WO2014129345A1 - Glass substrate - Google Patents

Glass substrate Download PDF

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Publication number
WO2014129345A1
WO2014129345A1 PCT/JP2014/053030 JP2014053030W WO2014129345A1 WO 2014129345 A1 WO2014129345 A1 WO 2014129345A1 JP 2014053030 W JP2014053030 W JP 2014053030W WO 2014129345 A1 WO2014129345 A1 WO 2014129345A1
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WO
WIPO (PCT)
Prior art keywords
glass substrate
concave portion
roughened surface
curved concave
light
Prior art date
Application number
PCT/JP2014/053030
Other languages
French (fr)
Japanese (ja)
Inventor
篤 虫明
智基 柳瀬
尚史 上坂
Original Assignee
日本電気硝子株式会社
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Filing date
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Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Publication of WO2014129345A1 publication Critical patent/WO2014129345A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • 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
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/08—Glass having a rough surface
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a glass substrate, and specifically to a glass substrate suitable for an organic EL device such as organic EL lighting.
  • the light source for illumination is divided into a “directional light source” that illuminates a limited area and a “diffuse light source” that illuminates a wide area.
  • LED lighting corresponds to a “directional light source” and is being adopted as an alternative to an incandescent bulb.
  • an alternative light source for a fluorescent lamp corresponding to a “diffusion light source” is desired, and organic EL (electroluminescence) illumination is a promising candidate.
  • FIG. 1 is a cross-sectional view showing the concept of the organic EL lighting 1.
  • the organic EL lighting 1 includes a glass substrate 11, a transparent conductive film as an anode 12, an organic EL layer 13 including a single or a plurality of light emitting layers made of an organic compound exhibiting electroluminescence that emits light by current injection, a cathode 14.
  • a hole injection layer, a hole transport layer, an electron transport A laminated structure with a layer, an electron injection layer and the like is formed.
  • the organic EL layer 13 having such a laminated structure is disposed between the anode 12 and the cathode 14 and an electric field is applied to the anode 12 and the cathode 14, holes injected from the transparent electrode as the anode 12 and the cathode The electrons injected from 14 recombine in the light emitting layer, and the light emission center is excited by the recombination energy to emit light.
  • Organic EL elements are being studied for use in mobile phones and displays, and some have already been put into practical use.
  • the organic EL element has a luminous efficiency equivalent to that of a thin television such as a liquid crystal display or a plasma display.
  • the conventional organic EL device has a large difference in refractive index between the transparent electrode film and the organic EL layer and the glass substrate, so that the light emitted from the organic EL layer is transmitted between the transparent electrode film and the organic EL layer and the glass substrate. There is a problem that light is reflected at the interface and the light extraction efficiency is lowered.
  • the light extraction efficiency is lowered due to the difference in refractive index between the glass substrate and air. That is, when the light radiated from the organic EL layer travels from the inside of the glass substrate to the air, it is reflected at the interface between the glass substrate and the air and is confined within the glass substrate.
  • n d refractive index
  • the proportion of light extracted outside is 20 to 20% of the light emitted from the organic EL layer. It is about 25%.
  • thermosetting resin such as polyimide
  • the present invention has been made in view of the above problems, and the technical problem thereof is a glass substrate that can efficiently extract light to the outside without sticking a transparent resin sheet to the surface of the glass substrate. Is to invent.
  • the present inventors have found that the above technical problem can be solved by regulating the refractive index of the glass substrate within a predetermined range and regulating the surface shape of the glass substrate. It is what we propose. That is, the glass substrate of the present invention is a glass substrate is 1.50 or more refractive index n d, has a roughened surface on at least one surface, it has a curved recess on the crude surface of surface It is characterized by.
  • the “refractive index n d ” can be measured by a commercially available refractive index measuring device (for example, a refractive index measuring device KPR-2000 manufactured by Calnew).
  • a glass substrate is cut into 25 mm square by dicing, and then the glass substrate is laminated in a state in which an immersion liquid having a refractive index n d is infiltrated between the glass substrates, and is 25 mm ⁇ 25 mm ⁇
  • a rectangular parallelepiped having a thickness of about 3 mm can be used.
  • “Curved concave portion” refers to a recess other than the crushed shape, for example, a smooth recess formed by chemical treatment.
  • the dents are overlapped with each other, the dents are evaluated on the assumption that the dents are not overlapped.
  • the ratio of the curved concave portion to the entire roughened surface is 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, or 70% or more by area ratio. In particular, 80% or more is preferable.
  • the glass substrate of the present invention has a refractive index n d of 1.50 or more. In this way, since the difference in refractive index between the organic EL layer and the glass substrate is reduced, light confined in the organic EL layer due to total reflection can be reduced. As a result, the light extraction efficiency of the organic EL device can be increased.
  • the glass substrate of the present invention has a roughened surface on at least one surface, and has a curved concave portion on the roughened surface.
  • a pyramid shape, a hemispherical convex lens shape, and the like have been proposed, but at present, it is unclear which shape is optimal. Therefore, the inventors have made a detailed investigation to form a curved concave portion on the roughened surface, so that the light in the glass substrate can be accurately scattered, and as a result, is confined in the glass substrate. It has been found that light is reduced and the light extraction efficiency of the organic EL device is improved. Furthermore, it has been found that when a curved concave portion is formed on the roughened surface, the in-plane strength of the glass substrate is improved.
  • the glass substrate of the present invention has a curved concave portion formed aperiodically on the roughened surface. In this way, the viewing angle dependency due to light interference is suppressed. As a result, even when the organic EL illumination is observed at different angles, the color change can be suppressed.
  • the curved concave portion is formed by performing chemical treatment after physical treatment.
  • a roughened surface can be uniformly formed in a short time on the surface of a large-area glass substrate by physical treatment.
  • a curved recess can be formed on the roughened surface by subsequent chemical treatment.
  • the physical treatment of the glass substrate of the present invention is preferably a sandblast treatment.
  • a roughened surface can be uniformly formed in a short time on the surface of a large glass substrate.
  • the chemical treatment of the glass substrate of the present invention is chemical treatment with an acid. If it does in this way, a curved-surface-shaped recessed part can be efficiently formed in a rough surface.
  • the glass substrate of the present invention preferably has an average radius of the curved concave portion of 0.1 to 100 ⁇ m. If it does in this way, it will become possible to scatter the light in a glass substrate efficiently.
  • Average radius of curved concave portion refers to an average distance from the center of the depression.
  • the depth of the curved concave portion is preferably 0.1 to 100 ⁇ m. If it does in this way, it will become possible to scatter the light in a glass substrate efficiently.
  • (depth of curved concave portion) / (average radius of curved concave portion) is 0.01 to 10. If it does in this way, it will become possible to scatter the light in a glass substrate efficiently.
  • the glass substrate of the present invention preferably has a smooth surface on one surface, and the smooth surface has a surface roughness Rt of 10 nm or less. If it does in this way, the quality of a transparent electrode film can be raised.
  • the “surface roughness Rt” is a value measured by a method based on JIS R0601 (2001).
  • the glass substrate of the present invention preferably contains 30 to 70% by mass of SiO 2 as a glass composition.
  • the glass substrate of the present invention preferably has a property that light traveling from the inside of the glass substrate into the air is extracted from the roughened surface into the air without being totally reflected even at a critical angle or more. . In this way, the light confined in the glass substrate is reduced, and the light extraction efficiency is improved.
  • the glass substrate of the present invention is preferably used for an organic EL device.
  • the glass substrate of the present invention is preferably used for illumination.
  • Sample No. 1 is an electron micrograph of a roughened surface of FIG.
  • Sample No. 2 is an electron micrograph of the roughened surface of No. 2
  • Sample No. 3 is an electron micrograph of a roughened surface 3.
  • Sample No. 4 is an electron micrograph of 4 roughened surface.
  • Sample No. 5 is an electron micrograph of a roughened surface of No. 5.
  • Sample No. 6 is an electron micrograph of a roughened surface of No. 6
  • Sample No. 7 is an electron micrograph of a roughened surface of No. 7
  • Sample No. 8 is an electron micrograph of a roughened surface of FIG.
  • Sample No. 9 is an electron micrograph of a roughened surface of No. 9; Sample No.
  • Sample No. 10 is an electron micrograph of 10 roughened surfaces.
  • Sample No. 11 is an electron micrograph of 11 roughened surfaces.
  • Sample No. 12 is an electron micrograph of 12 roughened surfaces.
  • Sample No. 13 is an electron micrograph of 13 roughened surfaces.
  • Sample No. 14 is an electron micrograph of 14 roughened surfaces.
  • Sample No. 15 is an electron micrograph of 15 roughened surfaces.
  • Sample No. 16 is an electron micrograph of 16 roughened surfaces. It is a schematic sectional drawing which shows typically the average radius and depth of a curved-surface-shaped recessed part.
  • Sample No. 8 is data obtained by measuring a cross-sectional shape of a roughened surface of 8 using a surf coder. It is a schematic sectional drawing which shows the evaluation method of a light-scattering function.
  • the refractive index nd is 1.50 or more, preferably 1.51 or more, 1.52 or more, 1.54 or more, 1.56 or more, or 1.58 or more, particularly preferably. Is 1.60 or more.
  • the refractive index n d is less than 1.50, the reflectance at the interface between the organic EL layer and the transparent conductive film-glass substrate increases, and light cannot be extracted efficiently.
  • the refractive index n d exceeds 2.3, the reflectance at the air-glass substrate interface increases, and the light extraction efficiency can be improved even if a roughened surface is formed on the surface of the glass substrate. It becomes difficult. Therefore, the refractive index n d is preferably 2.3 or less, 2.2 or less, 2.1 or less, 2.0 or less, or 1.9 or less, particularly preferably 1.75 or less.
  • Examples of the method for forming the roughened surface include chemical treatment and physical treatment.
  • physical treatment was performed in order to facilitate the formation of a curved concave portion on the roughened surface. It is preferable to perform chemical treatment later. If a roughened surface is formed only on the surface of the glass substrate by physical treatment, it becomes difficult to form a curved concave portion on the roughened surface, and the top end portion of the curved concave portion is sharpened. The in-plane strength of the steel tends to decrease.
  • sandblast treatment is preferable. In this way, a roughened surface can be uniformly formed in a short time on the surface of a large glass substrate.
  • the particle size of the blasting material used in the sandblasting treatment is preferably # 50 to # 4000, # 70 to # 1500, particularly # 100 to # 1000.
  • the particle size of the blast material is too fine, it becomes difficult to form a roughened surface.
  • the particle size of the blast material is too coarse, the in-plane strength of the glass substrate tends to decrease.
  • Polishing is also preferable as the physical treatment. In this way, a roughened surface can be uniformly formed in a short time on the surface of a large glass substrate.
