WO2013141044A1 - Verre, et élément de conversion de longueur d'onde mettant en œuvre celui-ci - Google Patents

Verre, et élément de conversion de longueur d'onde mettant en œuvre celui-ci Download PDF

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Publication number
WO2013141044A1
WO2013141044A1 PCT/JP2013/056467 JP2013056467W WO2013141044A1 WO 2013141044 A1 WO2013141044 A1 WO 2013141044A1 JP 2013056467 W JP2013056467 W JP 2013056467W WO 2013141044 A1 WO2013141044 A1 WO 2013141044A1
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Prior art keywords
glass
wavelength conversion
conversion member
powder
phosphor powder
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PCT/JP2013/056467
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English (en)
Japanese (ja)
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菊谷　武民
民雄 安東
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日本電気硝子株式会社
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Publication of WO2013141044A1 publication Critical patent/WO2013141044A1/fr

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    • 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
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • 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
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
    • 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
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus 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
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C09K11/77347—Silicon Nitrides or Silicon Oxynitrides
    • 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/16—Microcrystallites, e.g. of optically or electrically active material

Definitions

  • This invention relates to the glass used for the wavelength conversion member which is a structural member of light emitting devices, such as LED (light emitting diode) and LD (laser diode), for example.
  • LED light emitting diode
  • LD laser diode
  • the white LED has a configuration in which, for example, a light emitting surface of an LED chip is molded with an organic binder resin containing phosphor powder.
  • an organic binder resin containing phosphor powder When excitation light emitted from the LED chip passes through the mold part, a part of the excitation light is absorbed by the phosphor powder and wavelength-converted, and the other excitation light is transmitted without being wavelength-converted.
  • the light that has undergone wavelength conversion and the transmitted light that has not undergone wavelength conversion are combined to produce desired white light.
  • the mold resin that constitutes the LED element has a problem that it easily deteriorates due to high-power, short-wavelength excitation light in the blue to ultraviolet region.
  • a phosphor powder is incorporated into a glass matrix by sintering a material containing a lead-free glass powder having a softening point of 500 ° C. or higher and a phosphor powder at a temperature higher than the softening point of the glass.
  • Patent Document 1 proposes a wavelength conversion member in which the above is dispersed. Since the phosphor powder is dispersed in a glass matrix that is an inorganic material, the wavelength conversion member has an advantage that it is chemically stable and hardly deteriorated, and the member is not easily discolored by excitation light. However, some phosphor powders have low heat resistance, and when sintered together with a lead-free glass powder having a softening point of 500 ° C. or higher, the phosphor powder is thermally deteriorated and the luminous efficiency is lowered. There is a problem.
  • the wavelength conversion members described in Patent Documents 2 and 3 still have a problem that discoloration is likely to occur due to the reaction between glass and phosphor powder during sintering.
  • the weather resistance of glass is low, there is also a problem that the surface of the wavelength conversion member is altered during use, particularly in a high humidity environment, the transmittance is lowered, and the light emission efficiency is greatly lowered.
  • an object of the present invention is to provide a glass that is less likely to react with a phosphor powder, has excellent weather resistance, and can obtain a wavelength conversion member that is less deteriorated even when used over a long period of time. It is.
  • the glass of the present invention is characterized by containing a predetermined amount of ZrO 2 , Al 2 O 3 and MgO as essential components based on SnO—P 2 O 5 glass.
  • the glass of this invention can suppress reaction with fluorescent substance powder, and is excellent also in a weather resistance. Therefore, the wavelength conversion member formed by sintering the mixed powder containing the glass and the phosphor powder of the present invention is excellent in luminous efficiency and has a characteristic that it is less deteriorated even when used over a long period of time.
  • the glass of the present invention does not substantially contain ZnO.
  • the glass of the present invention does not substantially contain SiO 2 .
  • substantially does not contain means that the corresponding component is not intentionally contained (specifically, less than 0.1 mol%) except for inevitable impurities.
  • the glass of the present invention preferably has a yield point of 400 ° C. or lower.
  • the wavelength conversion material containing the glass and phosphor powder of the present invention can be sintered at low temperature, deterioration of the phosphor powder can be suppressed.
