JPS5896675A - Fluorescent material - Google Patents

Abstract

PURPOSE:To obtain a blue light-emitting fluorescent material having improved light-emitting efficiency and ordinary color characteristics, by adding specific amounts of aluminum, gallium, indium and thallium to an Eu(II)-doped haloborophosphate fluorescent material represented by a specific formula. CONSTITUTION:The objective fluorescent material is prepared by introducing specific amounts of Al, Ga, In and/or Tl into the matrix structure of an Eu(II)- doped haloborophosphate fluorescent material of formula (M and M' are Sr, Ca or Ba; M'' is Al, Ga, In or Tl; X is Cl, F or Br; 2.7<=x<=3.3; 0.50<=y<=1.5; 0.10<=a<=0.50; 0.01<=b<=0.50; 0<c<=0.10; 0.001<=p<=0.20). USE:A blue light-emitting component for a fluorescent lamp having excellent color rendering property.

Description

[Detailed description of the invention] Technical field of invention The present invention relates to a blue-emitting phosphor with improved luminous efficiency.

Technical backcharging of the invention and its problems Conventionally, calcium tungstate phosphor CaWO4, magnesium tungstate phosphor MgWO4゜antimony-activated calcium halosinate phosphor has been used as a blue-emitting phosphor excited by ultraviolet a or cathode rays. Light body Ca1・(PO4)
6(FICj)*:sb etc. are known. These phosphors have a wide emission range and do not emit highly pure w-color light, so their use may be limited when mixed with phosphors that emit light of other colors. arise.

In recent years, from the viewpoint of improving the quality of illumination, fluorescent lamps with narrow band emission peaks in the blue, green, and red regions and high efficiency and color rendering properties have been commercially available. As the blue-emitting phosphor for this fluorescent lamp, a divalent europium-activated phosphor having a relatively high color purity is used. A typical example of these phosphors is the divalent europium-activated halophosphate phosphor 3Sr3 (described in Japanese Patent Publication No. 46-40604).
Pot) 2・MCJ2: nu” (%, M is Sr,
Any one of Ca and Ba or a mixture thereof)
There is.

In the case of a three-color mixed fluorescent lamp, the emission intensity of the blue-emitting phosphor greatly influences the intensity of the total luminous flux of the fluorescent lamp. Although this phosphor has good color purity and fairly high luminous efficiency, there has been a desire for a blue-emitting phosphor with even higher luminous efficiency and good color purity.

In order to achieve this purpose, the present inventor first developed an alkaline earth metal halophosphate phosphor activated with divalent europium, the chemical formula of which is the general formula "(Mt- p
@Bu p・O) ・yP205 ・aM'X2 ・b
13203 (i, M and M' are 8r, Ca
and 191X (at least one of J, F, and Br, 2.7≦X≦3.
3.0.50≦y≦1.5゜0, 10≦-≦0.50.
0.01≦b≦0.50. O, OO1≦p≦0. In order to satisfy the vision, a bright blue-emitting phosphor with a brownish purity and a higher luminous efficiency than the conventional phosphate blue-emitting phosphor was proposed in Japanese Patent Application No. 178908/1983.

This phosphor is suitable for ultraviolet light, especially wavelengths of 254 am and 365 am.
It is effectively excited by both types of am and UV rays and has high luminous efficiency, and like the aforementioned halophosphate, the peak wavelength of luminescence changes from about 440 to 500 nm depending on the combination and blending ratio of alkaline earth metals. But on average 452
Since it emits light in a narrow band in the nanometer range, it provides very good characteristics when used in a mixed type fluorescent lamp.

However, since then, customers' demands regarding luminous efficiency have become increasingly strict, and a blue-emitting phosphor having a luminous efficiency superior to that of the phosphor of Japanese Patent Application No. 178908/1980 has been desired.

OBJECTS OF THE INVENTION It is an object of the invention to provide a blue-emitting phosphor which has superior luminous efficiency to the phosphor proposed in the above-mentioned Japanese Patent Application No. 11555-178908 and which has no inferior color characteristics.

