WO2011004844A1 - ガラス板 - Google Patents
ガラス板 Download PDFInfo
- Publication number
- WO2011004844A1 WO2011004844A1 PCT/JP2010/061542 JP2010061542W WO2011004844A1 WO 2011004844 A1 WO2011004844 A1 WO 2011004844A1 JP 2010061542 W JP2010061542 W JP 2010061542W WO 2011004844 A1 WO2011004844 A1 WO 2011004844A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass plate
- less
- glass
- content
- refractive index
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 200
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 35
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 30
- 230000003746 surface roughness Effects 0.000 claims description 26
- 238000002834 transmittance Methods 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 13
- 238000005286 illumination Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 8
- 230000007423 decrease Effects 0.000 description 29
- 238000000034 method Methods 0.000 description 23
- 238000000605 extraction Methods 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000007791 liquid phase Substances 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 238000004031 devitrification Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 230000001771 impaired effect Effects 0.000 description 8
- 229910006404 SnO 2 Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000007500 overflow downdraw method Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000007788 roughening Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000006060 molten glass Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000003280 down draw process Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000007088 Archimedes method Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000754 repressing effect Effects 0.000 description 1
- 238000007372 rollout process Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
-
- 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
- C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/30—Organic light-emitting transistors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/841—Self-supporting sealing arrangements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention relates to a glass plate suitable for lighting devices, organic EL devices, and the like, and particularly relates to a glass plate suitable for organic EL lighting.
- the glass plate includes a thin glass film having a film shape, specifically, a glass film having a thickness of 150 ⁇ m or less.
- the self-luminous EL element uses an EL (electroluminescence) phenomenon, it generates little heat, is light and thin, and has a low driving voltage and power saving. Has advantages.
- the organic EL lighting has a configuration in which a transparent electrode such as ITO or IZO, an organic light emitting layer, and a back electrode made of a light reflecting metal film are sequentially laminated on a substrate having a thickness of about 0.5 to 0.7 mm. is doing.
- the substrate for this application is required to have a high gas barrier property so that moisture and the like do not permeate into the device.
- the organic EL lighting is installed in a curved portion in addition to the flat portion, and in order to be installed in the curved portion, it is required to have flexibility (flexibility).
- flexibility flexibility
- An object of the present invention is to provide a substrate material having a high gas barrier property while efficiently extracting light generated from an organic light emitting layer to the outside, and to improve light extraction efficiency and reliability of organic EL lighting or the like.
- Another object of the present invention is to provide a flexible substrate material that has a high gas barrier property and can be placed on a curved portion.
- the present inventor adopted a glass plate as a substrate material to improve the gas barrier property and to regulate the thickness and refractive index of the glass plate within a predetermined range, so that the light generated from the organic light emitting layer is the substrate. -It is difficult to reflect at the transparent electrode interface, and the light extraction efficiency of organic EL lighting or the like is found to be improved and proposed as the present invention. That is, the glass plate of the present invention has a thickness of 2 mm or less and a refractive index nd of 1.55 or more.
- the “refractive index nd” can be measured by a commercially available refractive index measuring device (for example, a refractive index measuring device KPR-200 manufactured by Calnew).
- a refractive index measuring device KPR-200 manufactured by Calnew As a measurement sample, for example, a glass plate is cut into 25 mm square by dicing, and then the glass plate is laminated in a state in which an immersion liquid having a refractive index nd is infiltrated between the glass plates, and is 25 mm ⁇ 25 mm ⁇ about 3 mm.
- a thick rectangular parallelepiped can be used.
- the glass plate is thin and takes the form of a glass film, as a measurement sample, for example, a plurality of 25 mm square glass films are cut out using a laser scriber, and then the refractive index nd is between the glass films.
- a glass film can be laminated to form a rectangular parallelepiped having a thickness of 25 mm ⁇ 25 mm ⁇ about 3 mm.
- the glass plate of the present invention preferably has a refractive index nd of 1.60 or more, a thickness of 0.7 mm, and a transmittance of 75% or more at 400 nm.
- a glass plate having a thickness of 0.7 mm can be separately prepared as a measurement sample by the method described in paragraph [0065] or the like.
- the glass plate of the present invention is preferably in the form of a glass film having a thickness of 150 ⁇ m or less. Thereby, the glass plate becomes excellent in flexibility.
- the glass plate of the present invention has a glass composition of BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + ZnO + ZrO 2 (total amount of BaO, TiO 2 , Nb 2 O 5 , La 2 O 3 , ZnO, and ZrO 2 ). It is characterized by containing ⁇ 60% by mass.
