JPH01156391A - Luminescent composition for fluorescent lamp and fluorescent lamp using said composition - Google Patents

Abstract

PURPOSE:To produce the title luminescent compsn. having high luminous efficiency and satisfactory color rendering and capable of being produced at a low cost, by incorporating a particular proportion of a particular blue luminescent component as a blue luminescent component used for a multicomponent mixture type fluorescent lamp. CONSTITUTION:This luminescent composition is prepd. by incorporating the following compound as a blue luminescent component of a multicomponent mixture type fluorescent lamp. Said compound emits a color in a blue region upon being excited by UV at 253.7nm. Its main luminescent wavelength is 460-510nm, the half-value width of the emission spectrum is 50nm or more, the chromaticity coordinate of the emission spectrum is 0.10<=x<=0.30 and 0.20<=y<=0.40 in a CIE 1931 chromaticity diagram, and the spectral reflectance at 380-500nm is 70% or more when a deposited MgO film is supposed to be 10%. The compound is mixed in a proportion defined by solid lines in the diagram depending upon the color temp. in the fluorescent lamp. Examples of the blue phosphor include an Sb-activated calcium halophosphate blue phosphor and magnesium tungstate blue phosphor.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention emits light when stimulated by ultraviolet rays and has a color temperature of 250.
The present invention relates to a luminescent composition for a fluorescent lamp having a high efficiency and high color rendering in the range of 0 to 8000, and a fluorescent lamp using the same.

[Prior art and its problems] Antimony and manganese co-activated calcium halophosphate phosphors are the phosphors most commonly used in fluorescent lamps for general lighting. Although lamps using this phosphor have high luminous efficiency, their color rendering properties are white (color temperature of fluorescent lamp emission color: 4200K), average color rendering index Ra = 83, and daylight color (fluorescent color). The color temperature of the lamp emission color is 6700 K), and the average color rendering index Ra
= = about 77, which is very low, making it unsuitable for use in places where high color rendering properties are required.

As a fluorescent lamp having a relatively high color rendering property, a fluorescent lamp such as 45, as disclosed in Japanese Patent Publication No. 5B-21672,
Three-wavelength fluorescent lamps have been manufactured using a combination of three types of narrow-band emitting phosphors having emission peaks around 0 nm, 545 nm, and 610 nm.

This three-wavelength fluorescent lamp uses blue phosphor as
A divalent europium activated alkaline earth aluminate phosphor, a divalent europium activated alkaline earth chloroapatite phosphor, etc. are used as a green phosphor, a cerium and terbium coactivated lanthanum phosphate phosphor, cerium,
Terbium co-activated magnesium aluminate phosphor, etc.
In addition, a trivalent europium-activated yttrium oxide phosphor is used as the red phosphor, and the average color rendering index Ra is 82.
Fluorescent lamps with high luminous efficiency have been developed and put on the market.

However, compared to fluorescent lamps that use antimony- and manganese-activated calcium halophosphate fluorescent lamps, which are currently the most commonly used fluorescent lamps,
Although the luminous flux has been significantly improved, the color rendering properties are still not fully satisfactory.Furthermore, since the phosphor uses rare earth raw materials for blue, green, red, and three colors, antimony and manganese are used. It has the disadvantage that it is significantly more expensive than a co-activated calcium halophosphate phosphor, which is several tens of times more expensive.

In general, what is called a high color rendering lamp is DL (Ra≧75), SDL (R
a≧86), EDL (Ra≧95) type, and JISZ
9301, and fluorescent lamps using various combinations of phosphors have been known so far.

For example, the fluorescent lamp disclosed in Japanese Patent Application Laid-Open No. 54-102073 has an average color rendering index Ra=99 by combining four types of phosphors. Similarly, fluorescent lamps with Ra≧95 using five or six types of phosphors are also being developed.

However, the luminous flux of these high color rendering fluorescent lamps is
The 40W lamp FL40S has only about 1,800 to 2,300 Lm, which has the drawback of significantly lower luminous efficiency.

[Objective of the Invention] As described above, in conventional fluorescent lamps, attempts have been made to improve the average color rendering index Ra. Moreover, at present, a fluorescent lamp that can be manufactured at low cost has not been obtained.

