JPH09139191A - Luminescent composition and fluorescent lamp using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive red light emission fluorescent lamp by reducing the applying quantity of expensive deep red light emission phosphor. SOLUTION: A light emission compound mixing deep red light emission phosphor, ultra-violet ray reflection material, and yellow pigment having the following specific spectrum reflection rate is applied to the inner face of a fluorescent lamp glass tube: The spectrum reflection rate in 450nm is 10 to 35%, The spectrum reflection rate in 500nm is 50 to 80%, The spectrum reflection rate in 550nm is 75 to 100%, and; The spectrum reflection rate in 600nm is 75 to 100%. The spectrum reflection rate in each wave length is a value measured assuming that the value of the spectrum reflection rate in each wave length of standard white barium sulfate is 100%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a luminescent composition obtained by diluting an expensive deep red luminescent phosphor with an inexpensive ultraviolet reflecting substance and further coloring it with a specific yellow pigment, and a fluorescent lamp using the same. .

[0002]

2. Description of the Related Art A deep red light emitting phosphor for a fluorescent lamp includes
Manganese-activated magnesium arsenate phosphor and manganese-activated magnesium fluorogermanate phosphor have been used, but in recent years, manganese-activated magnesium arsenate phosphor is no longer produced due to its toxicity, A manganese-activated magnesium fluorogermanate phosphor is mainly used. However, since the manganese-activated magnesium fluorogermanate phosphor is very expensive, a phosphor capable of realizing deep red light emission obtained at low cost has been desired.

On the other hand, it is possible to reduce the amount of expensive phosphors used by mixing and diluting an inorganic substance which is a white substance in the range of 10 to 230% with respect to the weight of the phosphors. JP-A-57-128452 Is disclosed in. It is described that calcium pyrophosphate, orthophosphate, or a mixture of both can be used as the white powder inorganic substance. Further, a fluorescent lamp having a fluorescent layer in which the fluorescent layer on the inner surface of the bulb is composed of a fluorescent substance and an ultraviolet-reflecting material, and the proportion of the ultraviolet-reflecting material is set to 30 to 95% by weight of the whole, is disclosed in JP-A-58-58. 218745
It is possible to reduce the amount of expensive phosphors disclosed in Japanese Patent Laid-Open Publication No. 2003-242242, and the ultraviolet reflecting material is specifically titanium oxide (TiO 2).
2), alumina (Al2O3), magnesium oxide (Mg
O), calcium pyrophosphate (Ca2P2O7) and the like can be used.

Using these techniques, a deep red light-emitting phosphor, manganese-activated magnesium fluorogermanate phosphor is mixed with an ultraviolet-reflecting substance (white powder inorganic substance), and the phosphor is diluted to increase the fluorescence. We tried to reduce the manufacturing cost of the lamp. Furthermore, it was examined to apply the ultraviolet-reflecting substance to the first layer (the layer in contact with the inner surface of the glass tube) and the deep red light emitting phosphor to the second layer (on the first layer). As a result, even if the absolute amount of the phosphor was reduced by diluting with the ultraviolet reflecting substance, the decrease in the luminous flux of the fluorescent lamp was not a problem as expected.

However, as a result of increasing the amount of the deep red light emitting phosphor diluted, a new problem of color tone shift occurs. The problem is that the deep red color inherent to the manganese-activated magnesium fluorogermanate phosphor cannot be obtained, and the emission color of the lamp is drawn toward pink or purple. This problem occurs when blue-violet luminescence in the visible region due to mercury vapor discharge is added to deep red luminescence due to phosphor emission. Such a problem can be avoided by correcting the phosphor component ratio in a fluorescent lamp such as a three-wavelength type fluorescent lamp and a deluxe type fluorescent lamp that utilizes light emission by mixing multi-component phosphors. However, in the case of utilizing the light emission of the deep red light emitting phosphor having a high color purity alone, it is not possible to correct the color shift by mixing the other color phosphors.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems, and even if the manganese-activated magnesium fluorogermanate fluorophore is diluted with an ultraviolet-reflecting substance and the amount thereof is increased, It is an object of the present invention to provide a luminescent composition which does not significantly deviate from the target in luminescence chromaticity and has a manufacturing cost reduction effect, and a fluorescent lamp using the same.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors in order to solve the above-mentioned problems, as a result, visible light emitted from a mercury ray is efficiently absorbed and the brightness of a fluorescent lamp is not significantly reduced. The inventors have newly found that a specific yellow pigment is added to and mixed with the deep red light-emitting phosphor and the ultraviolet reflecting substance, and thus have completed the present invention.

