JP2000109826A - Fluorescent substance of alkaline earth aluminate and fluorescent lamp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To control lapsing deterioration on changes of luminous color and on luminous efficiency during lighting a fluorescent lamp as well as to improve coloring action and the efficiency by comprising a specific composition of Ba, Sr, Eu, Mg, Mn, Al and O. SOLUTION: A fluorescent substance is represented by a compositional formula, Ba1-x-ySrxEuyMg1-zMn2Al10O17. In the formula,(x), (y) and (z), fulfill 0.4<=x<=0.6, 0.03<=y<=0.3, 0<=z<=0.04, respectively. This fluorescent substance is obtained by mixing each oxide of Ba, Sr, Mg, Al, Eu and Mn or mixing compounds generating readily these oxides at a high temperature so as to make a stoichiometric ratio of this compositional formula, and this mixture is charged into a heat-resistant container followed by one or more of calcining at 1200-1700 deg.C for 2-40 hr in a reductive atmosphere. When this fluorescent substance is used as a blue luminous component of the luminous composition of a fluorescent lamp, the lamp which is less in lapsing deterioration with high coloring action and high efficiency, can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method of activating with divalent europium (Eu ²⁺ ) or divalent europium (Eu ²⁺ ).
Alkaline earth aluminate phosphor coactivated with ²⁺ ) and divalent manganese (Mn ²⁺ ), and a three-wavelength band fluorescent lamp using this phosphor as a phosphor film of a blue light emitting component. .

[0002]

2. Description of the Related Art In recent years, in the field of fluorescent lamps for general lighting,
A three-wavelength emission fluorescent lamp (hereinafter, simply referred to as “fluorescent lamp”) has been developed and put to practical use. The phosphor used in this fluorescent lamp is a mixture of three kinds of phosphors of red, green and blue having a relatively narrow band emission spectrum distribution at an appropriate ratio.

The phosphor used in this fluorescent lamp is a trivalent europium (Eu ³⁺ ) activated yttrium oxide as a red phosphor, and a cerium (Ce) and terbium (Tb) activated phosphoric acid as a green phosphor. Lanthanum and alkaline earth chlorophosphate or barium magnesium aluminate activated by divalent europium (Eu ²⁺ ) are used as the blue phosphor, respectively.

This fluorescent lamp is excellent in both luminous flux and color rendering properties, and has an average color rendering index (Ra) of 84. The luminous flux is, for example, FL20SSEX-N /
18 realizes 1470 lumens (1 m). Further, blue-green, or blue-green and deep-red phosphors are added to the above three kinds of phosphors, and four or five kinds of phosphors are mixed to achieve an average color rendering index Ra ≧ 87. Lamps have come into practical use. In Japanese Patent Application Laid-Open No. Hei 5-302082, the composition and emission color of Eu ²⁺ -activated alkaline earth chlorophosphate phosphor, which is a blue component, are specified, so that even if only three kinds of phosphors are mixed, the average is obtained. A fluorescent lamp having a color rendering index Ra ≧ 87 has been realized.

On the other hand, Eu as a blue component²⁺Activated barium
・ Fluorescent run using magnesium aluminate phosphor
As for the²⁺Activated barium / magnesium alloy
Mn as phosphoric acid for phosphoric acid²⁺Color rendering by co-activating
Those with improved properties have been put to practical use. In addition,
JP-B-56-86892 discloses Ba._1-xySr_xMg_p
Al_qO _{(1 + p + q) / 2q}: Eu²⁺ _y(Here, 0 <x ≦ 0.
1, 0.01 ≦ y ≦ 0.4, 0.8 ≦ p ≦ 4.0, 10
≦ q ≦ 30) by using a phosphor represented by the following formula:
It is described that an average color rendering index Ra = 89 can be realized.
You.