  • the glass of the present invention does not exhibit a crystallization peak temperature in a measurement curve obtained by differential thermal analysis.
  • the present invention relates to a glass powder made of any one of the above glasses.
  • the present invention relates to a wavelength conversion material containing the glass powder and the phosphor powder.
  • the present invention relates to a wavelength conversion member made of a sintered body of the wavelength conversion material.
  • the present invention relates to a light emitting device comprising: any one of the wavelength conversion members; and a light source that irradiates the wavelength conversion member with excitation light of a phosphor powder.
  • the present invention it is possible to provide glass capable of obtaining a wavelength conversion member that hardly reacts with phosphor powder, is excellent in weather resistance, and has little deterioration even when used over a long period of time.
  • composition of the glass of the present invention is limited as described above will be described below.
  • % means “mol%” unless otherwise specified.
  • SnO is a component that forms a glass skeleton and lowers the thermophysical temperature (glass transition point, yield point, softening point, etc.). Its content is 50 to 80%, preferably 53 to 75%, more preferably 56 to 72%, and particularly preferably 58 to 68%. When there is too little content of SnO, it exists in the tendency for a thermophysical temperature to rise. As a result, it becomes difficult to sinter the wavelength conversion material containing the glass of the present invention at a low temperature, and the phosphor powder tends to deteriorate.
  • P 2 O 5 is a component that forms a glass skeleton. Its content is 15 to 25% (however, 25% is not included), preferably 18 to 24%, more preferably 20 to 23%. When the content of P 2 O 5 is too small, it is difficult to vitrify. On the other hand, when the content of P 2 O 5 is too large, thermal properties temperature tends to increase. As a result, it becomes difficult to sinter the wavelength conversion material containing the glass of the present invention at a low temperature, and the phosphor powder tends to deteriorate. Further, the weather resistance tends to be remarkably lowered.
  • the SnO / P 2 O 5 value (molar ratio) needs to be 1.6 to 4.8, preferably 1.8 to 4.8. It is preferable to adjust to a range of 3.8, more preferably 2.3 to 3.3.
  • the thermophysical temperature tends to increase. As a result, it becomes difficult to sinter the wavelength conversion material containing the glass of the present invention at a low temperature, and the phosphor powder tends to deteriorate. Further, the weather resistance tends to be remarkably lowered.
  • ZrO 2 is a component that improves weather resistance. Its content is 0.3 to 3%, preferably 0.35 to 2, more preferably 0.4 to 1.5. When the content of ZrO 2 is too small, the effect is difficult to obtain. On the other hand, when the content of ZrO 2 is too large, turbid and devitrification or phase separation at the time of melting, the transmittance tends to decrease. As a result, the light emission efficiency of the wavelength conversion member using the glass of the present invention tends to decrease.
  • Al 2 O 3 is a component that improves the weather resistance and stabilizes the glass. Its content is 0.1 to 10%, preferably 0.1 to 7%, more preferably 1 to 5%. When the content of Al 2 O 3 is too small, the effect is difficult to obtain. When the content of Al 2 O 3 is too large, thermal properties temperature tends to increase. As a result, it becomes difficult to sinter the wavelength conversion material containing the glass of the present invention at a low temperature, and the phosphor powder tends to deteriorate.
  • B 2 O 3 is a component that stabilizes the glass and is also a component that suppresses the reaction with the phosphor powder. Its content is 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%. If the B 2 O 3 content is too large, thermal properties temperature tends to increase. As a result, it becomes difficult to sinter the wavelength conversion material containing the glass of the present invention at a low temperature, and the phosphor powder tends to deteriorate.
  • Li 2 O is a component that significantly lowers the thermophysical temperature and improves the luminous efficiency of the wavelength conversion member. Its content is 0 to 10%, preferably 0 to 7%, more preferably 1 to 5%. The content of Li 2 O is too large, the glass becomes significantly instable difficult to vitrify.
  • Na 2 O decreases the thermal property temperature, a component for slightly improve the luminous efficiency of the wavelength conversion member. Its content is 0 to 10%, preferably 0 to 7%, more preferably 0 to 5%. When the content of Na 2 O is too large, it is difficult to vitrify the glass becomes unstable.
