WO2005044946A1

WO2005044946A1 - Phosphorescence exhibiting phosphor and process for producing the same

Info

Publication number: WO2005044946A1
Application number: PCT/JP2004/016401
Authority: WO
Inventors: Yoneichi Hirata; Tomoya Sakaguchi; Nobuyoshi Takeuchi
Original assignee: Nemoto & Co., Ltd.
Priority date: 2003-11-06
Filing date: 2004-11-05
Publication date: 2005-05-19

Abstract

A phosphorescence exhibiting phosphor that upon the passage of a prolonged period of time after excitation, has an afterglow luminance property superior to that of conventional strontium aluminate base phosphorescence exhibiting phosphors of the same type, the phosphorescence exhibiting phosphor satisfying the relationships of proportion: 0.005≤Eu/(Sr+Ba+Eu+Dy)≤0.02, 1<Dy/Eu≤20, 0.015≤(Eu+Dy)/(Sr+Ba+Eu+Dy)≤0.42, 0.01≤Ba/(Sr+Ba)≤0.35, and 2.05≤Al/(Sr+Ba+Eu+Dy)≤3.0.

Description

Specification

Luminescent phosphor and method for producing the same

Technical field

The present invention relates to a phosphorescent phosphor, particularly to a phosphorescent phosphor having a long-term afterglow characteristic.

Background art

[0002] In general, the afterglow time of a phosphor is extremely short, and the luminescence is rapidly attenuated when an external stimulus is stopped. Afterglows can be observed with the naked eye for several tens of minutes (even for several hours). These phosphorescent phosphors are distinguished from ordinary phosphors by phosphorescent phosphors.

Examples of the phosphorescent phosphors include phosphors such as CaS: Bi (purple blue light emission), CaSrS: Bi (blue light emission), ZnS: Cu (green light emission), and ZnCdS: Cu (yellow-orange light emission). Any of these sulfide phosphors are chemically unstable, have poor light resistance, and are not suitable for use in luminous watches. However, there were many practical problems, such as the afterglow time for which the time was recognizable to the naked eye was about 30 minutes to 2 hours.

[0003] Therefore, the applicant of the present invention has a long-lasting property that is much longer than commercially available sulfide-based phosphors, is chemically stable, and has excellent light resistance over a long period of time. A compound represented by MAIO as a phosphor, where M is calcium, strontium, barium

twenty four

Power group power A phosphorescent phosphor in which at least one or more selected metal element power compound is used as a mother crystal was invented and a patent was obtained (for example, Japanese Patent No. 2543825). According to the invention of the aluminate-based phosphorescent phosphor described in this patent publication, the phosphorescent phosphor has a much longer afterglow characteristic than the conventional phosphorescent phosphor, and furthermore is a phosphorescent phosphor-based phosphor. Therefore, it has become possible to provide a long afterglow phosphorescent phosphor that is chemically stable and has excellent light resistance and is applicable to various uses.

Disclosure of the invention

[0004] However, due to further market needs, higher brightness and longer persistence characteristics There is a demand for a phosphorescent phosphor having the following. In the ISO standard, a method for measuring the afterglow luminance corresponding to a long-afterglow phosphorescent phosphor has been drafted, and it has been proposed to measure the afterglow luminance after a longer time than before. .

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and after a long period of time after excitation, a luminous phosphor having excellent afterglow luminance characteristics compared to conventional strontium aluminate phosphorescent phosphors of the same type. It is intended to provide a body and a method for producing the same.

In view of the above situation, the present inventor has proposed that, in the strontium aluminate-based phosphorescent phosphor described in the above-mentioned Patent Publication, the activator Yuguchi Pium (Eu) and the coactivator Dysprosium (Dy) were used. We will try to optimize the amount of soy sauce and further optimize the composition ratio of strontium (Sr), barium (Ba), calcium (Ca), and aluminum (A1), which are the constituent elements of the mother crystal. As a result, a phosphorescent phosphor having excellent afterglow luminance characteristics has been found as compared with the conventional strontium aluminate phosphorescent phosphor.

[0005] (1) First invention

The phosphorescent phosphor according to the first invention of the present invention is a compound represented by MAIO,

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In addition to making strontium! :) and a compound that also has barium (Ba) power into the mother crystal, palladium (Eu) is added as an activator and dysprosium (Dy) is added as a coactivator. The amount of spiked porridge (Eu) added is 0.5% or more and 2% or less in terms of mol%, based on the total number of moles of the metal element represented by M and the number of moles of euphyllium (Eu) and dysprosium (Dy). And the molar amount of dysperm shim (Dy) is 1 and Dy / Eu ≤ 20 in molar ratio with respect to palladium (Eu), and the addition of pium (Eu) and dysprosium (Dy). total卩量is a mole ^_0/0 1. 5% or less than 42% relative to the total number of moles of metallic element and Yu port Piumu (Eu) and dysprosium (Dy) expressed by M, aluminum (A1) Of the metal element represented by M and the total number of moles of palladium (Eu) and dysprosium (Dy) 3.0 or less, and the ratio of barium to M is 0.015 ≦ Ba / (Sr + Ba) ≦ 0.35 in molar ratio.

[0006] Then, first, Yu port Piumu as an activating agent (Eu), relative to the total mole number of the metal elements and Yu port Piumu (E u) and dysprosium (Dy) expressed by M, a molar ^_0/0 0 Add 5% or more and 2% or less, and add dysprosium (Dy) as a co-activator in a molar ratio of 1 Add DyZEu≤20 and add the total amount of palladium (Eu) and dysprosium (Dy) in the mouth to the total number of moles of the metal element represented by M and the total number of moles of pium (Eu) and dysprosium (Dy) in the mouth. By setting the percentage to 1.5% or more and 42% or less, the addition amount of the zipper opening seam that contributes to the afterglow luminance characteristic is increased compared to the addition amount of the europium pium that contributes to the fluorescent luminance characteristic, and optimization is difficult. Due to the force, even after a long time of about 10 to 12 hours after excitation, the phosphor has excellent afterglow luminance characteristics as compared with the conventional phosphorescent phosphor.

[0007] Furthermore, the ratio of aluminum (A1) is 2.05 or more in terms of molar ratio to the total number of moles of the metal element represented by M, the pium (Eu), and the dies (Dy). When the ratio is set to 0 or less, the ratio of the aluminum is increased from 2.0, which is the stoichiometric ratio, to 2.05 or more, so that the crystal structure is distorted and traps are easily formed. Even after a long period of time, it has better afterglow luminance characteristics than conventional phosphorescent phosphors.

Furthermore, since the molar ratio of barium to M is 0.01 ≤ Ba / (Sr + Ba) ≤ 0.35, moderate distortion occurs in the crystal by substituting barium for part of strontium. As a result, even after a long time has passed since the excitation, the phosphor has more excellent afterglow luminance characteristics than the conventional phosphorescent phosphor.

[0008] Here, 0. First, in mole ^_0/0 to the total mole number of the metal elements and Yuuropi © beam (Eu) and dysprosium (Dy) represented by添Ka卩量force M Yu port Piumu as an activator 5 When the content is less than 2%, the amount of the activator is too small, and the luminance of the phosphorescent phosphor is reduced as a whole, which is not preferable. When the content is more than 2%, the afterglow luminance is reduced due to concentration quenching and the like. Excellent afterglow luminance characteristics cannot be obtained after a long time. Therefore, it is optimal that the amount of palladium added is 0.5% or more and 2% or less.

And, in the case of DyZEu≤l, the added amount of dysprosium as a co-activator in the molar ratio of dysprosium as a coactivator with respect to the amount of palladium in Eu, ie, in the case of DyZEu≤l, the amount of added dysprosium contributing to the afterglow luminance characteristics Therefore, afterglow luminance characteristics cannot be obtained as desired. In addition, in the case of DyZEu, the molar ratio of dysprosium added to the amount of added casket to palladium in the mouth exceeds 20, that is, in the case of DyZEu, the dysprosium ratio increases, the base color becomes white, the excitation efficiency decreases, and light emission occurs. However, since luminous dysprosium (DyAlO) or the like is produced as a by-product, the luminance is greatly reduced as a whole. [0009] Furthermore, a mole ^_0/0 to the total mole number of the metal elements and Yu port Piumu (Eu) and dysprosium (Dy) representing a total force M of添Ka卩量Yu port Piumu dysprosium 1.5% If the amount is less than the above, the amount of the activator and the co-activator is too small, so that the luminance characteristics decrease. If the amount exceeds 42%, the amount of the strontium relatively decreases and the afterglow luminance characteristics decrease.

