JPH0260705B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a luminescent composition for fluorescent lamps that emits light when stimulated by ultraviolet rays, has a color temperature in the range of 2500K to 8000K, and has high efficiency and high color rendering. and a fluorescent lamp using this.

[Prior Art and its Problems] Antimony and manganese co-activated calcium halophosphate phosphors are the most commonly used phosphors in fluorescent lamps for general lighting. Although lamps using this phosphor have high luminous efficiency,
Its color rendering property is white (color temperature of fluorescent lamp emission color).
4200K), average color rendering index Ra = 63, and daylight color (color temperature of fluorescent lamp emitted color)
6700K) and has a very low average color rendering index Ra of around 77, making it unsuitable for use in places where high color rendering is required.

Fluorescent lamps with relatively high color rendering properties include a combination of three types of narrow-band light-emitting phosphors having emission peaks around 450 nm, 545 nm, and 610 nm, as disclosed in Japanese Patent Publication No. 58-21672. Three-wavelength fluorescent lamps are manufactured.

This three-wavelength fluorescent lamp uses a divalent europium-activated alkaline earth aluminate phosphor, a divalent europium-activated alkaline earth chloroapatite phosphor, etc. as a blue phosphor, and a green phosphor as a green phosphor. As a red phosphor, a lanthanum phosphate phosphor co-activated with cerium and terbium, a phosphor of magnesium aluminate co-activated with cerium and terbium, etc., and a trivalent europium-activated yttrium oxide phosphor as a red phosphor. Color rendering index Ra
=82, and a fluorescent lamp with high luminous efficiency was developed,
It has become a market.

However, compared to fluorescent lamps using antimony- and manganese-activated calcium halophosphate phosphors, which are currently most commonly used, this three-wavelength fluorescent lamp has significantly improved luminous flux, but the color rendering Sexuality is still not completely satisfying,
Furthermore, because blue, green, red, and three colors of phosphor use rare earth raw materials, the phosphor is significantly more expensive than antimony and manganese co-activated calcium halophosphate phosphor, which is several tens of times more expensive. There is a drawback.

In general, lamps with high color rendering properties are classified into DL (Ra≧75), SDL (Ra
≧86), EDL (Ra≧95) type, and JISZ9301, and fluorescent lamps using various combinations of phosphors are known.

For example, the fluorescent lamp disclosed in Japanese Unexamined Patent Publication No. 102073/1980 has an average color rendering index Ra=99 by combining four types of phosphors. Similarly, 5
Fluorescent lamps with Ra≧95 are also being developed using one or six types of phosphors. However, the luminous flux of these high color rendering fluorescent lamps is only 40W.
The FL40S lamp was only about 1,800 to 2,300 Lm, which had the disadvantage of significantly lower luminous efficiency.

Furthermore, Japanese Patent Application Laid-Open No. 60-220546 also describes a fluorescent lamp with high color rendering properties that is a mixture of four types of phosphors. The high color rendering fluorescent lamp disclosed in this publication uses the following four types of phosphors □1 to □4 to achieve an average color rendering index Ra≧97.

□1 First phosphor Strontium yttrium aluminate activated with divalent europium Strontium aluminate activated with divalent europium □2 Second phosphor Tin activated strontium/magnesium orthophosphate □3 Third phosphor With antimony Activated calcium halophosphate Antimony/manganese activated calcium halophosphate□4 Fourth phosphor Divalent europium activated strontium/calcium halophosphate The high color rendering fluorescent lamp described in this publication has a blue-green luminescent component. As a result, a divalent europium-activated strontium yttrium aluminate phosphor with a half width of 65 nm is used, thereby achieving an average color rendering index of Ra≧97.

The high color rendering fluorescent lamp disclosed in this publication is
Although it achieves excellent color rendering, the maximum total luminous flux of a 40W lamp is 2400 Lm, and a high color rendering fluorescent lamp with even better luminous flux is required.

As mentioned above, attempts have been made to improve the average color rendering index Ra of conventional fluorescent lamps. Currently, there is no fluorescent lamp that can do this.

The present invention was made to address these problems, and an object of the present invention is 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. shall be.

[Means for Solving the Problems] In order to solve the problems, the present invention aims to change the main peak wavelength of light emitted from 253.7 nm ultraviolet excitation to 460 nm to 460 nm as a blue light emitting component used in a multi-component mixed fluorescent lamp. 510 nm, and the half width of the emission spectrum is 50 nm or more, and
The emission chromaticity coordinates are within the range of x: 0.10≦x≦0.30, y: 0.20≦y≦0.40 in the CIE1931 chromaticity diagram, and the spectral reflectance of the magnesium oxide smoke film is 100%. In this case, a blue-emitting phosphor with a spectral reflectance of 70% or more in the 380 nm to 500 nm range is used.

