WO2022107794A1 - 波長変換部材及びその製造方法 - Google Patents

波長変換部材及びその製造方法 Download PDF

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Publication number
WO2022107794A1
WO2022107794A1 PCT/JP2021/042181 JP2021042181W WO2022107794A1 WO 2022107794 A1 WO2022107794 A1 WO 2022107794A1 JP 2021042181 W JP2021042181 W JP 2021042181W WO 2022107794 A1 WO2022107794 A1 WO 2022107794A1
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Prior art keywords
conversion member
wavelength conversion
phosphor particles
manufacturing
matrix
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PCT/JP2021/042181
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English (en)
French (fr)
Japanese (ja)
Inventor
知道 國本
恒友 奥村
智也 岩越
栄一 中村
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to KR1020237013377A priority Critical patent/KR20230104135A/ko
Priority to JP2022563789A priority patent/JPWO2022107794A1/ja
Priority to CN202180074844.9A priority patent/CN116569081A/zh
Publication of WO2022107794A1 publication Critical patent/WO2022107794A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means

Definitions

  • the present invention relates to a wavelength conversion member that converts the wavelength of light emitted by a light emitting diode (LED: Light Emitting Diode), a laser diode (LD: Laser Diode), or the like into another wavelength, and a method for manufacturing the wavelength conversion member.
  • LED Light Emitting Diode
  • LD Laser Diode
  • the wavelength conversion member a member in which phosphor particles are dispersed in a resin matrix has been used.
  • the resin matrix is discolored and deformed by receiving the heat or irradiation light generated by the LED or LD, which causes the performance of the wavelength conversion member to deteriorate.
  • a wavelength conversion member made of a completely inorganic solid in which phosphor particles are dispersed and fixed in an inorganic matrix such as glass has been proposed (see, for example, Patent Documents 2 and 3).
  • Such a wavelength conversion member has a feature that the glass matrix as a base material is less likely to be deteriorated by the heat generated by the LED or LD and the irradiation light, and problems such as discoloration and deformation are less likely to occur.
  • the wavelength conversion member as in Patent Document 2 and Patent Document 3 can be manufactured, for example, by molding a mixture containing an inorganic powder such as glass powder and phosphor particles and firing the mixture.
  • An object of the present invention is to provide a method for manufacturing a wavelength conversion member and a wavelength conversion member capable of accurately obtaining a wavelength conversion member having a desired chromaticity.
  • a broad aspect of the method for manufacturing a wavelength conversion member according to the present invention is a method for manufacturing a wavelength conversion member in which phosphor particles are dispersed in a matrix, and includes an inorganic powder serving as the matrix and phosphor particles. It comprises a step of producing a mixture and a step of forming the mixture and obtaining a wavelength conversion member by firing. In producing the mixture, after starting mixing of the material containing the inorganic powder, the fluorescence It is characterized by adding body particles and further mixing.
  • the ratio (T 1 / T) of the time T 1 (minutes) from the start of mixing to the introduction of the phosphor particles is preferably 50% or more with respect to the total mixing time T (minutes). ..
  • the ratio (T 1 / T) of the time T 1 (minutes) from the start of mixing to the introduction of the phosphor particles is preferably 99% or less with respect to the total mixing time T (minutes). ..
  • the difference (TT 1 ) between the total mixing time T (minutes) and the time T 1 (minutes) from the start of mixing until the phosphor particles are charged is 240 minutes or less. preferable.
  • the difference (TT 1 ) between the total mixing time T (minutes) and the time T 1 (minutes) from the start of mixing until the phosphor particles are charged must be 5 minutes or more. preferable.
  • the fluorescent particles are put into the mixing container and further mixed. Is preferable.
  • the inorganic powder and the boulder are put into the mixing container, it is more preferable to further put the solvent, the resin, and the plasticizer into the mixing container to mix the material containing the inorganic powder.
  • the inorganic powder is preferably glass powder.
