JP3008899U - Evacuation guide light - Google Patents

Abstract

(57) [Summary] [Purpose] Display during emergency evacuation even when there is no emergency power supply
Was made recognizable. Of the fluorescence characteristics,
By using a highly durable fluorescent phosphor,
The recognition of emergency evacuation was further improved. [Structure] A slit 21 is provided on one side and light is emitted inside.
A storage unit 20 for storing the source 30 is formed, and the storage unit 20 is formed.
And a light diffusing plate 40 continuous with the slit 21.
In addition to being provided, a phosphorescent phosphor is provided on one surface of the light diffusion plate 40.
The display unit 41 is provided. The surface on the side opposite to the display portion 41 is the reflection surface 4
It was set to 2. The phosphorescent phosphor is MAL₂ O _Four Represented by
Compounds, M is calcium, strontium, barium
At least one metal element selected from the group consisting of
A mother compound was formed from a compound consisting of the element.

Description

[Detailed description of the device]

[0001]

[Industrial applications]

 The present invention relates to an evacuation guidance light, and more specifically to an evacuation guidance light that can provide guidance display without requiring an emergency power source in the event of a power failure.

[0002]

[Prior art]

 In the past, especially in large buildings, evacuation guidance signs were provided to indicate directions to emergency stairs. Here, evacuation guidance displays are classified into those that do not have a light emitting source and those that have a light emitting source.

Here, as a device having no light emitting source, there is, for example, one in which a plate having a predetermined display is attached to a wall or the like. Such a thing is effective when there is a light inside the building, but it has no effect when the light inside the building disappears due to a power failure in an emergency. It was.

On the other hand, among the evacuation guidance displays, there is an evacuation guidance light as one having a light emitting source. With regard to this evacuation guidance light, the light source will go out in the event of an emergency with a power outage, and the AC power supply will be used to emit light in normal times, and in an emergency with a power outage, it will be switched to an abnormal power source (battery). Some continued to emit light.

Among such evacuation guidance lights, for evacuation guidance lights to be installed in a large building or the like, those that continue to emit light by switching to an emergency power source in an emergency accompanied by a power failure were often used. As such an evacuation guide light that has been conventionally used, for example, a square box-shaped display body is provided with a display section on which one direction or caution is written, and a fluorescent lamp or the like is arranged inside the display body. There was something that was formed.

[0006] Then, when the display is readable due to the light inside the building, it is used as it is, and when it is relatively dark and the display is difficult to read, the fluorescent lamp placed inside is used. It was turned on by a commercial AC power source and the light was used to recognize the display section. Furthermore, even if the commercial AC power supply is cut off during an emergency evacuation, etc., it is normally connected to the emergency power supply and the fluorescent lamp is turned on to display the indication on the display. Is recognizable.

An example of such an emergency evacuation is a time when the building is in a fire or earthquake and the commercial power supply is simultaneously shut down. If the evacuation guidance light described above is used, the evacuation guidance light display section can be recognized by the emergency power supply even in such a case, so that evacuation can be performed smoothly. However, conversely, such a conventional evacuation guidance light always required an emergency power source in case of emergency.

[0008]

[Problems to be solved by the device]

 Therefore, the invention according to claim 1 or 2 of the present invention is a case where the internal light source is cut off in an emergency evacuation or the like by forming the display portion using the phosphorescent phosphor. Also, it is an object of the present invention to provide an evacuation guide light in which the display section is formed so as to fluoresce for a certain period of time so that the display section can be recognized during an emergency evacuation even in the absence of emergency power.

Further, the invention according to claim 4, 5 or 6 has the object of the invention according to claim 1 or 2 and is excellent in fluorescence amount and persistence of fluorescence among fluorescence characteristics. It is an object of the present invention to provide an evacuation guidance light that further improves the recognizability in an emergency evacuation by using a fluorescent phosphor.

[0010]

[Means for Solving the Problems]

 In order to achieve the above-mentioned object, the device according to claim 1 of the present invention is provided with a slit on one side, and a storage part for storing a light emitting source is formed therein, and the slit has the storage part. Is provided with a continuous light diffusing plate, and a display portion is provided on one surface of the light diffusing plate with a phosphorescent phosphor.

In addition to the configuration of the invention according to claim 1, the invention according to claim 2 is characterized in that the surface of the light diffusion plate on the side opposite to the display part is a reflecting surface for reflecting light from the light emitting source. Characterize. In addition to the structure of the invention of claim 1 or 2, the invention of claim 3 is a compound in which the phosphorescent phosphor is a compound represented by MAl ₂ O ₄ , where M is calcium, strontium or barium. It is characterized in that a compound comprising at least one or more metal elements selected from the group consisting of is used as a mother crystal.

According to a fourth aspect of the invention, in addition to the structure of the first or second aspect of the invention, the phosphorescent phosphor is a compound represented by MAl ₂ O ₄ , where M is calcium or strontium. The invention of claim 5 is characterized in that a compound comprising a plurality of metal elements obtained by adding magnesium to at least one or more metal elements selected from the group consisting of barium is used as a mother crystal. In addition to the constitution of the invention described in 3 or 4, europium is added as an activator in a molar ratio of 0.001% to 10% with respect to the metal element represented by M.

Further, in addition to the constitution of the invention of claim 5, the invention of claim 6 further comprises, as a co-activator, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terribium, dysprosium, holmium, At least one element selected from the group consisting of erbium, thulium, ytterbium, lutetium, manganese, tin, and bismuth is added in a molar ratio of 0.001% to 10% with respect to the metal element represented by M.

[0014]

[Action]

 In the device according to the first aspect, the light from the light emitting source reaches the light diffusing plate by turning on the light emitting source inside. Then, this light illuminates the display part on the surface from the inside of the light diffusion plate, so that the display part can be sufficiently recognized.