Therefore, the amount of syrup added to palladium as an activator depends on the amount of metal element represented by M and the amount of pium

It is 0.5% or more and 2% or less in terms of mol% based on the total number of moles of (Eu) and dysprosium (Dy), and the amount of dysprosium added as a co-activator is determined by the molar ratio to palladium in the mouth. (1) DyZEu ≤ 20 and the total force of the added amounts of palladium (Eu) and dysprosium (Dy) in the mouth and the total number of moles of the metal element represented by M and pium (Eu) and dysprosium (Dy) in the mouth By being 1.5% or more and 42% or less in terms of mol%, the phosphorescent light has excellent afterglow brightness characteristics compared to conventional phosphorescent phosphors even after a long time of about 10 to 12 hours after excitation. A phosphor is obtained.

[0010] Furthermore, the ratio of aluminum (A1) is less than 2.05 in molar ratio with respect to the total number of moles of the metal element represented by M, the pium (Eu) and the shim (Dy), ie, When A1Z (M + Eu + Dy) <2.05, this is almost equal to or less than the stoichiometric ratio of 2.0, so the afterglow luminance characteristic is the same as that of the conventional phosphorescent fluorescent light. Equal to or lower than the body. Similarly, when the molar ratio exceeds 3.0, that is, 3.0 <A1Z (M + Eu + Dy), the ratio of by-products increases and the luminance decreases, which is not preferable. . Therefore, the ratio of aluminum (A1) was set to a molar ratio of 2.05 or more to 3.0 or less with respect to the total number of moles of the metal element represented by M, the europium (Eu), and the dysprosium (Dy). As a result, a phosphorescent phosphor having excellent afterglow luminance characteristics compared to conventional phosphorescent phosphors can be obtained even after a long time of about 10 to 12 hours after excitation.

[0011] Furthermore, if the molar ratio of barium to M is less than 0.01, that is, if BaZ (Sr + Ba) <0.01, the ratio of norium is too small, so that a moderate strain is generated in the crystal. It is hard to occur and has no effect. In addition, when the molar ratio to M exceeds 0.35, that is, when 0.35 <BaZ (Sr + Ba), the ratio of strontium relatively decreases, and the overall brightness decreases. Preferred,. Therefore, the ratio of barium to M in terms of molar ratio, 0.01 ≤ Ba / (Sr + Ba) ≤ 0.35, makes the conventional storage possible even after a long time of about 10 to 12 hours after excitation. A luminous phosphor having better afterglow luminance characteristics than the luminous phosphor can be obtained.

[0012] According to the phosphorescent phosphor of the first invention, the amount of dysprosium that contributes to the afterglow luminance characteristics is increased compared to the amount of europium that contributes to the fluorescent luminance characteristics, and optimization is achieved. By increasing the ratio of aluminum from the stoichiometric ratio of 2.0 to 2.05 or more, distortion occurs in the crystal structure, and furthermore, part of strontium is replaced by barium. As a result, an appropriate strain is generated in the crystal, so that even after a long time of about 10 to 12 hours after excitation, excellent afterglow luminance characteristics can be obtained as compared with the conventional phosphorescent phosphor.

(2) Second invention

The phosphorescent phosphor according to the second invention of the present invention is a compound represented by MAIO,

twenty four

In addition to strontium! :) and calcium (Ca) compound as a mother crystal, Yu-Pt (Eu) is added as an activator, and Dysprosium (Dy) is added as a co-activator. The amount of spiked pork (Eu) added is 0.5% or more and 2% or less in terms of mol%, based on the total number of moles of the metal element represented by M, and the number of moles of yuu-piu (Eu) and dysprosium (Dy). The molar amount of dysprosium (Dy) added to palladium (Eu) is 1 and the molar ratio of DyZEu is less than 20, and the amount of added potassium sulphate of palladium (Eu) and dysprosium (Dy) is relatively small. total is less 42% 1.5% or more by mole ^_0/0 to the total mole number of the metal elements and Yu port Piumu (Eu) and dysprosium (Dy) expressed by M, the ratio of aluminum (A1) is The molar ratio of the metal element represented by M to the total number of moles of europium (Eu) and dysprosium (Dy) is 2.05 or more. 3. is 0 or less, the ratio of calcium to M is characterized in that a 0. 005≤Ca / (Sr + Ca) ≤0. 15 in molar ratio.

[0013] Then, first, Yu port Piumu as an activating agent (Eu), relative to the total mole number of the metal elements and Yu port Piumu (E u) and dysprosium (Dy) expressed by M, a molar ^_0/0 0 Add dysprosium (Dy) as a co-activator in a molar ratio of 1 to Dyzeu (Eu) to DyZEu ≤ 20 and add Dyzeu ≤ 20 as a co-activator, and add Dyzeu ≤ 20 to Dyprosium (Eu) and Dysprosium (Dy). Is added to the total number of moles of the metal element represented by M, the palladium (Eu) and dysprosium (Dy). By adjusting the molar percentage to 1.5% or more and 42% or less, the amount of added disp-seam, which contributes to the afterglow luminance characteristics, is increased compared to the amount of palladium-pium, which contributes to the fluorescent luminance characteristics. Due to the weakness, even after a long time of about 10 to 12 hours after the excitation, the phosphor has excellent afterglow luminance characteristics as compared with the conventional phosphorescent phosphor.

[0014] Furthermore, the ratio of aluminum (A1) is 2.05 or more in terms of molar ratio to the total number of moles of the metal element represented by M, the pium (Eu), and the dies (Dy). When the ratio is set to 0 or less, the ratio of the aluminum is increased from 2.0, which is the stoichiometric ratio, to 2.05 or more, so that the crystal structure is distorted and traps are easily formed. Even after a long period of time, it has better afterglow luminance characteristics than conventional phosphorescent phosphors.

In addition, since the molar ratio of calcium to M is 0.005≤Ca / (Sr + Ca) ≤0.15, a certain amount of strain occurs in the crystal by substituting part of strontium with calcium. As a result, even after a long period of time after the excitation, the phosphor has more excellent afterglow luminance characteristics than the conventional phosphorescent phosphor.

[0015] Here, 0. First, in mole ^_0/0 to the total mole number of the metal elements and Yuuropi © beam (Eu) and dysprosium (Dy) represented by添Ka卩量force M Yu port Piumu as an activator 5 When the content is less than 2%, the amount of the activator is too small, and the luminance of the phosphorescent phosphor is reduced as a whole, which is not preferable. Excellent afterglow luminance characteristics cannot be obtained after a long time. Therefore, it is optimal that the amount of palladium added is 0.5% or more and 2% or less.

In addition, in the case of DyZEu≤l, the added amount of dysprosium as a coactivator in the molar ratio of the added amount of dysprosium to the palladium of Yuguchi, that is, in the case of DyZEu≤l, Therefore, afterglow luminance characteristics cannot be obtained as desired. In addition, in the case of DyZEu, the molar ratio of dysprosium added to the amount of added casket to palladium in the mouth exceeds 20, that is, in the case of DyZEu, the dysprosium ratio increases, the base color becomes white, the excitation efficiency decreases, and light emission occurs. However, since luminous dysprosium (DyAlO) or the like is produced as a by-product, the luminance is greatly reduced as a whole.

Three

[0016] Furthermore, a mole ^_0/0 to the total mole number of the metal elements and Yu port Piumu (Eu) and dysprosium (Dy) representing a total force M of添Ka卩量Yu port Piumu dysprosium 1.5% Less than If so, the amount of the activator and co-activator is too small, so that the luminance characteristics are reduced. If it exceeds 42%, the amount of strontium is relatively reduced, and the afterglow luminance characteristics are reduced.

Therefore, the amount of sulfur added to palladium as an activator is 0.5% or more and 2% or more in terms of mol% based on the total number of moles of the metal element represented by M and the number of mols of palladium (Eu) and dysprosium (Dy). The amount of dysprosium added as a co-activator is as follows: the molar ratio of dysprosium to euphyllium is 1 and DyZEu ≤ 20, and the amounts of euprosium (Eu) and dysprosium (Dy) added. The total force of the metal element expressed by M and the molar percentage of the total number of moles of palladium (Eu) and dysprosium (Dy) in the mouth are 1.5% or more and 42% or less. Even after a long period of time, a phosphorescent phosphor having excellent afterglow luminance characteristics compared to conventional phosphorescent phosphors can be obtained.