Incidentally, a fluorescent lamp using a barium magnesium aluminate phosphor activated by Eu ²⁺ as a blue component has a higher luminous flux than a fluorescent lamp using an alkaline earth chlorophosphate phosphor activated by Eu ^2+. However, there is also a problem that the emission color of the fluorescent lamp changes with time (color shift) due to the deterioration of the phosphor. As a method for solving this problem, Eu ²⁺ having a very limited composition or Eu ²⁺
Alkaline earth aluminate phosphor activated by chromium and Mn ²⁺ is Eu ³⁺ activated yttrium oxide (hereinafter referred to as “YOX red phosphor”), and lanthanum phosphate co-activated by Tb and Ce (hereinafter referred to as “Yb red phosphor”). , "LAP green phosphor") in a limited mixing ratio.
187 and JP-A-4-106188.

Furthermore, _{JP-A-3-106988, (Ba 1-xy Sr} x M y) O · a (Mg 1-pq Mn
_{p Zn q) O · bAl 2} O 3 ( where M is Sr and Ca
Represents at least one element of the following, wherein a, b,
x, y, p, and q are a + 3 ≦ b ≦ 4a + (3/2), (7
/ 3) a-1≤b≤ (11/9) a + (17/3), 0
<X ≦ 0.4, 0 ≦ y ≦ 0.4, 0 <x + y ≦ 0.4,
0.001 <(ap / x) ≦ 0.2, 0 ≦ q ≦ 0.3,
It has been proposed to use a phosphor represented by (0 ≦ p + q ≦ 0.3) for the same purpose as described above.

However, it is desired to realize a fluorescent lamp having higher color rendering, higher efficiency, and less color shift due to deterioration with time of emitted light than fluorescent lamps using these aluminate phosphors or phosphate phosphors. It is rare. The aluminate phosphor, which has been conventionally used as a blue light emitting phosphor for a high color rendering fluorescent lamp, has a high luminous efficiency. When this is used for a fluorescent lamp, the average color rendering index (Ra) is relatively good. Although a fluorescent lamp can be used, in particular, in the case of an aluminate phosphor containing Mn as an activator, the average color rendering index (Ra) ) Can be increased, but in that case, the efficiency (luminous flux when emitting white light) decreases, which is not preferable. Therefore, even when the aluminate phosphor is used as a blue light emitting phosphor for a high color rendering fluorescent lamp, the lamp has a higher average color rendering index (Ra) and higher luminous efficiency of the lamp. It is desired to develop such an aluminate phosphor.

[0009]

Accordingly, the present invention has been made to solve the above-mentioned disadvantages in a conventional Eu ²⁺ activated or Eu ²⁺ and Mn ²⁺ co-activated alkaline earth aluminate phosphor. ,
It is an object of the present invention to provide a fluorescent material having high color rendering, high efficiency, a change in emission color during lighting of a fluorescent lamp, and small deterioration of luminous efficiency with time, and a fluorescent lamp.

[0010]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied in more detail the composition of an alkaline earth phosphor used in a fluorescent lamp. A phosphor having a composition region in which the content of strontium (Sr) in the matrix of the phosphor is larger than that of an alkaline earth aluminate phosphor conventionally used is used as a blue light emitting phosphor for a high color rendering fluorescent lamp. In this case, even if the activation amount of Mn of the phosphor is reduced,
It was found that even when Mn was not co-activated, a higher Ra value and higher luminous efficiency were exhibited. That is, a predetermined amount of barium (Ba), which is an Eu ²⁺ -activated alkaline earth aluminate phosphor containing barium (Ba) and magnesium (Mg), is replaced with strontium (Sr) in a predetermined amount. Part of magnesium (Mg) with manganese (Mn)
(Ba + S)
r + Eu) component: (Mg + Mn) component: the ratio of each element of the Al component 1: 1: as 10, which either activated by Eu ^2+, or were co-activated by the Eu ²⁺ and Mn ²⁺ alkali The earth aluminate phosphor was found to exhibit high efficiency light emission and blue light emission with little deterioration over time.
By using a phosphor mixed with a red light-emitting phosphor or a LAP green light-emitting phosphor at a limited predetermined ratio as a phosphor film, the above-described problem was solved,
The present invention having the following configuration has been completed.

