JPWO2000011106A1 - Red-emitting afterglow photoluminescent phosphor and afterglow lamp using this phosphor - Google Patents

Abstract

(57) [Abstract] A red-emitting afterglow photoluminescent phosphor is a rare earth oxysulfide phosphor activated with europium, and its chemical composition formula is within the following range: _Ln2O2S :Eu _x , _{M y} 0.00001≦x≦0.5 0.00001≦y≦0.3, where Ln in the composition formula is at least one element selected from the group consisting of Y, La, Gd, and Lu, and M is a co-activator and is at least one element selected from the group consisting of Mg, Ti, Nb, Ta, and Ga.

Description

Detailed Description of the Invention

Technical Field The present invention relates to a red-emitting afterglow photoluminescent material that emits light when excited by visible light and ultraviolet light.
The present invention relates to a fluorescent phosphor and an afterglow lamp coated with this phosphor.
The present invention relates to a rare earth oxysulfide phosphor activated with europium and coactivated with a specific element.
The red-emitting photoluminescent phosphor is the light source, and the surface on which this phosphor is applied is
This article relates to afterglow lamps. Background Art Some phosphors emit light in the dark for a relatively long period of time when irradiated with sunlight or artificial light.
Some have an afterglow, and this phenomenon can be repeated many times, so they are called phosphorescent fireflies.
In recent years, as social life has become more sophisticated and complex,
Interest in this has increased, and in particular, the use of phosphorescent fluorescent materials that glow in the dark has expanded in the field of disaster prevention.
Recently, phosphorescent fluorescent materials have been mixed into plastics to make plates, sheets, etc.
By processing it into glass, its applications are expanding in many areas. Traditionally, green-emitting ZnS:Cu phosphors have been used as phosphorescent materials.
However, this was not necessarily satisfactory because the phosphor had the following essential properties:
One is that the phosphorescence brightness (afterglow brightness) is only several tens of
The other is that the concentration is not high enough to be detected over time.
Colloidal zinc metal is deposited on the surface of the phosphor crystal, causing the appearance to turn black and phosphorescence to disappear.
This type of deterioration occurs under high temperature and humidity conditions.
This is particularly likely to occur, and to improve this defect, the surface of the ZnS:Cu phosphor is usually
Although light-resistant treatment has been applied, it is difficult to completely prevent light.
The light source must be avoided from being used outdoors or in places where it is exposed to direct sunlight.
In contrast, MAl activated with divalent Eu₂O₄In the compound represented by the formula
At least one metal element selected from the group consisting of Ca, Sr, and Ba
A phosphorescent phosphor with blue-purple to green light emitted from a host crystal of the compound is disclosed in Japanese Patent Application Laid-Open No. 7-11250.
This phosphor overcomes the above-mentioned essential drawbacks of zinc sulfide phosphors.
The phosphor matrix is disclosed in U.S. Patent Publication No. 2,392,814,
This is already known from U.S. Patent Publication No. 3,294,699. Furthermore, MO·a(Al_1-bB_b)₂O₃:cR is a compound represented by MO
is at least one selected from the group consisting of MgO, CaO, SrO, and ZnO
valent metal oxide, R is Eu²⁺In addition, from the group consisting of Pr, Nd, Dy, and Tm
A blue-green emitting, long-lasting phosphor comprising at least one rare earth element selected from the group consisting of:
This is disclosed in Patent Publication No. 8-170076. Luminescent phosphors with long afterglow that emit blue-purple to green light have been extensively studied and used.
However, red-emitting phosphorescent phosphors are chemically unstable and have a short afterglow, such as CaS:Eu
When a phosphorescent phosphor is used for decoration purposes, many
Since a variety of color afterglow is required, a chemically stable, long-lasting red-emitting afterglow photocatalyst was selected.
The development of a luminescent phosphor was desired.
This means long-lasting photoluminescence phosphorescence. Also, rare earth oxides activated with europium are used as phosphors excited by electron beams.
Sulfide phosphors have been studied and used as cathodoluminescent phosphors for cathode ray tubes.
However, this phosphor is excited by an electron beam.
However, there has been little research on photoluminescence phosphors excited by ultraviolet light, etc.
By further improving this phosphor, the inventors have achieved an extremely long afterglow.
We have succeeded in realizing a red-emitting photoluminescent phosphor.
The first object of the present invention is to produce a material that is excited by ultraviolet rays or the like, rather than by electron beams.
The object of the present invention is to provide a photoluminescent phosphor that emits red light and has a long afterglow.
By the way, there are already developed phosphorescent fluorescent materials that emit blue-purple to green light with a long afterglow time.
This substance is applied to afterglow lamps and the like and used as emergency lights. Emergency lights are required by the Fire Service Act Enforcement Order and fire prevention ordinances of cities across the country, and are used in theaters, hotels, and other places where people are present.
In the event of a disaster such as an earthquake or fire, or other
If the normal power supply is cut off due to an unexpected accident, the system will automatically switch to the backup power supply.
However, in the event of a disaster, the backup power source
If the power supply circuit is broken or the light is cut off, the light will go out.
It is extremely dangerous to be in a crowded underground mall, a long tunnel, or a high-rise building at night.
In addition, conventional emergency lights have a complicated structure, which requires time and money to install.
It is rare for it to be applied outside of places where it is required. It is also not limited to emergencies such as those mentioned above, but is also used in companies, department stores, school buildings, and factories.
In almost all buildings, such as large buildings like factories, shops, or houses,
Turn off the lights in those rooms, hallways, or stairwells, then reach the exit.
It would be safer if there were inexpensive guide lights with a simple structure that would allow people to see their feet during this time.
You can live a comfortable life. In contrast, the light from the light source is emitted from a shade or other holding member located in the area where the light reaches.
The technology for providing a light storage body that has the property of absorbing and storing light energy is disclosed in Japanese Patent Application Laid-Open No. 2004-200504.
This is disclosed in the official gazette of SHO 58-121088.
However, conventional optical storage materials are chemically unstable and
It has the drawback of easily deteriorating due to external radiation, high temperatures, moisture, etc.
The afterglow of these light storage materials is dim and short.
However, the brightness is insufficient. The second object of this invention is to provide a long, bright afterglow without requiring a backup power source for emergencies.
The present inventors have developed a red-emitting photoluminescent fluorescent lamp that can be used for afterglow lamps.
As a result of various researches on the body to improve the long-lasting afterglow characteristics and phosphorescence brightness,
Introducing a specific coactivator into a europium-activated rare earth oxysulfide phosphor
The inventors discovered that this problem could be solved by using a red-emitting afterglow photoluminescent phosphor, which is a material that emits red light.
A rare earth oxysulfide phosphor activated with sodium, the chemical composition of which falls within the following range:
It is characterized by being in. Ln₂O₂S: EU_x, M_y 0.00001≦x≦0.5 0.00001≦y≦0.3 In the composition formula, Ln is selected from the group consisting of Y, La, Gd, and Lu.
At least one of Mg, Ti, Nb, Ta, and Ga is a coactivator.
At least one selected from the group consisting of: The activator and co-activator to be introduced into the red-emitting afterglow photoluminescent phosphor of the present invention.
The activator has a significant effect on the phosphorescence brightness. For example, when Ln in the above composition formula is Y,
In this case, adjust the concentration to the following ranges: The concentration x of Eu in the activator is 0.00001 mol per 1 mol of phosphor.
The range is adjusted to 0.5 mol or less because the amount is less than 0.00001 mol.
If the amount is less than 0.5 moles, the light absorption will be poor, resulting in a low phosphorescence brightness.
If x is too large, concentration quenching occurs and the phosphorescence brightness decreases.
The preferred range is 0.00001≦x≦0.1, and in this concentration range
The phosphorescence brightness is further increased. By introducing the co-activator M, the emission of Eu exhibits persistence.
The activator M is at least one element selected from the group consisting of Mg, Ti, Nb, Ta and Ga.
The concentration y of the coactivator M is in the range of 0.00001≦y≦0.
The phosphorescence brightness is improved when the value of y is in the range of 3. When the value of y is smaller than 0.00001, the phosphorescence
The luminance decreases, and when it is greater than 0.3, the coactivator M cannot be incorporated as a constituent element of the phosphor.
The optimum concentration range for the coactivator M is 0.01≦y≦0.2 in the case of Mg.
In the case of Ti, the range is 0.01≦y≦0.3, and in the case of Nb, the range is 0.005≦y≦
In the case of Ta or Ga, the range is 0.001≦y≦0.2.
In this concentration range, the phosphorescence brightness is significantly improved. When Mg is selected as the first coactivator, Ti,
By doping at least one element selected from the group consisting of Nb, Ta, and Ga,
This results in a synergistic effect and is effective in improving phosphorescence brightness.
The degree y is in the range of 0.00001≦y≦0.3, and the second coactivator M
Regarding the concentration z of ', in the range of 0.00001≦z≦0.3, the phosphorescence brightness is improved.
When the first coactivator is Mg, the optimum concentration range of the second coactivator M' is
In the case of Nb, the range is 0.0001≦z≦0.3, and in the case of Nb, the range is 0.005≦z≦0.
In the case of Ta or Ga, z is in the range of 0.001≦z≦0.2;
In this concentration range, the phosphorescence brightness is significantly improved. When the second coactivator M' is Ti, Nb, Ta, or Ga, the first coactivator
The preferred range for the Mg concentration y is 0.01≦y≦0.2. The red-emitting afterglow photoluminescent phosphor of the present invention can be prepared using raw materials such as Y
₂O₃, Eu₂O₃, MgO, TiO₂Metal oxides such as carbonates,
Acid salts, oxalates, and hydroxides are easily converted to oxides by firing at high temperatures.
The purity of the raw materials has a significant effect on the phosphorescence brightness, and the purity of the raw materials is 99.9%.
It is preferable that the content is 99.99% or more, and more preferable that the content is 99.99% or more.
