JPS58121541A - Fluorescent lamp - Google Patents

Abstract

PURPOSE:To decrease a quantity of use of an expensive fluorescent material further present a high efficient fluorescent lamp with a high color rendition. CONSTITUTION:The first fluorscent material of alkaline earth metal halophosphoric acid salt activated by dieuropium having a luminous peak in 480-500nm wavelength range, the second fluorescent material having a luminous peak in 480/570-575nm wavelength range, the third fluorescent material having a luminous peak in 610-640nm wavelength range and the fourth fluorscent material having a luminous peak in 650-660nm wavelength range, as shown by a general formula M5-xX (PO4)3:Eu<2+>(x) (where M is composed of three kinds of Ba, Ca, Mg and provided with Ba of 3.0-4.5 gram atom, Ca of 0.5-2.0 gram atom and Mg of 0.01-1.0 gram atom, respectively: X is a simple substance of F, Cl, Br or mixture of at least two kinds, further x is 0.01<x<=0.2), are mixed and coated on the internal surface of a glass tube to form an expensive fluorescent material of magnesium phlorogermanate activated with manganese, and a quantity of its use becomes 20% the total quantity of the fluorescent material or less to improve a color redition to 7 or more and efficiency to 10% or more.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention has a color temperature of 2,800 to 3,500K (Kelvin), and has a color temperature of D as defined in JIS Z9301.
This invention relates to a fluorescent lamp called an L-type fluorescent lamp with improved luminous efficiency and color rendering properties.

[Technical background of the invention and its problems]

Generally, in order to obtain a fluorescent lamp having a color temperature of 2,800 to 3,500, the peak wavelength range of emission must be 6.
A phosphor having an emission spectrum of 10 to f36Q nm and a half-width of 10 to 80 nm is essential.

Conventionally, a manganese-activated magnesium fluorogermanite phosphor has been frequently used as a phosphor that emits light in the above-mentioned emission spectrum. This phosphor ■ Significant process deterioration during rung manufacturing ■ Poor working characteristics during lighting ■ Ge (germanium) is extremely expensive, so it is desired to reduce its usage as much as possible. Despite this, the reality is that it accounts for about 50% of the total amount of phosphor used.

Furthermore, the color rendering property of conventional fluorescent lamps of this type is about 73, and the luminous efficiency is about 10 [W] clamp 330 [:1 m], so even higher efficiency and color rendering are desired.

[Purpose of the invention]

SUMMARY OF THE INVENTION In view of the above-mentioned needs, it is an object of the present invention to provide a phosphor lamp that uses less expensive phosphor and has high efficiency and high color rendering.

[Summary of the Invention] In order to achieve the above object, the present invention provides a new phosphor, a divalent euroum-activated haq IJ barium-calcium-magnesium phosphate blue-green phosphor. By developing this phosphor and mixing it with an antimony and manganese activated calcium halophosphate phosphor, a tin activated stronnium/magnesium orthosulfate phosphor, and a manganese activated magnesium 70 rhodiamanite phosphor, This is achieved by applying this phosphor to the inner surface of the glass tube of the lamp.

〔Effect of the invention〕

According to the present invention, the amount of expensive manganese-activated magnesium fluorogermanite phosphor used is less than 20% of the total amount of phosphor used, the color rendering property is 7 or more, and the efficiency is 10%.
More than that. 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. According to the present invention, a new phosphor is used before entering the station between the embodiments, so
The structure and manufacturing method of this phosphor and its characteristics will be explained below.

That is, the general formula Ms-xX(P 04) 3 : Eu
(X) (wherein M is the combination of Ba, Ca, and Mg, X17i: F, Cd.

It is a single substance of Br or a mixture of two or more types, and X is a positive number less than 5. ), the Mg value of M is 001~
By selecting a value of 1.0 gram atom, a phosphor with excellent properties was successfully obtained.

In the above general formula, the index X represents the number of gram atoms of divalent europium, and O<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 luminance of the obtained phosphor is extremely low FL, and even when it exceeds 0.2, no significant improvement in the luminance of the obtained phosphor is observed. More preferably, it is desirable to set 003≦X≦0.15.

Furthermore, B2, Ca, and Mg of M are each Ba = 3
．． 0~4.5 Gram atom* Ca"'0.5~2
．． It is preferable to set so as to satisfy the relationship of 0 gram atom and Iv1g=0.01 to 10 gram atom. Above Ba=3.0-4.5. When Ca=0.5 to 2.0, if the Mg substitution amount is less than 0.01, no significant improvement in brightness is observed compared to the case of only Ba and Ca. On the other hand, if it exceeds 1.0, the brightness will decrease, which is undesirable. Preferably, Mg is set to 0.1 to 0.5.

