CN1020743C - Luminescent composition, its production method and use for fluorescent lamps - Google Patents

Abstract

The present invention relates to a light-emitting composition containing a phosphor or particles formed by fusing a phosphor raw material and an alkaline earth metal sulfate, a method for producing the light-emitting composition, and a fluorescent lamp using the light-emitting composition.

Description

The present invention relates to a luminescent composition, a method for producing it, and a fluorescent lamp using the composition. More specifically, it relates to a luminescent composition composed of a luminophore and an alkaline earth metal sulfate, and a A very inexpensive luminescent composition containing a large amount of such non-luminescent substances but still maintaining extremely high luminance, a method for producing the composition, and a fluorescent lamp using the luminescent composition as a fluorescent film.

Phosphors generally have a special property of converting excitation energy invisible to the human eye into visible light, so they are expensive items compared with simple chemical materials. Especially in recent years, in order to meet various characteristics, it has been developed that a large number of rare earth elements and precious metal elements are used as raw materials, so the use is subject to various restrictions caused by prices, resulting in the most suitable phosphor often Questions like this cannot be used for their purpose. Therefore, it is very hoped that the price of this kind of phosphor can be lowered.

On the other hand, related to this technology, as a technology close to the present invention, there is, for example, British Patent No. 603326, which describes that, in a fluorescent lamp, by sandwiching a good ultraviolet reflector between the support and the phosphor High-efficiency substances can reduce the amount of luminescent substances used. In addition, as an improvement of this technology, a gas discharge lamp is disclosed in U.S. Patent No. 4,069,441. A film composed of a mixture obtained by mixing phosphors is placed on the side of the glass tube, and a film composed of only phosphors is laminated on it, and the ratio of white matter to phosphors in the film composed of the above mixture is set toward the glass tube side. The tube side becomes progressively larger. In addition, there is JP-A-57-128452 as a related art. Similarly, other mixtures that simply mix phosphors and white pigments have been described in U.S. Patent No. 4,039,840, Japanese Patent Publication No. 56-5478, and Japanese Patent Laid-Open No. 55-55- It has been disclosed in publications such as No. 146447.

In addition, for example, the sulfate-based phosphors of alkaline earth metals (that is, the phosphors with sulfates of alkaline earth metals as the matrix) disclosed in Japanese Patent Publication No. 54-37069 and Japanese Patent Publication No. 57-50832 are also known. . These phosphors contain lead and divalent europium as activators, which exhibit ultraviolet or blue luminescence for excitation energy.

The mixture of the above-mentioned luminescent phosphor and the white substance, if considered from a practical level, the decrease in the luminous brightness is extremely large. In order to reduce this decrease in luminance, and to produce other effects, it is necessary to use the above-mentioned patent publications. As described, complex measures such as forming a special layer structure are required, and the usage amount thereof is often limited to less than a few percent by weight.

As mentioned above, none of the existing technologies can greatly reduce the price of these luminescent substances without reducing the brightness of these luminescent substances. Therefore, there is a strong demand for the emergence of such fluorescent substances.

It is an object of the present invention to provide a luminescent substance which hardly reduces the luminosity for excitation energy, surprisingly even increases its luminosity and which enables a considerable reduction in the price of the luminescent substance.

In order to achieve the above object, the inventors of the present invention have conducted various studies on combinations of inexpensive non-luminescent materials and expensive phosphors. As a result, they have found that once phosphors and alkaline earth metal sulfates are mixed and fired, The present invention has been accomplished by obtaining a luminescent substance satisfying the above objects.

The present invention relates to a light-emitting composition containing particles formed by fusion-bonding phosphors and alkaline earth metal sulfates.

In addition, the present invention relates to a method for producing a light-emitting composition characterized in that firing is carried out in a state where phosphors or phosphor raw materials and alkaline earth metal sulfates coexist.

Furthermore, the present invention relates to a fluorescent lamp characterized in that the fluorescent film contains a luminescent composition comprising particles formed by melting and adhering sulfates of alkaline earth metals as phosphors.

Fig. 1 shows the relationship between the relative luminous brightness under ultraviolet excitation and the material cost reduction rate when the composition ratio of phosphor and alkaline earth metal sulfate is changed in the luminescent composition of the present invention, curves 1 and 2 are For the luminescent composition of the present invention, curve 3 is a mixture of the prior art. Fig. 2 shows the relationship between the luminous color (x value) and the relative luminous brightness of phosphors, luminescent compositions of the present invention, luminescent compositions and mixtures other than the present invention, etc. under ultraviolet excitation. Fig. 3 shows the relationship between firing temperature (°C) and relative luminance (%) when producing the luminescent composition of the present invention. Fig. 4-a is an electron micrograph showing the particle structure of the mixture, and Fig. 4-b and Fig. 4-c are electron micrographs showing the particle structure of the luminescent composition of the present invention, respectively. Similarly, Fig. 5-a, Fig. 5-b and Fig. 5-c are electron micrographs respectively showing the particle structure of the luminescent composition of the present invention. Fig. 6-a and Fig. 6-b are diagrams respectively showing X-ray diffraction images of the luminescent composition of the present invention.

Hereinafter, the present invention will be described in more detail.

As an example, the light-emitting composition of the present invention is produced as follows (hereinafter referred to as manufacturing method 1). First, the phosphor and the sulfate of the alkaline earth metal are thoroughly mixed, and then the mixture is fired at any temperature in the range of 550 to 1600°C.

The phosphor used in the above-mentioned present invention can use any of the conventionally known phosphors, but in view of the gas medium for firing, etc., in fact, it is mainly used to contain oxides, oxysulfides, etc. in the parent element. Phosphors of oxygen oxide series such as phosphors, vanadates, silicates, phosphates, aluminates, borates, etc. That is to say, it is suitable for phosphors fired in an oxygen gas medium, a neutral gas medium, and a weakly reducing gas medium. In addition, further analysis from a practical point of view, from the point of view of the reduction effect of material costs, is suitable for phosphors containing at least one of rare earth elements and noble metal elements, especially the phosphors containing a large amount of these elements, the greater the effect. big. For example, if the present invention is applied to a rare earth oxide phosphor containing europium as an activator, which is the most expensive oxide phosphor among a large number of practical lamp phosphors (the composition formula is Ln ₂ O ₃ : Eu Phosphor, but Ln is at least one of Y, Gd, La, Lu), then this effect will be great. In addition, the sulfates of alkaline earth metals referred to in the present invention are sulfates of at least one element among barium (Ba), strontium (Sr), calcium (Ca), and magnesium (Mg). Representative examples thereof include Barium sulfate (BaSO ₄ ), strontium sulfate (S-SO ₄ ), calcium sulfate (CaSO ₄ ), etc. The sulfates of these alkaline earth metals are usually sieved to loosen the agglomerates before being mixed with the phosphor, and the small particles are sieved out, and then used in a timely manner. In addition, the mixing of the two can be sufficiently performed using a mortar, a grinder, or the like, and both dry and wet methods may be used.

