WO2006103942A1 - 紫外線吸収ガラス及びそれを用いた蛍光ランプ用ガラス管及び蛍光ランプ用紫外線吸収ガラスの製造方法 - Google Patents
紫外線吸収ガラス及びそれを用いた蛍光ランプ用ガラス管及び蛍光ランプ用紫外線吸収ガラスの製造方法 Download PDFInfo
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- WO2006103942A1 WO2006103942A1 PCT/JP2006/305219 JP2006305219W WO2006103942A1 WO 2006103942 A1 WO2006103942 A1 WO 2006103942A1 JP 2006305219 W JP2006305219 W JP 2006305219W WO 2006103942 A1 WO2006103942 A1 WO 2006103942A1
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- WO
- WIPO (PCT)
- Prior art keywords
- glass
- fluorescent lamp
- sno
- ultraviolet
- wavelength
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 129
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000005388 borosilicate glass Substances 0.000 claims abstract description 16
- 238000002834 transmittance Methods 0.000 claims description 27
- 230000006866 deterioration Effects 0.000 claims description 20
- 239000004973 liquid crystal related substance Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 30
- 230000000694 effects Effects 0.000 description 13
- 230000007423 decrease Effects 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 229910000833 kovar Inorganic materials 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910020203 CeO Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/02—Details
- H01J61/30—Vessels; Containers
- H01J61/302—Vessels; Containers characterised by the material of the vessel
Definitions
- Ultraviolet absorbing glass fluorescent lamp glass tube using the same, and method for producing ultraviolet absorbing glass for fluorescent lamp
- the present invention relates to an ultraviolet absorbing glass, and is suitable for a fluorescent lamp used for a backlight of a display device such as an envelope of a light source accompanied by ultraviolet radiation, particularly a liquid crystal display (hereinafter referred to as LCD).
- a display device such as an envelope of a light source accompanied by ultraviolet radiation, particularly a liquid crystal display (hereinafter referred to as LCD).
- the present invention relates to a glass, a glass tube for a fluorescent lamp using the glass, and a method for producing an ultraviolet absorbing glass for a fluorescent lamp.
- LCDs liquid crystal displays
- their applications have expanded, their weight, thickness, power consumption, and brightness have increased.
- Low cost has been required.
- high-quality display devices are required for LCD displays, in-vehicle display devices, and TV monitors.
- a transmissive liquid crystal display element using a backlight using a fluorescent lamp as a light source is used in the above-described applications.
- a front light is used as an irradiation light source from the front.
- the glass is designed to transmit some ultraviolet light so that it can withstand the flash of the lamp.
- the application is a fluorescent lamp, it is necessary to consider measures for preventing leakage of ultraviolet rays, discoloration of glass due to ultraviolet irradiation generated in the lamp, so-called ultraviolet solarization measures, and components that improve these characteristics. Glass with a small amount of is used.
- Patent Document 1 or Patent Document 2 is a typical example of the glass in this application, and contains TiO, PbO, or SbO based on borosilicate glass.
- the composition has improved ultraviolet resistance solarization resistance of the glass.
- the glass disclosed in Patent Document 3 or Patent Document 4 can be added with Fe 2 O and CeO to add water.
- the composition is such that the ultraviolet transmittance at 253.7 nm, which is the resonance line of silver, is kept low.
- Glass tube forming methods in mass production include the updraw method, bellows method, dunner method, etc., but the glass tube used for the backlight is a thin tube, and high dimensional accuracy is required.
- the Danner method is most suitable.
- Patent Document 1 Japanese Patent Laid-Open No. 9-110467
- Patent Document 2 JP 2002-187734
- Patent Document 3 Japanese Patent Laid-Open No. 2002-293571
- Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-91308
- the light emission principle of the fluorescent lamp for backlight is the same as that for general lighting.
- Mercury vapor excited by the discharge between the electrodes emits ultraviolet rays
- the fluorescent material applied to the inner wall surface of the tube receives ultraviolet rays and is visible. It generates light.
- An ultraviolet ray of 253.7 nm is mainly generated in the lamp, and most of it is converted into visible light, but some of it is converted into visible light with a phosphor. Sometimes it reaches the glass.
- Measures are taken to reduce the intensity of ultraviolet rays that reach the glass by applying a phosphor and forming a multilayer film on it.
- a method inevitably increases the cost due to the increase in the number of coating steps due to the difficulty in coating due to the reduction in the diameter and length of the glass tube.
