JP2012121974A - Luminous fluorescent substance and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a luminous fluorescent substance in which at least one of a fluorescent color or a luminous color emits white light, and emission unevenness is little.SOLUTION: The luminous fluorescent substance includes the following components: (A) a crystal which contains Eu at least as a luminescent center to a crystal base material which consists of a compound oxide containing Ca and Al; (B) a crystal which contains Eu at least as a luminescent center to a crystal base material which consists of a compound oxide containing Sr and Al; and (C) a crystal which is a compound oxide containing Ca, Al, and Eu and/or Nd, and has a different crystalline form from the crystal base material of the component (A).

Description

  The present invention relates to a phosphorescent phosphor and a method for producing the same. More specifically, the present invention relates to a phosphorescent phosphor in which at least one of a fluorescent color and a phosphorescent color is visually recognized as white.

  A phosphorescent phosphor, which is a kind of phosphor, has a so-called afterglow function that emits light in the dark by absorbing light from the outside and storing the energy, as well as emitting fluorescence. Since such a phosphorescent phosphor is a solid-state element, it has the advantages of a long operating life and excellent vibration resistance. Therefore, various light-emitting elements such as various indicators and liquid crystal backlights that consume less power are used. It has been widely used as a light source.

  As phosphorescent phosphors, sulfide phosphors such as CsB: Bi (blue light emission), ZuCdS: Cu (yellow light emission) and the like are conventionally known, but in addition to insufficient light emission intensity and afterglow time, However, there are practical problems such as being unstable and containing harmful elements.

On the other hand, for example, an oxide-type phosphorescent phosphor with a long emission time has been developed by adding europium (Eu) and dysprosium (Dy) as an activator to a composite oxide composed of an alkaline earth element and aluminum. Has been. As such phosphorescent phosphors, CaAlO ₄ (blue light emission) containing rare earth elements such as europium (Eu) and dysprosium (Dy), SrAlO ₄ (yellow light emission), and the like are known (for example, patents). Reference 1).

JP 7-11250 A

  By the way, fluorescent lamps and incandescent lamps have been widely used as white light sources, but from the viewpoint of power consumption, operating life, etc., use of phosphorescent phosphors is expected depending on applications. However, there is no conventional phosphorescent phosphor that emits white light with a single base crystal.

  For this reason, white light is obtained by diffusing color mixing by combining multiple phosphorescent phosphors that have complementary colors, but light emission unevenness is likely to occur and uniform white light cannot be obtained, or depending on the combination of phosphorescent phosphors There was a problem that the brightness decreased in response to

  As described above, there are still many problems with phosphorescent phosphors that emit white light. Under such circumstances, an object of the present invention is to provide a phosphorescent phosphor that emits white light with at least one of a fluorescent color and a phosphorescent color and has little emission unevenness.

  As a result of intensive studies to solve the above problems, the present inventors have heated a mixture containing a Ca raw material compound, a Sr raw material compound, an Al raw material compound, and an Eu raw material compound at a predetermined temperature and time in a reducing atmosphere. It has been found that a phosphorescent phosphor meeting the above-mentioned purpose can be obtained by holding, and the present invention has been achieved.

That is, the present invention relates to the following inventions.
<1> A phosphorescent phosphor containing the following components.
(A) A crystal base material made of a composite oxide containing Ca and Al, a crystal containing at least Eu as a light emission center (B) a crystal base material made of a composite oxide containing Sr and Al, and a light emission center Crystalline (C) containing at least Eu and a composite oxide containing Ca and Al and Eu and / or Nd, and having a crystal form different from the crystal matrix of component (A) <2> Component ( The phosphorescence according to <1>, wherein the crystal base material in A) is CaAl ₂ O ₄ , the crystal base material in component (B) is SrAl ₂ O ₄ , and the component (C) is Ca (Eu, Nd) AlO ₄ . Phosphor.
<3> The content ratio (molar ratio) of Ca, Sr, and Al in the total amount of phosphorescent phosphor is Al: (Ca + Sr) = 1: 0.9 to 1.1, and Ca: Sr = 0.45. : The phosphorescent phosphor according to <1> or <2>, which satisfies a relationship of 0.55 to 0: 65: 0.35.
<4> The phosphorescent phosphor according to any one of <1> to <3>, wherein the Eu content is 0.1 to 10 mol% in the total amount of the phosphorescent phosphor.
<5> The phosphorescent phosphor according to any one of <1> to <4>, further containing Nd as an activating component in the component (A) and the component (B).
<6> The phosphorescent phosphor according to the above <5>, further containing Ag ⁺ .
<7> The phosphorescent phosphor according to <6>, wherein the content of Ag ⁺ is 1 to 10 mol% with respect to the total amount of the phosphorescent phosphor.
<8> The content ratio (molar ratio) of Ca, Sr, and Al in the total amount of phosphorescent phosphor of powdered Ca raw material compound, Sr raw material compound, Al raw material compound, Eu raw material compound is Al: (Ca + Sr) = 1 : 0.9 to 1.1, and satisfies the relationship of Ca: Sr = 0.45: 0.55 to 0: 65: 0.35, and the Eu content is based on the total amount of the phosphorescent phosphor. The phosphorescent phosphor is mixed so as to be 0.1 to 10 mol%, and the resulting mixture is heated and held under a reducing atmosphere at 1000 to 1400 ° C. for 15 hours or less.
<9> The method for producing a phosphorescent phosphor according to <8>, wherein the heating and holding condition is 1 to 5 hours.
<10> Further, the phosphorescent phosphor according to <8> or <9>, wherein the Nd raw material compound is mixed so that the content of Nd is 1 to 10 mol% with respect to the total phosphorescent phosphor. Manufacturing method.
<11> Furthermore, the Ag raw material compound is mixed so that the Ag content is 0.1 to 10 mol% with respect to the total amount of the phosphorescent phosphor. The manufacturing method of the luminous fluorescent substance of description.