These raw materials are weighed to a predetermined molar ratio, mixed, and then added to the mixture.
Sulfur and a suitable flux (such as an alkali metal carbonate) are mixed in the mixture and baked.
This results in the red-emitting photoluminescent phosphor of the present invention having afterglow. The particle size of the red-emitting photoluminescent phosphor of the present invention has a significant effect on phosphorescence brightness.
The average particle size is preferably adjusted to the range of 5 to 30 μm.
When the diameter is smaller than 5 μm, the phosphorescence brightness drops sharply, and when the diameter is larger than 30 μm,
However, the phosphorescence brightness decreases depending on the body color of the phosphor.
If the amount is too large, mixing and application properties may deteriorate when used for decoration or lamps.
The average particle size is more preferably in the range of 10 to 30 μm.
The phosphorescence brightness is even higher and more stable. In europium-activated rare earth oxysulfide phosphors,
At least one element selected from the group consisting of Mg, Ti, Nb, Ta, and Ga
By introducing
A chemically stable, long-lasting red-emitting photoluminescent phosphor was achieved.
Furthermore, by combining it with a co-activator, the phosphorescence brightness can be further increased. The red-emitting afterglow photoluminescent phosphor of the present invention can be applied to lamps. There are various lamps that can excite afterglow phosphors. For example, incandescent lamps,
All currently used fluorescent lamps, HID lamps, and halogen lamps
The lamp shown in Figure 1 is made of a transparent glass (
2) The inner surface and/or outer surface of the inner fluorescent lamp is coated with a persistent fluorescent material.
The fluorescent layer (3) and the outer fluorescent layer (4) are shown. Also shown is the reflector (5) for the lamp.
By forming a phosphor layer (6) on the surface of the phosphor layer (6), a phosphor layer (6) having afterglow properties is obtained.
A reflector can be realized. The thickness of the applied phosphor layer depends on the particle size of the afterglow phosphor used, but is 5 to 10
If the phosphor layer is thinner than this range, the thickness of the afterglow phosphor layer will be
The amount of coating is too small, so the afterglow is barely noticeable.
If the phosphor layer becomes too thick, the light from the lamp will be blocked by the phosphor layer, and the lamp will not function as intended.
The lamp's functionality is reduced. Afterglow lamps are designed as described above, but fluorescent lamps, in particular,
The phosphor in the phosphor layer on the inner surface of the lath tube is excited by ultraviolet light and emits light.
This ultraviolet energy can also be used directly.
When a fluorescent lamp is coated with a fluorescent substance, the afterglow phosphor radiates from the positive column, which is the light-emitting part of the fluorescent lamp.
Since the phosphor is also directly excited by the 253.7 nm mercury line,
By applying it alone to a fluorescent lamp, a fluorescent lamp with long afterglow can be obtained.
However, when used as a normal white fluorescent lamp,
Therefore, it is used in combination with a fluorescent substance for a fluorescent lamp, and receives the light emitted by this fluorescent substance.
It is preferable to have a structure that receives light emitted by another phosphor and outputs afterglow. For example, the fluorescent lamp shown in Figure 2
The explanation will be given in a cross section perpendicular to the direction.
The energy converted from the energy into light energy (in this case ultraviolet radiation energy)
The fluorescent material layer (3) formed on the inner surface of the transparent glass (2) is excited by the light.
In this case, the afterglow phosphor and the illumination phosphor that can excite it are completely contained in the phosphor layer.
It is also possible to mix them completely, and this method is the simplest. Also, as shown in the cross-sectional view of the fluorescent lamp in Figure 3,
A phosphor layer (6) for afterglow is formed on the first layer, and a phosphor layer (7) for illumination is formed on the second layer.
According to this method, a 253.7 nm mercury beam is
Almost all of these are used to excite phosphors for fluorescent lamps, and most of the afterglow phosphors are
All of these are excited by visible light from the phosphor layer.
The fluorescent lamp has high brightness for lighting purposes and also has a high afterglow. In addition, as shown in the cross-sectional view of the fluorescent lamp in Figure 4, the transparent glass (2)
A fluorescent layer (7) for illumination is formed on the inner surface, and a persistent fluorescent layer (6) is formed on the outside of the glass tube.
It is also possible to form a phosphor layer that is used simultaneously with the afterglow phosphor that occupies the phosphor layer.
Those commonly used in the field can be applied, for example, (SrCaBaMg)₅(P.O.₄)
₃Cl: Eu, BaMg₂Al₁₆O₂₇: Eu, Sr₅(P.O.₄)₃Cl:E
u, LaPO₄:Ce, Tb, MgAl₁₁O₁₉: Ce, Tb, Y₂O₃: E
u, Y(PV)O₄:Eu, 3.5MgO・0.5MgF₂GeO₂: Mn,
Ca₁₀(P.O.₄)₆FCl: Sb, Mn, Sr₁₀(P.O.₄)₆FCl:Sb
, Mn, (SrMg)₂P₂O₇: Eu, Sr₂P₂O₇: Eu, CaWO₄,
CaWO₄: Pb, MgWO₄, (BaCa)₅(P.O.₄)₃Cl:Eu, Sr
₄Al₁₄O₂₅: Eu, Zn₂SiO₄: Mn, BaSi₂O₅: Pb, Sr
B₄O₇:Eu, (CaZn)₃(P.O.₄)₂: Tl, LaPO₄: Ce etc. is used
For the purpose of exciting persistent phosphors, red light that emits light above 600 nm is used.
The reason is that even if such long wavelength phosphors are used, the excitation
However, fluorescent lamps for normal lighting emit light almost without any effect.
This often extends over the entire viewing area, and when adding persistence to such fluorescent lamps,
Even if red light is not necessary for afterglow phosphors, the light color of the fluorescent lamp can be set to the required range.
This is necessary to determine the wavelength of the fluorescent light. It is possible to strongly excite the afterglow phosphor and also to emit light in the white region as a fluorescent lamp for lighting.
The fluorescent material is 450% superior in that it can emit light and freely change the color of the light emitted by the fluorescent lamp.
blue-emitting phosphors with an emission peak around 545 nm, and
and a red-emitting phosphor having an emission peak around 610 nm.
The most preferred is a three-wavelength mixed phosphor.
g)₅(P.O.₄)₃Cl:Eu, and BaMg₂Al₁₆O₂₇: Eu is green
As a light-emitting phosphor, LaPO₄: Ce, Tb, and MgAl₁₁O₁₉: Ce,
Tb phosphor as a red-emitting phosphor, and Y₂O₃: Eu is preferably used. A mixture of an afterglow phosphor that occupies the phosphor layer and a fluorescent lamp phosphor that coexists with it.
The ratio can be freely changed depending on the purpose of use. For example, if the purpose is lighting,
In the case of priority, i.e., when the lamp luminous flux is the priority, the phosphor for the fluorescent lamp
On the other hand, if you want a brighter, longer afterglow, you can increase the amount of afterglow phosphor.
This can be achieved by increasing the ratio. Furthermore, the manufacturing method for afterglow fluorescent lamps is the same as that for ordinary fluorescent lamps.
For example, a fluorescent material that excites a fluorescent material in the presence of a fluorescent substance can be used as it is.
phosphors that cause photocatalysis, and alumina or calcium pyrophosphate, calcium barium
A binder such as borate is added to the nitrocellulose/butyl acetate solution and mixed.
The resulting phosphor coating suspension is mixed and suspended in a glass.
The mixture is poured into the inner surface of the tube, then dried by passing hot air through it, and baked.
The present invention is carried out according to the usual procedures such as exhaust, installation of the filament, and installation of the nozzle.
It can be used to finish fluorescent lamps. When applied to the glass tube, a protective film such as alumina is formed, and then a phosphor layer is formed.
It is also possible to further improve the luminous performance, such as luminous flux and luminous flux maintenance rate. These afterglow lamps do not require a backup power source in an emergency and can utilize a bright afterglow.
By applying this afterglow fluorescent lamp to an emergency light, it can be used as if a light storage material was applied.
No special lighting equipment is required, and existing lighting equipment can be used as is.
As a result, the economical cost involved in selecting the installation location of the emergency exit lights is reduced.
This reduces the number of restrictions on the use of emergency lights. It is also effective when incorporated into existing emergency lights with backup power supplies, and
Even if the backup power supply or power supply circuit is cut off due to a disaster, it will still function as an emergency light.
It is possible to provide an extremely reliable emergency exit light. Furthermore, it is not limited to emergencies, and when used for lighting indoors, corridors, or staircases,
The bright afterglow continues for a while after you turn off the switch, so you can
This can be used as auxiliary lighting for illuminating the feet. BEST MODE FOR CARRYING OUT THE INVENTION [Example 1] The phosphor materials used were 46.5 g of Y2O3, 46.5 g of Eu₂O₃3.0 g, MgCO
₃Weigh out 0.5 g of the mixture, place it in a ceramic pot, and mix thoroughly using a ball mill.
Then, sulfur (S) was added to the raw powder.
22.7 g, Na as a flux₂CO₃After adding 22.0 g of the above and mixing, alumina
The mixture was placed in a crucible and fired at 1100°C for 6 hours. After firing, the mixture was washed with water several times and then melted.
After washing off the agent, the product was dried at 120°C for 10 hours.₂
O₂S: EU_0.082, Mg_0.028The emission spectrum of the phosphor obtained in Example 1 when excited at 365 nm was measured in the fifth
This figure shows that the phosphor emits red light with a peak around 625 nm.
In addition, Figure 6 shows the excitation spectrum of this phosphor for 625 nm emission.
This figure shows that efficient excitation occurs across the entire ultraviolet range. [Examples 2-5] Examples 2-5 are the same as in Example 1, except for the MgCO₃Prepare in the same manner by changing the amount of
A phosphor of the formula is obtained. Example 2...Y₂O₂S: EU_0.082, Mg_0.011 Example 3...Y₂O₂S: EU_0.082, Mg_0.057 Example 4...Y₂O₂S: EU_0.082, Mg_0.115 Example 5...Y₂O₂S: EU_0.082, Mg_0.172 [Examples 6-10] Examples 6-10 use TiO instead of MgCO3 as in Example 1.₂and TiO
₂The amounts were changed and the phosphor of the following composition formula was obtained. Example 6...Y₂O₂S: EU_0.082, Ti_0.012 Example 7...Y₂O₂S: EU_0.082, Ti_0.030 Example 8...Y₂O₂S: EU_0.082, Ti_0.060 Example 9...Y₂O₂S: EU_0.082, Ti_0.120 Example 10...Y₂O₂S: EU_0.082, Ti_0.240 [Examples 11-14] Examples 11-14 are the same as those in Example 1 except for the MgCO₃Instead of Nb₂O₅Add N
b₂O₅The same procedure is repeated with different amounts to obtain a phosphor of the following composition: Example 11...Y₂O₂S: EU_0.082, Nb_0.007 Example 12...Y₂O₂S: EU_0.082, Nb_0.018 Example 13...Y₂O₂S: EU_0.082, Nb_0.037 Example 14...Y₂O₂S: EU_0.082, Nb_0.073 [Examples 15-18] Examples 15-18 are the same as Example 1 except that TiO₂and TiO₂Change the amount