These mixtures are put into a heat-resistant container and fired at the above temperature. This firing is usually carried out at a temperature below the melting point of the phosphor used and the sulfate of the alkaline earth metal used. At this time, the fired The completion time ranges from tens of minutes to several hours. The gaseous medium at the time of sintering is the generally used sintering gaseous medium at the time of phosphor production, but it is also required to have conditions that make it difficult for the sulfate of the alkaline earth metal to change. The above-mentioned firing temperature is preferably in the range of 800 to 1550°C.

Also, when mixing the above-mentioned raw materials, it is recommended to add some flux in an appropriate amount. In particular, the addition of a compound containing at least one of the elements barium, phosphorus and boron is recommended. A luminescent composition with good brightness and good granularity can be obtained by containing such a flux.

If the above-mentioned production method is adopted, the fused-adhesive body can be obtained by simply mixing the raw material of the phosphor and the sulfate of the alkaline earth metal in a dry or wet manner and firing, but generally speaking, the primary particle of the alkaline earth sulfate is The diameter is about 1μ, and after agglomeration, it will become large particles of more than 10μ. It is very difficult to disperse it completely. When the agglomerated large particles are directly mixed with phosphor and flux and fired, they will form Huge melt-adhesive particles. In addition, if the flux is reduced or the firing temperature conditions are lowered to prevent such occurrences, the number of individual particles of fine alkaline earth sulfate that cannot be completely fused with the phosphor increases. However, these are not ideal in terms of luminescence characteristics and coating film characteristics.

Another method for producing the luminescent composition of the present invention by reducing the particle size distribution with an appropriate particle size will be described below (hereinafter referred to as Production Method 2).

It is characterized in that oxalic acid or water-soluble oxalate and sulfuric acid or water-soluble sulfate solution are combined in a solution containing at least one metal element constituting the phosphor matrix and an alkaline earth metal salt solution Or after adding separately, a precipitate of the oxalate of the metal element constituting the matrix and the sulfate of the alkaline earth metal is obtained, and the phosphor material is further fired with the precipitate as the main part of the phosphor material.

Rare earth materials as phosphor materials often use oxides as the main raw materials, but as pretreatment, water-soluble rare earth salts (chloride, nitrate, sulfate, etc.) are generally made into aqueous solutions, or oxides, hydrogen Oxides and carbonates are dissolved in acid (hydrochloric acid, sulfuric acid, nitric acid) to make an aqueous solution, and an aqueous oxalic acid solution is added to the aqueous solution to precipitate rare earth oxalate, and this is carried out at 800-1000 ° C burnt to form oxides. This treatment is especially used for phosphors Ln ₂ O ₃ : Lu, Ln ₂ O ₂ S : Ln that contain a small amount of rare earth activator in the rare earth matrix.

Alkaline earth metal sulfates are formed by adding sulfuric acid to an aqueous solution of water-soluble alkaline earth salts (nitrates, etc., halides) or an aqueous solution of oxides, carbonates, etc. dissolved in hydrochloric acid or nitric acid. It is extremely stable in water and difficult to dissolve in acid.

Then, oxalic acid or water-soluble oxalate (ammonium oxalate , diethyl oxalic acid, alkali metal oxalates, especially ammonium oxalate and dimethyl oxalate are preferred), and sulfuric acid or water-soluble sulfates (ammonium sulfate, alkali metal sulfates, especially ammonium sulfate are preferred) (preferable) solution together or separately to make it to form the precipitates of metal element oxalate constituting the above-mentioned matrix and the above-mentioned alkaline-earth metal sulfate. When it is desired to form a precipitate, the solution is usually placed under stirring conditions, and by adjusting the stirring conditions, the concentration of the solution, the addition speed of oxalic acid and sulfuric acid, etc., a precipitate with a desired particle size can be formed.

As mentioned above, the precipitation of metal elements constituting the phosphor matrix and the precipitation of alkaline earth metal sulfate can be produced by co-precipitation. It can be formed or formed step by step to obtain a precipitate with well-dispersed components. Therefore, the desired particle properties can be obtained, and a light-emitting composition with good light-emitting properties can be stably obtained.

The thus-obtained precipitate is placed in, for example, a heat-resistant container, and fired to fuse the above-mentioned phosphor and alkaline earth metal sulfate, but the firing is carried out under the same firing conditions as above.

In addition, another production method of the present invention that produces the same effect is as follows.

When mixing the luminescent material composed of phosphor or solid-dissolving the activator in at least one parent material and the sulfate of alkaline earth metal, the sulfate of alkaline earth metal is dispersed in the solvent The state in the state adheres to the above-mentioned luminous material raw materials to form a composite body, and then it is dried, and then fired at any temperature in the range of 550-1600 ° C to complete (hereinafter referred to as preparation method 3).

More specifically, when mixing the above-mentioned luminescent material raw material and alkaline earth metal sulfate, it is necessary to disperse the sulfate in a solvent in advance. As the method of this dispersion, only stirring in a solvent may be used, but it is more preferable to perform mechanical dispersion in advance with a ball mill, or to strengthen dispersion in a solvent by ultrasonic waves. As a solvent, water is generally used, but especially when the raw material of the phosphor is an oxide that does not have water resistance, organic solvents such as methanol, ethanol, and isopropanol can be used. The alkaline earth metal sulfate dispersed in the solvent is then mixed with the above-mentioned phosphor raw materials. This mixing is usually carried out under stirring.

In this way, the sulfate of the alkaline earth metal and the raw material of the luminous body are physically adsorbed in the solvent depending on the mixing conditions, and the particles of the raw material of the luminous body and the sulfate of the alkaline earth metal are uniformly adhered to form a complex. Other substances do not produce physical adsorption, but in this case, it is advisable to use a small amount of organic binder in order to improve adhesion. Examples of such organic binders include acrylic resins, vinyl acetate resins, polyvinyl butyral resins, synthetic rubber latex, polyvinyl picolidone, polyvinyl alcohol, and gels.

The composite body thus obtained is dried and then fired, for example, in a heat-resistant container. This firing is carried out under the same conditions as above.

In the production method according to the present invention, the above-mentioned alkaline earth metal sulfate may not be used, and a primary material instead of the alkaline earth metal sulfate may be used in the above-mentioned firing process. The so-called alkaline earth metal sulfates according to the invention also contain such primary substances. As such primary substances, there are carbonates of alkaline earth metals, inorganic salts such as nitrates, or organic salts (acetate, citrate, oxalate) and sulfates (such as ammonium sulfate, etc.) mixture.