That is, the luminescent composition of the present invention is a mixture of a deep red light emitting phosphor, an ultraviolet reflecting substance, and a yellow pigment having the following spectral reflectance, and the ratio of the deep red light emitting phosphor is It is in the range of 25 to 75% by weight based on the total weight of the light emitting composition, the proportion of the ultraviolet reflective material is in the range of 25 to 75% by weight, and the proportion of the yellow pigment is 0.1 to 3.0. It is characterized by being in the range of% by weight. Spectral reflectance at 450 nm is 10 to 35% Spectral reflectance at 500 nm is 50 to 80% Spectral reflectance at 550 nm is 75 to 100% Spectral reflectance at 600 nm is 75 to 100% (however, the spectral reflectance at each wavelength is (Value measured with the spectral reflectance value at each wavelength of standard white barium sulfate as 100%)

The spectral reflectance characteristic of the yellow pigment is particularly important, and the effect of the present invention is expected only when the yellow pigment having the spectral reflectance in the above range is used. Even a yellow pigment having a spectral reflectance that deviates from this range cannot be expected to have an effect. 450nm wavelength based on mercury rays
Needless to say, it is desirable that the pigment is a pigment that can sufficiently absorb the following blue-violet visible light and sufficiently reflect red visible light of 600 nm or more based on the deep red light-emitting phosphor.
In particular, the yellow pigment used in the present invention is characterized by a wavelength of 5
It is to use a material having a remarkably higher reflectance than other yellow pigments near green of 00 nm and yellow-green of wavelength 550 nm. The luminous flux of the fluorescent lamp can be kept high by using a yellow pigment having a high reflectance in the wavelength range that affects the visibility.

The addition amount of the yellow pigment is preferably about 1% by weight with respect to the weight of the ultraviolet reflecting substance. If it exceeds 3%, the degree of coloring of the ultraviolet-reflecting substance becomes too large, which leads to a significant decrease in brightness. If it is less than 0.1, the effect of the pigment cannot be expected and it cannot be practically used.

The UV-reflecting material basically means a white material having a reflectance of 90% or more in the visible region to the ultraviolet region. Such substances include titanium oxide (TiO2), alumina (Al2O3), magnesium oxide (MgO), calcium pyrophosphate (Ca2P2O).
7), lanthanum phosphate (LaPO4) and the like can be used, and a cheaper material is more preferable from the purpose of use. The mixing amount of the UV-reflecting substance is set to be in the range of 25 to 75% by weight with respect to the total weight of the light emitting composition. When the amount is 25% by weight or less, there is no great effect on cost reduction. Because it will be insufficient. Furthermore, even with a specific spectral reflectance, the mixing amount of the yellow pigment in the light emitting composition is 0.
This is because if it is 2% or less, it is too small, and as a result, the luminescent color of the lamp is attracted to purple, and conversely, if it is 2.0% or more, it is inclined to orange.

A transparent glass tube filled with an enclosing gas containing mercury and a rare gas, and a phosphor layer containing phosphor particles provided on the inner wall surface of the transparent glass tube. The fluorescent lamp of the present invention can be obtained by forming it into a fluorescent lamp provided with a means for maintaining a discharge in the sunlight in a filled gas. The light-emitting composition can be applied to the translucent glass wall surface by a conventional method of applying a phosphor, for example, for the purpose of preventing the phosphor layer from falling off, fine particles of alumina, calcium pyrophosphate, and calcium. A binder such as barium borate may also be used. The amount of the light-emitting composition applied is about the same as when the phosphor alone is applied.

Further, as an application of the present invention, it is possible to apply a two-layer coating method which has been generally used in a conventional three-wavelength fluorescent lamp for the purpose of reducing the cost of the fluorescent lamp. The point that enables this is to form not only the ultraviolet-reflecting substance on the side close to the glass surface, but also a layer mixed with the yellow pigment having the above-mentioned specific spectral reflectance. As a result, the cost reduction effect is further enhanced. Here, the spectral reflectance of a yellow pigment with a specific reflectance is
The same yellow pigment as that used when the phosphor layer is formed as a single layer can be used. The optimum amount of the yellow pigment for the UV-reflecting substance is 100 g of the UV-reflecting substance.
However, when the amount of yellow pigment is less than 0.2 g, the emission color of the fluorescent lamp is attracted to purple, and conversely 3 g.
When it is more than g, the emission color is inclined to orange and the lamp brightness is lowered.