- the glass plate of the present invention has a glass composition, BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + Gd 2 O 3 + WO 3 + Ta 2 O 5 + ZrO 2 (BaO, TiO 2, Nb 2 O 5, La 2 O 3 , Gd 2 O 3 , WO 3 , Ta 2 O 5 , and ZrO 2 ) is preferably contained in an amount of 10 to 70% by mass. If it does in this way, refractive index nd can be raised, suppressing a loss of devitrification resistance.
- the glass plate of the present invention preferably contains 0 to 10% by mass (however, not including 10% by mass) of TiO 2 as a glass composition.
- TiO 2 has absorption around 310 nm. Therefore, when the TiO 2 content is 10 wt% or more, the transmittance at 400nm decreases the light extraction efficiency is likely to decrease.
- the glass plate of the present invention may contain 0 to 0.1% by mass (but not including 0.1% by mass) of Fe 2 O 3 as a glass composition.
- Fe 2 O 3 has an absorption around 230 nm. Therefore, when the content of Fe 2 O 3 is 0.1 wt% or more, the transmittance at 400nm decreases the light extraction efficiency is likely to decrease.
- the iron oxide content in the glass composition is expressed in terms of Fe 2 O 3 .
- At least one surface is an unpolished surface
- the surface roughness Ra of the unpolished surface is It is preferably less than 1 nm. If at least one surface is made into an unpolished surface, it will become difficult to destroy a glass plate. Further, if the surface roughness Ra of the unpolished surface is less than 1 nm, the quality of ITO formed on the unpolished surface is improved, so that the distribution of the electric field in the surface can be easily maintained. Therefore, uneven brightness is less likely to occur.
- the resin plate is inferior in surface smoothness, and it is difficult to improve the quality of ITO.
- “surface roughness Ra” is an arithmetic average roughness defined in JIS B0601: 2001.
- the surface roughness Ra of the other surface may be 1 nm or more.
- the surface of the other surface may be roughened so that the surface roughness is adjusted to 1 nm or more.
- the light generated from the organic light emitting layer is reflected at the glass plate-air interface due to the difference in refractive index between the glass plate and air, and is easily confined in the organic light emitting layer or the transparent electrode. As a result, the light extraction efficiency tends to decrease.
- the surface roughness Ra of the surface in contact with air to 1 nm or more by roughening treatment or the like, such a situation can be prevented and the light extraction efficiency can be easily improved.
- a glass film (film thickness of 150 ⁇ m or less) or a resin film having a surface roughness Ra of 1 nm or more and a matching refractive index is attached to the surface of at least one glass plate.
- a film having a surface roughness Ra of 1 nm or more and a matched refractive index may be formed on the surface of at least one glass plate. In this way, it becomes easy to improve the light extraction efficiency.
- the glass plate of the present invention preferably has a liquidus viscosity of 10 3.5 dPa ⁇ s or more.
- liquid phase viscosity refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.
- the “liquid phase temperature” is obtained by passing the standard sieve 30 mesh (500 ⁇ m) and putting the glass powder remaining on the 50 mesh (300 ⁇ m) into a platinum boat, and holding it in a temperature gradient furnace for 24 hours. The value which measured the temperature which precipitates.
- the higher the liquidus viscosity and the lower the liquidus temperature the better the devitrification resistance and the moldability.
- a glass plate with a high refractive index has a low liquidus viscosity and is difficult to be formed into a plate shape.
- the liquid phase viscosity is regulated to 10 3.5 dPa ⁇ s or more, it is easy to form into a plate shape.
- the glass plate of this invention is suitable as a board
- the glass plate of this invention is suitable for sealing (sealing board
- the substrate material which has high gas barrier property can be provided, and, thereby, the extraction efficiency and reliability of light, such as organic EL illumination Can be increased.
- the glass plate into the form of a thin glass film, it is possible to provide a flexible substrate material that has high gas barrier properties and can be installed on a curved portion.
- the refractive index nd is 1.55 or more, 1.58 or more, 1.60 or more, 1.62 or more, 1.65 or more, 1.68 or more, 1.70 or more, 1. It is preferably 72 or more, particularly 1.75 or more.
- the refractive index nd is less than 1.55, the probability that light is confined in the organic light emitting layer or ITO due to reflection at the ITO-glass plate interface increases, and as a result, the light extraction efficiency decreases.
- the refractive index nd is preferably 2.3 or less, 2.2 or less, 2.1 or less, particularly 2.0 or less.
- the refractive index nd can be increased by adjusting the glass composition.
- the plate thickness is preferably 2 mm or less, 1.5 mm or less, 1 mm or less, 0.7 mm or less, particularly 0.5 mm or less.
- the glass plate is preferably in the form of a thin glass film.
- the thickness of the glass plate is preferably 200 ⁇ m or less, particularly preferably 150 ⁇ m or less.