  • the particle size of the abrasive used in the polishing treatment is preferably # 220 to # 3000, # 300 to # 2000, or # 400 to # 1500, and particularly preferably # 400 to # 1200.
  • the grain size of the abrasive is too fine, it becomes difficult to form a roughened surface.
  • the abrasive particle size is too coarse, the in-plane strength of the glass substrate tends to decrease.
  • the chemical treatment a chemical treatment with an acid is preferable. If it does in this way, a curved-surface-shaped recessed part can be efficiently formed in a rough surface.
  • the chemical solution preferably contains one or more selected from the group consisting of HF, HCl, H 2 SO 4 , HNO 3 , NH 4 F, NaOH, and NH 4 HF 2 . These chemical solutions have good reactivity with the glass substrate and can efficiently form curved concave portions on the roughened surface. These chemical solutions are preferably used at a temperature of 10 to 40 ° C. or 15 to 35 ° C., particularly preferably at a temperature of 20 to 30 ° C.
  • the chemical solution When the chemical solution is processed at a temperature higher than 40 ° C., the chemical solution is likely to volatilize, which may cause problems in terms of safety and environment. On the other hand, when the chemical treatment is performed at a temperature lower than 10 ° C., the reaction rate with the glass substrate becomes too slow, and the production efficiency of the glass substrate tends to decrease.
  • Etching gases used for atmospheric pressure plasma treatment include rare gases such as He, Ar, and Xe, total fluorocarbon gases such as CF 4 , C 2 F 6 , and C 4 F 8 , CHF 3 , and CH 2 F 2 Hydrogenated fluorocarbon gas, fluorocarbon gas such as CCl 2 F 2 and CHClF 2 , fluorocarbon gas such as CBrF 3 and CF 3 I, organic halogen gas not containing F such as CCl 4 and COCl 2 , Cl 2 Inorganic halogen gases such as BCl 3 , SF 6 , NF 3 , HBr, SiCl 4 , hydrocarbon gases such as CH 4 , C 2 H 6 , and other gases (for example, O 2 , H 2 , N 2
  • the average radius of the curved concave portion is preferably 0.1 to 100 ⁇ m, 0.5 to 70 ⁇ m, 0.5 to 50 ⁇ m, or 1 to 30 ⁇ m, particularly preferably 1 to 10 ⁇ m. If the average radius of the curved concave portion is too small, the light is easily reflected on the roughened surface, and the light extraction efficiency tends to be lowered. On the other hand, if the average radius of the curved concave portion is too large, the glass substrate tends to be damaged. In addition, it is preferable that the average value of the average radius of the curved concave portion is also within the above range for the entire curved concave portion existing on the roughened surface.
  • the depth of the curved concave portion is preferably 0.1 to 100 ⁇ m, 0.5 to 70 ⁇ m, 0.5 to 50 ⁇ m, or 1 to 30 ⁇ m, particularly preferably 1 to 10 ⁇ m.
  • the depth of the curved concave portion is too small, the light is easily reflected on the roughened surface, and the light extraction efficiency is likely to be lowered.
  • the depth of the curved concave portion is too large, the glass substrate is easily damaged.
  • the average value of the depth of a curved-surface-shaped recessed part is also in the said range.
  • (depth of curved concave portion) / (average radius of curved concave portion) is preferably 0.01 to 10, 0.05 to 7, or 0.1 to 5, particularly preferably. Is 0.1-3. If (depth of curved concave portion) / (average radius of curved concave portion) is too small, light is likely to be reflected by the roughened surface and light extraction efficiency tends to be reduced. On the other hand, if (depth of curved concave portion) / (average radius of curved concave portion) is too large, the glass substrate tends to be damaged. In addition, it is preferable that the average value of (the depth of the curved concave portion) / (the average radius of the curved concave portion) is also within the above range for the entire curved concave portion existing on the roughened surface.
  • the surface roughness Rt of the roughened surface is preferably 50 to 10,000 nm. If the surface roughness Rt of the roughened surface is too small, light is easily reflected on the roughened surface, and it is difficult to increase the light extraction efficiency. Considering the light extraction efficiency, the surface roughness Rt of the roughened surface is preferably 300 nm or more, particularly preferably 500 nm or more. On the other hand, if the surface roughness Rt of the roughened surface is too large, the in-plane strength of the glass substrate tends to decrease. Considering the in-plane strength of the glass substrate, the surface roughness Rt of the roughened surface is preferably 9000 nm or less, and particularly preferably 8000 nm or less.
  • the surface roughness RSm of the roughened surface is preferably 0.1 to 1000 ⁇ m.
  • the surface roughness RSm of the roughened surface is preferably 1 ⁇ m or more, particularly preferably 5 ⁇ m or more.
  • the surface roughness RSm of the roughened surface is preferably 500 ⁇ m or less, particularly preferably 300 ⁇ m or less.
  • the “surface roughness RSm” is a value measured by a method based on JIS R0601 (2001).
  • the glass substrate of the present invention preferably has a smooth surface on one surface, and the surface roughness Rt of the smooth surface is preferably 10 nm or less, less than 10 nm, 5 nm or less, or 3 nm or less, particularly preferably 1 nm or less. If the surface roughness Rt of the smooth surface is too large, the quality of the transparent conductive film formed on the smooth surface is likely to deteriorate, and it becomes difficult to keep the electric field distribution in the surface uniform, resulting in uneven brightness in the surface. It tends to occur.
  • the smooth surface is preferably an unpolished surface. If it does in this way, it will become difficult to destroy a glass substrate. In addition, a resin board is inferior to surface smoothness, and it is difficult to improve the quality of a transparent conductive film.
  • the glass substrate of the present invention preferably contains 30 to 70% by mass of SiO 2 as a glass composition, particularly preferably 35 to 65% by mass.
  • SiO 2 is a component that forms a network of glass.
  • the content of SiO 2 is too large, the meltability and moldability are lowered, or the refractive index is too low, making it difficult to match the refractive index of the organic EL layer.
  • the content of SiO 2 is too small, vitrification becomes difficult, chemical resistance is lowered, and in-plane strength is liable to be lowered.
  • the glass substrate of the present invention has a glass composition of 30 to 70% by mass, SiO 2 30 to 70%, Al 2 O 3 0 to 20%, Li 2 O + Na 2 O + K 2 O 0 to 15%, MgO + CaO + SrO + BaO 5 to 55%, TiO 2. 2 0-20%, preferably contains ZrO 2 0 ⁇ 15%. If it does in this way, it will become possible to improve a refractive index and devitrification resistance.
  • Li 2 O + Na 2 O + K 2 O refers to the total amount of Li 2 O, Na 2 O and K 2 O.
  • MgO + CaO + SrO + BaO refers to the total amount of MgO, CaO, SrO and BaO.
  • SiO 2 is a component that forms a glass network, and its content is preferably 30 to 70%, particularly preferably 35 to 65%. If the content of SiO 2 is too large, the meltability and moldability will be lowered, or the refractive index will be too low, making it difficult to match the refractive index of the organic EL layer. On the other hand, when the content of SiO 2 is too small, vitrification becomes difficult, chemical resistance is lowered, and in-plane strength is liable to be lowered.
  • Al 2 O 3 is a component that forms a network of glass and is a component that improves weather resistance.
  • the content of Al 2 O 3 is preferably 0 to 20%, particularly preferably 1 to 20%. If the Al 2 O 3 content is too high, the refractive index will be too low, making it difficult to match the refractive index of the organic EL layer, and devitrifying crystals will easily precipitate on the glass, resulting in overflow down. It becomes difficult to form a glass substrate by a draw method or the like.
  • B 2 O 3 is a component that forms a glass network, and its content is preferably 0 to 20%, particularly preferably 0 to 15%.
  • the content of B 2 O 3 is too large, the chemical resistance decreases, the refractive index becomes too low, and it becomes difficult to match the refractive index of the organic EL layer. It becomes easy to precipitate and it becomes difficult to shape
  • the content of Li 2 O + Na 2 O + K 2 O is preferably 0 to 15%, 0 to 10% or 0 to 5%, particularly preferably 0 to 1%.
  • Li 2 O + Na 2 O + K content of 2 O is too large, or reduces the thermal shock resistance, so the acid resistance is low, in the patterning step of the ITO, a glass substrate is easily damaged by acid.
  • Li 2 O is a component that improves meltability and moldability, and further improves devitrification resistance.
  • the content of Li 2 O is preferably 0 to 10%, 0 to 5%, particularly preferably 0 to 1%. When the content of Li 2 O is too large, the thermal shock resistance is lowered or the acid resistance is lowered, and the glass substrate is easily damaged by acid in the ITO patterning step.
  • Na 2 O is a component that improves meltability and moldability, and further improves devitrification resistance.
  • the content of Na 2 O is preferably 0 to 10% or 0 to 5%, particularly preferably 0 to 1%. When the content of Na 2 O is too large, the thermal shock resistance is lowered or the acid resistance is lowered, and the glass substrate is easily damaged by an acid in the ITO patterning step.
  • K 2 O is a component that improves meltability and moldability, and further improves devitrification resistance.
  • the content of K 2 O is preferably 0 to 10% or 0 to 5%, particularly preferably 0 to 1%.
  • the content of K 2 O is too large, or reduces the thermal shock resistance, so the acid resistance is low, in the patterning step of the ITO, a glass substrate is easily damaged by acid.
  • MgO + CaO + SrO + BaO is a component that improves meltability and moldability. However, when there is too much content of MgO + CaO + SrO + BaO, devitrification resistance will fall easily. Therefore, the content of MgO + CaO + SrO + BaO is preferably 5 to 55% or 15 to 50%, particularly preferably 20 to 45%.
  • MgO is a component that improves meltability and moldability. However, when there is too much content of MgO, devitrification resistance will fall easily. Therefore, the content of MgO is preferably 0 to 20%.
  • CaO is a component that improves meltability and moldability. However, when there is too much content of CaO, devitrification resistance will fall easily. Therefore, the CaO content is preferably 0 to 20% or 1 to 15%, and particularly preferably 3 to 12%.
  • SrO is a component that enhances the meltability and moldability and also increases the refractive index. However, when there is too much content of SrO, devitrification resistance will fall easily. Therefore, the content of SrO is preferably 0 to 25% or 0.1 to 20%, particularly preferably 1 to 15%.
  • BaO is a component that improves the meltability and moldability and also increases the refractive index. However, when there is too much content of BaO, devitrification resistance will fall easily. Therefore, the content of BaO is preferably 0 to 45% or 5 to 40%, particularly preferably 15 to 35%.
  • TiO 2 is a component that increases the refractive index. However, if the content of TiO 2 is too large, the glass tends to be colored, the devitrification resistance is lowered, and the density tends to be high. Therefore, the content of TiO 2 is preferably 0 to 20% or 0.1 to 15%, particularly preferably 1 to 7%.