Prepare in the same manner to obtain a phosphor of the following composition formula: Example 15...Y₂O₂S: EU_0.082, Mg_0.028, Ti_0.012 Example 16...Y₂O₂S: EU_0.082, Mg_0.028, Ti_0.030 Example 17...Y₂O₂S: EU_0.082, Mg_0.028, Ti_0.060 Example 18...Y₂O₂S: EU_0.082, Nb_0.028, Ti_0.120
[Examples 19-23] Examples 19-23 are the same as Example 1 except that TiO₂Add MgCO₃Amount and Ti
O₂Prepare in the same manner but changing the amounts to obtain a phosphor of the following composition formula. Example 19...Y₂O₂S: EU_0.082, Mg_0.011, Ti_0.108 Example 20...Y₂O₂S: EU_0.082, Mg_0.028, Ti_0.090 Example 21...Y₂O₂S: EU_0.082, Mg_0.057, Ti_0.060 Example 22...Y₂O₂S: EU_0.082, Nb_0.086, Ti_0.030 Example 23...Y₂O₂S: EU_0.082, Nb_0.103, Ti_0.012 [Examples 24-27] Examples 24-27 are the same as Example 1 except that Nb₂O₅Add Nb₂O₅Change the amount
Add and prepare in the same manner to obtain a phosphor of the following composition formula: Example 24...Y₂O₂S: EU_0.082, Mg_0.028, Nb_0.007 Example 25...Y₂O₂S: EU_0.082, Mg_0.028, Nb_0.018 Example 26...Y₂O₂S: EU_0.082, Mg_0.028, Nb_0.037 Example 27...Y₂O₂S: EU_0.082, Nb_0.028, Nb_0.073 [Examples 28-31] Examples 28-31 are the same as Example 1 except that Nb₂O₅Add MgCO₃Quantity and N
b₂O₅Prepare in the same manner but changing the amounts to obtain a phosphor of the following composition formula. Example 28...Y₂O₂S: EU_0.082, Mg_0.011, Nb_0.065 Example 29...Y₂O₂S: EU_0.082, Mg_0.028, Nb_0.055 Example 30...Y₂O₂S: EU_0.082, Mg_0.057, Nb_0.037 Example 31...Y₂O₂S: EU_0.082, Nb_0.086, Nb_0.018 [Examples 32-38] Examples 32-38 are the same as those in Example 22 except for Eu₂O₃Prepare in the same way by changing the amount of
A phosphor having the following composition formula is obtained. Example 32...Y₂O₂S: EU_0.00003, Mg_0.086, Ti_0.0
30 Example 33...Y₂O₂S: EU_0.00028, Mg_0.086, Ti_0.0
30 Example 34...Y₂O₂S: EU_0.0028, Mg_0.086, Ti_0.03
0 Example 35...Y₂O₂S: EU_0.028, Mg_0.086, Ti_0.030 Example 36...Y₂O₂S: EU_0.055, Mg_0.086, Ti_0.030 Example 37: Y2O₂S: EU_0.110, Mg_0.086, Ti_0.030 Example 38...Y₂O₂S: EU_0.138, Mg_0.086, Ti_0.030 The emission spectrum of the phosphor obtained in Example 34 when excited at 365 nm is shown in
Figure 7 shows the results. [Examples 39-42] Examples 39-42 are the same as Example 22 except that Nb₂O₅Add Nb₂O₅Amount
By changing the composition and preparing in the same manner, a phosphor of the following composition formula is obtained. Example 39...Y₂O₂S: EU_0.082, Mg_0.086, Ti_0.030
, Nb_0.007 Example 40...Y₂O₂S: EU_0.082, Mg_0.086, Ti_0.030
, Nb_0.018 Example 41...Y₂O₂S: EU_0.082, Mg_0.086, Ti_0.030
, Nb_0.037 Example 42: Y2O₂S: EU_0.082, Mg_0.086, Ti_0.030
, Nb_0.073 [Examples 43 and 44] Examples 43 and 44 are the same as Example 22, except for Y.₂O₃Gd₂O₃Place some or all of
Substitute and prepare in the same manner to obtain a phosphor with the following composition formula. Example 43... (Y_0.5Gd_0.5)₂O₂S: EU_0.082, Mg_0.0
86, Ti_0.030 Example 44: Gd₂O₂S: EU_0.082, Mg_0.086, Ti_0.03
0 [Examples 45-48] Examples 45-48 are the same as those in Example 40.₂O₃Gd₂O₃Place some or all of
Replacement, Nb₂O₅The same procedure is repeated with different amounts to obtain a phosphor with the following composition formula. Example 45... (Y_0.5Gd_0.5)₂O₂S: EU_0.082, Mg_0.0
86, Ti_0.030, Nb_0.018 Example 46: Gd₂O₂S: EU_0.082, Mg_0.086, Ti_0.03
0, Nb_0.018 Example 47: Gd₂O₂S: EU_0.082, Mg_0.086, Ti_0.03
0, Nb_0.037 Example 48: Gd₂O₂S: EU_0.082, Mg_0.086, Ti_0.03
0, Nb_0.073 [Examples 49 and 50] Examples 49 and 50 are the same as Example 22, except for Y.₂O₃Lu₂O₃Place some or all of
Substitute and prepare in the same manner to obtain a phosphor with the following composition formula. Example 49... (Y_0.5Lu_0.5)₂O₂S: EU_0.082, Mg_0.0
86, Ti_0.030, Example 50...Lu₂O₂S: EU_0.082, Mg_0.086, Ti_0.03
0, [Examples 51 and 52] Examples 51 and 52 are the same as Example 40, except for Y.₂O₃Lu₂O₃Place some or all of
Substitute and prepare in the same manner to obtain a phosphor with the following composition formula: Example 51... (Y_0.5Lu_0.5)₂O₂S: EU_0.082, Mg_0.0
86, Ti_0.030, Nb_0.018 Example 52: Lu₂O₂S: EU_0.082, Mg_0.086, Ti_0.03
0, Nb_0.018 [Examples 53 and 54] Examples 53 and 54 are the same as Example 22, except for Y.₂O₃La₂O₃Place some or all of
Substitute and prepare in the same manner to obtain a phosphor with the following composition formula. Example 53... (Y_0.5La_0.5)₂O₂S: EU_0.082, Mg_0.0
86, Ti_{0.030 Example 54: La 2} O₂S: EU_0.082, Mg_0.086, Ti_0.03
0 [Examples 55 and 56] Examples 55 and 56 are the same as Example 40, except for Y.₂O₃La₂O₃Place some or all of
Substitute and prepare in the same manner to obtain a phosphor with the following composition formula. Example 55... (Y_0.5La_0.5)₂O₂S: EU_0.082, Mg_0.0
86, Ti_0.030, Nb_0.018 Example 56: La₂O₂S: EU_0.082, Mg_0.086, Ti_0.03
0, Nb_0.019 [Examples 57 and 58] Examples 57 and 58 are the same as Examples 22 and 40, respectively, except that Ta₂O₅Add
Prepare in the same manner to obtain a phosphor of the following composition formula: Example 57...Y₂O₂S: EU_0.082, Mg_0.086, Ti_0.030
, Ta_0.023 Example 58...Y₂O₂S: EU_0.082, Mg_0.086, Ti_0.030
, Nb_0.018, Ta_0.023 [Examples 59-62] Examples 59-62 are the same as Example 1 except that Ga₂O₃Add Ga₂O₃Change the amount
Add and prepare in the same manner to obtain a phosphor of the following composition formula. Example 59...Y₂O₂S: EU_0.082, Mg_0.028, Ga_0.005 Example 60...Y₂O₂S: EU_0.082, Mg_0.028, Ga_0.010 Example 61...Y₂O₂S: EU_0.082, Mg_0.028, Ga_0.015 Example 62...Y₂O₂S: EU_0.082, Mg_0.028, Ga_0.020 [Examples 63-66] Examples 63-66 are the same as Example 60 except that TiO₂and TiO₂Change the amount
and prepare in the same manner to obtain a phosphor of the following composition formula: Example 63...Y₂O₂S: EU_0.082, Mg_0.028, Ga_0.010
, Ti_0.012 Example 64...Y₂O₂S: EU_0.082, Mg_0.028, Ga_{0.010
, Ti 0.030} Example 65...Y₂O₂S: EU_0.082, Mg_0.028, Ga_0.010
, Ti_0.060 Example 66...Y₂O₂S: EU_0.082, Mg_0.028, Ga_0.010
, Ti_0.120 [Examples 67 and 68] Examples 67 and 68 are the same as Example 60 except that Nb₂O₅Or, Ta₂O₅Add
, and prepare in the same manner to obtain a phosphor of the following composition formula. Example 67...Y₂O₂S: EU_0.082, Mg_0.028, Ga_0.010
, Nb_0.018 Example 68...Y₂O₂S: EU_0.082, Mg_0.028, Ga_0.010
, Ta_0.023 [Examples 69 and 70] Examples 69 and 70 are the same as Example 65, except for Y.₂O₃La₂O₃Place some or all of
Substituting the above, the phosphor of the following composition formula is obtained. Example 69... (Y_0.5La_0.5)₂O₂S: EU_0.082, Mg_0.0
28, Ga_0.010, Ti_0.060 Example 70: La₂O₂S: EU_0.082, Mg_0.028, Ga_0.01
0, Ti_0.060 [Examples 71 and 72] Examples 71 and 72 are the same as those of Example 65, except for Y.₂O₃Gd₂O₃Place some or all of
Substitute and prepare in the same manner to obtain a phosphor with the following composition formula. Example 71... (Y_0.5Gd_0.5)₂O₂S: EU_0.082, Mg_0.0
28, Ga_0.010, Ti_0.060 Example 72: Gd₂O₂S: EU_0.082, Mg_0.028, Ga_0.01
0, Ti_0.060 [Examples 73 and 74] Examples 73 and 74 are the same as Example 65, except for Y.₂O₃Lu₂O₃Place some or all of
Substituting the above, the phosphor of the following composition formula is obtained. Example 73... (Y_0.5Lu_0.5)₂O₂S: EU_0.082, Mg_0.0
28, Ga_0.010, Ti_0.060 Example 74: Lu₂O₂S: EU_0.082, Mg_0.028, Ga_0.01
0, Ti_0.060 When measuring the phosphorescence brightness of the phosphor of the present invention, first prepare a fixed measurement sample as follows:
0.5 g of acrylic resin varnish is added to 1 g of phosphor sample, and the sample is rubbed.
Mix thoroughly, being careful not to crush the mixture, and place 100 mg of the sample on an aluminum plate.
/cm²The test piece was made by applying the paint to a thickness of 1000 or more and drying it.
The pieces were used to measure the phosphorescence brightness. The phosphorescence brightness was measured in accordance with JIS Z 9100 (Phosphorescence of phosphorescent safety sign boards)
The test piece was placed in a dark place and shielded from external light for more than 3 hours.
After storing in this state, the test piece was exposed to D65 light at an illuminance of 200 lux for 4 minutes.
The phosphorescence intensity was measured after the irradiation was stopped.
Black light lamp with 5 nm ultraviolet radiation (intensity 0.5 mW/cm²) and 1
After irradiating for 5 minutes, the phosphorescence brightness was measured in the same manner. The phosphors obtained in Examples 1 to 74 of the present invention and, for comparison, a conventional red-emitting storage
The photoluminescent phosphor CaS:Eu,Tm was measured 1 minute and 10 minutes after the excitation was stopped.
The phosphorescence luminance obtained by the phosphor of the present invention is shown in Tables 1, 2 and 3.
It can be seen that it has high phosphorescence brightness as well as afterglow characteristics. FIG. 8 shows the phosphors obtained in Examples 22 and 46 of the present invention and the conventional red phosphors for comparison.
The black light run of CaS:Eu,Tm phosphor, which is a color-emitting phosphorescent phosphor.
As is clear from this figure, Example 22
Y₂O₂S: EU_0.082, Mg_0.086, Ti_0.030Phosphors and
Gd of Example 46₂O₂S: EU_0.082, Mg_0.086, Ti_0.030,
Nb_0.018The phosphorescence brightness of the phosphor is higher than that of the conventional CaS:Eu,Tm phosphor.
It can be seen that the phosphorescence is extremely high and can be observed for a long time after the excitation is stopped. Figure 9 shows the phosphors obtained in Examples 3, 8, and 21 of the present invention, as well as the phosphors obtained in the conventional
Red-emitting phosphor Y₂O₂S:Eu phosphor by the black light lamp
As is clear from this figure, the Y of Example 3₂O
₂S: EU_0.082, Mg_0.057Phosphor and Y of Example 8₂O₂S: EU
_0.082, Ti_0.060The phosphorescence brightness of the phosphor is₂O₂S: Eu Firefly
The Y value of Example 21 is very high compared to that of the optical body.₂O₂S: EU_0.082, Mg
_0.057, Ti_0.060In the case of phosphors, the first coactivator is Mg, the second coactivator is
By adding Ti as a coactivator, a synergistic effect is achieved, and the phosphorescence brightness is further improved.
Figure 10 shows that the Y₂O₂S: EU_x, Mg_0.086, Ti_0.030Phosphor E
The content x of u and the value of u after 1 minute from the end of the excitation by the black light lamp
From this figure, the optimum concentration range is determined as x value 0.
It can be seen that the phosphorescence brightness is significantly improved in the range of 00001≦x≦0.1. Figure 11 shows Y₂O₂S: EU_0.082, Ti_yThe Ti content y value of the phosphor
The relationship between the phosphorescence brightness one minute after the excitation by the black light lamp was stopped and the
From this figure, the optimum concentration range is y=0.01≦y≦0.3
It can be seen that the phosphorescence brightness improves significantly within the range of Y.₂O₂S: EU_0.082, Mg_0.028, Ti_zPhosphor T
The content z value of i and the value of 1 minute after the excitation by the black light lamp was stopped
From this figure, the optimum concentration range is z value 0.
It can be seen that phosphorescence brightness is significantly improved within the range of 0001≦z≦0.3. [Example 75] Red-emitting afterglow phosphor Y, a three-wavelength mixed phosphor₂O₂S: EU_0.085, Mg_0
．089, Ti_0.016In particular, when exciting and emitting light from a fluorescent lamp,
We will explain the case where these phosphors are completely mixed in the phosphor layer. Y₂O₃90.5g (0.40mol), Eu₂O₃6
．． 0g (0.017mol), MgCO₃3.0 g (0.036 mol) of
TiO₂Weigh out 0.5g (0.0063mol) and place it in a ceramic pot.