[0017] Furthermore, the ratio of aluminum (A1) is less than 2.05 in molar ratio with respect to the total number of moles of the metal element represented by M, the pium (Eu), and the shim (Dy). When A1Z (M + Eu + Dy) <2.05, this is almost equal to or less than the stoichiometric ratio of 2.0. Equal to or lower than the body. Similarly, when the molar ratio exceeds 3.0, that is, when 3.0 <A1Z (M + Eu + Dy), the proportion of by-products increases and the luminance decreases, which is not preferable. . Therefore, the ratio of aluminum (A1) was set to a molar ratio of 2.05 or more to 3.0 or less with respect to the total number of moles of the metal element represented by M, the palladium (Eu) and the dysprosium (Dy). As a result, a phosphorescent phosphor having excellent afterglow luminance characteristics compared to conventional phosphorescent phosphors can be obtained even after a long time of about 10 to 12 hours after excitation.

Further, the ratio of calcium is less than 0.005 in molar ratio to M, that is, CaZ (Sr

In the case of + Ca) <0.005, calcium is too small, and there is no effect due to moderate distortion in the crystal. When the molar ratio to M exceeds 0.15, that is, when 0.15 <Ca Z (Sr + Ca), calcium aluminate (CaAl 04) and the like are produced as by-products and

2

On the contrary, the ratio of strontium is decreased, and the overall luminance is undesirably decreased.

Therefore, since the ratio of the molar ratio of calcium to M is 0.005≤Ca / (Sr + Ca) ≤0.15, even after a long time of about 10-12 hours after excitation, Phosphorescent phosphor with better afterglow luminance characteristics than phosphorescent phosphor

According to the phosphorescent phosphor according to the second aspect of the invention, the amount of dysprosium that contributes to the afterglow luminance characteristics is increased compared to the amount of palladium that contributes to the fluorescent luminance characteristics, and optimization is achieved. By increasing the ratio of aluminum from the stoichiometric ratio of 2.0 to 2.05 or more, the crystal structure is distorted, and a part of strontium is replaced with calcium. As a result, an appropriate strain is generated in the crystal, so that even after a long time of about 10 to 12 hours from the excitation, it is possible to obtain excellent afterglow luminance characteristics compared to the conventional phosphorescent phosphor. Monkey

(3) Third invention

The phosphorescent phosphor according to the third invention of the present invention is a compound represented by MAIO,

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Is to make a compound consisting of strontium (Sr), barium (Ba), and calcium (Ca) into a mother crystal, add palladium (Eu) as an activator, and add dysprosium (Dy) as a coactivator. has mosquito卩,添Ka卩量Yu port Piumu (Eu), relative to the total mole number of the metal elements and Yuuropi © beam (Eu) and dysprosium (Dy) expressed by M, a molar ^_0/0 0.5% or more and 2% or less, the amount of dysprosium (Dy) added is 1 <DyZEu≤20 in terms of molar ratio with respect to palladium (Eu) in the mouth, and pium (Eu) in the mouth and dysprosium (Dy) are used. ) Is 1.5% or more and 42% or less in terms of mol% based on the total number of moles of the metal element represented by M and the number of moles of palladium (Eu) and dysprosium (Dy). The ratio of A1) is expressed by the total number of moles of the metal element represented by M and the moles of palladium (Eu) and dysprosium (Dy). The ratio of barium to M is 0.011 ≤ Ba / (Sr + Ba + Ca) ≤ 0.3 in molar ratio, and the ratio of calcium to M is The molar ratio is 0.005≤Ca / (Sr + Ba + Ca) ≤0.1.

[0020] Then, first, Yu port Piumu as an activating agent (Eu), relative to the total mole number of the metal elements and Yu port Piumu (E u) and dysprosium (Dy) expressed by M, a molar ^_0/0 0 Add dysprosium (Dy) as a co-activator in a molar ratio of 1 to Dyzeu (Eu) to DyZEu ≤ 20 and add Dyzeu ≤ 20 as a co-activator, and add Dyzeu ≤ 20 to Dyprosium (Eu) and Dysprosium (Dy). Is added to the total number of moles of the metal element represented by M, the palladium (Eu) and dysprosium (Dy). By adjusting the molar percentage to 1.5% or more and 42% or less, the amount of added disp-seam, which contributes to the afterglow luminance characteristics, is increased compared to the amount of palladium-pium, which contributes to the fluorescent luminance characteristics. Due to the weakness, even after a long time of about 10 to 12 hours after the excitation, the phosphor has excellent afterglow luminance characteristics as compared with the conventional phosphorescent phosphor.

[0021] Furthermore, the ratio of aluminum (A1) is 2.05 or more in a molar ratio to the total number of moles of the metal element represented by M, the pium (Eu), and the shim (Dy). When the ratio is set to 0 or less, the ratio of the aluminum is increased from 2.0, which is the stoichiometric ratio, to 2.05 or more, so that the crystal structure is distorted and traps are easily formed. Even after a long period of time, it has better afterglow luminance characteristics than conventional phosphorescent phosphors.

Furthermore, the molar ratio of barium to M is 0.01 ≤Ba / (Sr + Ba + Ca) ≤0.3, and the calcium ratio to M is 0.005≤Ca / (Sr + (Ba + Ca) ≤ 0.1, by replacing a part of strontium with barium and calcium, an appropriate strain is generated in the crystal. It has better afterglow luminance characteristics than the luminescent phosphor.

[0022] Here, 0. First, in mole ^_0/0 to the total mole number of the metal elements and Yuuropi © beam (Eu) and dysprosium (Dy) represented by添Ka卩量force M Yu port Piumu as an activator 5 When the content is less than 2%, the amount of the activator is too small, and the luminance of the phosphorescent phosphor is reduced as a whole, which is not preferable. When the content is more than 2%, the afterglow luminance is reduced due to concentration quenching and the like. Excellent afterglow luminance characteristics cannot be obtained after a long time. Therefore, it is optimal that the amount of palladium added is 0.5% or more and 2% or less.

Three

[0023] Furthermore, the metal element expressed by the total force M of the added amount of the casket added to the palladium and dysprosium of Yu and the metal When the mole ^_0/0 1. less than 5% mouth Piumu and (Eu) to moles total of dysprosium (Dy), luminance characteristics for the amount of the activator and co-activator is too small is reduced and also 42% When it exceeds, the amount of strontium is relatively reduced, and the afterglow luminance characteristic is deteriorated.

[0024] Furthermore, the ratio of aluminum (A1) is less than 2.05 in molar ratio with respect to the total number of moles of the metal element represented by M, the pium (Eu) and the shim (Dy). When A1Z (M + Eu + Dy) <2.05, this is almost equal to or less than the stoichiometric ratio of 2.0, so the afterglow luminance characteristic is the same as that of the conventional phosphorescent fluorescent light. Equal to or lower than the body. Similarly, when the molar ratio exceeds 3.0, that is, 3.0 <A1Z (M + Eu + Dy), the ratio of by-products increases and the luminance decreases, which is not preferable. . Therefore, the ratio of aluminum (A1) was set to a molar ratio of 2.05 or more to 3.0 or less with respect to the total number of moles of the metal element represented by M, the europium (Eu), and the dysprosium (Dy). As a result, a phosphorescent phosphor having excellent afterglow luminance characteristics compared to conventional phosphorescent phosphors can be obtained even after a long time of about 10 to 12 hours after excitation.

Further, when the ratio of barium is less than 0.01 in terms of a molar ratio to M, that is, BaZ (Sr + Ba + Ca) <0.01, the ratio of norium is too small, so There is no effect due to little distortion. When the molar ratio to M exceeds 0.3, that is, when 0.3 <BaZ (Sr + Ba + Ca), the ratio of strontium is relatively reduced, and the overall luminance is reduced. It is not preferable because.

On the other hand, when the molar ratio of calcium to M is less than 0.005, that is, when CaZ (Sr + Ba + Ca) <0.005, the calcium ratio is too small, so Slight distortion is hard to occur and has no effect. In addition, when the molar ratio to M exceeds 0.1, that is, when it is 0.1 and CaZ (Sr + Ba + Ca) is used, calcium aluminate (CaAl 2 O 3) etc.

2 4, and the ratio of strontium is relatively reduced, and the overall luminance is undesirably reduced.