- the glass disclosed in Patent Document 1 has ultraviolet resistance to solarization and a sufficient shielding effect against 253.7 nm ultraviolet rays, but 315 nm ultraviolet rays corresponding to the deterioration of resin used in backlight units. There is a risk of deterioration of internal grease during long periods of use due to insufficient consideration for cutting.
- the glasses disclosed in Patent Documents 2, 3, and 4 are composed of WO, ZrO, SnO, FeO, and CeO.
- the glass containing it tends to absorb in the visible range, it is not suitable for LCD TVs that require sufficient brightness and color reproducibility.
- the present invention has been made in consideration of the various circumstances as described above, and is particularly excellent in the shielding property against harmful ultraviolet rays that affect the degradation of the oil having a wavelength of 315 nm or less, which is sufficient as a fluorescent lamp application. It is an object of the present invention to provide a glass suitable for a glass tube used in a fluorescent lamp for backlight, which has excellent ultraviolet solarization resistance.
- the mass percent is Fe O 0.001 to 0.0.
- borosilicate glass with an average linear expansion coefficient of 36-57 X 10 _7 Z ° C in the range of 0-300 ° C as defined in JIS R3102, with a wall thickness of 0.3 mm at a wavelength of 315 nm.
- a UV-absorbing glass for a fluorescent lamp characterized by having a transmittance of 10% or less and a deterioration degree of 5% or less in the following UV irradiation test, wherein the deterioration degree in the UV irradiation test is Walls with lmm thick glass mirror-polished on both sides are placed facing a position 20cm away from a 400W high-pressure mercury lamp with a main wavelength of 253.7nm, and after 300 hours of UV irradiation, the transmittance at a wavelength of 400nm (T) was measured, and the degree of deterioration from the initial transmittance (T) at a wavelength of 400 nm before UV irradiation was expressed by the following equation:
- the ultraviolet ray absorbing glass for a fluorescent lamp can be formed into a tubular shape.
- the outer diameter of the glass tube is 0.7-6mm, and the wall thickness is 0.07-0.7mm. It is preferably used for a knock light source of a liquid crystal display device.
- Still another embodiment of the present invention uses a divalent compound raw material as a Sn source, melts the glass raw material in a reducing manner, and is Fe O 0.001 to 0.05% in mass%. CeO 0.1 to 5%,
- Borosilicate system containing SnO + SnO 0.01-5%, ZrO + ZnO + Nb O 0.01-5%
- the borosilicate glass includes SiO 60-80%, Al O 1-7%, B 2 O 10-25%, Li 2 O
- still another embodiment of the present invention is that the glass raw material is melted in a reducing manner, in mass%, FeO 0.001 to 0.05%, CeO 0.1 to 5%, ZrO + ZnO. + Nb O 0.01 ⁇ 5% included
- the borosilicate glass includes SiO 60 to 80%, Al O 1 to 7%, B O 10
- the glass for a fluorescent lamp according to one embodiment of the present invention has a thermal expansion coefficient suitable for sealing with Kovar and tungsten, and has excellent ultraviolet solarization resistance with a high degree of rust.
- the glass according to one embodiment of the present invention has excellent ultraviolet cut-off characteristics at 315 nm, even when used in a fluorescent lamp for a backlight of a display device such as a liquid crystal display, the resin inside the display device Improve the reliability of display devices that do not deteriorate the material of parts.
- the glass tube for a fluorescent lamp manufactured using the glass according to one embodiment of the present invention has high resistance to ultraviolet solarization, deterioration of display quality such as a liquid crystal display due to discoloration of the glass is prevented. it can.
- Fe O is a component that strongly absorbs ultraviolet rays, and with a small amount of addition, it can cut ultraviolet rays.
- the effect cannot be expected if it is less than 0.001% by mass%. Moreover, if it exceeds 0.05%, it will have a negative effect on the resistance to ultraviolet solarization. Preferably, it is 0.003 to 0.04%, more preferably 0.005 to 0.03%.
- CeO is a component that strongly absorbs ultraviolet rays, and is an essential component of one embodiment of the present invention.
- CeO has a strong acidity and is itself reduced.
- Ce 3+ Although it tends to be in a trivalent state, it usually coexists in the state of Ce 3+ and Ce 4+ in glass, and Ce 3+ force has an absorption band at S316nm and Ce 4+ at 243nm. Ce 3+ shows sharp absorption, whereas Ce 4+ shows broad absorption that is strong in the visible range, so when the amount of addition increases, the glass turns yellowish brown. It is a colorless glass that does not absorb in the visible range, and it is necessary to increase the ratio of Ce 3+ in order to efficiently absorb ultraviolet rays of 315 nm or less.
