JP2002003837A - Phosphor and fluorescent lamp obtained by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescent lamp having good color rendering properties and a high luminous flux without deterioration in luminous intensity. SOLUTION: In an aluminate phosphor activated with bivalent europium and bivalent manganese, a phosphor having a chemical composition represented by the general formula: (Ba1-x-yEuxMy)O.a(Mg1-pMnp)O.bAl2O3.cLn2O3.zSiO2 is employed. In the formula, M is at least one element selected from Sr and Ca; Ln is at least one element selected from Y and Gd; 0.05<=x<=0.2; 0<=y<=0.5; 0<z<=2.0; 0.5<=a4.0: 4<=b<=10; 0<c<=1.0; and 0<p<=0.2. As an example, (Ba0.8Sr0.1 Eu0.1)O.1.1(Mg0.95Mn0.05)O.6Al2O3.0.1Y2O3.0.5SiO2 (blue phosphor) can be cited. This phosphor is mixed with (La0.5Ce0.2Tb0.3)PO4 (green phosphor) and (Y0.98Eu0.02)2O3 (red phosphor) to give a fluorescent lamp.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phosphor activated with divalent europium and divalent manganese, and a fluorescent lamp using the same.

[0002]

2. Description of the Related Art Since the three-wavelength fluorescent lamp was put into practical use, it has been widely used in the field of indoor lighting as a fluorescent lamp with high efficiency and high color rendering, and its performance has been improved. The three-wavelength fluorescent lamp uses a phosphor film in which a mixture of three colors of blue, green, and red, which emit light in a narrow band, is applied to the inner surface of the tube. Has a great effect on the brightness (luminous flux) and color rendering of the lamp, and is known to be a particularly important phosphor among the above phosphors.

[0003] Such a blue phosphor has been conventionally described in, for example, Japanese Patent Publication No. 52-22836.
An aluminate phosphor activated with divalent europium or a halophosphate phosphor activated with divalent europium described in JP-B-46-40604 has been used.

[0004]

However, when the above-mentioned conventional blue phosphor is used in a three-wavelength fluorescent lamp, satisfactory characteristics can be obtained with respect to the luminous flux, but it is more than required by the market society in recent years. There is a problem that the luminous flux is reduced when providing good color rendering properties.

That is, in order to obtain a good color rendering property exceeding 84 in the average color rendering index, the spectral distribution of the emission of the blue phosphor is improved, and the emission color is represented by y represented by CIE chromaticity coordinates (x, y). You need to increase the value. In order to adjust the spectral distribution of light emission of such a blue phosphor, a method of changing the crystal field of divalent europium, which is a light-emitting ion of these phosphors, is generally used.
In the case of an aluminate phosphor activated with divalent europium, a part of the barium element substituted with divalent europium is replaced with strontium, calcium, or the like. However, in such a conventional method, it is possible to adjust the spectral distribution of the emission of the blue phosphor to a desired one, but there is a problem that the emission intensity decreases at the same time.

Japanese Patent Publication No. Hei 7-2947 discloses a method in which silicon oxide is dissolved in an aluminate phosphor activated with divalent europium in which a part of barium element is replaced by strontium, calcium or the like. To increase the emission intensity. However, Japanese Patent Publication No. 7-2947 does not contain divalent manganese as an activator, so that the effect of solid solution of silicon oxide is 2%.
It is unknown how it is expressed in the case of an aluminate phosphor activated with monovalent europium and divalent manganese. This is because the emission of divalent manganese in this phosphor is called sensitized luminescence caused by energy transition from divalent europium in the same phosphor crystal, and the solid solution of silicon oxide forms this energy. This is because it is unpredictable how the transition probability is affected.

Furthermore, Japanese Patent Publication No. 52-22836 discloses an aluminate phosphor activated with divalent europium and divalent manganese. A phosphor that simultaneously emits green light based on divalent manganese is shown. This phosphor can be used as a blue component of a three-wavelength fluorescent lamp having a good color rendering property in which the average color rendering index exceeds 84. However, in this case, although satisfactory color rendering properties can be obtained, there is a problem that the luminous flux is greatly reduced.
This is because, in the case of this phosphor, an increase in green emission based on divalent manganese is accompanied by a decrease in blue emission based on divalent europium.

An object of the present invention is to solve such a problem, and an object of the present invention is to provide a phosphor exhibiting good color rendering properties without a decrease in luminous flux and a fluorescent lamp using the same.

[0009]

In order to solve this problem, the present inventor studied a conventional aluminate phosphor activated with divalent europium and divalent manganese,
The alkaline earth metal aluminate compound may be at least one selected from yttrium oxide and gadolinium oxide.
By dissolving a rare earth oxide and silicon oxide in a solid state, a blue phosphor having high emission intensity is realized.