[0026] Therefore, the ratio force of barium to M is 0.011≤Ba / (Sr + Ba + Ca) ≤0.3 in molar ratio, and the ratio of calcium to M is 0.005≤Ca / Since (Sr + Ba + Ca) ≤0.1, even after a long time of about 10-12 hours after excitation, the phosphorescent light has better afterglow luminance characteristics than the conventional phosphorescent phosphor. A luminescent phosphor is obtained.

According to the phosphorescent phosphor according to the third aspect of the invention, the amount of dysprosium that contributes to the afterglow luminance characteristics is increased as compared with the amount of europium that contributes to the fluorescent luminance characteristics, and optimization is achieved. By increasing the ratio of aluminum from 2.0, which is the stoichiometric ratio, to 2.05 or more, the crystal structure is distorted, and furthermore, a part of strontium is replaced by barium and calcium. Since an appropriate strain is generated in the crystal, even after a long time of about 10 to 12 hours after the excitation, excellent afterglow luminance characteristics can be obtained as compared with the conventional phosphorescent phosphor.

(4) Fourth Invention

The method for producing the alkaline earth metal aluminate phosphorescent phosphor according to the fourth aspect of the present invention comprises an aluminum (A1) compound, a strontium (Sr) compound, a barium compound (Ba), It is characterized in that a pium (Eu) compound and a dysprosium (Dy) compound are mixed so that each element has the following molar ratio, fired in a reducing atmosphere, and then cooled and pulverized.

0.005≤Eu / (Sr + Ba + Eu + Dy) ≤0.02,

l <Dy / Eu≤20,

0.0015≤ (Eu + Dy) / (Sr + Ba + Eu + Dy) ≤0.42,

0.01≤Ba / (Sr + Ba) ≤0.35,

2.05≤Al / (Sr + Ba + Eu + Dy) ≤3.0

In the method for producing an alkaline earth metal aluminate phosphorescent phosphor according to the fourth invention, According to this, even after a long time of about 10 to 12 hours after the excitation, an alkaline earth metal aluminate phosphorescent phosphor having excellent afterglow luminance characteristics as compared with the conventional phosphorescent phosphor can be manufactured.

(5) Fifth Invention

The method for producing an alkaline earth metal aluminate phosphorescent phosphor according to the fifth invention of the present invention is a method for producing an aluminum (A1) compound, a strontium (Sr) compound, a calcium compound (Ca), It is characterized in that an orifice (Eu) compound and a dysprosium (Dy) compound are mixed so that each element has the following molar ratio, fired in a reducing atmosphere, and then cooled and pulverized.

0.005≤Eu / (Sr + Ca + Eu + Dy) ≤0.02,

l <Dy / Eu≤20,

0.0015≤ (Eu + Dy) / (Sr + Ca + Eu + Dy) ≤0.42,

0.005≤Ca / (Sr + Ca) ≤0.15,

2.05≤Al / (Sr + Ca + Eu + Dy) ≤3.0

According to the method for producing an alkaline earth metal aluminate phosphorescent phosphor according to the fifth invention, even after a long time of about 10 to 12 hours after excitation, the phosphorescent phosphor is superior to the conventional phosphorescent phosphor. An alkaline earth metal aluminate phosphorescent phosphor having afterglow luminance characteristics can be manufactured.

(6) Sixth Invention

The method for producing an alkaline earth metal aluminate phosphorescent phosphor according to the sixth aspect of the present invention comprises: an aluminum (A1) compound, a strontium (Sr) compound, and a barium (Ba) compound. A calcium compound (Ca), a palladium (Eu) compound, and a dysprosium (Dy) compound were mixed at the following molar ratios, calcined in a reducing atmosphere, and then cooled and pulverized. It is characterized by:

0.005≤Eu / (Sr + Ba + Ca + Eu + Dy) ≤0.02,

l <Dy / Eu≤20,

0.0015≤ (Eu + Dy) / (Sr + Ba + Ca + Eu + Dy) ≤0.42,

0.01 ≤Ba / (Sr + Ba + Ca) ≤0.3, 0.005≤Ca / (Sr + Ba + Ca) ≤0.1,

2.05≤Al / (Sr + Ba + Ca + Eu + Dy) ≤3.0

According to the method for producing an alkaline earth metal aluminate phosphorescent phosphor according to the sixth aspect of the present invention, even after a long time of about 10 to 12 hours after excitation, the phosphorescent phosphor is superior to the conventional phosphorescent phosphor. An alkaline earth metal aluminate phosphorescent phosphor having afterglow luminance characteristics can be manufactured.

(7) Seventh Invention

The method for producing an alkaline earth metal aluminate luminous phosphor according to the seventh invention of the present invention includes the alkaline earth metal aluminate luminous phosphor according to the fourth, fifth, or sixth invention. The method for producing a phosphor is characterized in that a boron compound is added as a flux to the raw material and the mixture is fired. Then, by adding a boron compound as a flux to the raw material and firing the mixture, an alkaline earth metal element aluminate phosphorescent phosphor excellent at a low firing temperature can be manufactured. As the boron compound, for example, boric acid (HBO) is preferable.

3 3 It is suitably used, but the same effect can be obtained not only with boric acid but also with boron compounds. The amount of the boron compound to be added is preferably about 0.01 to 10%, more preferably about 0.5 to 3%, based on the total mass of the raw materials.

[0031] Here, when the amount of the boron compound to be added exceeds 10% of the total mass of the raw material, the fired product is hard and sintered, so that pulverization becomes difficult, and the reduction in luminance due to the pulverization decreases. Get offended. Therefore, the amount of the boron compound to be added is preferably 0.01% to 10% based on the total mass of the raw materials.

According to the method for producing an alkaline earth metal aluminate phosphorescent phosphor according to the seventh invention, the alkaline earth metal aluminate phosphorescent phosphor according to the fourth, fifth, or sixth invention is provided. According to the manufacturing method, an alkaline earth metal element aluminate phosphorescent phosphor which is excellent even at a low firing temperature can be manufactured.

Brief Description of Drawings

FIG. 1 is a view showing a particle size distribution of sample 1 (3).

FIG. 2 is an X-ray powder diffraction pattern of Sample 2- (9).

FIG. 3 is an X-ray powder diffraction pattern of Sample 3- (6). BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the steps of manufacturing the phosphorescent phosphor according to one embodiment of the present invention will be described.

First, strontium (Sr), barium (Ba) and barium (Ca) as raw materials of metal elements represented by M, such as strontium carbonate (SrCO) and barium carbonate (Ba

Three

CO 2) and calcium carbonate (CaCO 3) as raw materials for palladium (Eu) as an activator

3 3

And add porcelain (Eu 2 O 3) to the source of dysprosium (Dy) as a co-activator.

twenty three

Dysprosium oxide (Dy 2 O 3) is added as a raw material. At this time, the added calorie of pium (Eu)

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The amount is 2% 0.5% by molar ^_0/0 to moles total of metal elements and Yu port Piumu dysprosium expressed by M,添Ka卩量of dysprosium (Dy) are, Yu port Piumu (Eu) in a molar ratio of more than 1 to 20 or less, and the total amount of palladium (Eu) and dysprosium (Dy) added to the metal element represented by M, palladium (Eu) and dysprosium (Eu) mole ^_0/0 1. 5% or less than 42% relative to the total number of moles of dy). Furthermore, as a raw material of aluminum (A1), for example, alumina (Al 2 O 3) is converted to strontium, norium, calcium,

twenty three

The molar ratio of aluminum to the sum of the number of moles of palladium and dysprosium is 2.05 or more and 2.7 or less. For example, boric acid (HBO) is used as a boron compound as a flux. About 11% to 10%, and use a ball mill etc.

3 3

Mix. The mixture is calcined in a reducing atmosphere, for example, a mixed gas stream of nitrogen and hydrogen at a calcining temperature of about 1300 ° C to 1500 ° C for about 1 hour to 6 hours, and then to room temperature for about 1 hour to 6 hours. Cool over time. The obtained fired product is pulverized and sieved to obtain a phosphorescent phosphor having a predetermined particle size.