Summary of the Invention The divalent europium-activated halo proposed in the above-mentioned Japanese Patent Application No. 178908/1980 contains aluminum M, gallium Ga, indium In, and thallium T! in the matrix structure of a phosphate phosphor. The luminous efficiency is improved by introducing a predetermined amount of at least one of the elements 1111I.

The phosphor of the present invention has a chemical composition of the general formula "0jl-p・i".
up・0) ・yP205 ・sM'Xz ・bB20
B-cM'203 (However, M and M' are 8r, C
9Ml of at least one of a and Ba is AJ,
at least one of Gm, In and TI;
XFi (at least one of ?J, ? and Br, 27≦X≦3.3.0.5≦y≦1.50゜0, 10
≦1≦0.50.0.01≦b≦0.50.0 (c≦0
．． 10.

0001≦p≦0.20).

This phosphor is effective against ultraviolet light, especially at wavelengths of 254nm and 365nm.
The divalent europium-activated halo of the above-mentioned application No. 55-178908 is higher than the phosphate phosphor, and its emission color is almost the same. .

Next, in the above general formula, 1e'/e am b,
The reason why the values of e and p are set within the above ranges will be explained.

X and y are 2.7≦X≦3.3 and 0.50≦y≦
When it is outside the range of 150, the luminance of the phosphor decreases.
It becomes unbearable for actual use.

As the phosphor of the present invention, 3 (8r0.98・Eu0.02・
O)・0.882P205・acac12・0.0
F8 B2O3 0.04AJ203 1 is changed from Hinoki to Matsu, and this luminance is compared to the conventional 38R3 (PO4).
2.CaCl2: A relative value was taken with reference to that of the 0.02Eu phosphor, and the correlation between this relative brightness and 1 was determined and shown in FIG. From this figure, the range of 1 is 0.10≦1≦
It can be seen that 0.050 mol is preferable, and particularly 0.25≦a≦0.42 mol is even more preferable.

Next, 3 (8r0.98・guo
, 02・0) ・0.882P205 @0.33 C
a(Jz ・bB3o3 e O,04AJzOs b
38r3(PO4)2・CaCl2:0.02E as shown in Figure 1.
A relative value was taken with reference to that of the u phosphor, and the correlation between this relative brightness and b was determined and shown in FIG. From this figure b
It can be seen that the range of is preferably 0.01≦b≦0.50 mol, and particularly preferably 0.05≦b≦0.35 mol.

Therefore, as the phosphor of the present invention, 3 (8r O, 98.
Eu O,02・0) ・0.882P206 ・0
．． 33CaCJ2・o, o'ys B2O3・eM'2
Various variations of C in 03 are called various M', that is, M.

Prototypes were made for each of Ga, In, and TI, and the luminance was taken as a relative value with respect to c=0, and the correlation between the relative luminance and C was determined for each M' and is shown in FIG. In the figure, curve (A) (-〇-) is 49 curve (B) (-△
-) is Ga, curve cap) (-low) is In, curve (D) (
-x-) indicate the respective characteristic curves of 1. From this figure, the range of C is 0 (c≦0.10 mol is preferable, especially 0
．． It can be seen that 02≦C≦0.07 mol is more preferable.

Next, 3(8r1-p-Eup.
0)・0.882P201>・0.33 CaQfz
・0.078JO3・0.04Aj203 with various p values, and the luminance of the conventional 38r3 (PO4)2・CaCJ2:0 as in Figures 1 and 2.
．． A relative value was taken using that of the 02Ru phosphor as a reference, and the correlation between this relative brightness and p was determined and shown in FIG. From this figure, it can be seen that the range of p is preferably 0.001≦p≦020 mol, and more preferably 0.003≦p≦015 mol.

Next, 3 (8r0.98・Buo
,02・0) ・0.8g2P205 ・0.33
CaC1z ・0.078BzOs ・0.04 Ah
Os is taken, and as a comparative example, Japanese Patent Application No. 55-17890
3 belonging to No. 8 (8r0.98・RuO,020)・0
．． 92P205・0.33CaCJ2・0.08B! 0
Figure 5 shows a comparison of the luminescence values of the two. In the figure, if the emission peak value of each phosphor is set to 100, the phosphor of the present invention (solid line) and the comparative phosphor (broken line) almost match and are difficult to distinguish.
In the figure, the lines are shown close together. It can be seen from the figure that the phosphor of the present invention has almost the same color characteristics as the prior application.