[0014]

In FIG. 1, the compounding ratio of the manganese activated magnesium fluorogermanate phosphor, which is a deep red light emitting phosphor in the light emitting composition of the fluorescent lamp of the present invention, is variously changed.
The FL40SS fluorescent lamp was produced and the results of measuring the luminous flux of the lamp are shown. The optimum amount of pigment relative to the UV-reflecting material was set to 1%. Here, the coating weight of the luminescent composition is 4
It is fixed at g. When the manganese activated magnesium fluorogermanate phosphor in the light emitting composition is 75% by weight or more,
Although the decrease in the luminous flux of the lamp is small, the merit of reducing the cost is small. On the contrary, when the manganese-activated magnesium fluorogermanate phosphor is 25% by weight or less, the cost merit is large, but the decrease of the luminous flux of the lamp is too large.

FIG. 2 shows the chromaticity points of the lamp plotted on the CIE chromaticity coordinates. The 100% manganese-activated magnesium fluorogermanate phosphor in the light-emitting composition naturally has the largest x value for the reddish component. However, when the ratio of the deep red light emitting phosphor is 50% by weight or more, x
The decrease in value is not so great.

The luminous flux of the lamp, the chromaticity of the lamp, and the cost can be selected according to the specifications of the fluorescent lamp. That is, when the color tone of the lamp is emphasized, the compounding amount of the deep red light emitting phosphor should be set to 50% or more,
When focusing on the luminous flux of the lamp, the blending ratio of the deep red light emitting phosphor should be set to 25% or more.

[0017]

【Example】

[Example 1] -Manganese-activated magnesium fluorogermanate phosphor ... 75 g-Calcium pyrophosphate (ultraviolet reflecting substance) ... 24.75 g-Titanium yellow yellow pigment ...・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.25g (Dainichiseika Product No. Dai Proxite Color Yellow 9110) The spectral reflectance curve of this yellow pigment is at 450 nm as shown by the curve a in Fig. 1. Spectral reflectance is 22%, 500n
The spectral reflectance at m is 67%, and the spectral reflectance at 550 nm is 90%. The spectral reflectance at 600 nm is 85%. (However, the spectral reflectance at each wavelength is a value measured with the value of the spectral reflectance of standard white barium sulfate at each wavelength being 100%.)

These powders were dry mixed to obtain a luminescent composition of the present invention. This luminescent composition was suspended in a nitrocellulose / butyl acetate binder to prepare a coating solution, and 3 g of the luminescent composition was applied to a glass tube for a fluorescent lamp (FL40SS) by a conventional method to prepare a fluorescent lamp according to a conventional method. did. The component ratio of the thus obtained fluorescent layer is substantially equal to the charging ratio of the luminescent composition of the coating liquid. When the obtained fluorescent lamp was measured using an integrating sphere and a spectrophotometer, the emission color of the fluorescent lamp was x = 0.561, y = 0.
296 (CIE chromaticity coordinates), and the luminous flux of the lamp is 76
It was 9 lumens.

Example 2 Manganese Activated Magnesium Fluorogermanate Phosphor: 50 g Calcium Pyrophosphate (UV Reflecting Material): 49.5 g Titanium Yellow Yellow pigment: 0.5g (Dainichiseika product number Daiproxite color yellow 9110)

These powders were dry mixed to obtain a luminescent composition of the present invention. This luminescent composition was suspended in a nitrocellulose / butyl acetate binder to prepare a coating solution, and 3 g of the luminescent composition was applied to a glass tube for a fluorescent lamp (FL40SS) by a conventional method to prepare a fluorescent lamp according to a conventional method. did. When the obtained fluorescent lamp was measured using an integrating sphere and a spectrophotometer, the emission color of the fluorescent lamp was x = 0.55.
2, y = 0.299 (CIE chromaticity coordinates), and the luminous flux of the lamp was 709 lumens.