The present invention has been made to address these problems,
It is an object of the present invention to provide a luminescent composition and a fluorescent lamp that have high luminous efficiency and sufficiently satisfactory color rendering properties and can be manufactured at low cost.

[Means for Solving the Problems] In order to solve the problems, the present invention uses 253.
The main peak wavelength of emission due to 7 nm ultraviolet excitation is 460
nm to 510 nm, the half width of the emission spectrum is between 50 nm to 175 nm, and the emission chromaticity coordinate is x: 0.10≦x≦0.30 in the CIE 1931 chromaticity diagram. , y: o, within the range of 20≦y≦0.40, and when the spectral reflectance of the magnesium oxide smoke film is 100%, the spectral reflectance from 380 nm to 500 nm is 70%.
The above blue-emitting phosphor is used.

Furthermore, the weight mixing ratio of the blue-emitting phosphors is specified within the region indicated by the solid line in FIG. 1st
Fluorescent compositions with mixing ratios outside the range shown in the figure have a low average color rendering index Ra, and preferred color rendering properties cannot be obtained. The mixing amount of the blue phosphor is specified in the range shown in FIG. 1 in consideration of luminous flux, color rendering properties, and price.

[Operation and Effect] In order to clarify the operation and effect of this invention, the present inventors have
The following luminescent composition was experimentally produced.

As a blue light emitting component, the peak wavelength of light emitted by excitation of 253.7 nm ultraviolet light is between 460 nm and 510 nm, and the half width of the emission spectrum is between 50 nm and 510 nm.
175 nm, and the chromaticity coordinate of the emission spectrum is C
In IE1931 chromaticity diagram, 0°10≦x≦0.30.0
．． Within the range of 20≦y≦0.40, and from 380 nm to
Phosphors ① to ① were used as examples of blue phosphors whose spectral reflectance at 500 nm was 70% or more when the spectral reflectance of the smoked film of magnesium oxide was 100%.

One or more of the following phosphors (1) to (2) are mixed, and the weight mixing ratio thereof is specified in the area indicated by the solid line in FIG.

■ Antimony-activated calcium herophosphate blue phosphor, ■ Magnesium tungstate blue phosphor, ■ Titanium-activated barium birophosphate blue phosphor, ■ Divalent europium-activated barium magnesium silicate phosphor, etc. The spectral reflectance is shown in Figure 3.

In this figure, curve A is an antimony-activated calcium birophosphate blue phosphor, curve B is a magnesium tungstate blue phosphor, curve C is a titanium-activated barium birophosphate blue phosphor, and the curved line is a divalent europium-activated blue phosphor. The reflectance of active barium magnesium silicate phosphor is shown.

In addition, as a green luminescent component, the main peak wavelength of luminescence is 53
Examples of green phosphors whose wavelength is between 0 nm and 550 nm and whose emission spectrum has a half width of 30 nm or less include cerium and terbium coactivated lanthanum phosphate green phosphors and cerium and terbium coactivated aluminic acid. Magnesium green phosphor was used alone or in combination.

Furthermore, as a red luminescent component, the main peak wavelength of luminescence is 60
As an example of a red phosphor having a wavelength between 0 nm and 660 nm and a half-value width of an emission spectrum of 10 nm or less, one type or a mixture of two or more of the following phosphors were used.

■ Trivalent europium-activated yttrium oxide red phosphor, ■ Trivalent europium-activated phosphoric acid, yttrium vanadate red phosphor, ■ Trivalent europium-activated yttrium vanadate red phosphor, ■ Divalent manganese attached Active Magnesium Fluorogermanate Red Phosphor This fluorescent lamp has the excellent properties shown in Table 2, and achieves the properties shown in Table 3 that are superior to conventional fluorescent lamps.

