Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
  • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
  • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
  • C09K11/7774—Aluminates
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/12—Silica-free oxide glass compositions
  • C03C3/14—Silica-free oxide glass compositions containing boron
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
  • C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides

Definitions

• the present invention relates to a phosphor dispersion glass characterized in that a phosphor as a light emitting material is sealed in glass.
• white LEDs have been developed as white light sources, and power-saving and high color rendering white LEDs are required.
• commercially available white LEDs have a configuration in which a blue GaN-based LED is used as a light source and a cerium-doped YAG oxide phosphor that emits yellow fluorescence is excited. Light from the light source and fluorescence are mixed and appear to the human eye as pseudo white light.
• white light (daylight color) having a high color temperature can be obtained because there are few cyan ( ⁇ 500 nm) and red (600 nm) components.
• White light (bulb color) with a low color temperature cannot be obtained. Therefore, a white light source with high color rendering is realized by adding a plurality of phosphors to compensate for a short wavelength component such as red.
• nitride phosphors are known as high-efficiency red phosphors.
• Patent Document 1 a CaAlSiN 3 phosphor powder activated with Eu is produced, and evaporation of contained components during sintering is prevented. Therefore, it has been proposed to sinter raw materials at 1600 to 2000 ° C. in a high-pressure nitrogen atmosphere.
• the phosphor for LED used for illumination was sealed with an epoxy resin, a silicone resin, or a fluororesin.
• the sealing member is susceptible to deterioration due to heat generation of the element, light, and environmental moisture, and has a short life. Due to long-term use, the resin deteriorates due to ultraviolet light or blue light emitted from the LED, causing problems such as discoloration and deterioration of light transmission characteristics.
• Patent Document 2 a low melting point oxide glass as shown in Patent Document 2 has been proposed.
• a highly weather-resistant LED can be realized by encapsulating the phosphor in the glass.
• the mixture of the phosphor and the glass has a glass transition point.
• the temperature needs to be raised to the above temperature and sintered, and the phosphor may be deactivated by the heat at that time.
• the phosphor-dispersed glass described in Patent Document 3 and Patent Document 4 is used for the oxide phosphor, and Patent Document 5 is used for the oxynitride phosphor. Each phosphor-dispersed glass has been reported.
• Japanese Patent No. 5045432 Japanese Patent Laid-Open No. 2008-19109 JP 2005-11933 A Japanese Patent Laid-Open No. 2008-19109 JP 2011-162398 A
• the phosphor when glass is used as a material for sealing the phosphor, the phosphor may be deactivated by heat during sintering.
• Non-Patent Document 1 Sr 2-x Si 5 N 8: Eu 2+ phosphor the presence of oxygen during heating, divalent Eu has been reported to be oxidized to trivalent. That is, when the nitride phosphor and glass containing oxygen are mixed and sintered, the light emission efficiency of the nitride phosphor may be significantly reduced.
• an object of the present invention is to obtain a phosphor-dispersed glass in which phosphor deactivation is suppressed.
• the inventors have confirmed that when the nitride phosphor is mixed with glass containing oxygen and sintered, the resulting phosphor-dispersed glass becomes black or gray and the luminous efficiency is greatly impaired. From the above findings, it has been clarified that, when an oxide glass having a specific composition is used, the above deactivation can be suppressed even if it is mixed with a nitride phosphor powder and sintered. Further, further investigation shows that deactivation occurs due to the reaction between the components constituting the phosphor and the glass composition components. When an oxide glass having the above composition range is used, a wavelength of 350 to 475 nm is used. It has been clarified that inactivation of the luminous efficiency can be suppressed regardless of the type of phosphor if the phosphor has excitation light.
• the phosphor-dispersed glass according to the first aspect of the present invention is a phosphor-dispersed glass in which phosphor particles are dispersed in glass, and the glass contains 1 to 40% by mass of SiO 2 and B 2 O. 3 to 15 to 65% by mass, ZnO to 1 to 50% by mass, RO (total of at least one selected from the group consisting of MgO, CaO, SrO, and BaO) 0 to 40% by mass, R 2 O (Li 2 O, Na 2 O, and K 2 O at least one of total) selected from the group consisting of 0 to 30 wt%, including ZrO 2 0 ⁇ 5 wt% (however, SiO 2 + B 2 O 3 + ZnO + RO + R 2 O + ZrO 2 is 80% by mass or more).