- the plate thickness of the glass plate is 100 ⁇ m or less, 80 ⁇ m or less, particularly 50 ⁇ m or less, more preferably 30 ⁇ m or less, 20 ⁇ m or less, and most preferably 10 ⁇ m or less. The smaller the plate thickness, the easier it is to reduce the weight of the device and increase the flexibility of the glass plate.
- the glass plate tends to be damaged.
- the thickness is preferably 1 ⁇ m or more, 3 ⁇ m or more, particularly 5 ⁇ m or more.
- the minimum radius of curvature that the glass plate can take is preferably 200 mm or less, 150 mm or less, 100 mm or less, 50 mm or less, particularly 30 mm or less. Note that the smaller the minimum radius of curvature that can be taken, the better the flexibility, so the degree of freedom of installation of organic EL lighting or the like increases.
- the transmittance at a thickness of 0.7 mm and 400 nm is preferably 75% or more, 78% or more, 80% or more, 85% or more, particularly 90% or more.
- the glass plate of the present invention preferably has a high transmittance over the entire visible region. If the transmittance at 400 nm is restricted to the above range, the transmittance in the entire visible region can also be increased.
- permeability in 400 nm can be improved if the glass composition, especially the content of Fe 2 O 3 and TiO 2 are adjusted.
- the glass plate of the present invention has a glass composition of BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + Gd 2 O 3 + WO 3 + Ta 2 O 5 + ZrO 2 of 10 to 70% by mass, 10 to 60% by mass, 30 to 70% by mass. % Content is preferable.
- the content of BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + Gd 2 O 3 + WO 3 + Ta 2 O 5 + ZrO 2 increases, the balance of the glass composition is impaired, and the glass tends to devitrify.
- the upper limit of the content of BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + Gd 2 O 3 + WO 3 + Ta 2 O 5 + ZrO 2 is preferably 65% by mass or less, particularly preferably 60% by mass or less and 58% by mass or less.
- the content of BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + Gd 2 O 3 + WO 3 + Ta 2 O 5 + ZrO 2 is decreased, it is difficult to increase the refractive index nd while suppressing a decrease in devitrification resistance. .
- the lower limit of the content of BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + Gd 2 O 3 + WO 3 + Ta 2 O 5 + ZrO 2 is 20% by mass, 30% by mass, 35% by mass, 40% by mass, It is preferably 45% by mass or more, particularly 50% by mass or more.
- TiO 2 , Nb 2 O 5 , La 2 O 3 , Gd 2 O 3 , WO 3 , Ta 2 O 5 , ZrO 2 two or more, preferably three or more, more preferably four or more. When mixed and added, it becomes easier to enjoy the above effect.
- BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + ZnO + ZrO 2 is a component that increases the refractive index nd while suppressing a decrease in devitrification resistance.
- the content of BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + ZnO + ZrO 2 increases, the balance of the glass composition is impaired, and the glass tends to devitrify. Therefore, the content of BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + ZnO + ZrO 2 is preferably 70% or less, 60% or less, and particularly preferably 58% or less.
- BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + ZnO + ZrO 2 is a component that increases the refractive index nd while suppressing a decrease in devitrification resistance. Therefore, the content of BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + ZnO + ZrO 2 is preferably 10% or more, 20% or more, 30% or more, 35% or more, 40% or more, 45% or more, and particularly preferably 50% or more.
- the above-described effect can be further easily obtained.
- the glass plate of the present invention has a glass composition of TiO 2 of 0 to 10% by mass (excluding 10% by mass), 0 to 9.5% by mass, 0 to 8% by mass, particularly 0 to 7% by mass. It is preferable to contain.
- the TiO 2 content is preferably 1% by mass or more, 2% by mass or more, and particularly preferably 3% by mass or more.
- the glass plate of the present invention has a glass composition of Fe 2 O 3 of 0 to 0.1% by mass (however, 0.1% by mass is not included), 0 to 0.05% by mass, 0 to 0.03% by mass. %, 0 to 0.02 mass%, 0 to 0.01 mass%, 0 to 0.005 mass%.
- the transmittance at 400 nm decreases, so that the light extraction efficiency tends to decrease.
- the content of Fe 2 O 3 is preferably 0.001% by mass or more, particularly preferably 0.004% by mass or more.
- commercially available glass plate usually contains Fe 2 O 3 more than 0.05 wt% in the glass composition.
- At least one surface is an unpolished surface.