  • the wavelength conversion member according to the present invention is a wavelength conversion member in which phosphor particles are dispersed in a matrix, and the number-based cumulative 10 % of the phosphor particles and the frequency Da and the number-based cumulative 50 at a particle diameter D10. %
  • the ratio (D a / D b ) to the frequency D b at the particle diameter D 50 is 0.01 or more and 2 or less.
  • the cumulative number-based cumulative 10% particle diameter D 10 of the phosphor particles is 1 ⁇ m or more and 10 ⁇ m or less.
  • a method for manufacturing a wavelength conversion member in which phosphor particles are dispersed in a matrix wherein the inorganic powder serving as the matrix and the phosphor particles are used.
  • the slurry is provided with a step of producing a slurry containing the resin, a step of molding into a sheet using the slurry, and a step of obtaining a wavelength conversion member by firing the sheet-shaped molded body.
  • the inorganic powder and the material containing the resin are mixed to form a slurry, and then the phosphor particles are charged and further mixed.
  • Another broad aspect of the method for manufacturing a wavelength conversion member according to the present invention is a method for manufacturing a wavelength conversion member in which phosphor particles are dispersed in a matrix, wherein the inorganic powder serving as the matrix and the phosphor particles are used.
  • the mixed powder is produced by comprising a step of producing a mixed powder containing the above, a step of producing a green compact of the mixed powder, and a step of obtaining a wavelength conversion member by firing the green compact.
  • the step is characterized in that after the material containing the inorganic powder is mixed, the phosphor particles are charged and further mixed.
  • the present invention it is possible to provide a method for manufacturing a wavelength conversion member and a wavelength conversion member capable of accurately obtaining a wavelength conversion member having a desired chromaticity.
  • FIG. 1 is a schematic front sectional view showing a wavelength conversion member according to an embodiment of the present invention.
  • FIG. 2 (a) is a schematic cross-sectional view showing a wavelength conversion member manufactured under the condition that a material containing glass powder is mixed first and phosphor particles are charged later
  • FIG. 2 (b) is a schematic cross-sectional view. It is a schematic cross-sectional view which shows the wavelength conversion member manufactured under the condition that the phosphor particles are charged at the same time as the start of mixing of the material containing glass powder.
  • FIG. 3A is a diagram showing a scanning electron micrograph (SEM) of a cross section of the wavelength conversion member of Example 1
  • FIG. 3B is a diagram of phosphor particles in the wavelength conversion member of Example 1.
  • FIG. 4 is a diagram showing the relationship between the chromaticity and the luminous flux of the wavelength conversion member obtained in Example 1.
  • FIG. 5 is a diagram showing the relationship between the chromaticity and the luminous flux of the wavelength conversion member obtained in Example 2.
  • FIG. 6 is a diagram showing the relationship between the chromaticity and the luminous flux of the wavelength conversion member obtained in Example 3.
  • FIG. 7A is a diagram showing a scanning electron micrograph (SEM) of a cross section of the wavelength conversion member of Comparative Example 1
  • FIG. 7B is a diagram of phosphor particles in the wavelength conversion member of Comparative Example 1. It is a figure which shows the histogram of the particle size.
  • FIG. 4 is a diagram showing the relationship between the chromaticity and the luminous flux of the wavelength conversion member obtained in Example 1.
  • FIG. 5 is a diagram showing the relationship between the chromaticity and the luminous flux of the wavelength conversion member obtained in Example 2.
  • FIG. 6 is a diagram showing the relationship between the chromaticity and
  • FIG. 8 is a diagram showing the relationship between the chromaticity and the luminous flux of the wavelength conversion member obtained in Comparative Example 1 and Reference Example 1.
  • FIG. 9 is a diagram showing the relationship between the chromaticity and the luminous flux of the wavelength conversion member obtained in Example 4.
  • FIG. 10 is a diagram showing the relationship between the chromaticity and the luminous flux of the wavelength conversion member obtained in Comparative Example 2 and Reference Example 2.
  • FIG. 1 is a schematic front sectional view showing a wavelength conversion member according to an embodiment of the present invention.
