the present invention has high impact resistance is that a sintered body container is manufactured using a phosphor having a uniform particle size, and a phosphor having a uniform particle size is produced. It is thought that this is because the sintered container has a small physical distortion in the sintered container and is not easily damaged by external physical force. Can be
  • Example 3 BaO.9EuO.1MgA1 of Example 1 was used.
  • a phosphor-containing material other than a sintered container such as a resin molded product containing a phosphor and a method of manufacturing the same may also be used. It is equally feasible.
  • the longest particle length of the phosphor particles having the longest particle long axis length is the shortest, and the longest particle length of the phosphor particles having the longest particle length is reduced.
  • the phosphor particles within the range of 1 to 2 times, preferably 1 to 1.2 times are mainly used, and more preferably, the shape of the phosphor particles is 0.5 ⁇ (particle minor axis).
  • the particles having the longest particle major axis length among the main particles have the shortest particle length among the main particles. It is within the range of 1 to 2 times, preferably 1 to 1.2 times, the particle long axis length of the particles having the long axis length, and more preferably 0.5 ⁇ (particle short axis length Z Since the phosphor is manufactured using a phosphor material mainly composed of spherical or substantially spherical particles that satisfies ⁇ 1.0, the particle size is optimal for various phosphor-containing materials.
  • the phosphor has a uniform particle size, and has a characteristic that the specific surface area is small and the rate of various types of damage to the phosphor on the phosphor-containing material is small.
  • a phosphor having a uniform particle size can be produced.
  • the particle length axis length of the phosphor particles having the longest particle long axis length is 1 to 2 times the particle long axis length of the phosphor particles having the shortest particle long axis length. Times, preferably a phosphor mainly composed of phosphor particles in the range of 1 to 1.2 times, more preferably 0. (particle short axis length Z particle long axis length
  • Fluorescent substances containing spherical or substantially spherical particles that satisfy ⁇ 1.0 solids such as tiles and ashtrays, adhesive tapes, stickers, ropes, stationery such as underlays and pencil cases) (Including light-emitting devices, phosphor films, phosphor suspensions, and phosphor pastes), which provide phosphor-containing materials that do not contain particles other than the optimal particle size. It is also possible to provide a phosphor-containing material for a desired use, a phosphor-containing material having a desired property, and a phosphor-containing material having a desired shape.
  • phosphor suspensions and phosphor pastes that can reduce uneven light emission of phosphor films, phosphor-containing paints that can reduce uneven light emission of painted objects, and phosphor-containing solids that are not easily damaged by external impact It is possible to provide objects and light-emitting devices (fluorescent lamps, PDPs, CRTs) whose light emission performance does not deteriorate during operation.
  • the particle length of the phosphor particles having the longest particle length is one time longer than the particle length of the phosphor particles having the shortest particle length.
  • the range of the phosphor mainly composed of phosphor particles and more preferably, 0.1 (particle short axis length Z particle long axis length).
  • phosphors having a spherical or nearly spherical particle shape that satisfies ⁇ 1.0 solids such as tiles and ashtrays, adhesive tapes, seals, ropes, underlays, pencil cases, etc.
  • ⁇ 1.0 solids such as tiles and ashtrays, adhesive tapes, seals, ropes, underlays, pencil cases, etc.
  • various structures such as stationery, light-emitting devices, phosphor films, phosphor suspensions, and phosphor bases), so that phosphors that do not contain particles with sizes other than the optimal particle size are included.
  • Content can be manufactured, and the phosphor-containing material and And phosphor-containing substance having properties as desired can be also produced the phosphor-containing material having a shape as desired.
  • phosphor suspensions and phosphor pastes which can reduce uneven light emission of phosphor films, phosphor-containing paints, which can reduce uneven light emission of painted objects, and phosphors that are strong and not easily damaged by external impact It is possible to manufacture light-emitting devices (fluorescent lamps, PDPs, CRTs) that do not degrade luminescence performance during operation and contain solids.

Abstract

L'invention concerne le phosphore constitué de particules qui ont une taille uniforme et sont, de préférence, de forme globulaire, ainsi qu'une substance fluorescente à base dudit phosphore qui est capable de résister aux dommages dus au bombardement par pulvérisation d'ions de gaz rares, à l'irradiation avec des rayons UV ou des faisceaux d'électrons ainsi qu'à l'oxydation provoquée par la chaleur. On fabrique le phosphore à partir d'une matière première particulaire constituée de particules qui ont une taille uniforme et sont, de préférence, de forme globulaire. On fabrique la substance fluorescente à base dudit phosphore constitué de particules qui ont une taille uniforme et sont, de préférence, de forme globulaire, en utilisant le phosphore constitué de particules qui ont une taille uniforme et sont, de préférence, de forme globulaire.
PCT/JP1998/004054 1997-11-12 1998-09-10 Phosphore, substance fluorescente produite a partir de phosphore et procedes de leur fabrication WO1999024528A1 (fr)

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JP32962797 1997-11-12
JP9/329627 1997-11-12
JP10/64633 1998-02-26
JP6463398A JPH11199867A (ja) 1997-03-13 1998-02-26 蛍光体とこれを用いた蛍光体含有物ならびにこれらの製造方法

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Citations (6)

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JPH0920887A (ja) * 1995-07-06 1997-01-21 Maruwa Kogyo Kk 蛍光性物体および蓄光性蛍光体層の形成方法
JPH09151372A (ja) * 1995-09-29 1997-06-10 Matsushita Electric Ind Co Ltd アルミン酸塩蛍光体の製造方法
JPH09291275A (ja) * 1996-04-26 1997-11-11 Matsushita Electron Corp 蛍光体の製造方法及び蛍光体
JPH1088127A (ja) * 1996-09-10 1998-04-07 Nichia Chem Ind Ltd 希土類アルミネート蛍光体の製造方法
JPH10110165A (ja) * 1996-10-04 1998-04-28 Matsushita Electric Ind Co Ltd アルミン酸塩蛍光体の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62201989A (ja) * 1985-11-07 1987-09-05 Kasei Optonix Co Ltd 蛍光体の製造方法
JPH0920887A (ja) * 1995-07-06 1997-01-21 Maruwa Kogyo Kk 蛍光性物体および蓄光性蛍光体層の形成方法
JPH09151372A (ja) * 1995-09-29 1997-06-10 Matsushita Electric Ind Co Ltd アルミン酸塩蛍光体の製造方法
JPH09291275A (ja) * 1996-04-26 1997-11-11 Matsushita Electron Corp 蛍光体の製造方法及び蛍光体
JPH1088127A (ja) * 1996-09-10 1998-04-07 Nichia Chem Ind Ltd 希土類アルミネート蛍光体の製造方法
JPH10110165A (ja) * 1996-10-04 1998-04-28 Matsushita Electric Ind Co Ltd アルミン酸塩蛍光体の製造方法

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