WO2014162893A1 - Light conversion member, manufacturing method for same, illuminating light source, and liquid crystal display device - Google Patents
Light conversion member, manufacturing method for same, illuminating light source, and liquid crystal display device Download PDFInfo
- Publication number
- WO2014162893A1 WO2014162893A1 PCT/JP2014/057767 JP2014057767W WO2014162893A1 WO 2014162893 A1 WO2014162893 A1 WO 2014162893A1 JP 2014057767 W JP2014057767 W JP 2014057767W WO 2014162893 A1 WO2014162893 A1 WO 2014162893A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- conversion member
- light conversion
- light
- glass
- heat
- Prior art date
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 189
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000004973 liquid crystal related substance Substances 0.000 title description 21
- 239000011521 glass Substances 0.000 claims abstract description 109
- 239000002245 particle Substances 0.000 claims abstract description 92
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000945 filler Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims abstract description 8
- 238000010304 firing Methods 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 29
- 238000005286 illumination Methods 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 238000004898 kneading Methods 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 14
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 4
- 239000002223 garnet Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 150000004645 aluminates Chemical class 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 24
- 239000002002 slurry Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000007423 decrease Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 230000001771 impaired effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- -1 oxynitrides Chemical class 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005115 demineralization Methods 0.000 description 2
- 230000002328 demineralizing effect Effects 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 241001085205 Prenanthella exigua Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- 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
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7716—Chalcogenides
- C09K11/7718—Chalcogenides with alkaline earth metals
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
Definitions
- the present invention relates to a light conversion member for converting the color of a light source, a manufacturing method thereof, an illumination light source having the light conversion member, and a liquid crystal display device.
- White LEDs are used as a low-power white illumination light source, and are expected to be applied to illumination applications.
- the white light of a white LED is light of yellow, green, red, etc., which is a blue light emitted from a blue LED element serving as a light source and a color (wavelength) of a part of the blue light converted by a phosphor. And is obtained by synthesizing
- a material in which an inorganic phosphor is dispersed in glass is known (see, for example, Patent Document 1).
- the light conversion member having such a configuration can utilize the high transmittance of glass, and can efficiently release the heat generated from the LED element to the outside of the light conversion member. Moreover, the damage of the light conversion member (especially phosphor) by light and heat is low, and long-term reliability is obtained.
- light-dispersible particles are present in the glass in which the phosphor is dispersed (see Patent Document 2), or a light-scattering layer having light-scattering particles is present as a separate layer from the glass in which the phosphor is dispersed. (See Patent Document 3), a light conversion member that scatters light from a light source to improve luminous efficiency is also known.
- JP 2003-258308 A Japanese Patent No. 4286104 Japanese Patent Application Laid-Open No. 2011-074104
- the light conversion member itself may be greatly shrunk by firing when the light conversion member is manufactured.
- the amount of phosphor present varies due to the difference in the degree of contraction between the central portion and the outer peripheral portion in the plane of the light conversion member, and this causes unevenness in light conversion chromaticity within the surface of the light conversion member.
- the present invention suppresses shrinkage during the manufacture of the light conversion member to maintain good dispersibility of the phosphor particles, suppresses unevenness in chromaticity, and further suppresses the light from the light source.
- An object of the present invention is to provide a light conversion member that can maintain transmittance.
- the light conversion member of the present invention is a light conversion member made of glass containing phosphor particles dispersed therein, and further contains a heat resistant filler dispersed in the glass. Is characterized in that the relational expression [D 50 / n] between its 50% particle size D 50 and its refractive index n at a wavelength of 633 nm is in the range of 2-20.
- the method for producing a light conversion member of the present invention includes a kneading step of kneading glass powder, phosphor particles, a heat-resistant filler, a resin and an organic solvent to form a kneaded product, and molding the obtained kneaded product into a desired shape. And a firing step of firing the molded body of the kneaded product to form a light conversion member, wherein the heat-resistant filler has a 50% particle size D 50 and a wavelength of 633 nm.
- the relational expression [D 50 / n] with respect to the refractive index n is in the range of 2 to 20.
- the illumination light source of the present invention includes the light conversion member of the present invention and a light source capable of irradiating light to the outside through the light conversion member.
- the liquid crystal display device of the present invention is a liquid crystal display device comprising a liquid crystal display panel and a backlight for illuminating the liquid crystal display panel, and the light conversion member of the present invention and the above-described backlight are used as the backlight. It has the illumination light source which consists of a light source which can irradiate light outside through a light conversion member.
- the light conversion member of the present invention suppresses shrinkage during firing and suppresses variations in in-plane light conversion chromaticity, light with little chromaticity unevenness can be obtained. Furthermore, since the light conversion member of the present invention can suppress a decrease in the transmittance of the light conversion member, the light conversion efficiency can be relatively maintained while the amount of light flux is maintained.
- the method for producing a light conversion member of the present invention can efficiently produce the light conversion member of the present invention. And since the illumination light source of this invention uses the light conversion member of this invention, illumination light with little chromaticity nonuniformity is obtained. Since the liquid crystal display device of the present invention uses the illumination light source, it can maintain light emission conversion efficiency, can expect low power consumption, has high color reproducibility, and can provide high-definition expression.
- the present light conversion member the light conversion member of the present invention
- the manufacturing method thereof, and the illumination light source will be described.
- the light conversion member is made of glass containing phosphor particles dispersed therein, and further contains a predetermined heat-resistant filler dispersed in the glass.
- a light conversion member transmits a part of the light emitted from the light source, converts the wavelength of the remaining light, and synthesizes the transmitted light and the light having the converted wavelength, thereby obtaining a desired chromaticity. Can be irradiated to the outside.
- This light conversion member is particularly useful as a light conversion member for converting a blue light source into white.
- an LED light emitting element is preferable.
- the glass used for this light conversion member can be used without particular limitation as long as it is conventionally used as a light conversion member.
- the glass used here preferably has a glass transition point Tg (hereinafter also simply referred to as “Tg”) of 300 to 550 ° C.
- Tg glass transition point
- the firing temperature becomes high during the production process of the present light conversion member, and the uniform dispersibility of the phosphor particles may be reduced by shrinkage in cooling after firing. That is, the amount of phosphor particles present per unit area varies due to the difference in the degree of contraction between the central portion and the outer peripheral portion of the light conversion member, which causes chromaticity unevenness in the surface of the light conversion member. May occur. Or glass and fluorescent substance react and there exists a possibility that the quantum conversion yield of a light conversion member may fall.
- the Tg of the glass is preferably 520 ° C. or lower, more preferably 500 ° C. or lower, and further preferably 480 ° C. or lower.
- the glass transition point Tg is less than 300 ° C.
- the firing temperature is low, and the decalcification temperature is higher than the temperature at which the glass flows. Therefore, the carbon content in the light conversion member is increased, and the quantum conversion yield of the light conversion member may be reduced.
- the transmittance of the light conversion member is lowered, and the light emission efficiency of the light source may be lowered.
- the glass transition point Tg is more preferably 340 ° C. or higher, and further preferably 380 ° C. or higher. In this specification, Tg of glass is calculated from a DTA curve.
- the glass used here is preferably based on the Bi 2 O 3 —B 2 O 3 —ZnO system. Among them, a glass containing Bi 2 O 3 3 to 40%, B 2 O 3 10 to 50%, ZnO 0 to 45% in terms of mol% based on oxide is more preferable.
- Bi 2 O 3 3 to 40% B 2 O 3 10 to 50%, ZnO 0 to 45%, SiO 2 0 to 35%, BaO 0 to 20%, TeO 2 0 to 20%, Al 2 O 3 0-4%, TiO 2 0-5%, ZrO 2 0-5%, Nb 2 O 5 0-5%, MnO 2 0-1%, CeO 2 0-1%, Li 2 O 0-15%, More preferred are glasses containing Na 2 O 0-15% and K 2 O 0-15%.
- This glass is preferably essentially composed of the above components, but may contain other components as long as the object of the present invention is not impaired. Hereinafter, each component of this glass is demonstrated.
- Bi 2 O 3 is a component that lowers the Tg and raises the refractive index without lowering the chemical durability of the glass, and is an essential component in this system.
- the content of Bi 2 O 3 is preferably 3 to 40%. If Bi 2 O 3 is less than 3%, the Tg of the glass powder is increased, which is not preferable. More preferably, it is 5% or more. On the other hand, if it exceeds 40%, the glass becomes unstable and tends to be crystallized, which may impair the sinterability. In addition, the absorption edge of the glass shifts to the long wavelength side and absorbs the blue light of the LED element.
- the content of Bi 2 O 3 is more preferably 3 to 30%, further preferably 5 to 25%.
- B 2 O 3 is a glass network former and is a component that can stabilize glass, and is an essential component in this system.
- the content of B 2 O 3 is preferably 10 to 50%. If the content of B 2 O 3 is less than 10%, the glass becomes unstable, tends to be crystallized, and the sinterability may be impaired. On the other hand, if the content of B 2 O 3 exceeds 50%, the chemical durability of the glass may be lowered.
- the content of B 2 O 3 is more preferably 15 to 45%, further preferably 20 to 40%.
- ZnO is a component that lowers Tg and raises the refractive index, and is not an essential component in this system.
- the content of ZnO is preferably 0 to 45%. If the ZnO content exceeds 45%, it will be difficult to vitrify, and it will be difficult to produce glass.
- the content of ZnO is more preferably 5 to 40%, further preferably 5 to 35%.
- SiO 2 is a component that increases the stability of the glass and is not an essential component in this system.
- the content of SiO 2 is preferably 0 to 35%. If the content of SiO 2 exceeds 35%, Tg may be high.
- the content of SiO 2 is more preferably 0 to 30%, further preferably 0 to 20%.
- CaO, SrO, MgO and BaO alkaline earth metal oxides are components that increase the stability of the glass and lower the Tg, and are not essential components in this system.
- the total amount of alkaline earth metal oxide is preferably 0 to 20%. If this total amount exceeds 20%, the stability of the glass is lowered. More preferably, the total amount is 18% or less.
- TeO 2 is a component that lowers the Tg, raises the refractive index, raises the weather resistance, and lowers the liquidus temperature, but is not an essential component in the present invention.
- the content of TeO 2 is preferably 0 to 20%. If the TeO 2 content exceeds 20%, the sinterability may be impaired, or the phosphor may be deactivated by reacting with the phosphor during firing.
- the TeO 2 content is more preferably 16% or less, further preferably 14% or less, and particularly preferably 12% or less.
- Al 2 O 3 is a component that improves chemical durability and suppresses reaction with the phosphor during firing, but is not an essential component in the present invention.
- the content of Al 2 O 3 is preferably 0 to 4%. If the Al 2 O 3 content exceeds 4%, Tg may be too high, the liquidus temperature may be increased, or the sinterability may be impaired.
- the content of Al 2 O 3 is more preferably 3% or less.
- TiO 2 , ZrO 2 and Nb 2 O 5 are components that increase the refractive index, increase the weather resistance of the glass, and increase chemical durability, and are not essential components in this system. These components are TiO 2 0 to 5%, ZrO 2 0 to 5%, and Nb 2 O 5 0 to 5%, and the total amount is preferably 0 to 5%. If the total amount of these components exceeds 5%, the stability of the glass is lowered, Tg becomes too high, the absorption edge of the glass is shifted to the longer wavelength side, and the blue light of the LED element may be absorbed. There is. This total amount is preferably 4% or less, more preferably 3% or less.
- MnO 2 nor CeO 2 is an essential component in this system, but it is preferably contained because it functions as an oxidizing agent in the glass. In any case, reduction of Bi 2 O 3 in the glass can be prevented, so that this type of glass can be stabilized. Reduction of Bi 2 O 3 is not preferable because the glass is colored. Therefore, the contents of MnO 2 and CeO 2 are each preferably 0 to 1%. If the content exceeds 1%, coloring may increase. Preferably, it is 0 to 0.5%.
- Alkali metal oxides of Li 2 O, Na 2 O and K 2 O are components that lower Tg and are not essential components in this system.
- the total amount of alkali metal oxide is preferably 0 to 15%. If the total amount exceeds 15%, the refractive index is lowered, and the chemical durability of the glass may be lowered. More preferably, it is 0 to 10%, and still more preferably 0 to 5%.
- the glass may further include a glass that can degas the encapsulated foam.
- a glass that can degas the encapsulated foam examples include elements that can have a plurality of oxidation numbers by changing the valence, such as metal compounds having oxidation catalytic properties such as copper chloride and antimony oxide.
- the content of these components is preferably 0 to 15%.
- the density of the glass is preferably 3.5 to 7.0 g / cm 3 . Outside this range, the difference in specific gravity with the phosphor becomes large, and the phosphor particles are not uniformly dispersed in the glass powder, and conversion efficiency may be reduced when a light conversion member is used.
- the density is more preferably 3.7 to 6.5 g / cm 3 , still more preferably 4.1 to 6.0 g / cm 3 .
- the refractive index of glass is preferably 1.65 to 2.10 at a wavelength of 633 nm. If it is out of this range, the difference in refractive index from the phosphor particles becomes large, and there is a possibility that the conversion efficiency is lowered when the light conversion member is used.
- the refractive index is more preferably 1.70 to 2.05, still more preferably 1.75 to 2.00.
- the fluorescent substance particle used for this light conversion member can convert the wavelength of a light source, the kind will not be limited,
- the well-known fluorescent substance particle used for a light conversion member is mentioned.
- examples of such phosphor particles include oxides, nitrides, oxynitrides, sulfides, oxysulfides, halides, aluminate chlorides, halophosphates, and the like.
- those that convert blue light into red, green, or yellow are preferable, and those that have an excitation band at a wavelength of 400 to 500 nm and have an emission peak ( ⁇ p ) at a wavelength of 500 to 700 nm are more preferable.
- ⁇ p emission peak
- the phosphor only needs to contain one or more compounds selected from the group consisting of the above-mentioned compounds, and a plurality of types of compounds are mixed. May be contained, or any one of them may be contained alone. From the viewpoint of ease of color design, it is preferable to contain any one of them. From the viewpoint of increasing the quantum conversion yield, the phosphor is preferably an oxide or aluminate chloride.
- the phosphor of oxide or aluminate chloride is more preferably a garnet crystal. Garnet-based crystals are excellent in water resistance and heat resistance, and are hardly deactivated in a slurry or deactivated during firing when undergoing the production process of the present invention described later.
- Examples of the garnet-based crystal include a composite oxide of yttrium and aluminum (Y 3 Al 5 O 12 ; hereinafter abbreviated as YAG in this specification), a composite oxide of lutetium and aluminum (Lu 3 Al 5 O 12 ; Hereinafter, it is abbreviated as LAG in this specification.
- the average particle diameter (hereinafter abbreviated as 50% particle size) D 50 of the phosphor particles is preferably 1 to 30 ⁇ m. If the 50% particle size D 50 of the phosphor particles is less than 1 ⁇ m, the specific surface area of the phosphor particles is increased, and the phosphor particles may be easily deactivated.
- the 50% particle size D 50 is more preferably 3 ⁇ m or more, further preferably 5 ⁇ m or more, and particularly preferably 7 ⁇ m or more.
- the 50% particle diameter D 50 of the phosphor particles is more than 30 ⁇ m, the dispersibility is deteriorated in the light conversion member, the light conversion efficiency is deteriorated, and chromaticity unevenness may occur.
- the 50% particle diameter D 50 and more preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
- the 50% particle size D 50 is a value calculated as a 50% value in the integrated% on a volume basis from the particle size distribution obtained by laser diffraction particle size distribution measurement.
- the heat-resistant filler used in the present light conversion member is a heat-resistant filler having a relational expression [D 50 / n] of 2 to 20 between the 50% particle diameter D 50 and the refractive index n at a wavelength of 633 nm.
- a heat-resistant filler By including such a heat-resistant filler in the glass, when the light conversion member is produced, shrinkage that occurs during firing can be suppressed, and the uniform dispersibility of the phosphor particles in the light conversion member can be favorably maintained.
- the relational expression [D 50 / n] in this heat-resistant filler is less than 2, the light from the light source tends to be scattered, and the light transmittance of the light conversion member tends to decrease. The dispersibility of the resin may decrease, and shrinkage may not be suppressed uniformly.
- This relational expression [D 50 / n] is preferably in the range of 3 to 18, more preferably 4 to 15.