  • K 2 O is a component that slightly lowers the thermophysical temperature and improves the light emission efficiency of the wavelength conversion member. Its content is 0 to 10%, preferably 0 to 7%, more preferably 1 to 5%. When the content of K 2 O is too large, it is difficult to vitrify the glass becomes unstable.
  • the total amount of Li 2 O, Na 2 O and K 2 O is preferably 0 to 10%, more preferably 0 to 7%, and particularly preferably 1 to 5%. When there is too much total amount of these components, glass will become unstable and it will become difficult to vitrify.
  • MgO is a component that improves weather resistance. Moreover, there is an effect of remarkably improving the light emission efficiency of the wavelength conversion member.
  • the content is 0.1 to 10%, preferably 0.3 to 7%, more preferably 0.5 to 3%. If the content of MgO is too small, the above effect is difficult to obtain. When there is too much content of MgO, it will devitrify at the time of baking and the transmittance
  • the total amount of ZrO 2 , MgO and Al 2 O 3 is 0.5 to 11%, preferably 0.5 to 10%, more preferably 1 to 5%, still more preferably 2 to 4%.
  • the total amount of these components is too small, it is difficult to obtain the effect of improving the weather resistance.
  • permeability will fall easily. As a result, it becomes difficult to obtain a wavelength conversion member having high luminous efficiency.
  • CaO is a component that improves weather resistance. Its content is 0 to 3%, preferably 0 to 2.5%, more preferably 0 to 2%. When there is too much content of CaO, it will devitrify at the time of baking and the transmittance
  • SrO is a component that improves weather resistance. Its content is 0 to 2.5%, preferably 0 to 2%, more preferably 0 to 1.5%. When there is too much content of SrO, it will devitrify at the time of baking and the transmittance
  • BaO is a component that improves weather resistance. Its content is 0-2%, preferably 0-1.5%, more preferably 0-1%. When there is too much content of BaO, it will devitrify remarkably at the time of baking and it will become easy to reduce the transmittance
  • the total amount of MgO, CaO, SrO and BaO is preferably 0.1 to 10%, more preferably 0.1 to 7%, and particularly preferably 1 to 5%. If the total amount of these components is too small, it is difficult to obtain the effect of improving the weather resistance. On the other hand, when there is too much total amount of these components, it will devitrify at the time of baking and the transmittance
  • ZnO is a component that improves weather resistance, but if it is contained in a small amount in the composition system of the present invention, it tends to devitrify during firing. Therefore, in the present invention, it is preferable that ZnO is not substantially contained.
  • SiO 2 When SiO 2 is contained even in a small amount, the phase is separated and white turbid, and the transmittance tends to decrease. Therefore, in the present invention, it is preferred not to contain SiO 2 substantially.
  • Ta 2 O 5 , TiO 2 , Nb 2 O 5 , Gd 2 O 3 or La 2 O 3 may be contained up to 10% in total.
  • coloring components such as Fe 2 O 3 , Cr 2 O 3 , CoO, CuO, and NiO reduce internal transmittance, it is preferable that these components are combined in an amount of 0.02% or less.
  • the glass of the present invention preferably has an internal transmittance of 70% or more, more preferably 80% or more, particularly 90% or more at a thickness of 1 mm and a wavelength of 588 nm. If the internal transmittance is too low, it becomes difficult to obtain a wavelength conversion member having high luminous efficiency.
  • a glass raw material with few colored impurities such as iron, chromium, cobalt, copper and nickel is used, or the internal transmittance due to the precipitation of devitrification bumps caused by Sn.
  • a reducing atmosphere non-oxidizing atmosphere such as N 2 gas or Ar gas
  • a small amount of a reducing agent such as metallic aluminum
  • the glass of the present invention preferably has a yield point of 400 ° C. or lower, more preferably 380 ° C. or lower. If the yield point is too high, it becomes difficult to sinter the wavelength conversion material containing the glass of the present invention at a low temperature, and the phosphor powder tends to deteriorate. Further, the weather resistance tends to be remarkably lowered.
  • the glass of the present invention does not exhibit a crystallization peak temperature in a measurement curve obtained by differential thermal analysis. Thereby, the devitrification at the time of baking of the wavelength conversion material becomes difficult to occur.