[0034] At this time, the added amount of palladium (Eu) as an activator to be added refers to the amount of each of the metal element M, the activator palladium (Eu) and the co-activator dysprosium (Dy). It is expressed in mol% based on the total number of moles of the element. For example, when the metal element represented by M is strontium and norium, the molar ratio of barium to the total number of moles of strontium and barium is 0.1, Yu port Piumu 1 mole ^_0/0 added, to 2 mol ^_0/0添Ka卩dysprosium is strontium element is 0.873 mol, barium element 0.097 mol, Yu port Piumu element 0.01 mol The compound of each element is blended so that the dysprosium element becomes 0.02 mol. This makes it possible to determine the amount of pium Stood 1% mole ^_0/0, the molar ratio of barium to the total mole number of strontium and barium will be 0.1.

In the above embodiment, if the firing temperature using the boron compound as the flux is sufficiently higher than the temperature required for the reaction, for example, about 1450 ° C. In this case, the obtained fired product is weakly agglomerated, and crushing is facilitated, so that a decrease in luminance due to crushing can be reduced.

The metal element represented by M in the present invention is substantially a strontium and barium, a strontium and calcium, or a strontium, barium and calcium and a trace amount of another element in addition to these elements as long as they are also composed of power. Is included in the scope of the present invention.

Next, an example of the above embodiment will be described.

(1) Experimental example 1

First, the relationship between the added amount of palladium (Eu) and dysprosium (Dy) and the afterglow luminance characteristics after a long time after the excitation will be described.

First, strontium carbonate (SrCO) 128.88 g (0.873) was used as a raw material for strontium (Sr).

Three

Mol), and 19.14 g (0.097 mol) of barium carbonate (BaCO) as a raw material for norium (Ba).

Three

In addition, as a raw material of the palladium of Euguchi as an activator,

twenty three

1.76 g (0.01 mol as Eu) was added, and 3.73 g (0.02 mol as Dy) of dysprosium oxide (DyO) was added as a raw material of dysprosium (Dy) as a co-activator.

twenty three

117.26 g of alumina (Al 2 O 3) (2.3 moles as Al, ie AlZ (S

twenty three

r + Ba + Eu + Dy) = 2.3) and 3.2 g of boric acid (HBO) as a boron (B) compound as flux (that is, 1.2% by mass based on the raw material). For ball mill

3 3

And mix well. This mixture is calcined in a reducing atmosphere in a gas stream of 97% nitrogen-3% hydrogen at a calcining temperature of 1350 ° C for 4 hours, and then cooled to room temperature in about 1 hour. The obtained fired product was pulverized, sieved and passed through a # 250 mesh to obtain a phosphorescent phosphor sample 11 (3). In this sample 1- (3), strontium was 0.783 mol, barium was 0.097 mol, and the molar ratio of strontium to 0.97 mol of the total number of mols of strontium and barium was 0.9. The molar ratio is 0.1. In addition, strontium Roh potassium, Yu port Piumu, Yu port Piumu of添Ka卩量1 molar ^_0/0 to the sum of dysprosium is similarly添Ka卩量2 mol% of dysprosium, moles of Jisupuro Shiumu against Yu port Piumu The ratio, DyZEu, is 2. The molar ratio of aluminum, that is, AlZ (Sr + Ba + Eu + Dy) is 2.3, which exceeds the stoichiometric ratio of 2.0.

[0037] Similarly, the molar ratio of dysprosium (Dy) to europium (Eu), ie, DyZEu, is fixed at 2, and strontium (Sr), barium (Ba), europium (Eu), and dysporium (Eu). As shown in Table 1, phosphorescent phosphors were prepared in which the amount of addition of palladium (Eu) to the total number of moles of shim (Dy) was varied from 0.1 mol% to 5 mol% as shown in Table 1. Sample 1- (1), sample 1- (2), sample 1- (4) to sample 1- (6) were obtained. Further, as a comparative example, the compounding ratio listed as Patent Document 1 Sample 2- (1), the metal elements expressed by M and only strike strontium, 1 mol添力卩量Yu port Piumu ^_0/0 the dysprosium添力卩量1 molar ^_0/0, Arumi - © beam molar ratio AlZ a (Sr + Eu + Dy), the stoichiometric ratio 2.0, other manufacturing conditions, process the sample 1 A sample identical to that of (3) was prepared in the same manner as Comparative Example 1. The particle size distribution of Sample 11 (3) was measured by a laser diffraction type particle size distribution analyzer (SALD-2100, Shimadzu Corporation). This is shown in Figure 1.

[0038] [Table 1]

Next, the afterglow luminance characteristics of Samples 1- (1) to 1- (6) and Comparative Example 1 were examined. It was. After filling each sample in an aluminum sample container and heating in a dark place at 120 ° C for about 2 hours to eliminate the afterglow, use a D65 standard light source at 4001x brightness for 20 minutes. After excitation, the afterglow was measured using a luminance meter (Chromaticity Luminometer BM-5A Topcon Corporation). The results are shown in Table 2 as relative luminance when the afterglow luminance of Comparative Example 1 is set to 1.

[Table 2]

Based on the results shown in Table 2, firstly, in Sample 1 (5), i.e., when the amount of casket added to palladium in the mouth was 2%, the afterglow luminance characteristic power after a long period of time, particularly after 10 hours, was compared to Comparative Example 1. It can be seen that 2.5 times or more is excellent. In addition, Sample 1 (2) to Sample 1 (4), that is, afterglow after 0.5 hours or more and 1.5% or less, especially after a long time after 10 hours. excellent with both 3 times more than the luminance characteristics force Comparative example 1, the teeth force also Te odor when the sample 1 one (3) i.e. Yu port Piumu添Ka卩量is 1 mole ^_0/0, comparison The afterglow luminance was 6.69 times and 6 times or more that of the example, and more excellent and favorable results were obtained. And to force, in Sample 1- (1) i.e.添Ka卩量Yu port Piumu is 0.1 mole ^_0/0, a decrease in afterglow luminance for amount of Yu port Piumu is too small is observed, the sample 1 (6) In other words, when the amount of added palladium in the mouth is 5 mol%, the afterglow luminance is reduced overall due to the effect of concentration quenching.

[0040] From this, the metal elements represented by M are strontium and barium, and aluminum Ratio is 2.3 and the molar ratio of dysprosium to europium is fixed at 2, the amount of europium added is 0.5 mol% or more and 2 mol% or less. It can be seen that excellent afterglow luminance characteristics are obtained.

Next, the change of the afterglow luminance characteristic after a long time after the excitation when the ratio of the added amount of dysprosium and the amount of added syrup (DyZEu) of the palladium of Yuguchi is changed will be described.

From the results shown in Table 2, the conditions of sample 1 (3), which were more favorable, that is, the amount of sulfuric acid added to the total amount of strontium, barium, europium, and dysprosium was 1 mol%, and the amount of dysprosium added was 1 mol%. Mainly on the condition that the amount of syrup is 2 mol% and the ratio (Dy / Eu) of the syrup content of dysprosium and euphyllium pium is 2, as shown in Table 3, ^_0/0 to fixed ratio of添Ka卩量dysprosium and Yu port Piumu the (DyZEu) 1. varied in the range of 25 force 30, respectively samples 1 (3) Like the phosphorescent phosphor It was prepared and obtained as Sample 1 (7) to Sample 1- (16).

[Table 3]

Samples 11 (7) to 11 (16) are the same as Samples 11 (1) to 11 (6). It was excited under the same illuminance conditions (D65 standard light source Z4001xZ20 minutes) and the afterglow luminance characteristics were examined. The results are shown in Table 4 together with Comparative Example 1 and Sample 1- (3) as relative luminance when the afterglow luminance of Comparative Example 1 is 1.

[Table 4]

From the results shown in Table 4, it can be seen that the molar ratio of dysprosium to Eu pium exceeds 1 and that V is less than that of Sample 1 (7), and that of Sample 1— (15). It can be seen that the afterglow luminance characteristics are excellent, and the afterglow luminance characteristic power after a long time elapses after 10 hours is 3 times or more as compared with Comparative Example 1. Furthermore, when Sample 1 (9) to Sample 1- (14), that is, when the molar ratio of dysprosium to Eu-mouthed pium is 1.75 or more and 15 or less, the afterglow luminance after 10 hours is lower than that of the comparative example. More than 5 times, which is more preferable. More preferably, sample 1- (3), sample 1- (10) to sample 1- (11), that is, the condition that the molar ratio of dysprosium to europium pium is 2 or more and 4 or less, and after 10 hours The afterglow luminance is about 6.5 times or more as compared with the comparative example. However, in sample 1- (16), that is, when the molar ratio of dysprosium is 30 (that is, in this case, 30 mol% in the added amount of dysprosium), for example, by-products such as dysprosium aluminate (DvAlO) The mother color becomes whitish and the afterglow luminance decreases, partly due to the increased amount of generation.