• the phosphor dispersion glass according to the second aspect of the present invention is a phosphor dispersion glass which phosphor particles are dispersed in the glass, the glass is a SiO 2 1 ⁇ 20 wt%, B 2 10 to 40% by mass of O 3 , 20 to 50% by mass of ZnO, 20 to 40% by mass of RO (total of at least one selected from the group consisting of MgO, CaO, SrO, and BaO), R 2 O ( li 2 O, Na 2 O, and K 2 of at least one of total selected from the group consisting of O) 0 to 10 wt%, including ZrO 2 0 ⁇ 5 wt% (however, SiO 2 + B 2 O 3 + ZnO + RO + R 2 O + ZrO 2 is 80% by mass or more).
• Deactivation in the present specification refers to the case where the obtained phosphor-dispersed glass is visually black or gray, or has an internal quantum efficiency of less than 20%. It is not appropriate to use the phosphor-dispersed glass thus deactivated for the white LED.
• the phosphor-dispersed glass of the present invention can be obtained, for example, by preparing the glass powder material of glass described above, mixing the glass powder material and the phosphor powder, and then sintering.
• the present invention it is possible to obtain a phosphor-dispersed glass in which phosphor deactivation is suppressed. Further, the present invention is not limited to the type of phosphor as long as it is a phosphor having excitation light at a wavelength of 350 to 475 nm, and nitride phosphor particles are sealed in glass while suppressing the deactivation of luminous efficiency. Therefore, it is possible to obtain a high color rendering white LED.
• first embodiment is a phosphor-dispersed glass in which phosphor particles are dispersed in glass, and the glass contains 1 to 2 SiO 2.
• R 2 O total of at least one selected from the group consisting of Li 2 O, Na 2 O and K 2 O
• ZrO 2 in an amount of 0 to 5% by mass (provided that SiO 2 2 + B 2 O 3 + ZnO + RO + R 2 O + ZrO 2 is 80 mass% or more).
• said glass has the specific composition shown above, it was possible to suppress the reaction between the glass and the phosphor and to suppress the deactivation of the phosphor. Moreover, said glass is a composition which suppressed the raise of the softening point, and it can suppress that a fluorescent substance deactivates with a heat
• composition of the glass of the first embodiment will be described.
• content of the component contained in glass is represented by “mass%”, and may be described as “%” below.
• SiO 2 is a glass forming component, and can coexist with B 2 O 3 , which is another glass forming component, to form a stable glass, and is contained in the range of 1 to 40%. If it exceeds 40%, the softening point of the glass rises, and formability and workability become difficult. Preferably, it is in the range of 2 to 35%.
• B 2 O 3 is a glass-forming component, facilitates glass melting, suppresses an excessive increase in the linear expansion coefficient of the glass, and imparts moderate fluidity to the glass during baking.
• the glass is contained in the range of 15 to 65%. If it is less than 15%, depending on the relationship with other components, the fluidity of the glass may be insufficient, and the sinterability may be impaired. On the other hand, if it exceeds 65%, the softening point of the glass rises, making it difficult to form and work. Preferably, it is in the range of 20 to 61%. Also, the upper limit value is more preferably 44% or less.
• ZnO lowers the softening point of the glass and adjusts the linear expansion coefficient to an appropriate range, and is contained in the glass in a range of 1 to 50%. If it exceeds 50%, the glass becomes unstable and devitrification tends to occur. More preferably, it is in the range of 3 to 45%.
• the glass used in the present invention contains B 2 O 3 and ZnO in a total of 20 to 80% and contains other components so that the softening point and the coefficient of thermal expansion can be adjusted to suppress devitrification of the glass. It is preferable to do so. More preferably, it may be 30 to 78%. In particular, in order to suppress the deactivation of the phosphor, it is effective to prevent the phosphor from being damaged by heat. Therefore, while containing SiO 2 which stabilizes the glass and raises the softening point, the RO component and R 2 are contained. It is preferable to contain an O component to suppress an excessive increase in the softening point.
• ZrO 2 suppresses devitrification during melting or sintering of the glass and improves the chemical durability of the glass, and is contained in the range of 0 to 5%. If it exceeds 5%, the stability of the glass is lowered. Preferably it is in the range of 1-3%.