  • the wavelength conversion member of the present invention comprises a sintered body of a wavelength conversion material including the glass powder of the present invention and a phosphor powder.
  • the phosphor powder usable in the present invention is not particularly limited as long as it is generally available on the market. Examples thereof include phosphor powders made of at least one selected from oxides, nitrides, oxynitrides, sulfides, oxysulfides, rare earth sulfides, aluminate chlorides, and halophosphates. In addition, a phosphor powder made of an organic material may be used. Phosphor powders such as nitrides, oxynitrides, chlorides, acid chlorides, sulfides, oxysulfides, halides, chalcogenides, aluminates, and halophosphates are made into glass powders by heating during firing.
  • the glass used in the present invention has a low softening point and can be sintered at a low temperature (for example, 400 ° C. or lower), the above-described phosphor powder that easily reacts with the glass powder can also be used.
  • (Sr, Ba) 3 MgSi 2 O 8 : Eu 2+ is an example of the phosphor powder that emits blue light when irradiated with excitation light having a wavelength of 300 to 440 nm.
  • Examples of the phosphor powder that emits green light when irradiated with ultraviolet to near-ultraviolet excitation light having a wavelength of 300 to 440 nm include SrAl 2 O 4 : Eu 2+ .
  • Examples of the phosphor powder that emits green light when irradiated with blue excitation light having a wavelength of 440 to 480 nm include SrGa 2 S 4 : Eu 2+ .
  • Examples of phosphor powders that emit yellow light when irradiated with ultraviolet to near ultraviolet excitation light having a wavelength of 300 to 440 nm include ZnS: Eu 2+ .
  • Examples of the phosphor powder that emits red light when irradiated with ultraviolet to near ultraviolet excitation light having a wavelength of 300 to 440 nm include CaS: Yb 2+ .
  • Examples of the phosphor powder that emits red light when irradiated with blue excitation light having a wavelength of 440 to 480 nm include (Ca, Sr) 2 Si 5 N 8 : Eu 2+ .
  • a plurality of phosphor powders may be mixed and used in accordance with the wavelength range of excitation light or light emission. For example, when white light is obtained by irradiating excitation light in the ultraviolet region, phosphor powders that emit blue, green, yellow, and red fluorescence may be mixed and used.
  • the luminous efficiency of the wavelength conversion member varies depending on the type and content of the phosphor powder dispersed in the glass matrix, the thickness of the wavelength conversion member, and the like.
  • the phosphor powder content and the thickness of the wavelength conversion member may be adjusted so as to optimize the luminous efficiency.
  • the phosphor powder content is too high, sintering becomes difficult or the porosity is low. As a result, it becomes difficult to efficiently irradiate the phosphor powder with the excitation light, and the mechanical strength of the wavelength conversion member tends to decrease.
  • the content of the phosphor powder is too small, it becomes difficult to obtain sufficient light emission. Accordingly, the content of the phosphor powder in the wavelength conversion material is preferably 0.01 to 60%, more preferably 0.05 to 55%, and particularly preferably 0.08 to 50% by mass.
  • the wavelength conversion material of the present invention may contain a light diffusing material such as silica or alumina as long as the effects of the present invention are not impaired.
  • the wavelength conversion material may be fired in the air, but a dense sintered body can be easily obtained by firing in a reduced pressure or vacuum atmosphere or an inert gas atmosphere such as nitrogen or argon. It is preferable because the reaction between the glass powder and the phosphor powder can be suppressed.
  • the firing temperature of the wavelength conversion material is preferably in the range of 300 to 400 ° C. If the firing temperature is too low, the porosity of the sintered body increases and the transmittance may decrease. On the other hand, when the firing temperature is too high, the phosphor powder may be deteriorated, or the glass powder and the phosphor powder may react to significantly reduce the light emission efficiency.
  • the form of the wavelength conversion material of the present invention is not particularly limited, and examples thereof include powder, a pressure-molded body, a paste, and a green sheet.
  • the pressure-molded body of the wavelength conversion material can be prepared by adding 0 to 5% by mass of a resin binder to a mixed powder containing glass powder and phosphor powder, and pressure-molding with a mold.
  • the pressure-molded body is heated at a temperature of, for example, 250 ° C. or less to remove the binder, and then fired at the firing temperature described above to obtain a wavelength conversion member.