- the heat-resistant filler preferably has a 50% particle size D 50 of 5 to 30 ⁇ m. If it is less than 5 ⁇ m, light from the light source tends to be scattered and the light transmittance of the light conversion member may be reduced. If it exceeds 30 ⁇ m, the dispersibility of the heat-resistant filler in the light conversion member is reduced, and shrinkage during firing May not be sufficiently suppressed.
- the 50% particle size D 50 is more preferably 6 to 25 ⁇ m, still more preferably 8 to 22 ⁇ m.
- the refractive index n of the heat resistant filler at a wavelength of 633 nm is preferably 1.5 to 2.5. If the refractive index is out of the range, the difference in refractive index from the glass increases, so that the refraction at the interface between the heat-resistant filler and the glass increases and the light from the light source is easily scattered, and the light transmittance of the light conversion member is increased. May decrease.
- the refractive index n of the heat resistant filler is more preferably 1.6 to 2.3, and still more preferably 1.7 to 2.2.
- this heat-resistant filler should just have heat resistance with respect to the calcination temperature at the time of manufacture of a light conversion member, for example, an alumina, a zirconia, magnesia etc. are mentioned, Among these, at least 1 type or more is contained. If you do.
- the refractive index of the heat-resistant filler was measured using a bulk body and the refractive index n with respect to light having a wavelength of 633 nm using a model 2010 prism coupler manufactured by Metricon.
- the present light conversion member is configured by dispersing phosphor particles and heat-resistant filler in glass.
- the heat-resistant filler may contain 3 to 30% by volume fraction. preferable. If the content is less than 3%, the shrinkage may not be sufficiently suppressed, and if it exceeds 30%, the light transmittance of the light conversion member may be reduced, and the utilization efficiency of the light source may be reduced.
- the light conversion member can be manufactured in a well-balanced manner with the light transmittance from the light source and the light conversion amount of the phosphor particles. It is possible to suppress the occurrence of chromaticity unevenness.
- the quantum conversion yield of this light conversion member is preferably 80% or more. If the quantum conversion yield is less than 80%, the thickness of the light conversion member must be increased in order to obtain a desired color. When the thickness is increased, the transmittance of the light conversion member may be reduced.
- the quantum conversion yield of the light conversion member is more preferably 85% or more, and still more preferably 90% or more.
- the quantum conversion yield is expressed as a ratio between the number of photons emitted from the sample as light emission and the number of photons absorbed by the sample when irradiated with excitation light. The number of photons is measured by the integrating sphere method.
- the thickness of the light conversion member is preferably 50 to 500 ⁇ m. When the thickness of the light conversion member is 50 ⁇ m or more, handling of the light conversion member becomes easy, and cracking of the light conversion member can be suppressed particularly when cutting to a desired size.
- the thickness of the light conversion member is more preferably 80 ⁇ m or more, further preferably 100 ⁇ m or more, and particularly preferably 120 ⁇ m or more. When the thickness of the light conversion member is 500 ⁇ m or less, the total light flux transmitted through the light conversion member can be maintained high.
- the thickness of the light conversion member is preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less, and particularly preferably 250 ⁇ m or less.
- the thickness of the light conversion member may be selected from 250 to 500 ⁇ m in order to balance the total luminous flux and the light conversion efficiency.
- the planar shape of the light conversion member is not particularly limited.
- the shape of the light conversion member is manufactured according to the shape of the light source in order to prevent light leakage from the light source. Since the light source is generally rectangular or circular, the light conversion member is also preferably rectangular or circular.
- the light converting member is preferably plate-shaped, that is, the cross-sectional shape is rectangular. The smaller the variation in the plate thickness within the light conversion member, the smaller the in-plane color variation, which is preferable.
- the present light conversion member is preferably made of a sintered body of a mixed powder of glass powder, phosphor particles and heat-resistant filler.
- the light conversion member is more preferably composed of a sintered body obtained by firing a kneaded product obtained by kneading the mixed powder, a resin and an organic solvent, and the kneaded product is applied to a transparent resin. More preferably, it is made of a glass sheet obtained by sintering a green sheet obtained by drying.
- the mixture of the resin and the organic solvent may be referred to as a vehicle.
- this light conversion member as a sintered body, a kneading step of kneading glass powder, phosphor particles, heat-resistant filler, resin and organic solvent to obtain a kneaded product, What is necessary is just to perform sequentially the shaping
- the kneading step in the present invention involves kneading glass powder, phosphor particles, heat-resistant filler, resin and organic solvent into a kneaded product (slurry), and it is sufficient that these raw materials can be kneaded uniformly.
- a known kneading method for example, kneading using a dissolver, homomixer, kneader, roll mill, sand mill, attritor, ball mill, vibrator mill, high-speed impeller mill, ultrasonic homogenizer, shaker, etc. Good.
- the glass powder used here may be prepared by mixing a plurality of known glass powders so as to satisfy the above-mentioned glass composition, or by mixing and mixing components so as to have predetermined thermal characteristics. Then, it may be prepared by melting in an electric furnace or the like, rapidly cooling to produce glass having a predetermined composition, pulverizing and classifying it.
- the glass powder preferably has a 50% particle size D 50 of less than 2.0 ⁇ m.
- the 50% particle size D 50 is 2.0 ⁇ m or more, the phosphor particles and the heat-resistant filler are not uniformly dispersed in the glass powder, so that the light conversion efficiency decreases when the light conversion member is used, or the shrinkage amount during firing May increase.
- the 50% particle size D 50 is more preferably 1.5 ⁇ m or less, and still more preferably 1.4 ⁇ m or less.
- the maximum particle diameter Dmax of the glass powder is preferably 30 ⁇ m or less.
- D max is more preferably 20 ⁇ m or less, and still more preferably 15 ⁇ m or less.
- D max is the value of the maximum particle size calculated by laser diffraction particle size distribution measurement.
- the phosphor particles and the heat-resistant filler are the particles described in the light conversion member.
- the resin ethyl cellulose, nitrocellulose, acrylic resin, vinyl acetate, butyral resin, melamine resin, alkyd resin, or rosin resin can be used.
- the organic solvent aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, ketones or esters can be used.
- the vehicle preferably contains a butyral resin, a melamine resin, an alkyd resin, a rosin resin, or the like.
- the content of each component in the mixed powder is the volume fraction, and the phosphor particles are 1 to 40%.
- the heat resistant filler is preferably 3 to 30% and the glass powder is preferably 50 to 96%.
- the phosphor particles are contained at 1% or more and the glass powder at 96% or less, the quantum conversion yield can be increased, incident light can be efficiently converted, and light of a desired color can be obtained.
- the volume fraction of the phosphor particles is more preferably 5% or more, further preferably 7% or more, and particularly preferably 10% or more.
- the volume fraction of the glass powder is more preferably 91% or less, further preferably 87% or less, and particularly preferably 83% or less.
- volume fraction of the phosphor particles is more than 40% and the volume fraction of the glass powder is less than 50%, the sinterability of the mixture of the phosphor particles and the glass powder is impaired, and the transmittance of the light conversion member is low. There is a risk. Moreover, there is a possibility that light of a desired color cannot be obtained due to an increase in converted fluorescent light.
- the volume fraction of the phosphor particles is more preferably 35% or less, still more preferably 30% or less, and particularly preferably 25% or less.
- the volume fraction of the glass powder is more preferably 55% or more, further preferably 60% or more, and particularly preferably 65% or more.
- the volume fraction of the heat-resistant filler is 3% or more, because the shrinkage during firing of the light conversion member can be efficiently suppressed, and the state in which the phosphor particles are uniformly dispersed can be maintained.
- the volume fraction of the heat-resistant filler is more preferably 4% or more, further preferably 5% or more, and particularly preferably 7% or more. Further, if the volume fraction of the heat-resistant filler exceeds 30%, the sinterability of the mixed powder is impaired, and the transmittance of the light conversion member may be lowered.
- the volume fraction of the heat resistant filler is preferably 28% or less, more preferably 26% or less, still more preferably 20% or less, and particularly preferably 15% or less.
- a vehicle made of a resin and an organic solvent may be made into a slurry by mixing the above mixed powder with an amount of a viscosity that can be molded into a predetermined shape in the next molding step.
- the kneaded product obtained in the kneading step is molded into a desired shape to form a kneaded product.
- the molding method is not particularly limited as long as a desired shape can be imparted, and examples thereof include known methods such as a press molding method, a roll molding method, and a doctor blade molding method.
- a green sheet obtained by a doctor blade molding method is preferable because a light conversion member having a uniform film thickness can be efficiently produced in a large area.
- the green sheet can be manufactured, for example, by the following process. Glass powder, phosphor particles and heat-resistant filler are kneaded in a vehicle and defoamed to obtain a slurry. The obtained slurry is coated on a transparent resin by a doctor blade method and dried. After drying, it is cut into a desired size and the transparent resin is peeled off to obtain a green sheet. Furthermore, by pressing these to form a laminate, a molded body having a desired thickness can be secured.
- the transparent resin for applying the slurry is not particularly limited as long as it has releasability.
- the transparent resin used here is preferably a transparent film having a uniform thickness so that a green sheet having a uniform thickness can be obtained.
- Examples of such a transparent film include a PET film. It is done.
- the firing step of the present invention is a step in which the molded body of the kneaded product obtained in the molding step is sintered by firing to obtain a light conversion member. Firing in this firing step is to sinter the mixed powder to obtain a glass containing phosphor particles and heat-resistant filler dispersed therein, and the glass body may be produced by a known firing method.
- the conditions for the firing step are not particularly limited as long as it can be made into a glass body by firing, but the firing atmosphere is preferably a reduced pressure atmosphere of 10 3 Pa or less or an atmosphere having an oxygen concentration of 1 to 15%.
- the firing temperature is preferably in the range of 400 to 650 ° C., and the firing time is preferably in the range of 1 to 10 hours. In the manufacturing method of the light conversion member of this invention, when implemented outside the said range, there exists a possibility that the quantum conversion yield of a light conversion member may fall.
- the light conversion member obtained as described above contains a heat-resistant filler having predetermined characteristics, thereby suppressing the shrinkage during firing, thereby suppressing in-plane light conversion chromaticity variation. Light with less unevenness can be obtained. Furthermore, this light conversion member can suppress a decrease in the transmittance thereof, while maintaining the light flux amount, and containing a material whose [D 50 / n] deviates from the above definition as a heat-resistant filler with a light emission conversion efficiency. Higher than that can be maintained.
- the illumination light source of the present invention includes the above-described light conversion member and a light source capable of irradiating light to the outside through the light conversion member.
- the light conversion member By combining the light conversion member and the light source obtained as described above, it can be used as an illumination light source that emits a desired color.
- the light conversion member is preferably disposed in contact with the light source because it prevents light leakage.
- an LED light emitting element is preferable and a blue LED light emitting element is more preferable. If an LED light emitting element is used as a light source, it can be used as an LED illumination light source.
- the liquid crystal display device in the present embodiment is a liquid crystal display device including a liquid crystal display panel and a backlight that illuminates the liquid crystal display panel, and the light conversion member and the light conversion member are used as a backlight.
- an illumination light source comprising a light source capable of irradiating light to the outside.
- the backlight used in the present embodiment includes the above-described light conversion member and a light source that can emit light to the outside through the light conversion member.
- a light conversion member By combining the light conversion member and the light source obtained as described above, it can be suitably used as a backlight for a liquid crystal display device capable of obtaining a high luminance and a wide range of color reproducibility.
- the light conversion member is preferably disposed in contact with the light source because it prevents light leakage.
- a light source an LED light emitting element is preferable, a blue LED light emitting element is more preferable, and a backlight capable of irradiating white light is preferable.
- the liquid crystal display panel used in the present embodiment is not particularly limited as long as it is a known liquid crystal display panel.
- the liquid crystal display panel displays an image by providing an alignment film between two glass plates provided with a polarizing filter, changing the direction of liquid crystal molecules by applying a voltage, and increasing or decreasing light transmittance.
- the liquid crystal display panel can be illuminated with bright white light having a wide color gamut of the three primary colors of light. Therefore, pure white with high luminance can be obtained on the display screen of the liquid crystal display panel, color reproducibility is good, and the quality of the display screen can be improved.
- a Ce-activated YAG phosphor having a 50% particle size D 50 of 10 ⁇ m, a refractive index at 633 nm of about 1.9 nm and a phosphor peak wavelength of about 555 nm when excited, and a 50% particle size D 50 are 50% particle size D 50.
- Two kinds of Eu-activated CASN phosphors having a refractive index at 11 ⁇ m and a wavelength of 633 nm of about 2.3 and 460 nm and a phosphor peak wavelength of about 628 nm were used. In Tables 2 and 3, they are abbreviated as “YAG” and “CASN”, respectively.
- the heat-resistant filler, the refractive index 18 ⁇ m 50% particle diameter D 50, heat-resistant filler 1,50% particle diameter D 50 of refractive index at a wavelength of 633nm is made of a single crystal alumina which is 1.76 is 3 [mu] m, at a wavelength of 633nm 1 .76 heat-resistant filler 2 made of single crystal alumina, 50 % particle size D 50 is 12 ⁇ m, heat-resistant filler 3 made of YAG having a refractive index of 1.83 at a wavelength of 633 nm, and 50% particle size D 50 is 6 ⁇ m, A heat-resistant filler 4 made of magnesia having a refractive index of 1.7 at a wavelength of 633 nm was used.
- the heat-resistant filler 1 [D 50 / n] is 10.2, [D 50 / n] is 1.7 of heat-resistant filler 2, [D 50 / n] is 6.6 heat-resistant filler 3, heat-resistant filler 4 [D 50 / n] is 3.5.
- Glass raw materials were mixed so as to have the composition shown in Table 1 in terms of mol% based on oxide.
- the glass 1 is heated in an electric furnace to 1200 ° C. in a platinum crucible and melted, and the glasses 2 to 4 are heated in an electric furnace in a gold crucible to 900 ° C. to 1000 ° C. and melted to melt each.
- the liquid was quenched with a rotating roll to form a glass ribbon.
- the glass ribbon was pulverized with a ball mill, passed through a sieve having a mesh having an opening of 150 ⁇ m, and further subjected to air classification to obtain glass powder (glass powder).
- Glasses 1 to 4 had 50% particle size D 50 of 1.4 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, and 1.2 ⁇ m, respectively.
- the glass transition points Tg of the glass powder were 496 ° C., 420 ° C., 429 ° C., and 415 ° C., respectively.
- a part of the melt was cooled after molding to obtain a glass plate.
- the refractive indices n of the glass plate for light having a wavelength of 633 nm were 1.79, 1.97, 1.91, and 1.99, respectively.
- the glass transition point Tg of the obtained glass powder was measured using a differential thermal analyzer (manufactured by Rigaku Corporation, trade name: TG8110).
- the phosphor particles, the particle size D 50 of the heat-resistant filler and glass powder, a laser diffraction particle size distribution measurement was calculated by.
- the obtained glass plate was processed into a plate shape having a thickness of 2 mm and a size of 20 mm ⁇ 20 mm, and both surfaces thereof were mirror-polished to obtain a sample plate, and the refractive index n with respect to light having a wavelength of 633 nm was set as a model 2010 prism manufactured by Metricon. Measurement was performed using a coupler.
- Examples 1 to 18 Glass, phosphor particles, and heat-resistant filler were mixed so as to have the ratios shown in Tables 2 to 3, and further kneaded with a vehicle and defoamed to obtain a slurry.
- This slurry was applied to a PET film (manufactured by Teijin Limited) by the doctor blade method. This was dried in a drying furnace for about 30 minutes, cut into a size of about 7 cm square, and the PET film was peeled off to obtain a green sheet having a thickness of 0.5 to 0.7 mm.
- the plane shrinkage rate was obtained by averaging the vertical and horizontal shrinkage rates of the obtained light conversion member with respect to the vertical and horizontal lengths of the green sheet.
- the central portion of the obtained light conversion member is cut into a size of 1 cm square, and an absolute PL quantum yield measurement device (manufactured by Hamamatsu Photonics Co., Ltd., trade name: Quantauru-QY) is used. Then, measurement was performed at an excitation light wavelength of 460 nm. At the same time, chromaticity coordinates x and y are also obtained.
- In-plane chromaticity variations ⁇ x and ⁇ y are obtained by cutting the end of the obtained light conversion member into a size of 1 cm square like the center, measuring the chromaticity coordinates, and then calculating the difference from the chromaticity coordinates in the center. It was obtained by taking.