  • the wavelength conversion member 1 is a fluorescent glass including a glass matrix 2 and a fluorescent particle 3.
  • the phosphor particles 3 are dispersed in the glass matrix 2.
  • the wavelength conversion member 1 has a rectangular plate-like shape.
  • the shape of the wavelength conversion member 1 is not particularly limited.
  • the glass matrix 2 is not particularly limited as long as it can be used as a dispersion medium for the phosphor particles 3 such as an inorganic phosphor.
  • the glass matrix 2 for example, borosilicate-based glass, phosphate-based glass, tin phosphate-based glass, bismuthate-based glass, tellurite-based glass, and the like can be used.
  • borosilicate-based glass in terms of mass%, SiO 2 30% to 85%, Al 2 O 30 % to 30%, B 2 O 30 % to 50%, Li 2 O + Na 2 O + K 2 O 0% to Examples thereof include those containing 10% and MgO + CaO + SrO + BaO 0% to 50%.
  • tin phosphate-based glass examples include those containing 30% to 90% of SnO and 1 % to 70% of P2O in mol%.
  • the softening point of the glass matrix 2 is preferably 250 ° C to 1000 ° C, more preferably 300 ° C to 950 ° C, and even more preferably 500 ° C to 900 ° C. If the softening point of the glass matrix 2 is too low, the mechanical strength and chemical durability of the wavelength conversion member 1 may decrease. Further, since the heat resistance of the glass matrix 2 itself is low, there is a risk of softening and deformation due to heat generated from the phosphor particles 3. On the other hand, if the softening point of the glass matrix 2 is too high, the phosphor particles 3 may deteriorate in the firing step during manufacturing, and the emission intensity of the wavelength conversion member 1 may decrease.
  • the softening point of the glass matrix 2 is preferably 500 ° C. or higher, more preferably 600 ° C. or higher, still more preferably 700 ° C. or higher. Particularly preferably 800 ° C. or higher, most preferably 850 ° C. or higher.
  • the glass constituting such a glass matrix 2 include borosilicate-based glass.
  • the softening point of the glass matrix 2 becomes high, the firing temperature also becomes high, and as a result, the manufacturing cost tends to be high. Further, if the heat resistance of the fluorescent particle 3 is low, it may be deteriorated by firing.
  • the softening point of the glass matrix 2 is preferably 550 ° C or lower, more preferably 530 ° C or lower. It is more preferably 500 ° C. or lower, particularly preferably 480 ° C. or lower, and most preferably 460 ° C. or lower.
  • the glass constituting such a glass matrix 2 include tin phosphate-based glass, bismuth acid-based glass, and tellurite-based glass.
  • a ceramic matrix may be used instead of the glass matrix 2.
  • the thermal conductivity of the wavelength conversion member 1 can be further improved.
  • the ceramics constituting the ceramics matrix include Al2O3 , MgO, AlN and the like. Further, it may be an inorganic matrix other than glass or ceramics.
  • the phosphor particles 3 are not particularly limited as long as they emit fluorescence by the incident of excitation light.
  • Examples of the phosphor particle 3 include an oxide fluorescent substance, a nitride fluorescent substance, an oxynitride fluorescent substance, a chloride fluorescent substance, a acid compound fluorescent substance, a sulfide fluorescent substance, an acid sulfide fluorescent substance, and a halide fluorescent substance.
  • Examples thereof include a body, a chalcogenide fluorescent substance, an aluminate fluorescent substance, a halophosphate compound fluorescent substance, and a garnet-based compound fluorescent substance.
  • One of these fluorescent substances may be used alone, or a plurality of types may be used in combination.
  • the excitation light for example, a phosphor that emits yellow light as fluorescence can be used.
  • the fluorescent substance that emits yellow light as fluorescence include a YAG fluorescent substance.
  • the excitation light may be visible light other than blue, ultraviolet light, or infrared light, and the wavelength is not particularly limited. Further, the light emitted as fluorescence may be visible light other than yellow, ultraviolet light or infrared light, and the wavelength is not particularly limited.