(1) General formula Ba _1-xy Sr _x Eu _y Mg
_1-z Mn _z Al ₁₀ is represented by O _17, x in the formula, y and z are each 0.4 ≦ x ≦ 0.6,0.03 ≦ y ≦ 0.3 and 0 ≦ z ≦ 0.04 An alkaline earth aluminate phosphor characterized by being represented by a number satisfying the following conditions. (2) In formula _{Ba 1-xy Sr x Eu y} Mg 1-z Mn z A
expressed in l ₁₀ O _17, x in the formula, y and z are each 0.
4 <x ≦ 0.6, 0.075 ≦ y ≦ 0.225 and 0 ≦
An alkaline earth aluminate phosphor represented by a number satisfying a condition of z ≦ 0.0225.

(3) A fluorescent lamp using the alkaline earth aluminate phosphor according to (1) or (2) as a phosphor layer on the inner wall of a glass tube. (4) As the phosphor layer, the mixture ratio of alkaline earth aluminate phosphor, YOX red light-emitting phosphor, and LAP green light-emitting phosphor is 1: 0.5-2.5: 0.3-3. Wherein the mixed phosphor contained in the range of 0 is used.
(3) The fluorescent lamp as described above.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The alkaline earth aluminate phosphor of the present invention is a compound of Ba, Sr, Mg, Al, Eu and Mn, or a compound which easily produces these oxides at high temperatures. Stoichiometric compositional formula Ba _1-xy Sr _x Eu _y Mg
_{1-z Mn z Al 10 O} 17 ( where, x, y and z is 0.4 ≦ x ≦ 0.6,0.03 ≦ y ≦ 0.3 and 0 ≦ z ≦ 0.04, respectively in the formula Are mixed in a proportion that satisfies the conditions), filled in a heat-resistant container, and placed in a reducing atmosphere for 12 hours.
By calcining 2-40 hours over one or more times at a temperature of from 00 to 1,700 ° C., Eu ^2+, or Eu ²⁺ and an alkaline earth aluminate phosphor of the present invention activated by Mn ²⁺ is obtained Can be

[0014] Eu ²⁺ activated or Eu ²⁺ and Mn of the present invention
²⁺ co-activated alkaline earth aluminate phosphors _{(Ba 1-xy Sr x Eu} y Mg 1-z Mn z Al 10 O 17)
In order to achieve the object of the present invention, the substitution amount of Sr (x) for substituting a part of Ba, the concentration of Eu (y), and M
The concentration range of the concentration (z) of n is 0.4 ≦ x ≦ 0.
6, 0.03 ≦ y ≦ 0.3 and 0 ≦ z ≦ 0.04, where x, y and z are each 0.4 <
x ≦ 0.6, 0.075 ≦ y ≦ 0.225 and 0 ≦ z <
A value of 0.025 is particularly preferable because a phosphor having less change in emission luminance and emission color over time of the obtained phosphor can be obtained. Note that the Eu concentration (y) in the phosphor tends to increase due to heat in the baking step in the manufacture of the fluorescent lamp when the concentration increases, so the Eu concentration (y value) is 0.3 or less. It is desirable to do.

These phosphors are used as a luminescent composition for a fluorescent lamp.
When used as a blue light-emitting component phosphor,
Eu used as a blue light-emitting phosphor for lamps²⁺,
Mn ²⁺Co-activated barium, strontium, magnesium
Higher color rendering and higher efficiency than when using aluminate phosphor
To provide a fluorescent lamp with high efficiency and little deterioration over time
Becomes possible.

FIG. 1 shows the results when the Eu ²⁺ -activated alkaline earth aluminate phosphor of the present invention and the conventional Eu ²⁺ -activated alkaline earth aluminate phosphor were excited by ultraviolet rays of 253.7 nm. The emission spectrum is illustrated, and curves a and b in FIG. 1 are Eu ²⁺ -activated barium / strontium / magnesium aluminate phosphors (Ba _0.4 Sr _0.5 Eu), each of which is an example of the phosphor of the present invention. _0.1 Mg
Al ₁₀ O ₁₇ ) and a Eu ²⁺ -activated barium magnesium aluminate phosphor (Ba _0.9 Eu _0.1 MgAl) used as a blue light emitting phosphor of a conventional fluorescent lamp
₁₀ O ₁₇ ).