[0043] In addition to this, dysprosium-added kafun is not preferable in terms of economy because dysprosium itself is expensive, and if the added amount of dysprosium is too large, the brightness may be reduced due to concentration quenching. In consideration of the above, when the metal elements represented by M are strontium and barium, the ratio of aluminum is 2.3, and the amount of pium added to the mouth is 1 mol%, dysprosium with respect to the mouth of pium is considered. It can be seen that a phosphorescent phosphor having excellent afterglow luminance characteristics as compared with the conventional example can be obtained in a molar ratio of more than 1 and not more than 20. It was also confirmed that the same results were obtained when the amount of pulping pulp of Yuguchi pium was 0.5% and 2%.

(2) Experimental Example 2

Next, in the compound represented by MAI O, M is strontium (Sr) and barium (Ba)

twenty four

Explains the molar ratio of aluminum (A1) to the total number of moles of the metal element represented by M, the europium (Eu) and the dysprosium (Dy), and the afterglow luminance characteristics when a compound that is also powerful is used as the mother crystal. I do.

Strontium carbonate (SrCO) 128.88 g (0.873 mol) as a raw material for strontium (Sr)

Three

In addition, 19.14 g (0.097 mol) of barium carbonate (BaCO) as a raw material of norium (Ba)

Three

In addition, 1.76 g of Eu oxide (Eu 2 O) was used as a raw material for the activator.

twenty three

0.013 mol), and 3.73 g (0.02 mol as Dy) of dysprosium oxide (DyO) as a raw material of dysprosium (Dy) as a co-activator, and further as an aluminum raw material.

twenty three

107.06 g of all the alumina (Al 2 O 3) (2.1 moles as Al, ie, AlZ (Sr + Ba + Eu +

twenty three

Dy) = 2.1) and boric acid (HBO) as a boron (B) compound as a flux.

3 3

3. Add lg (that is, 1.2% by mass based on the raw material) and mix well using a ball mill. This mixture is fired at a firing temperature of 1350 ° C for 4 hours in a mixed gas stream of 97% nitrogen and 3% hydrogen in a reducing atmosphere, and then cooled to room temperature over about 1 hour. The obtained fired product was pulverized, sieved, and passed through # 250 mesh to obtain a phosphorescent phosphor sample 2 — (3). This sample 2- (3) has a strontium concentration of 0.787 mol and a norium concentration of 0.097 mol, and the strontium and strontium moles are 0.997 mol in total. The molar ratio is 0.9 and the molar ratio of norium is 0.1. Furthermore, strontium, Bruno potassium, Yu port Piumu,添Ka卩量1 mole of Yu port Piumu to the total dysprosium ^_0/0,添Ka卩量the same ingredients Soo Puroshiumu is 2 mol%, relative to Yu port Piumu The molar ratio of dysprosium, ie DyZEu, is 2. Further, the molar ratio of aluminum, that is, AlZ (Sr + Ba + Eu + Dy) is 2.1, which exceeds the stoichiometric ratio of 2.0.

Similarly, as shown in Table 5, the molar ratio of aluminum, that is, AlZ (Sr + Ba + Eu + Dy) was set to 2.0 as shown in Table 5 and to 2 . 05 Ryara Phosphorescent phosphors varied in the range of 3.1 were prepared, and Sample 2— (1) to Sample 2— (3), Sample 2— (4) or Sample 2— (10) As obtained. For sample 2- (9) (the molar ratio of aluminum was 3.0), powder X-ray diffraction analysis was performed using a Cu bulb to obtain a diffraction pattern. This is shown in FIG.

[0046] [Table 5]

Next, Samples 2- (1) to 2- (10) were excited under the same illuminance conditions (D65 standard light source Z4001xZ20 minutes) as Sample 11 (1) of Experimental Example 1, and the afterglow luminance characteristics Investigated. The results were compared with Sample 11 (3), which was the same conditions except that the molar ratio of aluminum was 2.3. Both are shown in Table 6 as relative luminance when the afterglow luminance of Comparative Example 1 was set to 1.

[Table 6]

From the results shown in Table 6, it can be seen that, when Sample 2- (2) and Sample 2- (9), that is, when the aluminum mole ratio is 2.05 to 3.0, especially after a long time elapses after 10 hours, It can be seen that the brightness characteristics are all three times or more superior to Comparative Example 1. Furthermore, in Samples 2- (4) to 2- (6) (the molar ratio of aluminum was 2.2 to 2.5), the afterglow luminance after 10 hours was more than 6 times that of Comparative Example 1. It can be seen that it has a more preferable and excellent afterglow luminance characteristic. These are considered to be due to the fact that a strain occurs in the crystal when the molar ratio of aluminum exceeds 2.0. However, in Sample 2— (1) (the molar ratio of aluminum was 2.0), the afterglow luminance after 10 hours was less than three times that of Comparative Example 1, and in Sample 2— (10) (aluminum At a molar ratio of 3.1), the afterglow luminance is reduced. This is thought to be because the increase in the molar ratio of aluminum increases the production of aluminates other than by-products such as!:, Ba) A10.

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It is. [0048] Thus, in the compound represented by MAI O, M is strontium (Sr) and barium

twenty four

(Ba) When a compound having a strong force is used as a mother crystal, the molar ratio of aluminum to the total number of moles of strontium, barium, europium, and dysprosium, that is, AlZ (Sr + Ba + Eu + Dy) is equal to or more than 2.05. It can be seen that when the value is 3.0 or less, the phosphor becomes a phosphorescent phosphor having excellent afterglow luminance characteristics.

(3) Experimental example 3

Next, when the metal element represented by M is strontium (Sr) and barium (Ba), the ratio of barium and the afterglow luminance characteristics after a long time after excitation will be described.

First, 141.77 g of strontium carbonate (SrCO 2) (0.996) was used as a raw material of strontium (Sr).

Three

1.91 g (0.0097 mol) of barium carbonate (BaCO 3) as a raw material of barium (Ba)

Three

In addition, as a raw material of the palladium of Euguchi as an activator,

twenty three

1.76 g (0.01 mol as Eu) was added, and 3.73 g (0.02 mol as Dy) of dysprosium oxide (DvO) was added as a raw material of dysprosium (Dy) as a co-activator.

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117.26 g of alumina (Al 2 O 3) (2.3 moles as Al, ie AlZ (S

twenty three

3 3

And mix well. This mixture is calcined in a reducing atmosphere in a gas stream of 97% nitrogen-3% hydrogen at a calcining temperature of 1350 ° C for 4 hours, and then cooled to room temperature in about 1 hour. The obtained fired product was pulverized, sieved, and passed through # 250 mesh to obtain a phosphorescent phosphor sample 3- (2). This sample 3- (2) has 0.9603 mol of strontium and 0.0097 mol of norium, and the molar ratio of strontium to 0.97 mol of the total number of mols of strontium and barium is 0.99. The molar ratio of lithium is 0.01. Further, strike opening Nchiumu, Bruno potassium, Yu port Piumu, added Caro of Yu port Piumu to the sum of dysprosium 1 mole ^_0/0, a likewise添Ka卩量2 mol% of dysprosium, dysprosium against Yu port Piumu The molar ratio of DyZEu is 2. Further, the molar ratio of aluminum, that is, AlZ (Sr + Ba + Eu + Dy) is 2.3 exceeding the stoichiometric ratio of 2.0.

[0050] Similarly, as shown in Table 7, the mixing ratio of strontium and barium was changed in the range of Sr: Ba = 0.995: 0.005-0.6: 0.4. Create a body, each sample 3 — (1), sample 3— (3) to sample 3— (8). In addition, powder X-ray diffraction analysis was performed on Sample 3- (6) using a Cu tube to obtain a diffraction pattern. This is shown in FIG.

[Table 7]

Next, these Samples 3- (1) to 3- (8) were excited under the same illuminance conditions (D65 standard light source Z4001xZ20 minutes) as Sample 11 (1) of Experimental Example 1, and the afterglow luminance characteristics were measured. Examined. The results were compared with Sample 1- (3) under the same conditions except that the mixing ratio of strontium and barium was 0.9: 0.1, and the relative value when the afterglow luminance of Comparative Example 1 was 1 was set. Table 8 shows the luminance.