Further, since the display portion is drawn by using the phosphorescent phosphor, even after the light emission from the light emitting source is stopped, the fluorescent light emission is continued for a certain period of time. . Therefore, even when the internal light source is cut off during an emergency evacuation, the display can be recognized during an emergency evacuation even when there is no emergency power supply. Further, as in the invention according to claim 2, the surface of the light diffusing plate on the side opposite to the display part is a reflecting surface for reflecting light from the light emitting source, so that the light emitting source can easily recognize when emitting light. Not only that, but also when the fluorescent color is emitted, the color is emitted with high brightness.

Further, the invention according to claim 4, 5 or 6 uses the fluorescent light storage material which is excellent in the fluorescence amount and the persistence of the fluorescence among the fluorescent characteristics, so that the visibility in the emergency evacuation is improved. Is further improved.

[0017]

【Example】

 An embodiment of the present invention will be described below with reference to the illustrated example shown in FIG. The evacuation guidance light according to this embodiment is used by being fixed to the ceiling 10 of the building. Specifically, the slit 21 is provided on one side, and the non-slit 21 side of the storage unit 20 that houses the light emitting source 30 inside is fixed to the ceiling 10. Further, a light diffusing plate 40 having a desired thickness surface is vertically provided in the slit 21 of the housing portion 20. Further, a display portion 41 drawn using a phosphorescent phosphor is formed on one surface of the light diffusion plate 40, and a reflection surface 42 is formed on the surface opposite to the display portion 41. There is.

Here, the reflecting surface 42 can be formed by applying white paint or the like. Further, as the phosphorescent phosphor for forming the display unit 41, conventionally known CaS: Bi, CaSrS: Bi, ZnS: Cu, ZnS: Cu and the like can be used.

Next, actual use of the evacuation guidance light according to such an embodiment will be described. This evacuation guidance light has a shape in which the side of the storage section 20 opposite to the slit 21 is fixed to the ceiling 10, and the storage section 20 is hung from the ceiling 10. Therefore, the internal light source 30 can emit light by wiring to the ceiling 10 side.

The light diffusing plate 40 continuous with the housing portion 20 has one surface of the thickness surface of the light diffusing plate 40 facing the light emitting source 30 of the housing portion 20, and the light emitting source 30. The light from is introduced into the light diffusion plate 40 from one thickness surface of the light diffusion plate 40. Then, the light introduced into the light diffusing plate 40 moves while repeating reflection inside the light diffusing plate 40. Although the reflection is repeated at this time, since the side opposite to the display section 41 is formed as a reflective surface, the display section 41 side is illuminated, so that various displays drawn on the display section 41 are displayed. It is recognizable.

Further, since the display unit 41 is drawn by using the phosphorescent phosphor, it is possible to continue the fluorescent color development for a certain period of time even after the light emission from the light emitting source 30 is stopped. Become. Therefore, even when the internal light source 30 is cut off during an emergency evacuation or the like, the display unit 41 can be recognized during an emergency evacuation even when there is no emergency power supply.

Although not shown in detail in the illustrated example, it is also effective to position a reflection plate inside the storage section 20 and efficiently collect the light from the light emitting source 30 into the light diffusion plate 40, for example. Also, a thickness surface other than the one thickness surface of the light diffusion plate 40 on the light emitting source 30 side can be formed as the reflection surface 42 similar to that described above. By doing so, the light from the light emitting source 30 is exposed to the outside only through the display section 41, and the recognition efficiency of the display section 41 is improved.

In the above description, the case where the light diffusion plate 40 is directly fixed to the slit 21 of the storage portion 20 has been described as an example, but the light diffusion plate 40 is fixed to the storage portion 20 via the fixing member. It is also possible to fix it to 20. Further, although the reflecting surface 42 has been described as a white paint, it may be a mirror finish having the reflecting surface 42 facing the inside of the light diffusion plate 40. Furthermore, it is possible to use the both surfaces of the light diffusion plate 40 as the display unit 41 without providing the reflection surface 42 so that the display of the display unit 41 can be recognized from any side.

Next, another type of phosphorescent phosphor used in the display unit 41 will be described. Examples of phosphorescent phosphors represented by MAl ₂ O ₄ are shown below, in which the kind of metal element (M), the concentration of europium as an activator or the kind and concentration of a co-activator were changed. This will be explained sequentially. First, a phosphorescent phosphor in which strontium is used as the metal element (M) and europium is used as the activator, but no co-activator is used will be described as Example 1. Example 1. Synthesis and Properties of SrAl ₂ O ₄ : Eu Phosphor Sample 1- (1) Europium oxide (Eu ₂ O) was added to europium oxide (Eu ₂ O) as an activator in 146.1 g (0.99 mol) of special grade reagent strontium carbonate and 102 g (1 mol) of alumina. ₃ ) was added at 1.76 g (0.005 mol), and further, for example, 5 g (0.08 mol) of boric acid was added as a flux, which was thoroughly mixed using a ball mill, and this sample was mixed with a nitrogen-hydrogen mixed gas using an electric furnace. Firing was performed at 1300 ° C. for 1 hour in a (97: 3) air flow (flow rate: 0.1 liter per minute). Then, the mixture was cooled to room temperature for about 1 hour, and the obtained compound powder was sieved and classified to pass through 100 mesh to obtain phosphor sample 1- (1).

FIG. 2 shows the result of analyzing the crystal structure of the synthesized phosphor by XRD (X-ray diffraction). It was revealed that the phosphor obtained from the characteristics of the diffraction peak has the spinel structure of SrAl ₂ O ₄ . FIG. 3 shows the excitation spectrum of this phosphor and the emission spectrum of the afterglow after the stimulus was stopped.

From the figure, it became clear that the peak wavelength of the emission spectrum was green emission with a wavelength of about 520 nm. Next, the afterglow characteristics of this SrAl ₂ O ₄ : Eu phosphor were measured using a commercially available ZnS: Cu phosphorescent phosphor (product name GSS manufactured by Nemoto Special Chemical Co., Ltd., product name GSS, emission peak wavelength: 530 nm). The results measured by comparison with the afterglow characteristics are shown in FIG. 4 and Table 2.