In addition, representative examples of the relationship between the firing conditions of the present invention and the luminance of the light-emitting composition are as follows.

Fig. 3 shows the relationship between the firing temperature (°C) of raw materials and the relative luminance (%) when excited by 253.7nm ultraviolet rays when producing the luminescent composition of the present invention. Point A in Figure 3 _is Y ₂ O ₃ : Eu phosphor (the relative luminance is set as 100% ₎ , curve 1 is the _mechanical In the case where the obtained mixture is used as a raw material for firing after mixing, curve 2 is a mixture of 50 weight units of Y ₂ O ₃ containing Eu as the raw material of Y ₂ O ₃ :Eu phosphor and 50 weight units of BSO ₄ The case where the mixture obtained later is fired as a raw material. As can also be seen from this curve 1, once the phosphor and the sulfate of the alkaline earth metal are fired, the two start to melt and adhere sequentially, and the luminance also increases at the same time. This phenomenon is not observed at 500°C or lower. Once the firing temperature reaches 800°C or higher, its luminance also rises sharply (20% higher than that of the raw material), thus reaching the same or exceeding the luminance of the phosphor itself. Also, as seen from curve 2, once the phosphor raw material and the alkaline earth metal sulfate are fired, the phosphor raw material grows as a phosphor, and at the same time, fusion adhesion with the alkaline earth metal sulfate begins sequentially. . If no change occurs between the two, it is impossible to rise above the relative luminous brightness of curve 1 below 500°C, and in the present invention, the brightness rises further. Thus, in the present invention, the firing temperature is above 550°C, more preferably above 800°C, most preferably above 1000°C, and the effect at this time is remarkable. In addition, from the viewpoint of thermal efficiency, if it is a common firing method, although it is also related to the firing time, it is generally carried out at below 1600°C, preferably below 1550°C.

After doing so, the light-emitting composition of the present invention can be obtained. Compared with the luminescent composition obtained by the above method and the simple mixture of phosphor and alkaline earth metal sulfate particles using materials other than phosphor and alkaline earth metal sulfate, the luminescent composition of the present invention shows extremely high brightness.

Figure 2 shows the luminescent colors of the phosphor (YGd) ₂ O ₃ :Eu, the above-mentioned simple mixture of the phosphor and alkaline earth metal sulfate, and the above-mentioned luminescent composition when excited by ultraviolet light at 253.7 nm (CIE chromaticity The relationship between the X value of the coordinate) and the relative luminance (%). Point A in Figure 2 shows the luminescent color and relative luminance of the (Y·Gd) ₂ O ₃ :Eu phosphor. Each value after mixing the materials at 50 weight units each time, and firing at about 12000°C for 4 hours. In addition, the triangular mark (▲) on the figure shows the value of the mixture obtained by mechanically mixing the above-mentioned phosphor with each of the materials indicated on the figure at a time of 50% by weight. It can also be clearly seen from Fig. 2 that each luminescent composition of the present invention composed of the above-mentioned phosphor, BaSO ₄ , and SrSO ₄ contains a large amount of non-luminescent substances up to 50% (by weight), but it is different from 100% Compared with the point A composed of phosphors, its luminous color and relative luminous brightness are almost unchanged. On the other hand, other ZnO, Al ₂ O ₃ , BaHPO ₄ Ca(PO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ and AlPO ₄ etc. are also used. For the luminescent composition not included in the present invention, its relative luminous brightness will be reduced by more than 20% to 80%, or the luminous color will also change, so the purpose of the present invention cannot be achieved, and in addition, it does not show unexpected effects like the present invention. Effect. Also, the mixture of the phosphor represented by (▲) and BaSO ₄ or SrSO ₄ contains a large amount of non-luminescent substances, and its luminance is about 20% lower than point A or the luminescent composition of the present invention. Although their brightness has been confirmed to have the effect described in US Patent No. 4,069,441, a 20% reduction in brightness cannot be used for practical use.

Figure 1 shows, in the luminescent composition of the present invention, when the composition ratio (% by weight) of the phosphor and the alkaline earth metal sulfate is changed, the relative luminous brightness (%) and material cost under the excitation of 253.7nm ultraviolet rays The relationship between the reduction rate (%).

Curve 1 in Figure 1 shows the relative luminous brightness characteristics of the luminescent composition of the present invention composed of Y ₂ O ₃ :Eu phosphor and BaSO ₄ , and curve 2 shows the relative luminance characteristics of the composition of (YGd) ₂ O ₃ :Eu phosphor and BaSO 4 The relative luminous brightness characteristics of the luminescent composition of the present invention with ₄ compositions, Curve 3 shows the respective relative luminous luminance characteristics of the prior art mixture obtained by mechanically mixing Y ₂ O ₃ :Eu phosphor with BaSO ₄ , curve 3 4 shows the relationship of material cost reduction rate (%) with respect to the composition of Y ₂ O ₃ :Eu phosphor and BaSO ₄ . It can be clearly seen from Fig. 1 that compared with the prior art shown in curve 3, the light-emitting composition of the present invention represented by curves 1 and 2, for example, when the amount of alkaline earth metal is 50% (weight), the The brightness of the display is increased by more than 20%, and at 80% (weight), the displayed brightness is increased by more than 30%. And when the amount of alkaline earth metals is below 80% (weight), for that kind does not contain this non-luminescent substance and promptly only relies on the brightness of phosphor itself, its brightness shows substantially the same or improves nearly 7% this exciting Amazing effect. Furthermore, the material cost reduction rate at this time is as high as 76%.

Therefore, from the viewpoints of luminance and material cost reduction, the content of alkaline earth metal sulfate in the luminescent composition of the present invention is preferably 5 to 95% by weight, more preferably 10 to 95% by weight. range, and practically the best is 25 to 90% (weight).

The sulfate salt of alkaline earth metal used in the present invention is preferably the sulfate salt of barium, strontium and calcium, from these points of above-mentioned effect, specific gravity, thermal stability, adopt a kind of in barium and strontium at least, or Sulfate mainly formed by this is also practically preferable, and the firing temperature at this time is preferably 800 to 1550°C, more preferably 1000 to 15000°C.

The above shows the effect when the light-emitting composition of the present invention is excited by ultraviolet rays, but the same effect is also shown by electron beams. Therefore, it can be clearly seen that the present invention does not use BaSO ₄ etc. only by the ultraviolet reflection effect itself like the prior art.