[Table 8]

Excitation conditions Standard light source, 400 〖x, 20 minutes Afterglow luminance characteristics (relative value, relative example 1 = L0)

After 10 minutes After 20 minutes After 60 minutes After 5 hours After 10 hours Comparative Example 1 1.00 1.00 1.00 1.00 1.00 Sample ^3- (1) 1.65.1.721.9 3 2.38 2.91 1 Sample 3 (2) 1.7 7 1.86 6 2.00 2.83 3 4.13 Sample 3-(3) 1.7 3 1.8 6 2.08 3 1 8 4.69 Sample 1 (3) 2.0 2 2.0 6 2.4 1 4.04 6.69 Sample 3-(4) 1.59 1.76 2.12 3. 78 6.39 Sample 3- (5) 1.37 1, 5 3 1.86 3.38 5.84 Sample 3- (6) 1.19 1.34 1.66 3.03 5. 1 1 Sample 3_ (7) 0.S 1 1.04 1.42 2.46 4.26 Sample 3 (8) 0.3 2 0.0.6 2 1.03 1.58 2.74 From the results, it can be seen that Sample 3-(2), Sample 3-(7), that is, when the barium ratio was 0.01 to 0.35, the afterglow luminance characteristic after a long period of time, especially after 10 hours, was lower than that of Comparative Example 1. It is also clear that the value is more than 3 times and more than 4 times. Furthermore, in Sample 11 (3) and Sample 3- (4) (barium ratios of 0.1 and 0.2), the afterglow luminance after 10 hours was more than 6 times that of Comparative Example 1, indicating a more preferable and excellent afterglow. It is clear that it has brightness characteristics. However, in Sample 3— (1) (the ratio of barium was 0.005), the percentage of norium was too small, so that, for example, the afterglow luminance characteristic after 10 hours was less than three times that of Comparative Example 1. 7) When the ratio of barium is 0.4, the ratio of strontium may decrease relatively, and the afterglow brightness decreases.For example, the afterglow brightness after 10 hours is less than three times that of Comparative Example 1. Further, the afterglow luminance after 10 minutes and 20 minutes was lower than that of Comparative Example 1.

From this fact, when the metal element represented by M is strontium and barium force, when the ratio of barium to M, that is, when BaZ (Sr + Ba) is 0.01 or more and 0.35 or less, the luminous properties with excellent afterglow luminance characteristics It turns out that it becomes a phosphor.

(4) Experimental example 4

Next, when the metal elements represented by M are strontium (Sr) and calcium (Ca) Will be described.

First, 141.77 g (0.960) of strontium carbonate (SrCO) as a raw material for strontium (Sr)

Three

0.97 g (0.0000 g) of calcium carbonate (CaCO 3) as a raw material of calcium (Ca).

Three

Mol), and as a raw material of palladium (Eu 2 O 3) as an activator

1.76 g (0.01 mol as Eu) of 23 was added, and 3.73 g (0.02 mol as Dy) of dysprosium oxide (DyO) as a raw material of dysprosium (Dy) as a co-activator was added.

twenty three

117.26 g of alumina (Al 2 O 3) as a raw material for minium (2.3 moles as Al, that is, AlZ (

twenty three

(Sr + Ca + Eu + Dy) = 2.3), and 3.2 g of boric acid (HBO) as a boron (B) compound as a flux (that is, 1.2 mass% based on the raw material). For ball mill

3 3

And mix well. This mixture is calcined in a reducing atmosphere in a gas stream of 97% nitrogen-3% hydrogen at a calcining temperature of 1350 ° C for 4 hours, and then cooled to room temperature in about 1 hour. The obtained fired product was pulverized, sieved, and passed through a # 250 mesh to obtain a phosphorescent phosphor sample 4 (3). This sample 4 (3) had 0.9603 mol of strontium and 0.0097 mol of calcium, and the molar ratio of strontium to 0.97 mol of the total number of mols of strontium and calcium was 0.99, and the molar ratio of calcium was 0.999 mol It will be 0.01. Further, the amount of added syrup of eutronic pium is 1 mol% and the amount of added dysprosium is 2 mol% based on the total of strontium, calcium, euproium and dysprosium. The ratio, DyZEu, is 2. Further, the molar ratio of aluminum, that is, AlZ (Sr + Ca + Eu + Dy) is determined to be 2.3, which exceeds the stoichiometric ratio of 2.0.

Similarly, as shown in Table 9, the luminous fluorescence in which the mixing ratio of strontium and calcium was changed in the range of Sr: Ca = 0.998: 0.002—0.8: 0.2. The bodies were prepared and obtained as Sample 41 (1), Sample 4 (2), Sample 4 (4), and Sample 4 (7), respectively.

[Table 9] M = S r + C a

E u = 1 mol%, D y = 2 mol% (vs. M + Eu + Dy) A 1 / (M + Eu + Dy): 2.3 ^-¾ 0.998 0.002

\! 0.995 95.005

Sample 4— (3) 0.99 0.01

Sample 4- (4) 0.95 0.05

Sample 4-(5) 0.9 9 0.1

Sample 4- (6) 0.85 0.15

Sample 4-(7) 0.8 0.2 Next, for these Samples 4-1 (1) to 4 (7), the same illumination conditions (D65 standard light source Z4001xZ20 Min), and the afterglow luminance characteristics were examined. The results are shown in Table 10 as relative luminance when the afterglow luminance of Comparative Example 1 was set to 1 [Table 10].

From the results shown in Table 10, it can be seen that Sample 4 (2) to Sample 4 (6), that is, the percentage of calcium was 0.005 to 0.15, and the afterglow luminance characteristics were superior to Comparative Example 1. It can be seen that, in particular, the afterglow luminance characteristics after a long period of time after 10 hours are all three times or more superior to Comparative Example 1. Further, in Sample 4 (4) and Sample 4 (5) (calcium proportions of 0.05 and 0.1), the afterglow luminance after 10 hours is more preferably 4 times or more that of Comparative Example 1. It can be seen that the device has excellent afterglow luminance characteristics. However, Sample 4 (1) (having a calcium ratio of 0.002) had an afterglow luminance characteristic less than three times that of Comparative Example 1 after 10 hours, and Sample 4 (7) (having a calcium ratio of 10%). In 0.2), the ratio of strontium may be relatively reduced, and the afterglow brightness is sharply reduced. Thus, when the metal element represented by M is strontium and calcium, when the ratio of calcium to M, that is, CaZ (Sr + Ca) is 0.005 or more and 0.15 or less, excellent afterglow luminance characteristics are obtained. It can be seen that the phosphor has a phosphorescent property.

(5) Experimental example 5

Next, the case where the metal element represented by M is strontium, norium and calcium will be described.

First, strontium carbonate (SrCO 2) 127.45 g (0.863) was used as a raw material for strontium (Sr).

Three

314 moles) and 19.14 g (0.097 moles) of barium carbonate (BaCO 3) as a raw material for barium (Ba)

Three

In addition, 0.97 g of calcium carbonate (CaCO 3) (0.0000 mol

Three

) In addition, as a raw material of palladium of Euguchi as an activator,

twenty three

117.26 g of alumina (Al 2 O 3) (2.3 moles as Al, ie AlZ (S

twenty three

r + Ba + Ca + Eu + Dy) = 2.3) In addition, 3.2 g of boric acid (HBO) as a boron (B) compound as flux (that is, 1.2 mass% based on the raw material) Sashimi and ball mill

3 3

Mix well using. The mixture is fired at a firing temperature of 1350 ° C for 4 hours in a mixed gas stream of 97% nitrogen and 3% hydrogen in a reducing atmosphere, and then cooled to room temperature over about 1 hour. The obtained fired product was pulverized, sieved, and passed through # 250 mesh to obtain a phosphorescent phosphor sample 5- (3). In this sample 5- (3), strontium was 0.8633 monol, norrium mosquito S0.097 monol, and kanoreshimuka ^ 0.0097, and it was based on 0.97 mol of the total number of moles of strontium, norium and calcium. The molar ratio of strontium is 0.89, burr The molar ratio of pum is 0.01 and the molar ratio of calcium is 0.01. Further, the added amount of caloric power of palladium based on the total amount of strontium, normium, calcium, palladium and dysprosium is Si mol%, and the added amount of dysprosium added with dysprosium is 2 mol%. , Ie, Dy / Eu is 2. The molar ratio of aluminum, that is, AlZ (Sr + Ba + Ca + Eu + Dy) is 2.3, which exceeds the stoichiometric ratio of 2.0.