To measure the afterglow characteristics, 0.05 g of the phosphor powder was weighed in an aluminum sample pan with an inner diameter of 8 mm (sample thickness: 0.1 g / cm 2), and stored in the dark for about 15 hours, and the afterglow was measured. After deleting, D₆₅It was stimulated with a standard light source at a brightness of 200 lux for 10 minutes, and the afterglow after that was measured with a luminance measuring device using a photomultiplier tube. As is clear from FIG. 4, SrAl according to the present invention₂ O_Four It can be seen that the afterglow of the: Eu phosphor is extremely large and the attenuation thereof is gentle, and the afterglow intensity difference with the ZnS: Cu phosphorescent phosphor increases with the passage of time. Also, in the figure, the level of emission intensity (corresponding to a brightness of about 0.3 mCd / m2) which is sufficiently perceptible to the naked eye is shown by a broken line.₂ O_Four It is estimated from the afterglow characteristics of the Eu phosphor that the emission can be recognized even after about 24 hours. This SrAl that has actually passed 15 hours after stimulation ₂ O_Four : When the Eu phosphor was observed with the naked eye, its afterglow could be sufficiently confirmed.

Further, in Sample 1- (1) in Table 2, the afterglow intensity 10 minutes, 30 minutes and 100 minutes after the stimulation was stopped was shown as a relative value with respect to the intensity of the ZnS: Cu phosphorescent phosphor. From this table, it can be seen that the afterglow brightness of the SrAl ₂ O ₄ : Eu phosphor according to the present invention is 2.9 times that of the ZnS: Cu phosphorescent phosphor after 10 minutes and 17 times after 100 minutes. Furthermore, the photoluminescence characteristics (glow curve) from room temperature to 250 ° C when the SrAl ₂ O ₄ : Eu phosphor according to the present invention was photostimulated were investigated using a TLD reader (KYOKKO TLD-2000 system). 5 shows. From the figure, it can be seen that the thermoluminescence of the present phosphor comprises three glow peaks of about 40 ° C, 90 ° C, and 130 ° C, and the peak of about 130 ° C is the main glow peak. In light of the fact that the main glow peak of the ZnS: Cu phosphorescent phosphor shown by the broken line in the figure is about 40 ° C, the deepness corresponding to the high temperature of 50 ° C or more of the SrAl ₂ O ₄ : Eu phosphor according to the present invention is high. It is considered that the trap levels increase the afterglow time constant and contribute to the long-term light storage characteristics.

Samples 1- (2) to (7) Next, in the same manner as described above, the SrAl ₂ O ₄ : Eu phosphor sample having the compounding ratio shown in Table 1 in which the concentration of europium was changed (Sample 1- (2) to (7)) were adjusted.

[0030]

[Table 1]

The results of examining the afterglow characteristics of Samples 1- (2) to (7) are shown in Table 2 together with the results of examining the afterglow characteristics of 1- (1). From Table 2, it can be seen that when the amount of Eu added is in the range of 0.0025 to 0.05 mol, the afterglow property is superior to that of the ZnS: Cu phosphorescent phosphor including the brightness after 10 minutes. Recognize. However, even if the amount of Eu added is 0.00001 mol or 0.1 mol, it has a brightness higher than that of the ZnS: Cu phosphorescent phosphor by the lapse of 30 minutes or more after the stimulation is stopped. I also know that.

Further, since Eu is expensive, considering economical efficiency and deterioration of afterglow characteristics due to concentration quenching, it is not so meaningful to set Eu to 0.1 mol (10 mol%) or more. Becomes On the contrary, judging from the afterglow characteristics, when Eu is between 0.00001 mol (0.001 mol%) and 0.00005 mol (0.005 mol%), the ZnS: Cu phosphorescent property is observed after 10 minutes of luminance. Although the brightness is inferior to that of the phosphor, a brightness higher than that of the ZnS: Cu phosphorescent phosphor is obtained 30 minutes or more after the stimulus is stopped. Therefore, the effect of adding Eu used as an activator is clear. .

Further, since the SrAl ₂ O ₄ : Eu phosphor is an oxide type, it is chemically stable and excellent in light resistance as compared with the conventional sulfide type phosphorescent phosphor. (See Tables 24 and 25).

[0034]

[Table 2]

Next, a phosphorescent phosphor using strontium as the metal element (M), europium as the activator, and dysprosium as the coactivator will be described as Example 2. Example 2. Synthesis of SrAl ₂ O ₄ : Eu, Dy Phosphor and Its Properties Sample 2- (1) Strontium carbonate 144.6 g (0.98 mol) of reagent grade and europium oxide (Eu) as an activator were added to 102 g (1 mol) of alumina. ₂ O ₃ ), 1.76 g (0.005 mol), dysprosium oxide (D y ₂ O ₃ ) 1.87 g (0.005 mol) as a co-activator, and 5 g (0.08 mol) boric acid as a flux. Mol) and thoroughly mixed using a ball mill, and then this sample was heated to 1300 ° C in a nitrogen-hydrogen mixed gas (97: 3) stream (flow rate: 0.1 liter per minute) using an electric furnace. It was baked for 1 hour. Then, the mixture was cooled to room temperature for about 1 hour, and the obtained compound powder was classified by sieving and passed through 100 mesh to obtain a phosphor sample 2- (1).

The afterglow characteristics of this phosphor were investigated by the same method as described above, and the results are shown in Sample 2- (1) of FIG. 6 and Table 4. As is clear from FIG. 6, SrAl according to the present invention₂ O_Four : The afterglow brightness of the Eu, Dy phosphors, especially the brightness at the initial stage of the afterglow is extremely high as compared with the ZnS: Cu phosphorescent phosphor, and its decay time constant is also large. It can be seen that it is a high brightness phosphorescent phosphor. The visible afterglow intensity level shown in the figure and this SrAl ₂ O_Four : It is possible to discriminate the emission even after about 16 hours from the afterglow characteristics of the Eu and Dy phosphors.