  According to the present invention, there is provided a phosphorescent phosphor in which at least one of a fluorescent color and a phosphorescent color emits white light and has little light emission unevenness.

It is a XRD pattern of samples 1-5. It is an emission spectrum of sample 1-2 and sample 4-5. It is an emission spectrum of sample 3 and sample 4. It is a XRD pattern of sample 3 and samples 6-8. It is an emission spectrum of sample 3 and samples 6-8. It is a result of chromaticity measurement of sample 3. It is the result of chromaticity measurement of sample 6. It is the result of chromaticity measurement of sample 7. It is the result of chromaticity measurement of sample 8. It is a XRD pattern of samples 8-11. It is an emission spectrum of samples 8-11.

The present invention relates to a phosphorescent phosphor containing the following components.
(A) A crystal base material made of a composite oxide containing Ca and Al, a crystal containing at least Eu as a light emission center component (B) a crystal base material made of a composite oxide containing Sr and Al, and emitting light Crystalline (C) containing at least Eu as a central component and a composite oxide containing Ca and Al and Eu and / or Nd, and having a different crystal form from the crystalline matrix of component (A)

The phosphorescent phosphor of the present invention is characterized in that it contains the component (C) in addition to the component (A) that emits blue light alone and the component (B) that emits yellow light. When the component (C) is not included, the phosphorescent phosphor does not emit white light in either the fluorescent color or the phosphorescent color, or the light emission unevenness becomes remarkable. Here, “light emission unevenness” means that it is possible to visually recognize that each portion of the phosphorescent phosphor has different luminance or that other colors are mixed.
The reason why it becomes a phosphorescent phosphor that emits white light with little emission unevenness by containing the component (C) is not clear at present, but the component (C) is composed of the component (A) and the component (B ) And other light-emitting central components such as Eu, and other activator components added as necessary are buffered, and the distribution of the light-emitting center components of the phosphorescent phosphor is uniform. May have contributed to
Hereinafter, each component will be described.

The composite oxide containing Ca and Al, which is the crystal matrix of the component (A), may be any one as long as it emits blue light by containing Eu as the light emission center component. It is desirable that the crystal base material of the component (A) having high stability and high emission luminance is CaAl ₂ O ₄ .

The composite oxide containing Sr and Al, which is the crystal matrix of the component (B), may be any one as long as it emits yellow light by containing Eu as the emission center component. It is desirable that the crystal base material of the component (B) having high stability and high emission luminance is SrAl ₂ O ₄ .

  Note that if the content of Eu in the crystal matrix of the component (A) and the component (B) is too small, light emission may be insufficient, and if too large, the crystal matrix becomes unstable. Preferably it is 0.1-10 mol% with respect to each crystal | crystallization base material, More preferably, it is 1-5 mol%.

