JP2007191702A - Light emission color converting material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material for the production of a light emission color converting member free from the deterioration of the properties of a fluorescent material in firing in spite of the presence of a fluorescent material having low heat-resistance. <P>SOLUTION: The converting material contains powder of ZnO-B<SB>2</SB>O<SB>3</SB>-SiO<SB>2</SB>glass and one or more kinds of powdery inorganic fluorescent materials selected from oxides, sulfides, oxysulfides, halides and aluminates. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a light emission color conversion material for producing a light emission color conversion member that converts a part of the wavelength of light emitted from a light emitting diode (LED) or the like into another wavelength.

  In an LED element that converts the wavelength using a phosphor, for example, a phosphor powder is mixed and molded into an organic binder resin or the like (mold resin) that seals the light emitting surface of the LED chip, and a part of the light emitted from the LED chip or All are absorbed and converted to the desired wavelength.

However, there is a problem that the mold resin constituting the LED element deteriorates due to heat generation of the LED chip or irradiation with high-output short wavelength (blue to ultraviolet) light, causing discoloration and the like. Therefore, it has been proposed to fix phosphor powder with glass instead of resin. (For example, Patent Document 1)
JP 2003-258308 A

  The luminescent color conversion member disclosed in Patent Document 1 is produced by firing a mixed powder of a glass powder having a high softening point and a phosphor powder. The conversion member manufactured in this way has a feature that the glass as a base material is not deteriorated by heat or irradiation light, and can be manufactured without any problem if it is a phosphor having high heat resistance.

  However, the luminescent color conversion member is an inorganic phosphor powder such as a phosphor having relatively low heat resistance, such as an oxide phosphor, a sulfide phosphor, an oxysulfide phosphor, a halide phosphor, and an aluminate phosphor. When it contains, there exists a possibility that a fluorescent substance may deteriorate at the time of baking.

  An object of the present invention is to provide a luminescent color conversion material for preparing a luminescent color conversion member that does not deteriorate the characteristics of the phosphor during firing, even though it contains a phosphor having low heat resistance.

  As a result of various experiments, the present inventors have found that if a glass having a specific composition system is used, even if a phosphor having low heat resistance is used, the characteristics are not deteriorated, and the present invention is proposed. Is.

That is, the luminescent color conversion material of the present invention includes one or more inorganic fluorescent materials selected from ZnO—B ₂ O ₃ —SiO ₂ glass powder and oxides, sulfides, oxysulfides, halides, and aluminates. It contains body powder. ZnO—B ₂ O ₃ —SiO ₂ -based glass has a feature that the softening point is relatively low, so that it is difficult to degrade the inorganic phosphor during firing. Therefore, the luminescent color conversion member can be used without degrading the properties of phosphors having low heat resistance such as oxide phosphors, sulfide phosphors, oxysulfide phosphors, halide phosphors, and aluminate phosphors. It can be produced.

  The mixing ratio of the glass powder and the inorganic phosphor powder is preferably in the range of 99.99: 0.01 to 70:30 by mass ratio.

It is preferable that glass powder contains 5 to 60% of ZnO, 5 to 50% of B ₂ O ₃ and _{2 to} 30% of SiO ₂ as a glass composition.

  The luminescent color conversion material of the present invention is preferably provided in the form of a green sheet or paste.

  Further, the luminescent color conversion member of the present invention emits fluorescence in the visible light region of 380 nm to 780 nm when irradiated with light having an emission peak in a wavelength range of 250 nm to 500 nm, and the luminescent color conversion material is fired. It is characterized by.

  Furthermore, the white LED of the present invention is characterized by using the emission color conversion member.

  If the luminescent color conversion material of the present invention is used, the characteristics of a phosphor having low heat resistance (oxide phosphor, sulfide phosphor, oxysulfide phosphor, halide phosphor or aluminate phosphor) are deteriorated. Without this, the luminescent color conversion member can be produced. Therefore, the degree of freedom in designing the luminescent color conversion member can be expanded. In addition, since the light emitting color conversion member obtained is stable to heat and irradiation light, the glass as a base material is not discolored and can produce an LED element having high weather resistance, high reliability, and long life.

  Moreover, by using it in the form of a green sheet or paste, it is possible to produce a light emitting color conversion member having a thin wall thickness and having phosphors dispersed uniformly. This luminescent color conversion member can efficiently convert light energy emitted from the LED. The energy conversion efficiency referred to in the present invention means that the energy of the light source is a (W: Watt), the energy of light having the same wavelength as that of the light source transmitted through the light emission color conversion member is b (W), and the light emission color conversion member This is a value represented by [c / (ab)] × 100 (%), where c (W) is the energy of light converted by the wavelength of the light source.