The reason why the luminescent composition of the present invention produces such surprising effects is still unclear. Figure 4-a shows the electron micrograph (3000 times) of the mixture obtained by mixing Y ₂ O ₃ : Eu phosphor and BaSO ₄ particles at 50% by weight each, and Figure 4-b shows the firing of the mixture An electron micrograph (3000 times) of the obtained luminescent composition of the present invention. In addition, Fig. 4-c shows the electron microscope of the light-emitting composition of the present invention obtained by firing the mixture formed by mixing (Y·Gd) ₂ O ₃ :Eu phosphor and BaSO ₄ particles at 50% by weight each. Photo (3000x) (above, the sample in Fig. 4 was measured by evaporating carbon). Figure 5-a and Figure 5-b show that the mixture formed by mixing Y ₂ O ₃ : Eu phosphor with BaSO ₄ particles (each 50% by weight) was fired under different conditions from the above. Each of the obtained electron micrographs of the luminescent composition of the present invention. In addition, Fig. 5-c shows the luminescent composition of the present invention obtained by firing the co-precipitated product formed by co-precipitating the Y ₂ O ₃ : Eu phosphor raw material and BaSO ₄ at a weight ratio of 50% each. Electron microscope photo (30,000 times). (Above, the samples in Fig. 5 were measured by evaporating gold).

Fig. 5-a and Fig. 5-b are the results of measurement with an X-ray microanalyzer. The miliary microparticles are Y ₂ O ₃ :Eu phosphors, and the substance fused with them is BaSO ₄ . Also, the large particles in Fig. 5-c are also BaSO ₄ , and the crystalline particles fused on the surface are Y ₂ O ₃ :Eu phosphors.

Figure 6-a shows the X-ray diffraction model diagram of the luminescent composition of the present invention shown in Figure 4-b, and Figure 6-b shows the X-ray diffraction model of the luminescent composition of the present invention shown in Figure 4-c picture. From these electron micrographs and X-ray diffraction model diagrams, it can be considered that although the light-emitting composition of the present invention is composed of particles formed by melting and adhering part or most of the sulfates of the phosphors and alkaline earth metals, However, it is considered that neither of these compositions forms a solid solution of the two. In addition, in order to obtain the spectrum, the spectrum other than the Y ₂ O ₃ :Eu phosphor, especially the spectrum in the ultraviolet region of the BaSO ₄ :Eu phosphor was not detected at this time. Therefore, the light-emitting composition of the present invention obtained by the above-mentioned production method is the composition formula (Ln, Eu) ₂ O ₃ ·xM ^II SO ₄ (but Ln is at least one of Y, Gd, La, and Lu, and N is Alkaline earth metals and X is a positive number representing the composition ratio). Also, from the above examples, it is possible to obtain such a concept that the particles formed by melting and adhering phosphors and alkaline earth metal sulfates according to the present invention not only include burning both at 550°C or higher, but preferably at 800°C or higher. After completion, the two are full of substances with unknown boundaries as shown in Figure 4-b, and the sintering of the two as shown in Figure 5 is also included.

In the present invention, the luminance of the light-emitting composition obtained when the alkaline earth metal sulfate contains a trace element as an activator is equal to or higher than that obtained when these trace elements are not included. Representative examples of the above-mentioned trace elements can be recommended such as europium (Eu), lead (pb), terbium (Tb), cerium (Ce), manganese (Mn), etc., especially from the above effects, europium and lead It is more desirable that at least one of them is an activator.

As described above, the luminescent composition of the present invention can exhibit extremely high luminance by ultraviolet rays. Therefore, fluorescent lamps produced by conventional methods using this luminescent composition are also extremely useful. In particular, the luminescent composition of the present invention has high brightness and can significantly reduce the price of phosphors containing rare earth elements and noble metal elements. Therefore, it is recommended to be practically used in high color rendering fluorescent lamps that use a large amount of such phosphors.

₂O₃∶Ce，Tb（但M^Ⅱ＝Mg、Zn，0＜n≤2）、GdMgB₅O₁₀∶Ce，Tb]、铽活化碱土类金属铈·铝酸盐荧光体[例如（Ce，Tb）M^ⅡAl₁₁O₁₉（但M^Ⅱ＝Mg·Zn）]、铈·铽活化稀土类硅酸盐荧光体[例如LnSiO₅Ce，Tb（但Ln＝Y、Gd、La）]，作为上述红色发光物质中所含有的荧光体有铕活化稀土类氧化物系列的荧光体[例如Ln₂O₃Eu（Ln＝Y、Gd、La）]，以上分别被推荐为有代表性的荧光体。再者，为了获得演色性也可加入在480～500nm范围内具有发光峰值波长的蓝绿色发光物质。作为该蓝绿色发光物质中所含有的荧光体有2价的铕活化锶铝酸盐荧光体[例如4SrO·nAl₂O₃∶Eu²⁺（但5≤n≤8）、2价的铕活化碱土类金属硼磷酸盐荧光体[例mM^ⅡO·（1-n）P₂O₅·nB₂O₃＝Eu²⁺（但M^Ⅱ＝Cu、Sr、Ba，1.75≤m≤2.30、0.05≤n≤0.23）]，这些可作为代表性的例子来推荐。That is to say, the fluorescent film of the fluorescent lamp includes a blue luminescent substance with a maximum wavelength of light emission in the range of 430-475nm, a green light-emitting substance with a maximum wavelength of light emission in the range of 520-560nm, and a green light-emitting substance with a maximum wavelength of light emission in the range of 595-630nm. Red luminescent substances having a maximum wavelength of luminescence, at least one of the above luminescent substances is composed of the luminescent composition of the present invention. Phosphors contained in the above-mentioned blue luminescent material include divalent europium-activated calcium chloroborate phosphors (e.g. /Ca ₂ B ₅ O ₉ Cl:Eu ²⁺ ), divalent europium-activated alkaline earth metal aluminum Acid series phosphors (such as BaMg ₂ Al ₁₆ O ₂₇ : Eu), divalent europium-activated alkaline earth metal halophosphate phosphors [such as aM 7/3 (PO ₄ ) ₂ : bM ^II Cl ₂ : Eu ^{2 +} (but M ^Ⅱ ＝Co, Sr, Ba, 1≤a/b≤3)], as the phosphors contained in the above-mentioned green luminescent substances, there are cerium, terbium activated lanthanum phosphate series phosphors (such as LaPO ₄ : Ce , Tb), cerium terbium activated alkaline earth metal borate series phosphor [such as nM ^Ⅱ O