Example 3 Manganese Activated Magnesium Fluorogermanate Phosphor: 25 g Calcium Pyrophosphate (UV Reflecting Material): 74.25 g Titanium Yellow Yellow Pigment: 0.75g (Dainichiseika Product No. Dai Proxite Color Yellow 9110)

These powders were dry mixed to obtain a luminescent composition of the present invention. This luminescent composition was suspended in a nitrocellulose / butyl acetate binder to prepare a coating solution, and 3 g of the luminescent composition was applied to a glass tube for a fluorescent lamp (FL40SS) by a conventional method to prepare a fluorescent lamp according to a conventional method. did. When the obtained fluorescent lamp was measured using an integrating sphere and a spectrophotometer, the emission color of the fluorescent lamp was x = 0.52.
4, y = 0.303 (CIE chromaticity coordinate), and the luminous flux of the lamp was 602 lumens.

[Comparative Example 1] A coating solution prepared by suspending manganese-activated magnesium fluoride germanate phosphor powder in a nitrocellulose / butyl acetate binder was prepared and applied to a glass tube for a fluorescent lamp (FL40SS) by an ordinary method. 3 g of the light emitting composition was applied, and a fluorescent lamp was manufactured according to a conventional method. When the obtained fluorescent lamp was measured using an integrating sphere and a spectrophotometer, the emission color of the fluorescent lamp was x = 0.56.
7, y = 0.291 (CIE chromaticity coordinate), and the luminous flux of the lamp was 809 lumens.

Comparative Example 2 Manganese Activated Magnesium Fluorogermanate Phosphor 25 g Calcium Pyrophosphate (UV Reflecting Material) 75 g

These powders were dry mixed to obtain a luminescent composition of the present invention. This luminescent composition was suspended in a nitrocellulose / butyl acetate binder to prepare a coating solution, and 3 g of the luminescent composition was applied to a glass tube for a fluorescent lamp (FL40SS) by a conventional method to prepare a fluorescent lamp according to a conventional method. did. When the obtained fluorescent lamp was measured using an integrating sphere and a spectrophotometer, the emission color of the fluorescent lamp was x = 0.53.
4, y = 0.277 (CIE chromaticity coordinate), and the luminous flux of the lamp was 649 lumens.

Comparative Example 3 Manganese Activated Magnesium Fluorogermanate Phosphor ... 75 g Calcium Pyrophosphate (UV Reflecting Material) 24.75 g Titanium Yellow Yellow Pigment: 0.25g (Dainichiseika Product Number: Diproxite Color Yellow 9110) The spectral reflectance curve of this yellow pigment is as shown in Fig. 1 curve b. , Spectral reflectance at 450 nm is 10%, 500n
The spectral reflectance at m is 20% and the spectral reflectance at 550 nm is 45%. The spectral reflectance at 600 nm is 65% (however, the spectral reflectance at each wavelength is a value measured with the spectral reflectance at the corresponding wavelength of barium sulfate being 100%).

These powders were dry mixed to obtain a luminescent composition of the present invention. A coating liquid was prepared by suspending this luminescent composition in a nitrocellulose / butyl acetate binder, and 3 g of the luminescent composition was applied to a glass tube for a fluorescent lamp (FL40SS) by a usual method to prepare a fluorescent lamp. When the obtained fluorescent lamp was measured using an integrating sphere and a spectrophotometer, the emission color of the fluorescent lamp was x = 0.573, y = 0.
Although it is 302 (CIE chromaticity coordinate) and a good red color is obtained,
The luminous flux of the lamp dropped to 580 lumens.

Table 1 summarizes the fluorescent lamp specifications and lamp performance of Examples 1 to 3 and Comparative Examples 1 to 3.

[0029]

[Table 1]

[Embodiment 4] In this example, one UV-reflecting substance is used.
A method of applying the deep red light emitting phosphor to the second layer will be described.・ Calcium pyrophosphate (ultraviolet ray reflecting substance) ・ ・ ・ ・ ・ ・ 99g ・ Titanium yellow yellow pigment ・ ・ ・ ・ 1g (Dainichi Seika product number Dailoxite color yellow 9110) A coating solution was prepared by suspending these powders in a nitrocellulose / butyl acetate binder, and the luminescent composition was added to the glass tube for a fluorescent lamp (FL40SS) in the first layer by the usual method. 5 g was applied to form a reflective layer. Subsequently, manganese-activated magnesium fluorogermanate phosphor was used as PEO.
The coating liquid suspended in (polyethylene oxide) / water binder was coated on a coating glass bulb to form a coating amount of 1.5 g of a second phosphor layer, and a fluorescent lamp was manufactured according to a conventional method. When the obtained fluorescent lamp was measured using an integrating sphere and a spectrophotometer, the emission color of the fluorescent lamp was x = 0.5.
60, y = 0.294 (CIE chromaticity coordinate), and the luminous flux of the lamp was 780 lumens. This two-layer coating is particularly effective in improving the deterioration of the fluorescent lamp.