As can be seen from a comparison of curves a and b in FIG. 1, by replacing a portion of the barium of the conventional barium magnesium aluminate phosphor with strontium (curve a in FIG. 1), -Compared to the magnesium aluminate phosphor (curve b in Fig. 1), the peak position of light emission due to Eu2 ⁺ moves to the longer wavelength side, and the light emission intensity at 460 to 600 nm increases.

The curves a and b in FIG.
Another Eu of the present invention²⁺Activated alkaline earth aluminate fireflies
Eu, the light body²⁺And Mn²⁺Barium and co-activated with
Strontium magnesium aluminate phosphor (B
a_0.4Sr_0.5Eu_0.1Mg _0.988Mn_0.012Al_TenO
₁₇) And used as blue light-emitting phosphor of conventional fluorescent lamps
Eu²⁺And Mn²⁺Barium and co-activated with
Strontium magnesium aluminate phosphor (B
a_0.6Sr_0.3Eu_0.1Mg_0.998Mn_0.012Al_TenO
₁₇) Were respectively excited by 253.7 nm ultraviolet rays.
3 illustrates an emission spectrum.

As can be seen from the comparison between the curves a and b in FIG. 2, the conventional barium / strontium / magnesium aluminate phosphor co-activated with Eu ²⁺ and Mn ²⁺ (FIG. 2).
Compared with the curve b), the barium / strontium / magnesium aluminate phosphor of the present invention co-activated with Eu ²⁺ and Mn ²⁺ (curve a in FIG. 2) can be obtained by increasing the amount of substitution by Sr. ^While the peak position of light emission due to ²⁺ moves to the longer wavelength side and the position of the light emission peak due to Mn ²⁺ does not change, the light emission intensity at 460 to 600 nm increases, so the light emission peak is caused by Eu ²⁺ . The relative intensity with respect to the emission peak increases.

As described above, in the alkaline earth aluminate phosphor of the present invention, the peak position of light emission due to Eu ²⁺ shifts to the longer wavelength side, and the light emission intensity at 460 to 600 nm further increases. Eu ²⁺ This means that the present invention, Mn ²⁺ coactivated barium strontium magnesium aluminate phosphor, Eu ²⁺ is used as the blue-emitting phosphor of the conventional fluorescent lamp, Mn ²⁺ with both From active barium / strontium / magnesium aluminate phosphor, Mg
Even if the amount of substitution with n is small or the amount of substitution is 0, the emission spectrum when excited with ultraviolet light of 253.7 nm contains an emission peak attributable to Mn ²⁺ of 515 nm and a wavelength of 460 to 600 nm. This means that the relative intensity of light emission can be made equal.

The alkaline earth aluminate phosphor co-activated with Eu ²⁺ or Eu ²⁺ and Mn ^{2+ of the} present invention has high brightness and is compared with the conventional alkaline earth aluminate phosphor. In particular, characteristics such as a decrease in luminous efficiency due to heat are suppressed and a variation in luminescent color over time is reduced. This is because a part of Ba in the phosphor host crystal is partially replaced with Sr. This is probably because the position of oxygen in the Ba-O layer in the crystal was stabilized.