- the theoretical strength of glass is inherently very high, but breakage often occurs even at a stress much lower than the theoretical strength. The reason is that a small defect called Griffith flow is generated on the surface of the glass in a post-molding process such as a polishing process. Therefore, if at least one surface of the glass plate is an unpolished surface, it is difficult to impair the original mechanical strength of the glass, and as a result, the glass plate is difficult to break. Moreover, if both surfaces of a glass plate are made into an unpolished surface, it will become difficult to destroy a glass plate further, and the manufacturing cost of a glass plate can be reduced because the grinding
- polishing process is abbreviate
- the surface roughness Ra of the unpolished surface is preferably 1 nm or less, 5 mm or less, 3 mm or less, particularly 2 mm or less.
- the surface roughness Ra of the unpolished surface is 1 nm or more, the quality of ITO formed on the unpolished surface is lowered, and uneven brightness tends to occur in the surface.
- the glass plate of the present invention may have a surface roughness Ra of the other surface of 1 nm or more, and in particular, the surface roughness is adjusted to 1 nm or more by being subjected to a roughening treatment. There may be.
- the surface roughness Ra of the other surface is preferably 2 nm or more, 3 nm or more, and particularly preferably 5 nm or more. If the other roughened surface is brought into contact with the air such as organic EL lighting, the roughened surface has a non-reflective structure, so that the light generated in the organic light emitting layer can enter the organic light emitting layer. As a result, the light extraction efficiency can be increased.
- the surface roughening treatment examples include etching with HF or the like, polishing, sand blasting, repress (including nanoimprint), atmospheric pressure plasma process, and the like.
- the surface roughness Ra of the other surface is 20 ⁇ m or more, light is scattered on the other surface, and conversely, the light extraction efficiency may be reduced.
- the surface roughness Ra of the other surface is preferably 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, 5 ⁇ m or less, 3 ⁇ m or less, and particularly preferably 2 ⁇ m or less.
- the other surface of the film may be attached or formed into a film.
- corrugated shape should just adjust the space
- the other surface of the glass plate can be uniformly roughened while maintaining the surface state of one surface of the glass plate.
- a gas containing F for example, SF 6 , CF 4
- the plasma containing HF type gas can be generated and the surface of a glass plate can be efficiently roughened by this plasma.
- non-reflective structure for example, surface roughness Ra1nm or more of one surface
- molding the same effect can be enjoyed even if it does not roughen.
- the glass plate of the present invention is preferably formed by an overflow downdraw method.
- the “overflow down draw method” is also referred to as a fusion method, in which molten glass overflows from both sides of a heat-resistant cage-like structure, and the overflowing molten glass is joined at the lower end of the cage-like structure.
- this is a method of producing a glass plate by drawing downward. In this way, it is possible to form a glass plate that is unpolished and has good surface quality. The reason is that, in the case of the overflow downdraw method, the surface to be the surface of the glass plate is not in contact with the bowl-like refractory and is molded in a free surface state.
- the structure and material of the bowl-shaped structure are not particularly limited as long as desired dimensions and surface quality can be realized.
- the method of applying force with respect to a glass plate will not be specifically limited if a desired dimension and surface quality are realizable.
- a method of rotating and stretching a heat-resistant roll having a sufficiently large width in contact with the glass plate may be adopted, or a plurality of pairs of heat-resistant rolls may be used only in the vicinity of the end face of the glass plate. You may employ
- the glass plate of the present invention is preferably formed by a slot down draw method.
- the slot down draw method can increase the dimensional accuracy of the glass plate in the same manner as the overflow down draw method.
- the surface of the glass plate can be roughened by changing the shape of the slot.
- various methods can be employed as the glass plate forming method of the present invention.
- a float method, a rollout method, a redraw method, or the like can be employed.
- the liquidus temperature is preferably 1150 ° C. or lower, 1110 ° C. or lower, 1090 ° C. or lower, 1070 ° C. or lower, 1050 ° C. or lower, 1020 ° C. or lower, 1000 ° C. or lower, 980 ° C. or lower, particularly 960 ° C. or lower.
- the liquid phase viscosity is 10 3.5 dPa ⁇ s or more, 10 3.8 dPa ⁇ s or more, 10 4.0 dPa ⁇ s or more, 10 4.3 dPa ⁇ s or more, 10 4.5 dPa ⁇ s or more.
- the density is 5 g / cm 3 or less, 4.8 g / cm 3 or less, 4.5 g / cm 3 or less, 4.3 g / cm 3 or less, 3.7 g / cm 3 or less, 3.6 g. / Cm 3 or less, 3.4 g / cm 3 or less, 3.3 g / cm 3 or less, and particularly preferably 3.0 g / cm 3 or less.
- density refers to a value measured by the well-known Archimedes method.
- 10 2.5 dPa ⁇ Temperature in s is 1350 ° C. or less, 1300 ° C. or less, 1270 ° C. or less, particularly preferably 1250 ° C. or less.