• RO total of at least one selected from the group consisting of MgO, CaO, SrO and BaO
• the thermal expansion coefficient of the glass may become too high.
• it is 37% or less of range.
• a lower limit as 0.2 mass% or more preferably.
• R 2 O (total of at least one selected from the group consisting of Li 2 O, Na 2 O, and K 2 O) lowers the softening point of the glass and adjusts the thermal expansion coefficient to an appropriate range. It is made to contain in 30% of range. On the other hand, if it exceeds 30%, the thermal expansion coefficient is excessively increased. Preferably it is 26% or less of range. Moreover, it is good also considering a lower limit as 0.2% or more preferably.
• the glass adjusts the content of each component of the glass so that SiO 2 + B 2 O 3 + ZnO + RO + R 2 O + ZrO 2 is 80% or more.
• an optional third component may be contained. Preferably it is 84% or more of range. Further, the upper limit may be 100%, more preferably 98% or less.
• second embodiment is a phosphor-dispersed glass comprising 1 to 20 mass% of SiO 2 and 10 of B 2 O 3 . -40 mass%, ZnO 20-50 mass%, RO (total of at least one selected from the group consisting of MgO, CaO, SrO, and BaO) 20-40 mass%, R 2 O (Li 2 O, Na 2 O, and K 2 of at least one of total selected from the group consisting of O) 0 to 10 wt%, including ZrO 2 0 ⁇ 5 wt% (however, SiO 2 + B 2 O 3 + ZnO + RO + R 2 O + ZrO 2 is 80% by mass or more).
• RO total of at least one selected from the group consisting of MgO, CaO, SrO, and BaO
• SiO 2 is contained in the range of 1 to 20%. Preferably, it may be 2 to 15%.
• B 2 O 3 is contained in the glass in the range of 10 to 40%. Preferably it may be 15 to 35%, more preferably 20 to 35%.
• ZnO is contained in the glass in a range of 20 to 50%. Preferably, it may be 25 to 45%.
• B 2 O 3 and ZnO are 30 to 70% in total. More preferably, it may be 40 to 65%.
• ZrO 2 is included at a content within a range of 0-5% in the glass. Preferably, it may be 1 to 3%.
• R 2 O (total of at least one selected from the group consisting of Li 2 O, Na 2 O, and K 2 O) is contained in the range of 0 to 10%.
• the lower limit may be 0.2% by mass or more.
• a further preferred embodiment of the present invention is the above phosphor dispersion glass, the glass is a SiO 2 10 ⁇ 40 wt%, B 2 O 3 to 15 to 65% by mass, ZnO to 1 to 40% by mass, RO (total of at least one selected from the group consisting of MgO, CaO, SrO, and BaO) 0 to 20% by mass, R 2 O (Li 2 O, Na 2 O, and K 2 O at least one total selected from the group consisting of) 8 to 30 wt%, including ZrO 2 0 ⁇ 5 wt% (however, SiO 2 + B 2 O 3 + ZnO + RO + R 2 O + ZrO 2 is 80% by mass or more).
• R 2 O (total of at least one selected from the group consisting of Li 2 O, Na 2 O, and K 2 O) is an essential component and is contained in the range of 8 to 30%. Preferably it is 10% or more and 15% or less of range.
• SiO 2 is contained in the range of 10 to 40%. Preferably, it may be 10 to 35%.
• the lower limit is preferably 12% or more, more preferably 20% or more.
• B 2 O 3 is included at a content within a range of 15 to 65% in the glass. Preferably, it may be 20 to 61%.
• ZnO is contained in the glass in the range of 1 to 40%. Preferably, it may be 5 to 35%. Further, the upper limit value may be more preferably 30% or less.
• the total content of B 2 O 3 and ZnO is 20 to 80%, the softening point and the thermal expansion coefficient are adjusted, and other components are contained so that devitrification of the glass can be suppressed. Is preferred. More preferably, it may be 30 to 78%. In particular, in order to suppress the deactivation of the phosphor, it is effective to prevent the phosphor from being damaged by heat. Therefore, while containing SiO 2 which stabilizes the glass and raises the softening point, the RO component and R 2 are contained. It is preferable to contain an O component to suppress an excessive increase in the softening point.