On the other hand, the fluorescent lamp of the present invention is a Eu ²⁺ -activated or Eu ²⁺ and Mn ²⁺ and co-activated alkaline earth aluminate phosphor of the invention described above and blue-emitting phosphor A europium-activated yttrium oxide phosphor represented by, for example, red light-emitting Y _2-x Eu _x O ₃ (where x is a number satisfying the condition of 0.02 ≦ x ≦ 0.1)
“YOX phosphor”) and La _1-yz C emitting green light.
e _y Tb _z PO ₄ (where y and z are each 0.1 ≦
cerium and terbium co-activated lanthanum phosphate phosphor (hereinafter referred to as “LAP phosphor”) represented by y ≦ 0.6 and 0.1 ≦ z ≦ 0.3). The mixed phosphor mixed in a ratio is mixed with a binder to form a phosphor slurry, which is applied to the inner wall of a glass tube, and then a fluorescent lamp is manufactured by a generally known method, thereby achieving high color rendering and high efficiency. A fluorescent lamp with little deterioration can be provided. The mixing weight ratio of the blue light emitting phosphor (aluminate phosphor), the red light emitting phosphor (YOX) and the green light emitting phosphor (LAP) in the fluorescent lamp of the present invention depends on the desired color temperature of the obtained fluorescent lamp. Although different, in order to emit light in a range that can be said to be white when the light is emitted, the mixture weight ratio of the blue phosphor: the red phosphor: the green phosphor is 1: 0.5 to 2.5: 0. The color temperature may be in the range of 3 to 3.0.
Assuming about 0 to 8000K, the mixing amounts of the three color phosphors are balanced, 1: 0.7 to 2.0: 0.3 to 3.0.
It is preferable to set the range to 0.

The alkaline earth phosphor of the present invention is Ba
Is replaced with Sr, and the replacement amount (x) of Sr at that time is increased to make the replacement range of 0.4 ≦ x ≦ 0.6, thereby manufacturing a fluorescent lamp using this phosphor. In this case, there is also an effect that deterioration due to heat in the baking step is reduced, and a highly efficient fluorescent lamp can be provided.

[0024]

(Example 1) BaCO ₃ 0.4 mol SrCO ₃ 0.5 mol Eu ₂ O ₃ 0.05 mol 3MgCO ₃ .Mg (OH) ₂ 0.245 mol MnO ₂ 0.02 mol γ-type Al ₂ O ₃ 5.0 mol AlF ₃ (flux) 0.010 mol The above-mentioned raw materials are mixed well, filled in a crucible, a lump of graphite is put on the raw materials, and a lid is put on to cover nitrogen and a small amount of hydrogen. The mixture was calcined at a maximum temperature of 1450 ° C. for 24 hours including a temperature rise / fall time while passing a gas mixture of the above. Next, the calcined powder was dispersed, washed, dried, and sieved, and treated in Example 1, E
u ²⁺ , Mn ²⁺ co-activated barium / strontium / magnesium aluminate blue-emitting phosphor (Ba _0.4 Sr
_0.5 Eu _0.1 Mg _0.98 Mn _0.02 Al ₁₀ O ₁₇ ) was obtained.

When the blue light-emitting phosphor of Example 1 thus obtained was excited by ultraviolet light of 253.7 nm, the emission color was such that the emission wavelength peak was 460 nm and the emission chromaticity point was x =
It emitted blue light of 0.143 and y = 0.187. The blue phosphor was heat-treated in an air atmosphere at a maximum temperature of 650 ° C. for 15 minutes, then cooled to room temperature and then 253.7 n.
m, the ratio of the luminous efficiency after the heat treatment to that before the heat treatment (the luminance retention rate during the heat treatment) is 98.
8%, which proved that the heat resistance hysteresis to the baking treatment was extremely good.

Next, this blue phosphor is applied to the inner surface of a glass bulb, and a blue monochromatic fluorescent lamp (FL20S)
After lighting for 1000 hours, the phosphor was peeled off from the tube wall of the lamp, and the emission color (X ′, Y ′) when excited with 253.7 nm ultraviolet rays was x ′ = 0.145,
y ′ = 0.190, and the difference between the emission chromaticity points of the phosphor before and after using this phosphor as the phosphor fluorescent film (difference in emission chromaticity due to use) is Δx = 0.002, Δy
= 0.003, which is a very small difference in chromaticity of the phosphor before and after use.