The mixture was thoroughly mixed in a ball mill to obtain a mixed raw material (hereinafter referred to as raw powder).
The raw powder was added with 45.4g (1.42mol) of sulfur (S) and Na as a flux.₂
CO₃After adding 44.0 g (0.415 mol) of the above and mixing, the mixture was poured into an alumina crucible.
After firing, the mixture was washed with water several times to remove the flux.
After that, it was dried at 120°C for 10 hours and passed through a 200 mesh sieve.
, the chemical formula is Y₂O₂S: EU_0.085, Mg_0.089, Ti_0.016
This phosphor has an emission peak wavelength of 625 nm.
It showed red light emission. The obtained afterglow phosphor and a SrCaBaMg
)₅(P.O.₄)₃Cl:Eu blue-emitting phosphor 36%, emission peak at 544 nm
LaPO with₄: Ce, Tb green emitting phosphor 32%, and emitting at 611 nm
Peaked Y₂O₃: Three-wavelength mixed phosphor obtained by mixing 32% Eu red-emitting phosphor
The combined phosphors are thoroughly mixed in a 1:4 ratio. 20 g of the mixed phosphor and 20 g of nitrocellulose/butyl acetate binder are added.
The mixture is thoroughly mixed in a porcelain pot to prepare a phosphor coating slurry.
Pour into the inside of an S glass tube, apply to the inside of the tube, and dry by blowing hot air over it.
The coated bulb was baked at 100°C for 15 minutes to form a phosphor film.
The amount of phosphor applied per unit was 4.0 g.
The lament was attached and the base was attached to complete the fluorescent lamp.
The measured values of the fluorescent lamp are summarized in Table 4. Here, the afterglow luminous flux is the luminous flux measured one minute after the lamp is turned off.
These are measurements taken at 1000 kJ/s. [Example 76] A so-called "light-emitting diode" (LED) is used, in which a persistent phosphor is applied as the first layer and a three-wavelength mixed phosphor is applied as the second layer.
The case of two-layer coating will be explained below.₂O₂S:E
u_0.085, Mg_0.089, Ti_0.01615g of phosphor and nitrocellulose
20 g of butyl acetate binder was added and mixed thoroughly in a porcelain pot to form a phosphor coating.
A cloth slurry is prepared. This is poured into the inside of an FL40SS glass tube.
This process coats the first layer of phosphorescent material on the surface and dries it by blowing hot air over it.
The amount of cloth was 3 g. Next, (SrCaBaMg)₅(P.O.₄)₃Cl:Eu blue
33% color-emitting phosphor, LaPO₄31% Ce, Tb green-emitting phosphor, and
Y₂O₃: Three-wavelength mixed phosphor 30 obtained by mixing 36% Eu red light emitting phosphor
50 g of polyethylene oxide aqueous solution was added to the 100 g of polyethylene oxide solution and mixed thoroughly in a porcelain pot.
This is poured into the glass tube as the second layer.
This process creates a three-wavelength mixed layer on the second layer.
The amount of the composite phosphor applied was 3 g. After that, the exhaust and filament were removed in the usual manner.
The fluorescent lamp was then fabricated by attaching the base.
The measured values are summarized in Table 4. [Example 77] Three-wavelength mixed phosphor, red-emitting afterglow phosphor Gd₂O₂S: EU_0.082, M
g_0.086, Ti_0.030In particular, when exciting and emitting light from fluorescent lamps,
This section explains the case where these phosphors are completely mixed in the phosphor layer of Example 75.₂O₃Instead of Gd₂O₃90.5g
A persistent phosphor was prepared in the same manner as in Example 75, except that 0.250 mol of HCl was used.
This phosphor emitted red light with a peak emission wavelength of 624 nm. The obtained afterglow phosphor and a three-wavelength mixed phosphor prepared in the same manner as in Example 75 were used.
The light sources were thoroughly mixed in a ratio of 1:4, and the mixture was used in a fluorescent lamp in the same manner as in Example 75.
The measured values of the resulting fluorescent lamp are summarized in Table 4. [Example 78] In Example 76, the Y prepared in Example 75 was used.₂O₂S: EU_0.085, M
g_0.089, Ti_0.016Instead of the phosphor, Gd prepared in Example 77₂
O₂S: EU_0.082, Mg_0.086, Ti_0.030Since phosphors are used,
In addition, a fluorescent lamp with two coating layers was produced in the same manner as in Example 76.
The light lamp measurement values are summarized in Table 4. [Comparative Example 1] ZnS:Cu phosphor was selected as the afterglow phosphor, (SrCaBaMg)₅(
P.O.₄)₃34.1% Cl:Eu blue-emitting phosphor, LaPO₄: Ce, Tb green
16.8% color-emitting phosphor, and Y₂O₃: Eu red light emitting phosphor mixed at 49.1%
The three-wavelength mixed phosphor obtained by combining these was thoroughly mixed in a ratio of 1:3, and the resulting phosphor was used in Example 75.
The fluorescent lamp was made in the same way as the previous one. The fluorescent lamp was completely blackened.
The lamp luminous flux was also extremely low, making it impossible to obtain a commercially viable fluorescent lamp.
[Comparative Example 2] The same ZnS:Cu afterglow phosphor as in Comparative Example 1 was applied to the first layer, and a three-wavelength phosphor was applied to the second layer.
The case of coating a mixed phosphor, that is, a two-layer coating, will be described below.
15 g of nitrocellulose/butyl acetate binder was added to 30 g of Cu phosphor.
The mixture is thoroughly mixed in a porcelain pot to prepare a phosphor coating slurry.
Pour the mixture into the inside of an S-glass tube, apply it to the inside surface, and then dry it by blowing hot air through it.
The coating amount of the first layer of persistent phosphor was 3 g.
aMg)₅(P.O.₄)₃30.2% Cl:Eu blue-emitting phosphor, LaPO₄:
29.4% Ce, Tb green emitting phosphor, and Y₂O₃: Eu red light emitting phosphor
12 g of the three-wavelength mixed phosphor obtained by mixing 40.4% polyethylene oxide
Add 50 g of the aqueous solution and mix thoroughly in a porcelain pot to prepare a phosphor coating slurry.
This is poured into a glass tube, coated on the inside surface, and dried by blowing hot air through it.
After this process, the amount of the three-wavelength mixed phosphor applied to the second layer was 3 g.
Follow the instructions to evacuate, install the filament, and attach the base, then install the fluorescent lamp.
The fluorescent lamp obtained was entirely blackened, the lamp luminous flux was extremely low, and the product
It was not possible to obtain a high-quality fluorescent lamp. Furthermore, the phosphorescence intensity of the red-emitting afterglow photoluminescent phosphor varied depending on the particle size.
This was tested in the following example. [Example 79] Y was used as a phosphor raw material.₂O₃(average particle size 1.0 μm) 46.5 g, Eu₂O
₃3.0 g, MgCO₃Weigh out 0.5g of the solution and place it in a ceramic pot.
The mixture was thoroughly mixed using a mill to obtain a mixed raw material (hereinafter referred to as raw raw powder).
The raw powder contains 22.7g of sulfur (S) and Na as a flux.₂CO₃Add 22.0g of
After mixing, the mixture was filled into an alumina crucible and fired at 1150°C for 6 hours.
After that, it was washed with water several times to wash off the flux, and then dried at 120°C for 10 hours.
Therefore, the chemical formula is Y₂O₂S: EU_0.082, Mg_0.028, the average particle size is
A 7.2 μm phosphor was obtained. [Examples 80-82] In Examples 80-82, the firing temperatures of Example 79 were changed to 1200°C and 1250°C, respectively.
The temperature was changed to 1300°C and 1300°C, and the composition formula was Y₂O₂S: EU_0.08
2, Mg_0.028The average particle size is 11.2 μm, 16.9 μm, and 22.7 μm, respectively.
A phosphor with a diameter of 100 μm was obtained. [Examples 83-86] Examples 83-86 were obtained by adding TiO to each of Examples 79-82.₂Add
Similarly prepared, the chemical formula is Y₂O₂S: EU_0.082, Mg_0.086, T
i_0.030, the average particle size is 7.4 μm, 11.5 μm, and 17.3 μm, respectively.
A 23.1 μm phosphor was obtained. [Example 87] Y of Example 79₂O₃(average particle size 1.0 μm) instead of Y₂O₃(Average particle size
1.5 μm) was used, and the chemical composition formula was Y₂O₂S: EU_0
．082, Mg_0.028A phosphor with an average particle size of 8.3 μm was obtained. [Examples 88-90] In Examples 88-90, the firing temperatures of Example 87 were changed to 1200°C and 1250°C, respectively.
The temperature was changed to 1300°C and 1300°C, and the composition formula was Y₂O₂S: EU_0.08
2, Mg_0.028, and the average particle size is 14.4 μm, 20.0 μm, and 25.
A 9 μm phosphor was obtained. [Examples 91-94] Examples 91-94 were obtained by further adding TiO to each of Examples 87-90.₂Add
Similarly prepared, the chemical formula is Y₂O₂S: EU_0.082, Mg_0.086, T
i_0.030, the average particle size is 8.8 μm, 14.8 μm, and 20.4 μm, respectively;
A phosphor with a particle size of 26.3 μm was obtained. In Examples 79 to 94, the average particle size was determined by measuring the specific surface area using the air permeability method.
, the average particle size of the primary particles,
The values were measured using F.S.S.S. The phosphors obtained in Examples 79 to 94 of the present invention were compared with conventional red-emitting phosphors.
The phosphorescent phosphor CaS:Eu,Tm phosphor was measured 1 minute and 10 minutes after the excitation was stopped.
The phosphorescence brightness and average particle size of the phosphors of the present invention are shown in Table 5.
It can be seen that it has high phosphorescence brightness, consistent with its characteristics. Figure 13 is Y₂O₂S: EU_0.082, Mg_0.086, Ti_0.030firefly
The average particle size of the photobody and the time 1 minute after the excitation by the black light lamp was stopped
As is clear from this figure, the average particle size is 5
When the particle size is smaller than 23 μm, the phosphorescence brightness decreases rapidly, and the phosphorescence brightness reaches its maximum.
When the particle size exceeds approximately μm, the body color of the phosphor changes from white to yellowish.
Therefore, the phosphorescence brightness gradually decreases and stabilizes within the average particle size range of 5 to 30 μm.
It can be seen that the phosphorescence brightness is high when the average particle size is in the range of 10 to 30 μm.
The phosphorescence brightness is higher and more stable in the range of 1000 to 10 ...
The same applies to other phosphors of the present invention, and the optimum particle size range of the average particle size is 5 to 1000 nm.
The preferred range was 10 to 30 μm, and the more preferred range was 10 to 30 μm. As explained above, in europium-activated rare earth oxysulfide phosphors,
and a coactivator selected from the group consisting of Mg, Ti, Nb, Ta and Ga.
By introducing at least one element and further adjusting the average particle size to 5 to 30 μm,
This makes it possible to achieve chemical stability and long-lasting properties that could not be achieved with conventional CaS:Eu,Tm phosphors.
The red-emitting afterglow photoluminescent phosphor of the present invention can achieve a red-emitting afterglow lamp. Industrial Applicability The red-emitting afterglow photoluminescent phosphor and afterglow lamp of the present invention can be stimulated.
Since it retains a long afterglow of several tens of minutes or more after the power is turned off, it is used in disaster prevention.
Lights that glow with an afterglow even after they are turned off, and lights that can be seen in the dark
It is used in many areas, such as clock faces.