The crystal base materials of the component (A) and the component (B) may contain other rare earth elements as an activation component in addition to Eu as the main luminescent center component. By adding other rare earth elements, it is possible to adjust the fluorescence emitted from the phosphorescent phosphor and the hue and luminance of the phosphorescent light.
Specific examples of other rare earth elements include Ce, Pr, Nd, Sm, Tb, Dy, and Tm.
Among these, it is preferable to contain Nd. By containing Nd as the activation component, there is an advantage that the luminance of the phosphorescent phosphor, particularly the luminance in the phosphorescence can be increased.
In addition, when there is too little content of the activation component in the crystal | crystallization base material of a component (A) and a component (B), the effect may not be recognized, and when too large, it becomes a cause of light emission nonuniformity and a brightness fall. Therefore, it is preferable that it is 0.01-5 mol% with respect to a crystal | crystallization base material.

Component (C) is a complex oxide containing Ca and Al and Eu and / or Nd, and is a crystal having a different crystal form from the crystal matrix of component (A).
Component (C) is usually heated and held at a predetermined temperature and time in a reducing atmosphere for a mixture containing a Ca raw material compound, a Sr raw material compound, an Al raw material compound, and an Eu raw material compound, as described later. As a mixed phase product, it can be produced together with component (A) and component (B).

In the phosphorescent phosphor of the present invention, the crystal base material in the component (A) is CaAl ₂ O ₄ , the crystal base material in the component (B) is SrAl ₂ O ₄ , and the component (C) is less colored unevenness. Is preferably Ca (Eu, Nd) AlO ₄ . Ca (Eu, Nd) AlO ₄ is a compound in which Ca and Eu are substituted for Ca sites in CaAlO ₄ .
Further, when the components (A), (B) and (C) are in such a combination, there is an advantage that they can be easily formed from the respective oxides as raw material compounds.

As is clear from the fluorescence spectrum, the phosphorescent phosphor of the present invention exhibits fluorescence emission in the vicinity of a wavelength of 450 nm and in the vicinity of 550 to 570 nm, and as a mixed color thereof, the fluorescence emission recognized visually as blue-white-white-yellow-white is obtained. Show.
In the phosphorescent luminescent material of the present invention, either or both of fluorescence and phosphorescence emit white light. However, considering the use in a dark place, it is particularly preferable that at least the phosphorescent light emits white light. The fluorescent color and the phosphorescent color can be evaluated visually or using a chromaticity meter.

Further, the content ratio (molar ratio) of Ca, Sr and Al in the total amount of the phosphorescent phosphor is Al: (Ca + Sr) = 1: 0.9 to 1.1, and Ca: Sr = 0.45: It is preferable to satisfy the relationship of 0.55 to 0: 65: 0.35. If it is out of this range, even if white light is obtained, the luminance may be insufficient, or color unevenness may occur.
In particular, from the stoichiometry of the crystal base material, the content ratio (molar ratio) of Ca, Sr and Al is Al: (Ca + Sr) = 1: 1 (that is, Al atom content, Ca atom content and Sr atom content) It is preferable to satisfy the same amount).

Furthermore, the phosphorescent phosphor of the present invention preferably contains Ag ⁺ . By containing Ag ⁺ which is a monovalent cation, solid solution of Eu and other rare earths to the crystal base material of the components (A) and (B) is promoted by the charge compensation effect. In some cases, the brightness of phosphorescence is increased.

Although the reason is not completely clear at present, the phosphorescence time (afterglow time) of the phosphorescent phosphor of the present invention tends to increase by containing Ag ⁺ . Other monovalent cations do not provide an effect comparable to Ag ⁺ .
The content of Ag ⁺ is preferably 1 to 10 mol%, more preferably 3 to 8 mol%, based on the total amount of the phosphorescent phosphor. In less than 1 mole% content of Ag ⁺ may effect the Ag ⁺ addition is insufficient, there is a possibility that brightness decreases when more than 10 mol%.

  The production method of the phosphorescent phosphor of the present invention is not particularly limited, but usually (a) Ca raw material compound, (b) Sr raw material compound, (c) Al raw material compound, (d) Eu raw material compound, and as required Accordingly, it can be produced by heating and holding a mixture obtained by mixing (e) another rare earth material compound and (f) Ag compound at a predetermined temperature in a reducing atmosphere.

Next, a preferred method for producing the phosphorescent phosphor of the present invention (hereinafter referred to as “the production method of the present invention”) will be described.
In the production method of the present invention, the powdered Ca raw material compound, Sr raw material compound, Al raw material compound, Eu raw material compound, the content ratio (molar ratio) of Ca, Sr and Al in the total amount of phosphorescent phosphor is Al :( Ca + Sr) = 1: 0.9 to 1.1 and satisfies the relationship of Ca: Sr = 0.45: 0.55 to 0: 65: 0.35, and the Eu content is phosphorescent fluorescence. It mixes so that it may be 0.1-10 mol% with respect to body whole quantity, and the obtained mixture is heat-held on 1000-1400 degreeC and conditions for 15 hours or less under reducing atmosphere.
By adopting the above conditions, the phosphorescent phosphor of the present invention can be obtained with good reproducibility.