This phosphor is prepared as follows.

That is, after the firing process, Ba, Ca, Mg, P, F,
Cl.

Each oxide and phosphate can serve as a source of Br and Eu.

After weighing a predetermined amount of compounds such as carbonate and ammonium salt, the raw material mixture is sufficiently ground and mixed using, for example, a ball mill. Thereafter, the resulting mixture was placed in a crucible made of alumina and quartz, and exposed to s in the atmosphere.
Calcinate for 1 to 5 hours at a temperature of oo'o to 1200"C. The resulting fired product is cooled, pulverized, and sieved, and then heated in a weakly reducing atmosphere with a mixed gas of hydrogen and nitrogen, for example.
Secondary firing is performed at a temperature of 0 to 1200°C.

The phosphor of the present invention can be obtained by cooling, crushing, sieving, washing, filtering, drying, and sieving the obtained fired product.

Specific example 1 Compositional formula Ms-x X (P 04
)! : In the phosphor represented by Eu (x),
x=ce.

Various phosphor samples (numbers 1 to 10 in Table 1) with different M were prepared by setting X=0.05. For comparison, a conventional phosphor containing no Mg (number 21) was used for comparison.
) was prepared in the same manner. These raw material mixtures were pulverized and mixed in a ball mill for 2 hours. Next, the mixture was sieved and placed in a quartz crucible, and heated at 950 °C in the atmosphere.
Firing was carried out for 3 hours at a temperature of .degree.

The obtained fired product was cooled, pulverized, and sieved, and subjected to secondary firing at a temperature of 950° C. for 1 hour in a mixed gas of 2 g of hydrogen and 98% nitrogen.

The obtained fired product was cooled, crushed, sieved, washed, filtered, dried, and sieved to obtain various phosphor samples. Chemical analysis of these various samples revealed stoichiometric compositions. matched. Furthermore, when the crystal type was examined by X-ray diffraction, it was found that it had a completely roloabatite structure. It was also found that the lattice constant changed depending on the blending ratio of Ba, Ca, and Mg.

Then, for each of these samples, (■) relative brightness.

(2) Maintenance rate ■ and (3) Maintenance rate ■ were measured, and the results are shown in FIG. 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 (Table 1A, No. 11) when irradiated with ultraviolet rays of the same wavelength is taken as 1000. 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 ■: This is the ratio of the brightness after baking each sample in the atmosphere at 600°C for 910 minutes to the brightness before baking. This is the brightness during the baking process during the manufacturing process of fluorescent lamps. There is a correlation with the deterioration of

(3) Maintenance rate ■: represents 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; There is a correlation with the luminous flux maintenance rate when used in

Specific example 2 Compositional formula M5-XX (P 04
)3 :B , 2 + (x ), in which X=C6°X=0.05 and Mg=0.
2, and various phosphor samples with different blending ratios of Ba':f3- and Ca (numbers 11 to 14 in Table 1) were prepared.
was prepared in the same manner as in Example 1.

For these samples, 254
The brightness was measured by irradiation with nanometer ultraviolet rays.

Note that the relative brightness in this case is the relative brightness when the brightness of the sample No. 21 in Table 1 is set to 100.0. The results are shown in FIG. 2 in correspondence with the number of grams of Ca added.

Specific example 3 Compositional formula M6-xX (P 04 ) shown in Table 1 below
3: In the phosphor represented by B u2+ (x), X=C1°Ca=1.0. Various phosphor samples (Nos. 15 to 20 in Table 1) were prepared in the same manner as in Example 1, with Mg=0.2 and different blending ratios of Ba and Bu(x) in M.

The brightness of each of these samples was measured by irradiating ultraviolet light at 2541 m. Note that the relative brightness in this case is calculated by multiplying the brightness of the sample number 21 (known example) in Table 1 by 1000.
This is the relative brightness when 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 12.13 in Table 1 of Example 2) was irradiated with 254 nm ultraviolet light.

As a result, blue-green light was emitted with an emission peak in the wavelength range of 48 Q nm to 5 Q Q 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 shows less reduction in brightness due to baking. It was also found that the luminance decreases little when irradiated with ultraviolet light at 1851 m, and that the phosphor has very low energy in the short wavelength emission region of the visible region below 450 nm. Below D: Using a divalent europium-activated barium/calcium/magnesium halophosphate phosphor with the above-mentioned characteristics, 5
An antimony- and manganese-activated calcium halophosphate phosphor having an emission peak in the wavelength range of 70 to 5,750 m, a tin-activated pressure stontium/magnesium halophosphate phosphor having an emission peak in the wavelength range of 610 to 6,401 m, and 650 to 660 m. 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 chlorogermanite phosphor having an emission peak in the wavelength range of 20 nm and a half-value of 20 nm.