- the transmittance of the light conversion member was measured with a C light source using a haze measuring device (trade name: Haze Meter HZ-2, manufactured by Suga Test Instruments Co., Ltd.).
- Examples 1 to 4 and 7 to 18 contain the heat-resistant filler specified in the present invention, so that the shrinkage rate is suppressed to less than 20%, and the in-plane chromaticity variation ⁇ x, Each ⁇ y is less than 0.02.
- Examples 1 to 4 maintain a high quantum conversion yield of 85% or more and a transmittance of 80% or more, high light emission conversion efficiency can be expected.
- Examples 7 to 18 use a glass having a higher refractive index than that of the glass 1 used in Examples 1 to 4, so the reflectance is high and the transmittance is a low value.
- Example 5 does not contain a heat-resistant filler, the shrinkage rate is as high as more than 20%, and the in-plane chromaticity variations ⁇ x and ⁇ y are as large as 0.02 or more, respectively.
- Example 6 since the D 50 of the heat resistant filler is as small as 3 ⁇ m, the transmittance is less than 80%, the total luminous flux is decreased, and the light emission conversion efficiency may be decreased.
- the light conversion member of the present invention maintains the uniform dispersibility of the phosphor particles by suppressing shrinkage during firing, reduces chromaticity variation, suppresses a decrease in light transmittance of the light source, and emits light.
- the conversion efficiency can be maintained, which is suitable for use as a lighting application.
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Abstract
Provided are a light conversion member and a method for manufacturing the same such that the light conversion member maintains favorable dispersion for phosphor particles therein and is able to retain light conversion efficiency in a manner that does not reduce transmittance of light from a light source. The light conversion member is made of glass that contains dispersed phosphor particles, and a heat resistance filler is also contained and dispersed in the glass, said heat resistance filler being such that the relational expression [D50/n] between the 50% particle diameter (D50) thereof and the refractive index (n) for a 633 nm wavelength is between 2 - 20. In the light conversion member manufacturing method, raw material mixed powder is mixed with a vehicle to produce a slurry, and the slurry is molded and then calcined.
Description
本発明は、光源の色を変換するための光変換部材、その製造方法、該光変換部材を有する照明光源および液晶表示装置に関する。
The present invention relates to a light conversion member for converting the color of a light source, a manufacturing method thereof, an illumination light source having the light conversion member, and a liquid crystal display device.
白色LEDは、微小電力の白色照明光源として利用され、照明用途への応用が期待されている。一般に、白色LEDの白色光は、光源となる青色LED素子から発せられる青色光と、その青色光の一部を蛍光体により光の色(波長)を変換した、黄色、緑色、赤色等の光とを合成して得られる。
White LEDs are used as a low-power white illumination light source, and are expected to be applied to illumination applications. In general, the white light of a white LED is light of yellow, green, red, etc., which is a blue light emitted from a blue LED element serving as a light source and a color (wavelength) of a part of the blue light converted by a phosphor. And is obtained by synthesizing
このような光源の光の色(波長)を変換する光変換部材としては、ガラス中に無機蛍光体を分散したものが知られている(例えば、特許文献1参照)。このような構成の光変換部材は、ガラスの高い透過率を利用でき、さらに、LED素子から発せられる熱を光変換部材の外部に効率よく放出できる。また、光や熱による光変換部材(特に、蛍光体)の損傷も低く、長期の信頼性が得られる。
As a light conversion member for converting the light color (wavelength) of such a light source, a material in which an inorganic phosphor is dispersed in glass is known (see, for example, Patent Document 1). The light conversion member having such a configuration can utilize the high transmittance of glass, and can efficiently release the heat generated from the LED element to the outside of the light conversion member. Moreover, the damage of the light conversion member (especially phosphor) by light and heat is low, and long-term reliability is obtained.
また、蛍光体を分散したガラス中に光分散性の粒子を存在させたり(特許文献2参照)、蛍光体を分散させたガラスとは別の層として光散乱粒子を有する光散乱層を存在させたり(特許文献3参照)、することで光源の光を散乱させて発光効率を向上させようとする光変換部材も知られている。
In addition, light-dispersible particles are present in the glass in which the phosphor is dispersed (see Patent Document 2), or a light-scattering layer having light-scattering particles is present as a separate layer from the glass in which the phosphor is dispersed. (See Patent Document 3), a light conversion member that scatters light from a light source to improve luminous efficiency is also known.
しかしながら、特許文献1記載のように、ガラス中に蛍光体を含有するだけでは、その光変換部材を製造する際の焼成により、光変換部材自体が大きく収縮してしまう場合がある。収縮が起こると、光変換部材の平面において、中心部分と外周部分との収縮度合いの差から、蛍光体の存在量のばらつきが生じ、これが光変換部材の面内において光変換色度のムラが生じる原因となる。そのため、収縮が大きくなると光変換色度のムラも大きくなり均一な色調の光を得られなくなってしまう。
However, as described in Patent Document 1, if the phosphor is contained only in the glass, the light conversion member itself may be greatly shrunk by firing when the light conversion member is manufactured. When contraction occurs, the amount of phosphor present varies due to the difference in the degree of contraction between the central portion and the outer peripheral portion in the plane of the light conversion member, and this causes unevenness in light conversion chromaticity within the surface of the light conversion member. Cause. Therefore, when the shrinkage increases, the unevenness of the light conversion chromaticity also increases, and it becomes impossible to obtain light with a uniform color tone.
また、特許文献2および3のように、光散乱粒子を有する光変換部材であった場合、光散乱により光路長を稼ぐことで変換効率を向上できる可能性がある一方、光源からの光の透過率が低減して光束量が低下してしまうため、全体的な光の利用効率が十分に向上しないおそれがある。
Moreover, when it is a light conversion member which has light-scattering particle | grains like patent document 2 and 3, while there is a possibility that conversion efficiency can be improved by earning optical path length by light scattering, on the other hand, transmission of the light from a light source Since the rate decreases and the amount of light flux decreases, the overall light utilization efficiency may not be sufficiently improved.
そこで、上記問題に鑑み、本発明は、光変換部材の製造時における収縮を抑制して蛍光体粒子の分散性を良好に維持すると共に、色度のムラを抑制し、さらに光源からの光の透過率を保持できる光変換部材の提供を目的とする。
Therefore, in view of the above problems, the present invention suppresses shrinkage during the manufacture of the light conversion member to maintain good dispersibility of the phosphor particles, suppresses unevenness in chromaticity, and further suppresses the light from the light source. An object of the present invention is to provide a light conversion member that can maintain transmittance.
本発明者らが鋭意検討した結果、所定の特性を有する耐熱フィラーを使用することで、光変換部材の焼成における収縮を抑制するとともに、光源からの光の透過率を保持できることを見出し、本発明を完成するに到った。
As a result of intensive studies by the present inventors, it has been found that by using a heat-resistant filler having predetermined characteristics, it is possible to suppress shrinkage during firing of the light conversion member and to maintain the light transmittance from the light source. It came to complete.
すなわち、本発明の光変換部材は、蛍光体粒子を分散して含有するガラスからなる光変換部材であって、前記ガラス中に、さらに、耐熱フィラーが分散して含有されており、該耐熱フィラーは、その50%粒径D50と波長633nmにおけるその屈折率nとの関係式[D50/n]が2~20の範囲であることを特徴とする。
That is, the light conversion member of the present invention is a light conversion member made of glass containing phosphor particles dispersed therein, and further contains a heat resistant filler dispersed in the glass. Is characterized in that the relational expression [D 50 / n] between its 50% particle size D 50 and its refractive index n at a wavelength of 633 nm is in the range of 2-20.
本発明の光変換部材の製造方法は、ガラス粉末、蛍光体粒子、耐熱フィラー、樹脂および有機溶媒を混練して混練物とする混練工程と、得られた混練物を所望の形状に成形する成形工程と、混練物の成形体を焼成して光変換部材とする焼成工程と、を有する光変換部材の製造方法であって、前記耐熱フィラーが、その50%粒径D50と波長633nmにおけるその屈折率nとの関係式[D50/n]が2~20の範囲であることを特徴とする。
The method for producing a light conversion member of the present invention includes a kneading step of kneading glass powder, phosphor particles, a heat-resistant filler, a resin and an organic solvent to form a kneaded product, and molding the obtained kneaded product into a desired shape. And a firing step of firing the molded body of the kneaded product to form a light conversion member, wherein the heat-resistant filler has a 50% particle size D 50 and a wavelength of 633 nm. The relational expression [D 50 / n] with respect to the refractive index n is in the range of 2 to 20.
また、本発明の照明光源は、本発明の光変換部材と、該光変換部材を通して外部へ光を照射可能な光源と、を有することを特徴とする。
The illumination light source of the present invention includes the light conversion member of the present invention and a light source capable of irradiating light to the outside through the light conversion member.
また、本発明の液晶表示装置は、液晶表示パネルと、該液晶表示パネルを照明するバックライトと、を備えた液晶表示装置であって、前記バックライトとして、上記本発明の光変換部材および前記光変換部材を通して外部に光を照射可能な光源からなる照明光源を有することを特徴とする。
The liquid crystal display device of the present invention is a liquid crystal display device comprising a liquid crystal display panel and a backlight for illuminating the liquid crystal display panel, and the light conversion member of the present invention and the above-described backlight are used as the backlight. It has the illumination light source which consists of a light source which can irradiate light outside through a light conversion member.
本発明の光変換部材は、焼成時の収縮を抑制して、面内の光変換色度のばらつきを抑えたため、色度ムラの少ない光を得ることができる。さらに、本発明の光変換部材は、光変換部材の透過率の低下を抑制できるため、光束量を維持しつつ、発光変換効率を比較的保持したものとできる。
Since the light conversion member of the present invention suppresses shrinkage during firing and suppresses variations in in-plane light conversion chromaticity, light with little chromaticity unevenness can be obtained. Furthermore, since the light conversion member of the present invention can suppress a decrease in the transmittance of the light conversion member, the light conversion efficiency can be relatively maintained while the amount of light flux is maintained.
本発明の光変換部材の製造方法は、本発明の光変換部材を効率よく製造できる。そして、本発明の照明光源は、本発明の光変換部材を使用するため、色度ムラの少ない照明光が得られる。本発明の液晶表示装置は、その照明光源を適用しているため、発光変換効率を保持し、低消費電力が期待でき、さらに色再現性が高く、高精細な表現が可能である。
The method for producing a light conversion member of the present invention can efficiently produce the light conversion member of the present invention. And since the illumination light source of this invention uses the light conversion member of this invention, illumination light with little chromaticity nonuniformity is obtained. Since the liquid crystal display device of the present invention uses the illumination light source, it can maintain light emission conversion efficiency, can expect low power consumption, has high color reproducibility, and can provide high-definition expression.
以下、本発明の光変換部材(以下、「本光変換部材」ともいう)、その製造方法および照明光源について説明する。
Hereinafter, the light conversion member of the present invention (hereinafter also referred to as “the present light conversion member”), the manufacturing method thereof, and the illumination light source will be described.
[光変換部材]
本光変換部材は、上記の通り、蛍光体粒子を分散して含有するガラスからなり、さらに、該ガラス中に、所定の耐熱フィラーが分散して含有されるものである。このような光変換部材は、光源から発せられた光の一部を透過し、残部の光の波長を変換し、透過する光と波長を変換した光とを合成することにより、所望の色度を有する光を外部へ照射可能とする。本光変換部材は、青色光源を白色に変換するための光変換部材として特に有用である。また、ここで使用する光源としてはLED発光素子が好ましい。 [Light conversion member]
As described above, the light conversion member is made of glass containing phosphor particles dispersed therein, and further contains a predetermined heat-resistant filler dispersed in the glass. Such a light conversion member transmits a part of the light emitted from the light source, converts the wavelength of the remaining light, and synthesizes the transmitted light and the light having the converted wavelength, thereby obtaining a desired chromaticity. Can be irradiated to the outside. This light conversion member is particularly useful as a light conversion member for converting a blue light source into white. Moreover, as a light source used here, an LED light emitting element is preferable.
本光変換部材は、上記の通り、蛍光体粒子を分散して含有するガラスからなり、さらに、該ガラス中に、所定の耐熱フィラーが分散して含有されるものである。このような光変換部材は、光源から発せられた光の一部を透過し、残部の光の波長を変換し、透過する光と波長を変換した光とを合成することにより、所望の色度を有する光を外部へ照射可能とする。本光変換部材は、青色光源を白色に変換するための光変換部材として特に有用である。また、ここで使用する光源としてはLED発光素子が好ましい。 [Light conversion member]
As described above, the light conversion member is made of glass containing phosphor particles dispersed therein, and further contains a predetermined heat-resistant filler dispersed in the glass. Such a light conversion member transmits a part of the light emitted from the light source, converts the wavelength of the remaining light, and synthesizes the transmitted light and the light having the converted wavelength, thereby obtaining a desired chromaticity. Can be irradiated to the outside. This light conversion member is particularly useful as a light conversion member for converting a blue light source into white. Moreover, as a light source used here, an LED light emitting element is preferable.
(ガラス)
本光変換部材に使用するガラスは、従来、光変換部材として使用されているものであれば特に限定されずに使用できる。 (Glass)
The glass used for this light conversion member can be used without particular limitation as long as it is conventionally used as a light conversion member.
本光変換部材に使用するガラスは、従来、光変換部材として使用されているものであれば特に限定されずに使用できる。 (Glass)
The glass used for this light conversion member can be used without particular limitation as long as it is conventionally used as a light conversion member.
ここで使用するガラスは、そのガラス転移点Tg(以下、単に「Tg」ともいう)が300~550℃を有することが好ましい。ガラス転移点が550℃超では、本光変換部材の製造工程中、焼成する際の温度が高くなり、焼成後の冷却における収縮によって蛍光体粒子の均一分散性が低下するおそれがある。すなわち、光変換部材の中心部分と外周部分との収縮度合いの差により蛍光体粒子の単位面積当たりの存在量がばらついてしまい、それが原因となって、光変換部材の面内における色度ムラが生じるおそれがある。または、ガラスと蛍光体が反応し、光変換部材の量子変換収率が低下するおそれがある。収縮または量子変換収率の低下を抑制するためには、ガラスのTgは、好ましくは520℃以下、より好ましくは500℃以下、さらに好ましくは480℃以下である。
The glass used here preferably has a glass transition point Tg (hereinafter also simply referred to as “Tg”) of 300 to 550 ° C. When the glass transition point is higher than 550 ° C., the firing temperature becomes high during the production process of the present light conversion member, and the uniform dispersibility of the phosphor particles may be reduced by shrinkage in cooling after firing. That is, the amount of phosphor particles present per unit area varies due to the difference in the degree of contraction between the central portion and the outer peripheral portion of the light conversion member, which causes chromaticity unevenness in the surface of the light conversion member. May occur. Or glass and fluorescent substance react and there exists a possibility that the quantum conversion yield of a light conversion member may fall. In order to suppress shrinkage or a decrease in quantum conversion yield, the Tg of the glass is preferably 520 ° C. or lower, more preferably 500 ° C. or lower, and further preferably 480 ° C. or lower.
一方で、ガラス転移点Tgが300℃未満では焼成温度が低く、ガラスが流動する温度よりも脱灰温度の方が高くなる。そのため、光変換部材中のカーボン含有量が多くなり、光変換部材の量子変換収率が低下するおそれがある。また、光変換部材の透過率が低下し、光源の発光効率が低くなるおそれがある。ガラス転移点Tgは、より好ましくは340℃以上、さらに好ましくは380℃以上である。なお、本明細書においてガラスのTgは、DTA曲線から算出されるものである。
On the other hand, when the glass transition point Tg is less than 300 ° C., the firing temperature is low, and the decalcification temperature is higher than the temperature at which the glass flows. Therefore, the carbon content in the light conversion member is increased, and the quantum conversion yield of the light conversion member may be reduced. In addition, the transmittance of the light conversion member is lowered, and the light emission efficiency of the light source may be lowered. The glass transition point Tg is more preferably 340 ° C. or higher, and further preferably 380 ° C. or higher. In this specification, Tg of glass is calculated from a DTA curve.
ここで使用するガラスは、Bi2O3-B2O3-ZnO系を主成分とすることが好ましい。中でも、酸化物基準のモル%表示で、Bi2O3 3~40%、B2O3 10~50%、ZnO 0~45%、を含有するガラスがより好ましい。
The glass used here is preferably based on the Bi 2 O 3 —B 2 O 3 —ZnO system. Among them, a glass containing Bi 2 O 3 3 to 40%, B 2 O 3 10 to 50%, ZnO 0 to 45% in terms of mol% based on oxide is more preferable.