  • the ratio (D a / D b ) of the frequency D a at the number-based cumulative 10% particle diameter D 10 and the frequency D b at the number-based cumulative 50% particle diameter D 50 of the phosphor particles 3 is 2. Below, it is preferably 1.5 or less, and more preferably 1 or less. When the ratio D a / D b is not more than the above upper limit value, the amount of fine particles of the phosphor particles 3 can be reduced, and the wavelength conversion member 1 having a desired chromaticity can be obtained more accurately.
  • the lower limit of D a / D b is not particularly limited, but is actually 0.01 or more, preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.5 or more. ..
  • the width of the histogram class (x-axis) used to calculate D a and D b is preferably 1 ⁇ m.
  • the number-based cumulative 10% particle diameter D 10 of the phosphor particles 3 is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more. If D 10 of the phosphor particles 3 is too small, color shift (chromaticity shift) of the emitted color tends to occur easily. On the other hand, if D 10 of the phosphor particles 3 is too large, the emission color tends to be non-uniform. Therefore, the D 10 of the phosphor particles 3 is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the number-based cumulative 50% particle diameter D 50 of the phosphor particles 3 is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more. If the D 50 of the phosphor particles 3 is too small, the emission intensity tends to decrease. On the other hand, if the D 50 of the phosphor particles 3 is too large, the emission color tends to be non-uniform. Therefore, the D 50 of the phosphor particles 3 is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the cumulative amount of D 10 of the phosphor particles 3 is the particles in the cumulative particle size distribution histogram based on the number obtained based on the scanning electron micrograph (SEM) of the cross section of the wavelength conversion member 1.
  • the particle size is 10% cumulatively from the smallest diameter.
  • the D50 of the phosphor particles 3 is obtained from the cumulative particle size distribution histogram based on the number obtained based on the scanning electron micrograph (SEM) of the cross section of the wavelength conversion member 1, from the one having the smaller integrated amount. It shows a particle size that is cumulatively 50%.
  • the number-based cumulative 10 % particle size D a of the phosphor particles 3 is the cumulative particle size distribution based on the number obtained based on the scanning electron micrograph (SEM) of the cross section of the wavelength conversion member 1.
  • SEM scanning electron micrograph
  • the frequency at the particle size where the accumulated amount is accumulated from the smaller particle size to 10% is shown.
  • the frequency D b at the number-based cumulative 50 % particle diameter D50 of the phosphor particles 3 is obtained in the cumulative particle size distribution histogram based on the number obtained based on the scanning electron micrograph (SEM) of the cross section of the wavelength conversion member 1.
  • the frequency at the particle size where the accumulated amount is 50% cumulatively from the smaller particle size is shown.
  • the content of the phosphor particles 3 in the wavelength conversion member 1 is preferably 1% by volume or more, more preferably 1.5% by volume or more, still more preferably 2% by volume or more, and particularly preferably 5% by volume or more. Is 7% by volume or more.
  • the content of the phosphor particles 3 in the wavelength conversion member 1 is preferably 70% by volume or less, more preferably 50% by volume or less, still more preferably 30% by volume or less, particularly preferably 20% by volume or less, and most preferably 15. It is less than% by volume. If the content of the phosphor particles 3 is too small, it is necessary to increase the thickness of the wavelength conversion member 1 in order to obtain a desired emission color, and as a result, the internal scattering of the wavelength conversion member 1 increases, resulting in light.
  • Extraction efficiency may decrease.
  • the content of the phosphor particles 3 is too large, it is necessary to reduce the thickness of the wavelength conversion member 1 in order to obtain a desired emission color, so that the mechanical strength of the wavelength conversion member 1 may decrease. ..
  • the thickness of the wavelength conversion member 1 is preferably 0.01 mm or more, more preferably 0.03 mm or more, further preferably 0.05 mm or more, particularly preferably 0.075 mm or more, and most preferably 0.1 mm or more.