Furthermore, the weight mixing ratio of the blue-emitting phosphors is specified within the region indicated by the solid line in FIG. Fluorescent compositions with mixing ratios outside the range shown in FIG. 1 have a low average color rendering index Ra, and do not provide a preferable color rendering property. The amount of blue phosphor mixed is
The region shown in FIG. 1 is specified in consideration of luminous flux, color rendering properties, and price.

Further, the present invention includes a phosphor having a main emission wavelength between 530 nm and 550 nm as a green emission component and a half width of the emission spectrum of 30 nm or less, and a phosphor with a main emission wavelength between 600 nm and 660 nm as a red emission component. , contains a phosphor whose emission spectrum has a half-width of 10 nm or less.

[Operation and Effect] In order to clarify the operation and effect of the present invention, the present inventors produced the following luminescent composition as a trial.

As a blue light-emitting component, the peak wavelength of light emitted by excitation of 253.7nm ultraviolet light is between 460nm and 510nm, and the half-value width of the emission spectrum is
50nm or more, and the chromaticity coordinates of the emission spectrum are
In CIE1931 chromaticity diagram, 0.10≦x≦0.30, 0.20≦y
≦0.40, and the spectral reflectance from 380nm to 500nm is the same as that of the magnesium oxide smoke film.
Phosphors ~ were used as examples of blue phosphors that were 70% or more when expressed as 100%.
One or more of the following phosphors are mixed, and the weight mixture ratio is specified in the area indicated by the solid line in FIG.

Antimony-activated calcium halophosphate blue phosphor, magnesium tungstate blue phosphor, titanium-activated barium pyrophosphate blue phosphor, divalent europium-activated barium magnesium silicate phosphor, and the spectral reflectance of these phosphors. Shown in Figure 3.
In this figure, curve A is antimony-activated calcium halophosphate blue phosphor, curve B is magnesium tungstate blue phosphor, curve C is titanium-activated barium pyrophosphate blue phosphor, and curve D is 2
Figure 2 shows the reflectance of a valent europium-activated barium magnesium silicate phosphor.

In addition, as a green emitting component, an example of a green phosphor whose main peak wavelength of emission is between 530 nm and 550 nm and whose emission spectrum half width is 30 nm or less is cerium and terbium coactivated lanthanum phosphate green. The phosphor and the cerium- and terbium-coactivated magnesium aluminate green phosphor were used alone or in combination.

Furthermore, as an example of a red phosphor having a main peak wavelength of emission between 600 nm and 660 nm and a half width of the emission spectrum of 10 nm or less as a red light emitting component, one or more of the following phosphors can be used. A mixture of multiple types was 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-activated germanium fluoride Magnesium oxide red phosphor This fluorescent lamp has the excellent characteristics shown in FIGS. 6 and 7, and achieves the characteristics superior to the conventional fluorescent lamp shown in FIG. 8.

That is, the fluorescent lamp of the present invention has an initial luminous flux improved by several to more than ten percent, and an average color rendering index of
Compared to the conventional 63-76, it is 89-95, an improvement of about 20. 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 increased from 82 to 89.
95, and moreover, compared to the blue-emitting phosphor used in three-wavelength fluorescent lamps, a large amount of inexpensive blue-emitting phosphor can be used, so the price of the fluorescent composition can be halved.

Furthermore, conventional natural color fluorescent lamps (color rendering AA type)
Compared to the fluorescent lamp of the present invention, the average color rendering index is almost the same and the initial luminous flux is improved by about 50%.
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, blue component phosphors (first phosphors, B1, B2, B3, B4) and green component phosphors (second phosphors, G1, G2) shown in FIG.
and 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 FIG. 5 are mixed at the mixing weight ratio shown in FIGS. 6 and 7 to form a luminescent composition, and this luminescent composition is poured into a glass tube with a tube diameter of 32 mm ( FL40S) was coated to form a fluorescent film, and a 40 watt straight tube fluorescent lamp was created.

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

Dissolve nitrocellulose [100 g] in butyl acetate [9.900 g]. Collect 500 g of this solution into two beakers, and add about 500 g of the phosphor composition of the present invention.
Stir g well to prepare a coating solution.

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

Next, the coated glass tube is baked for 10 minutes in an electric furnace heated to 600 degrees to burn off the nitrocellulose.

Furthermore, a filament was attached to each glass tube, 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 FIGS. 6 and 7 together with the phosphor mixture weight ratio.