  The luminescent color conversion material of the present invention contains a specific glass powder and phosphor powder, and the luminescent color conversion member of the present invention is produced from the luminescent color conversion material. The luminescent color conversion member referred to in the present invention emits fluorescence in a visible light region of 380 nm to 780 nm when irradiated with light having an emission peak in a wavelength region of 250 nm to 500 nm. In other words, it refers to a member that absorbs at least part of it and converts it into visible fluorescence when irradiated with excitation light of ultraviolet (250 to 400 nm) or blue (400 to 500 nm). The luminescent color conversion member of the present invention is obtained by sintering a luminescent color conversion material provided in the form of a simple mixture of glass powder and phosphor powder, as well as a green sheet and paste, and its shape is particularly limited. For example, it includes not only a member having a specific shape such as a plate shape, a columnar shape, and a hemispherical shape, but also a film formed on the surface of the substrate.

The glass powder has a role as a medium for stably holding the inorganic phosphor, and ZnO—B ₂ O ₃ —SiO ₂ glass is used in the present invention. This type of glass has a characteristic that the softening point is relatively low, so that the inorganic phosphor is hardly deteriorated during firing.

The ZnO—B ₂ O ₃ —SiO ₂ -based glass preferably contains 5 to 60% ZnO, 5 to 50% B ₂ O ₃ , and _{2 to} 30% SiO ₂ as a glass composition. The reason for determining the glass composition range is as follows.

  ZnO is a component that improves the meltability by lowering the melting temperature of the glass, and is preferably contained in the glass composition in an amount of 5 to 60%. If it is less than 5%, the sintering temperature becomes high, and if it is more than 60%, the chemical durability is deteriorated. A more preferable range of ZnO is 20 to 50%.

B ₂ O ₃ is a component that forms a glass network, and is preferably contained in an amount of 5 to 50% in the glass composition. If it is less than 5% in the glass composition, the sintering temperature tends to be high, and if it exceeds 50%, the chemical durability of the glass is deteriorated. A preferable range of B ₂ O ₃ is 30 to 48%.

SiO ₂ is a component that forms a glass network and improves durability. It is preferable to contain 2 to 30% in the glass composition. If it is less than 2% in the glass composition, the effect is not obtained, and if it exceeds 30%, the sintering temperature becomes high. The preferred range for SiO ₂ is 2-15%.

  In addition to the above components, various components may be added up to a total of 20% by mass%, preferably up to 10%, within a range not impairing the gist of the present invention.

For example, Al ₂ O ₃ can be contained up to 5%, preferably 0.1 to 4%, more preferably 0.5 to 2% for the purpose of improving water resistance. When the content of Al ₂ O ₃ exceeds 5%, the firing temperature tends to be high.

Further, as an alkali metal oxide, Li ₂ O is 0 to 5%, particularly 0 to 3%, Na ₂ O is 0 to 10%, particularly 2 to 8%, K ₂ O is 0 to 5%, particularly 0 to 2%. % Can be contained. Alkali metal oxides are components that lower the softening point of glass. When there is too much content of an alkali metal oxide, there exists a tendency for a weather resistance to fall.

  Further, the total amount of alkaline earth metal oxide can be up to 10%, preferably 0 to 8%. Further, as an alkaline earth metal oxide, MgO is 0 to 5%, particularly 0 to 3%, CaO is 0 to 5%, particularly 0 to 3%, SrO is 0 to 5%, particularly 0 to 3%, BaO. 0 to 5%, especially 0 to 3% can be contained. Alkaline earth metal oxides are components that improve the meltability by lowering the melting temperature of the glass. When there is too much content of alkaline-earth metal oxide, there exists a tendency for the chemical durability of glass to fall.

Further, P ₂ O ₅ may be added up to 10% for the purpose of stabilizing the glass, and La ₂ O ₃ may be added up to 10% for the purpose of improving the water resistance. When the content of P ₂ O ₅ is too large, the water resistance tends to be inferior. Further, when the content of La ₂ O ₃ is too large, crystals of La ₂ O ₃ core is likely to precipitate, they tend to devitrification increases.