Here, (a) Examples of the Ca raw material compound include Ca oxide, hydroxide, oxyhydroxide, carbonate, sulfate, nitrate, acetate, halide, ammonium salt, oxalate and the like. Can do. Among these, carbonate (CaCO ₃ ) which is easily available and highly reactive is preferable.

(B) Sr raw material compounds include Sr oxide, hydroxide, oxyhydroxide, carbonate, sulfate, nitrate, acetate, halide, ammonium salt, oxalate and the like. it can. Among these, carbonate (SrCO ₃ ), which is easily available and highly reactive, is preferable.

(C) Al raw material compounds include Al oxides, hydroxides, oxyhydroxides, carbonates, sulfates, nitrates, acetates, halides, ammonium salts, oxalates, and the like. it can. Among these, an oxide (Al ₂ O ₃ ) that is easily available and highly reactive is usually preferable.

(D) Eu raw material compounds include Eu oxide, hydroxide, oxyhydroxide, carbonate, sulfate, nitrate, acetate, halide, ammonium salt, oxalate, fluoride, chloride And the like. Among these, a high oxide (Eu ₂ O ₃ ) that is easily available is usually used.

In addition, in the manufacturing method of this invention, raw materials other than the said raw material compound may be included.
Examples include (e) other rare earth raw material compounds as chromaticity adjustment and activation components of the emission spectrum, and (f) silver ion (Ag ⁺ ) raw material compounds exhibiting a charge compensation effect.

(E) Other rare earth raw material compounds include oxides, hydroxides, oxyhydroxides, carbonates, sulfates, nitrates, acetic acids of rare earth elements such as Ce, Pr, Nd, Sm, Tb, Dy, and Tm. Examples thereof include salts, halides, ammonium salts, oxalates, fluorides, chlorides and the like, and oxides that are easily available are usually used.

  In addition, from the viewpoint of improving the luminous characteristics, it is particularly preferable to include Nd and Dy compounds.

(F) As a raw material compound of silver ion (Ag ⁺ ), each oxide, hydroxide, oxyhydroxide, carbonate, sulfate, nitrate, acetate, halide, ammonium salt, oxalate, etc. Can be mentioned.
Among monovalent cations, Ag ⁺ is preferably used because it can increase the phosphorescence time. As a raw material compound of silver ion (Ag ⁺ ), an easily available and highly reactive oxide (Ag ₂ O) is preferable.

  Further, the content ratio (molar ratio) of Ca, Sr and Al in the total amount of the phosphorescent phosphor is Al: (Ca + Sr) = 1: 0.9 to 1.1, and Ca: Sr = 0.45: It is necessary to satisfy the relationship of 0.55 to 0: 65: 0.35. In particular, from the stoichiometry of the crystal base material, the content ratio (molar ratio) of Ca, Sr and Al is Al: (Ca + Sr) = 1. 1 (that is, the amount of Al in the raw material and the total amount of Ca and Sr are preferably the same).

The raw materials may be mixed by either dry mixing or wet mixing.
As the dry mixing, a conventionally known method may be arbitrarily selected, and for example, a method of mixing with a ball mill or the like may be mentioned.
As the wet mixing, a conventionally known method may be arbitrarily selected, and an appropriate medium such as ethanol may be added to the raw material compound powder, followed by mixing with a ball mill or the like and then drying.

The mixture obtained by mixing the raw material compounds is heated and held at 1000 to 1400 ° C. in a reducing atmosphere. By this heating and holding step, the above-described raw material compounds react, and the compounds of components (A) to (C) described in the phosphorescent phosphor of the present invention are generated in a mixed phase.
Before heating, the raw material mixture obtained as described above may be pulverized, classified and dried as necessary.

  A reducing atmosphere is preferable as the atmosphere for heating and holding. That is, a reducing atmosphere such as a hydrogen atmosphere, an inert gas atmosphere containing hydrogen, or a carbon dioxide atmosphere containing carbon monoxide is preferable. In particular, from the viewpoint of safety, an inert gas atmosphere containing hydrogen gas is preferable.

  The heating and holding time is 15 hours or less, and preferably 1 to 5 hours. When the heating and holding time is less than 1 hour, the reaction of the raw material compound becomes insufficient, and the target components (A) to (C) may not be obtained. If it exceeds 5 hours, the amount of the component (C) may be excessively reduced due to overreaction, and if it exceeds 15 hours, the phosphorescent phosphor of the present invention may not be formed.