• ZrO 2 is included at a content within a range of 0-5% in the glass. Preferably, it may be 1 to 3%.
• RO total of at least one selected from the group consisting of MgO, CaO, SrO, and BaO
• the glass in an amount of 0 to 20%. Further, it may be preferably 0 to 15%.
• the reaction between the glass and the phosphor can be suppressed by containing specific components. It became clear that the deactivation of the phosphor could be further suppressed.
• One kind of the specific component may be used, or a plurality of kinds may be used.
• the glass preferably contains 0 to 18% by mass of Al 2 O 3 .
• Al 2 O 3 suppresses devitrification at the time of melting and sintering of the glass or suppresses reactivity with the phosphor, and is preferably contained in the range of 0 to 18% by mass. When it exceeds 18 mass%, stability of glass will be reduced. More preferably, it is the range of 16 mass% or less. Moreover, it is good also considering a lower limit as 0.2 mass% or more preferably.
• the glass preferably contains 0 to 10% by mass of antimony oxide.
• Antimony oxide is presumed to be contained in the glass in the form of Sb 2 O 3 and Sb 2 O 5 , and is considered to exist mainly as Sb 2 O 3 .
• Sb 2 O 3 suppresses the reactivity with the phosphor and is preferably contained in the range of 0 to 10% by mass. When it exceeds 10 mass%, stability of glass will be reduced. More preferably, it is the range of 8 mass% or less. Moreover, it is good also considering a lower limit as 0.2 mass% or more preferably.
• the glass preferably contains 0 to 10% by mass of tin oxide.
• Tin oxide is presumed to be contained in the form of SnO (2-x) (where 0 ⁇ x ⁇ 2), and is considered to exist as SnO 2 or SnO, for example.
• the tin oxide suppresses the reactivity with the phosphor and is preferably contained in the range of 0 to 10% by mass. When it exceeds 10 mass%, stability of glass will be reduced. More preferably, it is 8% or less. Moreover, it is good also considering a lower limit as 0.2 mass% or more preferably.
• the glass contains 0.2% by mass or more and 18% by mass or less of a total of at least one selected from the group consisting of Al 2 O 3 , antimony oxide, and tin oxide.
• SiO 2 + B 2 O 3 + ZnO + RO + R 2 O + ZrO 2 + Al 2 O 3 + antimony oxide + tin oxide may be 100% by mass.
• Nb 2 O 5 , TiO 2 , WO 3 , TeO 2 , La 2 O 3 , CeO 2 , P 2 O 5 or the like represented by a general oxide may be added.
• the transmittance of the glass may be lowered, which is not suitable for the purpose of the present invention. Therefore, it is preferable not to contain the said component substantially.
• the content of the above components is preferably 0.01% by mass or less.
• the glass when PbO is contained in the glass, the glass is colored yellow and absorbs excitation light. Therefore, it is preferable that PbO is not substantially contained.
• the content of the above components is preferably 0.01% by mass or less.
• the glass of the present invention preferably has a linear expansion coefficient of 6 to 13 ppm / ° C. and a softening point of 650 ° C. or less at 30 ° C. to 300 ° C.
• a softening point of 650 ° C. or less at 30 ° C. to 300 ° C.
• it is good also as 630 degrees C or less.
• the softening point is too low, the moisture resistance may be lowered, so the lower limit may be preferably 500 ° C. or higher.
• phosphors have different wavelengths for emitting excitation light depending on components constituting the phosphors.
• any phosphor having excitation light at a wavelength of 350 to 475 nm can be used for the phosphor-dispersed glass without any particular limitation on the type of the phosphor. That is, in the present invention, the phosphor particles preferably have excitation light at a wavelength of 350 to 475 nm.
• the present invention since the present invention is particularly suitable for phosphor particles having excitation light at 415 nm to 475 nm, it may be more preferably 415 to 475 nm.
• the present invention can be particularly suitably used for nitrides that are considered to be easily deactivated.
• (SrCa) AlSiN 3 : Eu 2+ which is a nitride phosphor and Lu 3 Al 5 O 12 : Ce 3+ which is an oxide red phosphor are mixed and used. Since the results are obtained, the present invention may include a plurality of types of phosphors.