  • the thickness of the wavelength conversion member 1 is preferably 1 mm or less, more preferably 0.5 mm or less, still more preferably 0.35 mm or less, particularly preferably 0.3 mm or less, and most preferably 0.25 mm or less. If the thickness of the wavelength conversion member 1 is too thick, the scattering and absorption of light in the wavelength conversion member 1 may become too large, and the emission efficiency of fluorescence may be lowered. If the thickness of the wavelength conversion member 1 is too thin, it may be difficult to obtain sufficient emission intensity. In addition, the mechanical strength of the wavelength conversion member 1 may be insufficient.
  • a mixture containing glass powder to be a glass matrix and phosphor particles is prepared.
  • the wavelength conversion member can be obtained by molding the obtained mixture and firing it.
  • the ceramic powder may be used instead of the glass powder.
  • an inorganic matrix other than glass or ceramics is used, an inorganic powder other than glass powder or ceramic powder may be used.
  • a mixture containing glass powder and phosphor particles is prepared by, for example, adding glass powder, phosphor particles, jade stones, and if necessary, a solvent, a resin, a plasticizer, and a diffusing material into a mixing container and mixing them.
  • a material containing glass powder other than the fluorescent substance particles is first charged into the mixing container and mixed, and the fluorescent substance particles are later charged into the mixing container and further mixed.
  • the chromaticity deviation of the obtained wavelength conversion member can be suppressed, and the wavelength conversion member having a desired chromaticity can be accurately obtained. Obtainable.
  • the present inventors have obtained wavelength conversion by first mixing a material containing an inorganic powder such as glass powder other than the fluorescent particles, and then adding the fluorescent particles and further mixing them. It has been found that the chromaticity shift of the member can be suppressed and the wavelength conversion member having a desired chromaticity can be obtained with high accuracy. This can be explained as follows.
  • a solvent, resin, plasticizer, and diffusing material are put into a mixing container, and the mixing container is used. By rotating, the powders can be mixed uniformly. In addition, the powder can be crushed by hitting with a boulder to obtain a mixed powder in which the material is uniformly dispersed.
  • the glass powder may be primary particles or secondary particles in which particles having a size of several ⁇ m are in the form of granules, but in the case of secondary particles in particular, the granules (aggregation) are eliminated. Therefore, a long mixing time is required.
  • the particle size of the glass powder it is preferable to design the particle size of the glass powder to be smaller than the particle size of the phosphor powder, and in that case, especially the glass powder. The particles tend to aggregate with each other.
  • the mixing is performed over a period of time such that the granules of the glass powder are eliminated, the fluorescent particles are crushed into boulders, and the crushing of the fluorescent particles also proceeds. Therefore, in this case, as shown in FIG. 2B, the obtained wavelength conversion member 11 contains a large amount of fine particles 3A of the phosphor particles 3.
  • the particle size distribution of the phosphor particles 3 changes from the design value, and the scattering factor inside the wavelength conversion member 11 increases. It is considered that this causes an unintended increase in chromaticity and a decrease in quantum efficiency, resulting in a decrease in luminous flux.
  • the cause of the difference in chromaticity from the small-quantity prototype in the actual mass production is that in the case of mass production, it takes time to mix evenly compared to the small-quantity prototype, so the mixing time becomes long. It is considered that the fine powder 3A of the phosphor particles 3 increases and the particle size distribution changes, resulting in a deviation from the chromaticity of the small-quantity prototype.
  • the fluorescent particles are not charged at the start of mixing, and only the fluorescent particles are charged later.
  • the crushing of the phosphor particles due to boulders can be reduced, and the chromaticity shift and the luminous flux decrease due to an unintended increase in chromaticity are suppressed. ..
  • the wavelength conversion member having a desired chromaticity can be obtained with high accuracy.
  • the phosphor particles are charged from the start of mixing with respect to the entire mixing time T (minutes).
  • the ratio (T 1 / T) of T 1 (minutes) is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, particularly preferably 80% or more, and most preferably 90. % Or more.