[Brief explanation of the drawings]

Figure 1 is a cross-sectional view of an afterglow lamp and afterglow reflector of the present invention. Figure 2 is a cross-sectional view of an afterglow lamp of the present invention. Figure 3 is a cross-sectional view of an afterglow lamp of the present invention. Figure 4 is a cross-sectional view of an afterglow lamp of the present invention. Figure 5 shows the emission spectrum of the phosphor obtained in Example 1 of the present invention when excited at 365 nm.
Graph showing the excitation spectrum for 625 nm emission of the phosphor obtained in Example 1 of the present invention.
Graph showing the spectrum. Figure 7 shows the emission of the phosphor obtained in Example 34 of the present invention upon excitation at 365 nm.
Graph showing the spectrum. Figure 8 shows the comparison of the phosphors obtained in Examples 22 and 46 of the present invention with the conventional CaS:Eu
, Tm phosphors. Figure 9 shows the afterglow characteristics of the phosphors obtained in Examples 3, 8, and 21 of the present invention and the conventional Y₂O₂S
: A graph comparing the decay characteristics of Eu phosphors. Figure 10 shows the Y₂O₂S: EU_x, Mg_0.086, Ti_0.030Phosphor
The Eu content x value and the phosphorus content 1 minute after the excitation by the black light lamp was stopped
A characteristic diagram showing the relationship between light brightness. Figure 11 shows the Y₂O₂S: EU_0.082, Ti_yTi content y value of phosphor
The relationship between the phosphorescence intensity and the intensity of the black light lamp excitation one minute after it was stopped was shown.
Figure 12 shows the characteristics of Y₂O₂S: EU_0.082, Mg_0.028, Ti_zPhosphor
The Ti content z value and the phosphorus content 1 minute after the black light lamp excitation was stopped
Figure 13 shows the relationship between light intensity and Y₂O₂S: EU_0.082, Mg_0.086, Ti_0.030
The average particle size of the phosphor and the phosphor density after one minute of stopping the excitation by the black light lamp
FIG.