Comparative Example 1 BaCO ₃ 0.6 mol SrCO ₃ 0.3 mol Eu ₂ O ₃ 0.05 mol 3MgCO ₃ .Mg (OH) ₂ 0.245 mol MnO ₂ 0.02 mol γ-type Al ₂ O ₃ 5.0 mol AlF ₃ (flux) 0.010 mol Except for using the above-mentioned raw materials as the phosphor raw material, the same procedure as in the blue light-emitting phosphor of Example 1 was carried out, and Eu ²⁺ and Mn of Comparative Example 1 were used.
²⁺ co-activated barium / strontium / magnesium aluminate blue-emitting phosphor (Ba _0.6 Sr _0.3 Eu _0.1 M
g _0.98 Mn _0.02 Al ₁₀ O ₁₇ ).

When the blue light-emitting phosphor of Comparative Example 1 thus obtained was excited with ultraviolet light of 253.7 nm, the light-emitting color had a light-emitting wavelength peak of 450 nm and a light-emitting chromaticity point of x =
It emitted blue light of 0.144 and y = 0.153. When this phosphor was heat-treated in the same manner as in Example 1, the ratio of the luminous efficiency after the heat treatment to that before the heat treatment (the luminance retention rate during the heat treatment) was 85.5%, which was a heat resistance history with respect to the baking treatment. Sex was bad.

Further, using this blue phosphor, a fluorescent lamp (FL20
After S) was manufactured and lit for 1000 hours in the same manner as in Example 1, the phosphor was peeled off from the tube wall of the lamp and 253.7.
The emission color (X ′, Y ′) when excited by ultraviolet light of nm is x ′ = 0.145 and y ′ = 0.155, and the emission color of the phosphor before and after using this phosphor as a lamp The difference between the degree points (Δx, Δy) is Δx = 0.001, Δy =
0.002.

Tables 1 and 2 show the phosphor compositions of the blue light emitting phosphors of Example 1 and Comparative Example 1, and the emission colors (emission peak wavelength, emission chromaticity point color (x, y), The ratio of the luminous efficiency after heat treatment to that before heat treatment (luminance maintenance rate during heat treatment), and the phosphor collected by peeling off the phosphor film after using the phosphor for 1000 hours using this phosphor as the phosphor film of the lamp , And the difference (Δx, Δy) in the emission chromaticity of the phosphor before and after use as the fluorescent film of the lamp, that is, the difference (−) in the emission chromaticity due to use, respectively. Indicated.

(Examples 2 to 28) Each phosphor material of Example 1
The ingredients were mixed to have the respective compositions shown in Tables 1 and 2.
Except for the above, the example was performed in the same manner as the blue light emitting phosphor of the example 1.
2 to 28 Eu²⁺, Mn ²⁺Co-activated barium stron
Manufactured blue phosphor
Built. Each blue of Examples 2 to 28 thus obtained
The composition of the emitting phosphors, these phosphors were 253.7 nm
Emission color when excited by ultraviolet rays ｛emission peak wavelength, emission color
Degree point (x, y)｝, these phosphors are the same as in Example 1.
Heat treatment before and after heat treatment
Light efficiency ratio (luminance maintenance rate during heat treatment), each of these blue
In the same manner as in Example 1 using a color phosphor,
Example 1 A fluorescent lamp (FL20S) was manufactured, and
After lighting for 1000 hours in the same manner as in
Peeled off from the tube wall and excited with ultraviolet light of 253.7 nm.
Emission chromaticity of phosphor at the time ｛Emission chromaticity point after use
(X ′, Y ′)} and the emission chromaticity of the phosphor by use.
The differences (Δx, Δy), that is, (−) are shown in Table 1 and
The results are shown in Table 2.

[0032]

[Table 1]

[0033]

[Table 2]

(Example 29) Eu of Example 1²⁺, Mn²⁺
Co-activated barium, strontium, magnesium alloy
Blue luminescent phosphor (Ba)_0.4Sr_0.5Eu_0.1M
g_0.98Mn_0.02Al _TenO₁₇) At 30.6% by weight and the composition
Expression is Y_1.92E_0.08O_ThreeYOX red light-emitting phosphor
7.2% by weight, composition formula is La_0.55Ce_0.30Tb_0.15PO
_Four32.2% by weight of LAP green light-emitting phosphor
Butyl acid with nitrocellulose lacquer
To form a phosphor slurry, apply it to a glass tube and dry it.
After drying, the color temperature of Example 29, 5000
A three-wavelength fluorescent lamp K (FL20S) was manufactured.
The initial characteristics of the fluorescent lamp thus obtained are as follows:
Phase when the lamp luminous flux of the fluorescent lamp of Comparative Example 2 is set to 100
The logarithmic value is 99.5, and the average color rendering index Ra is 9
0.1 (Table 3).