  • ZrO 2 is a component that increases the refractive index. However, if the content of ZrO 2 is too large, the devitrification resistance may be extremely lowered. Therefore, the content of ZrO 2 is preferably 0 to 15% or 0.001 to 10%, particularly preferably 1 to 7%.
  • the addition amount of components other than the above components is preferably 25% or less or 20% or less, and particularly preferably 15% or less.
  • ZnO is a component that improves meltability and moldability. However, when there is too much content of ZnO, devitrification resistance will fall easily. Therefore, the content of ZnO is preferably 0 to 20%, particularly preferably 0 to 5%.
  • Rare earth oxides such as Nb 2 O 5 , La 2 O 3 , and Gd 2 O 3 are components that increase the refractive index, but the cost of the raw material itself is high, and when added in a large amount in the glass composition, devitrification resistance May decrease. Therefore, the total content of rare earth oxides is preferably 0 to 25%, particularly preferably 0 to 15%.
  • the Nb 2 O 5 content is preferably 0 to 15%, particularly preferably 0 to 3%.
  • the La 2 O 3 content is preferably 0 to 18% or 0.1 to 15%, particularly preferably 1 to 12%.
  • the content of Gd 2 O 3 is preferably 0 to 12%, particularly preferably 0 to 3%.
  • 0.001 to 3% of one or more selected from the group consisting of As 2 O 3 , Sb 2 O 3 , SnO 2 , CeO 2 , SO 3 , F, and Cl can be added.
  • As 2 O 3 and Sb 2 O 3 are concerned about environmental influences, and therefore the content of these components is preferably less than 0.1%, particularly preferably less than 0.01%.
  • CeO 2 is a component that lowers the transmittance, so its content is preferably less than 0.1%, particularly preferably less than 0.01%.
  • F is a component that lowers moldability, its content is preferably less than 0.1%, and particularly preferably less than 0.01%.
  • the fining agent is preferably one or more selected from the group of SnO 2 , SO 3 , Cl, and the content of these components is 0.001 to 3% in total, 0.001 to 1% or 0.01 to 0.5% is preferable, and 0.05 to 0.4% is more preferable.
  • PbO is a component that increases the refractive index, but is a component that is concerned about environmental influences. Therefore, the PbO content is preferably less than 0.1%.
  • the glass substrate of the present invention is preferably formed by an overflow down draw 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 bowl-like structure, and the overflowing molten glass is joined at the lower end of the bowl-like structure.
  • this is a method of producing a glass substrate by drawing downward. In this way, a glass substrate that is unpolished and has good surface quality can be formed. The reason is that, in the case of the overflow downdraw method, the surface to be the surface of the glass substrate 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 a force to the glass in order to perform the downward stretch molding is not particularly limited as long as desired dimensions and surface quality can be realized.
  • a method may be adopted in which a heat-resistant roll having a sufficiently large width is rotated and stretched in contact with glass, or a plurality of pairs of heat-resistant rolls are contacted only near the end face of the glass. It is also possible to adopt a method of stretching by stretching.
  • the glass substrate 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 substrate in the same manner as the overflow down draw method.
  • the slot down draw method can also form a roughened surface (curved concave portion) on the surface of the glass substrate by changing the shape of the slot.
  • the molding method various methods other than the overflow downdraw method and the slot downdraw method can be adopted.
  • a float method, a rollout method, a redraw method, or the like can be employed.
  • a glass substrate is formed by a float process, a large glass substrate can be manufactured at low cost.
  • the plate thickness of the glass substrate of the present invention the smaller the plate thickness, the easier it is to reduce the weight of the organic EL device, and the flexibility of the glass substrate can be increased.
  • the plate thickness is preferably 2 mm or less, 1.5 mm or less, or 1 mm or less, and particularly preferably 0.7 mm or less.
  • the plate thickness of the glass substrate is preferably 50 ⁇ m or more or 100 ⁇ m or more, and particularly preferably 200 ⁇ m or more.
  • the minimum curvature radius that the glass substrate can take is preferably 200 mm or less, 150 mm or less, 100 mm or less, or 50 mm or less, and particularly preferably 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 radiant flux value taken into the air from the surface where the roughened surface is formed when incident on the surface from the surface where the roughened surface is not formed at an incident angle of 60 ° / (light However, when the incident angle is 0 ° and the light is incident on the air from the surface on which the roughened surface is not formed, the radiant flux value taken into the air from the surface on which the roughened surface is formed).
  • the value is preferably 0.01 or more, 0.1 or more, 0.15 or more, or 0.2 or more, and particularly preferably 0.25 or more. In this way, the light confined in the glass plate is reduced, and the light extraction efficiency is improved.
  • the sand blast treatment is performed by spraying the blast material onto the surface of the glass substrate at 2 MPa using a blast material having a particle size shown in Table 1 (4 kg of Al 2 O 3 dispersed in 20 L of water). It was.
  • the HF treatment was performed by immersing each sample in a 10% HF solution at 25 ° C. for a predetermined time.
  • Refractive index n d is the value measured by the refractive index measuring instrument KPR-2000 of Kalnew Corporation.
  • FIGS. 2 to 17 Sample No. Photomicrographs of roughened surfaces 1 to 16 are shown in FIGS. 2 to 17, respectively. Specifically, FIG. No. 1 roughened surface, FIG. 2 roughened surface, FIG. 3 roughened surface, FIG. 4 is a roughened surface, FIG. No. 5 roughened surface, FIG. 6 is a roughened surface, FIG. 7 is a roughened surface, FIG. No. 8 roughened surface, FIG. 9 is a roughened surface, FIG. No. 10 roughened surface, FIG. 11 is a roughened surface, FIG. 12 roughened surface, FIG. 13 is a roughened surface, FIG. 14 is a roughened surface, FIG. 15 roughened surface, FIG. It is a microscope picture which shows 16 roughening surfaces, respectively.
  • FIG. 18 is a schematic cross-sectional view schematically showing the average radius and depth of the curved concave portion.
  • a indicates the average radius and b indicates the depth.
  • FIG. 19 shows sample no. 8 is data obtained by measuring a cross-sectional shape of a roughened surface of 8 using a surf coder. From FIG. 9 and FIG. It can be seen that curved concave portions are formed aperiodically on the roughened surface 8.
  • FIG. 20 is a schematic cross-sectional view showing a method for evaluating the light scattering function.
  • a hemispherical lens 22 having a refractive index n d 1.74 is installed on one surface of the glass substrate 21 (a surface on which a roughened surface is not formed) using an immersion liquid, and toward the center of the hemispherical lens 22. Then, light was incident from the light source 24.
  • the light extracted from the other surface (the surface on which the roughened surface is formed) of the glass substrate 21 through the inside of the glass substrate 21 was detected by the integrating sphere 23. Further, the inclination from a plane perpendicular to the surface of the glass substrate 21 was ⁇ , and the same experiment was repeated while changing the incident angle ⁇ , and the light extracted at each incident angle was detected by the integrating sphere 23.
  • the measurement results are shown in Table 1.
  • P50-2-UV-VIS manufactured by Ocean Optics was used as the optical fiber connecting the integrating sphere 23 and the spectroscope.
  • a red laser SNF-660-5 manufactured by Moritex was used as the light source 24
  • a fiber multichannel spectrometer USB4000 manufactured by Ocean Photonics was used as the spectrometer
  • OPWave manufactured by Ocean Photonics was used as the software.

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Abstract

The problem addressed by the present invention is the formation of an original idea of a glass substrate that can extract light to the outside with excellent efficiency even if a transparent resin film is not made to adhere to the surface of the glass substrate. This glass substrate is a glass substrate (11) having an index of refraction (nd) of 1.50 or greater and is characterized by having a coarsened surface on at least one surface thereof and having curved surface shaped recesses in the coarsened surface.

Description

ガラス基板Glass substrate
　本発明は、ガラス基板に関し、具体的には、有機ＥＬ照明等の有機ＥＬデバイスに好適なガラス基板に関する。 The present invention relates to a glass substrate, and specifically to a glass substrate suitable for an organic EL device such as organic EL lighting.
　近年、家電製品の普及、大型化、多機能化等の理由から、家庭等の生活空間で消費されるエネルギーが増えている。特に、照明機器のエネルギー消費が多くなっている。このため、高効率の照明が活発に検討されている。 In recent years, the energy consumed in living spaces such as homes has increased due to the widespread use, increase in size, and multifunctionality of home appliances. In particular, the energy consumption of lighting equipment is increasing. For this reason, highly efficient illumination is actively studied.
　照明用光源は、限られた範囲を照らす「指向性光源」と、広範囲を照らす「拡散光源」とに分けられる。ＬＥＤ照明は、「指向性光源」に相当し、白熱球の代替として採用されつつある。その一方で、「拡散光源」に相当する蛍光灯の代替光源が望まれており、その候補として、有機ＥＬ（エレクトロルミネッセンス）照明が有力である。 The light source for illumination is divided into a “directional light source” that illuminates a limited area and a “diffuse light source” that illuminates a wide area. LED lighting corresponds to a “directional light source” and is being adopted as an alternative to an incandescent bulb. On the other hand, an alternative light source for a fluorescent lamp corresponding to a “diffusion light source” is desired, and organic EL (electroluminescence) illumination is a promising candidate.
　図１は、有機ＥＬ照明１の概念を示す断面図である。有機ＥＬ照明１は、ガラス基板１１と、陽極１２である透明導電膜と、電流の注入によって発光するエレクトロルミネッセンスを呈する有機化合物からなる一層又は複数層の発光層を含む有機ＥＬ層１３と、陰極１４とを備えた素子である。有機ＥＬ照明１に用いられる有機ＥＬ層１３として、低分子色素系材料、共役高分子系材料等が用いられており、有機ＥＬ層１３を形成する場合、ホール注入層、ホール輸送層、電子輸送層、電子注入層等との積層構造が形成される。このような積層構造を有する有機ＥＬ層１３を、陽極１２と陰極１４の間に配置し、陽極１２と陰極１４に電界を印加すると、陽極１２である透明電極から注入された正孔と、陰極１４から注入された電子とが、発光層内で再結合し、その再結合エネルギーによって発光中心が励起されて、発光する。 FIG. 1 is a cross-sectional view showing the concept of the organic EL lighting 1. The organic EL lighting 1 includes a glass substrate 11, a transparent conductive film as an anode 12, an organic EL layer 13 including a single or a plurality of light emitting layers made of an organic compound exhibiting electroluminescence that emits light by current injection, a cathode 14. As the organic EL layer 13 used in the organic EL lighting 1, a low molecular dye material, a conjugated polymer material or the like is used. When the organic EL layer 13 is formed, a hole injection layer, a hole transport layer, an electron transport A laminated structure with a layer, an electron injection layer and the like is formed. When the organic EL layer 13 having such a laminated structure is disposed between the anode 12 and the cathode 14 and an electric field is applied to the anode 12 and the cathode 14, holes injected from the transparent electrode as the anode 12 and the cathode The electrons injected from 14 recombine in the light emitting layer, and the light emission center is excited by the recombination energy to emit light.