  • the difference (TT 1 ) between the entire mixing time T (minutes) and the time T 1 (minutes) from the start of mixing until the phosphor particles are charged is preferably 240 minutes or less, more preferably. It is 180 minutes or less, more preferably 120 minutes or less, and particularly preferably 60 minutes or less.
  • the ratio (T 1 / T) is preferably 99% or less, more preferably 99% or less, from the viewpoint of further improving the dispersed state of the phosphor particles 3 and further suppressing the chromaticity variation in the same wavelength conversion member. Is 98% or less, more preferably 97.5% or less.
  • (TT 1 ) is preferably 5 minutes or longer, more preferably 10 minutes or longer, still more preferably 15 minutes or longer, and particularly preferably 30 minutes or longer.
  • the ratio (T 1 / T) and / or (T-T 1 ) in particular, by setting the ratio (T 1 / T) and / or (T-T 1 ) to be equal to or greater than the above lower limit value and equal to or less than the above upper limit value, fine powder can be obtained as shown in FIG. 2 (a). It can be further reduced, and the dispersed state can be further improved. As a result, it is possible to obtain a wavelength conversion member in which the deviation and variation of the chromaticity are further suppressed, and it is possible to accurately obtain a wavelength conversion member having a desired chromaticity.
  • the same glass powder material as the above-mentioned glass matrix material can be used.
  • the average particle size of the glass powder is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more. If the average particle size of the glass powder is too small, the grain boundaries between the glass powders increase when sintered, so that light is likely to be scattered and the transmittance of the glass matrix tends to decrease. In addition, it becomes easy to aggregate and it becomes difficult to disperse uniformly. On the other hand, if the average particle size of the glass powder is too large, it becomes difficult for each raw material to be uniformly dispersed, and the emission color of the wavelength conversion member 1 tends to be uneven. Therefore, the average particle size of the glass powder is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the average particle size of the glass powder refers to the average particle size D 50 measured by a laser diffraction type particle size distribution measuring device.
  • the above-mentioned phosphor particles can be used.
  • the material of the boulder for example, zirconia, alumina and the like can be used.
  • the solvent for example, methyl ethyl ketone, toluene and the like can be used.
  • the resin for example, an acrylic resin or the like can be used.
  • the plasticizer for example, a phthalate ester or the like can be used.
  • the diffusing material for example, alumina can be used.
  • the average particle size of the diffusing material is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more.
  • the average particle size of the diffusing material is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and further preferably 3 ⁇ m or less. If the average particle size of the diffusing material is too small, it may easily aggregate and be difficult to disperse uniformly, or the scattering to visible light may be weakened and the emission color may become non-uniform. On the other hand, if the average particle size of the diffusing material is too large, it may be difficult to disperse uniformly, or a sufficient scattering effect may not be obtained and light emission may become non-uniform.
  • the average particle size of the diffusing material refers to the average particle size D 50 measured by a laser diffraction type particle size distribution measuring device.
  • the glass powder and the phosphor particles can be mixed, for example, by rotating them using a ball mill. Further, it may be performed by a rotation / revolution stirrer.
  • a slurry composed of the above-mentioned mixture is applied onto a resin film such as polyethylene terephthalate by a doctor blade method or the like, and heat-dried to form a green sheet.
  • the above slurry may be applied onto a substrate to form a film, and the obtained film may be dried to form a film.
  • the glass powder and the material containing the resin are mixed to form a slurry, and then the phosphor particles are added and further mixed.
  • it may be molded by producing a green compact of a mixed powder composed of the above-mentioned mixture.
  • the material containing the glass powder is mixed, and then the phosphor particles are added and further mixed.
  • the firing temperature is preferably within ⁇ 150 ° C., which is the softening point of the glass powder, and more preferably within ⁇ 100 ° C., which is the softening point of the glass powder. If the firing temperature is too low, the glass powder may not soften and flow, and a dense sintered body may not be obtained. On the other hand, if the firing temperature is too high, the fluorophore particles may elute into the glass and the emission intensity may decrease, or the phosphor components may diffuse into the glass and the glass may be colored to decrease the emission intensity. ..
