JPH0330262B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention has a light emission color temperature of 2800 to 3500K (Kelvin), and has a DL specified in JIS Z9301.
This article relates to a fluorescent lamp called a shape with improved luminous efficiency and color rendering properties. [Technical background of the invention and its problems] Generally, in order to obtain a fluorescent lamp with a color temperature of 2,800 to 3,500 K, the peak wavelength range of light emission is from 610 to 660 nm and the half-width is from 10 to 80 nm. A phosphor having a specific emission spectrum is essential. Conventionally, manganese-activated magnesium fluorodiamanite phosphors have been frequently used as phosphors that emit light in the above-mentioned emission spectrum. It is desirable to reduce the amount of this phosphor used as much as possible for several reasons, including: large deterioration during the manufacturing process of the lamp, poor working characteristics during lighting, and the extremely high cost of Ge (germanium). Despite this, approximately 5% of the total amount of phosphor used
The reality is that it accounts for a large proportion of the population. In addition, conventional fluorescent lamps of this type have a color rendering property of about 73, and a luminous efficiency of 330 [m] with a 10 [W] lamp.
Even higher efficiency and higher color rendering properties are desired. [Object of the Invention] In view of the above-mentioned needs, an object of the present invention is to provide a phosphor lamp with high efficiency and high color rendering while reducing the amount of expensive phosphor used. [Summary of the Invention] In order to achieve the above object, the present invention has developed a novel phosphor, a divalent europium-activated barium-calcium-magnesium halophosphate blue-green phosphor, and This phosphor can be produced by mixing the phosphor with antimony and manganese-activated calcium halophosphate phosphor, tin-activated strontium/magnesium orthophosphate phosphor, and manganese-activated magnesium fluorophosphate phosphor. This is achieved by coating the inner surface of the glass tube of the lamp. [Effects of the Invention] According to the present invention, the amount of manganese-activated magnesium fluorodiermanite phosphor used, which is an expensive phosphor, is less than 20% of the total amount of phosphor used, and the color rendering properties are 7 or more. Efficiency improved by more than 10%. Furthermore, since the inside of the glass tube is coated with a single layer, it is easy to mass-produce and has the advantage of greatly improving lamp characteristics. [Embodiments of the Invention] Examples of the present invention will be described in detail below. Before going into the description of the embodiments, since a new phosphor is used according to the present invention, the structure and manufacturing method of this phosphor and its characteristics will be explained. That is, the general formula M _5-X X(PO ₄ ) ₃ :Eu ²⁺ (x)
(In the formula, M consists of three types of Ba, Ca, and Mg, X is a single substance or a mixture of two or more types of F, Cl, and Br, and x is a positive number less than 5.)
By selecting the Mg value of 0.01 to 1.0 gram atom, we succeeded in obtaining a phosphor with excellent properties. In the above general formula, the index x represents the number of graph atoms of divalent eurobium, 0<x<5,
Preferably, it is set to satisfy the relationship 0.01<x≦0.2. When the index x is less than 0.01, the brightness of the obtained phosphor is significantly reduced, and even when it exceeds 0.2, no significant improvement in the brightness of the obtained phosphor is observed. More preferably, it is set to 0.03≦x≦0.15. Furthermore, B of M;, Ca, and Mg are each Ba=3.0 to 4.5
gram atom, Ca=0.5-2.0 gram atom, Mg=
It is preferable to set it to satisfy the relationship of 0.01 to 1.0 gram atom. Above Ba=3.0~4.5, Ca=0.5
~2.0, when the amount of Mg substitution is less than 0.01, no significant improvement in brightness is seen compared to the case of only Ba and Ca. Moreover, if it exceeds 1.0, the brightness will conversely decrease, which is not preferable. Preferably Mg=0.1-0.5
It is to set it to . This phosphor is prepared as follows. That is, after the firing process, Ba, Ca, Mg, P,
Each oxide that can be a source of F, Cl, Br and Eu,
After weighing out a predetermined amount of a compound such as a phosphate, carbonate, or ammonium salt, the raw material mixture is thoroughly ground and mixed using, for example, a ball mill. Thereafter, the resulting mixture was placed in a crucible made of alumina and quartz, and heated at 800°C to 1200°C in the atmosphere.
Bake at a temperature of 1 to 5 hours. The obtained fired product is cooled, pulverized, and sieved, and heated to 800 to
Secondary firing is performed at a temperature of 1200℃. The obtained fired product is cooled, crushed, sieved, washed,
The phosphor of the present invention can be obtained by filtering, drying, and sieving. Specific example 1 Compositional formula M _5-X X(PO ₄ ) ₃ shown in Table 1 below:
In the phosphor represented by Eu ²⁺ (x), X=
Various phosphor samples (numbers 1 to 10 in Table 1) with different M were prepared by setting Cl and x=0.05.
For comparison, a conventional phosphor containing no Mg (No. 21) was also prepared in the same manner. These raw material mixtures were milled in a ball mill for 2
Grind and mix for hours. Next, the mixture was sieved and placed in a quartz crucible, and fired in the air at a temperature of 950° C. for 3 hours. The obtained fired product is cooled, crushed, and sieved, and hydrogen 2
%, in a mixed gas of 98% nitrogen at a temperature of 950°C.
A secondary firing was performed for an hour. The obtained fired product is cooled, crushed, sieved, washed,
Various phosphor samples were obtained by filtering, drying, and sieving. Chemical analysis of these various samples revealed that the compositions were consistent with stoichiometric composition. Furthermore, when the crystal form was examined by X-ray diffraction, it was found that it had a complete chloroabatite structure. In addition,
It was found that the lattice constant also changed depending on the blending ratio of Ba, Ca, and Mg. Next, for each of these samples, (1) relative brightness, (2) retention rate, and (3) retention rate were measured, and the results are shown in Figure 1 in correspondence with the number of gram atoms of Mg blended. . Note that the above measurement items are based on the following specifications. (1) Relative brightness: Comparison of brightness when each sample is irradiated with 254 nm ultraviolet rays. This is a relative value when the brightness of the sample (number 11 in Table 1) when irradiated with ultraviolet rays of the same wavelength is set to 100.0. It also indicates the magnitude of the luminous flux, and is correlated with the initial luminous flux when used in a fluorescent lamp. (2) Maintenance rate: Ratio of the brightness after baking each sample at 600℃ for 10 minutes in the air and the brightness before baking (Brightness after baking / Brightness before baking x 100 (%) ), which is correlated with the deterioration in brightness during the baking process during the manufacturing process of fluorescent lamps. (3) Maintenance rate: The ratio of the brightness after irradiating each sample with ultraviolet rays (including strong 185 nm bright line) from a quartz low-pressure mercury lamp for 4 hours to the brightness when not irradiated (after irradiating the above ultraviolet rays for 4 hours) Brightness/Brightness when not illuminated×
100 (%)), which correlates with the luminous flux maintenance rate when used in a fluorescent lamp. Specific example 2 Compositional formula M _5-X X(PO ₄ ) ₃ shown in Table 1 below:
In the phosphor represented by Bu ²⁺ (x), X=
Ba of M by setting Cl, x=0.05 and Mg=0.2
Various phosphor samples (numbers 11 to 14 in Table 1) having different blending ratios of Ca and Ca were prepared in the same manner as in Example 1. The luminance of these samples was measured by irradiating them with 254 nm ultraviolet rays in the same manner as described above. Note that the relative brightness in this case is the relative brightness when the brightness of the sample numbered 21 in Table 1 is set to 100.0.
The results are shown in FIG. 2 in correspondence with the number of gram atoms of Ca added. Specific example 3 Compositional formula M _5-X X(PO ₄ ) ₃ shown in Table 1 below:
In the phosphor represented by Bu ²⁺ (x), X=
Set Cl, Ca=1.0, Mg=0.2, Ba and M
Various phosphor samples (numbers 15 to 20 in Table 1) having different blending ratios of Bu(x) were prepared in the same manner as in Example 1. The brightness of these various samples was measured by irradiation with 254 nm ultraviolet rays. In addition, the relative brightness in this case is the sample number 21 in Table 1 (known example)
This is the relative brightness when the brightness of is set to 100.0. These results are shown in FIG. 3 in correspondence with the number of grams of Eu added. Further, FIG. 4 shows the emission spectrum when the phosphor of the present invention (representatively numbered 12 and 13 in Table 1 of Example 2) was irradiated with 254 nm ultraviolet rays.
As a result, blue-green light was emitted with an emission peak in the wavelength range of 480 nm to 500 nm. As is clear from these results, this phosphor has higher brightness when irradiated with 254 nm ultraviolet rays than the conventionally known divalent europium-activated halophosphate phosphor, and also has a lower brightness due to baking. It was also found that the luminance decreases little when irradiated with ultraviolet light at 185 nm, and the phosphor has very low energy in the short wavelength emission region of the visible region below 450 nm.