That is, the fluorescent lamp of the present invention has an initial luminous flux improved by several to several percent compared to the fluorescent lamp for general illumination that is most commonly used at present, and an average color rendering index of 63 to 76 compared to the conventional one. That's an improvement of about 20 points, from 89 to 95. In addition, although the fluorescent lamp of the present invention has a somewhat lower initial luminous flux than a conventional three-wavelength fluorescent lamp, the average color rendering index has significantly improved from 82 to 89-95, and moreover, Compared to the blue-emitting phosphor used in three-wavelength fluorescent lamps, cheaper blue-emitting phosphors can be used in large quantities.
The price of fluorescent compositions can be halved. Furthermore, compared to conventional natural color fluorescent lamps (color rendering AA type), the fluorescent lamp of the present invention has approximately the same average color rendering index and an initial luminous flux of approximately 50%.
It also improves. Furthermore, the fluorescent lamp of the present invention has a somewhat lower color rendering property than a conventional high color rendering fluorescent lamp (color rendering AAA type), but its initial luminous flux is improved by about 50%.

[Preferred Embodiments] Hereinafter, embodiments of the present invention will be described based on the drawings.

First, the blue component phosphor shown in Table 2 (first phosphor, B
1, B2, B3, B4), a green component phosphor (second phosphor, G1, G2), and a red component phosphor (third phosphor, R1, R2, R3, R4) are prepared. . The energy distribution diagram of the blue component phosphors B1, B2, B3, and B4 is shown in FIG.

The phosphors shown in Table 1 are mixed at the mixing weight ratio shown in Table 2 to form a luminescent composition, and this luminescent composition is applied to a glass tube (FL4O8) with a tube diameter of 32 mm in the same manner as before. A 40 watt straight tube fluorescent lamp was fabricated using this as a fluorescent film.

That is, a fluorescent lamp was prototyped in the following steps.

Butyl acetate [9,900g] and nitrocellulose [10
Dissolve 0g1. 500 g of this solution is collected into two beakers, and about 500 g of the phosphor composition of the present invention is thoroughly stirred to prepare a coating solution.

This coating solution was injected from the top of each of five 40-watt glass tubes with a diameter of 32 mm and coated on the inner surfaces, and then dried. The average weight of the five coatings is 5.3
It was g.

Next, these coated glass tubes are baked for 10 minutes in an electric furnace heated to 600 degrees to burn off the nitrocellulose. Furthermore, each glass tube was fitted with a filament, placed on an exhaust stand, and Ar and Hg were injected to produce an FL40S type fluorescent lamp.

The obtained fluorescent lamp was subjected to photometry, and the measurement results are shown in Table 2 together with the phosphor mixture weight ratio.

As shown in Table 2, the fluorescent lamps of the present invention obtained in Examples 1 to 60 have an average color rendering index Ra of about 90 or more, and an initial luminous flux due to antimony and manganese co-activation. This is an improvement over the currently most commonly used fluorescent lamp, which uses calcium phosphate as a fluorescent film.

The luminescent composition of this invention and the fluorescent lamp using the same are:
Color temperature can be adjusted by adjusting the mixing ratio of blue light emitting components.

As shown in Table 2, when the mixing ratio of the blue-emitting component is decreased and the mixing ratio of the red-emitting component is increased, the color temperature decreases; By reducing the mixing ratio of the components, the color temperature can be increased. Typically, the color temperature of fluorescent lamps is adjusted to a range of 2,500 to 8,000 degrees Celsius. Therefore, the luminescent composition of the present invention and the fluorescent lamp using the same have a mixing ratio of blue luminescent components that is
It is specified in the area shown by the solid line in the figure.

Furthermore, in order to achieve excellent light output and high color rendering properties, the luminescent composition of the present invention and the fluorescent lamp using the composition have the main emission wavelength of the blue luminescent component, the half-width of the emission spectrum,
The X value and y value are specified. X value and y of blue luminescent component
0.10≦x≦0.30.0.20≦y≦0.
40, high color rendering properties can be achieved, and if the main emission wavelength of the blue light emitting component is too long or too short, excellent color rendering properties cannot be achieved, and furthermore, if the half-value width is 50 nm or less, However, it is not possible to achieve excellent light output and high color rendering properties.