In Table 4, the afterglow intensity after 10, 30, and 100 minutes after stimulation is shown as a relative value with respect to the intensity of the ZnS: Cu phosphorescent phosphor. From the table, SrAl ₂ O according to the present invention is shown. It can be seen that the afterglow brightness of the ₄ : Eu, Dy phosphor is 12.5 times that of the ZnS: Cu phosphorescent phosphor after 10 minutes and 37 times after 100 minutes. Further, FIG. 7 shows the results of investigation of the thermoluminescence property (glow curve) from room temperature to 250 ° C. when the SrAl ₂ O ₄ : Eu, Dy phosphor according to the present invention was photostimulated. From FIG. 7 and FIG. 5, it can be seen that the main glow peak temperature of thermoluminescence changed from 130 ° C. to 90 ° C. by the action of Dy added as a co-activator. The large emission from the trap level corresponding to the temperature of 90 ° C. is considered to be the cause of exhibiting higher brightness at the initial stage of afterglow as compared with the SrAl ₂ O ₄ : Eu phosphor.

Samples 2- (2) to (7) Next, in the same manner as described above, the SrAl ₂ O ₄ : Eu, Dy phosphor sample ((SrAl ₂ O ₄ : Eu, Dy phosphor sample having the composition ratio shown in Table 3 in which the concentration of dysprosium was changed ( Samples 2- (2) to (7)) were prepared.

[0039]

[Table 3]

The results of examining the afterglow characteristics of Samples 2- (2) to (7) are shown in Table 4 together with the results of examining the afterglow characteristics of 2- (1). From Table 4, 0.0025 to 0 based on the fact that the amount of Dy added as a co-activator is far superior to the ZnS: Cu phosphorescent phosphor including the brightness after 10 minutes. It can be seen that 0.05 mol is optimum. However, even if the amount of Dy added is 0.00001 mol, it becomes more bright than that of the ZnS: Cu phosphorescent phosphor when 30 minutes or more has elapsed after the stimulation was stopped. The effect of adding Eu and Dy used as agents and co-activators is clear. Moreover, since Dy is expensive, considering economic efficiency and deterioration of afterglow characteristics due to concentration quenching, it is meaningless to set Dy to 0.1 mol (10 mol%) or more. Become.

Since the SrAl ₂ O ₄ : Eu, Dy phosphor is an oxide type, it is chemically stable and excellent in light resistance as compared with the conventional sulfide type phosphorescent phosphor. (See Tables 24 and 25).

[0042]

[Table 4]

Next, a phosphorescent phosphor using strontium as the metal element (M), europium as the activator, and neodymium as the coactivator will be described as Example 3. Example 3. Synthesis of SrAl ₂ O ₄ : Eu, Nd Phosphor and Its Properties Sample 3- (1) to (7) SrAl _{2 of the} compounding ratio shown in Table 5 in which the concentration of neodymium was changed by the same method as described above. O ₄ : Eu, Nd-based phosphor samples (Samples 3- (1) to (7)) were prepared.

[0044]

[Table 5]

Table 6 shows the results of investigating the afterglow characteristics of these samples 3- (1) to (7).

[0046]

[Table 6]

From Table 6, when the amount of Nd added as the co-activator is in the range of 0.0025 to 0.10 mol, the amount of Nd remaining after 10 minutes is higher than that of the ZnS: Cu phosphorescent phosphor. It can be seen that it has excellent light characteristics. Even when the amount of Nd added is 0.00001 mol, the activator has a brightness higher than that of the ZnS: Cu phosphorescent phosphor 60 minutes after the stimulation is stopped. Also, the effect of adding Eu and Nd used as co-activators is clear. Further, since Nd is expensive, it is meaningless to set Nd to 0.1 mol (10 mol%) or more in consideration of economy and deterioration of afterglow characteristics due to concentration quenching.

Since the SrAl ₂ O ₄ : Eu, Nd phosphor is an oxide type, it is chemically stable and excellent in light resistance as compared with the conventional sulfide type phosphorescent phosphor. (See Tables 24 and 25). Further, the thermoluminescence characteristics (glow curve) from room temperature to 250 ° C. when photostimulating the SrAl ₂ O ₄ : Eu, Nd phosphor according to the present invention was investigated for Sample 3- (4), and the results are shown in FIG. It was From the figure, it can be seen that the main glow peak temperature of thermoluminescence of the phosphor to which Nd is added as a co-activator is about 50 ° C.

Next, strontium is used as the metal element (M), europium is used as the activator, and further lanthanum, cerium, praseodymium, samarium, gadolinium, terbium, holmium, erbium, thulium, and ytterbium are used as co-activators. Example 4 will be described as a phosphorescent phosphor in the case of using any of the elements of bimium, lutetium, manganese, tin, and bismuth.

Here, regarding the activator and each co-activator, from the example in the case of using europium, neodymium, or dysprosium, the activator and the co-activator are each 0. Considering that high afterglow brightness can be obtained when about 005 mol is added, the Eu concentration of the activator is 0.5 mol% (0.005 mol) and the concentration of the coactivator is 0.5 mol% (0.005 mol). Only the sample is illustrated. Example 4. Effect of Other Co-Activator on SrAl ₂ O ₄ : Eu-Based Phosphor As described above, lanthanum, cerium, praseodymium, samarium, gadolinium, terbium, holmium, erbium, thulium, ytterbium, lutetium as a co-activator. Table 7 shows the results of investigating the afterglow characteristics of phosphor samples to which manganese, tin, and bismuth were added.