Comparative Example 2 For comparison, the blue phosphor of Example 1 was replaced with the Eu of Comparative Example 1 for the blue phosphor.
²⁺ and Mn ²⁺ co-activated barium / strontium / magnesium aluminate blue-emitting phosphor (Ba _0.6 Sr _0.3
Using _{Eu 0.1 Mg 0.98 Mn 0.02 Al 10} O 17), 3 -wavelength fluorescent lamp and 3 wavelength of Comparative Example 2 in the same manner of Examples 29 except that the mixing weight ratio was as shown in Table 3 for each color phosphor A fluorescent lamp (FL2OS) was manufactured. Table 3 shows the relative values of the luminous flux and the average color rendering index Ra immediately after the three-wavelength fluorescent lamps of Example 29 and Comparative Example 2 were turned on.

Examples 30 to 56 Examples 2 to 2
Example 29, except that each of the blue light-emitting phosphors of Example 8, the LAP green light-emitting phosphor and the YOX red light-emitting phosphor used in Example 29 were mixed at the mixing weight ratios shown in Table 2, respectively. Examples 30 to 30 in the same manner as in the fluorescent lamp of
56 three-wavelength fluorescent lamps were manufactured. Table 3 shows the relative values of the luminous flux and the average color rendering index Ra measured immediately after the lighting of each of the obtained fluorescent lamps.

[0037]

[Table 3]

As apparent from Table 3, the fluorescent lamps of the present invention (Examples 29 to 56) have almost the same luminous flux as the fluorescent lamp of Comparative Example 2 using the blue phosphor having the same europium concentration. The average color rendering index (Ra) was improved, and the color rendering was further improved, or the average color rendering index (Ra) was almost equal, the luminous flux was improved, and the luminous efficiency was improved. In particular, Examples 30 to 34 and Example 3
The fluorescent lamps of Examples 6 to 40, Examples 45 to 47 and Examples 52 to 56 have improved luminous flux and average color rendering index as compared with the fluorescent lamp of Comparative Example 2, and have both color rendering properties and luminous efficiency. Improved.

Further, although not shown in the table, it was confirmed that the fluorescent lamps of Examples 29 to 56 also exhibited improved deterioration over time due to continuous lighting as compared with Comparative Example 2. Among these, in particular, Examples 29 to 33 and Examples 36 to 4
1 and Examples 44 to 48 and Examples 51 to 55 show the degree of improvement of the deterioration over time during lighting of the fluorescent lamps, as compared with Comparative Example 2, Example 34, Example 35, Example 42, Example 43, Example 49, The size was larger than the fluorescent lamps of Examples 50 and 56.

(Examples 57 to 84, Comparative Example 3) Further, each of the blue light emitting phosphors of Examples 1 to 28 and Comparative Example 1, YOX
Examples 57 to 84 were performed in the same manner as in the fluorescent lamp of Example 29 except that a mixed phosphor prepared by mixing the red light emitting phosphor and the LAP green light emitting phosphor at the weight ratios shown in Table 4 was used as the fluorescent film. And the color temperature 650 of Comparative Example 3.
A 0K three-wavelength fluorescent lamp (FL20S) was manufactured. Table 4 shows the results of measuring the initial luminous flux (relative value) and the average color rendering index (Ra) of the fluorescent lamp thus obtained immediately after lighting.