[Procedure Amendment] Submission of Translation of Amendment under Article 34 of the Patent Cooperation Treaty

[Submission date] June 16, 2000 (2000.6.16)

[Procedural Correction 1]

[Name of document to be corrected] Statement

[Item to be amended] Claims

[Correction method] Change

[Correction details]

[Claims]

[Procedural Correction 2]

[Name of document to be corrected] Statement

[Item name to be corrected] 0004

[Correction method] Change

[Correction details]

[0004] The afterglow of these optical storage materials is dim and short. Furthermore, the method of applying the optical storage material to the holding member
However, the brightness is insufficient. The second object of this invention is to provide a long, bright afterglow without requiring a backup power source for emergencies.
The present inventors have developed a red-emitting photoluminescent fluorescent lamp that can be used for afterglow lamps.
As a result of various researches on the body to improve the long-lasting afterglow characteristics and phosphorescence brightness,
In this case, a specific coactivator is introduced into a rare earth oxysulfide phosphor activated with europium.
The inventors discovered that the problem could be solved by using a red-emitting afterglow photoluminescent phosphor, and thus completed the present invention.
A rare earth oxysulfide phosphor activated with sodium, the chemical composition of which falls within the following range:
It is characterized by being in. Ln₂O₂S: EU_x, M_y 0.00001≦x≦0.5 0.00001≦y≦0.3 In the composition formula, Ln is selected from the group consisting of Y, La, Gd, and Lu.
At least one of M is a coactivator selected from the group consisting of Nb, Ta, and Ga.
At least one selected from the following: The activator and co-activator to be introduced into the red-emitting afterglow photoluminescent phosphor of the present invention
The activator has a significant effect on the phosphorescence brightness. For example, when Ln in the above composition formula is Y,
In this case, adjust the concentration to the following ranges: The concentration x of Eu in the activator is 0.00001 mol per 1 mol of phosphor.
The range is adjusted to 0.5 mol or less because the amount is less than 0.00001 mol.
If the amount is less than 0.5 moles, the light absorption will be poor, resulting in a low phosphorescence brightness.

[Procedural Correction 3]

[Name of document to be corrected] Statement

[Item name to be corrected] 0005

[Correction method] Change

[Correction details]

[0005] This is because, as x increases, concentration quenching occurs, resulting in a decrease in phosphorescence brightness. A more preferable range for x is 0.00001≦x≦0.1, and within this concentration range, phosphorescence brightness is further increased. By introducing coactivator M, the emission of Eu exhibits afterglow. At least one element selected from the group consisting of Nb, Ta, and Ga is effective as coactivator M. Regarding the concentration y of coactivator M, phosphorescence brightness is improved within the range of 0.00001≦y≦0.3. If the value of y is less than 0.00001, phosphorescence brightness decreases, and if it is greater than 0.3, coactivator M is less likely to be incorporated as a constituent element of the phosphor, resulting in a decrease in phosphorescence brightness. The optimum concentration range of the coactivator M is 0.005≦y≦0.1 in the case of Nb, and 0.001≦y≦0.2 in the case of Ta or Ga, and the phosphorescence brightness is significantly improved within this concentration range. When Mg is selected as the first coactivator, Ti,
By doping at least one element selected from the group consisting of Nb, Ta, and Ga, a synergistic effect is exhibited, which is effective in improving phosphorescence brightness. The concentration y of the first coactivator Mg is in the range of 0.00001≦y≦0.3, and the concentration y of the second coactivator Mg is in the range of 0.00001≦y≦0.3.
The concentration z of M' is effective in improving phosphorescence brightness when it is in the range of 0.00001≦z≦0.3. When the first coactivator is Mg, the optimum concentration range of the second coactivator M' is 0.0001≦z≦0.3 for Ti, and 0.005≦z≦0.
In the case of Ta or Ga, z is in the range of 0.001≦z≦0.2;
In this concentration range, the phosphorescence brightness is significantly improved. When the second coactivator M' is Ti, Nb, Ta, or Ga, the preferred range of the concentration y of the first coactivator Mg is 0.01≦y≦0.2.

[Procedural Correction 4]

[Name of document to be corrected] Statement

[Item name to be corrected] 0006

[Correction method] Change

[Correction details]

The red-emitting afterglow photoluminescent phosphor of the present invention is prepared by using, as a raw material, for example, Y
Metal oxides such as _2O3 , _Eu2O3 , _MgO , and _{TiO2 ,} or compounds that can be easily converted to oxides by firing at high temperatures, such as carbonates, nitrates, oxalates, and hydroxides, are selected. The purity of the raw materials has a significant effect on the phosphorescence brightness, and a purity of 99.9% or higher is recommended.
Preferably, the molar ratio is 99.99% or more, and more preferably 99.99% or more. These raw materials are weighed to a predetermined molar ratio, mixed, and then this mixture is further mixed with sulfur and an appropriate flux (such as an alkali metal carbonate), followed by firing to obtain the red-emitting afterglow photoluminescent phosphor of the present invention. The particle size of the red-emitting afterglow photoluminescent phosphor of the present invention significantly affects the phosphorescence brightness, and the average particle size is preferably adjusted to a range of 5 to 30 μm. If the average particle size is smaller than 5 μm, the phosphorescence brightness drops sharply, and even if it is larger than 30 μm, the phosphorescence brightness drops depending on the body color of the phosphor. Furthermore, if the average particle size is larger than 30 μm, the mixing and coating properties deteriorate when used for decoration, lamps, etc. A more preferred range for the average particle size is 10 to 30 μm, and within this range, the phosphorescence brightness is even higher and more stable. In the europium-activated rare earth oxysulfide phosphor, the co-activator
By introducing at least one element selected from the group consisting of Nb, Ta, and Ga, it is possible to achieve a chemically stable red-emitting photoluminescent phosphor with a long afterglow that could not be achieved with conventional CaS:Eu,Tm phosphors. Furthermore, by combining with a co-activator, the phosphorescence brightness can be further increased. The red-emitting photoluminescent phosphor of the present invention can be applied to lamps. There are various lamps that can excite afterglow phosphors. For example, incandescent lamps,
All currently used lamps, including fluorescent lamps, HID lamps, and halogen lamps, can be used. Figure 1 shows the transparent glass (
2) The inner surface and/or outer surface of the inner fluorescent lamp is coated with a persistent fluorescent material.