  • a resin binder having a decomposition end temperature of 250 ° C. or lower is preferably used.
  • nitrocellulose, polyisobutyl acrylate, polyethyl carbonate, aliphatic polypropylene carbonate, polybutyl methacrylate, polyvinyl butyral, polymethyl methacrylate And polyethyl methacrylate can be used alone or in admixture of two or more.
  • a paste-form wavelength conversion material can be produced by adding a resin binder, a solvent, and the like to a mixed powder containing glass powder and phosphor powder and kneading them.
  • the proportion of the mixed powder in the entire paste is generally 30 to 90% by mass.
  • Resin binder is a component that enhances the film strength after drying the paste and imparts flexibility to the film.
  • resin binder those described above can be used, and the content is generally about 0.1 to 20% by mass.
  • the solvent content is generally about 10 to 50% by mass.
  • the solvent include terpineol, isoamyl acetate, toluene, methyl ethyl ketone, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3 pentadiol monoisobutyrate and the like.
  • a wavelength conversion member can be produced as follows. First, an inorganic material base material having a thermal expansion coefficient similar to that of glass powder is prepared, and a paste-like wavelength conversion material is applied to the surface by a screen printing method, a batch coating method, or the like, and a coating layer having a predetermined film thickness And then dried. Subsequently, after firing at the firing temperature described above, the wavelength conversion member can be obtained by removing the inorganic material substrate.
  • the wavelength conversion material in the form of a green sheet can be produced as follows. First, a resin binder, a plasticizer, a solvent, etc. are added and kneaded with respect to the mixed powder containing glass powder and fluorescent substance powder, and a slurry is obtained. The obtained slurry is formed into a sheet shape on a film of polyethylene terephthalate (PET) or the like by a doctor blade method. By drying the sheet molded body, the organic solvent and the like can be removed to obtain a green sheet.
  • the ratio of the mixed powder in the green sheet is generally about 50 to 80% by mass.
  • the resin binder and the solvent those described above can be used.
  • the resin binder content is generally about 0.1 to 30% by mass, and the solvent content is generally about 1 to 40% by mass.
  • the plasticizer is a component that controls the drying speed and imparts flexibility to the dried film, and the content thereof is generally about 0 to 10% by mass.
  • the plasticizer include dibutyl phthalate, butyl benzyl phthalate, dioctyl phthalate, diisooctyl phthalate, dicapryl phthalate, and dibutyl phthalate, and these can be used alone or in combination.
  • a wavelength conversion member can be produced as follows. First, an inorganic material base material having a thermal expansion coefficient comparable to that of glass powder is prepared, a green sheet is laminated on the surface, and thermocompression bonding is performed. Thereafter, the wavelength conversion member can be obtained by firing at the firing temperature described above and removing the inorganic material substrate.
  • a light emitting device can be obtained by combining the wavelength conversion member obtained as described above and a light source (for example, LED or LD) that irradiates the wavelength conversion member with excitation light of the phosphor powder.
  • a light source for example, LED or LD
  • Tables 1 and 2 show examples of the present invention (sample Nos. 1 to 12 and a to l), and Tables 3 and 4 show comparative examples (samples No. 13 to 20 and m to t).
  • the glass sheet After annealing, cutting and polishing were performed, and the glass transition point and yield point were measured. Further, the surface condition after the weather resistance test was evaluated. The glass powder was measured for softening point, crystallization temperature, and internal transmittance. The results are shown in Tables 1 and 3.
  • the mixed powder was put into a mold and pressure-molded to produce a pressure-molded body having a size of 15 mm ⁇ 15 mm and a thickness of 5 mm.
  • the pressure-molded body was sintered at a firing temperature shown in the table under a reduced pressure atmosphere of 100 Pa, and then processed to obtain a wavelength conversion member having a size of 10 mm ⁇ 10 mm and a thickness of 1 mm.
  • the luminous efficiency before and behind a weather resistance test and the surface state after a weather resistance test were evaluated. The results are shown in Tables 2 and 4.
  • the softening point and crystallization temperature were measured using a DTA (Differential Thermal Analysis) apparatus (TAS-100, manufactured by Rigaku Corporation).