[0041]

[Table 4]

As is clear from Table 4, the fluorescent lamps of the present invention (Examples 57 to 84) have almost the same luminous flux as the fluorescent lamp of Comparative Example 3 using a blue phosphor having the same europium concentration. And the average color rendering index (Ra) is improved, and the color rendering is further improved, or the average color rendering index (Ra) is almost the same, the luminous flux is improved, and the luminous efficiency is improved. Was done. In particular, Examples 58 to 62, Examples 65 to 69, Examples 72 to 76, and Example 8
Compared with the fluorescent lamp of Comparative Example 3, the luminous flux and the average color rendering index Ra of the fluorescent lamps of 0 to 84 both improved, and both the color rendering and the luminous efficiency were improved.

Example 85, Comparative Example 4 In the same manner as in Example 1, the blue phosphor of Example 85 (Ba _0.3 Sr _0.5 E
u _0.2 Mg _0.98 Mn _0.02 Al ₁₀ O ₁₇ ) and the blue phosphor of Comparative Example 4 (Ba _0.7 Sr _0.1 Eu _0.2 Mg _0.986 Mn)
_0.014 Al ₁₀ O ₁₇ ). Table 5 shows the compositions, emission peak wavelengths, and emission chromaticities (x, y) of the blue phosphors of Example 85 and Comparative Example 4 thus obtained.

Next, the blue phosphor of Example 85 and the blue phosphor of Comparative Example 4 (the phosphor composition, the emission peak wavelength and the emission chromaticity point are shown in Table 5) were changed to YOX red phosphor and LAP. A green phosphor was mixed with the mixture at the mixing ratio shown in Table 6 to prepare a mixed phosphor.
5 and Comparative Example 4, the color temperature was 5000K,
A FL20S three-wavelength band fluorescent lamp was manufactured. For each of the obtained fluorescent lamps, the mixing ratio (% by weight) of each color phosphor used as the fluorescent film, the initial luminous flux (relative value) and the average color rendering index (Ra) of the obtained fluorescent lamp were measured.
The results are shown in Table 6.

[0045]

[Table 5]

[0046]

[Table 6]

As is clear from Table 6, the fluorescent lamp of the present invention of Example 85 has a higher luminous flux and average color rendering as compared with the fluorescent lamp of Comparative Example 4 using a blue phosphor having the same europium concentration. The sex index (Ra) was improved, and the color rendering properties and the luminous efficiency were both improved.

[0048]

According to the present invention, by adopting the above structure, the emission spectrum when excited by ultraviolet rays of 253.7 nm compared with the conventional alkaline earth aluminate phosphor with both Eu and Mn is obtained. In, the peak position of the emission due to europium shifts to the longer wavelength side, and
In particular, when used as a blue light-emitting component phosphor of a three-wavelength fluorescent lamp, the three-wavelength fluorescent lamp has high color rendering, high efficiency, and little change in emitted color during lamp operation and little deterioration over time. An area emission type fluorescent lamp can be provided.

[Brief description of the drawings]

FIG. 1 shows an alkaline earth aluminate phosphor of one composition of the present invention and a conventional alkaline earth aluminate phosphor
It is the figure which showed the light emission spectrum when excited with 53.7 nm ultraviolet rays.

FIG. 2 is a diagram showing an optical spectrum when an alkaline earth aluminate phosphor of another composition of the present invention and a conventional alkaline earth aluminate phosphor are excited with ultraviolet rays of 253.7 nm.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4H001 CA07 XA08 XA12 XA13 XA38 XA56 YA25 YA63 5C043 AA01 AA02 AA03 AA05 CC08 DD28 EA19 EB04 EC20

Claims (2)

[Claims] 1. The formula of Ba _1-xy Sr _x Eu _y Mg
_1-z Mn _z Al ₁₀ is represented by O _17, x in the formula, y and z are each 0.4 ≦ x ≦ 0.6,0.03 ≦ y ≦ 0.3 and 0 ≦ z ≦ 0.04 An alkaline earth aluminate phosphor characterized by being represented by a number satisfying the following conditions. 2. A fluorescent lamp, wherein a phosphor layer on the inner wall of a glass tube is formed using the alkaline earth aluminate phosphor according to claim 1.