To obtain the phosphors of the invention, for example, 8 r HP
04 IeaHPO4, BaHPO4, 8rCO3,
CaCO3,'BaCO3,Eu2O3゜gucO3,
H3BO3,B2O3,CmC/I2.8rC12,A
j203. Various raw material compounds such as Ga2O3°In2O3+ T7zOs are used.

Moreover, instead of these compounds, compounds that easily form oxides containing these component elements at temperatures may be used. First, these raw material compounds are mixed in predetermined amounts and heated to a temperature of about 900 to 1200°C, preferably F'110, in a reducing atmosphere, for example, a mixed atmosphere of 95-nitrogen and 5-hydrogen.
Bake at a temperature of 00-1150°C for 1-4 hours. This is then pulverized, washed with distilled water to remove unreacted substances, and dried. To make the reaction more complete, 9
It may be refired at a temperature of 00 to 1200°C, in particular 1000 to 1150°C.

First example of the invention 8rHPO41,764 mol, 5rCO31,176
mole, Eu2030.03 mok, H3BO30
, 156-f-le, A72030.04-v-le,
For each raw material mixture of 20.33 moles of CaCJ, additional C
After adding and mixing 20.87 mol of aCJ, the mixture was placed in a quartz container and fired at a temperature of 1100'C for 2 hours in a reducing atmosphere consisting of 95'1611 element and 5-hydrogen. At this time, the excessively added CaCl12Fi acts as a fluxing agent during firing. After cooling the baked product thus obtained, it is immersed in distilled water, pulverized, and further washed with warm water at 70 to 80°C to remove unreacted substances. Then, it is dried, sieved and re-fired at a temperature of 1100° C. for 2 hours. After cooling, it is crushed and sieved to give 3 (8r0.9B・'Bu0.02・O
) ・0.882P OS+10.33C1C1!・0
．． 078B! 03/0.04 A phosphor with a composition of AI203 was obtained.

The peak wavelength of the emission of this 41 element is 452 nm, and its wavelength is similar to that shown in Figure 5 above.
．． 020) ・0.92P20s0.33CaCJ2・
The luminance was almost the same as 0.088203, and the luminance was improved by about 1 compared to the conventional one.

Second embodiment of the invention 8rHPO41,76 mol, 8rCO31,176 mol, Eu2O30,03 mol, H3BO30,156
Mo, Ga 2030.04 mol* CaC120,
For every 33 moles of each raw material mixture, an additional 0.8 CaC1z
After adding and mixing 7 moles, the mixture was placed in a quartz container and fired at a temperature of 1100° C. for 2 hours in a reducing atmosphere consisting of 95 nitrogen and 5 moles. This calcined product is pulverized and washed to remove unreacted materials in the same manner as in the first example.

Then, it is dried and, after sieving, is recalcined at a temperature of 1100° C. for 2 hours in a reducing atmosphere. After cooling, crush and sieve 3
(8r0.98 ・EuO,02・O) ・0.882
P205 0.33CaCj2 ・0.078B20
A phosphor having a composition of 3.0.04Ga203 was obtained.

The luminescence of this phosphor is similar to that shown in FIG.
8r0.98・EuO,02・O)・0.92P205
・Almost the same as α33CaC12・0.088203, and the luminance was improved by about 5% compared to the conventional one.

Third embodiment of the invention 8rHPO41,76 mole, 8rCO30,906 mole, Eu2O30,015 mole, H3BO30,15 mole
6 mol #lBO30.04 mol, CaC1z1-
After mixing 2 moles of each raw material, put it in a quartz container and heat it at 95-
1100℃ in a reducing atmosphere consisting of nitrogen and 5-hydrogen
Bake at a temperature of 2 hours. This calcined product is pulverized and washed to remove unreacted materials in the same manner as in the first example. Then, after drying and sieving, it is recalcined at a temperature of 1100° C. for 2 hours in a reducing atmosphere. After cooling, it was crushed and sieved to 3 (8 rO
,89・CaO,1(lBuO,Q,1 ・0) ・0
．． 882P20B @0.330a (7200,078
A phosphor having a composition of B203.0.04 In2O3 was obtained.