  • the firing time (holding time at the maximum temperature in the firing profile) can be, for example, 5 minutes or more and 120 minutes or less. Further, it is preferable to perform firing in a reduced pressure atmosphere. Specifically, the atmosphere during firing is preferably less than 1.013 ⁇ 105 Pa, more preferably 1000 Pa or less, and even more preferably 400 Pa or less. Thereby, the amount of bubbles remaining in the obtained wavelength conversion member can be reduced. As a result, the scattering factor in the obtained wavelength conversion member can be reduced, and the luminous efficiency can be improved.
  • Example 1 A glass powder having a composition of SiO 2 61.4%, B 2 O 3 5.3%, Al 2 O 3 3.6%, CaO 13.2%, BaO 12%, ZnO 4.5% in mol%. (Softening point: 850 ° C., average particle size D 50 : 2 ⁇ m) Binder resin (manufactured by Kyoeisha Chemical Co., Ltd., Oricox) 7.2% by mass, plasticizer (dioctyl adipate) 4.
  • the obtained slurry-like mixture was sheet-molded by the doctor blade method to obtain a molded body.
  • the obtained molded product was fired near the softening point of the glass powder.
  • the fired compact was polished to a thickness of 0.2 mm to obtain a wavelength conversion member.
  • Example 2 A wavelength conversion member was obtained in the same manner as in Example 1 except that the YAG phosphor particles were charged 22 hours and 30 minutes after the start of mixing when the slurry-like mixture was prepared. Also in Example 2, the total mixing time was set to 23 hours. In Example 2, the ratio (T 1 / T) was 97.8%.
  • Example 3 A wavelength conversion member was obtained in the same manner as in Example 1 except that the YAG phosphor particles were charged 22 hours and 45 minutes after the start of mixing when the slurry-like mixture was prepared. Also in Example 3, the total mixing time was set to 23 hours. In Example 3, the ratio (T 1 / T) was 98.9%.
  • Example 4 Glass powder having a composition of SiO 2 61.4%, B 2 O 3 5.3%, Al 2 O 3 3.6%, CaO 13.2%, BaO 12%, ZnO 4.5% in mol%. (Softening point: 850 ° C., average particle size D 50 : 2 ⁇ m) Binder resin (manufactured by Kyoeisha Chemical Co., Ltd., Oricox) 7.2% by mass, plasticizer (dioctyl adipate) 4.
  • Comparative Example 1 A wavelength conversion member was obtained in the same manner as in Example 1 except that YAG phosphor particles were charged at the start of mixing when the slurry-like mixture was prepared. Also in Comparative Example 1, the total mixing time was set to 23 hours. In Comparative Example 1, the ratio (T 1 / T) was 0%.
  • Comparative Example 2 A wavelength conversion member was obtained in the same manner as in Example 4 except that YAG phosphor particles were charged at the start of mixing when the slurry-like mixture was prepared. Also in Comparative Example 2, the total mixing time was set to 23 hours. In Comparative Example 2, the ratio (T 1 / T) was 0%.
  • FIG. 3A is a diagram showing a scanning electron micrograph (SEM) of a cross section of the wavelength conversion member of Example 1
  • FIG. 3B is a diagram of phosphor particles in the wavelength conversion member of Example 1. It is a figure which shows the histogram of the particle size.
  • FIG. 7A is a diagram showing a scanning electron micrograph (SEM) of a cross section of the wavelength conversion member of Comparative Example 1
  • FIG. 7B is a phosphor in the wavelength conversion member of Comparative Example 1. It is a figure which shows the histogram of the particle diameter of a particle. In the histograms of FIGS.
  • x ⁇ m indicates the frequency of the phosphor particles having a particle size of "x ⁇ m to less than x + 1 ⁇ m".
