JP3257947B2 - Phosphorescent phosphor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention can be used as a display or a light source in dark places such as indoors and outdoors and underwater, and has excellent weather resistance, long afterglow, ultraviolet light and / or ultraviolet light.
The present invention also relates to europium-mainly activated silicate phosphorescent phosphors that emit blue to blue-green light when excited by visible light.

[0002]

2. Description of the Related Art A phosphorescent phosphor is a phosphor that emits light by applying some kind of excitation to the phosphor and continues to emit light even after the excitation is stopped. By the way, with the diversification of display and the sophistication of functions, the phosphorescent phosphor is required to be multicolored, have a long afterglow, and improve weather resistance of the phosphorescent phosphor. Conventional phosphorescent phosphors are limited in the types of light emission and afterglow colors, have poor weather resistance, and have short afterglow times.

[0003] Incidentally, a blue light emitting phosphorescent phosphor is (Ca, Sr) S: Bi phosphor, a yellow green light emitting phosphorescent phosphor is ZnS: Cu phosphor, and a red light emitting phosphorescent phosphor is. Is known as a (Zn, Cd) S: Cu phosphor.

However, the (Ca, Sr) S: Bi phosphor is hardly used at present because of its extremely poor chemical stability and insufficient luminance and afterglow characteristics. Further, the (Zn, Cd) S: Cu phosphor is hardly used at present because the toxic substance Cd occupies about half of the base material and the luminance and the afterglow characteristics cannot be satisfied. ZnS: Cu is also decomposed by ultraviolet rays in the presence of moisture, is easily blackened, and has an unsatisfactory afterglow property.
It is inexpensive and is often used indoors such as clock faces and evacuation guidance signs.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks, has a long afterglow characteristic, emits blue to blue-green light, and is chemically stable and has excellent weather resistance. It is intended to provide a phosphor.

[0006]

That is, the present invention provides a blue to blue-green luminous phosphor having the following constitution.
(1) In the Eu activated silicate phosphorescent phosphor, the composition formula m
^{_{(Sr 1-a M 1 a}} ) O · n (Mg 1-b M 2 b) O · 2
_{(Si 1-c Ge c)} O 2: Eu x Ln is represented by _y, one or more elements wherein M ¹ is selected from Ca and Ba, M
² is at least one element selected from Be, Zn and Cd, and co-activator Ln is Sc, Y, La, Ce, Pr, N
d, Sm, Gd, Tb, Dy, Ho, Er, Tm, Y
represents one or more elements selected from b, Lu, In, Bi, and Sn , wherein a, b, c, m, n, x, and y are in the following ranges, and the phosphor is F, One or more halogen elements selected from Cl, Br and I
A luminous phosphor characterized in that it is contained in the range of 0 ^-5 to 1 × 10 ^-1 g · atm / mole of the base material. 0 ≦ a ≦ 0.80 ≦ b ≦ 0.20 ≦ c ≦ 0.2 2.5 <m ≦ 3.5 0.5 0.5 ≦ n ≦ 1.5 1 × 10 ⁻⁵ ≦ x ≦ 1 × 10 ^-1 1 × 10 ^-5 ≦ y ≦ 1 × 10 ^-1

(2) When the coactivator Ln is Dy, Nd, T
The phosphorescent phosphor according to the above (1), which is one or more elements selected from m, Sn, In and Bi.

(3) The method according to the above (1) or (2), wherein, upon excitation by ultraviolet light and / or visible light in the range of 140 to 450 nm and heating and heating, the compound emits thermoluminescence at least at room temperature or higher. Phosphorescent phosphor

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present inventors have proposed (Sr, M ¹ ) O
-(Mg, M ² ) O- (Si, Ge) O ₂ -based phosphor matrix (M ¹ = Ca, Sr, Ba, M ² = Be, Zn, C
(d), and found that a phosphor matrix suitable for long afterglow was present in the composition region of the region shown by oblique lines in FIG. That is, the composition formula m (Sr, M ¹ )
On · (Mg, M ² ) O · 2 (Si, Ge) O ₂ , where m and n are 2.5 <m ≦ 3.5 and 0.5 ≦ n ≦
A range of 1.5 is suitable.