₂ O ₃ : Ce, Tb (but M ^Ⅱ =Mg, Zn, 0<n≤2), GdMgB ₅ O ₁₀ : Ce, Tb], terbium activated alkaline earth metal cerium aluminate phosphor [such as (Ce, Tb) M ^Ⅱ Al ₁₁ O ₁₉ (but M ^Ⅱ = Mg Zn)], cerium terbium activated rare earth silicate phosphor [such as LnSiO ₅ Ce, Tb (but Ln = Y, Gd, La)], as Phosphors contained in the above-mentioned red luminescent substances include europium-activated rare earth oxide series phosphors [such as Ln ₂ O ₃ Eu (Ln=Y, Gd, La)], and the above are recommended as representative phosphors respectively . Furthermore, in order to obtain color rendering, a blue-green luminescent substance having a luminescence peak wavelength in the range of 480-500 nm may also be added. Phosphors contained in this blue-green luminescent substance include divalent europium-activated strontium aluminate phosphor [for example, 4SrO·nAl ₂ O ₃ : ^{Eu 2+} (but 5≤n≤8), divalent europium-activated Alkaline earth metal borophosphate phosphor [example mM ^Ⅱ O·(1-n)P ₂ O ₅ ·nB ₂ O ₃ =Eu ²⁺ (but M ^Ⅱ =Cu, Sr, Ba, 1.75≤m≤2.30, 0.05 ≤n≤0.23)], these can be recommended as representative examples.

Using the light-emitting composition of the present invention in which at least one of the above-mentioned phosphors and sulfates of alkaline earth metals are melt-bonded can greatly reduce the amount of the above-mentioned phosphors used. From this purpose, it is recommended that the luminescent composition of the present invention, as the above-mentioned phosphor, either contain a rare earth element constituting a matrix element, or be a phosphor of an oxide series containing a large amount of rare earth element as an activator. body. That is, such phosphors refer to phosphors of europium-activated rare-earth oxides, cerium and terbium-activated rare-earth silicate phosphors, and the like.

Also, the surprising effect of the luminescent composition of the present invention is that it not only improves the brightness of the fused phosphor, but also improves the brightness of other phosphors that have not been fused mechanically mixed with the luminescent composition of the present invention. The effect of improving the luminous efficiency is brought about. For example, the high color rendering fluorescent lamp of the present invention having a fluorescent film obtained by mixing (LnEu) ₂ O ₃ ·BaSO ₄ as the light-emitting composition of the present invention with the above-mentioned green light-emitting phosphor and the above-mentioned blue light-emitting phosphor is for To obtain the same luminous color as the existing high color rendering phosphors that do not contain the above-mentioned BaSO ₄ , not only the amount of (LnEu) ₂ O ₃ phosphors used is reduced, but also the use of other green luminescent phosphors and blue luminescent phosphors volume can also be reduced. This example can be illustrated by Example. Based on this fact, it is recommended that in the high color-rendering fluorescent lamp of the present invention, the phosphor that is the most stable with the sulfate of the alkaline earth metal or the luminescent composition of the present invention should be selected appropriately. A typical example of such a phosphor is a phosphor of the europium-activated rare earth oxide series that emits red light. Therefore, the following examples are for explaining fluorescent lamps using the light-emitting composition of the present invention using such phosphors, but the present invention is not limited by these examples.

Hereinafter, the present invention will be described in more detail by enumerating several embodiments.

Example 1

76 weight units of gadolinium oxide (Gd ₂ O ₃ ), 20 weight units of yttrium oxide (Y ₂ O ₃ ), and 4 weight units of europium oxide (Eu ₂ O ₃ ) were used as oxalate precipitates, and then These were fired at 1000°C for 3 hours to obtain an oxide represented by (Gd,Y,Eu ₂ )O ₃ . Then 50 weight units of this (Gd, Y, Eu) ₂ O ₃ and 50 weight units of barium sulfate (BaSO ₄ special reagent) were mixed, and fluxing agents (1% by weight of BaCl ₂ ·2H ₂ O and 0.1% by weight of H ₃ BO ₄ ), mixed thoroughly, filled into a crucible and fired at 1200°C for 4 hours. After washing and drying, the luminescent composition (Y, Gd, Eu) ₂ O ₃ ·BaSO ₄ of the present invention can be obtained [Figure 4-c shows an electron micrograph (3000 times). Also, Figure 6-b shows the X-ray diffraction model]. On the other hand, the phosphor obtained by firing only the above-mentioned oxide (Gd, Y, Eu) ₂ O ₃ under the same conditions is used as a standard product, and the above-mentioned luminescent composition and the standard product are respectively filled into quartz The container was irradiated with 253.7nm ultraviolet rays to measure the luminous brightness and luminous color (hereinafter, this measurement is referred to as ultraviolet measurement). There is no difference at all. The characteristics when the composition ratio is changed by the same manufacturing method are shown on curve 2 in FIG. 1 .

Example 2

The yttrium oxide (Y ₂ O ₃ ) of 95 weight units and the europium oxide (Eu ₂ O ₃ ) of 5 weight units are used as starting materials, and the others are all used in the same way as in Example 1, thereby making a compound made of (Y , Eu) ₂ O ₃ oxides, then, add barium sulfate (BaSO ₄ ) to the (Y, Eu) ₂ O at a certain mixing ratio (weight %) shown in the following table, and at 1400 ° C Firing for 4 hours, other methods are the same as in Example 1, so as to obtain the light-emitting composition of the present invention (Y, Eu) ₂ O ₃ ·XBaSO ₄ [ The electron micrograph (3000 times) of the third product of the present invention in Table 1 is shown in Fig. 4-b. Also, the X-ray diffraction model is shown in Fig. 6-a].

Using only the above-mentioned oxides, a standard product was produced in the same manner as in Example 1, and the relative luminance and material cost reduction of each ultraviolet measurement are shown in the table below. Also, the luminous color at this time did not change at all. In addition, the material cost reduction amount is calculated by calculating the material cost of (Y·Eu) ₂ O ₃ as 4,200 yen/kg and the material cost of BaSO ₄ as 2,000 yen/kg Calculated.

Example 3

Use 94.6 weight units of yttrium oxide (Y ₂ O ₃ ) and 5.4 weight units of europium oxide (Eu ₂ O ₃ ) as starting materials, and other methods are the same as in Example 1 to obtain (Y.Eu ) Oxide represented by ₂ O ₃ . Next, mix 50 weight units of this (Y, Eu) ₂ O ₃ with 50 weight units of barium sulfate (BaSO ₄ ), and then use the same method as in Example 2 to prepare the luminescent composition of the present invention (Y, Eu) ₂ O ₃ ·(BaSO ₄ ). On the other hand, the phosphor obtained by firing only the above-mentioned oxide (Y, Eu) ₂ O ₃ under the same conditions was used as a standard product, and the above-mentioned light-emitting composition and the standard product were used as a fluorescent film after excitation. The luminous color and luminous brightness were measured, and it was found that there was no difference between the two in luminous color (X/Y=0.64/0.353) and luminous brightness.