[Procedural Correction 5]

[Name of document to be corrected] Statement

[Item name to be corrected] 0010

[Correction method] Change

[Correction details]

[0010] This is extremely economical. As a result, it is possible to reduce the economical restrictions that come with selecting the installation location of the emergency exit light. In addition, it is effective when incorporated into a conventional emergency exit light with a backup power supply, and it continues to function as an emergency exit light even if the backup power supply or power supply circuit is cut off due to a disaster.
It is possible to provide an extremely reliable emergency exit light. Furthermore, when used for lighting indoors, corridors, or stairs, not only in emergencies, the high-intensity afterglow continues for a while even after the switch is turned off, so it can be used as auxiliary lighting to illuminate the floor until you reach the exit. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view of the afterglow lamp and afterglow reflector of the present invention. Figure 2 is a cross-sectional view of the afterglow lamp of the present invention. Figure 3 is a cross-sectional view of the afterglow lamp of the present invention. Figure 4 is a cross-sectional view of the afterglow lamp of the present invention. Figure 7 is a graph showing the emission spectrum of the phosphor obtained in Example 34 of the present invention when excited at 365 nm. Figure 8 is a graph showing the emission spectrum of the phosphors obtained in Examples 22 and 46 of the present invention and the conventional CaS:Eu
9 is a graph comparing the decay characteristics of the phosphors obtained in Examples 3, 8, and 21 of the present invention with those of the conventional Y ₂ O ₂ S
10 is a graph comparing the decay characteristics of Y ₂ O ₂ S:Eu _x ,Mg _0.086 ,Ti _0.030 phosphors with different Eu contents x.

[Procedural Correction 6]

[Name of document to be corrected] Statement

[Item name to be corrected] 0011

[Correction method] Change

[Correction details]

[0011] The relationship between the value and the phosphorescence brightness one minute after excitation by the black light lamp was stopped was
Figure 12 shows the characteristics of Y₂O₂S: EU_0.082, Mg_0.028, Ti_zPhosphor
The Ti content z value and the phosphorus content 1 minute after the black light lamp excitation was stopped
Figure 13 shows the relationship between light intensity and Y₂O₂S: EU_0.082, Mg_0.086, Ti_0.030
The average particle size of the phosphor and the phosphor density after one minute of stopping the excitation by the black light lamp
A characteristic diagram showing the relationship between the light intensity and the phosphor. BEST MODE FOR CARRYING OUT THE INVENTION [Specific Example 1 of Manufacturing Method] However, this specific example does not represent an embodiment of the present invention. Y₂O₃46.5 g of Eu₂O₃3.0 g, MgCO
₃Weigh out 0.5 g of the mixture, place it in a ceramic pot, and mix thoroughly using a ball mill.
Then, sulfur (S) was added to the raw powder.
22.7 g, Na as a flux₂CO₃After adding 22.0 g of the above and mixing, alumina
The mixture was placed in a crucible and fired at 1100°C for 6 hours. After firing, the mixture was washed with water several times and then melted.
After washing off the agent, the product was dried at 120°C for 10 hours.₂
O₂S: EU_0.082, Mg_0.028A phosphor represented by the formula:

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[0012] [Examples 11-14] Examples 11-14 are the same as those in Example 1 except for the MgCO₃Instead of Nb₂O₅Add N
b₂O₅The same procedure is repeated with different amounts to obtain a phosphor of the following composition: Example 11...Y₂O₂S: EU_0.082, Nb_0.007 Example 12...Y₂O₂S: EU_0.082, Nb_0.018 Example 13...Y₂O₂S: EU_0.082, Nb_0.037 Example 14...Y₂O₂S: EU_0.082Nb_0.073 [Examples 15-18] Examples 15-18 are the same as Example 1 except that TiO₂and TiO₂Change the amount
Prepare in the same manner to obtain a phosphor of the following composition formula: Example 15...Y₂O₂S: EU_0.082, Mg_0.028, Ti_0.012

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[0019]

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[0022] Figure 8 shows the afterglow characteristics of the phosphors obtained in Examples 22 and 46 of the present invention, and for comparison, the conventional red-emitting phosphorescent phosphor CaS:Eu,Tm phosphor, as measured with the black light lamp. As is clear from this figure, Example 22
and _the Gd ₂ O _{2 S} :Eu _0.082 , Mg _0.086 , Ti _0.030 phosphor _{of Example} 46 _.
The phosphorescence brightness of the Nb _0.018 phosphor is much higher than that of the conventional CaS:Eu,Tm phosphor, and the phosphorescence can be observed for a long time after the excitation is stopped. Figure 9 shows the afterglow characteristics of the phosphor obtained in Example 21 of the present invention and, for comparison, the conventional red-emitting phosphor Y ₂ O ₂ S:Eu phosphor, measured under the black light lamp. As is clear from this figure, the Y ₂ O ₂ S:Eu phosphor of Example 21 has a high phosphorescence brightness.
In the case of the Eu _0.082 , Mg _0.057 , Ti _0.060 phosphor, it can be seen _that by using Mg as the first coactivator and Ti as the _second coactivator, a synergistic effect is exhibited, and the phosphorescence brightness _is further _increased .
1 shows the relationship between the content x of u and the phosphorescence brightness one minute after the excitation by the black light lamp is stopped.
It can be seen that the phosphorescence brightness is significantly improved in the range of 0.01≦x≦0.1. Figure 11 shows the relationship between the Ti content y value of the Y ₂ O ₂ S:Eu _0.082 ,Ti _y phosphor and the phosphorescence brightness 1 minute after the excitation by the black light lamp is stopped. From this figure, it is clear that the optimum concentration range is when the y value is 0.01≦y≦0.3
It can _be seen _that the phosphorescence _brightness is significantly improved in _the range _of .
Relationship between the content z of i and the phosphorescence brightness 1 minute after the excitation by the black light lamp is stopped

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Comparative Example 2 A so-called two-layer coating method will be described below, in which the same ZnS:Cu afterglow phosphor as in Comparative Example 1 is applied to the first layer, and a three-wavelength mixed phosphor is applied to the second layer.
15 g of nitrocellulose/butyl acetate binder was added to 30 g of Cu phosphor and mixed thoroughly in a porcelain pot to prepare a phosphor coating slurry.
The solution was poured into an S-glass tube, coated on the inner surface, and dried by blowing hot air. This process resulted in a coating amount of 3 g of the afterglow phosphor for the first layer.
a)Mg) ₅ ( _PO4 ) _3Cl : 30.2% Eu blue-emitting phosphor, _LaPO4 :
50 g of polyethylene oxide aqueous solution was added to 12 g of a three-wavelength mixed phosphor obtained by mixing 29.4% of Ce, Tb green-emitting phosphor and 40.4% of Y ₂ O ₃ :Eu red-emitting phosphor, and the mixture was thoroughly mixed in a porcelain pot to prepare a phosphor coating slurry. This slurry was poured into a glass tube, coated on its inner surface, and dried by passing hot air through it.
This procedure resulted in a coating amount of 3 g of three-wavelength mixed phosphor in the second layer. The rest of the process was carried out in the usual manner, including evacuation, installation of a filament, and attachment of a base, to produce a fluorescent lamp. The resulting fluorescent lamp was entirely blackened, and the lamp luminous flux was extremely low, making it impossible to obtain a commercially viable fluorescent lamp. Furthermore, the following example was used to test whether the phosphorescence intensity of a red-emitting afterglow photoluminescent phosphor differed depending on the particle size. [Specific Example 2 Showing the Manufacturing Method] However, this specific example does not represent an example of the present invention. 46.5 g of Y ₂ O ₃ (average particle size 1.0 μm), Eu ₂ O 46.5 g, and 1.0 g of SiO 2 were used as phosphor raw materials.
3.0 g of ₃ and 0.5 g of _MgCO3 were weighed out, placed in a ceramic pot, and thoroughly mixed in a ball mill to obtain a mixed raw material (hereinafter referred to as raw material powder).
22.7 g of sulfur (S) and 22.0 g of Na ₂ CO ₃ as a flux were added to the raw powder and mixed, then the mixture was placed in an alumina crucible and fired at 1150° C. for 6 hours. After firing, the mixture was washed with water several times to remove the flux, and then dried at 120° C. for 10 hours to obtain the compound.

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The chemical composition formula is Y ₂ O ₂ S:Eu _0.082 , Mg _0.028 , and the average particle size is 7.2 μm.
[Examples 83 to 86] In Examples 83 to 86, _TiO2 was further added to Specific Example 2, and phosphors having a chemical composition formula of _Y2O2S : _Eu0.082 , _Mg0.086 , _Ti0.030 and average particle sizes of 7.4 _μm , 11.5 μm, 17.3 μm, and 23.1 μm were obtained, respectively. [Examples 91 to 94] In Examples 91 to 94, _TiO2 was further added to Specific Example 2, and phosphors having a chemical composition formula of _Y2O2S : _Eu0.082 , _Mg0.086 , _Ti0.030 and average particle sizes of 8.8 μm, 14.8 μm, 20.4 μm, and 26.3 μm were obtained, respectively _.