また、Bi2O3 3~40%、B2O3 10~50%、ZnO 0~45%、SiO2 0~35%、BaO 0~20%、TeO2 0~20%、Al2O3 0~4%、TiO2 0~5%、ZrO20~5%、Nb2O50~5%、MnO2 0~1%、CeO2 0~1%、Li2O 0~15%、Na2O 0~15%、K2O 0~15%、を含有するガラスがさらに好ましい。
Also, Bi 2 O 3 3 to 40%, B 2 O 3 10 to 50%, ZnO 0 to 45%, SiO 2 0 to 35%, BaO 0 to 20%, TeO 2 0 to 20%, Al 2 O 3 0-4%, TiO 2 0-5%, ZrO 2 0-5%, Nb 2 O 5 0-5%, MnO 2 0-1%, CeO 2 0-1%, Li 2 O 0-15%, More preferred are glasses containing Na 2 O 0-15% and K 2 O 0-15%.
このガラスは本質的に上記成分からなることが好ましいが、本発明の目的を損なわない範囲でその他の成分を含有していてもよい。以下、このガラスの各成分について説明する。
This glass is preferably essentially composed of the above components, but may contain other components as long as the object of the present invention is not impaired. Hereinafter, each component of this glass is demonstrated.
Bi2O3は、ガラスの化学的耐久性を下げることなく、Tgを低くする、かつ屈折率を高くする成分であり、この系では、必須の成分である。Bi2O3の含有量は、3~40%が好ましい。Bi2O3が3%未満では、ガラス粉末のTgが高くなり好ましくない。より好ましくは5%以上である。一方、40%超では、ガラスが不安定になり、結晶化しやすく焼結性を損ねるおそれがある。さらに、ガラスの吸収端が長波長側にシフトし、LED素子の青色光を吸収してしまう、また、屈折率が高くなり過ぎて蛍光体との屈折率差が大きくなり、LEDの発光効率が低くなるおそれがある。Bi2O3の含有量は、3~30%がより好ましく、5~25%がさらに好ましい。
Bi 2 O 3 is a component that lowers the Tg and raises the refractive index without lowering the chemical durability of the glass, and is an essential component in this system. The content of Bi 2 O 3 is preferably 3 to 40%. If Bi 2 O 3 is less than 3%, the Tg of the glass powder is increased, which is not preferable. More preferably, it is 5% or more. On the other hand, if it exceeds 40%, the glass becomes unstable and tends to be crystallized, which may impair the sinterability. In addition, the absorption edge of the glass shifts to the long wavelength side and absorbs the blue light of the LED element. Also, the refractive index becomes too high and the difference in refractive index from the phosphor increases, so that the luminous efficiency of the LED is increased. May be lowered. The content of Bi 2 O 3 is more preferably 3 to 30%, further preferably 5 to 25%.
B2O3は、ガラスのネットワークフォーマーであり、ガラスを安定化できる成分であり、この系では、必須の成分である。B2O3の含有量は、10~50%が好ましい。B2O3の含有量が10%未満では、ガラスが不安定になり、結晶化しやすく、また、焼結性を損ねるおそれがある。一方で、B2O3の含有量が50%超では、ガラスの化学的耐久性が低下するおそれがある。B2O3の含有量は、15~45%がより好ましく、20~40%がさらに好ましい。
B 2 O 3 is a glass network former and is a component that can stabilize glass, and is an essential component in this system. The content of B 2 O 3 is preferably 10 to 50%. If the content of B 2 O 3 is less than 10%, the glass becomes unstable, tends to be crystallized, and the sinterability may be impaired. On the other hand, if the content of B 2 O 3 exceeds 50%, the chemical durability of the glass may be lowered. The content of B 2 O 3 is more preferably 15 to 45%, further preferably 20 to 40%.
ZnOは、Tgを下げる、かつ屈折率を高くする成分であり、この系では必須成分ではない。ZnOの含有量は、0~45%が好ましい。ZnOの含有量が45%超では、ガラス化し難くなり、ガラスの製造が困難になる。ZnOの含有量は、5~40%がより好ましく、5~35%がさらに好ましい。
ZnO is a component that lowers Tg and raises the refractive index, and is not an essential component in this system. The content of ZnO is preferably 0 to 45%. If the ZnO content exceeds 45%, it will be difficult to vitrify, and it will be difficult to produce glass. The content of ZnO is more preferably 5 to 40%, further preferably 5 to 35%.
SiO2は、ガラスの安定性を高くする成分であり、この系では必須成分ではない。SiO2の含有量は、0~35%が好ましい。SiO2の含有量が、35%超では、Tgが高くなるおそれがある。SiO2の含有量は、0~30%がより好ましく、0~20%がさらに好ましい。
SiO 2 is a component that increases the stability of the glass and is not an essential component in this system. The content of SiO 2 is preferably 0 to 35%. If the content of SiO 2 exceeds 35%, Tg may be high. The content of SiO 2 is more preferably 0 to 30%, further preferably 0 to 20%.
CaO、SrO、MgOおよびBaOのアルカリ土類金属酸化物は、ガラスの安定性を高めるとともに、Tgを下げる成分であり、この系では必須成分ではない。アルカリ土類金属酸化物の合計量は、0~20%が好ましい。この合計量が、20%超では、ガラスの安定性が低下する。より好ましくは、合計量は18%以下である。
CaO, SrO, MgO and BaO alkaline earth metal oxides are components that increase the stability of the glass and lower the Tg, and are not essential components in this system. The total amount of alkaline earth metal oxide is preferably 0 to 20%. If this total amount exceeds 20%, the stability of the glass is lowered. More preferably, the total amount is 18% or less.
TeO2は、Tgを下げ、屈折率を高くし、耐候性を上げ、かつ液相温度を下げる成分であるが、本発明においては必須成分ではない。TeO2の含有量は、0~20%が好ましい。TeO2の含有量が20%超では、焼結性を損ねる、もしくは焼成時に蛍光体と反応して蛍光体を失活させるおそれがある。TeO2の含有量は、16%以下がより好ましく、14%以下がさらに好ましく、12%以下が特に好ましい。
TeO 2 is a component that lowers the Tg, raises the refractive index, raises the weather resistance, and lowers the liquidus temperature, but is not an essential component in the present invention. The content of TeO 2 is preferably 0 to 20%. If the TeO 2 content exceeds 20%, the sinterability may be impaired, or the phosphor may be deactivated by reacting with the phosphor during firing. The TeO 2 content is more preferably 16% or less, further preferably 14% or less, and particularly preferably 12% or less.
Al2O3は化学的耐久性を向上させ、焼成時に蛍光体との反応を抑制する成分であるが、本発明においては必須成分ではない。Al2O3の含有量は、0~4%が好ましい。Al2O3の含有量が4%超では、Tgが高くなり過ぎる、液相温度を上げる、焼結性を損ねるなどのおそれがある。Al2O3の含有量は、3%以下がより好ましい。
Al 2 O 3 is a component that improves chemical durability and suppresses reaction with the phosphor during firing, but is not an essential component in the present invention. The content of Al 2 O 3 is preferably 0 to 4%. If the Al 2 O 3 content exceeds 4%, Tg may be too high, the liquidus temperature may be increased, or the sinterability may be impaired. The content of Al 2 O 3 is more preferably 3% or less.
TiO2、ZrO2およびNb2O5は、屈折率を上げ、ガラスの耐候性を上昇させるとともに、化学的耐久性を上げる成分であり、この系では必須成分ではない。これらの成分は、TiO2 0~5%、ZrO2 0~5%、Nb2O5 0~5%、であり、その合量が0~5%が好ましい。これら成分の合量が5%超では、ガラスの安定性が低下し、Tgが高くなりすぎ、ガラスの吸収端が長波長側にシフトし、LED素子の青色光を吸収してしまうなどのおそれがある。この合量は、好ましくは4%以下、より好ましくは3%以下である。
TiO 2 , ZrO 2 and Nb 2 O 5 are components that increase the refractive index, increase the weather resistance of the glass, and increase chemical durability, and are not essential components in this system. These components are TiO 2 0 to 5%, ZrO 2 0 to 5%, and Nb 2 O 5 0 to 5%, and the total amount is preferably 0 to 5%. If the total amount of these components exceeds 5%, the stability of the glass is lowered, Tg becomes too high, the absorption edge of the glass is shifted to the longer wavelength side, and the blue light of the LED element may be absorbed. There is. This total amount is preferably 4% or less, more preferably 3% or less.
MnO2およびCeO2は、いずれもこの系では必須成分ではないが、ガラス中で酸化剤として機能するため、含有することが好ましい。いずれもガラス中のBi2O3の還元を防止できるため、この系のガラスを安定化できる。Bi2O3が還元されると、ガラスが着色するため、好ましくない。そのため、MnO2およびCeO2の含有量はそれぞれ0~1%が好ましい。含有量が、1%超では、着色が大きくなるおそれがある。好ましくは0~0.5%である。
Neither MnO 2 nor CeO 2 is an essential component in this system, but it is preferably contained because it functions as an oxidizing agent in the glass. In any case, reduction of Bi 2 O 3 in the glass can be prevented, so that this type of glass can be stabilized. Reduction of Bi 2 O 3 is not preferable because the glass is colored. Therefore, the contents of MnO 2 and CeO 2 are each preferably 0 to 1%. If the content exceeds 1%, coloring may increase. Preferably, it is 0 to 0.5%.
Li2O、Na2OおよびK2Oのアルカリ金属酸化物は、Tgを下げる成分であり、この系では必須成分ではない。アルカリ金属酸化物の合計量は0~15%が好ましい。上記合計量が15%超では、屈折率が低下し、ガラスの化学的耐久性が低下するおそれがある。より好ましくは0~10%、さらに好ましくは0~5%である。
Alkali metal oxides of Li 2 O, Na 2 O and K 2 O are components that lower Tg and are not essential components in this system. The total amount of alkali metal oxide is preferably 0 to 15%. If the total amount exceeds 15%, the refractive index is lowered, and the chemical durability of the glass may be lowered. More preferably, it is 0 to 10%, and still more preferably 0 to 5%.
ガラスは、内包泡を脱泡できるものをさらに含んでもよい。このようなものとしては、塩化銅のような酸化触媒性を持つ金属化合物や酸化アンチモンのような、価数変化により複数の酸化数を持てるような元素が挙げられる。これらの成分の含有量は、0~15%が好ましい。
The glass may further include a glass that can degas the encapsulated foam. Examples of such elements include elements that can have a plurality of oxidation numbers by changing the valence, such as metal compounds having oxidation catalytic properties such as copper chloride and antimony oxide. The content of these components is preferably 0 to 15%.
ガラスの密度は3.5~7.0g/cm3であることが好ましい。この範囲を外れると蛍光体との比重差が大きくなり、蛍光体粒子がガラス粉末中に均一に分散されなくなり、光変換部材にした場合に変換効率が低下するおそれがある。密度はより好ましくは3.7~6.5g/cm3、さらに好ましくは4.1~6.0g/cm3である。
The density of the glass is preferably 3.5 to 7.0 g / cm 3 . Outside this range, the difference in specific gravity with the phosphor becomes large, and the phosphor particles are not uniformly dispersed in the glass powder, and conversion efficiency may be reduced when a light conversion member is used. The density is more preferably 3.7 to 6.5 g / cm 3 , still more preferably 4.1 to 6.0 g / cm 3 .
ガラスの屈折率は、波長633nmにおいて、1.65~2.10であることが好ましい。この範囲を外れると蛍光体粒子との屈折率差が大きくなり、光変換部材にした場合に変換効率が低下するおそれがある。屈折率はより好ましくは1.70~2.05、さらに好ましくは1.75~2.00である。
The refractive index of glass is preferably 1.65 to 2.10 at a wavelength of 633 nm. If it is out of this range, the difference in refractive index from the phosphor particles becomes large, and there is a possibility that the conversion efficiency is lowered when the light conversion member is used. The refractive index is more preferably 1.70 to 2.05, still more preferably 1.75 to 2.00.
(蛍光体粒子)
本光変換部材に使用する蛍光体粒子は、光源の波長を変換できるものであれば、その種類は限定されず、例えば、光変換部材に使用される公知の蛍光体粒子が挙げられる。このような蛍光体粒子としては、例えば、酸化物、窒化物、酸窒化物、硫化物、酸硫化物、ハロゲン化物、アルミン酸塩化物またはハロリン酸塩化物等が挙げられる。上記した蛍光体の中でも、青色の光を赤、緑または黄色に変換するものが好ましく、波長400~500nmに励起帯を有し、波長500~700nmに発光ピーク(λp)を有するものがより好ましい。 (Phosphor particles)
If the fluorescent substance particle used for this light conversion member can convert the wavelength of a light source, the kind will not be limited, For example, the well-known fluorescent substance particle used for a light conversion member is mentioned. Examples of such phosphor particles include oxides, nitrides, oxynitrides, sulfides, oxysulfides, halides, aluminate chlorides, halophosphates, and the like. Among the phosphors described above, those that convert blue light into red, green, or yellow are preferable, and those that have an excitation band at a wavelength of 400 to 500 nm and have an emission peak (λ p ) at a wavelength of 500 to 700 nm are more preferable. preferable.
本光変換部材に使用する蛍光体粒子は、光源の波長を変換できるものであれば、その種類は限定されず、例えば、光変換部材に使用される公知の蛍光体粒子が挙げられる。このような蛍光体粒子としては、例えば、酸化物、窒化物、酸窒化物、硫化物、酸硫化物、ハロゲン化物、アルミン酸塩化物またはハロリン酸塩化物等が挙げられる。上記した蛍光体の中でも、青色の光を赤、緑または黄色に変換するものが好ましく、波長400~500nmに励起帯を有し、波長500~700nmに発光ピーク(λp)を有するものがより好ましい。 (Phosphor particles)
If the fluorescent substance particle used for this light conversion member can convert the wavelength of a light source, the kind will not be limited, For example, the well-known fluorescent substance particle used for a light conversion member is mentioned. Examples of such phosphor particles include oxides, nitrides, oxynitrides, sulfides, oxysulfides, halides, aluminate chlorides, halophosphates, and the like. Among the phosphors described above, those that convert blue light into red, green, or yellow are preferable, and those that have an excitation band at a wavelength of 400 to 500 nm and have an emission peak (λ p ) at a wavelength of 500 to 700 nm are more preferable. preferable.
蛍光体は、光変換部材を通過する光が所望の色に変換されるのであれば、上記した化合物からなる群から選ばれる1以上の化合物を含有していればよく、複数種の化合物を混合して含有していてもよいし、いずれか1つを単独で含有していてもよい。色設計の容易さの観点から、いずれか1つを単独で含有することが好ましい。また、量子変換収率を高くする観点から、蛍光体は酸化物またはアルミン酸塩化物が好ましい。酸化物またはアルミン酸塩化物の蛍光体としては、ガーネット系結晶がより好ましい。ガーネット系結晶は耐水性や耐熱性に優れ、後述する本発明の製造工程を経る場合、スラリー中における失活や焼成中の失活が生じにくい。上記したガーネット系結晶としては、イットリウムとアルミニウムの複合酸化物(Y3Al5O12;以下、本明細書ではYAGと略す)や、ルテチウムとアルミニウムの複合酸化物(Lu3Al5O12;以下、本明細書ではLAGと略す)が挙げられる。
As long as the light passing through the light conversion member is converted into a desired color, the phosphor only needs to contain one or more compounds selected from the group consisting of the above-mentioned compounds, and a plurality of types of compounds are mixed. May be contained, or any one of them may be contained alone. From the viewpoint of ease of color design, it is preferable to contain any one of them. From the viewpoint of increasing the quantum conversion yield, the phosphor is preferably an oxide or aluminate chloride. The phosphor of oxide or aluminate chloride is more preferably a garnet crystal. Garnet-based crystals are excellent in water resistance and heat resistance, and are hardly deactivated in a slurry or deactivated during firing when undergoing the production process of the present invention described later. Examples of the garnet-based crystal include a composite oxide of yttrium and aluminum (Y 3 Al 5 O 12 ; hereinafter abbreviated as YAG in this specification), a composite oxide of lutetium and aluminum (Lu 3 Al 5 O 12 ; Hereinafter, it is abbreviated as LAG in this specification.