That is, the phosphor of the present invention is an aluminate phosphor activated with divalent europium and divalent manganese, and has a chemical composition represented by the following general formula.

(Ba _1-xy Eu _x M _y ) O · a (Mg _1-p Mn _p ) O · bAl ₂ O ₃ · cLn ₂ O ₃ · zSiO ₂ where M is at least one selected from Sr and Ca Ln represents at least one element selected from Y and Gd, wherein x, y, z, a, b, c and p are 0.05 ≦ x ≦ 0.2, 0 ≦ y ≦ 0.5, 0 <z
≦ 2.0, 0.5 ≦ a ≦ 4.0, 4 ≦ b ≦ 10, 0 <c
≦ 1.0, 0 <p ≦ 0.2.

Further, a fluorescent lamp of the present invention is characterized in that the above-mentioned phosphor of the present invention is formed on a tube inner surface.

[0013] This makes it possible to obtain higher light emission than the conventional one using an aluminate phosphor activated with divalent europium and divalent manganese, which does not contain yttrium oxide, gadolinium oxide, and silicon oxide. Intense phosphors and fluorescent lamps are obtained.

Further, the fluorescent lamp of the present invention comprises the above-mentioned phosphor of the present invention (first phosphor), trivalent cerium and trivalent cerium exhibiting a spectral distribution having a maximum emission wavelength in a wavelength range of 530 to 550 nm. Rare earth silicate phosphor activated with terbium, rare earth magnesium aluminate phosphor,
A second phosphor made of at least one selected from the group consisting of a rare earth phosphate phosphor, a rare earth silicate phosphor, and a magnesium borate phosphor, and 600 to 620 nm.
A mixture comprising a trivalent europium-activated rare earth oxide phosphor and a third phosphor which exhibits a spectral distribution having a maximum emission wavelength in the wavelength range described above. Features.

[0015] Thereby, the light flux is not reduced,
A fluorescent lamp having good color rendering properties is obtained.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of an aluminate phosphor activated by divalent europium and divalent manganese and a fluorescent lamp using the same according to the present invention will be described in detail.

(Embodiment 1) When a phosphor is used as a blue light-emitting component of a three-wavelength fluorescent lamp, in order to enhance the color rendering of the fluorescent lamp to an average color rendering index of 84 or more,
As a method of adjusting the spectral distribution of light emission of the aluminate phosphor activated with divalent europium and divalent manganese, a plurality of alkaline earth metals are used as shown in the general formula of the phosphor of the present invention. To increase the spectral distribution of luminescence due to divalent europium toward the longer wavelength side, and to increase the amount of divalent manganese ions to increase the luminescence of divalent manganese. However, these two methods
All reduce the main emission of this phosphor, and when used as a blue emission component of a three-wavelength fluorescent lamp,
Although the color rendering properties are improved, a decrease in the luminous flux cannot be avoided.

Therefore, an alkaline earth metal aluminate phosphor activated with divalent europium and divalent manganese having a spectral distribution of light emission suitable for a three-wavelength fluorescent lamp having an average color rendering index of 84 or more is provided. Attention was paid to studying to increase the emission intensity.

As a result, the conventional divalent europium and 2
The luminescence intensity is obtained by dissolving at least one rare earth oxide selected from yttrium oxide and gadolinium oxide and silicon oxide in an alkaline earth metal aluminate phosphor activated with divalent manganese. Was found to be able to be raised. By using this blue phosphor, it is possible to obtain a three-wavelength fluorescent lamp that achieves high color rendering without reducing the luminous flux.

[0020] In the phosphor of the present invention, the following general formula The chemical composition of the phosphor _{(Ba 1-xy Eu x M} y) O · a (Mg 1-p Mn p) O · bAl 2 O 3 · cLn 2 When represented by O ₃ · zSiO ₂ , M represents at least one element selected from Sr and Ca, and Ln represents at least one element selected from Y and Gd, wherein x, y, z, a , B,
The amounts of c and p are limited as shown below.

That is, x indicates the concentration of europium, which is an activator, and is limited within the range of 0.05 ≦ x ≦ 0.2. If x is less than 0.05, sufficient emission intensity cannot be obtained, and if x exceeds 0.2, the emission intensity decreases due to concentration quenching. y indicates the amount of addition of at least one element selected from Sr or Ca, and 0 ≦ y ≦
In the range of 0.5, characteristics equal to or higher than the characteristics at y = 0 can be obtained. z indicates the amount of silicon oxide added, and 0 <
Limited by z ≦ 2.0. Also, c indicates the amount of Ln added, and is limited to 0 <c ≦ 1.0. The emission intensity increases as z and c increase, but as shown in FIG. 1, when c exceeds z = 1.0 in the range of 0 <c ≦ 1.0, the emission intensity is lower than that at z = 0. turn into. In addition,
In FIG. 1, c is 0.1.