In the present invention, the phosphor matrix is activated with Eu and Ln (Sc, Y, La,
Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, E
at least one element selected from the group consisting of r, Tm, Yb, Lu, In, Bi, and Sn ), and a halogen element (at least one element selected from the group consisting of F, Cl, Br, and I). By containing it, the luminescence center (Eu) and the contained elements were successfully optimized, and a phosphorescent phosphor that emits blue to green light, which has extremely long afterglow characteristics, is chemically stable, and has excellent weather resistance is obtained. Succeeded. The above co-activator L
Among n, Dy, Nd, Tm, Sn, In and Bi are particularly excellent.

In the composition formula of the present invention, the substitution amount of Sr a
(Mol) is preferably in the range of 0 ≦ a ≦ 0.8, and more preferably in the range of 0 ≦ a ≦ 0.4. When the substitution exceeds 0.8, the effect of improving the afterglow characteristics is reduced. Further, the substitution amount b (mol) of Mg is suitably in the range of 0 ≦ b ≦ 0.2, preferably 0 ≦ b ≦ 0.1, and when the substitution exceeds 0.2, the effect of improving the afterglow characteristics is reduced. Less. The amount c (mol) of substituting Si for Ge is preferably in the range of 0 ≦ c ≦ 0.2, and more preferably in the range of 0 ≦ c ≦ 0.1. Less, and the luminance also decreases.

Further, m (S
r, M ¹ ) O, n (Mg, M ² ) O and 2 (Si, G
e) The values of m and n for determining the composition ratio of O ₂ are 2.5 <m
≦ 3.5 and 0.5 ≦ n ≦ 1.5, preferably 2.7 ≦
The range of m ≦ 3.3 and the range of 0.7 ≦ n ≦ 1.3 are suitable. If the range is out of this range, a compound other than the intended one is formed or the raw material oxide remains, so that the brightness is reduced.

The amount of Eu activator x (g · atm)
Is 1 × 10 ⁻⁵ ≦ x ≦ 1 × 10 ⁻¹ , preferably 1 × 10 ^−5
-4 ≦ x ≦ 5 × 10 range ^-2 are suitable, 1 × 10 emitting center is less than ^-5 - is reduced, not the brightness of the object is obtained. When the concentration exceeds 1 × 10 ⁻¹ , concentration quenching occurs,
The luminance decreases and the afterglow characteristic also decreases.

The amount y (g · at) of the coactivator element Ln
m) is 1 × 10 ⁻⁵ ≦ y ≦ 1 × 10 ⁻¹ , preferably 1 × 10 ⁻⁵ ≦ y ≦ 1 × 10 ⁻¹
The range of 10 ⁻⁴ ≦ y ≦ 5 × 10 ⁻² is suitable, and 1 × 10
^If it is less than ^-5 , there is no effect on the afterglow characteristic, and if it exceeds 1 × 10 ^-1 , light is emitted by the co-activator element, so that light emission in the blue to blue-green region cannot be obtained.

The halogen element added to the phosphor of the present invention acts as a flux as part of the crystal growth and the diffusion of the luminescence center and the co-activator element Ln, thereby improving the luminance and afterglow characteristics. The addition amount z (g · atm) of the halogen element is 1 × 10 ⁻⁵ ≦ z ≦ 1 × 10
⁻¹ , preferably 1 × 10 ⁻⁴ ≦ z ≦ 1 × 10 ⁻² is suitable. If it exceeds 1 × 10 ⁻¹ , the phosphor is sintered and it is difficult to treat the powder. If it is less than 1 × 10 ^-5 , problems such as a decrease in instantaneous emission luminance and afterglow occur.