蛍光体粒子の平均粒子直径(以下、本明細書では50%粒径と略す)D50は、1~30μmが好ましい。蛍光体粒子の50%粒径D50が1μm未満であると、蛍光体粒子の比表面積が大きくなり、失活しやすくなるおそれがある。この50%粒径D50は、より好ましくは3μm以上、さらに好ましくは5μm以上、特に好ましくは7μm以上である。一方、蛍光体粒子の50%粒径D50が30μm超では、光変換部材中で分散性が悪くなり、光の変換効率が悪くなると共に、色度ムラが生じるおそれがある。そのため、50%粒径D50は、より好ましくは20μm以下、さらに好ましくは15μm以下である。なお、本明細書において、50%粒径D50は、レーザ回折式粒度分布測定により得られた粒度分布から、体積基準での積算%における50%値として算出した値である。
The average particle diameter (hereinafter abbreviated as 50% particle size) D 50 of the phosphor particles is preferably 1 to 30 μm. If the 50% particle size D 50 of the phosphor particles is less than 1 μm, the specific surface area of the phosphor particles is increased, and the phosphor particles may be easily deactivated. The 50% particle size D 50 is more preferably 3 μm or more, further preferably 5 μm or more, and particularly preferably 7 μm or more. On the other hand, when the 50% particle diameter D 50 of the phosphor particles is more than 30 μm, the dispersibility is deteriorated in the light conversion member, the light conversion efficiency is deteriorated, and chromaticity unevenness may occur. Therefore, the 50% particle diameter D 50, and more preferably 20μm or less, more preferably 15μm or less. In the present specification, the 50% particle size D 50 is a value calculated as a 50% value in the integrated% on a volume basis from the particle size distribution obtained by laser diffraction particle size distribution measurement.
(耐熱フィラー)
本光変換部材に使用される耐熱フィラーは、その50%粒径D50と波長633nmにおけるその屈折率nとの関係式[D50/n]が2~20である耐熱フィラーである。このような耐熱フィラーをガラス中に含有させることで、光変換部材を製造する際に、焼成時に生じる収縮を抑制し、光変換部材中の蛍光体粒子の均一分散性を良好に保持できる。この耐熱フィラーにおける上記の関係式[D50/n]が2未満であると、光源の光を散乱しやすくなり光変換部材の光の透過率が低下する傾向があり、20を超えるとガラス中への分散性が低下し、収縮を均一に抑制できなくなるおそれがある。この関係式[D50/n]は好ましくは3~18、より好ましくは4~15の範囲である。 (Heat resistant filler)
The heat-resistant filler used in the present light conversion member is a heat-resistant filler having a relational expression [D 50 / n] of 2 to 20 between the 50% particle diameter D 50 and the refractive index n at a wavelength of 633 nm. By including such a heat-resistant filler in the glass, when the light conversion member is produced, shrinkage that occurs during firing can be suppressed, and the uniform dispersibility of the phosphor particles in the light conversion member can be favorably maintained. If the relational expression [D 50 / n] in this heat-resistant filler is less than 2, the light from the light source tends to be scattered, and the light transmittance of the light conversion member tends to decrease. The dispersibility of the resin may decrease, and shrinkage may not be suppressed uniformly. This relational expression [D 50 / n] is preferably in the range of 3 to 18, more preferably 4 to 15.
本光変換部材に使用される耐熱フィラーは、その50%粒径D50と波長633nmにおけるその屈折率nとの関係式[D50/n]が2~20である耐熱フィラーである。このような耐熱フィラーをガラス中に含有させることで、光変換部材を製造する際に、焼成時に生じる収縮を抑制し、光変換部材中の蛍光体粒子の均一分散性を良好に保持できる。この耐熱フィラーにおける上記の関係式[D50/n]が2未満であると、光源の光を散乱しやすくなり光変換部材の光の透過率が低下する傾向があり、20を超えるとガラス中への分散性が低下し、収縮を均一に抑制できなくなるおそれがある。この関係式[D50/n]は好ましくは3~18、より好ましくは4~15の範囲である。 (Heat resistant filler)
The heat-resistant filler used in the present light conversion member is a heat-resistant filler having a relational expression [D 50 / n] of 2 to 20 between the 50% particle diameter D 50 and the refractive index n at a wavelength of 633 nm. By including such a heat-resistant filler in the glass, when the light conversion member is produced, shrinkage that occurs during firing can be suppressed, and the uniform dispersibility of the phosphor particles in the light conversion member can be favorably maintained. If the relational expression [D 50 / n] in this heat-resistant filler is less than 2, the light from the light source tends to be scattered, and the light transmittance of the light conversion member tends to decrease. The dispersibility of the resin may decrease, and shrinkage may not be suppressed uniformly. This relational expression [D 50 / n] is preferably in the range of 3 to 18, more preferably 4 to 15.
この耐熱フィラーの50%粒径D50は5~30μmが好ましい。5μm未満であると光源の光を散乱しやすくなり光変換部材の光の透過率が低下するおそれがあり、30μmを超えると光変換部材中の耐熱フィラーの分散性が低下し、焼成時における収縮を十分に抑制できなくなるおそれがある。この50%粒径D50は、より好ましくは6~25μm、さらに好ましくは8~22μmである。
The heat-resistant filler preferably has a 50% particle size D 50 of 5 to 30 μm. If it is less than 5 μm, light from the light source tends to be scattered and the light transmittance of the light conversion member may be reduced. If it exceeds 30 μm, the dispersibility of the heat-resistant filler in the light conversion member is reduced, and shrinkage during firing May not be sufficiently suppressed. The 50% particle size D 50 is more preferably 6 to 25 μm, still more preferably 8 to 22 μm.
また、波長633nmにおける、この耐熱フィラーの屈折率nは1.5~2.5が好ましい。屈折率が当該範囲から外れると、ガラスとの屈折率差が大きくなるため、耐熱フィラーとガラスの界面での屈折が大きくなって光源の光を散乱しやすくなり光変換部材の光の透過率が低下するおそれがある。この耐熱フィラーの屈折率nは、より好ましくは1.6~2.3、さらに好ましくは1.7~2.2である。
Further, the refractive index n of the heat resistant filler at a wavelength of 633 nm is preferably 1.5 to 2.5. If the refractive index is out of the range, the difference in refractive index from the glass increases, so that the refraction at the interface between the heat-resistant filler and the glass increases and the light from the light source is easily scattered, and the light transmittance of the light conversion member is increased. May decrease. The refractive index n of the heat resistant filler is more preferably 1.6 to 2.3, and still more preferably 1.7 to 2.2.
また、この耐熱フィラーは、光変換部材の製造時における焼成温度に対して耐熱性を有するものであればよく、例えば、アルミナ、ジルコニア、マグネシア等が挙げられ、これらのうち少なくとも1種以上を含有していればよい。
Moreover, this heat-resistant filler should just have heat resistance with respect to the calcination temperature at the time of manufacture of a light conversion member, for example, an alumina, a zirconia, magnesia etc. are mentioned, Among these, at least 1 type or more is contained. If you do.
なお、耐熱フィラーの屈折率は、そのバルク体を用い、波長633nmの光に対する屈折率nを、メトリコン社製モデル2010プリズムカプラを用いて測定した。
In addition, the refractive index of the heat-resistant filler was measured using a bulk body and the refractive index n with respect to light having a wavelength of 633 nm using a model 2010 prism coupler manufactured by Metricon.
上記のように、本光変換部材は、ガラス中に蛍光体粒子と耐熱フィラーとが分散して構成されている。光変換部材の焼成時における収縮を十分に抑制するために、ガラス、蛍光体粒子および耐熱フィラーの合計量を100%としたとき、体積分率で、耐熱フィラーを3~30%含有することが好ましい。この含有率が3%未満であると十分に収縮を抑制できなくなるおそれがあり、30%を超えると光変換部材の光の透過率が低下して光源の利用効率が低下するおそれがある。
As described above, the present light conversion member is configured by dispersing phosphor particles and heat-resistant filler in glass. In order to sufficiently suppress the shrinkage during firing of the light conversion member, when the total amount of the glass, the phosphor particles and the heat-resistant filler is 100%, the heat-resistant filler may contain 3 to 30% by volume fraction. preferable. If the content is less than 3%, the shrinkage may not be sufficiently suppressed, and if it exceeds 30%, the light transmittance of the light conversion member may be reduced, and the utilization efficiency of the light source may be reduced.
このとき、体積分率で、ガラスを50~96%、蛍光体粒子を1~40%、含有することが好ましい。このような含有量とすることで、光変換部材として、光源からの光の透過率、蛍光体粒子の光変換量、をバランスよく製造でき、かつ、製造時の収縮を抑制して、光変換色度のムラが生じることを抑制できる。
At this time, it is preferable to contain 50 to 96% glass and 1 to 40% phosphor particles in terms of volume fraction. With such a content, the light conversion member can be manufactured in a well-balanced manner with the light transmittance from the light source and the light conversion amount of the phosphor particles. It is possible to suppress the occurrence of chromaticity unevenness.
本光変換部材の量子変換収率は80%以上が好ましい。量子変換収率が80%未満では、所望の色を得るために、光変換部材の厚みを大きくしなければならない。厚みが大きくなると、光変換部材の透過率が低下するおそれがある。光変換部材の量子変換収率は、より好ましくは85%以上、さらに好ましくは90%以上である。なお、上記量子変換収率は、励起光を照射した時の、発光としてサンプルから放出されたフォトン数と、サンプルにより吸収されたフォトン数との比率で表される。上記フォトン数は、積分球法で測定する。
The quantum conversion yield of this light conversion member is preferably 80% or more. If the quantum conversion yield is less than 80%, the thickness of the light conversion member must be increased in order to obtain a desired color. When the thickness is increased, the transmittance of the light conversion member may be reduced. The quantum conversion yield of the light conversion member is more preferably 85% or more, and still more preferably 90% or more. The quantum conversion yield is expressed as a ratio between the number of photons emitted from the sample as light emission and the number of photons absorbed by the sample when irradiated with excitation light. The number of photons is measured by the integrating sphere method.
本光変換部材は、量子変換収率が高く保持できるので、光変換部材を薄くしても、上記した光変換部材の機能を発揮できる。光変換部材の厚みは50~500μmが好ましい。光変換部材の厚みが50μm以上では、光変換部材のハンドリングが容易になり、特に所望の大きさにカットする際に光変換部材の割れを抑制できる。光変換部材の厚みは、より好ましくは80μm以上、さらに好ましくは100μm以上、特に好ましくは120μm以上である。光変換部材の厚みが500μm以下では、光変換部材を透過する全光束量を高く維持できる。光変換部材の厚みは、好ましくは400μm以下、さらに好ましくは300μm以下、特に好ましくは250μm以下である。
Since this light conversion member can maintain a high quantum conversion yield, even if the light conversion member is made thin, the above-described function of the light conversion member can be exhibited. The thickness of the light conversion member is preferably 50 to 500 μm. When the thickness of the light conversion member is 50 μm or more, handling of the light conversion member becomes easy, and cracking of the light conversion member can be suppressed particularly when cutting to a desired size. The thickness of the light conversion member is more preferably 80 μm or more, further preferably 100 μm or more, and particularly preferably 120 μm or more. When the thickness of the light conversion member is 500 μm or less, the total light flux transmitted through the light conversion member can be maintained high. The thickness of the light conversion member is preferably 400 μm or less, more preferably 300 μm or less, and particularly preferably 250 μm or less.
なお、用いる蛍光体が著しく高価な場合、光変換部材に含有させる蛍光体量を極力抑えたいため、全光束量を犠牲にしても光変換部材の厚みを大きくして光変換効率を担保させる可能性がある。その場合、全光束量と光変換効率のバランスをとって、光変換部材の厚みを250~500μmの間で選択することがある。
If the phosphor to be used is extremely expensive, the amount of the phosphor to be contained in the light conversion member is to be suppressed as much as possible. Therefore, even if the total amount of light flux is sacrificed, the thickness of the light conversion member can be increased to ensure the light conversion efficiency. There is sex. In that case, the thickness of the light conversion member may be selected from 250 to 500 μm in order to balance the total luminous flux and the light conversion efficiency.
本光変換部材の平面形状は特に限定されない。例えば、光変換部材が光源と接して使用される場合、光源からの光の漏れを防ぐために、光変換部材の形状は光源の形状に合わせて製造される。光源は矩形状または円状が一般的であるため、光変換部材も矩形状または円状が好ましい。また、本光変換部材は板状、すなわち断面形状は矩形状が好ましい。光変換部材内で板厚にばらつきが小さいほど、面内の色のばらつきを小さくできるため好ましい。
The planar shape of the light conversion member is not particularly limited. For example, when the light conversion member is used in contact with the light source, the shape of the light conversion member is manufactured according to the shape of the light source in order to prevent light leakage from the light source. Since the light source is generally rectangular or circular, the light conversion member is also preferably rectangular or circular. The light converting member is preferably plate-shaped, that is, the cross-sectional shape is rectangular. The smaller the variation in the plate thickness within the light conversion member, the smaller the in-plane color variation, which is preferable.
[光変換部材の製造方法]
本光変換部材は、ガラス粉末、蛍光体粒子および耐熱フィラーの混合粉末の焼結体からなることが好ましい。また、本光変換部材は、該混合粉末と樹脂および有機溶媒を混練して得られる混練物を焼成して得られる焼結体からなることがより好ましく、上記混練物を透明樹脂に塗工し、乾燥させて得られるグリーンシートを焼結して得られるガラスシートからなることがさらに好ましい。なお、本明細書において上記樹脂および有機溶媒の混合物をビヒクルということもある。 [Production Method of Light Conversion Member]
The present light conversion member is preferably made of a sintered body of a mixed powder of glass powder, phosphor particles and heat-resistant filler. The light conversion member is more preferably composed of a sintered body obtained by firing a kneaded product obtained by kneading the mixed powder, a resin and an organic solvent, and the kneaded product is applied to a transparent resin. More preferably, it is made of a glass sheet obtained by sintering a green sheet obtained by drying. In the present specification, the mixture of the resin and the organic solvent may be referred to as a vehicle.
本光変換部材は、ガラス粉末、蛍光体粒子および耐熱フィラーの混合粉末の焼結体からなることが好ましい。また、本光変換部材は、該混合粉末と樹脂および有機溶媒を混練して得られる混練物を焼成して得られる焼結体からなることがより好ましく、上記混練物を透明樹脂に塗工し、乾燥させて得られるグリーンシートを焼結して得られるガラスシートからなることがさらに好ましい。なお、本明細書において上記樹脂および有機溶媒の混合物をビヒクルということもある。 [Production Method of Light Conversion Member]
The present light conversion member is preferably made of a sintered body of a mixed powder of glass powder, phosphor particles and heat-resistant filler. The light conversion member is more preferably composed of a sintered body obtained by firing a kneaded product obtained by kneading the mixed powder, a resin and an organic solvent, and the kneaded product is applied to a transparent resin. More preferably, it is made of a glass sheet obtained by sintering a green sheet obtained by drying. In the present specification, the mixture of the resin and the organic solvent may be referred to as a vehicle.
このように、焼結体として本光変換部材を製造するには、ガラス粉末、蛍光体粒子、耐熱フィラー、樹脂および有機溶媒を混練して混練物とする混練工程と、得られた混練物を所望の形状に成形する成形工程と、混練物の成形体を焼成して光変換部材とする焼成工程と、を順次行えばよい。
Thus, in order to produce this light conversion member as a sintered body, a kneading step of kneading glass powder, phosphor particles, heat-resistant filler, resin and organic solvent to obtain a kneaded product, What is necessary is just to perform sequentially the shaping | molding process shape | molded in a desired shape, and the baking process which bakes the molded object of a kneaded material and makes it a light conversion member.
(混練工程)
本発明における混練工程は、ガラス粉末、蛍光体粒子、耐熱フィラー、樹脂および有機溶媒を混練して混練物(スラリー)とするもので、これら原料を均一に混練できればよい。この混練にあたっては、公知の混練方法、例えば、ディゾルバー、ホモミキサー、ニーダー、ロールミル、サンドミル、アトライター、ボールミル、バイブレーターミル、高速インペラーミル、超音波ホモジナイザー、振とう機等を使用した混練を行えばよい。 (Kneading process)
The kneading step in the present invention involves kneading glass powder, phosphor particles, heat-resistant filler, resin and organic solvent into a kneaded product (slurry), and it is sufficient that these raw materials can be kneaded uniformly. In this kneading, a known kneading method, for example, kneading using a dissolver, homomixer, kneader, roll mill, sand mill, attritor, ball mill, vibrator mill, high-speed impeller mill, ultrasonic homogenizer, shaker, etc. Good.