Prior to the heating and holding step, calcination may be performed.
For example, by calcining a mixture of raw material compounds at about 800 to 1100 ° C. to remove carbon impurities contained in the raw material compound or when using carbonate as the raw material compound, the raw material compound is sufficiently decomposed. , And can be subjected to the heating and holding step.
The atmosphere at the time of calcination is not particularly limited, and may be any of an oxidizing atmosphere such as air, an inert gas such as nitrogen and argon, and an inert gas atmosphere containing hydrogen gas.

  Alternatively, the mixture of raw material compounds after calcination may be taken out and further pulverized and mixed so as to be uniform, and then subjected to the heating and holding step.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is changed.

"Evaluation methods"
The evaluation methods in the examples are as follows.
(I) X-ray diffraction (XRD) measurement In order to identify the crystal phase of a sample, the XRD measurement was performed with the following apparatus and conditions.
Measuring device: RINT, XRD-610D (manufactured by Rigaku Corporation)
Radiation source: CuKα
Tube voltage: 40 kV
Tube current: 30 mA

(Ii) Luminance measurement (a) Fluorescence measurement In the dark room, after the distance between the sample and the luminance meter (Konica Minolta, product number: LS-100) is adjusted to about 3 cm, the sample is irradiated with black light (10 W). Then, luminance (L value) [unit: cdm ⁻² ] was recorded.
(B) Luminous measurement In a dark room, the distance between the sample and the luminance meter (manufactured by Konica Minolta, product number: LS-100) was adjusted to about 3 cm, and then irradiated with black light (10 W).
The time-dependent change in the phosphorescence is that the black light (10 W) is irradiated for 5 minutes and it is confirmed that the brightness has become constant, then the black light is shut off and the brightness (L value) becomes 0 cdm ^−2. Changes were evaluated.

(Iii) Measurement of emission spectrum In order to evaluate the emission spectrum of fluorescence or phosphorescence emitted from the sample, emission spectrum measurement was performed under the following conditions.
Measuring device: USB4000 (Optosirius Corporation)
Wavelength measurement range: 400 to 650 nm

1. Synthesis of phosphorescent phosphor Sample 1
A phosphorescent phosphor (sample 1) with Ca: Sr = 1: 0 (molar ratio) was synthesized by the following procedure.
First, CaCO ₃ (48 mol%), Al ₂ O ₃ (48 mol%), Eu ₂ O ₃ (2 mol%), and Nd ₂ O ₃ (2 mol%) powders were weighed, and an appropriate amount of ethanol was added. In addition, the ball mill was mixed for 0.5 hours until uniform. Next, the mixed powder was heated and held at 1300 ° C. for 4 hours in a reducing atmosphere composed of 10% H ₂ and 90% N ₂ , and then the obtained sintered body was pulverized to obtain Sample 1. The charge composition is shown in Table 1.

Sample 2
A phosphorescent phosphor (sample 2) with Ca: Sr = 0.75: 0.25 (molar ratio) was synthesized by the following procedure.
First, powders of CaCO ₃ (36 mol%), SrCO ₃ (12 mol%), Al ₂ O ₃ (48 mol%), Eu ₂ O ₃ (2 mol%), Nd ₂ O ₃ (2 mol%) are used. Each was weighed, an appropriate amount of ethanol was added, and the ball mill was mixed until uniform. Next, the mixed powder was heated and held under the same conditions as Sample 1, and Sample 2 was obtained. The charge composition is shown in Table 1.

Sample 3
A phosphorescent phosphor (sample 3) with Ca: Sr = 0.6: 0.4 (molar ratio) was synthesized by the following procedure.
First, CaCO ₃ (28.8 mol%), SrCO ₃ (19.2 mol%), Al ₂ O ₃ (48 mol%), Eu ₂ O ₃ (2 mol%), Nd ₂ O ₃ (2 mol%) ) Were weighed, an appropriate amount of ethanol was added, and the ball mill was mixed until uniform. Next, the mixed powder was heated and held under the same conditions as Sample 1, and Sample 3 was obtained. The charge composition is shown in Table 1.

Sample 4
A phosphorescent phosphor (sample 4) with Ca: Sr = 0.5: 0.5 (molar ratio) was synthesized by the following procedure.
First, powders of CaCO ₃ (24 mol%), SrCO ₃ (24 mol%), Al ₂ O ₃ (48 mol%), Eu ₂ O ₃ (2 mol%), and Nd ₂ O ₃ (2 mol%) are used. Each was weighed, an appropriate amount of ethanol was added, and the ball mill was mixed until uniform. Next, the mixed powder was heated and held under the same conditions as Sample 1, and Sample 4 was obtained. The charge composition is shown in Table 1.