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[0028] was obtained. In Examples 83 to 86 and 91 to 94, the average particle size was determined by measuring the specific surface area by the air permeability method and finding the average particle size of the primary particles, and this value was measured using a Fischer Subsieve Sizer (FSSS). Table 5 shows the phosphorescence brightness and average particle size 1 minute and 10 minutes after excitation was stopped for the phosphors obtained in Examples 83 to 86 and 91 to 94 of the present invention and, for comparison, a conventional red-emitting phosphorescent phosphor, CaS:Eu,Tm phosphor. This table shows that the phosphors of the present invention have high phosphorescence brightness as well as long afterglow characteristics.

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[0029]

─────────────────────────────────────────────────────── Continued from the front page (31) Priority Number: Patent Application No. 11-88279 (32) Priority Date: March 30, 1999 (March 30, 1999) (33) Priority Country: Japan (JP) (31) Priority Number: Patent Application No. 11-117774 (32) Priority Date: April 26, 1999 (April 26, 1999) (33) Priority Country: Japan (JP) (31) Priority Number: Patent Application No. 11-147733 (32) Priority Date: May 27, 1999 (May 27, 1999) (33) Priority Country: Japan (JP) (81) Designated States EP(AT,BE,CH,CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP(GH, GM, K E, LS, MW, SD, SL, SZ, UG, ZW), U A(AM, AZ, BY, KG, KZ, MD, RU, TJ , TM), AE, AL, AM, AT, AU, AZ, BA , BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE , DK, DM, EE, ES, FI, G B, GD, GE, GH, GM, HR, HU, ID, IL , IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, M G, MK, MN, MW, MX, NO, NZ, PL, PT , RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, V N, YU, ZA, ZW (Note) This publication is based on the publication published internationally by the International Bureau (WIPO). Please note that the effect of the international publication of the Japanese-language patent application (Japanese-language utility model registration application) related to this publication arises pursuant to Article 184-10, Paragraph 1 of the Patent Act (Article 48-13, Paragraph 2 of the Utility Model Act), and is unrelated to this publication.

Claims (28)

[Claims] Claim 1: A rare earth oxysulfide phosphor activated with europium,
A red-emitting afterglow photoluminescent material having a chemical formula in the following range:
ance phosphor. Ln₂O₂S: EU_x, M_y 0.00001≦x≦0.5 0.00001≦y≦0.3 In the composition formula, Ln is selected from the group consisting of Y, La, Gd, and Lu.
At least one of Mg, Ti, Nb, Ta, and Ga is a coactivator.
At least one selected from the group consisting of: 2. The red-emitting photoluminescent phosphor having a long afterglow according to claim 1, wherein the range of x in the composition formula is 0.00001≦x≦0.1. 3. In the composition formula, M is Mg, and the Mg concentration y is 0.01≦y≦0.
2. The red-emitting afterglow photoluminescent phosphor according to claim 1, wherein the luminescence intensity is in the range of 1.2. 4. The red-emitting photoluminescent phosphor according to claim 1, wherein the average particle size is in the range of 5 to 30 μm. Claim 5: A rare earth oxysulfide phosphor activated with europium,
A red-emitting afterglow photoluminescent material having a chemical formula in the following range:
ance phosphor. Ln₂O₂S: EU_x, Mg_y, M'_z 0.00001≦x≦0.5 0.00001≦y≦0.3 0.00001≦z≦0.3 In the composition formula, Ln is selected from the group consisting of Y, La, Gd, and Lu.
At least one of Mg and M' is a first coactivator and a second coactivator.
At least one element selected from the group consisting of Ti, Nb, Ta, and Ga
. 6. The red-emitting photoluminescent phosphor having a long afterglow according to claim 5, wherein M' is Ti and z is in the range of 0.0001≦z≦0.3. Claim 7: Claim 5, wherein M' is Nb and z is in the range of 0.005≦z≦0.1.
1. A red-emitting afterglow photoluminescent phosphor as described above. Claim 8: Claim 5, wherein M' is Ta and z is in the range of 0.001≦z≦0.2.
1. A red-emitting afterglow photoluminescent phosphor as described above. 9. Claim 5, wherein M' is Ga and z is in the range of 0.001≦z≦0.2.
1. A red-emitting afterglow photoluminescent phosphor as described above. 10. The red-emitting afterglow photoluminescent phosphor according to claim 5, wherein the average particle size is in the range of 5 to 30 μm. 11. A light-emitting part that converts electrical energy into light energy, and a light-emitting element that covers the light-emitting part.
In an afterglow lamp made of translucent glass, a phosphor layer is provided on at least one of the inner and outer surfaces of the translucent glass.
The phosphor layer is a red-emitting afterglow photoluminescent material represented by the following general formula:
An afterglow lamp characterized by comprising a phosphor. Ln₂O₂S: EU_x, M_y 0.00001≦x≦0.5 0.00001≦y≦0.3 In the composition formula, Ln is selected from the group consisting of Y, La, Gd, and Lu.
At least one of Mg, Ti, Nb, Ta, and Ga is a coactivator.
At least one selected from the group consisting of: 12. A red-emitting afterglow photoluminescent phosphor, wherein x in the composition formula
12. The afterglow lamp of claim 11, wherein the range of x is 0.00001≦x≦0.1. 13. A red-emitting afterglow photoluminescent phosphor, wherein M in the composition formula
12. The afterglow lamp of claim 11, wherein is Mg, and the concentration y of Mg is in the range 0.01≦y≦0.2. 14. The red-emitting afterglow photoluminescent phosphor has an average particle size of 5 to 3
12. The afterglow lamp of claim 11, wherein the afterglow wavelength is in the range of 0 μm. 15. The afterglow lamp of claim 11, wherein the afterglow lamp is a fluorescent lamp. 16. The afterglow lamp according to claim 15, wherein the phosphor layer of the fluorescent lamp comprises the red-emitting afterglow photoluminescent phosphor and a phosphor that excites it, and the emitted light color is in the white region. [Claim 17] The afterglow lamp described in Claim 16, characterized in that the phosphor layer contains at least one of the three-wavelength mixed phosphors consisting of the red-emitting afterglow photoluminescent phosphor and a blue-emitting phosphor having an emission peak near 450 nm, a green-emitting phosphor having an emission peak near 545 nm, and a red-emitting phosphor having an emission peak near 610 nm. 18. The phosphor layer according to claim 16, wherein the phosphor layer is formed of two or more phosphor layers, and an afterglow phosphor is applied to the side closest to the glass bulb.
10. The afterglow lamp according to claim 1 . 19. A light-emitting part that converts electrical energy into light energy, and a light-emitting element that covers the light-emitting part.
In a lamp made of translucent glass, a phosphor layer is provided on at least one of the inner and outer surfaces of the translucent glass.
The phosphor layer is a red-emitting afterglow photoluminescent material represented by the following general formula:
An afterglow lamp characterized by comprising a phosphor. Ln₂O₂S: EU_x, Mg_y, M'_z 0.00001≦x≦0.5 0.00001≦y≦0.3 0.00001≦z≦0.3 In the composition formula, Ln is selected from the group consisting of Y, La, Gd, and Lu.
At least one of Mg and M' is a first coactivator and a second coactivator.
At least one element selected from the group consisting of Ti, Nb, Ta, and Ga
. 20. A red-emitting afterglow photoluminescent phosphor, wherein M in the composition formula
20. The afterglow lamp of claim 19, wherein ' is Ti and z is in the range 0.0001≦z≦0.3. 21. The afterglow lamp of claim 19, wherein M' is Nb and z is in the range 0.005≦z≦0.1. 22. The afterglow lamp of claim 19, wherein M' is Ta and z is in the range 0.001≦z≦0.2. 23. The afterglow lamp of claim 19, wherein M' is Ga and z is in the range 0.001≦z≦0.2. 24. The red-emitting afterglow photoluminescent phosphor has an average particle size of 5 to 3
20. The afterglow lamp of claim 19, wherein the afterglow wavelength is in the range of 0 μm. 25. The afterglow lamp of claim 19, wherein the afterglow lamp is a fluorescent lamp. 26. The afterglow lamp according to claim 25, wherein the phosphor layer of the fluorescent lamp comprises the red-emitting afterglow photoluminescent phosphor and a phosphor that excites it, and the emitted light color is in the white region. [Claim 27] A persistent lamp as described in Claim 26, characterized in that the phosphor layer contains at least one of the three-wavelength mixed phosphors consisting of the red-emitting persistent photoluminescent phosphor and a blue-emitting phosphor having an emission peak near 450 nm, a green-emitting phosphor having an emission peak near 545 nm, and a red-emitting phosphor having an emission peak near 610 nm. 28. The phosphor layer according to claim 26, wherein the phosphor layer is formed of two or more phosphor layers, and an afterglow phosphor is applied to the side closest to the glass bulb.
10. The afterglow lamp according to claim 1 .