本発明における混練工程は、ガラス粉末、蛍光体粒子、耐熱フィラー、樹脂および有機溶媒を混練して混練物(スラリー)とするもので、これら原料を均一に混練できればよい。この混練にあたっては、公知の混練方法、例えば、ディゾルバー、ホモミキサー、ニーダー、ロールミル、サンドミル、アトライター、ボールミル、バイブレーターミル、高速インペラーミル、超音波ホモジナイザー、振とう機等を使用した混練を行えばよい。 (Kneading process)
The kneading step in the present invention involves kneading glass powder, phosphor particles, heat-resistant filler, resin and organic solvent into a kneaded product (slurry), and it is sufficient that these raw materials can be kneaded uniformly. In this kneading, a known kneading method, for example, kneading using a dissolver, homomixer, kneader, roll mill, sand mill, attritor, ball mill, vibrator mill, high-speed impeller mill, ultrasonic homogenizer, shaker, etc. Good.
ここで使用するガラス粉末は、上記したガラスの組成を満足するように公知のガラス粉末の複数種を混合して調製してもよいし、所定の熱特性を有するように成分を調合して混合し、電気炉などで溶融し、急冷して所定の組成を有するガラスとして製造しておき、これを粉砕し、分級して調製してもよい。
The glass powder used here may be prepared by mixing a plurality of known glass powders so as to satisfy the above-mentioned glass composition, or by mixing and mixing components so as to have predetermined thermal characteristics. Then, it may be prepared by melting in an electric furnace or the like, rapidly cooling to produce glass having a predetermined composition, pulverizing and classifying it.
このときガラス粉末の50%粒径D50は2.0μm未満が好ましい。50%粒径D50が2.0μm以上では、蛍光体粒子や耐熱フィラーがガラス粉末中に均一に分散されなくなり、光変換部材にした場合に光変換効率が低下したり、焼成時の収縮量が大きくなったりするおそれがある。50%粒径D50は、より好ましくは1.5μm以下、さらに好ましくは1.4μm以下である。
At this time, the glass powder preferably has a 50% particle size D 50 of less than 2.0 μm. When the 50% particle size D 50 is 2.0 μm or more, the phosphor particles and the heat-resistant filler are not uniformly dispersed in the glass powder, so that the light conversion efficiency decreases when the light conversion member is used, or the shrinkage amount during firing May increase. The 50% particle size D 50 is more preferably 1.5 μm or less, and still more preferably 1.4 μm or less.
また、ガラス粉末の最大粒径Dmaxは、30μm以下が好ましい。最大粒径Dmaxが30μm超では、蛍光体粒子や耐熱フィラーがガラス粉末中に均一に分散されにくくなり、光変換部材を製造した場合に、蛍光体の光変換効率が低下したり、焼成時の収縮量が大きくなったりするおそれがある。Dmaxは、より好ましくは20μm以下、さらに好ましくは15μm以下である。なお、本明細書において、Dmaxはレーザ回折式粒度分布測定により算出した最大粒径の値である。
The maximum particle diameter Dmax of the glass powder is preferably 30 μm or less. When the maximum particle size D max is more than 30 μm, the phosphor particles and the heat-resistant filler are difficult to be uniformly dispersed in the glass powder, and when the light conversion member is produced, the light conversion efficiency of the phosphor is reduced, or during firing. There is a risk that the amount of shrinkage of the material increases. D max is more preferably 20 μm or less, and still more preferably 15 μm or less. In the present specification, D max is the value of the maximum particle size calculated by laser diffraction particle size distribution measurement.
また、蛍光体粒子および耐熱フィラーは、上記光変換部材において説明した粒子である。
Moreover, the phosphor particles and the heat-resistant filler are the particles described in the light conversion member.
そして、上記樹脂としては、エチルセルロース、ニトロセルロース、アクリル樹脂、酢酸ビニル、ブチラール樹脂、メラミン樹脂、アルキッド樹脂またはロジン樹脂などを使用できる。また、上記有機溶媒としては、芳香族炭化水素、脂肪族炭化水素、アルコール、エーテル、ケトンまたはエステル類などを使用できる。なお、グリーンシートの強度向上のためには、ビヒクルに、ブチラール樹脂、メラミン樹脂、アルキッド樹脂またはロジン樹脂などを含有することが好ましい。
As the resin, ethyl cellulose, nitrocellulose, acrylic resin, vinyl acetate, butyral resin, melamine resin, alkyd resin, or rosin resin can be used. As the organic solvent, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, ketones or esters can be used. In order to improve the strength of the green sheet, the vehicle preferably contains a butyral resin, a melamine resin, an alkyd resin, a rosin resin, or the like.
上記成分を混練する際、蛍光体粒子、耐熱フィラーおよびガラス粉末の合計量を100%としたとき、混合粉末中の各成分の含有量は、体積分率で、蛍光体粒子が1~40%、耐熱フィラーが3~30%、ガラス粉末が50~96%とするのが好ましい。
When kneading the above components, when the total amount of the phosphor particles, the heat-resistant filler and the glass powder is 100%, the content of each component in the mixed powder is the volume fraction, and the phosphor particles are 1 to 40%. The heat resistant filler is preferably 3 to 30% and the glass powder is preferably 50 to 96%.
蛍光体粒子を1%以上、ガラス粉末を96%以下で含有すれば、量子変換収率を高くでき、入射光を効率的に変換でき、所望の色の光が得られる。蛍光体粒子の体積分率は、より好ましくは5%以上、さらに好ましくは7%以上、特に好ましくは10%以上である。ガラス粉末の体積分率は、より好ましくは91%以下、さらに好ましくは87%以下、特に好ましくは83%以下である。
If the phosphor particles are contained at 1% or more and the glass powder at 96% or less, the quantum conversion yield can be increased, incident light can be efficiently converted, and light of a desired color can be obtained. The volume fraction of the phosphor particles is more preferably 5% or more, further preferably 7% or more, and particularly preferably 10% or more. The volume fraction of the glass powder is more preferably 91% or less, further preferably 87% or less, and particularly preferably 83% or less.
蛍光体粒子の体積分率が40%超で、ガラス粉末の体積分率が50%未満では、蛍光体粒子とガラス粉末の混合体の焼結性を損ね、さらに光変換部材の透過率が低くなるおそれがある。また、変換される蛍光色の光が多くなり、所望の色の光が得られないおそれがある。蛍光体粒子の体積分率は、より好ましくは35%以下、さらに好ましくは30%以下、特に好ましくは25%以下である。ガラス粉末の体積分率は、より好ましくは55%以上、さらに好ましくは60%以上、特に好ましくは65%以上である。
If the volume fraction of the phosphor particles is more than 40% and the volume fraction of the glass powder is less than 50%, the sinterability of the mixture of the phosphor particles and the glass powder is impaired, and the transmittance of the light conversion member is low. There is a risk. Moreover, there is a possibility that light of a desired color cannot be obtained due to an increase in converted fluorescent light. The volume fraction of the phosphor particles is more preferably 35% or less, still more preferably 30% or less, and particularly preferably 25% or less. The volume fraction of the glass powder is more preferably 55% or more, further preferably 60% or more, and particularly preferably 65% or more.
また、耐熱フィラーの体積分率が3%以上であると、光変換部材の焼成時の収縮を効率的に抑制でき、蛍光体粒子が均一に分散している状態を保持でき好ましい。耐熱フィラーの体積分率は、より好ましくは4%以上、さらに好ましくは5%以上、特に好ましくは7%以上である。また、耐熱フィラーの体積分率が30%超となると、混合粉末の焼結性を損ね、さらに光変換部材の透過率が低くなるおそれがある。耐熱フィラーの体積分率は、好ましくは28%以下、より好ましくは26%以下、さらに好ましくは20%以下、特に好ましくは15%以下である。
In addition, it is preferable that the volume fraction of the heat-resistant filler is 3% or more, because the shrinkage during firing of the light conversion member can be efficiently suppressed, and the state in which the phosphor particles are uniformly dispersed can be maintained. The volume fraction of the heat-resistant filler is more preferably 4% or more, further preferably 5% or more, and particularly preferably 7% or more. Further, if the volume fraction of the heat-resistant filler exceeds 30%, the sinterability of the mixed powder is impaired, and the transmittance of the light conversion member may be lowered. The volume fraction of the heat resistant filler is preferably 28% or less, more preferably 26% or less, still more preferably 20% or less, and particularly preferably 15% or less.
樹脂および有機溶剤からなるビヒクルは、上記混合粉末に対して、次の成形工程で所定形状に成形可能な程度の粘度となる量を混合してスラリーとすればよい。
A vehicle made of a resin and an organic solvent may be made into a slurry by mixing the above mixed powder with an amount of a viscosity that can be molded into a predetermined shape in the next molding step.
(成形工程)
本発明における成形工程は、上記混練工程で得られた混練物を、所望の形状に成形して混練物の成形体とするものである。成形方法としては、所望の形状が付与できれば、特に制限されるものではなく、例えば、プレス成形法、ロール成形法、ドクターブレード成形法などの公知の方法が挙げられる。ドクターブレード成形法で得られるグリーンシートは、均一な膜厚の光変換部材を大面積で効率よく製造できるため好ましい。 (Molding process)
In the molding step of the present invention, the kneaded product obtained in the kneading step is molded into a desired shape to form a kneaded product. The molding method is not particularly limited as long as a desired shape can be imparted, and examples thereof include known methods such as a press molding method, a roll molding method, and a doctor blade molding method. A green sheet obtained by a doctor blade molding method is preferable because a light conversion member having a uniform film thickness can be efficiently produced in a large area.
本発明における成形工程は、上記混練工程で得られた混練物を、所望の形状に成形して混練物の成形体とするものである。成形方法としては、所望の形状が付与できれば、特に制限されるものではなく、例えば、プレス成形法、ロール成形法、ドクターブレード成形法などの公知の方法が挙げられる。ドクターブレード成形法で得られるグリーンシートは、均一な膜厚の光変換部材を大面積で効率よく製造できるため好ましい。 (Molding process)
In the molding step of the present invention, the kneaded product obtained in the kneading step is molded into a desired shape to form a kneaded product. The molding method is not particularly limited as long as a desired shape can be imparted, and examples thereof include known methods such as a press molding method, a roll molding method, and a doctor blade molding method. A green sheet obtained by a doctor blade molding method is preferable because a light conversion member having a uniform film thickness can be efficiently produced in a large area.
グリーンシートは、例えば、以下の工程で製造できる。ガラス粉末、蛍光体粒子および耐熱フィラーをビヒクルに混練し、脱泡してスラリーを得る。得られたスラリーをドクターブレード法により、透明樹脂上に塗工し、乾燥する。乾燥後、所望の大きさに切り出し、透明樹脂を剥がして、グリーンシートを得る。さらに、これらをプレスし、積層体にすることで、所望の厚みの成形体を確保できる。
The green sheet can be manufactured, for example, by the following process. Glass powder, phosphor particles and heat-resistant filler are kneaded in a vehicle and defoamed to obtain a slurry. The obtained slurry is coated on a transparent resin by a doctor blade method and dried. After drying, it is cut into a desired size and the transparent resin is peeled off to obtain a green sheet. Furthermore, by pressing these to form a laminate, a molded body having a desired thickness can be secured.
ここで、スラリーを塗工する透明樹脂としては、剥離性を有するものであれば、特に限定されない。ここで使用する透明樹脂は、均一な膜厚のグリーンシートが得られるように、均一な厚さの透明フィルムを使用することが好ましく、このような透明フィルムとしては、例えば、PETフィルムなどが挙げられる。
Here, the transparent resin for applying the slurry is not particularly limited as long as it has releasability. The transparent resin used here is preferably a transparent film having a uniform thickness so that a green sheet having a uniform thickness can be obtained. Examples of such a transparent film include a PET film. It is done.
(焼成工程)
本発明の焼成工程は、成形工程で得られた混練物の成形体を焼成することで焼結させ、光変換部材とする工程である。この焼成工程における焼成は、混合粉末を焼結させて、蛍光体粒子と耐熱フィラーとを分散して含有するガラスを得るものであり、公知の焼成方法によりガラス体を製造すればよい。 (Baking process)
The firing step of the present invention is a step in which the molded body of the kneaded product obtained in the molding step is sintered by firing to obtain a light conversion member. Firing in this firing step is to sinter the mixed powder to obtain a glass containing phosphor particles and heat-resistant filler dispersed therein, and the glass body may be produced by a known firing method.
本発明の焼成工程は、成形工程で得られた混練物の成形体を焼成することで焼結させ、光変換部材とする工程である。この焼成工程における焼成は、混合粉末を焼結させて、蛍光体粒子と耐熱フィラーとを分散して含有するガラスを得るものであり、公知の焼成方法によりガラス体を製造すればよい。 (Baking process)
The firing step of the present invention is a step in which the molded body of the kneaded product obtained in the molding step is sintered by firing to obtain a light conversion member. Firing in this firing step is to sinter the mixed powder to obtain a glass containing phosphor particles and heat-resistant filler dispersed therein, and the glass body may be produced by a known firing method.
焼成工程は焼成してガラス体とできれば、その条件は特に限定されないが、焼成雰囲気は103Pa以下の減圧雰囲気もしくは酸素濃度が1~15%の雰囲気が好ましい。また、焼成温度は、400~650℃の範囲が、焼成時間は1~10時間の範囲が好ましい。本発明の光変換部材の製造方法において、前記範囲外で実施すると、光変換部材の量子変換収率が低下するおそれがある。
The conditions for the firing step are not particularly limited as long as it can be made into a glass body by firing, but the firing atmosphere is preferably a reduced pressure atmosphere of 10 3 Pa or less or an atmosphere having an oxygen concentration of 1 to 15%. The firing temperature is preferably in the range of 400 to 650 ° C., and the firing time is preferably in the range of 1 to 10 hours. In the manufacturing method of the light conversion member of this invention, when implemented outside the said range, there exists a possibility that the quantum conversion yield of a light conversion member may fall.
上記のようにして得られる光変換部材により、所定の特性を有する耐熱フィラーを含有させることで、焼成時の収縮を抑制することで、面内の光変換色度のばらつきを抑えたため、色度ムラの少ない光を得ることができる。さらに、この光変換部材は、その透過率の低下を抑制でき、光束量を維持しつつ、発光変換効率を耐熱フィラーとして[D50/n]が上記の規定を外れたものを含有する場合と比べて高く保持できる。
The light conversion member obtained as described above contains a heat-resistant filler having predetermined characteristics, thereby suppressing the shrinkage during firing, thereby suppressing in-plane light conversion chromaticity variation. Light with less unevenness can be obtained. Furthermore, this light conversion member can suppress a decrease in the transmittance thereof, while maintaining the light flux amount, and containing a material whose [D 50 / n] deviates from the above definition as a heat-resistant filler with a light emission conversion efficiency. Higher than that can be maintained.
[照明光源]
本発明の照明光源は、上記本光変換部材と、該光変換部材を通して外部へ光を照射可能な光源と、から構成される。 [Light source]
The illumination light source of the present invention includes the above-described light conversion member and a light source capable of irradiating light to the outside through the light conversion member.
本発明の照明光源は、上記本光変換部材と、該光変換部材を通して外部へ光を照射可能な光源と、から構成される。 [Light source]
The illumination light source of the present invention includes the above-described light conversion member and a light source capable of irradiating light to the outside through the light conversion member.
上記のようにして得られた光変換部材と光源とを組合せることで、所望の色を発する照明光源として利用できる。光変換部材は、光源と接して配置されると、光の漏れを防げるため好ましい。また、光源としては、LED発光素子が好ましく、青色LED発光素子がより好ましい。LED発光素子を光源として使用すれば、LED照明光源として利用できる。
By combining the light conversion member and the light source obtained as described above, it can be used as an illumination light source that emits a desired color. The light conversion member is preferably disposed in contact with the light source because it prevents light leakage. Moreover, as a light source, an LED light emitting element is preferable and a blue LED light emitting element is more preferable. If an LED light emitting element is used as a light source, it can be used as an LED illumination light source.