Further, the phosphorescent phosphor of the present invention comprises 140
When the phosphor is heated and heated after excitation by ultraviolet light and / or visible light in the range of 450 nm to 450 nm, it emits heat at room temperature or higher.

The phosphorescent phosphor of the present invention is synthesized as follows. The phosphor material is composed of a host element Sr, M ¹ (M ¹
= Ca, Ba), Mg, M ² (M ² = Be, Zn, C
d) Si, Ge, the activator Eu and the coactivator Ln are each used in the form of an oxide or a salt such as a carbonate, a nitrate, or a chloride which can be easily turned into an oxide by firing. The halogen element is used in the form of an ammonium salt, an alkali metal salt or a halogen compound of the above constituent elements (base constituent element, activator element Eu, and coactivator element Ln). Then, the sample is collected so as to be within the composition range of the above composition formula, and is sufficiently mixed by a wet process or a dry process. The rare earth raw materials may be mixed by coprecipitation.

This mixture is filled in a heat-resistant container such as an alumina crucible and fired at least once at 800 to 1400 ° C. for 1 to 12 hours in a reducing atmosphere of a hydrogen-containing neutral gas or a carbon reducing atmosphere. When performing multiple firings, the final firing step is always performed in a reducing atmosphere. The calcined product is pulverized and subjected to weak mineral pickling, washing with water, drying, sieving and the like to obtain the phosphorescent phosphor of the present invention.

[0019] Figure 2, Example 1 phosphorescent phosphor synthesized in _{Sr 2.97 MgSi 2 O 8: Eu} 0. 03 Dy 0.025 Cl
FIG. 3 is an X-ray diffraction diagram confirming a crystal structure of _0.025 . Substantially the same results were obtained even when a part of Sr, Mg, and Si in this phosphor composition was replaced with another element within the scope described in the claims.

FIG. 3 shows the phosphorescent phosphor of Example 1 (curve a) and the phosphorescent phosphor Sr _2.07 Ca synthesized in Example 2.
_0.9 MgSi ₂ O ₈ : Eu _0.03 Dy _0.025 Cl
_0.025 (curve b), the phosphorescent phosphor Sr _2.375 Ba _0.6 MgSi ₂ O ₈ : Eu _0.025 Dy synthesized in Example 3.
_It shows the emission spectrum when excited by 365 nm ultraviolet rays with respect to _0.03 Br _0.015 (curve c), and the emission peak wavelengths are respectively 460 nm, 471 nm and 450 nm.
nm. Substantially the same results were obtained when a part of these phosphor compositions were replaced with other elements within the scope described in the claims.

FIG. 4 shows the measurement of the region of the excitation spectrum using the phosphorescent phosphor of Example 1. The measurement of the region of the excitation spectrum is obtained by fixing the spectral wavelength on the output side of the spectrophotometer to 460 nm and plotting the intensity of 460 nm (output light) when the excitation wavelength of the light applied to the sample is changed. The vertical axis indicates the relative emission intensity at 460 nm, and the horizontal axis indicates the wavelength of the excitation light to be scanned. Substantially the same results were obtained even when a part of the phosphor composition was replaced with another element within the scope described in the claims.

FIG. 5 shows the phosphorescent phosphor of the first embodiment (emission spectrum peak wavelength: 460 nm), the phosphorescent phosphor of the second embodiment (emission spectrum peak wavelength: 471 nm), and the phosphorescent phosphor of the third embodiment (light emission spectrum). 450n peak wavelength
m), the phosphorescent phosphor of Comparative Example 1 (Sr _2.97 MgSi ₂ O)
₈ : Eu _0.03 , emission spectrum peak wavelength 460 nm)
The phosphorescent phosphor (ZnS: Cu, emission spectrum peak wavelength: 516 nm) of Comparative Example 2 was irradiated with a daylight fluorescent lamp at 300 lux for 30 minutes, and the afterglow characteristic was measured 2 minutes after stopping the irradiation. . As described above, as described above, the sample was irradiated with a 30 W daylight fluorescent lamp, and the afterglow of the phosphor after the lamp was turned off was measured for the luminance of the afterglow using a luminance meter with a visibility filter.