Sample 5
A phosphorescent phosphor (sample 5) with Ca: Sr = 0.25: 0.75 (molar ratio) was synthesized by the following procedure.
First, powders of CaCO ₃ (12 mol%), SrCO ₃ (36 mol%), Al ₂ O ₃ (48 mol%), Eu ₂ O ₃ (2 mol%), and Nd ₂ O ₃ (2 mol%) are used. Each was weighed, an appropriate amount of ethanol was added, and the ball mill was mixed until uniform. Next, the mixed powder was heated and held and pulverized under the same conditions as in Sample 1 to obtain a phosphorescent phosphor of Sample 5. The charge composition is shown in Table 1.

Sample 6
In the synthesis method of Sample 3, the raw material powders of Sample 3 were 97 mol%, and the Ag ₂ O powder was 3 mol% in terms of Ag atoms (with respect to 1 mol of the base crystal), whereby each raw material powder was powdered. Next, the mixed powder was heated, held, and pulverized under the same conditions as in Sample 1 to obtain a phosphorescent phosphor of Sample 6. Table 2 shows the Ca: Sr atomic ratio, the Ag addition amount, and the heating and holding conditions.

Sample 7
In the synthesis method of Sample 3, each raw material powder was made with the total raw material powder of Sample 3 being 97 mol% and the Ag ₂ O powder being 5 mol% in terms of Ag atoms (based on 1 mol of the base crystal). Next, the mixed powder was heated and held under the same conditions as in Sample 1 to obtain a phosphorescent phosphor of Sample 7. Table 2 shows the Ca: Sr atomic ratio, the Ag addition amount, and the heating and holding conditions.

Sample 8
In the synthesis method of Sample 3, the raw material powders of Sample 3 were 97 mol%, and the Ag ₂ O powder was 8 mol% in terms of Ag atoms (based on 1 mol of the base crystal), thereby starting each raw material powder. Next, the mixed powder was heated, held, and pulverized under the same conditions as Sample 1 to obtain a phosphorescent phosphor of Sample 8. Table 2 shows the Ca: Sr atomic ratio, the Ag addition amount, and the heating and holding conditions.

Sample 9
In the synthesis method of Sample 8, the phosphorescent phosphor of Sample 9 was obtained in the same manner as the synthesis method of Sample 8, except that the heating and holding time was 5 hours. Table 2 shows the Ca: Sr atomic ratio, the Ag addition amount, and the heating and holding conditions.

Sample 10
In the synthesis method of Sample 8, the phosphorescent phosphor of Sample 10 was obtained in the same manner as the synthesis method of Sample 8, except that the heating and holding time was 8 hours. Table 2 shows the Ca: Sr atomic ratio, the Ag addition amount, and the heating and holding conditions.

Sample 11
In the synthesis method of Sample 8, the phosphorescent phosphor of Sample 11 was obtained in the same manner as the synthesis method of Sample 8, except that the heating and holding time was 12 hours. Table 2 shows the Ca: Sr atomic ratio, the Ag addition amount, and the heating and holding conditions.

2. Evaluation (1) Evaluation of relationship between Ca, Sr preparation ratio and light emission FIG. 1 shows the results of XRD measurement of Samples 1-5. 2 and 3 show the emission spectra of Samples 1-5. Table 3 shows the result of visual color evaluation of fluorescence and phosphorescence.

In sample 1 in which the raw material powder does not contain SrCO ₃ , a signal of (Eu, Nd) Al ₃ O ₇ which is a crystal phase of CaAl ₂ O ₄ and a by-product was confirmed in XRD. In sample 1, a signal was confirmed in the vicinity of 450 nm (blue region) as the fluorescence spectrum. This signal is derived from CaAl ₂ O ₄ : Eu. Moreover, in the evaluation by visual observation, the fluorescence of Sample 1 was blue, which was consistent with the emission spectrum result.
Comparing the results of XRD in samples 2 to 5 containing SrCO ₃ in the raw material powder, as shown in FIG. 1, in samples 3 and 4, CaAl ₂ O ₄ , SrAl ₂ O ₄ , Ca (Eu, Nd) AlO ₄ Signals of three types of crystal phases were confirmed. In sample 2, there are only two phases of CaAl ₂ O ₄ and Ca (Eu, Nd) AlO ₄ , and in sample 5, SrAl ₂ O ₄ and Ca (Eu, There were only two phases of Nd) AlO ₄ .