- “temperature at 10 2.5 dPa ⁇ s” refers to a value measured by a platinum ball pulling method.
- the thermal expansion coefficient is 50 ⁇ 10 ⁇ 7 / ° C. to 120 ⁇ 10 ⁇ 7 / ° C., 60 ⁇ 10 ⁇ 7 / ° C. to 120 ⁇ 10 ⁇ 7 / ° C., 70 ⁇ 10 ⁇ 7 / ° C. 110 ⁇ 10 ⁇ 7 / ° C., 70 ⁇ 10 ⁇ 7 / ° C. to 100 ⁇ 10 ⁇ 7 / ° C., particularly 70 ⁇ 10 ⁇ 7 / ° C. to 95 ⁇ 10 ⁇ 7 / ° C. are preferable.
- thermal expansion coefficient refers to an average value measured by a dilatometer in a temperature range of 30 to 380 ° C.
- the water vapor permeability is 1 g / (m 2 ⁇ day) or less, 0.1 g / (m 2 ⁇ day) or less, 0.01 g / in an environment of a temperature of 40 ° C. and a humidity of 90%.
- (m 2 ⁇ day) or less 0.001 g / (m 2 ⁇ day) or less, 0.0001 g / (m 2 ⁇ day) or less, 0.00001 / (m 2 ⁇ day) or less, 0.000001g / (m 2 ⁇ day) or less, and particularly preferably 0.0000001 g / (m 2 ⁇ day) or less. If it does in this way, it will become easy to prevent characteristic deterioration, such as an organic light emitting layer, and it will become easy to improve reliability, such as organic EL illumination.
- the oxygen permeability is 1 cc / (m 2 ⁇ day) or less, 0.1 cc / (m 2 ⁇ day) or less, 0.01 cc / in an environment of a temperature of 40 ° C. and a humidity of 90%.
- (m 2 ⁇ day) or less 0.001 cc / (m 2 ⁇ day) or less, 0.0001 cc / (m 2 ⁇ day) or less, 0.00001 cc / (m 2 ⁇ day) or less, 0.000001 cc / (m 2 ⁇ day) or less, particularly preferably 0.0000001 cc / (m 2 ⁇ day) or less. If it does in this way, it will become easy to prevent characteristic deterioration, such as an organic light emitting layer, and it will become easy to improve reliability, such as organic EL illumination.
- the glass plate of the present invention has a glass composition of SiO 2 0 to 55%, Al 2 O 3 0 to 10%, B 2 O 3 0 to 20%, MgO + CaO + SrO (a combination of MgO, CaO, and SrO).
- Amount) 0 to 25%, BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + Gd 2 O 3 + WO 3 + Ta 2 O 5 + ZrO 2 (or BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + ZnO + ZrO 2 ) 10% Fe 2 O 3 is preferably contained in an amount of 0 to 0.1% (but not 0.1%).
- the reason for limiting the glass composition range as described above will be described below. In the description of the glass composition range below,% represents mass%.
- the content of SiO 2 is 0 to 55%.
- the content of SiO 2 is preferably 50% or less, 45% or less, 42% or less, 40% or less, 38% or less, particularly 35% or less.
- the content of SiO 2 is preferably 2% or more, 5% or more, 7% or more, particularly 10% or more.
- the content of Al 2 O 3 is 0 to 10%.
- the content of Al 2 O 3 is more than 10%, devitrified crystals are likely to be deposited on the glass, and the liquid phase viscosity is likely to be lowered. Further, when the content of Al 2 O 3 is reduced, the balance of the glass composition is impaired, liable glass devitrified. Therefore, the content of Al 2 O 3 0.1 to 8 percent, 0.5 to 6%, particularly 1-5% is preferred.
- the content of B 2 O 3 is 0 to 20%.
- the content of B 2 O 3 is preferably 17% or less, 15% or less, and particularly preferably 11% or less.
- B 2 O 3 may be added in an amount of 1% or more, 2% or more, 3% or more, particularly 5% or more.
- MgO + CaO + SrO is a component that increases the liquid phase viscosity while increasing the refractive index nd, and its content is 0 to 25%.
- the content of MgO + CaO + SrO is 22% or less, 20% or less, 16% or less, and particularly 13% or less.
- the content of MgO + CaO + SrO is preferably 3% or more, 5% or more, and particularly preferably 8% or more.
- MgO is a component that increases the refractive index nd, Young's modulus, and strain point, and lowers the high-temperature viscosity. However, when added in a large amount, the liquidus temperature increases, devitrification resistance decreases, and density and thermal expansion increase. The coefficient is too high. Therefore, the content of MgO is preferably 10% or less, 8% or less, 5% or less, 3% or less, 2% or less, 1.5% or less, 1% or less, particularly preferably 0.5% or less.