  The softening point of the glass powder is preferably 750 ° C. or lower, and more preferably 650 ° C. or lower. If the softening point exceeds 750 ° C., the firing temperature also increases, so the inorganic phosphor powder tends to deteriorate and the light emission intensity tends to be inferior. In addition, although a minimum is not specifically limited, Generally it is 400 degreeC or more, Furthermore, it is 450 degreeC or more.

As the inorganic phosphor powder, one or more selected from the group consisting of oxide phosphor, sulfide phosphor, oxysulfide phosphor, halide phosphor and aluminate phosphor with low heat resistance is used. Examples of the oxide phosphor include Ba ₂ SiO ₄ : Eu ²⁺ , SrBaSiO ₄ : Eu ²⁺ , and examples of the sulfide phosphor include ZnS: Cu ⁺ , Al ³⁺ , SrS: Eu ^{2+, and the} like. Examples of the oxysulfide phosphor include Y ₂ O ₂ S: Eu ³⁺ . Examples of the halide phosphor include M ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ (M is Sr, Ca, Ba or Mg). Examples of the aluminate phosphor include BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , Mn ²⁺ , SrAl ₂ O ₄ : Eu ^{2+ and the} like. Many of these phosphors have low chemical durability, and are deteriorated by moisture, heat, and light when used alone for a long time. Therefore, it is usually used in a vacuum or a rare gas. However, when the sintered body is made of glass powder, the phosphor is not directly exposed to the atmosphere, and deterioration due to the influence from the atmosphere hardly occurs.

  In addition to the phosphor powder, a phosphor having relatively high heat resistance, for example, a YAG phosphor, a nitride phosphor, an oxynitride phosphor, etc. may be used in combination.

  In the present invention, the mixing ratio of the glass powder and the inorganic phosphor powder may be adjusted so as to optimize the energy conversion efficiency. However, if the phosphor is too much, it becomes difficult to sinter and the porosity increases. As a result, problems arise such that the excitation light is not efficiently irradiated onto the phosphor efficiently, and the mechanical strength of the resulting luminescent color conversion member tends to decrease. On the other hand, if the amount is too small, it is difficult to obtain sufficient light emission intensity. From such a viewpoint, the mixing ratio of the glass powder and the inorganic phosphor powder is preferably in the range of 99.99: 0.01 to 70:30 in terms of mass ratio. Furthermore, it is preferable to adjust in the range of 99.95: 0.05 to 80:20, particularly 99.92: 0.08 to 85:15.

  The energy conversion efficiency of the luminescent color conversion member varies depending on the type and content of the phosphor particles dispersed in the glass and the thickness of the luminescent color conversion member. And the mixing ratio of the inorganic phosphor powder may be appropriately selected.

  In order to produce a light emitting color conversion member with high energy conversion efficiency, it is important that the thickness is thin and the phosphor is uniformly dispersed in the member. In order to produce such a member, the material of the present invention may be provided in the form of a green sheet or paste.

  When used in the form of a green sheet, a binder, a plasticizer, a solvent and the like are used together with the glass powder and the inorganic phosphor powder.

  The content ratio of the glass powder and the inorganic phosphor powder may be appropriately adjusted according to the type and content of the inorganic phosphor powder and the thickness of the luminescent color conversion member, but in any case, the mass ratio is 99.99. : It is preferable to adjust within the range of 0.01-70: 30.

  The ratio of the glass powder and the inorganic phosphor powder in the green sheet is generally about 50 to 80% by mass.

  The binder is a component that increases the film strength after drying and imparts flexibility, and the content thereof is generally about 0.1 to 30% by mass. If the content of the binder is too small, it is difficult to obtain the effect sufficiently. On the other hand, if the content of the binder is too large, the binder residue foams during firing, so that bubbles are likely to increase in the resulting luminescent color conversion member, and there is fluorescence that lowers the emission intensity. As the binder, for example, polyvinyl butyral resin, methacrylic resin, ethyl cellulose, nitrocellulose and the like can be used, and these can be used alone or in combination.

  The plasticizer is a component that controls the drying speed and imparts flexibility to the dry film. As the plasticizer, for example, dibutyl phthalate, butyl benzyl phthalate and the like can be used, and these can be used alone or in combination. Although content of a plasticizer is not specifically limited, About 0-10 mass% is common.

  The solvent is a material for slurrying the material, and its content is generally about 1 to 30% by mass. If the content of the solvent is too small, it is difficult to sufficiently disperse the luminescent color conversion material. On the other hand, if the content is too large, the viscosity becomes too low. It is difficult to obtain a coating film having As the solvent, for example, toluene, methyl ethyl ketone or the like can be used alone or in combination.