[液晶表示装置]
さらに、上記した光変換部材を光源と組み合わせて、液晶表示装置を構成する場合を説明する。すなわち、本実施形態における液晶表示装置は、液晶表示パネルと、該液晶表示パネルを照明するバックライトと、を備えた液晶表示装置であって、バックライトとして、上記光変換部材および該光変換部材を通して外部に光を照射可能な光源からなる照明光源を有することを特徴とする。 [Liquid Crystal Display]
Furthermore, a case where a liquid crystal display device is configured by combining the above-described light conversion member with a light source will be described. That is, the liquid crystal display device in the present embodiment is a liquid crystal display device including a liquid crystal display panel and a backlight that illuminates the liquid crystal display panel, and the light conversion member and the light conversion member are used as a backlight. And an illumination light source comprising a light source capable of irradiating light to the outside.
さらに、上記した光変換部材を光源と組み合わせて、液晶表示装置を構成する場合を説明する。すなわち、本実施形態における液晶表示装置は、液晶表示パネルと、該液晶表示パネルを照明するバックライトと、を備えた液晶表示装置であって、バックライトとして、上記光変換部材および該光変換部材を通して外部に光を照射可能な光源からなる照明光源を有することを特徴とする。 [Liquid Crystal Display]
Furthermore, a case where a liquid crystal display device is configured by combining the above-described light conversion member with a light source will be described. That is, the liquid crystal display device in the present embodiment is a liquid crystal display device including a liquid crystal display panel and a backlight that illuminates the liquid crystal display panel, and the light conversion member and the light conversion member are used as a backlight. And an illumination light source comprising a light source capable of irradiating light to the outside.
(バックライト)
本実施形態で使用するバックライトは、上記説明した光変換部材と、該光変換部材を通して外部へ光を照射可能な光源と、から構成される。
上記のようにして得られた光変換部材と光源とを組合せることで、高輝度かつ広範囲な色再現性が得られる液晶表示装置用のバックライトとして好適に利用できる。光変換部材は、光源と接して配置されると、光の漏れを防げるため好ましい。また、光源としては、LED発光素子が好ましく、青色LED発光素子がより好ましく、バックライトは白色光を照射可能とするものが好ましい。 (Backlight)
The backlight used in the present embodiment includes the above-described light conversion member and a light source that can emit light to the outside through the light conversion member.
By combining the light conversion member and the light source obtained as described above, it can be suitably used as a backlight for a liquid crystal display device capable of obtaining a high luminance and a wide range of color reproducibility. The light conversion member is preferably disposed in contact with the light source because it prevents light leakage. Moreover, as a light source, an LED light emitting element is preferable, a blue LED light emitting element is more preferable, and a backlight capable of irradiating white light is preferable.
本実施形態で使用するバックライトは、上記説明した光変換部材と、該光変換部材を通して外部へ光を照射可能な光源と、から構成される。
上記のようにして得られた光変換部材と光源とを組合せることで、高輝度かつ広範囲な色再現性が得られる液晶表示装置用のバックライトとして好適に利用できる。光変換部材は、光源と接して配置されると、光の漏れを防げるため好ましい。また、光源としては、LED発光素子が好ましく、青色LED発光素子がより好ましく、バックライトは白色光を照射可能とするものが好ましい。 (Backlight)
The backlight used in the present embodiment includes the above-described light conversion member and a light source that can emit light to the outside through the light conversion member.
By combining the light conversion member and the light source obtained as described above, it can be suitably used as a backlight for a liquid crystal display device capable of obtaining a high luminance and a wide range of color reproducibility. The light conversion member is preferably disposed in contact with the light source because it prevents light leakage. Moreover, as a light source, an LED light emitting element is preferable, a blue LED light emitting element is more preferable, and a backlight capable of irradiating white light is preferable.
(液晶表示パネル)
本実施形態で使用する液晶表示パネルは、公知の液晶表示パネルであれば特に限定されずに使用できる。液晶表示パネルは、偏光フィルタを備える2枚のガラス板の間に配向膜を設け、電圧をかけることによって液晶分子の向きを変えて、光の透過率を増減させることで像を表示する。 (LCD panel)
The liquid crystal display panel used in the present embodiment is not particularly limited as long as it is a known liquid crystal display panel. The liquid crystal display panel displays an image by providing an alignment film between two glass plates provided with a polarizing filter, changing the direction of liquid crystal molecules by applying a voltage, and increasing or decreasing light transmittance.
本実施形態で使用する液晶表示パネルは、公知の液晶表示パネルであれば特に限定されずに使用できる。液晶表示パネルは、偏光フィルタを備える2枚のガラス板の間に配向膜を設け、電圧をかけることによって液晶分子の向きを変えて、光の透過率を増減させることで像を表示する。 (LCD panel)
The liquid crystal display panel used in the present embodiment is not particularly limited as long as it is a known liquid crystal display panel. The liquid crystal display panel displays an image by providing an alignment film between two glass plates provided with a polarizing filter, changing the direction of liquid crystal molecules by applying a voltage, and increasing or decreasing light transmittance.
このように構成される液晶表示装置では、バックライトに本発明の照明光源を用いるため、例えば、光の3原色による色域が広い明るい白色光で、液晶表示パネルを照明することができる。よって、液晶表示パネルの表示画面において輝度の高い純白色を得ることができ、色再現性が良好で表示画面の品質の向上を図ることができる。
In the liquid crystal display device configured as described above, since the illumination light source of the present invention is used for the backlight, for example, the liquid crystal display panel can be illuminated with bright white light having a wide color gamut of the three primary colors of light. Therefore, pure white with high luminance can be obtained on the display screen of the liquid crystal display panel, color reproducibility is good, and the quality of the display screen can be improved.
以下、実施例および比較例に基づき本発明をさらに詳しく説明するが、本発明はこれら実施例および製造例に限定して解釈されるものではない。本発明の光変換部材の実施例(例1~4、7~18)および比較例(例5~6)を表2および3に示す。
Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not construed as being limited to these Examples and Production Examples. Examples (Examples 1 to 4, 7 to 18) and comparative examples (Examples 5 to 6) of the light conversion member of the present invention are shown in Tables 2 and 3.
蛍光体粒子として、50%粒径D50が10μm、633nmにおける屈折率が約1.9、460nm励起で蛍光体ピーク波長が約555nmであるCe付活YAG蛍光体および50%粒径D50が11μm、633nmにおける屈折率が約2.3、460nm励起で蛍光体ピーク波長が約628nmであるEu付活CASN蛍光体の2種類を使用した。それぞれ、表2~3中で、「YAG」、「CASN」と略して記載する。
As phosphor particles, a Ce-activated YAG phosphor having a 50% particle size D 50 of 10 μm, a refractive index at 633 nm of about 1.9 nm and a phosphor peak wavelength of about 555 nm when excited, and a 50% particle size D 50 are 50% particle size D 50. Two kinds of Eu-activated CASN phosphors having a refractive index at 11 μm and a wavelength of 633 nm of about 2.3 and 460 nm and a phosphor peak wavelength of about 628 nm were used. In Tables 2 and 3, they are abbreviated as “YAG” and “CASN”, respectively.
耐熱フィラーとしては、50%粒径D50が18μm、波長633nmにおける屈折率が1.76である単結晶アルミナからなる耐熱フィラー1、50%粒径D50が3μm、波長633nmにおける屈折率が1.76である単結晶アルミナからなる耐熱フィラー2、50%粒径D50が12μm、波長633nmにおける屈折率が1.83であるYAGからなる耐熱フィラー3、および50%粒径D50が6μm、波長633nmにおける屈折率が1.7であるマグネシアからなる耐熱フィラー4を使用した。すなわち、耐熱フィラー1の[D50/n]は10.2、耐熱フィラー2の[D50/n]は1.7、耐熱フィラー3の[D50/n]は6.6、耐熱フィラー4の[D50/n]は3.5である。
The heat-resistant filler, the refractive index 18μm 50% particle diameter D 50, heat-resistant filler 1,50% particle diameter D 50 of refractive index at a wavelength of 633nm is made of a single crystal alumina which is 1.76 is 3 [mu] m, at a wavelength of 633nm 1 .76 heat-resistant filler 2 made of single crystal alumina, 50 % particle size D 50 is 12 μm, heat-resistant filler 3 made of YAG having a refractive index of 1.83 at a wavelength of 633 nm, and 50% particle size D 50 is 6 μm, A heat-resistant filler 4 made of magnesia having a refractive index of 1.7 at a wavelength of 633 nm was used. That is, the heat-resistant filler 1 [D 50 / n] is 10.2, [D 50 / n] is 1.7 of heat-resistant filler 2, [D 50 / n] is 6.6 heat-resistant filler 3, heat-resistant filler 4 [D 50 / n] is 3.5.
ガラスとしては、次に記載する製造法により、以下の特性を有するものを得た。酸化物基準のモル%表記で、表1に記載の配合となるようにガラス原料を混合した。これを、ガラス1は白金ルツボ中で1200℃に電気炉で加熱し、溶融して、ガラス2~4は金坩堝中で900℃~1000℃に電気炉で加熱し、溶融して、それぞれ融液を回転ロールで急冷して、ガラスリボンを形成した。ガラスリボンを、ボールミルで粉砕し、目開き150μmの網目を有する篩にかけ、さらに気流分級し、ガラスの粉末(ガラス粉末)を得た。ガラス1~4の50%粒径D50はそれぞれ1.4μm、1.2μm、1.3μm、1.2μmであった。また、ガラス粉末のガラス転移点Tgはそれぞれ496℃、420℃、429℃、415℃であった。また、融液の一部は成形後冷却し、ガラス板を得た。このガラス板の波長633nmの光に対する屈折率nはそれぞれ1.79、1.97、1.91、1.99であった。
As glass, what has the following characteristics was obtained by the manufacturing method described below. Glass raw materials were mixed so as to have the composition shown in Table 1 in terms of mol% based on oxide. The glass 1 is heated in an electric furnace to 1200 ° C. in a platinum crucible and melted, and the glasses 2 to 4 are heated in an electric furnace in a gold crucible to 900 ° C. to 1000 ° C. and melted to melt each. The liquid was quenched with a rotating roll to form a glass ribbon. The glass ribbon was pulverized with a ball mill, passed through a sieve having a mesh having an opening of 150 μm, and further subjected to air classification to obtain glass powder (glass powder). Glasses 1 to 4 had 50% particle size D 50 of 1.4 μm, 1.2 μm, 1.3 μm, and 1.2 μm, respectively. The glass transition points Tg of the glass powder were 496 ° C., 420 ° C., 429 ° C., and 415 ° C., respectively. A part of the melt was cooled after molding to obtain a glass plate. The refractive indices n of the glass plate for light having a wavelength of 633 nm were 1.79, 1.97, 1.91, and 1.99, respectively.
得られたガラス粉末のガラス転移点Tgは、示差熱分析計(リガク社製、商品名:TG8110)を使用して測定した。また、蛍光体粒子、耐熱フィラーおよびガラス粉末の粒径D50は、レーザ回折式粒度分布測定(島津製作所社製、装置名:SALD2100)により算出した。
The glass transition point Tg of the obtained glass powder was measured using a differential thermal analyzer (manufactured by Rigaku Corporation, trade name: TG8110). The phosphor particles, the particle size D 50 of the heat-resistant filler and glass powder, a laser diffraction particle size distribution measurement (manufactured by Shimadzu Corporation, apparatus name: SALD2100) was calculated by.
さらに、得られたガラス板を、厚み2mm、大きさ20mm×20mmの板状に加工後その両面を鏡面研磨してサンプル板とし、波長633nmの光に対する屈折率nを、メトリコン社製モデル2010プリズムカプラを用いて測定した。
Further, the obtained glass plate was processed into a plate shape having a thickness of 2 mm and a size of 20 mm × 20 mm, and both surfaces thereof were mirror-polished to obtain a sample plate, and the refractive index n with respect to light having a wavelength of 633 nm was set as a model 2010 prism manufactured by Metricon. Measurement was performed using a coupler.
(例1~18)
ガラス、蛍光体粒子、耐熱フィラー、を表2~3に記載した割合となるように混合し、さらにビヒクルと混練し、脱泡してスラリーを得た。このスラリーをPETフィルム(帝人社製)にドクターブレード法で塗工した。これを、乾燥炉で約30分間乾燥し、約7cm四方の大きさに切り出し、PETフィルムを剥がして、厚み0.5~0.7mmのグリーンシートを得た。 (Examples 1 to 18)
Glass, phosphor particles, and heat-resistant filler were mixed so as to have the ratios shown in Tables 2 to 3, and further kneaded with a vehicle and defoamed to obtain a slurry. This slurry was applied to a PET film (manufactured by Teijin Limited) by the doctor blade method. This was dried in a drying furnace for about 30 minutes, cut into a size of about 7 cm square, and the PET film was peeled off to obtain a green sheet having a thickness of 0.5 to 0.7 mm.
ガラス、蛍光体粒子、耐熱フィラー、を表2~3に記載した割合となるように混合し、さらにビヒクルと混練し、脱泡してスラリーを得た。このスラリーをPETフィルム(帝人社製)にドクターブレード法で塗工した。これを、乾燥炉で約30分間乾燥し、約7cm四方の大きさに切り出し、PETフィルムを剥がして、厚み0.5~0.7mmのグリーンシートを得た。 (Examples 1 to 18)
Glass, phosphor particles, and heat-resistant filler were mixed so as to have the ratios shown in Tables 2 to 3, and further kneaded with a vehicle and defoamed to obtain a slurry. This slurry was applied to a PET film (manufactured by Teijin Limited) by the doctor blade method. This was dried in a drying furnace for about 30 minutes, cut into a size of about 7 cm square, and the PET film was peeled off to obtain a green sheet having a thickness of 0.5 to 0.7 mm.
これを、離型剤を塗布したムライト基板に載せて、表2および3に示した脱灰温度および脱灰時間、そして大気雰囲気下で焼成して脱灰後、表2および3に示した焼成温度、焼成時間および焼成雰囲気で焼成して光変換部材を製造した。
なお、表中の「減圧」は、到達真空度が10Paであった。 This was placed on a mullite substrate coated with a release agent, decalcified at the demineralization temperature and demineralization time shown in Tables 2 and 3, and fired in an air atmosphere, and then decalcified and then fired as shown in Tables 2 and 3 A light conversion member was produced by firing at a temperature, firing time and firing atmosphere.
In the table, “reduced pressure” has an ultimate vacuum of 10 Pa.
なお、表中の「減圧」は、到達真空度が10Paであった。 This was placed on a mullite substrate coated with a release agent, decalcified at the demineralization temperature and demineralization time shown in Tables 2 and 3, and fired in an air atmosphere, and then decalcified and then fired as shown in Tables 2 and 3 A light conversion member was produced by firing at a temperature, firing time and firing atmosphere.
In the table, “reduced pressure” has an ultimate vacuum of 10 Pa.
(試験例)
得られた例1~18の光変換部材について、平面収縮率、量子変換収率、色度座標x、y、面内色度ばらつきΔx、Δyおよび透過率を測定した。これらの結果を表2~3に示す。 (Test example)
With respect to the obtained light conversion members of Examples 1 to 18, the planar shrinkage rate, quantum conversion yield, chromaticity coordinates x and y, in-plane chromaticity variations Δx and Δy, and transmittance were measured. These results are shown in Tables 2-3.
得られた例1~18の光変換部材について、平面収縮率、量子変換収率、色度座標x、y、面内色度ばらつきΔx、Δyおよび透過率を測定した。これらの結果を表2~3に示す。 (Test example)
With respect to the obtained light conversion members of Examples 1 to 18, the planar shrinkage rate, quantum conversion yield, chromaticity coordinates x and y, in-plane chromaticity variations Δx and Δy, and transmittance were measured. These results are shown in Tables 2-3.
平面収縮率は、グリーンシートの縦と横の長さに対し、得られた光変換部材の縦と横のそれぞれの収縮率を平均して得た。
The plane shrinkage rate was obtained by averaging the vertical and horizontal shrinkage rates of the obtained light conversion member with respect to the vertical and horizontal lengths of the green sheet.
光変換部材の量子変換収率は、得られた光変換部材の中央部を1cm四方の大きさに切り出し、絶対PL量子収率測定装置(浜松ホトニクス社製、商品名:Quantauru-QY)を使用して、励起光波長460nmにて測定した。また、この時同時に色度座標x、yも得られる。
For the quantum conversion yield of the light conversion member, the central portion of the obtained light conversion member is cut into a size of 1 cm square, and an absolute PL quantum yield measurement device (manufactured by Hamamatsu Photonics Co., Ltd., trade name: Quantauru-QY) is used. Then, measurement was performed at an excitation light wavelength of 460 nm. At the same time, chromaticity coordinates x and y are also obtained.