In addition, when comparing the results of the emission characteristics of Samples 2 to 5, as shown in FIG. 3, in Samples 3 and 4, as a fluorescence spectrum, a signal around 450 nm (blue region) derived from CaAl ₂ O ₄ : Eu , SrAl ₂ O ₄ : Eu, a signal around 550 to 570 nm (yellowish green region) was confirmed. In visual observation, sample 3 was confirmed to emit white light during phosphorescence, and sample 4 was confirmed to emit white light during fluorescence.
In sample 2, which did not contain the SrAl ₂ O ₄ crystal phase, only a signal around 450 nm (blue region) was observed as in sample 1, and neither fluorescence nor phosphorescence emitted white light. On the other hand, in sample 5 containing no CaAl ₂ O ₄ crystal phase, only a signal in the vicinity of 550 to 570 nm (yellow-green region) was observed, and neither fluorescence nor phosphorescence emitted white light.

Based on the above results, the obtained sample contains three types of crystals of CaAl ₂ O ₄ , SrAl ₂ O ₄ , and Ca (Eu, Nd) AlO ₄ in order to exhibit white fluorescence or white phosphorescence. It was suggested that is necessary.

2. Changes in fluorescence and phosphorescence characteristics due to addition of Ag The Ca: Sr atomic ratio was fixed at 0.6: 0.4, and changes in fluorescence and phosphorescence characteristics due to addition of Ag were evaluated.

The result of the XRD measurement of samples 3 and 6 to 8 is shown in FIG.
The signal confirmed in XRD of samples 6 to 8 with Ag added was the same as that of sample 3 to which no Ag was added. From this, it was suggested that the added Ag was dissolved in the crystals of CaAl ₂ O ₄ , SrAl ₂ O ₄ , and Ca (Eu, Nd) AlO ₄ .

FIG. 5 shows emission spectra of Samples 3 and 6-8.
Similar to Sample 3 to which Ag was not added, Samples 6 to 8 were confirmed to have a maximum peak near 450 nm (blue region) and a peak near 550 to 570 nm (yellowish green region). The emission intensity was highest in Sample 3 to which no Ag was added.

Moreover, the result of the chromaticity measurement of the fluorescence of the sample 3 and 6-8 and a phosphorescence is shown to FIGS. The results of these chromaticity measurements are based on XYZ (Yxy display system) and are the basis of each color system as the CIE standard color system. In the figure, xy is the chromaticity, the achromatic color (white) is at the center of the chromaticity diagram, and the saturation increases as it goes to the periphery.
Table 4 shows the results of color evaluation of fluorescence and phosphorescence by visual observation and chromaticity measurement, and Table 5 shows the fluorescence luminance of samples 3, 6 and 8. In Table 5, the fluorescence luminance is the luminance after 3 seconds of black light irradiation.
Table 6 shows the time-dependent changes in the light accumulation of Sample 3, Sample 6 and Sample 8. The luminous intensity was measured as 0 seconds immediately after the black light was cut off.

First, when the fluorescent color and the intensity are compared, as shown in FIGS. 6 to 9, the chromaticity of the fluorescence of the samples 3 and 6 to 8 by the chromaticity measurement is a blue-white region, and the fluorescence luminance becomes maximum. This was a sample with no Ag added. This result agrees with the emission spectrum measurement result.
On the other hand, it can be seen that the luminous intensity is increased by adding Ag. Immediately after the black light is interrupted (0 second), the fluorescence is also measured at the same time, so it is considered that the luminance is apparently high.
Although the cause of the increase in the luminous intensity due to the addition of Ag is unknown, the amount of Nd ^{3+ in} the CaAl ₂ O ₄ crystal and SrAl ₂ O ₄ crystal may increase due to the solid solution of Ag. Guessed. Since the afterglow times of the samples 6 and 8 to which Ag is added are clearly longer than those of the sample 3 to which no Ag is added, it is clear that the phosphorescence characteristics of the phosphorescent phosphor are improved by adding Ag. became. In particular, Sample 8 to which 8 mol% Ag was added had an afterglow time of 30 seconds or longer.

3. Evaluation of dependency of fluorescence and phosphorescence characteristics on heating and holding time The Ca: Sr atomic ratio is fixed at 0.6: 0.4 and the addition amount of Ag is fixed at 8 mol%. evaluated.