- the CaO content is preferably 0 to 15%.
- the CaO content increases, the refractive index nd, density, and thermal expansion coefficient tend to increase.
- the content exceeds 15%, the balance of the glass composition is impaired and the glass tends to devitrify. Become. Therefore, the CaO content is preferably 12% or less, 10% or less, 9% or less, and particularly preferably 8.5% or less.
- the CaO content is preferably 0.5% or more, 1% or more, 2% or more, 3% or more, and particularly preferably 5% or more.
- the SrO content is preferably 0 to 15%. If the SrO content increases, the refractive index nd, density, and thermal expansion coefficient tend to increase. However, if the SrO content exceeds 15%, the balance of the glass composition is impaired and the glass tends to devitrify. Become. Therefore, the SrO content is preferably 12% or less, 10% or less, 9% or less, and particularly preferably 8.5% or less. On the other hand, when the content of SrO decreases, the meltability and the refractive index nd tend to decrease. Therefore, the content of SrO is preferably 0.5% or more, 1% or more, 2% or more, 3% or more, particularly 3.5% or more.
- BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + Gd 2 O 3 + WO 3 + Ta 2 O 5 + ZrO 2 is a component that increases the refractive index nd while suppressing a decrease in devitrification resistance.
- BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + Gd 2 O 3 + WO 3 + Ta 2 O 5 + preferred content range of ZrO 2 such as are described above.
- BaO is a component having the greatest effect of increasing the refractive index nd without extremely reducing the viscosity of the glass among alkaline earth metal oxides, and its content is preferably 0 to 40%.
- the content of BaO increases, the refractive index nd, density, and thermal expansion coefficient tend to increase.
- the content exceeds 40% the balance of the glass composition is impaired, and the glass tends to devitrify. Therefore, the content of BaO is preferably 35% or less.
- the content of BaO is preferably 0.5% or more, 1% or more, 2% or more, 5% or more, 10% or more, 15% or more, 20% or more, particularly 25% or more.
- TiO 2 is a component that increases the refractive index nd, but is also a component that decreases the transmittance at 400 nm.
- the preferred content range, etc. of TiO 2 are as described above.
- Nb 2 O 5 , La 2 O 3 , Gd 2 O 3 , WO 3 , Ta 2 O 5 , and ZrO 2 are components that increase the refractive index nd. Therefore, the contents of Nb 2 O 5 , La 2 O 3 , Gd 2 O 3 , WO 3 , Ta 2 O 5 and ZrO 2 are each preferably 1% or more, particularly preferably 3% or more. In particular, the content of La 2 O 3 is preferably 4% or more. However, when the content of Nb 2 O 5 , La 2 O 3 , Gd 2 O 3 , WO 3 , Ta 2 O 5 , ZrO 2 increases, the density and thermal expansion coefficient increase, and the balance of the glass composition is impaired.
- the devitrification resistance may be extremely lowered. Therefore, the content of Nb 2 O 5 , La 2 O 3 , Gd 2 O 3 , WO 3 , Ta 2 O 5 , ZrO 2 is 35% or less, 30% or less, 25% or less, 20% or less, 15 % Or less, particularly preferably 12% or less.
- the value of the mass ratio TiO 2 / La 2 O 3 is preferably 0.01 to 2.45.
- Fe 2 O 3 is a component that decreases the transmittance in the ultraviolet region.
- the preferred content range, such as the Fe 2 O 3 is as defined above.
- ZnO may be contained.
- the content of ZnO is preferably 0 to 15%.
- the ZnO content increases, the refractive index nd, density, and thermal expansion coefficient tend to increase.
- the content exceeds 15%, the balance of the glass composition is impaired and the glass tends to devitrify. Become. Therefore, the ZnO content is preferably 12% or less, 10% or less, 9% or less, and particularly preferably 8.5% or less.
- the content of ZnO decreases, the meltability, Young's modulus, and refractive index nd tend to decrease.
- the ZnO content is preferably 0.5% or more, 1% or more, 2% or more, 3% or more, and particularly preferably 5% or more.
- the content of MgO + CaO + SrO + ZnO is preferably 0 to 25%.
- the content of MgO + CaO + SrO + ZnO is preferably 22% or less, 20% or less, 16% or less, and particularly preferably 13% or less.
- the content of MgO + CaO + SrO + ZnO decreases, it becomes difficult to increase the refractive index nd.
- the content of MgO + CaO + SrO + ZnO is preferably 3% or more, 5% or more, and particularly preferably 8% or more.
- BaO + TiO 2 + Nb 2 O 5 + La 2 O 3 + ZnO + ZrO 2 is a component that increases the refractive index nd while suppressing a decrease in devitrification resistance.