- SnO + SnO is a component necessary for controlling the valence of Ce ions.
- Sn is preferably used as a divalent compound such as SnO, but it is oxidized in glass to form SnO.
- Sn is an effective reducing agent when used as a divalent compound.
- the reducing agent organic raw materials such as carbon can also be used, but the organic reducing agent becomes a gas state by acting as a reducing agent and volatilizes from the glass during the melting process, so it does not remain in the final product. .
- the redox state of the glass depends on the melting atmosphere, and it is difficult to maintain the reducibility when staying in a tank furnace for a long time.
- SnO remains as a glass component and has an effect of stabilizing the valence of ions in the glass.
- SnO + SnO is an essential component. If SnO + SnO is less than 0.01%, the Ce 4+
- the glass is colored yellowish brown and the transmittance in the visible region is lowered. Also, over 5% In other words, the tendency of the glass to devitrify becomes strong, which is not preferable.
- SnO + SnO is Ce ion
- Ce ions are reduced by Ce 3+ and reduced by Ce 4+ .
- SnO + SnO is a glass of Sn 2+ and Sn 4+.
- Sn 2+ has an absorption band around 240 nm. Therefore, Sn 2+ can compensate for the decrease in UV absorption characteristics of 253.7 nm due to the decrease in Ce 4+ .
- a manufacturing method for reducing melting by adding SnO + SnO is an embodiment of the present invention.
- a composition not containing SnO can be made reducible using other means.
- organic reducing agents such as ammonia salts such as carbon sucrose may be added to the raw material, or control of the melting atmosphere may be considered.
- the valence of Ce ions can be changed to Ce 3+ .
- a part of SnO + SnO can be substituted with the above reducing agent and used together.
- organic reducing agents such as ammonia salts such as carbon sucrose
- the upper limit of unfavorable cover is 1%.
- ZrO, ZnO, and NbO are effective components for enhancing the ultraviolet solarization resistance.
- the total amount is 0.01% or more in terms of mass%, if the required force exceeds 5%, the devitrification becomes high, which is not preferable.
- These components may be used alone or in combination of two or more.
- the upper limit of NbO is 0.2% to prevent glass coloring.
- the average coefficient of linear expansion of the glass was set in the range of 36 to 57 X 10 _7 Z ° C in order to ensure thermal expansion consistency with Kovar or tungsten serving as the electrode material and to improve sealing performance. It is.
- the preferred range for each electrode material is 36 to 46 X 10_7 Z ° C for tungsten and 46 to 57 X 10 _7 Z ° C for Kovar. To do.
- the ultraviolet ray transmittance at a wavelength of 315 nm is set to 10% or less in a state where glass is optically polished to a thickness of 0.3 mm with the above-mentioned components having an ultraviolet cut characteristic. As a result, it is possible to reduce the 313 ⁇ m ultraviolet rays emitted outside the tube by about 80% to 90% compared to conventional glass.
- the reason why the degree of deterioration in the ultraviolet irradiation test is determined as described above is as follows. Normally, in an accelerated test in which glass is exposed in the vicinity of a strong ultraviolet light source, it tends to become colored in 1 hour to several hours (the glass power weakness that tends to be colored can be confirmed, but after 100 hours, the degree gradually decreases. At the end of 300 hours, it is possible to confirm that the color is almost close to the limit of coloration due to solarization, so it is possible to more accurately grasp the effect of the decrease in transmittance when used for a long time in actual products.
- the brightness of the lamp is adversely affected, especially in the vicinity of 400 nm, where there is a blue-violet spectral energy distribution of the fluorescent lamp, which is transmitted by solarization.
- the transmittance at the wavelength of 400 nm was used as the evaluation scale because it is considered that the brightness deterioration is most likely to affect the brightness. If the degree of deterioration of the rate is 5% or less, can be suppressed to the extent that the user does not recognize the ⁇ I spoon of LCD display due to the glass tube for the fluorescent lamp can be maintained practical display quality.
- the borosilicate glass is formed by mass%, SiO 60-80%,
- SiO is a glass-forming component of glass, but if it exceeds 80%, the meltability of the glass and formability
- a decrease in chemical durability causes waethering, blurring, etc., causing a decrease in brightness of the fluorescent lamp and color unevenness.