• the conversion efficiency (excitation light to fluorescence intensity ratio) and light emission efficiency of the phosphor-dispersed glass of the present invention vary depending on the type and content of phosphor particles dispersed in the glass and the thickness of the phosphor-dispersed glass. .
• the content of phosphor particles and the thickness of the phosphor-dispersed glass may be adjusted so as to optimize the luminous efficiency and color rendering properties. There arises a problem that phosphor particles are not efficiently irradiated. Moreover, when there is too little content, it will become difficult to make it fully light-emit. Therefore, it is preferable to mix so that the content of the phosphor particles is 0.01 to 50% by mass with respect to the total mass of the phosphor-dispersed glass. In particular, the content is preferably 0.5 to 40% by mass.
• the phosphor-dispersed glass of the present invention can be obtained by mixing a glass powder material and a phosphor powder and then sintering the mixture.
• the glass powder material and the phosphor powder may be mixed and then melted once and then molded using a mold or the like.
• the phosphor may be deactivated and is not suitable for the purpose of the present invention.
• the phosphor-dispersed glass of the present invention may contain an inorganic filler.
• the inorganic filler By containing the above inorganic filler, it is possible to adjust thermal properties such as a linear expansion coefficient and a softening point when the phosphor-dispersed glass is sintered.
• the inorganic filler examples include zircon, mullite, silica, titania, and alumina.
• content of this inorganic filler suitably, For example, you may mix so that it may become 0.1 mass% or more and 40 mass% or less with respect to the total mass of this fluorescent substance dispersion
• Glass used for phosphor-dispersed glass is a glass powder material pulverized to a size close to the particle diameter (1 to 100 ⁇ m) of the phosphor powder to be mixed Is preferably used.
• the pulverization may be performed using a mortar or a ball mill, but a jet mill type pulverizer with less contamination in the work process may be used.
• the mixture obtained by mixing the glass powder material of the base material and the phosphor powder obtained in the above manner in a desired ratio is molded into a pellet by pressurization, and the pellet is sintered by heating to obtain a phosphor-dispersed glass. It is possible to obtain.
• the phosphor powder content is preferably 0.01 to 50% by mass. When the phosphor powder exceeds 50% by mass, it becomes difficult to sinter, or the excitation light is not efficiently irradiated onto the phosphor particles. On the other hand, when the content is less than 0.01% by mass, the content is too small, and it becomes difficult to emit light sufficiently.
• the pellet When the pellet is formed by pressurization, it is preferably performed in a process in which heat is not applied, and it is preferable to use a press molding method or the like.
• the atmosphere at the time of heating may be in the air or in an inert gas atmosphere such as nitrogen gas or Ar gas, but the air atmosphere is desirable in view of manufacturing costs.
• sintering may be performed under reduced pressure, or pressure may be applied during sintering.
• a phosphor-dispersed glass may be obtained by kneading a glass powder material of a base material and a phosphor powder into an organic vehicle, applying the paste in a paste form, and then sintering. At this time, you may mix the inorganic filler mentioned above according to the objective.
• the organic vehicle can be suitably used as long as it desorbs at the glass sintering temperature.
• the phosphor-dispersed glass of the present invention can be suitably used as a white LED.
• a nitride phosphor useful as a red phosphor can be sealed, a high color rendering white LED can be obtained.
• the remaining glass was formed into flakes with a rapid cooling twin roll molding machine, and sized into glass powder samples having an average particle size of 1 to 30 ⁇ m and a maximum particle size of less than 100 ⁇ m by a pulverizer.
• SnO was used as a raw material for tin oxide.
• Tin oxide in the glass is SnO (2-x) (where 0 ⁇ x ⁇ 2), and it is difficult to measure a clear oxidation state. Therefore, in Tables 1 and 2, SnO (2-x) is used. It was described.
• the above softening point was measured using a thermal analyzer TG-DTA (manufactured by Rigaku Corporation).
• the thermal expansion coefficient was determined from the amount of elongation at 30 to 300 ° C. when the temperature was raised at 5 ° C./min using a thermal dilatometer.
• Nitride red phosphor powder (SrCa) AlSiN 3 : Eu 2+ , emission center wavelength 610 nm) was added to the obtained glass powder material and mixed to obtain a mixed powder (phosphor content: 4 mass%).