  • 0 ⁇ m indicates the frequency of the phosphor particles having a particle size of 0 ⁇ m to less than 1 ⁇ m.
  • the measurement conditions for the scanning electron micrograph (SEM) were an image range of about 1 mm ⁇ about 1 mm, and an actual size conversion value of 0.5 ⁇ m for one pixel.
  • SEM scanning electron micrograph
  • a product number "S-4300SE” manufactured by Hitachi High-Tech Corporation was used as the scanning electron micrograph (SEM).
  • the wavelength conversion member of Example 1 has a reduced amount of fine particles of the phosphor particles as compared with the wavelength conversion member of Comparative Example 1.
  • the number-based cumulative 10% particle diameter D 10 is 4 ⁇ m and the frequency D a is 14, and the number-based cumulative 50% particle diameter D 50 is 17 ⁇ m.
  • the frequency D b was 14, and the ratio (D a / D b ) was 1.
  • the number-based cumulative 10% particle diameter D 10 is 4 ⁇ m and the frequency D a is 13
  • the number-based cumulative 50% particle diameter D 50 is 18 ⁇ m and the frequency D.
  • b was 16, and the ratio (D a / D b ) was 0.81.
  • the number-based cumulative 10% particle diameter D 10 is 4 ⁇ m and the frequency D a is 11, and the number-based cumulative 50% particle diameter D 50 is 18 ⁇ m and the frequency D.
  • b was 20 and the ratio (D a / D b ) was 0.55.
  • the number-based cumulative 10% particle diameter D 10 is 3 ⁇ m and the frequency D a is 37, and the number-based cumulative 50% particle diameter D 50 is 12 ⁇ m.
  • the frequency D b was 52 and the ratio (D a / D b ) was 0.71.
  • the number-based cumulative 10% particle diameter D 10 is 2 ⁇ m and the frequency D a is 60
  • the number-based cumulative 50% particle diameter D 50 is 10 ⁇ m.
  • the frequency D b was 18, and the ratio (D a / D b ) was 3.33.
  • the number-based cumulative 10% particle diameter D 10 is 1 ⁇ m and the frequency D a is 143, and the number-based cumulative 50% particle diameter D 50 is 7 ⁇ m.
  • the frequency D b was 61 and the ratio (D a / D b ) was 2.34.
  • the phosphor particles D 10 and D 50 were determined by performing image processing on a scanning electron micrograph of a cross section of the wavelength conversion member and measuring the diameter of the phosphor particles detected on the image.
  • the total luminous flux was measured by multiplying the energy distribution spectrum of the obtained light by the standard luminosity factor.
  • 4 to 6 and 8 are diagrams showing the relationship between the chromaticity and the luminous flux of the wavelength conversion members obtained in Examples 1 to 3, Comparative Example 1 and Reference Example 1.
  • the wavelength conversion member obtained in Examples 1 to 3 has a chromaticity close to that of the wavelength conversion member obtained in Reference Example 1 corresponding to a small amount of trial production (that is,). It can be seen that the chromaticity deviation is small). Further, it was confirmed that the wavelength conversion members obtained in Examples 1 to 3 suppressed the variation in chromaticity and luminous flux within the same lot. In particular, in the wavelength conversion members obtained in Examples 1 and 2, it was confirmed that the variation in chromaticity within the same lot was small.
  • FIGS. 9 and 10 are diagrams showing the relationship between the chromaticity and the luminous flux of the wavelength conversion member obtained in Example 4, Comparative Example 2, and Reference Example 2.
  • the wavelength conversion member obtained in Example 4 has a chromaticity close to that of the wavelength conversion member obtained in Reference Example 2 corresponding to a small amount trial production (that is, the chromaticity deviation is small). ) Is understood. Further, it was confirmed that in the wavelength conversion member obtained in Example 4, variations in chromaticity and luminous flux within the same lot were suppressed.
  • Wavelength conversion member 1 Wavelength conversion member 2 . Glass matrix 3 . Fluorescent particles 3A . Fine powder 4 . Molded body

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