　有機ＥＬ素子は、携帯電話、ディスプレイ用途として検討が進められており、一部では既に実用化されている。また、有機ＥＬ素子は、液晶ディスプレイ、プラズマディスプレイ等の薄型テレビと同等の発光効率を有している。 Organic EL elements are being studied for use in mobile phones and displays, and some have already been put into practical use. In addition, the organic EL element has a luminous efficiency equivalent to that of a thin television such as a liquid crystal display or a plasma display.
　しかし、照明用光源に適用するためには、輝度が未だ実用レベルに到達しておらず、更なる発光効率の改善が必要である。 However, in order to be applied to an illumination light source, the luminance has not yet reached a practical level, and further improvement in light emission efficiency is necessary.
　輝度が低い原因の一つとして、屈折率の不整合が挙げられる。具体的には、インジウム－錫酸化物（ＩＴＯ）等の透明電極膜及び有機ＥＬ層の屈折率ｎdは１．７～２．０である。これに対して、ガラス基板の屈折率ｎdは、通常、１．５０程度である。よって、従来の有機ＥＬデバイスは、透明電極膜及び有機ＥＬ層とガラス基板の屈折率差が大きいことに起因して、有機ＥＬ層から放射した光が透明電極膜及び有機ＥＬ層とガラス基板の界面で反射し、光取り出し効率が低下するという問題があった。更に、ガラス基板と空気の屈折率差に起因して、光取り出し効率が低下するという問題も生じる。すなわち、有機ＥＬ層から放射した光が、ガラス基板内部から空気中へ進行する際に、ガラス基板と空気の界面で反射し、ガラス基板内に閉じ込められるという問題が生じる。例えば、汎用の有機ＥＬ層及び透明電極膜に対して屈折率ｎd１．５０のガラス基板を用いた場合、外部に取り出される光の割合は、有機ＥＬ層から放射した光の内、２０～２５％程度である。 One of the causes of low luminance is refractive index mismatch. Specifically, indium - the refractive index n d of the transparent electrode film and the organic EL layer, such as tin oxide (ITO) is 1.7 to 2.0. On the other hand, the refractive index n d of the glass substrate is usually about 1.50. Therefore, the conventional organic EL device has a large difference in refractive index between the transparent electrode film and the organic EL layer and the glass substrate, so that the light emitted from the organic EL layer is transmitted between the transparent electrode film and the organic EL layer and the glass substrate. There is a problem that light is reflected at the interface and the light extraction efficiency is lowered. Furthermore, there arises a problem that the light extraction efficiency is lowered due to the difference in refractive index between the glass substrate and air. That is, when the light radiated from the organic EL layer travels from the inside of the glass substrate to the air, it is reflected at the interface between the glass substrate and the air and is confined within the glass substrate. For example, when a glass substrate having a refractive index n d of 1.50 is used for a general-purpose organic EL layer and a transparent electrode film, the proportion of light extracted outside is 20 to 20% of the light emitted from the organic EL layer. It is about 25%.
　有機ＥＬ層から放射した光を外部に効率良く取り出すために、ガラス基板の表面に対して、凹凸形状を有する透明樹脂シート（例えばマイクロレンズアレイフィルム）を貼着する方法が検討されている。 In order to efficiently extract the light emitted from the organic EL layer to the outside, a method of sticking a transparent resin sheet (for example, a microlens array film) having an uneven shape to the surface of the glass substrate has been studied.
　透明樹脂シートとして、通常、熱硬化性樹脂、例えばポリイミドが用いられる。しかし、熱硬化性樹脂の表面に凹凸形状を付与することは容易ではなく、有機ＥＬデバイスの製造コストの高騰を招く。 As the transparent resin sheet, a thermosetting resin such as polyimide is usually used. However, it is not easy to give the uneven shape to the surface of the thermosetting resin, resulting in an increase in the manufacturing cost of the organic EL device.
　本発明は、上記問題に鑑み成されたものであり、その技術的課題は、ガラス基板の表面に対して、透明樹脂シートを貼着しなくても、光を外部に効率良く取り出し得るガラス基板を創案することである。 The present invention has been made in view of the above problems, and the technical problem thereof is a glass substrate that can efficiently extract light to the outside without sticking a transparent resin sheet to the surface of the glass substrate. Is to invent.
　本発明者等は、鋭意検討の結果、ガラス基板の屈折率を所定範囲に規制すると共に、ガラス基板の表面形状を規制することにより、上記技術的課題を解決し得ることを見出し、本発明として提案するものである。すなわち、本発明のガラス基板は、屈折率ｎdが１．５０以上のガラス基板であって、少なくとも一方の表面に粗面化面を有し、該粗面化面に曲面状凹部を有することを特徴とする。ここで、「屈折率ｎd」は、市販の屈折率測定器（例えば、カルニュー社製の屈折率測定器ＫＰＲ－２０００）により測定することができる。測定試料として、例えば、ダイシングにより、ガラス基板を２５ｍｍ角に切り出し、次にこのガラス基板間に屈折率ｎdが整合する浸液を浸透させた状態で、ガラス基板を積層し、２５ｍｍ×２５ｍｍ×約３ｍｍ厚の直方体としたものを用いることができる。「曲面状凹部」は、破砕形状以外の窪みを指し、例えば、化学的処理により形成された滑らかな窪みを指す。また、窪み同士が重なっている場合には、窪みが重なっていない状態を仮定して、その窪みそれぞれについて評価することになる。なお、本発明の効果を的確に享受する観点から、一方の表面の有効面全体に粗面化面を有することが好ましい。また、粗面化面全体に占める曲面状凹部の割合は、面積比で５％以上、１０％以上、２０％以上、３０％以上、４０％以上、５０％以上、６０％以上または７０％以上が好ましく、特に８０％以上が好ましい。 As a result of intensive studies, the present inventors have found that the above technical problem can be solved by regulating the refractive index of the glass substrate within a predetermined range and regulating the surface shape of the glass substrate. It is what we propose. That is, the glass substrate of the present invention is a glass substrate is 1.50 or more refractive index n d, has a roughened surface on at least one surface, it has a curved recess on the crude surface of surface It is characterized by. Here, the “refractive index n d ” can be measured by a commercially available refractive index measuring device (for example, a refractive index measuring device KPR-2000 manufactured by Calnew). As a measurement sample, for example, a glass substrate is cut into 25 mm square by dicing, and then the glass substrate is laminated in a state in which an immersion liquid having a refractive index n d is infiltrated between the glass substrates, and is 25 mm × 25 mm × A rectangular parallelepiped having a thickness of about 3 mm can be used. “Curved concave portion” refers to a recess other than the crushed shape, for example, a smooth recess formed by chemical treatment. In addition, when the dents are overlapped with each other, the dents are evaluated on the assumption that the dents are not overlapped. In addition, from a viewpoint of enjoying the effect of this invention exactly, it is preferable to have a roughening surface in the whole effective surface of one surface. Further, the ratio of the curved concave portion to the entire roughened surface is 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, or 70% or more by area ratio. In particular, 80% or more is preferable.
　本発明のガラス基板は、屈折率ｎdが１．５０以上である。このようにすれば、有機ＥＬ層とガラス基板間の屈折率差が小さくなるため、全反射により有機ＥＬ層内に閉じ込められる光を低減することができる。その結果、有機ＥＬデバイスの光取り出し効率を高めることができる。 The glass substrate of the present invention has a refractive index n d of 1.50 or more. In this way, since the difference in refractive index between the organic EL layer and the glass substrate is reduced, light confined in the organic EL layer due to total reflection can be reduced. As a result, the light extraction efficiency of the organic EL device can be increased.
　また、本発明のガラス基板は、少なくとも一方の表面に粗面化面を有し、該粗面化面に曲面状凹部を有する。透明樹脂シートの表面構造として、ピラミッド形状、半球凸レンズ形状等が提案されているが、現時点で、何れの形状が最適かは不明である。そこで、本発明者等は、詳細な調査により、粗面化面に曲面状凹部を形成すると、ガラス基板中の光を的確に散乱させることが可能になり、結果として、ガラス基板中に閉じ込められる光が低減されて、有機ＥＬデバイスの光取り出し効率が向上することを見出した。更に、粗面化面に曲面状凹部を形成すると、ガラス基板の面内強度が向上することを見出した。 The glass substrate of the present invention has a roughened surface on at least one surface, and has a curved concave portion on the roughened surface. As the surface structure of the transparent resin sheet, a pyramid shape, a hemispherical convex lens shape, and the like have been proposed, but at present, it is unclear which shape is optimal. Therefore, the inventors have made a detailed investigation to form a curved concave portion on the roughened surface, so that the light in the glass substrate can be accurately scattered, and as a result, is confined in the glass substrate. It has been found that light is reduced and the light extraction efficiency of the organic EL device is improved. Furthermore, it has been found that when a curved concave portion is formed on the roughened surface, the in-plane strength of the glass substrate is improved.
　第二に、本発明のガラス基板は、粗面化面に曲面状凹部が非周期的に形成されていることが好ましい。このようにすれば、光の干渉による視野角依存性を抑制される。結果として、異なる角度で有機ＥＬ照明を観察した場合でも、色の変化を抑制することができる。 Second, it is preferable that the glass substrate of the present invention has a curved concave portion formed aperiodically on the roughened surface. In this way, the viewing angle dependency due to light interference is suppressed. As a result, even when the organic EL illumination is observed at different angles, the color change can be suppressed.
　第三に、本発明のガラス基板は、曲面状凹部が、物理的処理後に化学的処理を行うことにより形成されていることが好ましい。物理的処理により、大面積のガラス基板の表面に対して、短時間で粗面化面を均一に形成することができる。その後の化学的処理により、粗面化面に曲面状凹部を形成することができる。 Thirdly, in the glass substrate of the present invention, it is preferable that the curved concave portion is formed by performing chemical treatment after physical treatment. A roughened surface can be uniformly formed in a short time on the surface of a large-area glass substrate by physical treatment. A curved recess can be formed on the roughened surface by subsequent chemical treatment.
　第四に、本発明のガラス基板は、物理的処理がサンドブラスト処理であることが好ましい。このようにすれば、大型のガラス基板の表面に対して、短時間で粗面化面を均一に形成することができる。 Fourthly, the physical treatment of the glass substrate of the present invention is preferably a sandblast treatment. In this way, a roughened surface can be uniformly formed in a short time on the surface of a large glass substrate.
　第五に、本発明のガラス基板は、化学的処理が酸による薬液処理であることが好ましい。このようにすれば、粗面化面に曲面状凹部を効率良く形成することができる。 Fifth, it is preferable that the chemical treatment of the glass substrate of the present invention is chemical treatment with an acid. If it does in this way, a curved-surface-shaped recessed part can be efficiently formed in a rough surface.