As is clear from Table 7, in comparison with the afterglow characteristics of the commercially available ZnS: Cu phosphor used as a standard, all of the SrAl ₂ O ₄ : Eu phosphor samples were 30% after the stimulation was stopped. After a long time of 100 minutes to 100 minutes, the afterglow characteristic is improved, and it can be seen that it is at a practical level. Since the SrAl ₂ O ₄ : Eu-based phosphor is an oxide-based phosphor, it is chemically stable and excellent in light resistance as compared with the conventional sulfide-based phosphorescent phosphor ( See Tables 24 and 25).

[0052]

[Table 7]

Next, although calcium is used as a metal element (M) and europium is used as an activator, a phosphorescent phosphor without a co-activator, and calcium as a metal element, and europium as an activator By using at least one element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin, and bismuth as a coactivator. The case where it is used will be described as Example 5. Example 5. Synthesis of CaAl ₂ O ₄ : Eu-based phosphorescent phosphors and their characteristics: Europium oxide (Eu ₂ O ₃ ) as an activator added to special grade calcium carbonate and alumina, as a coactivator. , Lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin, or bismuth, each added with its oxide. On the other hand, 5 g (0.08 mol) of boric acid, for example, was further added as a flux and thoroughly mixed using a ball mill, and then this sample was placed in an electric furnace in a nitrogen-hydrogen mixed gas (97: 3) stream (flow rate: It was calcined at 1300 ° C. for 1 hour. Then, the mixture was cooled to room temperature for about 1 hour, and the obtained compound powder was classified by sieving and passed through 100 mesh to obtain phosphor samples 5- (1) to (42).

The result of XRD analysis of the sample 5- (2) obtained here is shown in FIG. From the figure, it was revealed that this phosphor was composed of a monoclinic CaAl ₂ O ₄ crystal. Next, as a representative example, the thermoluminescence of samples 5- (10), 5- (16), 5- (22) and 5- (28) using neodymium, samarium, dysprosium and thorium as co-activators The results of examining the characteristics (glow curve) are shown in FIGS. 10 and 11. Since each of them has a glow peak in a high temperature region of 50 ° C. or higher, it is suggested that these phosphors have long afterglow characteristics. Further, when the emission spectrum of the afterglow of the sample was measured, as shown in FIG. 12, all the phosphors emitted blue light with an emission peak wavelength of about 442 nm.

Therefore, the afterglow characteristics of each of the conventional blue-light-emitting phosphorescent phosphors CaSrS: Bi (trade name BA-S: emission wavelength 454 nm manufactured by Nemoto Special Chemical Co., Ltd.) are used as a standard. Tables 8 to 13 show the results of comparative comparison of the above. From Table 8, for the CaAl ₂ O ₄ : Eu phosphor, when Eu is 0.005 mol (0.5 mol%), the brightness in the initial afterglow is low, but after 100 minutes, it is almost the same as the commercial standard product. And the like, and as shown in Tables 9 to 13, it is greatly sensitized by adding a co-activator, and any of the co-activators has sufficiently high practical fluorescence. I got a body. Especially for Nd, Sm, and Tm, the effect of addition is extremely large, and it is clear that an ultrahigh-luminance blue-light-emitting phosphorescent phosphor that is more than an order of magnitude brighter than commercial products can be obtained, and it can be said that this is an epoch-making phosphor. FIG. 13 shows the results of investigating the afterglow characteristics of the high-brightness phosphor obtained by co-activating Nd, Sm, and Tm over a long period of time.

In detail, although calcium is used as the metal element (M) and europium is used as the activator, 5- (1) to (6) are used as the phosphorescent phosphor in the case where the coactivator is not used. Table 8 shows the afterglow characteristics of the phosphorescent phosphor shown in FIG.

[0057]

[Table 8]

In addition, when calcium is used as the metal element (M), europium is used as the activator, and neodymium is used as the co-activator, phosphorescent phosphors shown in 5- (7) to (12) are shown. Table 9 shows the afterglow characteristics of the phosphorescent phosphor.

[0059]

[Table 9]

Furthermore, calcium is used as the metal element (M), europium is used as the activator, and samarium is used as the co-activator, as the phosphorescent phosphors shown in 5- (13) to (18). Table 10 shows the afterglow characteristics of the phosphorescent phosphor.

[0061]

[Table 10]

In addition, when calcium is used as the metal element (M), europium is used as the activator, and dysprosium is used as the coactivator, phosphorescent phosphors shown in 5- (19) to (24) are shown. Table 11 shows the afterglow characteristics of the phosphorescent phosphors.

[0063]

[Table 11]

When calcium is used as the metal element (M), europium is used as the activator, and thulium is used as the co-activator, 5- (25) to (30) are shown as phosphorescent phosphors. Table 12 shows the afterglow characteristics of the phosphorescent phosphors.

[0065]

[Table 12]

Calcium is used as the metal element (M), europium is used as the activator, and lanthanum, cerium, praseodymium, gadolinium, terbium, holmium, erbium, ytterbium, lutetium, manganese, tin, and bismuth are used as coactivators. Table 13 collectively shows the afterglow characteristics of the phosphorescent phosphors shown in 5- (31) to (42) as the phosphorescent phosphors when any of the above elements was used.

In the phosphorescent phosphors shown in 5- (31) to (42), 0.5 mol% each of europium as an activator and another co-activator was added.

[0068]

[Table 13]

Next, a case will be described as Example 6 in which calcium is used as the metal element (M), europium is used as the activator, and neodymium is used as the co-activator, but other co-activators are also added at the same time. Example 6. CaAl ₂ O _4: Eu, adding europium as Nd-based phosphorescent phosphors synthesized with activator to its characteristics reagent grade calcium carbonate and alumina as europium oxide (Eu ₂ O _3), neodymium thereto as a co-activator In addition to, and as other co-activators, elements other than neodymium such as lanthanum, cerium, praseodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, soot, and bismuth. 5 g (0.08 mol) of boric acid, for example, was added as a flux to each of these oxides added, and thoroughly mixed using a ball mill, and this sample was mixed with a nitrogen-hydrogen mixture using an electric furnace. 1300 ℃ in a gas (97: 3) stream (flow rate: 0.1 liters per minute) It was baked for one hour. Then, the mixture was cooled to room temperature for about 1 hour, and the obtained compound powder was classified by sieving and passed through 100 mesh to obtain phosphor samples 6- (1) to (43).