  As a method for producing a green sheet, the above glass powder and inorganic phosphor powder are mixed, and a predetermined amount of a binder, a plasticizer, a solvent and the like are added to the obtained mixture to form a slurry. Next, this slurry is formed into a sheet on a film of polyethylene terephthalate (PET) or the like by a doctor blade method. Subsequently, after forming the sheet, the organic solvent binder is removed by drying to form a green sheet.

  In order to produce a light emitting color conversion member using the material of the present invention formed into a green sheet in this way, the following method can be suitably used.

First, a green sheet produced using the above-described method and a restraining member that does not react at the firing temperature of the green sheet are prepared and cut into desired dimensions. The reason for using the restraining member is to prevent the material from shrinking in the plane direction due to the surface tension of the glass during firing. As the restraining member, a green sheet-like inorganic material or a porous ceramic substrate can be used. When an inorganic material formed into a green sheet is used as the restraining member, the inorganic material is not particularly limited as long as it is a material that does not sinter at the firing temperature of the luminescent color conversion material. For example, Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , BeO, or BN may be used alone or in combination. Moreover, when making an inorganic material into a green sheet, it can obtain by the method similar to the above. Further, when a porous ceramic substrate is used as the restraining member, there is no particular limitation as long as the luminescent color conversion member and the porous ceramic are difficult to adhere during firing. For example, SiAl ₂ O ₅ , Al ₂ O ₃ MgO, ZrO ₂ can be used. Further, the cutting of the green sheet and the restraining member may be performed after the laminate is manufactured. If it does in this way, the luminescent color conversion member with a small dimensional change rate before and behind baking can be obtained.

  Next, a constraining member is laminated on both sides or one side of the green sheet, integrated by thermocompression bonding to produce a laminate, and then fired to obtain a sintered body. Firing is preferably performed at 450 to 750 ° C, particularly 450 to 700 ° C. When the temperature is lower than 450 ° C., it becomes difficult to obtain a dense sintered body. On the other hand, at a temperature higher than 750 ° C., the inorganic phosphor deteriorates or the glass and the inorganic phosphor react. In addition, when it is desired to obtain a large amount of luminescent color conversion member at a time, it can be obtained by alternately laminating a plurality of green sheets and restraining members, thermocompression bonding, and firing. In addition, if you want to obtain a thicker conversion member, after laminating a plurality of phosphor composite green sheets, laminate the constraining member on both sides or one side of the laminated green sheets, heat-press and fire Can be obtained at

  Subsequently, the restraining member is removed. When a green sheet containing an inorganic composition is used as a restraining member, an unsintered inorganic composition remains on the surface of the luminescent color conversion member after firing, but ultrasonic cleaning is performed. Thus, the remaining inorganic composition can be removed.

  In this way, it is possible to produce a light emitting color conversion member that is chemically stable, has a small thickness, has a uniform thickness, and high energy conversion efficiency. Furthermore, the light emitting color conversion member produced using the restraining member can easily have a porosity of 10% or less. If the porosity can be reduced to 10% or less, light scattering does not increase and a sufficient amount of light is transmitted, so that energy conversion efficiency is improved. Further, the mechanical strength of the luminescent color conversion member is also increased. A more preferable range of the porosity is 8% or less. The porosity means a value obtained by (1−actual density / theoretical density) × 100 (%) based on the actual density and the theoretical density measured by the Archimedes method. The “theoretical density” means a density calculated based on the density and the mixing ratio of the glass powder and the inorganic phosphor powder.

  Next, the case where it supplies with the form of a paste is demonstrated.

  When used in the form of a paste, glass powder, inorganic phosphor powder and vehicle are used.

  As the vehicle, for example, one obtained by dissolving ethyl cellulose in terpineol, one obtained by dissolving nitrocellulose with isoamyl acetate, or the like can be used.

  The paste is prepared by kneading glass powder, phosphor powder and vehicle using a three-roll mill and performing uniform dispersion treatment. In addition, although the example which used the three roll mill was given as a preparation method of a paste, it is not restricted to this, Various methods generally used for preparation of glass paste are applicable.

  A method for producing a luminescent color conversion member using the luminescent color conversion material of the present invention thus pasted will be described below.