　第六に、本発明のガラス基板は、曲面状凹部の平均半径が０．１～１００μｍであることが好ましい。このようにすれば、ガラス基板中の光を効率良く散乱させることが可能になる。「曲面状凹部の平均半径」は、窪みの中心からの平均距離を指す。 Sixth, the glass substrate of the present invention preferably has an average radius of the curved concave portion of 0.1 to 100 μm. If it does in this way, it will become possible to scatter the light in a glass substrate efficiently. “Average radius of curved concave portion” refers to an average distance from the center of the depression.
　第七に、本発明のガラス基板は、曲面状凹部の深さが０．１～１００μｍであることが好ましい。このようにすれば、ガラス基板中の光を効率良く散乱させることが可能になる。 Seventh, in the glass substrate of the present invention, the depth of the curved concave portion is preferably 0.1 to 100 μm. If it does in this way, it will become possible to scatter the light in a glass substrate efficiently.
　第八に、本発明のガラス基板は、（曲面状凹部の深さ）／（曲面状凹部の平均半径）が０．０１～１０であることが好ましい。このようにすれば、ガラス基板中の光を効率良く散乱させることが可能になる。 Eighth, in the glass substrate of the present invention, it is preferable that (depth of curved concave portion) / (average radius of curved concave portion) is 0.01 to 10. If it does in this way, it will become possible to scatter the light in a glass substrate efficiently.
　第九に、本発明のガラス基板は、一方の表面に平滑面を有し、平滑面の表面粗さＲｔが１０ｎｍ以下であることが好ましい。このようにすれば、透明電極膜の品位を高めることができる。ここで、「表面粗さＲｔ」は、ＪＩＳ　Ｒ０６０１（２００１）に準拠した方法により測定した値である。 Ninth, the glass substrate of the present invention preferably has a smooth surface on one surface, and the smooth surface has a surface roughness Rt of 10 nm or less. If it does in this way, the quality of a transparent electrode film can be raised. Here, the “surface roughness Rt” is a value measured by a method based on JIS R0601 (2001).
　第十に、本発明のガラス基板は、ガラス組成として、ＳｉＯ2を３０～７０質量％含むことが好ましい。 Tenth, the glass substrate of the present invention preferably contains 30 to 70% by mass of SiO 2 as a glass composition.
　第十一に、本発明のガラス基板は、ガラス基板内部から空気中へ進行する光が、臨界角以上でも全反射せずに、粗面化面から空気中に取り出される性質を有することが好ましい。このようにすれば、ガラス基板内に閉じ込められる光が低減されて、光取り出し効率が向上する。 Eleventh, the glass substrate of the present invention preferably has a property that light traveling from the inside of the glass substrate into the air is extracted from the roughened surface into the air without being totally reflected even at a critical angle or more. . In this way, the light confined in the glass substrate is reduced, and the light extraction efficiency is improved.
　第十二に、本発明のガラス基板は、有機ＥＬデバイスに用いることが好ましい。 Twelfth, the glass substrate of the present invention is preferably used for an organic EL device.
　第十三に、本発明のガラス基板は、照明に用いることが好ましい。 Thirteenth, the glass substrate of the present invention is preferably used for illumination.
有機ＥＬ照明の概念を示す断面図である。It is sectional drawing which shows the concept of organic electroluminescent illumination. 試料Ｎｏ．１の粗面化面の電子顕微鏡写真である。Sample No. 1 is an electron micrograph of a roughened surface of FIG. 試料Ｎｏ．２の粗面化面の電子顕微鏡写真である。Sample No. 2 is an electron micrograph of the roughened surface of No. 2; 試料Ｎｏ．３の粗面化面の電子顕微鏡写真である。Sample No. 3 is an electron micrograph of a roughened surface 3. 試料Ｎｏ．４の粗面化面の電子顕微鏡写真である。Sample No. 4 is an electron micrograph of 4 roughened surface. 試料Ｎｏ．５の粗面化面の電子顕微鏡写真である。Sample No. 5 is an electron micrograph of a roughened surface of No. 5. 試料Ｎｏ．６の粗面化面の電子顕微鏡写真である。Sample No. 6 is an electron micrograph of a roughened surface of No. 6; 試料Ｎｏ．７の粗面化面の電子顕微鏡写真である。Sample No. 7 is an electron micrograph of a roughened surface of No. 7; 試料Ｎｏ．８の粗面化面の電子顕微鏡写真である。Sample No. 8 is an electron micrograph of a roughened surface of FIG. 試料Ｎｏ．９の粗面化面の電子顕微鏡写真である。Sample No. 9 is an electron micrograph of a roughened surface of No. 9; 試料Ｎｏ．１０の粗面化面の電子顕微鏡写真である。Sample No. 10 is an electron micrograph of 10 roughened surfaces. 試料Ｎｏ．１１の粗面化面の電子顕微鏡写真である。Sample No. 11 is an electron micrograph of 11 roughened surfaces. 試料Ｎｏ．１２の粗面化面の電子顕微鏡写真である。Sample No. 12 is an electron micrograph of 12 roughened surfaces. 試料Ｎｏ．１３の粗面化面の電子顕微鏡写真である。Sample No. 13 is an electron micrograph of 13 roughened surfaces. 試料Ｎｏ．１４の粗面化面の電子顕微鏡写真である。Sample No. 14 is an electron micrograph of 14 roughened surfaces. 試料Ｎｏ．１５の粗面化面の電子顕微鏡写真である。Sample No. 15 is an electron micrograph of 15 roughened surfaces. 試料Ｎｏ．１６の粗面化面の電子顕微鏡写真である。Sample No. 16 is an electron micrograph of 16 roughened surfaces. 曲面状凹部の平均半径と深さを模式的に示す概略断面図である。It is a schematic sectional drawing which shows typically the average radius and depth of a curved-surface-shaped recessed part. 試料Ｎｏ．８の粗面化面について、サーフコーダによる断面形状を測定したデータである。Sample No. 8 is data obtained by measuring a cross-sectional shape of a roughened surface of 8 using a surf coder. 光散乱機能の評価方法を示す概略断面図である。It is a schematic sectional drawing which shows the evaluation method of a light-scattering function.
　本発明のガラス基板において、屈折率ｎdは１．５０以上であり、好ましくは１．５１以上、１．５２以上、１．５４以上、１．５６以上または１．５８以上であり、特に好ましくは１．６０以上である。屈折率ｎdが１．５０未満になると、有機ＥＬ層及び透明導電膜－ガラス基板界面での反射率が高くなり、光を効率良く取り出せなくなる。なお、屈折率ｎdが２．３超になると、空気－ガラス基板界面での反射率が高くなり、ガラス基板の表面に粗面化面を形成しても、光の取り出し効率を高めることが困難になる。よって、屈折率ｎdは２．３以下、２．２以下、２．１以下、２．０以下または１．９以下が好ましく、特に１．７５以下が好ましい。 In the glass substrate of the present invention, the refractive index nd is 1.50 or more, preferably 1.51 or more, 1.52 or more, 1.54 or more, 1.56 or more, or 1.58 or more, particularly preferably. Is 1.60 or more. When the refractive index n d is less than 1.50, the reflectance at the interface between the organic EL layer and the transparent conductive film-glass substrate increases, and light cannot be extracted efficiently. When the refractive index n d exceeds 2.3, the reflectance at the air-glass substrate interface increases, and the light extraction efficiency can be improved even if a roughened surface is formed on the surface of the glass substrate. It becomes difficult. Therefore, the refractive index n d is preferably 2.3 or less, 2.2 or less, 2.1 or less, 2.0 or less, or 1.9 or less, particularly preferably 1.75 or less.
　粗面化面の形成方法として、例えば、化学的処理、物理的処理等が挙げられるが、本発明では、粗面化面に曲面状凹部を形成し易くするために、物理的処理を行った後に、化学的処理を行うことが好ましい。なお、ガラス基板の表面に対して、物理的処理のみで粗面化面を形成すると、粗面化面に曲面状凹部を形成し難くなると共に、曲面状凹部の頂端部が先鋭化し、ガラス基板の面内強度が低下し易くなる。 Examples of the method for forming the roughened surface include chemical treatment and physical treatment. In the present invention, physical treatment was performed in order to facilitate the formation of a curved concave portion on the roughened surface. It is preferable to perform chemical treatment later. If a roughened surface is formed only on the surface of the glass substrate by physical treatment, it becomes difficult to form a curved concave portion on the roughened surface, and the top end portion of the curved concave portion is sharpened. The in-plane strength of the steel tends to decrease.
　物理的処理として、サンドブラスト処理が好ましい。このようにすれば、大型のガラス基板の表面に対して、短時間で粗面化面を均一に形成することができる。サンドブラスト処理で使用するブラスト材の粒度は＃５０～＃４０００、＃７０～＃１５００、特に＃１００～＃１０００が好ましい。ブラスト材の粒度が細か過ぎると、粗面化面を形成し難くなる。一方、ブラスト材の粒度が粗過ぎると、ガラス基板の面内強度が低下し易くなる。 As the physical treatment, sandblast treatment is preferable. In this way, a roughened surface can be uniformly formed in a short time on the surface of a large glass substrate. The particle size of the blasting material used in the sandblasting treatment is preferably # 50 to # 4000, # 70 to # 1500, particularly # 100 to # 1000. When the particle size of the blast material is too fine, it becomes difficult to form a roughened surface. On the other hand, if the particle size of the blast material is too coarse, the in-plane strength of the glass substrate tends to decrease.
　物理的処理として、研磨処理も好ましい。このようにすれば、大型のガラス基板の表面に対して、短時間で粗面化面を均一に形成することができる。研磨処理で用いる研磨材の粒度は＃２２０～＃３０００、＃３００～＃２０００または＃４００～＃１５００が好ましく、特に＃４００～＃１２００が好ましい。研磨材の粒度が細か過ぎると、粗面化面を形成し難くなる。一方、研磨材の粒度が粗過ぎると、ガラス基板の面内強度が低下し易くなる。 Polishing is also preferable as the physical treatment. In this way, a roughened surface can be uniformly formed in a short time on the surface of a large glass substrate. The particle size of the abrasive used in the polishing treatment is preferably # 220 to # 3000, # 300 to # 2000, or # 400 to # 1500, and particularly preferably # 400 to # 1200. When the grain size of the abrasive is too fine, it becomes difficult to form a roughened surface. On the other hand, if the abrasive particle size is too coarse, the in-plane strength of the glass substrate tends to decrease.