• the glass powder material the compositions A to N in Table 1 were used.
• a button-shaped preform having a diameter of 10 mm and a thickness of 2 mm was produced by pressure molding with a mold. Next, it sintered by heating for 30 minutes in air
• Table 3 shows the used glass powder material, phosphor powder, sintering temperature, and color tone of the obtained sintered body.
• Example 2 Example 1 except that the composition of B and I in Table 1 was used for the glass powder material and a nitride red phosphor (CaAlSiN 3 : Eu 2+ , emission center wavelength of 630 nm) powder was used for the phosphor powder. Thus, a sintered body was obtained. The sintering temperature is as described in Table 3.
• Example 1 A sintered body was obtained in the same manner as in Example 1 except that the composition of O to S shown in Table 2 was used for the glass powder material.
• the sintering temperature is as described in Table 3.
• Example 3 Example 1 except that the composition of E in Table 1 was used for the glass powder material, and oxide red phosphor (Y 3 Al 5 O 12 : Ce 3+ , emission center 555 nm) powder was used for the phosphor powder. A sintered body was obtained in the same manner. The sintering temperature is as described in Table 4.
• Example 4 The composition of C, E and J to N in Table 1 was used for the glass powder material, and oxide red phosphor (Lu 3 Al 5 O 12 : Ce 3+ , emission center 540 nm) powder was used for the phosphor powder. Obtained the sintered compact by the same method as Example 1. The sintering temperature is as described in Table 4.
• Example 5 The obtained glass powder material is mixed with an inorganic filler (SiO 2 filler, particle diameter 0.3 ⁇ m) and nitride red phosphor powder ((SrCa) AlSiN 3 : Eu 2+ , emission center wavelength 610 nm). Powder (inorganic filler content: 2 mass%, phosphor content: 4 mass%) was used. In addition, the composition of N of Table 1 was used for the glass powder material. Next, a button-shaped preform having a diameter of 10 mm and a thickness of 2 mm was produced by pressure molding with a mold. Next, it sintered by heating for 30 minutes in air
• an inorganic filler SiO 2 filler, particle diameter 0.3 ⁇ m
• nitride red phosphor powder ((SrCa) AlSiN 3 : Eu 2
• Example 6 A sintered body was obtained in the same manner as in Example 5 except that oxide red phosphor (Y 3 Al 5 O 12 : Ce 3+ , emission center 555 nm) powder was used as the phosphor powder to be used.
• Table 4 shows the glass powder material, inorganic filler, phosphor powder, sintering temperature, and color tone of the obtained sintered body.
• the internal quantum efficiency was 60 to 81%.
• the internal quantum efficiency of the oxide red phosphor before glass sealing was 83% and 81%, respectively, and the internal quantum efficiency did not decrease or the internal quantum efficiency was suppressed from decreasing.
• the color tone of the sintered body was light yellow. From the above, it was shown that the present invention can suppress the deactivation of the oxide red phosphor.
• Examples 5 and 6 in which the inorganic filler was mixed were able to suppress the decrease in internal quantum efficiency and external quantum efficiency as in the other examples in which the inorganic filler was not mixed. Moreover, since there was no big change in the color tone of a sintered compact, it was shown that this invention can utilize an inorganic filler.
• Example 7 Composition of E in Table 1 as a glass powder sample, 5% by weight of (SrCa) AlSiN 3 : Eu 2+ powder as nitride phosphor powder, and Lu 3 Al 5 O 12 : Ce 3+ powder as oxide red phosphor 3% by weight were mixed to make a mixed powder. Next, the mixed powder was pressure-molded with a mold to prepare a button-shaped preform having a diameter of 10 mm and a thickness of 2 mm. Next, it was heated at 610 ° C. for 30 minutes in the air to obtain a sintered body. As a result, the sintered body became bright orange.
• the internal quantum efficiency and the external quantum efficiency of the sintered body obtained in Example 7 were measured using the method described above.
• the internal quantum efficiency was 61% and the external quantum efficiency was 50%. That is, it has been clarified that the deactivation of the phosphor can be suppressed even when the oxide phosphor and the nitride phosphor are used in combination. Therefore, it was confirmed that the present invention can also be used for phosphor-dispersed glass that is sealed by using a plurality of types of phosphors in combination.

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