The luminescence of this phosphor is similar to that shown in Figure 5, and the conventional halo containing no Ifl is a phosphate phosphor 3 (8r0.89 ・CaO, 10 ・luO, 0
) ・0.92P205 ・0.33 CaCl2 ・
0.08B203, and the emission brightness was improved by about 40 compared to the conventional one. Fourth Example of the Invention
58 mol, 8rCj2 ・6H200, 33 mol*T
Add 8rC to the raw material mixture containing 0.04 mol of zOs.
-6H3OO, 57 mol, was added and mixed, and the mixture was calcined at a temperature of 1100° C. for 2 hours in a reducing atmosphere. In this case, over 1
! 8rC12・6H with IIK! 0 is 1st to 3rd
It acts as a fluxing agent similar to CaCl2 in the example. This calcined product is pulverized and washed to remove unreacted materials in the same manner as in the above embodiment. Then, dry and sieve 3.
(Sr0.99・Bu O,01・0) @0.90
2P205 ・0.338rCJ2 ・0.058 B
A phosphor having a composition of 2O3.0.04TjzO3 was obtained.

This emission spectrum is similar to that shown in FIG.
A conventional halo that does not contain phosphate phosphor 3 (8r0
．． 99・EuO, 01・O)・0.94PzOs・0.
338rCJz ·0.068203, its peak wavelength was 446 nm, and the luminance was improved by about 3.5 inches compared to the conventional one.

Modifications of the Invention Each of the above-mentioned embodiments describes a case in which one of each of AJ, Ga, In, and Tj is contained in the halo-ninephosphate salt, but two or more of the above elements may be contained. ,
In this case, the number of moles of this element may be within the range of the above-mentioned limitations. In addition, by changing the combination and blending ratio of alkaline earth metals, the peak wavelength can be adjusted to approximately 440.
~500 nm, so it can be used as the blue component of various mixed fluorescent lamps.

Invention and Effect The phosphor of the present invention has a general formula x (Ml-poRup 0)
-yP205-bB203 ・cM'203 (However, M and M' are 8r.

1 ml of at least one of C1 and Ba is M.

At least one of Ga, In and Tj, X
is C4,? and B [at least one type 2.7
≦X≦3.3.0.50≦y≦1.5, 0.10≦1≦
0.50, 0.01≦b≦0.50.0<c≦0.10
．． 0.001≦p≦0.2), has high efficiency and excellent color purity, and is effective as a blue component of a high color rendering fluorescent lamp.

[Brief explanation of drawings]

Figure 1 is a graph showing the appropriate range of a in the correlation between 1 and relative brightness in the general formula of the phosphor of the present invention, and Figure 2 is a graph showing the appropriate range of b in the correlation between b and relative brightness. , FIG. 3 is a graph showing the appropriate range of C for each Ml in the correlation between M', C, and relative brightness, and FIG. 4 is a graph showing the appropriate range of p in the correlation between p and relative brightness. FIG. 5 is a graph showing that the luminescence intensity of the phosphor of the present invention is not inferior to that of the conventional phosphor. Agent Patent Attorney Inoue - Male No. 1 Figure □ m (Mo, Ru) Figure 2, 6 (Mo, Ru) Figure 3 C (4 = Ru) Figure 4 p (Morno

Claims (1)

[Claims] The general formula is "(Ml-p-Bup -0) ・yP20
5 ・aM'X2 ・bB203 ・cM'203 (
However, M and M' are 8r, at least one of Ca and Ba, M' is at least one of AI, Ga, In and Tjf, X is at least one of CJ, F and Br, 2 .7≦X≦33゜0
．． 50 ≦ff≦1.5.0.10 ≦a≦0.50.
0.01 ≦b≦0.50゜0 (c≦014), 0
．． 001≦p≦0.20).