Comparative Example 4 A coating solution prepared by suspending calcium pyrophosphate (ultraviolet reflecting substance) powder in a nitrocellulose / butyl acetate binder was prepared, and the glass tube for a fluorescent lamp (FL40SS) was made to emit light by a conventional method. Thing 1
1.5 g was applied to the layer to form a reflective layer. Subsequently, manganese-activated magnesium fluorogermanate phosphor was used as a PE.
A coating liquid suspended in O (polyethylene oxide) / water binder was coated on a coating glass bulb to form a coating amount of 1.5 g of a second phosphor layer, and a fluorescent lamp was manufactured according to a conventional method. When the obtained fluorescent lamp was measured using an integrating sphere and a spectrophotometer, the emission color of the fluorescent lamp was x = 0.
534, y = 0.278 (CIE chromaticity coordinate), and the luminous flux of the lamp was 783 lumen. This two-layer coating is particularly effective in improving the deterioration of the fluorescent lamp.

Table 2 compares fluorescent lamp specifications and lamp performance of Example 4 and Comparative Example 4.

[0033]

[Table 2]

[0034]

EFFECT OF THE INVENTION By using the luminescent composition of the present invention, the amount of expensive manganese-activated magnesium fluorogermanate phosphor to be used can be reduced with almost no change in the color tone of deep red light emission. It is possible to reduce the cost.

[0035]

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the compounding amount of a deep red light emitting phosphor and the luminous flux of a lamp in a light emitting composition of the present invention.

FIG. 2 is a graph showing the relationship between the amount of deep red light emitting phosphor compounded in the light emitting composition of the present invention and lamp chromaticity.

FIG. 3 Spectral reflectance curve diagram of yellow pigment

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Keiji Ichinomiya 491, Oka, Kaminaka-cho, Anan City, Tokushima Prefecture Nichia Kagaku Kogyo Co., Ltd.

Claims (3)

[Claims] 1. A mixture of a deep red light emitting phosphor, an ultraviolet reflecting substance, and a yellow pigment having a spectral reflectance within the following range, and the ratio of the deep red light emitting phosphor is 25 relative to the total weight of the light emitting composition. To 75% by weight, the ratio of the UV-reflecting substance is in the range of 25 to 75% by weight, and the ratio of the yellow pigment is 0.1 to 3.0.
A luminescent composition, characterized in that it is in the range of% by weight. Spectral reflectance at 450 nm is 10 to 35% Spectral reflectance at 500 nm is 50 to 80% Spectral reflectance at 550 nm is 75 to 100% Spectral reflectance at 600 nm is 75 to 100% (however, the spectral reflectance at each wavelength is (Value measured with the spectral reflectance value at each wavelength of standard white barium sulfate as 100%) 2. A translucent glass tube filled with an encapsulating gas containing mercury and a rare gas, a phosphor layer containing phosphor particles provided on an inner wall surface of the translucent glass tube, and in the encapsulating gas. A fluorescent lamp comprising means for maintaining a discharge in sunlight, wherein the phosphor layer comprises the luminescent composition according to claim 1. 3. A translucent glass tube filled with an encapsulating gas containing mercury and a rare gas, a phosphor layer containing phosphor particles provided on an inner wall surface of the translucent glass tube, and the encapsulating gas. In the fluorescent lamp provided with means for maintaining discharge in sunlight, the phosphor layer has a two-layer structure, of which a layer near the glass surface is a layer in which an ultraviolet-reflecting substance and a yellow pigment are mixed. , A deep red light-emitting phosphor is coated on the side far from the glass surface, and the spectral reflectance of the yellow pigment is 10 to 35% at 450 nm and 50 to 80% at 500 nm. The reflectance is 75 to 100%, and the spectral reflectance at 600 nm is 75 to 100% (however, for the spectral reflectance at each wavelength, the spectral reflectance value at each wavelength of standard white barium sulfate is 10%. Fluorescent lamp, which is a range of measured values) as%.