  • DTA Different Thermal Analysis
  • the internal transmittance was determined as follows. A sintered body obtained by firing the glass powder at the sintering temperatures shown in Tables 1 and 3 was subjected to optical polishing processing so that the thickness became 1 mm to prepare a sample. For the obtained sample, the transmittance and reflectance at a wavelength of 588 nm were measured using a spectrophotometer, and the internal transmittance (the reflectance on both sides of the sample was added to the transmittance from the measured value of the transmittance and reflectance). Value).
  • the weather resistance was evaluated by using a pressure cooker tester, allowing the sample to stand for 24 hours under conditions of atmospheric pressure of 2 atm, humidity of 95%, and temperature of 121 ° C., and visually and microscopically checking for the presence or absence of cloudiness on the sample surface after the test. This was done by observation (PCT test). “ ⁇ ” indicates that no white cracks due to elution of microcracks or glass components were observed visually and by observation with a microscope, “ ⁇ ” indicates that no white turbidity was observed by visual inspection, but white turbidity was observed by a microscope. In addition, the case where cloudiness was observed visually and under a microscope was evaluated as “x”.
  • the luminous efficiency was determined as follows. First, a sample was placed on a blue LED (wavelength 465 nm) lit at a current of 20 mA, and an energy distribution spectrum of light emitted from the upper surface of the member was measured in an integrating sphere. Next, the total luminous flux was calculated by multiplying the obtained spectrum by the standard relative luminous sensitivity, and the luminous efficiency was calculated by dividing the obtained total luminous flux by the power of the light source (0.072 W).
  • sample No. Glasses 1 to 12 had low thermophysical temperatures (glass transition point 294 to 333 ° C., yield point 314 to 354 ° C., softening point 352 to 393 ° C.), and could be sintered at a low temperature of 366 to 399 ° C. Further, the crystallization peak temperature was not expressed. Furthermore, the internal transmittance was as high as 83% or more. Sample No. The glass of 1 to 12 and the wavelength conversion members of a to l produced using these glasses had no change in the surface state after the weather resistance test. Moreover, the luminous efficiency of the wavelength conversion member was high, and almost no change in the luminous efficiency before and after the weather resistance test was confirmed.
  • Sample No. which is a comparative example.
  • the surfaces of 13, 15 and 16 became cloudy after the weather resistance test.
  • the wavelength conversion member produced using these glasses showed a luminous efficiency of 10 to 12 lm / W before the weather resistance test, but the luminous efficiency was remarkably lowered to 2 to 3 lm / W after the weather resistance test.
  • No. No. 14 glass could not be evaluated because melt separation occurred during melting and it did not vitrify.
  • No. The 18-20 glass had strong crystallinity and was devitrified during firing, so the internal transmittance was as low as 55-59%. Therefore, no.
  • the wavelength conversion member produced using 17-20 glass had a low luminous efficiency of 4-6 lm / W.

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  • Organic Chemistry (AREA)
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  • Luminescent Compositions (AREA)

Abstract

L'invention fournit un verre permettant d'obtenir un élément de conversion de longueur d'onde peu susceptible d'entrer en réaction avec une poudre de phosphore, d'une excellente résistance aux intempéries et présentant peu de dégradations y compris lors d'une mise en œuvre sur le long terme. Ce verre est caractéristique en ce qu'il comprend dans sa composition, en % en moles : SnO 50 à 80%, P2O5 15 à 25% (mais ne contient pas 25%), ZrO2 0,3 à 3%, Al2O3 0,1 à 10%, B2O3 0 à 10%, Li2O 0 à 10%, Na2O 0 à 10%, K2O 0 à 10%, Li2O+ Na2O+ K2O 0 à 10%, MgO　0,1 à 10%, CaO 0 à 3%, SrO 0 à 2,5%, BaO 0 à 2%, MgO+CaO+SrO+BaO 0,1 à 11%, et ZrO2+ Al2O3+MgO 0,5 à 10%. Enfin, SnO/P2O5 vaut à 1,6 à 4,8.
PCT/JP2013/056467 2012-03-23 2013-03-08 Verre, et élément de conversion de longueur d'onde mettant en œuvre celui-ci WO2013141044A1 (fr)

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