Here, first, various phosphor samples were prepared with Eu: 0.5 mol%, Nd: 0.5 mol%, and other co-activator: 0.5 mol%, and after 10 minutes the luminance and after 30 minutes The brightness and the brightness after 100 minutes were measured. The results are shown in Table 14 as 6- (1) to (15).

[0071]

[Table 14]

From these measurement results, among the coactivators added together with neodymium, it was confirmed that lanthanum, dysprosium, gadolinium, holmium, erbium, and the like had particularly excellent afterglow brightness. Therefore, next, an experiment was conducted by changing the concentration of lanthanum from 0.1 mol% to 10 mol% after setting Eu: 0.5 mol% and Nd: 0.5 mol%. The results are shown in Table 15 as 6- (16) to (21).

[0073]

[Table 15]

An experiment was conducted by changing the concentration of dysprosium from 0.1 mol% to 10 mol% after setting Eu: 0.5 mol% and Nd: 0.5 mol%. The results are shown in Table 16 as 6- (22) to (27).

[0075]

[Table 16]

An experiment was conducted by changing the concentration of gadolinium from 0.1 mol% to 10 mol% after setting Eu: 0.5 mol% and Nd: 0.5 mol%. The results are shown in Table 17 as 6- (28) to (32).

[0077]

[Table 17]

An experiment was conducted by changing the concentration of holmium from 0.1 mol% to 10 mol% after setting Eu: 0.5 mol% and Nd: 0.5 mol%. The results are shown in Table 18 as 6- (33) to (37).

[0079]

[Table 18]

Experiments were carried out by changing the concentration of erbium from 0.1 mol% to 5 mol% after setting Eu: 0.5 mol% and Nd: 0.5 mol%. The results are shown in Table 19 as 6- (38) to (43).

[0081]

[Table 19]

From these measurement results, it was confirmed that when a plurality of types of co-activators were mixed, the afterglow brightness was improved. Furthermore, in that case, it was also confirmed that the best afterglow characteristics were exhibited when Eu: 0.5 mol% and Nd: 0.5 mol% and other co-activators were also added at about 0.5 mol%. It was Next, a phosphorescent phosphor using barium as the metal element (M), europium as the activator, and neodymium or samarium as the coactivator will be described as Example 7. Example 7. BaAl ₂ O ₄ : Eu-based phosphor Here, 7- (1) and 7- (2) are obtained by adding 0.5 mol% of Eu and further adding 0.5 mol% of Nd or Sm, respectively.

FIG. 14 shows the excitation spectrum and the afterglow emission spectrum after 30 minutes from the termination of stimulation, when neodymium was used as a co-activator in the present phosphor. Further, FIG. 15 shows the excitation spectrum and the afterglow emission spectrum after 30 minutes from the stimulus stop when samarium was used as a co-activator.

Since the peak wavelengths of the emission spectra are all about 500 nm and green light is emitted, Table 20 shows that the ZnS: Cu phosphorescent phosphor (Numoto Special Chemicals) whose afterglow characteristics are commercially available and emits green light. (Manufactured by Co., Ltd .: product name GSS, emission peak wavelength: 530 nm), and the afterglow intensity 10 minutes, 30 minutes, and 100 minutes after the stimulation was stopped was shown as a relative value.

[0085]

[Table 20]

From this Table 20, BaAl₂ O_Four It can be seen that: Eu and Nd are superior to the ZnS: Cu phosphorescent phosphor in the afterglow brightness for about 30 minutes after the stimulation is stopped. Also BaAl ₂ O_Four : Eu and Sm were slightly inferior in afterglow brightness to the ZnS: Cu phosphorescent phosphor. However, without adding Eu or other co-activator, BaAl₂ O _Four As a result of an experiment conducted only with crystals, it was confirmed that fluorescence and afterglow were not observed at all, so it is clear that the activation effect can be obtained by adding Eu and Nd or Sm.

Since the BaAl ₂ O ₄ : Eu phosphor is an oxide phosphor, it is chemically stable and excellent in light resistance as compared with the conventional sulfide phosphorescent phosphor. Yes (see Tables 24 and 25). Next, a case where a mixture of calcium and strontium is used as the metal element (M) will be described as Example 8. Example 8. Synthesis and characteristics of Sr _X Ca _1-X Al ₂ O ₄ -based phosphorescent phosphors Special grade reagent strontium carbonate and calcium carbonate were mixed at different ratios, alumina was added to the sample, and europium was added as an activator. As a co-activator, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin, or bismuth was added. For example, 5 g (0.08 mol) of boric acid was added as a flux, and a Sr _X Ca _1-X Al ₂ O ₄ -based phosphor sample was synthesized by the method described above.

As a typical characteristic of the obtained phosphor, the emission spectrum of the afterglow of the Sr _0.5 Ca _0.5 Al ₂ O ₄ : Eu, Dy phosphor (Eu _0.5 mol% and Dy _0.5 mol% added) was examined. The results obtained are shown in FIG. From the figure, when a part of Sr is replaced by Ca, the emission spectrum shifts to the short wavelength side, and the afterglow of the intermediate color between the emission by the SrAl ₂ O ₄ -based phosphor and the emission by the CaA 1 ₂ O ₄ -based phosphor is generated. It became clear that we could get it.