- it is 62 to 78%.
- Al O has a power of improving glass devitrification and mechanical durability.
- the meltability deteriorates due to the occurrence of striae. If it is less than 1%, phase separation or devitrification tends to occur, and the chemical durability of the glass also decreases. Preferably it is 2 to 5% of range.
- B 2 O is a component used for the purpose of improving the meltability and adjusting the viscosity.
- the content is less than 10%, the meltability deteriorates. Preferably, it is 12 to 20%.
- Li 0, Na 0, K O acts as a flux, improves the meltability of the glass and increases the viscosity
- the content of each component is% by mass, Li 2 O
- Lugum is known to form, and excess Na 2 O in the glass is present in fluorescent lamps.
- the additive amount exceeding the above upper limit value of Na 2 O is not preferable, more preferably 0-4%.
- CaO, MgO, BaO, and SrO are components that have the effect of lowering the viscosity of glass at high temperatures and improving its meltability, and can be added up to 5% in total if necessary. upper limit When it exceeds the value, the glass state becomes unstable and devitrification tends to occur.
- the refining agent used for melting the glass is desirably a reducing refining agent.
- a feature of one embodiment of the present invention is that good ultraviolet absorption characteristics can be obtained by controlling CeO used as an ultraviolet absorber to a state of Ce 3+ ions.
- the ultraviolet ray transmittance at a wavelength of 315 nm is set to 10% or less in the state where the ultraviolet ray is cut by the above component composition and the glass is optically polished to a thickness of 0.3 mm. If a more desirable quality level is desired without affecting the transmission of visible light, the thickness can be reduced to 1% or less at a thickness of 0.3 mm by adjusting trace components.
- the glass according to one embodiment of the present invention can be produced as follows. First, the raw materials are weighed and mixed so that the obtained glass has the above composition range. This raw material mixture is placed in a stone crucible or platinum crucible and heated and melted in an electric furnace. Stir well • After clarification, shape into desired shape. In the case of mass production molding into a tubular shape in order to produce a thin tube for a fluorescent lamp according to another embodiment of the present invention, glass melted in a tank furnace is made from fore hearth using a platinum member and glass supply molding. Depending on the mechanism, molding can be performed without problems by known pipe drawing methods such as the Danner method and redraw.
- Table 1 shows examples and comparative examples of the present invention.
- Samples Nos. 1 to 10 are examples of the present invention, and Nos. 11 and 12 are comparative examples showing conventional glass.
- the composition in the table is expressed in mass%.
- the glass listed in the table is prepared by weighing and mixing raw materials such as silica sand, carbonates, nitrates and hydroxides of each metal so that each oxide composition shown in the table is obtained. Used and melted at 1450 ° C for 5 hours. At this time, Sn is stannous oxide, etc. These are introduced as divalent compounds, but in the table they are all converted to SnO.
- Macroporous oxide etc.
- No. 5 and 10 glasses were melted by mixing 2% of carbon as a reducing agent in a total batch ratio. Thereafter, a sufficiently stirred and clarified glass was poured out into a rectangular frame, and after slow cooling, a sample processed into a desired shape according to the evaluation items shown below was created.
- the thermal expansion coefficient of the gas is equal to or slightly lower than that of the metal of the electrode material. If the difference in coefficient of thermal expansion between the glass and the electrode material becomes large, it will cause leaks and cracks from the sealed part and cannot be used for fluorescent lamps.
- the degree of transmittance degradation in the UV-resistant solarization test was determined by cutting each glass sample into a 30 mm square plate and performing optical polishing on both sides so that the thickness was 1 mm.
- the —400P) force was also placed at a position of 20 cm and irradiated with UV light for 300 hours, and then the transmittance at a wavelength of 400 nm was measured and displayed as the degree of deterioration from the initial transmittance before UV irradiation.
- Degree of degradation (%) [(initial transmittance, transmittance after UV irradiation) Z initial transmittance] X 100.
- No. 1 to 10 which are examples of the present invention
- No. 1 to 5 are Kovar seals
- No. 6 to: L0 is adjusted to an average linear expansion coefficient suitable for tungsten seals It is.
- the average linear expansion coefficient is relatively close to the average linear expansion coefficient of Kovar 55 X 10 _7 Z ° C and the average linear expansion coefficient of tungsten 45 X 10 _7 Z ° C. High sealing can be obtained.
- the average linear expansion coefficient of the glass in the embodiment of the present invention is set to 36 to 57 ⁇ 10 _7 Z ° C.