As is apparent from FIG. 5, Example 1 which is a phosphorescent phosphor having an emission spectrum peak wavelength of 460 nm.
It can be seen that has extremely remarkable afterglow characteristics with respect to Comparative Example 1. The phosphorescent phosphors of Examples 2 and 3 also emit different colors, but ZnS of Comparative Example 2 corresponding to a commercial product:
It can be seen that the device has excellent afterglow characteristics even when compared with the Cu yellow-green light emitting phosphor.

FIG. 6 shows that the phosphorescent phosphors of Examples 1 to 3 were irradiated with a 300-lux daylight fluorescent lamp for 15 seconds and the thermal emission characteristics (glow curve) one minute after the irradiation was stopped were TLD manufactured by Kasei Optonics. It is the graph which measured using the leader (KYOKKO TLD-1300 improvement type) at the temperature rising rate of about 8-10 degreeC / second, and showed the result. As is clear from the curves a to c in FIG. 6, when the phosphorescent phosphors of Examples 1 to 3 are heated at the above-mentioned heating rate in a temperature range of room temperature or higher, the relative thermoluminescent intensity increases. You can see that.

As described above, the phosphorescent phosphor of the present invention exhibits extremely high luminance and long persistence, is excellent in weather resistance, and is chemically stable. Can be used not only indoors but also for a wide range of uses such as outdoors. For example, it can be applied to the surface of various articles, mixed with plastics, rubber, vinyl chloride, synthetic resin, glass, or the like, and formed as a molded product or a fluorescent film to provide various signs for traffic safety (for example, a traffic armband). , Traffic gloves, car reflectors, reflective flags, traffic lights, road signs, emergency ropes, footwear, safety umbrellas, blind sticks, stickers, school bags, rain covers, safety covers, etc.), visual indicators (eg, telephone) Dial covers, switches, non-slip for stairs, guide plates for fire, tires, mannequins, fire extinguishers, keys, doors, fluorescent lamps, display tapes, etc.), ornaments (eg, artificial flowers, accessories, interior plates, etc.) , Various leisure goods (fishing floats, toys, golf balls, tow ropes, kites, artificial trees, jigsaw puzzles, etc.), clocks (eg, dials, hands, eyes Rinado),
Office supplies and OA equipment (eg, writing instruments, underlays, rulers, marker pens, stickers, liquid crystal backlights, solar cells, desktop calculators, printers, inks, etc.), educational supplies and equipment (eg, constellations, planet models, It can be widely used for transparent paintings, keyboard instruments, maps, etc., and building materials (for example, concrete, guardrails, construction scales, scaffolding for manholes, tiles, decorative boards, surveying devices, tape measures, etc.).

[0026]

【Example】

EXAMPLE 1 _{SrCO 3 43.8 g MgO 4.0 g SiO} 2 12.0 g Eu 2 O 3 0.53g Dy 2 O 3 0.47g NH 4 Cl 2.3 g The above raw materials thoroughly mixed And packed in an alumina crucible using an electric furnace in a reducing atmosphere of 98% nitrogen and 2% hydrogen.
Baking was performed at 50 ° C. for 2 hours. The obtained fired product was pulverized, washed with water, dried and sieved to obtain a phosphorescent phosphor.

This phosphor is composed of Sr _2.97 MgSi ₂ O ₈ :
It has a composition of Eu _0.03 Dy _0.025 Cl _0.025 , and X in FIG.
FIG. 3 shows a line diffraction diagram, and the emission spectrum when excited by 365 nm ultraviolet rays is as shown in FIG. 3 (curve a), and the emission peak wavelength was 460 nm, which had blue light emission and luminous properties. Further, the excitation spectrum was spread to the visible region as shown in FIG. The afterglow characteristic showed a long afterglow as shown in FIG. 5 (curve a). The glow curve was as shown in FIG. Further, the emission peak wavelength and the afterglow characteristic of the phosphor (the emission intensity after 2 minutes and 60 minutes after stopping the irradiation, ZnS:
Table 1 and Table 2 show the peak intensity values of the glow curve and the emission intensity ratio when the Cu-yellow green light-emitting phosphorescent phosphor is set to 100%.
It described in.