　化学的処理として、酸による薬液処理が好ましい。このようにすれば、粗面化面に曲面状凹部を効率良く形成することができる。薬液として、ＨＦ、ＨＣｌ、Ｈ2ＳＯ4、ＨＮＯ3、ＮＨ4Ｆ、ＮａＯＨ、ＮＨ4ＨＦ2の群から選ばれる一種又は二種以上を含むことが好ましい。これらの薬液は、ガラス基板との反応性が良好であり、粗面化面に曲面状凹部を効率良く形成することができる。また、これらの薬液は、１０～４０℃または１５～３５℃の温度で使用されることが好ましく、特に２０～３０℃の温度で使用されることが好ましい。４０℃超の温度で薬液処理すると、薬液が揮発し易くなり、安全面、環境面で問題が生じ得る。一方、１０℃未満の温度で薬液処理すると、ガラス基板との反応速度が遅くなり過ぎて、ガラス基板の製造効率が低下し易くなる。 As the chemical treatment, a chemical treatment with an acid is preferable. If it does in this way, a curved-surface-shaped recessed part can be efficiently formed in a rough surface. The chemical solution preferably contains one or more selected from the group consisting of HF, HCl, H 2 SO 4 , HNO 3 , NH 4 F, NaOH, and NH 4 HF 2 . These chemical solutions have good reactivity with the glass substrate and can efficiently form curved concave portions on the roughened surface. These chemical solutions are preferably used at a temperature of 10 to 40 ° C. or 15 to 35 ° C., particularly preferably at a temperature of 20 to 30 ° C. When the chemical solution is processed at a temperature higher than 40 ° C., the chemical solution is likely to volatilize, which may cause problems in terms of safety and environment. On the other hand, when the chemical treatment is performed at a temperature lower than 10 ° C., the reaction rate with the glass substrate becomes too slow, and the production efficiency of the glass substrate tends to decrease.
　化学的処理として、大気圧プラズマ処理も好ましい。このようにすれば、粗面化面に曲面状凹部を形成し易くなると共に、処理後の洗浄工程が不要になり、製造コストを低廉化することができる。大気圧プラズマ処理に用いられるエッチングガスとして、Ｈｅ、Ａｒ、Ｘｅ等の希ガス、ＣＦ4、Ｃ2Ｆ6、Ｃ4Ｆ8等の全フッ化炭素ガス、ＣＨＦ3、ＣＨ2Ｆ2等の水素化フッ化炭素ガス、ＣＣｌ2Ｆ2、ＣＨＣｌＦ2等のフッ化塩化炭素ガス、ＣＢｒＦ3、ＣＦ3Ｉ等のフルオロカーボンガス、ＣＣｌ4、ＣＯＣｌ2等のＦを含まない有機ハロゲンガス、Ｃｌ2、ＢＣｌ3、ＳＦ6、ＮＦ3、ＨＢｒ、ＳｉＣｌ4等の無機ハロゲンガス、ＣＨ4、Ｃ2Ｈ6等の炭化水素ガス、その他のガス（例えばＯ2、Ｈ2、Ｎ2、ＣＯ）が挙げられる。 As the chemical treatment, atmospheric pressure plasma treatment is also preferable. In this way, it becomes easy to form a curved concave portion on the roughened surface, and a cleaning step after the treatment is not necessary, so that the manufacturing cost can be reduced. Etching gases used for atmospheric pressure plasma treatment include rare gases such as He, Ar, and Xe, total fluorocarbon gases such as CF 4 , C 2 F 6 , and C 4 F 8 , CHF 3 , and CH 2 F 2 Hydrogenated fluorocarbon gas, fluorocarbon gas such as CCl 2 F 2 and CHClF 2 , fluorocarbon gas such as CBrF 3 and CF 3 I, organic halogen gas not containing F such as CCl 4 and COCl 2 , Cl 2 Inorganic halogen gases such as BCl 3 , SF 6 , NF 3 , HBr, SiCl 4 , hydrocarbon gases such as CH 4 , C 2 H 6 , and other gases (for example, O 2 , H 2 , N 2 , CO) Can be mentioned.
　本発明のガラス基板において、曲面状凹部の平均半径は、好ましくは０．１～１００μｍ、０．５～７０μｍ、０．５～５０μｍまたは１～３０μｍであり、特に好ましくは１～１０μｍである。曲面状凹部の平均半径が小さ過ぎると、粗面化面で光が反射し易くなり、光取り出し効率が低下し易くなる。一方、曲面状凹部の平均半径が大き過ぎると、ガラス基板が破損し易くなる。なお、粗面化面に存在する曲面状凹部全体について、曲面状凹部の平均半径の平均値も上記範囲内であることが好ましい。 In the glass substrate of the present invention, the average radius of the curved concave portion is preferably 0.1 to 100 μm, 0.5 to 70 μm, 0.5 to 50 μm, or 1 to 30 μm, particularly preferably 1 to 10 μm. If the average radius of the curved concave portion is too small, the light is easily reflected on the roughened surface, and the light extraction efficiency tends to be lowered. On the other hand, if the average radius of the curved concave portion is too large, the glass substrate tends to be damaged. In addition, it is preferable that the average value of the average radius of the curved concave portion is also within the above range for the entire curved concave portion existing on the roughened surface.
　本発明のガラス基板において、曲面状凹部の深さは、好ましくは０．１～１００μｍ、０．５～７０μｍ、０．５～５０μｍまたは１～３０μｍであり、特に好ましくは１～１０μｍである。曲面状凹部の深さが小さ過ぎると、粗面化面で光が反射し易くなり、光取り出し効率が低下し易くなる。一方、曲面状凹部の深さが大き過ぎると、ガラス基板が破損し易くなる。なお、粗面化面に存在する曲面状凹部全体について、曲面状凹部の深さの平均値も上記範囲内であることが好ましい。 In the glass substrate of the present invention, the depth of the curved concave portion is preferably 0.1 to 100 μm, 0.5 to 70 μm, 0.5 to 50 μm, or 1 to 30 μm, particularly preferably 1 to 10 μm. When the depth of the curved concave portion is too small, the light is easily reflected on the roughened surface, and the light extraction efficiency is likely to be lowered. On the other hand, if the depth of the curved concave portion is too large, the glass substrate is easily damaged. In addition, about the whole curved-surface-shaped recessed part which exists in a rough surface, it is preferable that the average value of the depth of a curved-surface-shaped recessed part is also in the said range.
　本発明のガラス基板において、（曲面状凹部の深さ）／（曲面状凹部の平均半径）は、好ましくは０．０１～１０、０．０５～７または０．１～５であり、特に好ましくは０．１～３である。（曲面状凹部の深さ）／（曲面状凹部の平均半径）が小さ過ぎると、粗面化面で光が反射し易くなり、光取り出し効率が低下し易くなる。一方、（曲面状凹部の深さ）／（曲面状凹部の平均半径）が大き過ぎると、ガラス基板が破損し易くなる。なお、粗面化面に存在する曲面状凹部全体について、（曲面状凹部の深さ）／（曲面状凹部の平均半径）の平均値も上記範囲内であることが好ましい。 In the glass substrate of the present invention, (depth of curved concave portion) / (average radius of curved concave portion) is preferably 0.01 to 10, 0.05 to 7, or 0.1 to 5, particularly preferably. Is 0.1-3. If (depth of curved concave portion) / (average radius of curved concave portion) is too small, light is likely to be reflected by the roughened surface and light extraction efficiency tends to be reduced. On the other hand, if (depth of curved concave portion) / (average radius of curved concave portion) is too large, the glass substrate tends to be damaged. In addition, it is preferable that the average value of (the depth of the curved concave portion) / (the average radius of the curved concave portion) is also within the above range for the entire curved concave portion existing on the roughened surface.
　本発明のガラス基板において、粗面化面の表面粗さＲｔは５０～１００００ｎｍが好ましい。粗面化面の表面粗さＲｔが小さ過ぎると、粗面化面で光が反射し易くなり、光取り出し効率を高め難くなる。光取り出し効率を考慮すると、粗面化面の表面粗さＲｔは３００ｎｍ以上が好ましく、特に５００ｎｍ以上が好ましい。一方、粗面化面の表面粗さＲｔが大き過ぎると、ガラス基板の面内強度が低下し易くなる。ガラス基板の面内強度を考慮すると、粗面化面の表面粗さＲｔは９０００ｎｍ以下が好ましく、特に８０００ｎｍ以下が好ましい。 In the glass substrate of the present invention, the surface roughness Rt of the roughened surface is preferably 50 to 10,000 nm. If the surface roughness Rt of the roughened surface is too small, light is easily reflected on the roughened surface, and it is difficult to increase the light extraction efficiency. Considering the light extraction efficiency, the surface roughness Rt of the roughened surface is preferably 300 nm or more, particularly preferably 500 nm or more. On the other hand, if the surface roughness Rt of the roughened surface is too large, the in-plane strength of the glass substrate tends to decrease. Considering the in-plane strength of the glass substrate, the surface roughness Rt of the roughened surface is preferably 9000 nm or less, and particularly preferably 8000 nm or less.
　本発明のガラス基板において、粗面化面の表面粗さＲＳｍは０．１～１０００μｍが好ましい。粗面化面の表面粗さＲＳｍが小さ過ぎると、粗面化面で光が反射し易くなり、光取り出し効率を高め難くなる。光取り出し効率を考慮すると、粗面化面の表面粗さＲＳｍは１μｍ以上が好ましく、特に５μｍ以上が好ましい。一方、粗面化面の表面粗さＲｔが大き過ぎると、ガラス基板の面内強度が低下し易くなる。ガラス基板の面内強度を考慮すると、粗面化面の表面粗さＲＳｍは５００μｍ以下が好ましく、特に３００μｍ以下が好ましい。なお、「表面粗さＲＳｍ」は、ＪＩＳ　Ｒ０６０１（２００１）に準拠した方法により測定した値である。 In the glass substrate of the present invention, the surface roughness RSm of the roughened surface is preferably 0.1 to 1000 μm. When the surface roughness RSm of the roughened surface is too small, light is easily reflected on the roughened surface, and it is difficult to increase the light extraction efficiency. Considering the light extraction efficiency, the surface roughness RSm of the roughened surface is preferably 1 μm or more, particularly preferably 5 μm or more. On the other hand, if the surface roughness Rt of the roughened surface is too large, the in-plane strength of the glass substrate tends to decrease. Considering the in-plane strength of the glass substrate, the surface roughness RSm of the roughened surface is preferably 500 μm or less, particularly preferably 300 μm or less. The “surface roughness RSm” is a value measured by a method based on JIS R0601 (2001).