As shown in FIGS. 6 and 7, Examples 1 to 60
The fluorescent lamp of the present invention obtained in the above has an average color rendering index Ra of about 90 or more, and an initial luminous flux using antimony and manganese co-activated calcium halophosphate as the fluorescent film, which is currently the most commonly used fluorescent lamp. Improved compared to fluorescent lamps.

The color temperature of the luminescent composition of the present invention and the fluorescent lamp using the composition can be adjusted by adjusting the mixing ratio of the blue luminescent component. As shown in Figures 6 and 7,
Decreasing the mixing ratio of the blue emitting component and increasing the mixing ratio of the red emitting component lowers the color temperature; conversely, increasing the mixing ratio of the blue emitting component and decreasing the mixing ratio of the red emitting component, You can increase the color temperature.

Typically, the color temperature of fluorescent lamps is adjusted to a range of 2500-8000K. Therefore, in the luminescent composition of the present invention and the fluorescent lamp using the same, the mixing ratio of the blue luminescent component is specified in the range shown by the solid line in FIG.

Furthermore, in order to achieve excellent luminous output and high color rendering properties, the luminescent composition of the present invention and the fluorescent lamp using the composition have the following characteristics: the main emission wavelength of the blue luminescent component, the half width of the emission spectrum, and the x value. and the y value. The x value and y value of the blue luminescent component are 0.10≦x
High color rendering properties can be achieved when the range is ≦0.30, 0.20≦y≦0.40, 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; Even if the value width is 50 nm or less, excellent luminous output and high color rendering properties cannot be achieved.

Furthermore, in the present invention, the spectral reflectance of the blue light emitting component is adjusted to a wavelength of 380 so that the blue light emitting component effectively reflects the emitted light and the phosphor itself does not absorb the emitted color.
In the range of ~500 nm, it is specified to be 70% or more for the magnesium oxide smoked film, but if a blue light emitting component with a spectral reflectance of less than this is used, a light emitting composition with excellent light output will be obtained. It can't be achieved.

As shown by curves A, B, C, and D in FIG. 3, antimony-activated calcium halophosphate blue phosphor,
The magnesium tungstate blue phosphor, the titanium-activated barium pyrophosphate blue phosphor, and the divalent europium-activated barium magnesium silicate phosphor have a preferable reflectance as the blue light-emitting component of the present invention, as shown in FIG. Like, 380nm
A divalent europium-activated strontium borate phosphor (curve E) and a divalent europium-activated strontium aluminate phosphor (curve F), whose reflectance decreases at ~500 nm, are used as the blue-emitting component of this invention. Can not.

Further, in the luminescent composition of the present invention, a blue luminescent component is mixed with a green luminescent component and a red luminescent component having specific luminescent properties, thereby realizing excellent luminescent output and high color rendering properties as a whole.

[Brief explanation of drawings]

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, Figure 3 is a graph showing the spectral reflection characteristics of the phosphor used as a blue luminescent component in the luminescent composition of the present invention, Figure 4.
Figure 5 is a graph showing the spectral reflectance of a blue-emitting phosphor that is not used as a blue-emitting component in the luminescent composition of the present invention; Figure 5 is a chart showing specific examples of the phosphor used in the luminescent composition of the present invention; FIGS. 6 and 7 are charts showing the luminescent properties of the luminescent compositions according to examples of the present invention, and FIG. 8 is a chart showing the luminescent properties of a conventional phosphor.

Claims (1)

[Scope of Claims] 1. A blue light-emitting component used in a multi-component mixed fluorescent lamp, which emits light in the blue region upon excitation of ultraviolet light at 253.7 nm, whose main emission wavelength is between 460 nm and 510 nm, and whose emission spectrum is The half width is 50 nm or more, and the chromaticity coordinates of the emission spectrum are CIE1931.
In the chromaticity diagram, it is within the range of 0.10≦x≦0.30, 0.20≦y≦0.40, and the smoke film of magnesium oxide is 100%.
%, the spectral reflectance from 380nm to 500nm is 70
% or more of phosphor, and has a main emission wavelength of 530 nm or more as a green emitting component.
550nm, and the half width of the emission spectrum is
Contains a phosphor with a wavelength of 30 nm or less, and has a main emission wavelength of 600 nm or more as a red light emitting component.
660nm, and the half width of the emission spectrum is
It is characterized by containing a phosphor with a diameter of 10 nm or less, and mixing a blue light-emitting component in a proportion within the range surrounded by the solid line in attached Figure 1 according to the color temperature of the multi-component mixed fluorescent lamp. Luminescent composition for fluorescent lamps. 2. A fluorescent lamp characterized in that a fluorescent film contains the luminescent composition for a fluorescent lamp according to claim 1.