  First, a pasted luminescent color conversion material is applied onto a substrate. As the base material, a plate glass or the like suitable for the thermal expansion coefficient of the luminescent color conversion member after sintering is preferably used. As a coating method, for example, a screen printing method can be employed. When the screen printing method is adopted, it is possible to easily form a coating layer having a uniform thickness. The thickness of the coating layer may be appropriately adjusted according to the desired fluorescent color. In addition, if a paste is applied after masking, letters and pictures that emit fluorescent colors can be formed on the substrate.

  Next, the applied paste material is degreased at a temperature of 300 to 400 ° C. and subsequently baked at 450 to 700 ° C. In this manner, a film-like luminescent color conversion member can be formed on a substrate such as plate glass. In addition, it is preferable to select the temperature at which the glass powder flows sufficiently as the firing temperature. However, if it exceeds 700 ° C., the phosphor reacts with the glass and it becomes difficult to obtain a desired emission color, which is not preferable.

  The luminescent color conversion member thus obtained can be used as a white light source typified by a white LED, for example, by combining with a blue light source such as a blue LED element. In the white LED, part of the blue light incident on the luminescent color conversion member is converted into light having a different wavelength by the inorganic phosphor, and the remaining blue light is transmitted. Blue light is converted into white light by combining the light with the converted wavelength and the blue light transmitted through the light emitting color conversion member to synthesize a spectrum close to white light.

Example 1
Table 1 evaluates the difference in luminance change rate due to the difference in the composition system of the glass powder used.

  First, the luminescent color conversion member was produced as follows.

Glass (ZnO—B ₂ O ₃ —SiO ₂ glass 1 having a glass composition of 35% by weight of ZnO 35%, B ₂ O ₃ 40%, SiO ₂ 10%, Na ₂ O 10%, Al ₂ O ₃ 5%. ) And glass having a glass composition of SiO ₂ 45%, B ₂ O ₃ 25%, Al ₂ O ₃ 25%, CaO 5% by mass (SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ glass) After preparing glass materials of various oxides and mixing them uniformly, they were put in a platinum crucible and melted at 1200 ° C. for 2 hours to obtain uniform glass. This was pulverized with alumina balls and classified to obtain glass powder having an average particle diameter of 2.5 μm. Next, an inorganic phosphor powder was mixed with the prepared glass powder at a mass ratio shown in Table 1 to prepare a mixed powder. Further, the mixture was pressure-molded with a mold to prepare a cylindrical preform with a diameter of 1 cm.

  Next, the cylindrical preform was heated in an electric furnace (atmosphere) at the firing temperature shown in the table for 20 minutes, and UV light (emission peak wavelength 365 nm, 254 nm) and near ultraviolet diode (emission peak wavelength 400 nm) 3 Relative luminance was measured with a luminance meter (LS-100, manufactured by Minolta Co., Ltd.) by irradiating light of three different wavelengths. The luminance change rate indicates the luminance change rate before and after firing the fluorescent color conversion member, and is represented by (luminance after firing / luminance before firing) × 100 (%). It can be said that the conversion efficiency of a conversion member is so high that this value is large.

As a result, the sample No. 1 of the present invention using ZnO—B ₂ O ₃ —SiO ₂ glass powder. 1, it was confirmed that the luminance change rate was large.

(Example 2)
A luminescent color conversion member was prepared using the luminescent color conversion material of the present invention in the form of a green sheet, and its energy conversion efficiency was evaluated.

  First, a green sheet was produced as follows.

The glass powder (ZnO—B ₂ O ₃ —SiO ₂ glass 1) prepared in Example 1 and the ZnS phosphor powder (average particle size: 8 μm, manufactured by Kasei Optonics Co., Ltd.) are in a mass ratio of 95: 5. And mixed to prepare a mixed powder. Next, 30% by mass of methacrylic acid resin as a binder, 3% by mass of dibutyl phthalate as a plasticizer, and 20% by mass of toluene as a solvent are added to the prepared mixed powder 100 and mixed to prepare a slurry. did. Subsequently, the slurry was formed into a sheet on a PET film by a doctor blade method and dried to obtain a green sheet of a light emitting color conversion material having a thickness of 50 μm.

  Next, an inorganic material made into a green sheet was prepared as a restraining member. As the inorganic material, alumina powder (ALM-21 manufactured by Sumitomo Aluminum Co., Ltd., average particle size: 2 μm) is used, and the mixing ratio and method are the same as those for the green sheet made of the light emitting color conversion member forming material. A thickness-constrained green sheet (alumina green sheet) was obtained.