The result of the XRD measurement of Samples 8 to 11 is shown in FIG.
Sample 9 with a heating and holding time of 5 h showed the same product phase as Sample 8 with a heating and holding time of 4 h, but the peak intensity of the CaAl ₂ O ₄ crystal was slightly lower than that of Sample 8.
Furthermore, in the sample 10 (heated for 8 hours) and the sample 10 (heated for 12 hours) with a longer holding time, the generation rate of SrAl ₂ O ₄ crystals increased significantly, which was different from the results so far.
Moreover, it was confirmed from the comparison of strength ratios that the strength of Ca (Eu, Nd) AlO ₄ decreases as the heat holding time increases.

FIG. 11 shows emission spectra of Samples 8-11. Table 7 shows the results of color evaluation of fluorescence and phosphorescence in visual observation and chromaticity measurement of Samples 8-11.
Table 8 shows the fluorescence luminance and luminous intensity of samples 8 to 11. The fluorescence luminance is the luminance 3 seconds after the black light irradiation, and the luminous intensity is the luminance 5 seconds after the black light is cut off.

Samples 8 and 9 having a holding time of 4 h and 5 h, respectively, were compared, but no significant difference was observed in the fluorescence color, and both showed blue-white fluorescence. Further, as long as it was visually confirmed, there was no difference in the emission intensity, but in the luminance measurement, the sample 9 was slightly smaller.
On the other hand, the fluorescent colors of Sample 10 and Sample 11 whose retention times were 8 h and 12 h, respectively, were yellowish white derived from SrAl ₂ O ₄ crystals, which was consistent with the XRD results.
On the other hand, the phosphorescent color was white in both sample 8 and sample 9 for visual observation and chromaticity measurement, but was not white in sample 10 and sample 11.

  The phosphorescent phosphor of the present invention can be applied to various light emitting devices and display devices because at least one of the fluorescent color and the phosphorescent color emits white light and has little light emission unevenness.

Claims (11)

A phosphorescent phosphor comprising the following components.
(A) A crystal base material made of a composite oxide containing Ca and Al, a crystal containing at least Eu as a light emission center (B) a crystal base material made of a composite oxide containing Sr and Al, and a light emission center Crystalline (C) containing at least Eu and a composite oxide containing Ca and Al and Eu and / or Nd, and having a crystal form different from the crystal matrix of component (A) The phosphorescent according to claim 1, wherein the crystal base material in component (A) is CaAl ₂ O ₄ , the crystal base material in component (B) is SrAl ₂ O ₄ , and component (C) is Ca (Eu, Nd) AlO _4. Fluorescent material.   The content ratio (molar ratio) of Ca, Sr, and Al in the total amount of the phosphorescent phosphor is Al: (Ca + Sr) = 1: 0.9 to 1.1, and Ca: Sr = 0.45: 0. The luminous phosphor according to claim 1 or 2, satisfying a relationship of 55 to 0: 65: 0.35.   The phosphorescent phosphor according to any one of claims 1 to 3, wherein the Eu content is 0.1 to 10 mol% in the total amount of the phosphorescent phosphor.   The phosphorescent phosphor according to any one of claims 1 to 4, further comprising Nd as an activating component in the component (A) and the component (B). Furthermore, the luminous phosphor of Claim 5 containing Ag ^<+> . The phosphorescent phosphor according to claim 6, wherein the content of Ag ⁺ is 1 to 10 mol% with respect to the total amount of the phosphorescent phosphor.   When the powdered Ca raw material compound, Sr raw material compound, Al raw material compound, and Eu raw material compound are used, the content ratio (molar ratio) of Ca, Sr and Al in the total amount of the phosphorescent phosphor is Al: (Ca + Sr) = 1: 0. 9 to 1.1, satisfying the relationship of Ca: Sr = 0.45: 0.55 to 0: 65: 0.35, and the Eu content is 0 with respect to the total amount of the phosphorescent phosphor. A method for producing a phosphorescent phosphor, wherein the mixture is mixed so as to be 1 to 10 mol%, and the obtained mixture is heated and held under a reducing atmosphere at 1000 to 1400 ° C. for 15 hours or less.   The method for producing a phosphorescent phosphor according to claim 8, wherein the heating and holding condition is 1 to 5 hours.   Furthermore, the manufacturing method of the luminous phosphor of Claim 8 or 9 which mixes Nd raw material compound so that content of Nd is 1-10 mol% with respect to luminous phosphor whole quantity.   The phosphorescent phosphor according to any one of claims 8 to 10, wherein the Ag raw material compound is mixed so that the Ag content is 0.1 to 10 mol% with respect to the total amount of the phosphorescent phosphor. Manufacturing method.