Example 2 SrCO ₃ 30.6 g CaCO ₃ 9.1 g MgO 4.0 g SiO ₂ 12.0 g Eu ₂ O ₃ 0.52 g Dy ₂ O ₃ 0.47 g NH ₄ Cl 6 g The above raw materials were sufficiently mixed, packed in an alumina crucible, and fired at 1200 ° C. for 2 hours in a carbon reducing atmosphere using an electric furnace. The obtained fired product was pulverized, washed with water, dried and sieved to obtain a phosphorescent phosphor.

This phosphor is made of Sr _2.07 Ca _0.9 MgSi
₂ O _8: has the composition _{Eu 0.03 Dy 0.025 Cl 0. 02,} 3
The emission spectrum when excited by 65 nm ultraviolet light is shown in FIG.
As shown in (curve b), the peak had a blue-green luminous luminous property of 471 nm. The afterglow characteristic showed a long afterglow as shown in FIG. 5 (curve b). Also,
The glow curve was as shown in FIG. 6 (curve b). Further, the emission peak wavelength of the phosphor, the afterglow characteristics (the emission intensity after 2 minutes and 60 minutes after stopping the irradiation, the emission intensity ratio of 100% ZnS: Cu yellow-green light-emitting and phosphorescent material) and the glow Bee
Tables 1 and 2 show the lock temperature values.

Example 3 SrCO ₃ 35.1 g BaCO ₃ 11.8 g MgO 4.0 g SiO ₂ 12.0 g Eu ₂ O ₃ 0.44 g Dy ₂ O ₃ 0.56 g NH ₄ Br 6 g The above raw materials were thoroughly mixed, packed in an alumina crucible and used in an electric furnace in an atmosphere of 97% nitrogen, 3% hydrogen, and 3% reducing.
Bake at 0 ° C. for 3 minutes. The obtained fired product was pulverized, washed with water, dried and sieved to obtain a phosphorescent phosphor.

This phosphor is made of Sr_2.375Ba_0.6MgS
i_TwoO₈: Eu_0.025Dy_0.03Br _0.015With the composition
And the emission spectrum when excited by 365 nm ultraviolet light
Is as shown in FIG. 3 (curve c), and its peak is 450 nm
Having a blue light emission luminous property. In addition, afterglow
The property exhibited long afterglow as shown in FIG. 5 (curve c). Ma
The glow curve was as shown in FIG. 6 (curve c).
Further, the emission peak value and the afterglow characteristic of the phosphor (irradiation stop 2
The emission intensity after 60 minutes and 60 minutes was measured by ZnS: Cu yellow-green phosphorescence.
Intensity ratio with 100% luminescent phosphor) and gloker
Table 1 shows the peak temperature values of the tubes.

[Examples 4 to 18] In the same manner as in Example 1, the phosphorescent phosphors of Examples 4 to 18 having the compositions shown in Tables 1 and 2 were obtained. The emission peak values and the afterglow characteristics of the phosphors of Examples 4 to 18 (the emission intensity ratio when the ZnS: Cu yellow-green light-emitting and phosphorescent phosphor is 100% after 2 minutes and 60 minutes after stopping irradiation) ) And glow peak temperature values are shown in Tables 1 and 2.