[Table] Using a divalent europium-activated barium/calcium/magnesium halophosphate phosphor with the above-mentioned characteristics, we can produce an antimony- and manganese-activated calcium halophosphate phosphor having an emission peak in the wavelength range of 570 to 575 nm. Tin-activated stontium/magnesium orthohalophosphate phosphor with an emission peak in the wavelength range of 610 to 640nm, and 650 to 660nm
It has an emission peak in the wavelength range of m, and the half-width is 20n.
It has been found that it is suitable to coat the inside of the glass tube in a layer with a phosphor mixed with a manganese-activated magnesium chlorodiamanite phosphor. Antimony and manganese-activated calcium halophosphate phosphors can be produced by changing the mixing ratio of antimony and manganese and the mixing ratio of fluorine and chlorine, as shown in Japanese Patent Publication No. 33-4324, to improve the emission energy ratio between the antimony band and the manganese band. It is already known that the peak wavelength of the manganese band also changes. Compositional formula of the phosphor used in the fluorescent lamp of the present invention,
The chromaticity, emission peak wavelength, and half width are shown in Table 2.
Moreover, the spectral distribution of these phosphors is shown in FIG.
The symbols in the figure correspond to the symbols in Table 2. Example 1 In the fluorescent lamp shown in Fig. 7, the symbols A, B, C, and D in Table 2 are set to the color temperature 3200K shown in Fig. 6a.
The mixture 71 is mixed at a ratio such that the deviation is -0.005 [uv], and the mixture 71 is applied to the inner surface of a glass tube 72 with a diameter of 25 mm as shown in FIG. 7, and discharge electrodes 73, A 10 [W] fluorescent lamp having a power of 74 was tested and colorimetry and photometry were carried out. These measurement results are compared and summarized in Table 3 as a conventional example.