A represents M partially substituted by Mn.
Indicates the composition of gO, and is limited by 0.5 ≦ a ≦ 4.0. As described above, when utilizing the luminescence of divalent manganese in which a part of Mg is substituted, it is also known to substitute a part of Mg with Zn. In the phosphor of the present invention, the emission intensity was not significantly improved by the substitution of Zn, but may be added in a small amount. In addition, b indicates the composition of Al ₂ O ₃ and is limited to 4 ≦ b ≦ 10.

These a and b affect each other. It is better to reduce b if a is small, and it is possible to obtain high luminous intensity by increasing b if a is large. The range satisfying both is limited as described above. p indicates the concentration of manganese as the other activator, and is limited to 0 <p ≦ 0.2.

The emission of divalent manganese is 510 to 520 n
m shows the main light emission, and when added to the blue light-emitting component of a three-wavelength fluorescent lamp, it is known that it has the effect of improving the color rendering properties, but excessive addition significantly reduces the lamp luminous flux. Was revealed. Therefore, p is limited to 0.2 or less.

Embodiment 2 In Embodiment 2, an example of a fluorescent lamp of the present invention will be described.

FIG. 3 shows a partially cutaway sectional view of the fluorescent lamp of the second embodiment. The fluorescent lamp according to the second embodiment includes a glass bulb 11, electrodes 12 formed at both ends of the glass bulb 11, and a fluorescent film 13 formed on the inner surface of the glass bulb.
And mercury and an inert gas (not shown) sealed in the glass bulb 11. Although FIG. 3 shows only one end of the fluorescent lamp, the other end is the same, so that the illustration is omitted. The fluorescent film 13 is provided in the first embodiment.
At least.

Embodiment 3 In Embodiment 3, another example of the fluorescent lamp of the present invention will be described.

The structure of the fluorescent lamp of the third embodiment is the same as that of FIG. 3 described in the second embodiment. The fluorescent film 13 is made of the phosphor (first phosphor) described in the first embodiment and trivalent cerium and trivalent terbium exhibiting a spectral distribution having a maximum emission wavelength in a wavelength range of 530 to 550 nm. An activated rare earth silicate phosphor, a rare earth magnesium aluminate phosphor, a rare earth phosphate phosphor, a rare earth silicate phosphate and a magnesium borate phosphor selected from at least one selected from the group consisting of: At least a mixture comprising a phosphor of No. 2 and a third phosphor made of a trivalent europium-activated rare earth oxide phosphor exhibiting a spectral distribution having a maximum emission wavelength in a wavelength range of 600 to 620 nm. In.

As the second phosphor, LaPO ₄ : (C
e, Tb), CeMgAl ₁₁ O ₁₉ : (Tb) and GdM
_{gB 5 O 10: (Ce,} Tb) , and the like.

As the third phosphor, Y ₂ O ₃ : E
u.

[0031]

Embodiments of the present invention will be described below.

(Example 1) As raw materials of the phosphor, BaCO ₃ : 0.80 mol SrCO ₃ : 0.10 mol MgO: 1.05 mol Al ₂ O ₃ : 6.00 mol Y ₂ O ₃ : 0.10 mol SiO ₂ : 0.50 mol Eu ₂ O ₃ : 0.05 mol MnCO ₃ : 0.06 mol is weighed and mixed well. This raw material mixture was placed in an alumina crucible and calcined at 1400 ° C. for 3 hours in a reducing atmosphere using a mixed gas of 95% by volume of nitrogen and 5% by volume of hydrogen. The obtained fired product was pulverized, washed with pure water, filtered and dried to obtain a phosphor of the present invention. When this phosphor was analyzed, the composition was (Ba _0.8 Sr _0.1 Eu _0.1 ) O ・ 1.1 (Mg _0.95 Mn _0.05 ) O ・ 6Al ₂ O ₃・ 0.1Y
₂ O ₃ · 0.5 SiO ₂ .

The emission intensity of this phosphor by excitation with ultraviolet light of 254 nm was determined by a composition fired without using silicon oxide (Ba _0.8
Compared with the phosphor of Sr _0.1 Eu _0.1 ) O.1.1 (Mg _0.95 Mn _0.05 ) O.6Al ₂ O ₃ , the value was greatly improved to 113%. Further, this phosphor is used as a blue phosphor and as a green phosphor (La _0.5 Ce _0.2 Tb
_0.3 ) PO ₄ and (Y _0.98 Eu _0.02 ) ₂ O ₃ as red phosphors are mixed at a mass ratio of 16%, 43%, and 41%, respectively, and straight pipes belonging to day white light color classification are produced by a normal production method. A 40 W fluorescent lamp was made.