Also, a mixture obtained by sufficiently mixing 50 weight units of the above standard (Y, Eu) ₂ O ₃ phosphor and 50 weight units of barium sulfate (BaSO ₄ ) was measured under the above conditions. changed, but the luminance was significantly reduced.

Example 4

Add flux to 50 weight units of (Y, Eu) ₂ O ₃ oxide shown in Example 2 and 50 weight units of strontium sulfate (SrSO ₄ ), mix thoroughly, fill into a crucible, and Calcination at high temperature for 4 hours, followed by washing and drying, so as to obtain the light-emitting composition (Y, Eu) ₂ O ₅ SrSO ₄ of the present invention. Ultraviolet measurement was performed between this luminescent composition and the standard (Y, Eu) ₂ O ₃ phosphor of Example 2. As a result, it was found that there was no difference in luminous brightness and luminous color between the two.

Example 5

Mix 70 weight units of terbium-activated yttrium aluminate phosphor (Y ₂ Al ₅ O ₁₂ : Tb) with 30 weight units of barium sulfate (BaSO ₄ ), and then add flux (1 weight unit of BaCl ₂ ·2H ₂ O and 0.1 weight unit of H ₂ BO ₃ ), after being thoroughly mixed, calcined at 1200°C for 2 hours, followed by washing and drying, so as to obtain the luminescent composition of the present invention. The luminance of this luminescent composition when excited by ultraviolet light (253.7 nm) was 83% when the Y ₃ Al ₅ O ₁₂ :Tb phosphor was 100%. In addition, the emission luminance of the simple mixture before firing was 62%.

Example 6

Mix 70 weight units of europium-activated yttrium oxysulfide phosphor (Y ₂ O ₂ S:Eu) with 30 weight units of barium sulfate, then add flux (1 weight unit of lithium phosphate), then use the same method as in Example 5 In the same manner, the luminescent composition of the present invention was obtained. The luminance of this luminescent composition when excited by ultraviolet light (253.7 nm) showed 101% when Y ₂ O ₃ S:Eu phosphor was 100%. However, the emission luminance of the simple mixture before firing was 67%.

Example 7

Mix 70 weight units of terbium-activated yttrium oxysulfide phosphor (Y ₂ SiO ₅ : Tb) with 30 weight units of barium sulfate (BaSO ₄ ), and then add flux (1 weight unit of Li ₂ B ₄ O ₇ ) After thorough mixing, it was fired at 1300° C. for 2 hours, followed by washing and drying to obtain the light-emitting composition of the present invention. The luminance of this luminescent composition when excited by ultraviolet rays (253.7 nm) showed 110% when the Y ₂ SiO ₅ :Tb phosphor was 100%. However, the emission luminance of the simple mixture before firing was 60%.

Example 8

Mix 50 weight units of terbium-activated gadolinium oxysulfide phosphor (Gd ₂ O ₂ S:Tb) with 50 weight units of barium sulfate (BaSO ₄ ), and then use the same method as in Example 5 to obtain the Luminous composition. The luminance of this luminescent composition when excited by ultraviolet light (253.7 nm) was 91% when the Gd ₂ O ₂ S:Tb phosphor was 100%. In addition, the emission luminance of the simple mixture before firing was 65%.

Example 9

After mixing 50 weight units of europium-activated yttrium oxysulfide vanadate phosphor (YVO ₄ : Eu) and 50 weight units of barium sulfate (BaSO ₄ ), the same method as in Example 5 was adopted to obtain the luminescence of the present invention. Composition. The luminance of this luminescent composition when excited by ultraviolet rays (253.7nm) was 83% when the YVO ₄ :Eu phosphor was 100%.

Example 10

Prepare liquid medicine A liquid, B liquid, C liquid and D liquid according to the following method.

Solution A: Dissolve 950 grams of Y ₂ O ₃ and 50 grams of Eu ₂ O ₃ in a given amount of hydrochloric acid and dilute to 10 liters.

Solution B: Dissolve 1000 g of BaCl ₂ ·2H ₂ O in water and dilute to 5 liters.

Solution C: Dissolve 600 grams of oxalic acid in 3 liters of warm water.

Solution D: Make 3 liters of dilute sulfuric acid solution from 500 grams of sulfuric acid.

Slowly add liquid D into the mixture of liquid A and liquid B while stirring. After the addition is complete, continue to add liquid C slowly. After the addition, after a sufficient stirring time, the obtained precipitate product was washed with water, dehydrated after washing, placed in a quartz furnace container, and sintered at a temperature of 1000°C in air for 3 hours to become Burn raw materials.

Add flux (0.1% BaCl ₂ ·2H ₂ O and 0.1% H ₃ BO ₃ ) to the above firing raw materials and mix thoroughly, fill it into a crucible and fire at 1400°C for 4 hours. Thereafter, it was taken out, washed with water sufficiently, dehydrated and dried after washing, and sieved with a 150-mesh sieve to form a luminescent composition.

Table 2 shows the results of measuring the particle sizes of the firing raw materials and the luminescent composition.

Example 11

In the mixture of solution A and solution B of Example 10, slowly add the mixture of solution C and solution D while stirring, and then the precipitate product obtained after fully stirring is prepared according to the same steps as in Example 10. Firing raw materials and luminescent composition.

Comparative example 1

Slowly add liquid C to liquid A in Example 10 while stirring, and then follow the same procedure as in Example 10 to obtain a raw material for firing.

Put 50 weight units of the calcined raw material (Y, Eu) ₂ O ₃ and 50 weight units of commercially available BaSO ₄ and flux (1% BaCl ₂ 2H ₂ O and 0.2 H ₃ BO ₃ ) were added together, filled into a crucible, and then made a luminescent composition under the same conditions as in Example 10. Table 2 shows the particle sizes of the fired raw materials and the luminescent composition.

Example 12

Wash and dehydrate the precipitate obtained in Example 10, then add flux (0.5% BaCl ₂ 2H ₂ O and 0.1% H ₃ BO ₃ ), mix thoroughly, and place in a quartz furnace container at 1400°C Calcined at the temperature of 4 hours, then washed with water, dried after washing, and then sieved with a 150-mesh sieve to obtain a luminescent composition. Table 2 shows the particle sizes of the fired raw materials and the luminescent composition.

Example 13

Barium sulfate (BaSO ₄ ) was dispersed for 40 minutes in a ball mill equipped with water and an aluminum bowl in advance, and then the slurry containing 30 weight units of BaSO ₄ was put into water, and 70 weight units were added to it while stirring. Units of (Y,Eu) ₂ O ₃ co-precipitated oxides. After further stirring, 0.5 weight units of a diluted solution of propylene emulsion (Nippon Propylene Co., Ltd. HA-24) was added. Then the obtained complex was dehydrated, dried and sieved, then adding flux (0.1% BaCl ₂ 2H ₂ O and 0.3% H ₃ BO ₃ ), mixed thoroughly and then filled into the crucible. Fired at a temperature of 1350°C for 4 hours. The fired composition was taken out from the crucible, thoroughly washed with water, then dehydrated and dried, and screened with a 150-mesh sieve to obtain the luminescent composition of the present invention.