　本発明のガラス基板は、一方の表面に平滑面を有することが好ましく、平滑面の表面粗さＲｔは１０ｎｍ以下、１０ｎｍ未満、５ｎｍ以下または３ｎｍ以下が好ましく、特に１ｎｍ以下が好ましい。平滑面の表面粗さＲｔが大き過ぎると、平滑面に形成される透明導電膜の品位が低下し易くなり、面内の電界分布を均一に保ち難くなり、結果として、面内に輝度ムラが発生し易くなる。また、平滑面が未研磨面であることが好ましい。このようにすれば、ガラス基板が破壊し難くなる。なお、樹脂板は、表面平滑性に劣り、透明導電膜の品位を高めることが困難である。 The glass substrate of the present invention preferably has a smooth surface on one surface, and the surface roughness Rt of the smooth surface is preferably 10 nm or less, less than 10 nm, 5 nm or less, or 3 nm or less, particularly preferably 1 nm or less. If the surface roughness Rt of the smooth surface is too large, the quality of the transparent conductive film formed on the smooth surface is likely to deteriorate, and it becomes difficult to keep the electric field distribution in the surface uniform, resulting in uneven brightness in the surface. It tends to occur. The smooth surface is preferably an unpolished surface. If it does in this way, it will become difficult to destroy a glass substrate. In addition, a resin board is inferior to surface smoothness, and it is difficult to improve the quality of a transparent conductive film.
　本発明のガラス基板は、ガラス組成として、ＳｉＯ2を３０～７０質量％含むことが好ましく、特に３５～６５質量％含むことが好ましい。ＳｉＯ2は、ガラスのネットワークを形成する成分である。しかし、ＳｉＯ2の含有量が多過ぎると、溶融性、成形性が低下したり、屈折率が低くなり過ぎて、有機ＥＬ層の屈折率に整合させ難くなる。一方、ＳｉＯ2の含有量が少な過ぎると、ガラス化し難くなったり、耐薬品性が低下したり、面内強度が低下し易くなる。 The glass substrate of the present invention preferably contains 30 to 70% by mass of SiO 2 as a glass composition, particularly preferably 35 to 65% by mass. SiO 2 is a component that forms a network of glass. However, if the content of SiO 2 is too large, the meltability and moldability are lowered, or the refractive index is too low, making it difficult to match the refractive index of the organic EL layer. On the other hand, when the content of SiO 2 is too small, vitrification becomes difficult, chemical resistance is lowered, and in-plane strength is liable to be lowered.
　本発明のガラス基板は、ガラス組成として、質量％で、ＳｉＯ2　３０～７０％、Ａｌ2Ｏ3　０～２０％、Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ　０～１５％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ　５～５５％、ＴｉＯ2　０～２０％、ＺｒＯ2　０～１５％含有することが好ましい。このようにすれば、屈折率、耐失透性を高めることが可能になる。以下、各成分の含有範囲を上記のように規定した理由を示す。なお、「Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ」は、Ｌｉ2Ｏ、Ｎａ2Ｏ及びＫ2Ｏの合量を指す。「ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ」は、ＭｇＯ、ＣａＯ、ＳｒＯ及びＢａＯの合量を指す。 The glass substrate of the present invention has a glass composition of 30 to 70% by mass, SiO 2 30 to 70%, Al 2 O 3 0 to 20%, Li 2 O + Na 2 O + K 2 O 0 to 15%, MgO + CaO + SrO + BaO 5 to 55%, TiO 2. 2 0-20%, preferably contains ZrO 2 0 ~ 15%. If it does in this way, it will become possible to improve a refractive index and devitrification resistance. Hereinafter, the reason for defining the content range of each component as described above will be shown. “Li 2 O + Na 2 O + K 2 O” refers to the total amount of Li 2 O, Na 2 O and K 2 O. “MgO + CaO + SrO + BaO” refers to the total amount of MgO, CaO, SrO and BaO.
　ＳｉＯ2は、ガラスのネットワークを形成する成分であり、その含有量は３０～７０％が好ましく、特に３５～６５％が好ましい。ＳｉＯ2の含有量が多過ぎると、溶融性、成形性が低下したり、屈折率が低くなり過ぎて、有機ＥＬ層の屈折率に整合させ難くなる。一方、ＳｉＯ2の含有量が少な過ぎると、ガラス化し難くなったり、耐薬品性が低下したり、面内強度が低下し易くなる。 SiO 2 is a component that forms a glass network, and its content is preferably 30 to 70%, particularly preferably 35 to 65%. If the content of SiO 2 is too large, the meltability and moldability will be lowered, or the refractive index will be too low, making it difficult to match the refractive index of the organic EL layer. On the other hand, when the content of SiO 2 is too small, vitrification becomes difficult, chemical resistance is lowered, and in-plane strength is liable to be lowered.
　Ａｌ2Ｏ3は、ガラスのネットワークを形成する成分であり、また耐候性を高める成分である。Ａｌ2Ｏ3の含有量は０～２０％が好ましく、特に１～２０％が好ましい。Ａｌ2Ｏ3の含有量が多過ぎると、屈折率が低くなり過ぎて、有機ＥＬ層の屈折率に整合させ難くなることに加えて、ガラスに失透結晶が析出し易くなって、オーバーフローダウンドロー法等でガラス基板を成形し難くなる。 Al 2 O 3 is a component that forms a network of glass and is a component that improves weather resistance. The content of Al 2 O 3 is preferably 0 to 20%, particularly preferably 1 to 20%. If the Al 2 O 3 content is too high, the refractive index will be too low, making it difficult to match the refractive index of the organic EL layer, and devitrifying crystals will easily precipitate on the glass, resulting in overflow down. It becomes difficult to form a glass substrate by a draw method or the like.
　Ｂ2Ｏ3は、ガラスのネットワークを形成する成分であり、その含有量は０～２０％が好ましく、特に０～１５％が好ましい。Ｂ2Ｏ3の含有量が多過ぎると、耐薬品性が低下したり、屈折率が低くなり過ぎて、有機ＥＬ層の屈折率に整合させ難くなることに加えて、ガラスに失透結晶が析出し易くなって、オーバーフローダウンドロー法等でガラス基板を成形し難くなる。 B 2 O 3 is a component that forms a glass network, and its content is preferably 0 to 20%, particularly preferably 0 to 15%. When the content of B 2 O 3 is too large, the chemical resistance decreases, the refractive index becomes too low, and it becomes difficult to match the refractive index of the organic EL layer. It becomes easy to precipitate and it becomes difficult to shape | mold a glass substrate by the overflow downdraw method etc.
　Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏの含有量は０～１５％、０～１０％または０～５％が好ましく、特に０～１％が好ましい。Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏの含有量が多過ぎると、耐熱衝撃性が低下したり、耐酸性が低くなって、ＩＴＯのパターニング工程において、酸によりガラス基板が破損し易くなる。 The content of Li 2 O + Na 2 O + K 2 O is preferably 0 to 15%, 0 to 10% or 0 to 5%, particularly preferably 0 to 1%. When Li 2 O + Na 2 O + K content of 2 O is too large, or reduces the thermal shock resistance, so the acid resistance is low, in the patterning step of the ITO, a glass substrate is easily damaged by acid.
　Ｌｉ2Ｏは、溶融性、成形性を高める成分であり、更には耐失透性を改善する成分である。Ｌｉ2Ｏの含有量は０～１０％、０～５％、特に０～１％が好ましい。Ｌｉ2Ｏの含有量が多過ぎると、耐熱衝撃性が低下したり、耐酸性が低くなって、ＩＴＯのパターニング工程において、酸によりガラス基板が破損し易くなる。 Li 2 O is a component that improves meltability and moldability, and further improves devitrification resistance. The content of Li 2 O is preferably 0 to 10%, 0 to 5%, particularly preferably 0 to 1%. When the content of Li 2 O is too large, the thermal shock resistance is lowered or the acid resistance is lowered, and the glass substrate is easily damaged by acid in the ITO patterning step.
　Ｎａ2Ｏは、溶融性、成形性を高める成分であり、更には耐失透性を改善する成分である。Ｎａ2Ｏの含有量は０～１０％または０～５％が好ましく、特に０～１％が好ましい。Ｎａ2Ｏの含有量が多過ぎると、耐熱衝撃性が低下したり、耐酸性が低くなって、ＩＴＯのパターニング工程において、酸によりガラス基板が破損し易くなる。 Na 2 O is a component that improves meltability and moldability, and further improves devitrification resistance. The content of Na 2 O is preferably 0 to 10% or 0 to 5%, particularly preferably 0 to 1%. When the content of Na 2 O is too large, the thermal shock resistance is lowered or the acid resistance is lowered, and the glass substrate is easily damaged by an acid in the ITO patterning step.
　Ｋ2Ｏは、溶融性、成形性を高める成分であり、更には耐失透性を改善する成分である。Ｋ2Ｏの含有量は０～１０％または０～５％が好ましく、特に０～１％が好ましい。Ｋ2Ｏの含有量が多過ぎると、耐熱衝撃性が低下したり、耐酸性が低くなって、ＩＴＯのパターニング工程において、酸によりガラス基板が破損し易くなる。 K 2 O is a component that improves meltability and moldability, and further improves devitrification resistance. The content of K 2 O is preferably 0 to 10% or 0 to 5%, particularly preferably 0 to 1%. When the content of K 2 O is too large, or reduces the thermal shock resistance, so the acid resistance is low, in the patterning step of the ITO, a glass substrate is easily damaged by acid.
　ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯは、溶融性、成形性を高める成分である。しかし、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有量が多過ぎると、耐失透性が低下し易くなる。よって、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有量は５～５５％または１５～５０％が好ましく、特に２０～４５％が好ましい。 MgO + CaO + SrO + BaO is a component that improves meltability and moldability. However, when there is too much content of MgO + CaO + SrO + BaO, devitrification resistance will fall easily. Therefore, the content of MgO + CaO + SrO + BaO is preferably 5 to 55% or 15 to 50%, particularly preferably 20 to 45%.
　ＭｇＯは、溶融性、成形性を高める成分である。しかし、ＭｇＯの含有量が多過ぎると、耐失透性が低下し易くなる。よって、ＭｇＯの含有量は０～２０％が好ましい。 MgO is a component that improves meltability and moldability. However, when there is too much content of MgO, devitrification resistance will fall easily. Therefore, the content of MgO is preferably 0 to 20%.
　ＣａＯは、溶融性、成形性を高める成分である。しかし、ＣａＯの含有量が多過ぎると、耐失透性が低下し易くなる。よって、ＣａＯの含有量は０～２０％または１～１５％が好ましく、特に３～１２％が好ましい。 CaO is a component that improves meltability and moldability. However, when there is too much content of CaO, devitrification resistance will fall easily. Therefore, the CaO content is preferably 0 to 20% or 1 to 15%, and particularly preferably 3 to 12%.
　ＳｒＯは、溶融性、成形性を高めると共に、屈折率を高める成分である。しかし、ＳｒＯの含有量が多過ぎると、耐失透性が低下し易くなる。よって、ＳｒＯの含有量は０～２５％または０．１～２０％が好ましく、特に１～１５％が好ましい。 SrO is a component that enhances the meltability and moldability and also increases the refractive index. However, when there is too much content of SrO, devitrification resistance will fall easily. Therefore, the content of SrO is preferably 0 to 25% or 0.1 to 20%, particularly preferably 1 to 15%.