- the transmittance at a wavelength of 315 nm at a wall thickness of 0.3 mm is extremely low compared to conventional glass, and hardly transmits harmful ultraviolet rays that have an effect on the deterioration of the resin.
- the transmittance deterioration due to ultraviolet irradiation was suppressed to 5% or less, and it had a very high resistance to ultraviolet solarization.
- the sample No. 11 as a comparative example is an example of a composition not containing SnO.
- the transmittance at 315 nm is low, and the transmittance deterioration due to ultraviolet irradiation is small, but the glass turns yellowish brown. It was colored.
- the sample No. 12 has a low level of transmittance degradation due to UV irradiation, but the transmittance at 315 nm is high. Since 313 nm UV rays cannot be shielded by a glass tube, the deterioration of the grease component of the backlight unit is accelerated. The risk of being caught is very high.
- the glass according to one embodiment of the present invention does not contain PbO, which is an environmentally hazardous substance.
- PbO an environmentally hazardous substance.
- substantially free means that it is not intentionally added, and raw material isotropic force is inevitably mixed in, and the content is excluded without affecting the intended characteristics. It ’s not something.
- the glass according to the present invention is suitable as a glass tube for a fluorescent lamp, and has excellent ultraviolet cut characteristics. Therefore, even when used in a backlight fluorescent lamp such as a liquid crystal display. It is possible to prevent the deterioration of display quality, which can be prevented from deteriorating the materials such as the grease parts inside the display device.
- it has an excellent ultraviolet ray cut-off property and a visible light transmissive filter, which is not limited to this, and an ultraviolet ray cut filter, and also has a high ultraviolet ray resistance solarization property. It can be used for J IJ in enclosures.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Glass Compositions (AREA)
- Vessels And Coating Films For Discharge Lamps (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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JP2007510381A JP4445013B2 (ja) | 2005-03-25 | 2006-03-16 | 紫外線吸収ガラス及びそれを用いた蛍光ランプ用ガラス管及び蛍光ランプ用紫外線吸収ガラスの製造方法 |
EP06729216A EP1905746A4 (en) | 2005-03-25 | 2006-03-16 | ULTRAVIOLET ABSORBENT GLASS, FLUORES FOR FLUORESCENT LAMPS AND METHOD FOR THE PRODUCTION OF ULTRAVIOLET ABSORBENT GLASS FOR FLUORESCENT LAMP |
US11/908,417 US7667791B2 (en) | 2005-03-25 | 2006-03-16 | Ultraviolet absorbing glass, glass tube for fluorescent lamp using same, and method for producing ultraviolet absorbing glass for fluorescent lamp |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP2005088476 | 2005-03-25 | ||
JP2005-088476 | 2005-03-25 | ||
JP2006-009628 | 2006-01-18 | ||
JP2006009628 | 2006-01-18 |
Publications (1)
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WO2006103942A1 true WO2006103942A1 (ja) | 2006-10-05 |
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PCT/JP2006/305219 WO2006103942A1 (ja) | 2005-03-25 | 2006-03-16 | 紫外線吸収ガラス及びそれを用いた蛍光ランプ用ガラス管及び蛍光ランプ用紫外線吸収ガラスの製造方法 |
Country Status (6)
Country | Link |
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US (1) | US7667791B2 (ja) |
EP (1) | EP1905746A4 (ja) |
JP (1) | JP4445013B2 (ja) |
KR (1) | KR100910093B1 (ja) |
TW (1) | TW200642982A (ja) |
WO (1) | WO2006103942A1 (ja) |
Cited By (5)