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. Furthermore, it is already known that the peak wavelength of Emperor Manganese also changes.

The compositional formula of the phosphor used in the fluorescent lamp of the present invention.

Chromaticity 9 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 of the second Shishi.

Example 1 In the fluorescent lamp shown in FIG. 7, symbols A and R in Table 2 are used.
, C, D to a color temperature of 3200 shown in Fig. 6(a) -
o, oo5cz1. Mix in a ratio such that
The mixture 71 was applied to the inner surface of a glass tube 72 having a tube diameter of 251nTn shown in FIG. and photometry was performed. These measurement results are summarized in Table 3 in comparison with the conventional example.

Table 2 Table 3 The conventional fluorescent lamp has a two-layer coating, with the glass tube side coated with manganese-activated fluorogermanite phosphor, and the second layer coated with antimony and manganese-activated calcium phosphor. .

The fluorescent lamp according to the present invention has an initial luminous flux of 360 to 365C6.
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 Fluorescent materials with symbols A', B, C, and D in Table 2 were used as shown in Figure 6(b).
When the color temperature is 3000, the deviation is -〇, 005ctzv'
Mix in a ratio such that ll, and use that mixture,
A fluorescent lamp was produced as a prototype in the same manner as in Example 1, and colorimetry and photometry were performed. 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 comprises a divalent europium-activated barium-calcium-magnesium halophosphate phosphor, a tin-activated pressurized strontium-lambum-magnesium phosphate phosphor, and a manganese phosphor. Activated magnesium fluorogermanite phosphor, 570-575
By using a mixed phosphor of four types of antimony- and manganese-activated calcium halophosphate phosphors, the present invention has the excellent effect of increasing the total luminous flux by 10 C% with a single coated phosphor layer. Moreover, divalent europium-activated barium/calcium halophosphate and magnesium phosphors have 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 also 7.
By using this phosphor, which is improved by ~9 and is also very inexpensive, the amount of extremely expensive manganese-activated magnesium fluorogermanite phosphor used can be reduced to 2 of the total amount of phosphor used.
It has an effect that can be suppressed relatively. Furthermore, since a single layer of coating was applied to the lamp manufacturing surface, 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]

FIG. 1 is a line showing the relationship between the number of gram atoms of the phosphor magnesium used in the fluorescent lamp according to the present invention, relative brightness (1), maintenance rate (2), and maintenance rate (3). Similarly, Figure 2 is a diagram showing the relationship between the gram and gram atoms of calcium and relative brightness, Figure 3 is a diagram showing the relationship between the number of grams atoms of europium and relative brightness, and Figure 4 is a diagram showing the relationship between the number of grams atoms and relative brightness of europium. FIG. 5 is a diagram showing the emission spectrum of the above-mentioned fluorescent material under 254 nm ultraviolet irradiation. A comparison of the spectral energy distribution of the lamp shown in No. 2 with that of the conventional (two-layered cloth) lamp is shown in the characteristic diagram. FIG. 3 is a cross-sectional view of the fluorescent lamp of the present invention. 71... Fluorescent material 72... Glass tube 73.7
4...Discharge Goku (7317) Representative Patent Attorney Nori Chika Atsuke (and 1 others)
Name) Fig. 1 Mg (Gela, J, child) Fig. 2 Cα (Gra 4 I)

Claims (1)

[Claims] ■ General formula, M5-xX('PO<)s:Bu (xX
In the formula, M is composed of three types of Ba, Ca, and Mg, each consisting of 3.0 to 4.5 gram atoms of Ba, 0.5 to 20 gram atoms of Ca, and 0.01 to 1.0 gram atoms of Mg
X is F, C1. Br alone or a mixture of two or more, and 0
．． 01<x≦0,2. ), 480-50
The first alkaline earth metal halophosphate activated with divalent europium has an emission peak in the wavelength range of 0.01 m.
a second phosphor having an emission peak in the wavelength range of 4801570 to 575 nm;
a third phosphor having an emission peak in a wavelength range of 650
A fluorescent lamp characterized in that a fourth phosphor having an emission peak in a wavelength range of ~55 Qnm is adhered to a mixing port and an inner surface of a glass tube. ■ The second phosphor is an antimony- and manganese-activated calcium halophosphate phosphor, the third phosphor is a tin-activated pressurized nutrontheum, magnesium phosphate phosphor, and the fourth
2. A fluorescent lamp according to claim 1, wherein the phosphor is a manganese-activated magnesium fluorogermanite phosphor.