Similarly, barium was fixed at 0.1 in terms of molar ratio to M, which was suitable in Experimental Example 3, and the mixing ratio of strontium to calcium was as shown in Table 11, where Ca: 0.0002-0 The phosphorescent phosphors varied in the range of 2 were prepared and obtained as Sample 5— (1), Sample 5— (2), Sample 5— (4), and Sample 5— (7), respectively. .

[Table 11]

Next, these samples 5- (1) to 5- (7) were excited under the same illuminance conditions (D65 standard light source Z4001xZ20 minutes) as Sample 11 (1) of Experimental Example 1 and the afterglow luminance characteristics were measured. Examined. The results are shown in Table 12 as relative luminance when the afterglow luminance of Comparative Example 1 was set to 1.

[0060] [Table 12] Excitation conditions D ₆₅ standard light source, 400 lx, 20 minutes

Sample Afterglow luminance characteristics (relative value, Comparative Example 1 = 1.0)

After 10 minutes After 20 minutes After 60 minutes After 5 hours After 10 hours Comparative Example 1 1.00 1.00 1.00 1.00 1.00 Sample 5 (1) 1.82 1.82 2.01 2.81 2.92 sample 5- (2) 1.80 1.83 2.02 3.01 4.01 sample 5- (3) 1.72 1.83 2.02 2.99 3.97 sample 5- (4 ) 1.67 1.81 2.02 3.30 4.67 Sample 5- (5) 1.35 1.46 1.67 2.73 3.74 Sample 5-(6) 0.80 0.80 90 1.46 1.87 Sample 5_ (7) 0.61 0.65 0.71 1.20 1.50 From the results shown in Table 12, Samples 5— (2) to 5— (5) When the barium ratio was 0.1 and the calcium ratio was 0.005 to 0.1, the afterglow luminance characteristics were superior to Comparative Example 1. It can be seen that each of them is 3 times or more superior to 1. Further, in Sample 5 (2) to Sample 5— (4) (the ratio of barium was 0.1 and the ratio of calcium to M was 0.005 to 0.05), the afterglow luminance after 10 hours was almost 4 times that of Comparative Example 1. It can be seen that the excellent afterglow luminance characteristic is more preferable when the ratio is twice or more. However, in Sample 5— (1) (the percentage of balm was 0.1 and the percentage of calcium was 0.002), the afterglow luminance after 10 hours was less than three times that of Comparative Example 1, and Samples 5— (5) and Sample 5- (6) (barium ratio of 0.1 and power ratio of 0.15 to 0.2) may cause a relative decrease in the strontium ratio. Afterglow luminance after 10 minutes, 20 minutes, and 60 minutes was lower than that of Comparative Example 1.

In addition to these Samples 5- (1) to 5- (7), experiments were conducted by changing the mixing ratio of barium and calcium. In each case, the preferred range of norium was 0.01. It was confirmed that the range was more than 0.3 and less than 0.3, and the suitable range of calcium was more than 0.005 and 0.1 or less.

From this, when the metal element represented by M is strontium, norium and calcium, the ratio of barium to M, that is, BaZ (Sr + Ba + Ca) is 0.01 or more. When the ratio of calcium to M, that is, CaZ (Sr + Ba + Ca) is 0.01 or more and 0.1 or less, it is understood that the phosphorescent phosphor has excellent afterglow luminance characteristics. Industrial applicability

The invention can be used, for example, for luminous watches.

Claims

The scope of the claims

[1] A compound represented by MAI O, where M also has strontium (Sr) and barium (Ba) forces.

twenty four

Compound into a mother crystal,

Add palladium (Eu) as an activator,

A phosphorescent phosphor to which dysprosium (Dy) is added as a co-activator, and the amount of palladium (Eu) added to the metal element represented by M, the amount of palladium (Eu) and dysprosium (Dy) 0.5% or more and 2% or less in mol% based on the total number of moles,

The amount of dysprosium (Dy) to be added is 1 in molar ratio

≤ 20;

And amount total of Yu port Piumu (Eu) and dysprosium (Dy) is 1 mol ^_0/0 to the total mole number of the metal elemental and Yu port Piumu (Eu) and dysprosium (Dy) expressed by M. 5% or more and 42% or less,

The ratio of aluminum (A1) is 2.05 or more and 3.0 or less with respect to the total number of moles of the metal element represented by M, the number of moles of palladium (Eu) and dysprosium (Dy).

Luminescent phosphor characterized by the ratio of barium (Ba) to M: 0.01 ≤ Ba / (Sr + Ba) ≤ 0.35.

[2] A compound represented by MAI O, where M is derived from strontium (Sr) and calcium (Ca).

twenty four

Compound as a mother crystal,

Add palladium (Eu) as an activator,

The amount of dysprosium (Dy) to be added is 1 in molar ratio

≤ 20;

The ratio of aluminum (A1) is determined by the metal element represented by M, the palladium (Eu), and dysprosium. The molar ratio is 2.05 or more and 3.0 or less with respect to the total number of moles of the

A phosphorescent phosphor characterized in that the ratio of calcium (Ca) to M is 0.005≤Ca / (Sr + Ca) ≤0.15.

[3] A compound represented by MAI O, where M is strontium (Sr), barium (Ba) and

twenty four

In addition to turning a compound (Ca) into a mother crystal,

Add palladium (Eu) as an activator,

The amount of dysprosium (Dy) to be added is 1 in molar ratio

≤ 20;

And amount total of Yu port Piumu (Eu) and dysprosium (Dy) is in molar ^_0/0 to moles total of metal elemental) and Yu port Piumu (Eu) and dysprosium (Dy) expressed by M 1 Between 5% and 42%,

The ratio of barium (Ba) to M is 0.01 ≤Ba / (Sr + Ba + Ca) ≤0.3, and the ratio of calcium (Ca) to M is 0.005≤Ca / (Sr + Ba + Ca) ≤0.1. Luminescent phosphor, characterized in that:

[4] An aluminum (A1) compound, a strontium (Sr) compound, a barium compound (Ba), an europium pium (Eu) compound, and a dysprosium (Dy) compound such that each element has the following molar ratio. And calcination in a reducing atmosphere, followed by cooling and pulverization, and a method for producing an alkaline earth metal aluminate phosphorescent phosphor.

0.005≤Eu / (Sr + Ba + Eu + Dy) ≤0.02,

l <Dy / Eu≤20,

0.0015≤ (Eu + Dy) / (Sr + Ba + Eu + Dy) ≤0.42,

0.01≤Ba / (Sr + Ba) ≤0.35,

2.05≤Al / (Sr + Ba + Eu + Dy) ≤3.0

[5] An aluminum (Al) compound, a strontium (Sr) compound, a calcium compound (Ca), a europium (Pu) (Eu) compound, and a dysprosium (Dy) compound such that each element has the following molar ratio: And calcination in a reducing atmosphere, followed by cooling and pulverization, thereby producing a phosphorescent phosphor of an alkaline earth metal aluminate.

0.005≤Eu / (Sr + Ca + Eu + Dy) ≤0.02,

l <Dy / Eu≤20,

0.0015≤ (Eu + Dy) / (Sr + Ca + Eu + Dy) ≤0.42,

0.005≤Ca / (Sr + Ca) ≤0.15,

2.05≤Al / (Sr + Ca + Eu + Dy) ≤3.0

[6] Each element is composed of an aluminum (A1) compound, a strontium (Sr) compound, a barium (Ba) compound, a calcium (Ca) compound, a palladium (Eu) compound, and a dysprosium (Dy) compound. A method for producing an alkaline earth metal aluminate phosphorescent phosphor, comprising mixing in the following molar ratio, firing in a reducing atmosphere, and then cooling and pulverizing.

0.005≤Eu / (Sr + Ba + Ca + Eu + Dy) ≤0.02,

l <Dy / Eu≤20,

0.0015≤ (Eu + Dy) / (Sr + Ba + Ca + Eu + Dy) ≤0.42,

0.01 ≤Ba / (Sr + Ba + Ca) ≤0.3,

0.005≤Ca / (Sr + Ba + Ca) ≤0.1,

2.05≤Al / (Sr + Ba + Ca + Eu + Dy) ≤3.0

[7] The production of the alkaline earth metal aluminate phosphorescent phosphor according to claim 4, wherein a boron compound is added as a flux to the raw material and calcined. Method.