Next, FIG. 17 shows the results of examining the afterglow characteristics of Sr _x Ca _{1 -x} Al ₂ O ₄ -based phosphor samples to which 0.5 mol% of Eu and Dy were added as activators and co-activators, respectively. Indicated. It can be seen from FIG. 17 that for any of the phosphors, a highly practical phosphorescent phosphor having excellent afterglow characteristics equivalent to or higher than that of the commercial standard product shown by the broken line in the figure can be obtained.

Next, a case where a mixture of strontium and barium is used as the metal element (M) will be described as Example 9. Example 9. Synthesis of Sr _X Ba _1-X Al ₂ O ₄ -based phosphorescent phosphor and its characteristics A reagent grade strontium carbonate and barium carbonate were mixed in different proportions, and alumina was added to the sample, followed by europium as an activator. A flux of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin, or bismuth was added as a coactivator. For example, 5 g (0.08 mol) of boric acid was added, and a Sr _X Ba _{1 -X} Al ₂ O ₄ -based phosphor sample was synthesized by the method described above.

As a typical characteristic of the obtained phosphor, afterglow of a Sr _X Ba _{1 -X} Al ₂ O ₄ -based phosphor sample prepared by adding 0.5 mol% of Eu and 0.5 mol% of Dy The results of examining the characteristics are shown in FIG. It can be seen from FIG. 18 that for any of the phosphors, a highly practical phosphorescent phosphor having an excellent afterglow characteristic equivalent to or higher than that of the commercial standard product shown by the broken line in the figure can be obtained.

Next, a case where a mixture of strontium and magnesium is used as the metal element (M) will be described as Example 10. Example 10. Synthesis and characteristics of Sr _X Mg _1-X Al ₂ O ₄ -based phosphorescent phosphors Strontium carbonate and magnesium carbonate of reagent grade were mixed at different ratios, alumina was added to the sample, and europium was added as an activator. , To which lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin, or bismuth was added as a coactivator. For example, 5 g (0.08 mol) of boric acid was added as a flux, and a Sr _X Mg _1-X Al ₂ O ₄ -based phosphor sample was synthesized by the method described above. Afterglow characteristics of Sr _X Mg _1-X Al ₂ O ₄ -based phosphor samples prepared by adding 0.5 mol% of Eu and 0.5 mol% of Dy as a representative property of the obtained phosphor were investigated. The results obtained are shown in FIG.

From FIG. 19, except for the case where strontium / magnesium was 0.1 / 0.9, all the phosphors were equal to or better than the commercial standard product shown by the broken line in the figure. It can be seen that a highly practical phosphorescent phosphor having afterglow characteristics can be obtained. Next, a case where a plurality of metal elements are used as the metal element (M), europium is used as the activator, and two kinds of co-activators are used will be described as Example 11. Example 11. Synthesis of Ca _1-X Sr _X Al ₂ O ₄ : Eu, Nd, X phosphor and its characteristics Reagent grade strontium carbonate and calcium carbonate were mixed at different ratios, and alumina was added to the sample, followed by activator. With 0.5 mol% europium as the coactivator, and 0.5 mol% neodymium as the coactivator, and 0.5 mol% of any of the elements of lanthanum, dysprosium, and holmium as the other coactivator. For example, 5 g (0.08 mol) of boric acid was added as a flux, and Ca _1-X Sr _X Al ₂ O ₄ : Eu, Nd, X-based phosphor samples 11- (1) to (9) were added by the method described above. ) Was synthesized and its afterglow characteristics were investigated.

First, strontium carbonate as a reagent grade and calcium carbonate were mixed in different proportions, alumina was added to the sample, and 0.5 mol% of europium as an activator and 0.5 mol of neodymium as a coactivator were added. %, And 0.5% by mol of lanthanum as another co-activator is shown in Table 21 as 11- (1) to 11- (3).

[0095]

[Table 21]

Further, strontium carbonate and calcium carbonate, which are special grade reagents, were mixed in different proportions, alumina was added to the sample, and 0.5 mol% of europium as an activator and 0.5 mol% of neodymium as a coactivator were added. In addition, as another co-activator, the addition of 0.5 mol% of dysprosium is shown in Table 22 as 11- (4) to 11- (6).

[0097]

[Table 22]

Further, strontium carbonate and calcium carbonate, which are special grade reagents, were mixed in different ratios, alumina was added to the sample, and 0.5 mol% of europium as an activator and 0.5 mol% of neodymium as a coactivator were added. In addition, as another co-activator, the addition of 0.5 mol% of holmium is shown in Table 23 as 11- (7) to 11- (9).

[0099]

[Table 23]

From these measurement results, when the metal element (M) was a plurality of metal elements (M) composed of calcium and strontium, europium was added as an activator, and a plurality of coactivators were added It was confirmed that even after 10 minutes, including the luminance, it was superior to CaSrS 2: Bi. Example 12. Moisture resistance property test Table 24 shows the results of investigation of the moisture resistance property of the phosphorescent phosphor obtained by the present invention.

In this investigation, a plurality of phosphor samples were left in a thermo-hygrostat controlled at 40 ° C. and 95% RH for 500 hours, and the change in luminance before and after that was measured. From the table, it can be seen that the phosphors of any composition are stable and hardly affected by humidity.

[0102]

[Table 24]

Example 13. Results of light resistance test The results of light resistance test of the phosphorescent phosphor obtained according to the present invention are shown in Table 25 in comparison with the result of zinc sulfide-based phosphor. In this test, according to JIS standard, the sample was placed in a transparent container whose humidity was adjusted to saturated humidity, and light was irradiated under a 300 W mercury lamp at a position of 30 cm for 3 hours, 6 hours, and 12 hours, and the change in luminance after that was measured. .

From the table, it can be seen that it is extremely stable as compared with the conventional zinc sulfide-based phosphor.

[0105]

[Table 25]

The phosphorescent phosphor according to the present invention can be used by coating it on the surface of various products, or it can be mixed with plastic, rubber, glass or the like.