【table】

[Table] The conventional fluorescent lamp is a two-layer coating, with the glass tube side coated with a manganese-activated fluorodiermanite phosphor, and the second layer coated with an antimony- and manganese-activated calcium phosphor. The fluorescent lamp according to the present invention has an initial luminous flux of 360 to 365
[m] was obtained, and it was confirmed that the decrease in luminous flux during lighting was extremely small. FIG. 8 shows a spectral energy distribution diagram. Example 2 The phosphors with symbols A', B, C, and D in Table 2 were
The mixture was mixed at a ratio such that the color temperature was 3000K and the deviation was -0.005 [uv] as shown in Figure b. Using the mixture, a prototype fluorescent lamp was manufactured in the same manner as in Example 1, and colorimetry and photometry were performed. Summer. These measurement results are summarized and listed in Table 3. Figure 8 shows a spectral energy distribution diagram. As is clear from the above examples, the fluorescent lamp of the present invention includes a divalent europium-activated barium/calcium/magnesium halophosphate phosphor, a tin-activated strontium/magnesium orthophosphate phosphor, and a manganese-activated strontium/magnesium orthophosphate phosphor. By using a mixture of four types of phosphors: a magnesium fluorodiermanite phosphor, and a 570-575nm antimony and manganese-activated calcium halophosphate phosphor, the total luminous flux is 10% with a single coated phosphor layer. It has the excellent effect of improving In addition, the divalent europium-activated barium/calcium/magnesium halophosphate phosphor has very little energy in the short wavelength emission region of the visible region below 450 nm, which is a factor that inhibits color rendering, so the color rendering is improved by 7 to 9. Furthermore, by using this extremely inexpensive phosphor, the amount of extremely expensive manganese-activated magnesium fluorodiamanite phosphor used can be reduced to 20% of the total amount of phosphor used. There is. In addition, since the lamp manufacturing process required more coating, production efficiency was greatly improved, and variations in lamp light color and color rendering properties were also improved, making quality control easier.

[Brief explanation of the drawing]

Figure 1 shows the number of gram atoms and relative brightness of magnesium in the fluorescent material used in the fluorescent lamp according to the present invention.
(1), a diagram showing the relationship between maintenance rate (2) and maintenance rate (3), Figure 2 is a diagram showing the relationship between calcium gram atoms and relative brightness, and Figure 3 is a diagram showing the relationship between calcium gram atoms and relative brightness. Figure 4, a diagram showing the relationship between the number of gram atoms and relative brightness, shows the typical phosphor 254n described above.
FIG. 5 is a characteristic diagram showing the emission spectrum distribution of each phosphor used in the fluorescent lamp of the present invention; FIG.
FIG. 6 is a chromaticity diagram showing the light color of the lamp, and FIG. 8 is a comparison between the spectral energy distribution of the lamp shown in Examples 1 and 2 of the present invention and the conventional (two-layer coating) one. The characteristic diagram, FIG. 7, is a sectional view of the fluorescent lamp of the present invention. 71... Fluorescent material, 72... Glass tube, 73,7
4... Discharge poles.

Claims (1)

[Claims] 1 General formula, M _5-X X(PO ₄ ) ₃ : Eu ²⁺ (x) (in the formula M
consists of three species, Ba, Ca, and Mg, each having 3.0 to 4.5 gram atoms of Ba, 0.5 to 2.0 gram atoms of Ca, and 0.01 to 1.0 gram atoms of Mg;
Cl, Br alone or a mixture of two or more,
Moreover, 0.01<x0.2. ), 480~
A first fluorophore of alkaline earth metal halophosphate activated with divalent europium having an emission peak in the wavelength range of 500 nm, and a second fluorophore having an emission peak in the wavelength range of 480/570 to 575 nm. body and 610
The third one has an emission peak in the wavelength range of ~640nm.
1. A fluorescent lamp comprising a mixture of a phosphor and a fourth phosphor having an emission peak in a wavelength range of 650 to 660 nm and deposited on the inner surface of a glass tube. 2 The second phosphor is an antimony and manganese activated calcium halophosphate phosphor, the third phosphor is a tin activated strontium or magnesium phosphor, and the fourth phosphor is a manganese activated phosphor. A fluorescent lamp according to claim 1, characterized in that it is a magnesium fluorodiamanite phosphor.