Furthermore, in the present invention, the spectral reflectance of the blue light emitting component is adjusted in the wavelength range of 380 to 500 nm so that the blue light emitting component effectively reflects the emitted light and the phosphor itself does not absorb the emitted color. Although it is specified that the blue light emitting component has a spectral reflectance of 70% or more relative to the magnesium oxide smoked film, if a blue light emitting component having a spectral reflectance lower than this is used, a light emitting composition with excellent light emitting output cannot be realized.

As shown by curves A, B, C, and D in Figure 3, antimony-activated calcium halophosphate blue phosphor, magnesium tungstate blue phosphor, titanium-activated barium pyrophosphate blue phosphor, divalent europium-activated silicon The barium magnesium oxide phosphor has a preferable reflectance as the blue emitting component of the present invention, but as shown in FIG. 4, the reflectance decreases in the range of 380 nm to 500 nm.
A valent europium-activated strontium borate phosphor (curve E) and a divalent europium-activated strontium aluminate phosphor (curve F) cannot be used as the blue-emitting component of this invention.

Further, in the luminescent composition of the present invention, a green luminescent component and a red luminescent component having specific luminescent characteristics are mixed with the blue luminescent component -15=, thereby realizing excellent light output and high color rendering properties as a whole. ing.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the mixing weight ratio range of the blue component phosphor used in the fluorescent lamp of the present invention, and FIG. 2 is a graph showing the spectral emission characteristics of the blue component phosphor used in the fluorescent lamp of the example of the present invention. Graph, FIG. 3 is a graph showing the spectral reflection characteristics of the phosphor used as the blue emitting component in the luminescent composition of the present invention, and FIG. 4 is a graph showing the spectral reflection characteristics of the phosphor used as the blue luminescent component in the luminescent composition of the present invention. FIG. 5 is a graph showing specific examples of phosphors used in the luminescent composition of the present invention, and FIGS. 6 and 7 are graphs showing the spectral reflectance of the luminescent composition of the present invention. FIG. 8 is a chart showing the light emitting characteristics of a conventional phosphor.

Claims (4)

[Claims] (1) The blue light emitting component used in a multi-component mixed fluorescent lamp emits light in the blue region upon excitation of ultraviolet light at 253.7 nm, the main emission wavelength is between 460 nm and 510 nm, and the half width of the emission spectrum is 50 nm or more, and the chromaticity coordinates of the emission spectrum are 0.10≦x≦0.30, 0.20≦y≦0 in the CIE1931 chromaticity diagram.
It is within the range of 40, and the smoke film of magnesium oxide is 10
When set to 0%, the spectral reflectance from 380 nm to 500 nm is 70% or more, and the ratio is within the range surrounded by the solid line in attached Figure 1 according to the color temperature of the multi-component mixed fluorescent lamp. A luminescent composition comprising a mixture of a blue luminescent component. (2) The multicomponents used in the above multicomponent mixed fluorescent lamp include a green light emitting component with a main emission wavelength between 530 nm and 550 nm and a half width of the emission spectrum of 30 nm or less, and a green light emission component with a main emission wavelength between 600 nm and 660 nm. 2. The luminescent composition according to claim 1, wherein the luminescent composition comprises at least a red luminescent component having an emission spectrum with a half-width of 10 nm or less. (3) It emits light in the blue region upon excitation of ultraviolet light at 253.7 nm, the main emission wavelength is between 460 nm and 510 nm, the half width of the emission spectrum is 50 nm or more, and the chromaticity coordinates of the emission spectrum are CIE1931 colors. In the degree diagram, 0.10≦x≦0.30, 0.20≦y≦0.40
and the smoke film of magnesium oxide is within the range of 1
00%, a luminescent composition made by mixing blue luminescent components with a spectral reflectance of 70% or more in the range of 380 nm to 500 nm at a ratio within the range enclosed by the solid line in attached Figure 1 according to the set color temperature. A fluorescent lamp characterized by having a substance as a fluorescent film. (4) The luminescent composition has a main emission wavelength of 530 nm to 5 nm.
50 nm, and a green emission component with a half width of the emission spectrum of 30 nm or less, and a main emission wavelength of 600 nm to 66 nm.
4. The fluorescent lamp according to claim 3, wherein the fluorescent lamp is mixed with at least a red light-emitting component whose emission spectrum has a half-width of 10 nm or less.