Example 14

Add 30 weight units of commercially available BaSO ₄ into the solution obtained by fully dissolving 0.5 weight units of gelatin in warm water, and then add 70 weight units of (Y, Eu) ₂ O ₃ co-precipitated oxides after fully stirring. After stirring, a solution of 0.3 weight units of rubber arabic was added. Thereafter, the obtained composite was dehydrated, dried, sieved, mixed with a flux, fired, etc., and subjected to the same treatment as in Example 13 to obtain the light-emitting composition of the present invention.

Comparative example 2

Combine 70 weight units of (Y,Eu) ₂ O ₃ co-precipitated oxide with 30 weight units of commercially available BaSO ₄ passing through 150 mesh and flux (1% BaCl ₂ 2H ₂ O and 0.2% H ₃ BO ₃ ) were mixed, the resulting mixture was filled into a crucible, and then fired under the same conditions as in Example 3, thereby obtaining a luminescent composition.

As above, the particle size, particle diameter and luminance of each light-emitting composition of Examples 13, 14, and Comparative Example 2 were measured, and the results are shown in Table 3.

It can be clearly seen from Table 3 that the luminescent composition of the present invention exhibits excellent brightness and is a luminescent composition with a narrow particle size distribution range.

Add 38 weight units of (Y,Eu) ₂ O ₃ co-precipitated oxide and rib flux (1% by weight of BaCl·2H ₂ O and 0.3% H ₃ BO ₃ ), filled into the crucible after thorough mixing, and then fired under the same conditions as in Example 13, so as to obtain the present invention consisting of europium-activated yttrium oxide phosphor and barium sulfate luminous composition.

Example 16

Except for the use of 27 weight units of calcium carbonate, 37 weight units of ammonium sulfate and (Y, Eu) ₂ O ₃ co-precipitated oxides, the others are the same as in Example 15, thereby obtaining the fluorescence of yttrium oxide activated by europium The luminescent composition of the present invention is composed of body and calcium sulfate.

Example 17

Using 40 weight units of strontium nitrate, 25 weight units of ammonium sulfate and 35 weight units of (Y, Eu) ₂ O ₃ co-precipitated oxides, in addition to adopting the same method as in Example 15, thereby obtaining the activated oxidation by europium The luminescent composition of the present invention is composed of yttrium phosphor and strontium sulfate.

Comparative example 3

A co-precipitated oxide of 50 weight units of strontium sulfate and 50 weight units of (Y,Eu) ₂ O ₃ was used, and the same procedure as in Example 15 was used for the rest, so as to obtain a luminescent composition with the same composition as in Example 17.

The particle size and particle diameter of each light-emitting composition of Examples 15, 16, 17 and Comparative Example 3 were measured above, and the results are shown in Table 4.

As can be clearly seen from Table 4, the light-emitting composition of the present invention obtained by this production method has a narrower particle size distribution range.

Example 18

43.5 weight units of the red light-emitting composition (Y, E) ₂ O ₃ BaSO ₄ (X/Y=0.657/0.348) of the present invention shown in Example 1, 33.7 weight units of LaPO ₄ : Ce , the green luminescent component of Tb phosphor (X/Y=0.359/0.547) and the blue luminescent component of 22.8 weight units of Ca ₂ B ₅ O ₉ Cl:Eu phosphor (X/Y=0.134/0.094) are thoroughly mixed , using this mixed phosphor to make a coating liquid, and then apply the liquid in a glass tube so that the coating amount as a mixed phosphor reaches about 4 mg/cm, and then manufacture a fluorescent lamp by an existing method. This fluorescent lamp showed high color rendering of white emission among the emitted colors (X/Y=0/345/0.347), and its luminance was 99% for the same fluorescent lamp (Br=100%) except that BaSO ₄ was not used.

Example 19

Mix 50 weight units of the red light-emitting composition of the luminescent composition (Y _0.93 , Eu _0.637 ) ₂ O ₃ ·BaSO ₄ , 35 weight units of the green light-emitting composition of LaPO ₄ : Ce, Tb phosphor, and 15 weight units of (Sr, Ca) ₅ (PO ₄ ) Cl:Eu ²⁺ blue light-emitting components of the phosphor are thoroughly mixed, and then the mixed phosphor is used to make a coating liquid, and then coated in a glass tube to obtain a 30-watt white light-emitting fluorescent lamp . The coating amount was 4 mg/cm. The fluorescent lamp showed a luminous efficiency of 711m/w and a color rendering index of 82.

Example 20

35 weight units of red light emitting composition (Y _0.1 Gd _0.87 Eu _0.03 ) ₂ O ₃ BaSO ₄ and 35 weight units of LaPO ₄ : Ce, green light emitting composition of Tb phosphor and 15 weight units of BaMg ₂ Al ₁₆ O ₂₇ : the blue light-emitting component of the Eu phosphor, and the same white light-emitting fluorescent lamp as in Example 16 was produced. The fluorescent lamp exhibited a luminous efficiency of 691m/w and a color rendering index of 83.

Example 21

Using 50 weight units of luminescent composition (Gd _0.955 Eu _0.045 ) ₂ O ₃ ·0.7BaSO ₄ red luminescent component, 30 weight units of LaPO ₄ : Ce, green luminescent component of Tb phosphor, 15 weight units of Ca ₂ B ₅ O ₉ Cl; the blue-green luminescent component of Eu ²⁺ phosphor and the blue-green luminescent component of 30 weight units of 2(Ba, Ca, Sr)O·0.9P ₂ O ₅ 0.1B ₂ O ₃ phosphor. Become the same white luminescent fluorescent lamp as in Example 16. The fluorescent lamp exhibited a luminous efficiency of 70ml/w and a color rendering index of 82.

Comparative example 4

Using 37 weight units of (Y _0.693 Eu _0.037 ) ₂ O ₃ phosphor for red emission, 43 weight units of LaPO ₄ : Ce, green emission of Tb phosphor and 20 weight units of (Sr, Ca) ₅ (PO ₄ ) _3Cl :Eu phosphor, by the same method as in Example 16, a white-emitting fluorescent lamp having a composition ratio known in the past was produced. The fluorescent lamp exhibited a luminous efficiency of 701 m/w and a color rendering index of 82.