- BaO + preferred content range, etc. of TiO 2 + Nb 2 O 5 + La 2 O 3 + ZnO + ZrO 2 are as described above.
- the following components can be added up to 30%.
- Li 2 O + Na 2 O + K 2 O (total amount of Li 2 O, Na 2 O, and K 2 O) is a component that decreases the viscosity of the glass and adjusts the thermal expansion coefficient. If added, the viscosity of the glass is too low, making it difficult to increase the liquid phase viscosity. Therefore, the content of Li 2 O + Na 2 O + K 2 O is preferably 15% or less, 10% or less, 5% or less, 2% or less, 1% or less, 0.5% or less, and particularly preferably 0.1% or less.
- Bi 2 O 3 and Y 2 O 3 are components that increase the refractive index nd.
- the contents of Bi 2 O 3 and Y 2 O 3 are preferably 0 to 30%, 0 to 25%, 0 to 20%, 1 to 15%, particularly 3 to 12%, respectively.
- PbO also has an effect of increasing the refractive index, but it is desirable not to contain it from an environmental viewpoint.
- As a fining agent 0 to 3% of one or more selected from the group consisting of As 2 O 3 , Sb 2 O 3 , CeO 2 , SnO 2 , F, Cl, and SO 3 can be added.
- As 2 O 3 , Sb 2 O 3 , F, especially As 2 O 3 , Sb 2 O 3 should be refrained from use as much as possible from an environmental point of view, and each content is less than 0.1% Is preferred.
- SnO 2 , Cl, and SO 3 are preferable as the fining agent.
- the content of SnO 2 + Cl + SO 3 (total amount of SnO 2 , Cl, and SO 3 ) is preferably 0.001 to 1%, 0.01 to 0.5%, and particularly preferably 0.01 to 0.3%.
- SnO 2 is configured to act as a clarifying agent has the effect (the effect of changing the valence of Fe to trivalent from divalent) interfere with the absorption of light Fe 2 O 3.
- the SnO 2 content is preferably 0 to 1%, 0 to 0.5%, particularly preferably 0.01 to 0.4%. Incidentally, when the content of SnO 2 increases, devitrification resistance is liable to decrease.
- the glass plate of the present invention can be produced by preparing a glass raw material so as to have a desired glass composition, and then melting the glass raw material and then forming the molten glass into a plate shape.
- Tables 1 and 2 show examples of the present invention (sample Nos. 1 to 11).
- glass raw materials were prepared so as to have the glass composition described in the table, and then supplied to a glass melting furnace and melted at 1300 to 1500 ° C.
- the molten glass was supplied to an overflow downdraw molding apparatus and molded so as to have a width of 1000 mm and a plate thickness of 0.5 mm.
- the surface roughness Ra of the glass plate was 0.2 nm on both sides.
- the refractive index nd is a value measured with a refractive index measuring device KPR-200 manufactured by Carnew. Using a commercially available dicer as a measurement sample, the glass plates were cut into 25 mm squares, and then the glass plates were laminated with the immersion liquid infiltrating with a refractive index nd between the glass plates, 25 mm ⁇ 25 mm X A rectangular parallelepiped having a thickness of about 3 mm was used.
- the transmittance T at 400 nm is a value measured with UV-3100 manufactured by Shimadzu Corporation.
- a 0.7 mm thick glass plate produced by the method described in paragraph [0065] was used.
- the density ⁇ is a value measured by a known Archimedes method.
- the thermal expansion coefficient ⁇ is an average value measured with a dilatometer in a temperature range of 30 to 380 ° C.
- a measurement sample a plurality of glass plates were put into a platinum boat, remelted at 1400 to 1450 ° C. for 30 minutes, and then processed into a cylindrical shape of ⁇ 5 mm ⁇ 20 mm (having R processing on the end face).
- strain point Ps and the annealing point Ta are values measured based on the method of ASTM C336-71.
- the softening point Ts is a value measured based on the method of ASTM C338-93.
- the temperature at 10 4.0 dPa ⁇ s, 10 3.0 dPa ⁇ s, 10 2.5 dPa ⁇ s, 10 2.0 dPa ⁇ s is a value measured by a platinum ball pulling method.
- the liquidus temperature TL is a temperature at which crystals pass through a standard sieve 30 mesh (500 ⁇ m) and the glass powder remaining on 50 mesh (300 ⁇ m) is placed in a platinum boat and then kept in a temperature gradient furnace for 24 hours to crystallize. Is a measured value.
- the liquid phase viscosity log ⁇ TL is a value obtained by measuring the viscosity of the glass at the liquid phase temperature by a platinum ball pulling method.
- Tables 3 to 10 show examples of the present invention (sample Nos. 12 to 78).