(Comparative Example) As a blue phosphor, (Ba _0.9 Eu _0.1 ) O.MgO.6Al ₂ O ₃ which was conventionally used was used.
In the same manner as in Example 1, a straight tube 40 W fluorescent lamp was manufactured.

Comparing the fluorescent lamps of Example 1 and the comparative example, the luminous flux of the fluorescent lamp of the present invention of Example 1 after 100 hours of operation is improved by 7% as compared with the luminous flux of the fluorescent lamp of the comparative example. Was.

On the other hand, the average color rendering index Ra of the fluorescent lamp of the present invention was 89, and it was confirmed that the fluorescent lamp had a satisfactory high color rendering property.

FIG. 2 is a diagram showing the spectral distribution of the fluorescent lamp in the first embodiment.

(Examples 2 to 14) In the same manner as in Example 1, each of the phosphors A to Q shown in Table 1 was combined as shown in Table 2 to produce a 40 W straight tube fluorescent lamp. 1 for each lamp
Table 2 shows the values of the light flux L and the average color rendering index Ra after lighting for 00 hours. The luminous flux L in Table 2 was obtained according to the following equation.

L = m / n × 100 where m = luminous flux (lm) of the fluorescent lamp of the embodiment after lighting for 100 hours n = luminous flux (l of the fluorescent lamp of the comparative example after lighting for 100 hours
m)

[0040]

[Table 1]

[0041]

[Table 2]

As is clear from Table 2, the fluorescent lamps of Examples 1 to 14 of the present invention have been frequently used as a blue phosphor of a three-wavelength fluorescent lamp (Ba _0.9 Eu _0.1 ) O.MgO.
It can be seen that, as compared with the fluorescent lamp shown in the comparative example using the 6Al ₂ O ₃ phosphor, it has a higher luminous flux while maintaining and improving good color rendering properties.

In this embodiment, a straight tube fluorescent lamp is used. However, the present invention is applicable to a ring-type fluorescent lamp or a compact fluorescent lamp either directly or with a protective film. .

[0044]

As described above, according to the present invention, it is possible to provide a fluorescent lamp having a higher luminous flux than conventional three-wavelength fluorescent lamps in addition to good color rendering properties. The target value is great.

[Brief description of the drawings]

FIG. 1 is a view showing a relative peak height of emission intensity when the amount of solid solution of SiO ₂ is changed in the phosphor of the present invention.

FIG. 2 is a diagram showing a spectral distribution of a fluorescent lamp in Example 1.

FIG. 3 is a partially cutaway sectional view showing an example of the fluorescent lamp of the present invention.

[Description of Signs] 11 Glass bulb 12 Electrode 13 Phosphor film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 11/79 CPR C09K 11/79 CPR 11/81 CPM 11/81 CPM CPW CPW CQD CQD CQF CQF H01J 61 / 44 H01J 61/44 NPF term (reference) 4H001 CA04 CA07 CC14 XA00 XA05 XA08 XA12 XA13 XA14 XA15 XA20 XA21 XA38 XA39 XA56 XA57 XA64 YA25 YA58 YA63 YA65 5C043 AA01 AA03 EC02 CD14 DD14 EC02

Claims (3)

[Claims] 1. An aluminate phosphor activated by divalent europium and divalent manganese, wherein the chemical composition is represented by the following general formula. (Ba _1-xy Eu _x M _y ) Oa (Mg _1-p Mn _p ) ObAl ₂ O ₃ cLn ₂ O ₃ zSiO ₂ where M is at least one element selected from Sr and Ca Ln represents at least one element selected from Y and Gd, wherein x, y, z, a, b, c and p are 0.05 ≦ x ≦ 0.2, 0 ≦ y ≦ 0 .5, 0 <z
≦ 2.0, 0.5 ≦ a ≦ 4.0, 4 ≦ b ≦ 10, 0 <c
≦ 1.0, 0 <p ≦ 0.2. 2. A fluorescent lamp formed by attaching the phosphor according to claim 1 to an inner surface of a tube. 3. The phosphor according to claim 1, further comprising:
A rare earth silicate phosphor, a rare earth magnesium aluminate phosphor, a rare earth phosphate phosphor activated with trivalent cerium and trivalent terbium exhibiting a spectral distribution having a maximum emission wavelength in a wavelength range of 50 nm; A second phosphor made of at least one selected from the group consisting of a rare earth silicate phosphor and a magnesium borate phosphor;
A mixture comprising a trivalent europium-activated rare earth oxide phosphor and a third phosphor, which exhibits a spectral distribution having a maximum emission wavelength in a wavelength range of up to 620 nm, is formed on the inner surface of the tube. Fluorescent lamp.