  Subsequently, the luminescent color conversion material green sheet and the constrained green sheet are cut into a size of 100 × 100 mm, three luminescent color conversion material green sheets are laminated on the constrained green sheet, and further, the constrained green sheet is further formed thereon. Were laminated and integrated by thermocompression bonding to produce a laminate, which was then fired at 600 ° C. Thereafter, ultrasonic cleaning was performed to remove the unsintered alumina layer remaining on the surface of the obtained sintered body, and a luminescent color conversion member having a size of 100 × 100 mm and a thickness of 120 μm was produced.

  When the emission color conversion member thus obtained was irradiated with ultraviolet light (emission peak wavelength 400 nm) from behind the member, green light of ZnS was obtained. Moreover, when the energy conversion efficiency and the porosity were measured, the energy conversion efficiency was 12% and the porosity was 2%.

  The energy conversion efficiency depends on the energy (a) of the light source, the energy (b) of the light having the same wavelength as the light source transmitted through the luminescent color conversion member, and the wavelength of the light source in the luminescent color conversion member using a spectrophotometer. The energy of the converted light was measured from (c) and obtained from [c / (ab)] × 100 (%).

  The porosity was determined by measuring the measured density and the theoretical density using Archimedes' method, and calculating from (1−measured density / theoretical density) × 100 (%).

(Example 3)
Glass containing ZnO 35%, B ₂ O ₃ 45%, SiO ₂ 10%, Na ₂ O 7%, Al ₂ O ₃ 1%, Li ₂ O 2% by mass (ZnO—B ₂ O ₃ —SiO _{2 2} type glass 2) and glass containing SiO ₂ 50%, BaO 25%, CaO 12%, Al ₂ O ₃ 6%, B ₂ O ₃ 5%, ZnO 2% by mass percentage (SiO ₂ —BaO type glass) After preparing glass materials of various oxides and mixing them uniformly, the mixture was melted and vitrified at a melting temperature shown in Table 2 for 2 hours in a platinum crucible and formed into a film. . Next, the obtained film-like glass was pulverized with a ball mill and then passed through a 325 mesh sieve to obtain a glass powder.

  Next, the obtained glass powder and oxide phosphor powder are mixed so as to have the phosphor content shown in Table 2, and pressure-molded with a mold to produce a button-shaped preform having a diameter of 1 cm. did. The preform was fired at the sintering temperature shown in Table 2, and then the fired body was processed to obtain a disk-like light emitting color conversion member having a diameter of 8 mm and a thickness of 0.55 mm.

  About the obtained luminescent color conversion member, the luminescence spectrum was measured and the luminous efficiency was calculated | required by calculation. In the emission spectrum, light from a blue LED (emission peak wavelength: 460 nm) is incident on one side of a sample in an integrating sphere, and light emitted from the surface opposite to the surface is taken into a PC through a small multichannel spectrometer. It is. The luminous efficiency was calculated by multiplying the obtained emission spectrum by the standardized visibility to obtain the total luminous flux (lm) and then dividing by the power (W) applied to the excitation blue LED. The luminous efficiency is shown in Table 2.

As can be seen from Table 2, Sample No. of the present invention using ZnO—B ₂ O ₃ —SiO ₂ glass powder. 3, it was confirmed that the luminous efficiency was high. On the other hand, Sample No. using SiO ₂ —BaO glass powder having a high firing temperature. In 4, the luminous efficiency was extremely inferior.

Claims (6)

Light emission comprising ZnO—B ₂ O ₃ —SiO ₂ glass powder and at least one inorganic phosphor powder selected from oxides, sulfides, oxysulfides, halides and aluminates Color conversion material.   2. The luminescent color conversion material according to claim 1, wherein a mixing ratio of the glass powder and the inorganic phosphor powder is in a range of 99.99: 0.01 to 70:30 by mass ratio. The light emission according to claim 1 or 2, wherein the glass powder contains, by mass%, ZnO 5 to 60%, B ₂ O ₃ 5 to 50%, SiO ₂ 2 to 30% as a glass composition. Color conversion material.   The luminescent color conversion material according to any one of claims 1 to 3, which is provided in the form of a green sheet or a paste.   A luminescent color conversion member obtained by firing the luminescent color conversion material according to any one of claims 1 to 4, wherein when irradiating light having an emission peak in a wavelength range of 250 nm to 500 nm, 380 nm An emission color conversion member that emits fluorescence in a visible light region of ˜780 nm.   A white LED comprising the luminescent color conversion member according to claim 5.