Comparative Example 5

Put 25 weight units of (Y _0.963 , Eu _0.037 ) ₂ O ₃ phosphor, 35 weight units of LaPO ₄ : Ce, Tb phosphor, 15 weight units of (Sr, Ca) ₅ (PO ₄ ) ₃ Cl: Eu ^{2 +} and 25 weight units of BaSO ₄ (special grade reagent) were mixed, and the same method as in Example 16 was used to manufacture a white light-emitting fluorescent lamp. The fluorescent lamp showed a luminous efficiency of 591 m/w and a color rendering index of 79, which was insufficient in brightness and lowered in the color rendering index.

Table 1

Mixing ratio of luminescent composition (% by weight) Relative luminescence Reduced material cost

no

(Y, Eu) ₂ O ₃ B _a SO ₄ brightness (%) amount (yen/kg) rate (%)

1 Standard 100 0 100 0 0

2 Invention product 90 10 106 4000 9.5

3 Invention product 50 50 106 20000 47.5

4 Invention product 30 70 105 28000 66.7

5 Invention product 20 80 103 32000 76.2

6 Invention product 10 90 95 36000 85.7

7 Comparative example 0 100 0 40000 95.2

Table 2

Example

Comparative example 1

10 11 12

(Y, Eu) ₂ O ₃ BaSO ₄

-

Central particle size d ₅₀ 5.1μ 6.1μ 4.9μ 17.0μ

-

Burnt average particle size d5.5μ 6.5μ 5.7μ 20.5μ

become

Original particle size distribution

Material ~4μ 26% 27% - 35% 0%

4～16μ 72% 71% 63% 37%

16μ～ 2% 2% - 2% 63%

Central particle size d ₅₀ 8.2μ 8.4μ 8.5μ 6.3μ

hair average particle size d8.5μ 8.8μ 8.9μ 11.3μ

Light particle size distribution

Group

Cheng ~5μ 17% 18% 18% 33%

Object 5～15μ 81% 77% 76% 49%

16μ～ 2% 5% 6% 18%

3

Example Example 13 Example 14 Comparative Example 2

Central particle size d ₅₀ 6.5 6.7 7.1

Average particle size 7.8 8.4 12.2

Particle size distribution

0～4μ 145.% 17.7% 18.2%

4～16μ 80.6% 77.7% 59.2%

Above 16μ 4.9% 4.6% 22.6%

Powder Brightness 102 101 100

Film Brightness 107% 105% 100%

Table 4

Example 15 Example 16 Example 17 Comparative Example 3

Central particle size d ₅₀ 9.9 10.0 9.2 8.5

Particle size distribution

0～5μ 12% 11% 13% 18%

5～15μ 68% 71% 75% 56%

Above 15 20% 18% 12% 20%

Claims (18)

1. A luminescent composition, which contains particles formed by fusion of an oxide-based phosphor and an alkaline earth metal sulfate with a content of 5% (weight) to 95% (weight), the oxide-based phosphor The phosphor contains at least one of rare earth elements and noble metal elements, and the alkaline earth metal sulfate contains at least one of barium, strontium and calcium, and contains trace elements as activators as needed. 2. The luminescent composition according to claim 1, characterized in that the content of said sulfate is 10-95% by weight. 3. The luminescent composition according to claim 1, wherein said alkaline earth metal is at least one of barium and strontium, or is mainly composed of these. 4. The luminescent composition according to claim 1, wherein the phosphor is a rare earth oxide phosphor containing europium as an activator. 5. The luminescent composition according to claim 1, wherein said trace element is at least one of europium and lead. 6. A method for producing a luminescent composition, characterized in that the same content of oxide-based phosphors or phosphor raw materials containing at least one of rare earth elements and noble metal elements is 5% (weight) to 95% (weight) ), containing at least one of barium, strontium, and calcium, and containing alkaline earth metal sulfate as needed as an activator of trace elements, the phosphor or its activator is placed in at least one The phosphor raw material obtained by solid-solution in the matrix raw material is mechanically mixed with alkaline earth metal sulfate, adjusted, and fired at a temperature ranging from 550°C to 1600°C. 7. The method for producing a luminescent composition according to claim 6, wherein a compound containing at least one of barium, phosphorus and boron is added as a flux. 8. The method for producing a luminescent composition according to claim 6, wherein the content of said alkaline earth metal sulfate is 10-95% by weight. 9. The method for producing a luminescent composition according to claim 6, wherein said firing is carried out at any temperature in the range of 800-1550°C. 10. The method for producing a luminescent composition according to claim 6, characterized in that oxalic acid or a soluble Water oxalate, and sulfuric acid or water-soluble sulfate solution are added together or separately, and the oxalate of the above-mentioned metal elements constituting the matrix and the precipitate of the above-mentioned alkaline earth metal sulfate obtained in this way are used as the raw material of the phosphor. In the main part, the phosphor raw material is fired. 11. The manufacturing method of the luminescent composition according to claim 6, characterized in that the luminescent material composed of phosphor or obtained by putting its activator in at least one matrix raw material for solid solution and When the alkaline earth metal sulfate is mixed, the alkaline earth metal sulfate is adhered to the phosphor raw material in a dispersed state in a solvent to form a complex, which is then dried and then fired. 12. The method for producing a luminescent composition according to claim 6, wherein said alkaline earth metal sulfate is composed of its primary substance. 13. The method for producing a luminescent composition according to claim 12, wherein said primary substance is composed of an alkaline earth metal compound and ammonium sulfate. 14. A use of a luminescent composition for a fluorescent lamp, characterized in that the luminescent composition contains particles formed by fusion bonding the oxide-based phosphor as claimed in claim 1 with an alkaline earth metal sulfate as a luminescent substance And included in the fluorescent film. 15. The use of the luminescent composition in a fluorescent lamp according to claim 14, characterized in that the fluorescent film contains a blue luminescent substance with a maximum luminescence wavelength in the range of 430-475nm, and a blue luminescent substance with a maximum luminescence wavelength in the range of 520-560nm. Green luminescent substances with a wavelength of 595-630nm, and red luminescent substances with a maximum emission wavelength within the range of 595-630nm. 16. The use of the luminescent composition in a fluorescent lamp according to claim 15, wherein the fluorescent film further contains a blue-green luminescent substance having a maximum luminescence wavelength within the range of 480-500nm. 17. The use of the luminescent composition for fluorescent lamps according to claim 15, characterized in that the above-mentioned red luminescent substance is composed of a luminescent composition containing a kind of particle, and the particle is prepared by adding europium as an activator It is formed by melting and adhering rare earth oxide phosphors and alkaline earth metal sulfates. 18. The use of the luminescent composition in a fluorescent lamp according to claim 14, wherein the phosphor is an oxide-based phosphor containing a rare earth element as a constituent element.

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