- glass raw materials were prepared so as to have the glass composition described in the table, and then supplied to a glass melting furnace and melted at 1500 to 1600 ° C.
- the molten glass was supplied to an overflow downdraw molding apparatus and molded so as to have a width of 1000 mm and a plate thickness of 30 ⁇ m.
- the average surface roughness Ra of the surface of the glass plate (glass film) was 0.2 nm on both sides.
- Refractive index nd is determined by first cutting 100 pieces of 25 mm square glass films using a laser scriber, and then laminating glass films with an immersion liquid in which refractive index nd is matched between the glass films. This is a value calculated by using a refractometer KPR-200 manufactured by Kalnew after preparing a rectangular parallelepiped measurement sample of ⁇ 25 mm ⁇ about 3 mm thickness.
- the density ⁇ is the strain point Ps, the annealing point Ta, the softening point Ts, the temperature at 10 4.0 dPa ⁇ s, 10 3.0 dPa ⁇ s, 10 2.5 dPa ⁇ s, and the thermal expansion coefficient ⁇ is the liquid
- the phase temperature TL and the liquid phase viscosity log ⁇ TL are values measured using the methods described above.
- sample no When a glass film of 12 to 78 was roughened on one surface by an atmospheric pressure plasma process using CF 4 gas, the average surface roughness Ra of the surface was changed from 2 to 5 nm.
Abstract
Description
Claims (17)
- 板厚が2mm以下であり、且つ屈折率ndが1.55以上であることを特徴とするガラス板。
- 屈折率ndが1.60以上であり、且つ厚み0.7mm、400nmにおける透過率が75%以上であることを特徴とする請求項1に記載のガラス板。
- 板厚が150μm以下であることを特徴とする請求項1又は2に記載のガラス板。
- ガラス組成として、BaO+TiO2+Nb2O5+La2O3+ZnO+ZrO2を10~60質量%含有することを特徴とする請求項1~3のいずれかに記載のガラス板。
- ガラス組成として、BaO+TiO2+Nb2O5+La2O3+Gd2O3+WO3+Ta2O5+ZrO2を10~70質量%含有することを特徴とする請求項1~3のいずれかに記載のガラス板。
- TiO2を0~10質量%含有することを特徴とする請求項1~5のいずれかに記載のガラス板。
- ガラス組成として、Fe2O3を0~0.1質量%含有することを特徴とする請求項1~6のいずれかに記載のガラス板。
- 少なくとも一方の表面が未研磨面であり、且つ該未研磨面の表面粗さRaが1nm未満であることを特徴とする請求項1~7のいずれかに記載のガラス板。
- 他方の表面の表面粗さRaが1nm以上であることを特徴とする請求項8に記載のガラス板。
- 前記他方の表面に粗面化処理が施されていることを特徴とする請求項9に記載のガラス板。
- 少なくとも一方のガラス板の表面に、表面の表面粗さRaが1nm以上であり、且つ屈折率が整合したガラスフィルムが貼り付けられてなることを特徴とする請求項1~8のいずれかに記載のガラス板。
- 少なくとも一方のガラス板の表面に、表面の表面粗さRaが1nm以上であり、且つ屈折率が整合した膜が成膜されてなることを特徴とする請求項1~8のいずれかに記載のガラス板。
- 液相粘度が103.5dPa・s以上であることを特徴とする請求項1~12のいずれかに記載のガラス板。
- 照明デバイス又は有機ELデバイスの基板に用いることを特徴とする請求項1~13のいずれかに記載のガラス板。
- 照明デバイス又は有機ELデバイスの封止に用いることを特徴とする請求項1~13のいずれかに記載のガラス板。
- 請求項1~15のいずれかに記載のガラス板を備えていることを特徴とする照明デバイス。
- 請求項1~16のいずれかに記載のガラス板を備えていることを特徴とする有機ELデバイス。
Priority Applications (7)
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CN2010800233247A CN102448898A (zh) | 2009-07-08 | 2010-07-07 | 玻璃板 |
KR1020137033725A KR101452882B1 (ko) | 2009-07-08 | 2010-07-07 | 유리판 |
KR1020137005566A KR101276593B1 (ko) | 2009-07-08 | 2010-07-07 | 유리판 |
KR1020117023954A KR101393474B1 (ko) | 2009-07-08 | 2010-07-07 | 유리판 |
US13/382,650 US9670089B2 (en) | 2009-07-08 | 2010-07-07 | Glass sheet |
EP10797155.8A EP2452926B1 (en) | 2009-07-08 | 2010-07-07 | Glass sheet |
KR1020137005568A KR101276587B1 (ko) | 2009-07-08 | 2010-07-07 | 유리판 |
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