[0107]

[Effect of device]

 As described above, in the invention according to claim 1 or 2, among the present invention, the internal light source is cut off in an emergency evacuation or the like by forming the display portion using the phosphorescent phosphor. Even in such a case, the display unit is formed so that it emits fluorescent light for a certain period of time so that the display unit can be recognized during an emergency evacuation even when there is no emergency power supply.

Further, the invention according to claim 4, 5 or 6 has the effect of the invention according to claim 1 or 2, and is excellent in fluorescence amount and persistence of fluorescence among the fluorescence characteristics. By using a fluorescent phosphor, the recognizability during an emergency evacuation is further improved.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a state of being attached to a ceiling.

FIG. 2 shows an XR crystal structure of a SrAl ₂ O ₄ : Eu phosphor.
It is a graph which showed the result analyzed by D.

FIG. 3 is a graph showing an excitation spectrum of a SrAl ₂ O ₄ : Eu phosphor and an emission spectrum after 30 minutes have passed since the stimulation was stopped.

FIG. 4 shows the afterglow characteristics of SrAl ₂ O ₄ : Eu phosphor as Z.
6 is a graph showing the results of comparison with the afterglow characteristics of the n: S phosphor.

FIG. 5 is a graph showing thermoluminescence characteristics of SrAl ₂ O ₄ : Eu phosphor.

FIG. 6 is a graph showing a result of comparison of afterglow characteristics of a SrAl ₂ O ₄ : Eu, Dy phosphor with those of a Zn: S phosphor.

FIG. 7 is a graph showing thermoluminescence characteristics of SrAl ₂ O ₄ : Eu, Dy phosphor.

FIG. 8 is a graph showing thermoluminescence characteristics of SrAl ₂ O ₄ : Eu, Nd phosphor.

FIG. 9 shows the X-ray crystal structure of a CaAl ₂ O ₄ : Eu-based phosphor.
It is a graph which showed the result analyzed by RD.

FIG. 10 is a graph showing thermoluminescence characteristics of CaAl ₂ O ₄ : Eu-based phosphors using neodymium or samarium as a co-activator.

FIG. 11 is a graph showing thermoluminescence characteristics of CaAl ₂ O ₄ : Eu phosphors using dysprosium or thorium as a coactivator.

FIG. 12 is a graph showing an emission spectrum of a CaAl ₂ O ₄ : Eu-based phosphor after 5 minutes have elapsed since the stimulation was stopped.

FIG. 13: CaAl ₂ O ₄ : Eu, Sm phosphor and Ca
6 is a graph showing a result of comparison of afterglow characteristics of Al ₂ O ₄ : Eu, Nd phosphor with afterglow characteristics of Zn: S phosphor.

FIG. 14 is a graph showing an excitation spectrum of a BaAl ₂ O ₄ : Eu, Nd phosphor and an emission spectrum after 30 minutes have elapsed since the stimulation was stopped.

FIG. 15 is a graph showing an excitation spectrum of a BaAl ₂ O ₄ : Eu, Sm phosphor and an emission spectrum after 30 minutes have passed since the stimulation was stopped.

FIG. 16 is a graph showing an emission spectrum of a Sr _0.5 Ca _0.5 Al ₂ O ₄ : Eu, Dy phosphor.

FIG. 17 is a graph comparing afterglow characteristics of Sr _x Ca _1-x Al ₂ O ₄ : Eu, Dy phosphors with afterglow characteristics of Zn: S phosphors and CaSrS: Bi phosphors.

FIG. 18 is a graph comparing afterglow characteristics of Sr _x Ba _1-x Al ₂ O ₄ : Eu, Dy phosphors with afterglow characteristics of Zn: S phosphors.

FIG. 19 is a graph comparing the afterglow characteristics of the Sr _x Mg _1-x Al ₂ O ₄ : Eu, Dy phosphor with the afterglow characteristics of the Zn: S phosphor.

[Explanation of symbols]

10 Ceiling 20 Storage 21 Slit 30 Light Emitting Source 40 Light Diffusing Plate 41
Display 42 Anti-slope

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuyoshi Takeuchi 1-1-15-1 Kamiogi, Suginami-ku, Tokyo Marusan Building Inside Nemoto Specialty Chemicals Co., Ltd. (72) Yasumitsu Aoki 1-1-15-1, Kamiogi, Suginami-ku, Tokyo Maruzan Building Nemoto Special Chemical Co., Ltd. (72) Inventor Takatsugu Matsuzawa Maruzan Building 1-1-15-1, Kamiogi, Suginami-ku, Tokyo Nemoto Special Chemical Co., Ltd.

Claims (6)

[Scope of utility model registration request] 1. A slit is provided on one side, and a storage portion for storing a light emitting source is formed in the slit. A light diffusing plate continuous with the slit is provided in the storage portion, and the light diffusing plate is An evacuation guidance light having a display portion provided with a phosphorescent phosphor on one surface. 2. The evacuation guide light according to claim 1, wherein the surface of the light diffusing plate on the side opposite to the display portion is a reflecting surface for reflecting light from the light emitting source. 3. A phosphorescent phosphor is a compound represented by MAl ₂ O ₄ , and M is a compound having at least one metal element selected from the group consisting of calcium, strontium and barium as a mother crystal. The evacuation guidance light according to claim 1 or 2, characterized in that. 4. The phosphorescent phosphor is a compound represented by MAl ₂ O ₄ , wherein M is a plurality of metals obtained by adding magnesium to at least one metal element selected from the group consisting of calcium, strontium and barium. The evacuation guidance light according to claim 1 or 2, wherein a compound consisting of an element is used as a mother crystal. 5. The evacuation guidance light according to claim 3, wherein europium is added as an activator in an amount of 0.001% or more and 10% or less in mol% with respect to the metal element represented by M. 6. A co-activator comprising at least one or more of the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, teribium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin and bismuth. 0.001% of the element in mol% with respect to the metal element represented by M
The evacuation guide light according to claim 5, wherein the content is added in the range of 10% or less.