面内色度ばらつきΔx、Δyは得られた光変換部材の端部を、中央部同様に1cm四方の大きさに切り出し、色度座標を測定した後、中央部の色度座標との差をとることで得た。
In-plane chromaticity variations Δx and Δy are obtained by cutting the end of the obtained light conversion member into a size of 1 cm square like the center, measuring the chromaticity coordinates, and then calculating the difference from the chromaticity coordinates in the center. It was obtained by taking.
光変換部材の透過率は、ヘイズ測定装置(スガ試験機社製、商品名:ヘイズメーターHZ-2)を使用して、C光源にて測定した。
The transmittance of the light conversion member was measured with a C light source using a haze measuring device (trade name: Haze Meter HZ-2, manufactured by Suga Test Instruments Co., Ltd.).
表2~3より明らかなように、例1~4および7~18は本発明で規定する耐熱フィラーを含有しているため、収縮率は20%未満に抑えられ、面内色度ばらつきΔx、Δyはそれぞれ0.02未満である。また、例1~4は85%以上の高い量子変換収率と80%以上の透過率を維持しているため、高い発光変換効率も期待できる。
例7~18は、例1~4で用いているガラス1よりも屈折率が高いガラスを使用しているため、反射率も高く、透過率は低めの値となっているが、蛍光体の屈折率とより近い値になっているため、ガラス/蛍光体の散乱効率が低下し、耐熱フィラーとして[D50/n]が本発明の規定を外れたものと比べ、より高い発光変換効率が期待できる。また、CASN蛍光体は、C光源の波長域で大きな吸収を示すことより、例8、10、13、14、17、18の光変換部材の透過率は低い値を示す。
また、ガラス2~4は焼成温度が低くても焼結できるため、例1~4のように減圧雰囲気下で焼成せず、大気雰囲気下で焼成しても高い量子変換収率が得られる。そのため、低コストで光変換部材を製造することができる。
ただし、例12、14、16、18は、用いている耐熱フィラーの[D50/n]の値が、耐熱フィラー1に比べ低くなっていることから、耐熱フィラーの含有量を20体積%まで多くすると、著しく透過率が低下し、量子変換収率も低下してしまう。その結果、発光変換効率の低下が予想される。 As is apparent from Tables 2 to 3, Examples 1 to 4 and 7 to 18 contain the heat-resistant filler specified in the present invention, so that the shrinkage rate is suppressed to less than 20%, and the in-plane chromaticity variation Δx, Each Δy is less than 0.02. In addition, since Examples 1 to 4 maintain a high quantum conversion yield of 85% or more and a transmittance of 80% or more, high light emission conversion efficiency can be expected.
Examples 7 to 18 use a glass having a higher refractive index than that of the glass 1 used in Examples 1 to 4, so the reflectance is high and the transmittance is a low value. Since it is a value closer to the refractive index, the scattering efficiency of the glass / phosphor is lowered, and as a heat-resistant filler, [D 50 / n] is higher in luminescence conversion efficiency than that outside the definition of the present invention. I can expect. Moreover, since the CASN phosphor exhibits large absorption in the wavelength region of the C light source, the transmittance of the light conversion members of Examples 8, 10, 13, 14, 17, and 18 is low.
Further, since the glasses 2 to 4 can be sintered even at a low firing temperature, a high quantum conversion yield can be obtained by firing in an air atmosphere instead of firing in a reduced pressure atmosphere as in Examples 1 to 4. Therefore, a light conversion member can be manufactured at low cost.
However, in Examples 12, 14, 16, and 18, since the value of [D 50 / n] of the heat-resistant filler used is lower than that of the heat-resistant filler 1, the content of the heat-resistant filler is up to 20% by volume. If the amount is increased, the transmittance is significantly lowered, and the quantum conversion yield is also lowered. As a result, a decrease in luminescence conversion efficiency is expected.
例7~18は、例1~4で用いているガラス1よりも屈折率が高いガラスを使用しているため、反射率も高く、透過率は低めの値となっているが、蛍光体の屈折率とより近い値になっているため、ガラス/蛍光体の散乱効率が低下し、耐熱フィラーとして[D50/n]が本発明の規定を外れたものと比べ、より高い発光変換効率が期待できる。また、CASN蛍光体は、C光源の波長域で大きな吸収を示すことより、例8、10、13、14、17、18の光変換部材の透過率は低い値を示す。
また、ガラス2~4は焼成温度が低くても焼結できるため、例1~4のように減圧雰囲気下で焼成せず、大気雰囲気下で焼成しても高い量子変換収率が得られる。そのため、低コストで光変換部材を製造することができる。
ただし、例12、14、16、18は、用いている耐熱フィラーの[D50/n]の値が、耐熱フィラー1に比べ低くなっていることから、耐熱フィラーの含有量を20体積%まで多くすると、著しく透過率が低下し、量子変換収率も低下してしまう。その結果、発光変換効率の低下が予想される。 As is apparent from Tables 2 to 3, Examples 1 to 4 and 7 to 18 contain the heat-resistant filler specified in the present invention, so that the shrinkage rate is suppressed to less than 20%, and the in-plane chromaticity variation Δx, Each Δy is less than 0.02. In addition, since Examples 1 to 4 maintain a high quantum conversion yield of 85% or more and a transmittance of 80% or more, high light emission conversion efficiency can be expected.
Examples 7 to 18 use a glass having a higher refractive index than that of the glass 1 used in Examples 1 to 4, so the reflectance is high and the transmittance is a low value. Since it is a value closer to the refractive index, the scattering efficiency of the glass / phosphor is lowered, and as a heat-resistant filler, [D 50 / n] is higher in luminescence conversion efficiency than that outside the definition of the present invention. I can expect. Moreover, since the CASN phosphor exhibits large absorption in the wavelength region of the C light source, the transmittance of the light conversion members of Examples 8, 10, 13, 14, 17, and 18 is low.
Further, since the glasses 2 to 4 can be sintered even at a low firing temperature, a high quantum conversion yield can be obtained by firing in an air atmosphere instead of firing in a reduced pressure atmosphere as in Examples 1 to 4. Therefore, a light conversion member can be manufactured at low cost.
However, in Examples 12, 14, 16, and 18, since the value of [D 50 / n] of the heat-resistant filler used is lower than that of the heat-resistant filler 1, the content of the heat-resistant filler is up to 20% by volume. If the amount is increased, the transmittance is significantly lowered, and the quantum conversion yield is also lowered. As a result, a decrease in luminescence conversion efficiency is expected.
一方で、例5は耐熱フィラーを含有していないため、収縮率は20%超と高く、面内色度ばらつきΔx、Δyはそれぞれ0.02以上と大きい。
On the other hand, since Example 5 does not contain a heat-resistant filler, the shrinkage rate is as high as more than 20%, and the in-plane chromaticity variations Δx and Δy are as large as 0.02 or more, respectively.
例6は、耐熱フィラーのD50が3μmと小さいため、透過率は80%未満となり、全光束量が低下し、発光変換効率の低下のおそれがある。
In Example 6, since the D 50 of the heat resistant filler is as small as 3 μm, the transmittance is less than 80%, the total luminous flux is decreased, and the light emission conversion efficiency may be decreased.
本発明の光変換部材は、焼成時の収縮を抑制することで、蛍光体粒子の均一分散性を維持し、色度ばらつきが少なく、かつ、光源の光の透過性の低下を抑制し、発光変換効率を保持でき、照明用途としての利用に好適である。
The light conversion member of the present invention maintains the uniform dispersibility of the phosphor particles by suppressing shrinkage during firing, reduces chromaticity variation, suppresses a decrease in light transmittance of the light source, and emits light. The conversion efficiency can be maintained, which is suitable for use as a lighting application.
Claims (15)
- 蛍光体粒子を分散して含有するガラスからなる光変換部材であって、
前記ガラス中に、さらに、耐熱フィラーが分散して含有されており、該耐熱フィラーは、その50%粒径D50と波長633nmにおけるその屈折率nとの関係式[D50/n]が2~20の範囲であることを特徴とする光変換部材。 A light conversion member made of glass containing dispersed phosphor particles,
The glass further contains a heat-resistant filler dispersed therein, and the heat-resistant filler has a relational expression [D 50 / n] between its 50% particle size D 50 and its refractive index n at a wavelength of 633 nm is 2. A light conversion member characterized by being in the range of ˜20. - 前記耐熱フィラーの50%粒径D50が5~30μmであり、かつ、波長633nmにおける前記耐熱フィラーの屈折率nが1.5~2.5である請求項1に記載の光変換部材。 The light conversion member according to claim 1, wherein the heat-resistant filler has a 50% particle size D 50 of 5 to 30 µm, and the refractive index n of the heat-resistant filler at a wavelength of 633 nm is 1.5 to 2.5.
- 前記耐熱フィラーが、アルミナ、ジルコニアおよびマグネシアからなる群から選ばれる1種類以上の耐熱フィラーであり、前記ガラス中に含有する前記耐熱フィラーの体積分率が3~30%である請求項1または2に記載の光変換部材。 The heat-resistant filler is at least one heat-resistant filler selected from the group consisting of alumina, zirconia and magnesia, and the volume fraction of the heat-resistant filler contained in the glass is 3 to 30%. The light conversion member according to 1.
- 前記光変換部材が50~500μmの厚みを有する請求項1~3のいずれか1項に記載の光変換部材。 The light conversion member according to any one of claims 1 to 3, wherein the light conversion member has a thickness of 50 to 500 袖 m.
- 前記蛍光体粒子が、波長400~500nmに励起帯を有し、波長500~700nmに発光ピークを有し、酸化物、窒化物、酸窒化物、硫化物、酸硫化物、ハロゲン化物、アルミン酸塩化物およびハロリン酸塩化物からなる群から選ばれる1以上の化合物である請求項1~4のいずれか1項に記載の光変換部材。 The phosphor particles have an excitation band at a wavelength of 400 to 500 nm, an emission peak at a wavelength of 500 to 700 nm, and an oxide, nitride, oxynitride, sulfide, oxysulfide, halide, aluminate The light conversion member according to any one of claims 1 to 4, wherein the light conversion member is one or more compounds selected from the group consisting of chlorides and halophosphates.
- 前記蛍光体粒子がガーネット系結晶である請求項1~5のいずれか1項記載の光変換部材。 The light conversion member according to any one of claims 1 to 5, wherein the phosphor particles are garnet crystals.
- 前記蛍光体粒子の50%粒径D50が1~30μmである請求項1~6のいずれか1項に記載の光変換部材。 Light converting member according to any one of the phosphor claims 1-50% particle diameter D 50 is 1 ~ 30 [mu] m particle 6.
- 前記ガラスは、DTA曲線から算出されるガラス転移点Tgが300~550℃である請求項1~7のいずれか1項に記載の光変換部材。 The light conversion member according to any one of claims 1 to 7, wherein the glass has a glass transition point Tg calculated from a DTA curve of 300 to 550 ° C.
- 前記ガラスが、Bi2O3-B2O3-ZnO系である請求項1~8のいずれか1項に記載の光変換部材。 The light conversion member according to any one of claims 1 to 8, wherein the glass is a Bi 2 O 3 -B 2 O 3 -ZnO system.
- 前記ガラスは、モル%表示で、Bi2O3 3~40%、B2O3 10~50%、ZnO 0~45%を含有する請求項1~9のいずれか1項に記載の光変換部材。 10. The light conversion according to claim 1, wherein the glass contains Bi 2 O 3 3 to 40%, B 2 O 3 10 to 50%, ZnO 0 to 45% in terms of mol%. Element.
- 前記光変換部材が、ガラス粉末、蛍光体粒子および耐熱フィラーの混合粉末の焼結体である請求項1~10のいずれか1項に記載の光変換部材。 The light conversion member according to any one of claims 1 to 10, wherein the light conversion member is a sintered body of a mixed powder of glass powder, phosphor particles and heat-resistant filler.
- 請求項1~11のいずれか1項に記載の光変換部材と、該光変換部材を通して外部へ光を照射可能な光源と、を有することを特徴とする照明光源。 An illumination light source comprising: the light conversion member according to any one of claims 1 to 11; and a light source capable of irradiating light to the outside through the light conversion member.
- 前記光源が、LED発光素子である請求項12に記載の照明光源。 The illumination light source according to claim 12, wherein the light source is an LED light emitting element.
- ガラス粉末、蛍光体粒子、耐熱フィラー、樹脂および有機溶媒を混練して混練物とする混練工程と、得られた混練物を所望の形状に成形する成形工程と、混練物の成形体を焼成して光変換部材とする焼成工程と、を有する光変換部材の製造方法であって、
前記耐熱フィラーが、その平均粒径D50と波長633nmにおけるその屈折率nとの関係式[D50/n]が2~20であることを特徴とする光変換部材の製造方法。 A kneading step of kneading glass powder, phosphor particles, heat-resistant filler, resin and organic solvent to form a kneaded product, a molding step of molding the obtained kneaded product into a desired shape, and firing the molded product of the kneaded product A process for producing a light conversion member, and a method for producing a light conversion member comprising:
The method for producing a light conversion member, wherein the heat-resistant filler has a relational expression [D 50 / n] of 2 to 20 between its average particle diameter D 50 and its refractive index n at a wavelength of 633 nm. - 前記蛍光体粒子、前記耐熱フィラーおよび前記ガラス粉末の合計量を100%としたとき、体積分率で、前記蛍光体粒子を1~40%、前記耐熱フィラーを3~30%、前記ガラス粉末を50~96%、含有する請求項14に記載の光変換部材の製造方法。 When the total amount of the phosphor particles, the heat-resistant filler and the glass powder is 100%, the phosphor particles are 1 to 40%, the heat-resistant filler is 3 to 30%, and the glass powder is a volume fraction. The method for producing a light conversion member according to claim 14, wherein the content is 50 to 96%.
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WO2015041204A1 (en) * | 2013-09-20 | 2015-03-26 | 旭硝子株式会社 | Light-converting member, method for manufacturing light-converting member, method for adjusting chromaticity of light-converting member, illuminating light source, and liquid crystal display device |
WO2016132888A1 (en) * | 2015-02-18 | 2016-08-25 | 日東電工株式会社 | Method of producing phosphor ceramic |
TWI609943B (en) * | 2017-06-06 | 2018-01-01 | 陳明進 | Process of manufacturing phosphor composite |
US11329198B2 (en) | 2018-12-18 | 2022-05-10 | Panasonic Intellectual Property Management Co., Ltd. | Wavelength conversion member, optical device, and projector |
US11474423B2 (en) | 2018-12-18 | 2022-10-18 | Panasonic Intellectual Property Management Co., Ltd. | Wavelength conversion member, optical device, projector, and manufacturing method for wavelength conversion member |
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JP2010278474A (en) * | 2010-09-01 | 2010-12-09 | Nichia Corp | Light emitting device |
JP2011071404A (en) * | 2009-09-28 | 2011-04-07 | Kyocera Corp | Light-emitting device and illumination apparatus |
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JP5689243B2 (en) * | 2010-03-24 | 2015-03-25 | 日本電気硝子株式会社 | Semiconductor light emitting device sealing material and method for manufacturing semiconductor light emitting device using the same |
JP5510312B2 (en) * | 2010-12-28 | 2014-06-04 | コニカミノルタ株式会社 | Method for manufacturing light emitting device |
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Cited By (5)
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WO2015041204A1 (en) * | 2013-09-20 | 2015-03-26 | 旭硝子株式会社 | Light-converting member, method for manufacturing light-converting member, method for adjusting chromaticity of light-converting member, illuminating light source, and liquid crystal display device |
WO2016132888A1 (en) * | 2015-02-18 | 2016-08-25 | 日東電工株式会社 | Method of producing phosphor ceramic |
TWI609943B (en) * | 2017-06-06 | 2018-01-01 | 陳明進 | Process of manufacturing phosphor composite |
US11329198B2 (en) | 2018-12-18 | 2022-05-10 | Panasonic Intellectual Property Management Co., Ltd. | Wavelength conversion member, optical device, and projector |
US11474423B2 (en) | 2018-12-18 | 2022-10-18 | Panasonic Intellectual Property Management Co., Ltd. | Wavelength conversion member, optical device, projector, and manufacturing method for wavelength conversion member |
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