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JP2007039281A (ja) * | 2005-08-03 | 2007-02-15 | Maeda Kogyo Kk | 液晶表示照明用紫外線吸収ガラス及びガラス管 |
EP1870384A1 (en) * | 2005-04-01 | 2007-12-26 | Matsushita Electric Industrial Co., Ltd. | Glass composition for lamp, lamp, backlight unit and method for producing glass composition for lamp |
JP2009013002A (ja) * | 2007-07-03 | 2009-01-22 | Agc Techno Glass Co Ltd | 蛍光ランプ用紫外線吸収ガラスおよび蛍光ランプ用ガラス管 |
WO2015087812A1 (ja) * | 2013-12-11 | 2015-06-18 | 旭硝子株式会社 | 発光ダイオードパッケージ用カバーガラス、封着構造体および発光装置 |
WO2017199738A1 (ja) * | 2016-05-16 | 2017-11-23 | 旭硝子株式会社 | ガラス物品 |
Families Citing this family (6)
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JPWO2007017928A1 (ja) * | 2005-08-08 | 2009-02-19 | 独立行政法人産業技術総合研究所 | 透明白色蛍光ガラス |
US20090280277A1 (en) * | 2006-09-06 | 2009-11-12 | Agc Techno Glass Co., Ltd | Ultraviolet-absorbing glass tube for fluorescent lamp and glass tube comprising the same for fluorescent lamp |
DE102011084543B4 (de) | 2011-10-14 | 2017-04-27 | Schott Ag | Borosilicatglas mit hoher hydrolytischer Beständigkeit |
TWI692459B (zh) | 2015-05-29 | 2020-05-01 | 日商Agc股份有限公司 | 紫外線透射玻璃 |
US10341567B2 (en) * | 2016-03-16 | 2019-07-02 | Ricoh Imaging Company, Ltd. | Photographing apparatus |
EP3696149A1 (de) * | 2019-02-14 | 2020-08-19 | Ivoclar Vivadent AG | Fluoreszierende glaskeramiken und gläser mit gehalt an cer und zinn |
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- 2006-03-16 KR KR1020077024452A patent/KR100910093B1/ko not_active IP Right Cessation
- 2006-03-16 US US11/908,417 patent/US7667791B2/en not_active Expired - Fee Related
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- 2006-03-22 TW TW095109915A patent/TW200642982A/zh unknown
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1870384A1 (en) * | 2005-04-01 | 2007-12-26 | Matsushita Electric Industrial Co., Ltd. | Glass composition for lamp, lamp, backlight unit and method for producing glass composition for lamp |
JPWO2006106659A1 (ja) * | 2005-04-01 | 2008-09-11 | 松下電器産業株式会社 | ランプ用ガラス組成物、ランプ、バックライトユニットおよびランプ用ガラス組成物の製造方法 |
EP1870384A4 (en) * | 2005-04-01 | 2010-05-26 | Panasonic Corp | GLASS COMPOSITION FOR LAMPS, LAMP, BACKLIGHT UNIT AND METHOD FOR MANUFACTURING GLASS COMPOSITION FOR LAMPS |
KR101031662B1 (ko) * | 2005-04-01 | 2011-04-29 | 파나소닉 주식회사 | 램프용 유리조성물, 램프, 백라이트 유닛 및 램프용유리조성물의 제조방법 |
US7977262B2 (en) | 2005-04-01 | 2011-07-12 | Panasonic Corporation | Glass composition for lamp, lamp, backlight unit and method for producing glass composition for lamp |
JP2007039281A (ja) * | 2005-08-03 | 2007-02-15 | Maeda Kogyo Kk | 液晶表示照明用紫外線吸収ガラス及びガラス管 |
JP2009013002A (ja) * | 2007-07-03 | 2009-01-22 | Agc Techno Glass Co Ltd | 蛍光ランプ用紫外線吸収ガラスおよび蛍光ランプ用ガラス管 |
WO2015087812A1 (ja) * | 2013-12-11 | 2015-06-18 | 旭硝子株式会社 | 発光ダイオードパッケージ用カバーガラス、封着構造体および発光装置 |
JPWO2015087812A1 (ja) * | 2013-12-11 | 2017-03-16 | 旭硝子株式会社 | 発光ダイオードパッケージ用カバーガラス、封着構造体および発光装置 |
US9831392B2 (en) | 2013-12-11 | 2017-11-28 | Asahi Glass Company, Limited | Cover glass for light emitting diode package, sealed structure, and light emitting device |
WO2017199738A1 (ja) * | 2016-05-16 | 2017-11-23 | 旭硝子株式会社 | ガラス物品 |
US10927038B2 (en) | 2016-05-16 | 2021-02-23 | AGC Inc. | Glass article |
Also Published As
Publication number | Publication date |
---|---|
US7667791B2 (en) | 2010-02-23 |
EP1905746A1 (en) | 2008-04-02 |
TW200642982A (en) | 2006-12-16 |
EP1905746A4 (en) | 2010-12-22 |
JPWO2006103942A1 (ja) | 2008-09-04 |
US20090009691A1 (en) | 2009-01-08 |
KR20070117683A (ko) | 2007-12-12 |
KR100910093B1 (ko) | 2009-07-30 |
JP4445013B2 (ja) | 2010-04-07 |
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