Comparative Examples 1 and ₂ Sr _2.97 MgSi ₂ O ₈ : Eu _0.03 luminous fluorescence of Comparative Example 1 in the same manner as in Example 1 except that the blending of the coactivator element Ln and the halogen element was omitted. I got a body. In Comparative Example 2, a ZnS: Cu yellow-green luminescent phosphor (LC-G1) manufactured by Kasei Optonics was used as a reference sample. The emission peak wavelengths and afterglow characteristics of these phosphors (the emission intensities at 2 minutes and 60 minutes after stopping the irradiation were ZnS:
Tables 1 and 2 show the peak intensity of the glow curve and the emission intensity ratio when the Cu-yellow green light-emitting phosphorescent phosphor was set to 100%.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

According to the present invention, by adopting the above-mentioned structure, it is chemically stable, and exhibits high luminance and much longer afterglow as compared with a commercially available ZnS-based yellow-green luminescent phosphor. , For the first time to provide blue to blue-green phosphorescent phosphor,
This greatly contributes to multicolor display and multifunctional display.

[Brief description of the drawings]

FIG. 1 shows a matrix (Sr, M) of a phosphorescent phosphor of the present invention.
^{1) O- (Mg, M 2} ) is O- (Si, Ge) graph showing a ternary phase diagram of the ₂ O-based oxide.

FIG. 2 is an X-ray diffraction diagram confirming the crystal structure of the phosphorescent phosphor synthesized in Example 1.

FIG. 3 is a graph showing an emission spectrum when the phosphorescent phosphor synthesized in Examples 1 to 3 is excited by 365 nm ultraviolet rays.

FIG. 4 is a graph showing an excitation spectrum at each emission spectrum peak of the phosphorescent phosphor of Example 1.

5 is a graph comparing the afterglow characteristics of the blue to blue-green luminous phosphors of Examples 1 to 3 and Comparative Example 1 and the yellow-green luminous phosphor of Comparative Example 2. FIG.

FIG. 6 is a graph showing thermoluminescence characteristics (glow curves) of the phosphorescent phosphors of Examples 1 to 3.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Norio Miura 1060 Narita, Odawara-shi, Kanagawa Prefecture Inside Kasei Optonics Co., Ltd. References JP-A-64-90289 (JP, A) JP-A-3-219228 (JP, A) JP-A-51-119690 (JP, A) JP-B-49-3834 (JP, B1) JP-B-48 −37715 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09K 11/08-11/89

Claims (3)

(57) [Claims] 1. An Eu-activated silicate phosphorescent phosphor,
Formula ^{_{m (Sr 1-a M 1}} a) O · n (Mg 1-b M 2 b)
_{O · 2 (Si 1-c} Ge c) O 2: represented by Eu _x Ln _y, wherein M ¹ is one or more elements selected from Ca and Ba, M ² is selected Be, and Zn and Cd One or more elements, co-activator Ln is Sc, Y, La, Ce, P
r, Nd, Sm, Gd, Tb, Dy, Ho, Er, T
represents one or more elements selected from m, Yb, Lu, In, Bi and Sn , wherein a, b, c, m, n, x and y are in the following ranges, and the phosphor is F, Cl,
One or more halogen elements selected from Br and I,
A phosphorescent phosphor, characterized in that the phosphor is contained in a range of 1 × 10 ^-5 to 1 × 10 ^-1 g · atm / mole of a host. 0 ≦ a ≦ 0.80 ≦ b ≦ 0.20 ≦ c ≦ 0.2 2.5 <m ≦ 3.5 0.5 0.5 ≦ n ≦ 1.5 1 × 10 ⁻⁵ ≦ x ≦ 1 × 10 ^-1 1 × 10 ^-5 ≦ y ≦ 1 × 10 ^-1 2. The method according to claim 1, wherein the coactivator Ln is Dy, Nd, Tm,
2. The phosphorescent phosphor according to claim 1, wherein the phosphor is at least one element selected from Sn, In, and Bi. When wherein ultraviolet and / or Atsushi Nobori after excitation by visible light in the range of 140～450Nm, phosphorescent according to claim 1 or 2, wherein the exhibiting thermoluminescence at least above room temperature body.