　ＢａＯは、溶融性、成形性を高めると共に、屈折率を高める成分である。しかし、ＢａＯの含有量が多過ぎると、耐失透性が低下し易くなる。よって、ＢａＯの含有量は０～４５％または５～４０％が好ましく、特に１５～３５％が好ましい。 BaO is a component that improves the meltability and moldability and also increases the refractive index. However, when there is too much content of BaO, devitrification resistance will fall easily. Therefore, the content of BaO is preferably 0 to 45% or 5 to 40%, particularly preferably 15 to 35%.
　ＴｉＯ2は、屈折率を高める成分である。しかし、ＴｉＯ2の含有量が多過ぎると、ガラスが着色したり、耐失透性が低下したり、密度が高くなり易い。よって、ＴｉＯ2の含有量は０～２０％または０．１～１５％が好ましく、特に１～７％好ましい。 TiO 2 is a component that increases the refractive index. However, if the content of TiO 2 is too large, the glass tends to be colored, the devitrification resistance is lowered, and the density tends to be high. Therefore, the content of TiO 2 is preferably 0 to 20% or 0.1 to 15%, particularly preferably 1 to 7%.
　ＺｒＯ2は、屈折率を高める成分である。しかし、ＺｒＯ2の含有量が多過ぎると、耐失透性が極端に低下する場合がある。よって、ＺｒＯ2の含有量は０～１５％または０．００１～１０％が好ましく、特に１～７％が好ましい。 ZrO 2 is a component that increases the refractive index. However, if the content of ZrO 2 is too large, the devitrification resistance may be extremely lowered. Therefore, the content of ZrO 2 is preferably 0 to 15% or 0.001 to 10%, particularly preferably 1 to 7%.
　上記成分以外にも、例えば、以下の成分を添加してもよい。なお、上記成分以外の成分の添加量は、２５％以下または２０％以下が好ましく、特に１５％以下が好ましい。 In addition to the above components, for example, the following components may be added. In addition, the addition amount of components other than the above components is preferably 25% or less or 20% or less, and particularly preferably 15% or less.
　ＺｎＯは、溶融性、成形性を高める成分である。しかし、ＺｎＯの含有量が多過ぎると、耐失透性が低下し易くなる。よって、ＺｎＯの含有量は０～２０％が好ましく、特に０～５％が好ましい。 ZnO is a component that improves meltability and moldability. However, when there is too much content of ZnO, devitrification resistance will fall easily. Therefore, the content of ZnO is preferably 0 to 20%, particularly preferably 0 to 5%.
　Ｎｂ2Ｏ5、Ｌａ2Ｏ3、Ｇｄ2Ｏ3等の希土類酸化物は、屈折率を高める成分であるが、原料自体のコストが高く、またガラス組成中に多量に添加すると、耐失透性が低下する場合がある。よって、希土類酸化物の含有量は、合量で０～２５％、特に０～１５％が好ましい。なお、Ｎｂ2Ｏ5の含有量は０～１５％が好ましく、特に０～３％が好ましい。Ｌａ2Ｏ3の含有量は０～１８％または０．１～１５％が好ましく、特に１～１２％が好ましい。Ｇｄ2Ｏ3の含有量は０～１２％が好ましく、特に０～３％が好ましい。 Rare earth oxides such as Nb 2 O 5 , La 2 O 3 , and Gd 2 O 3 are components that increase the refractive index, but the cost of the raw material itself is high, and when added in a large amount in the glass composition, devitrification resistance May decrease. Therefore, the total content of rare earth oxides is preferably 0 to 25%, particularly preferably 0 to 15%. The Nb 2 O 5 content is preferably 0 to 15%, particularly preferably 0 to 3%. The La 2 O 3 content is preferably 0 to 18% or 0.1 to 15%, particularly preferably 1 to 12%. The content of Gd 2 O 3 is preferably 0 to 12%, particularly preferably 0 to 3%.
　清澄剤として、Ａｓ2Ｏ3、Ｓｂ2Ｏ3、ＳｎＯ2、ＣｅＯ2、ＳＯ3、Ｆ、Ｃｌの群から選択された一種又は二種以上を０．００１～３％添加することができる。ただし、Ａｓ2Ｏ3、Ｓｂ2Ｏ3は、環境的な影響が懸念されるため、これらの成分の含有量は、各々０．１％未満が好ましく、特に０．０１％未満が好ましい。また、ＣｅＯ2は、透過率を低下させる成分であるため、その含有量は０．１％未満が好ましく、特に０．０１％未満が好ましい。更に、Ｆは、成形性を低下させる成分であるため、その含有量は０．１％未満が好ましく、特に０．０１％未満が好ましい。以上の点を考慮すると、清澄剤は、ＳｎＯ2、ＳＯ3、Ｃｌの群から選択された一種又は二種以上が好ましく、これらの成分の含有量は、合量で０．００１～３％、０．００１～１％または０．０１～０．５％が好ましく、更には０．０５～０．４％が好ましい。 As a fining agent, 0.001 to 3% of one or more selected from the group consisting of As 2 O 3 , Sb 2 O 3 , SnO 2 , CeO 2 , SO 3 , F, and Cl can be added. However, As 2 O 3 and Sb 2 O 3 are concerned about environmental influences, and therefore the content of these components is preferably less than 0.1%, particularly preferably less than 0.01%. CeO 2 is a component that lowers the transmittance, so its content is preferably less than 0.1%, particularly preferably less than 0.01%. Furthermore, since F is a component that lowers moldability, its content is preferably less than 0.1%, and particularly preferably less than 0.01%. Considering the above points, the fining agent is preferably one or more selected from the group of SnO 2 , SO 3 , Cl, and the content of these components is 0.001 to 3% in total, 0.001 to 1% or 0.01 to 0.5% is preferable, and 0.05 to 0.4% is more preferable.
　ＰｂＯは、屈折率を高める成分であるが、環境的な影響が懸念される成分である。よって、ＰｂＯの含有量は０．１％未満が好ましい。 PbO is a component that increases the refractive index, but is a component that is concerned about environmental influences. Therefore, the PbO content is preferably less than 0.1%.
　本発明のガラス基板は、オーバーフローダウンドロー法で成形されてなることが好ましい。ここで、「オーバーフローダウンドロー法」は、フュージョン法とも称されており、耐熱性の樋状構造物の両側から溶融ガラスを溢れさせて、溢れた溶融ガラスを樋状構造物の下端で合流させながら、下方に延伸成形してガラス基板を作製する方法である。このようにすれば、未研磨で表面品位が良好なガラス基板を成形することができる。その理由は、オーバーフローダウンドロー法の場合、ガラス基板の表面となるべき面は樋状耐火物に接触せず、自由表面の状態で成形されるからである。樋状構造物の構造や材質は、所望の寸法や表面品位を実現できるものであれば、特に限定されない。また、下方への延伸成形を行うために、ガラスに対して力を印加する方法は、所望の寸法や表面品位を実現できるものであれば、特に限定されない。例えば、充分に大きい幅を有する耐熱性ロールをガラスに接触させた状態で回転させて延伸する方法を採用してもよいし、複数の対になった耐熱性ロールをガラスの端面近傍のみに接触させて延伸する方法を採用してもよい。 The glass substrate of the present invention is preferably formed by an overflow down draw method. Here, 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 bowl-like structure, and the overflowing molten glass is joined at the lower end of the bowl-like structure. However, this is a method of producing a glass substrate by drawing downward. In this way, a glass substrate that is unpolished and has good surface quality can be formed. The reason is that, in the case of the overflow downdraw method, the surface to be the surface of the glass substrate 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. In addition, the method of applying a force to the glass in order to perform the downward stretch molding is not particularly limited as long as desired dimensions and surface quality can be realized. For example, a method may be adopted in which a heat-resistant roll having a sufficiently large width is rotated and stretched in contact with glass, or a plurality of pairs of heat-resistant rolls are contacted only near the end face of the glass. It is also possible to adopt a method of stretching by stretching.
　本発明のガラス基板は、スロットダウンドロー法で成形されてなることも好ましい。スロットダウンドロー法は、オーバーフローダウンドロー法と同様にして、ガラス基板の寸法精度を高めることができる。なお、スロットダウンドロー法は、スロットの形状を変更することにより、ガラス基板の表面に粗面化面（曲面状凹部）を形成することもできる。 The glass substrate 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 substrate in the same manner as the overflow down draw method. The slot down draw method can also form a roughened surface (curved concave portion) on the surface of the glass substrate by changing the shape of the slot.
　成形方法として、オーバーフローダウンドロー法、スロットダウンドロー法以外にも、種々の方法を採用することができる。例えば、フロート法、ロールアウト法、リドロー法等を採用することができる。特に、フロート法でガラス基板を成形すれば、大型のガラス基板を安価に作製することができる。 As the molding method, various methods other than the overflow downdraw method and the slot downdraw method can be adopted. For example, a float method, a rollout method, a redraw method, or the like can be employed. In particular, if a glass substrate is formed by a float process, a large glass substrate can be manufactured at low cost.
　本発明のガラス基板において、板厚が小さい程、有機ＥＬデバイスを軽量化し易くなると共に、ガラス基板の可撓性を高めることができる。板厚は２ｍｍ以下、１．５ｍｍ以下または１ｍｍ以下が好ましく、特に０．７ｍｍ以下が好ましい。一方、板厚が極端に小さ過ぎると、ガラス基板が破損し易くなる。よって、ガラス基板の板厚は、５０μｍ以上または１００μｍ以上が好ましく、特に２００μｍ以上が好ましい。ガラス基板が取り得る最小曲率半径は２００ｍｍ以下、１５０ｍｍ以下、１００ｍｍ以下または５０ｍｍ以下が好ましく、特に３０ｍｍ以下が好ましい。なお、取り得る最小曲率半径が小さい程、可撓性に優れるため、有機ＥＬ照明等の設置の自由度が高まる。 In the glass substrate of the present invention, the smaller the plate thickness, the easier it is to reduce the weight of the organic EL device, and the flexibility of the glass substrate can be increased. The plate thickness is preferably 2 mm or less, 1.5 mm or less, or 1 mm or less, and particularly preferably 0.7 mm or less. On the other hand, if the plate thickness is extremely small, the glass substrate tends to be damaged. Therefore, the plate thickness of the glass substrate is preferably 50 μm or more or 100 μm or more, and particularly preferably 200 μm or more. The minimum curvature radius that the glass substrate can take is preferably 200 mm or less, 150 mm or less, 100 mm or less, or 50 mm or less, and particularly preferably 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.
　ガラス基板の一方の表面が粗面化面が形成されている表面であり、他方の表面が粗面化面が形成されていない表面である場合、ガラス基板と空気の界面において、（光が、入射角６０°で、粗面化面が形成されていない表面から空気中に向かって入射された時に、粗面化面が形成されている表面から空気中に取り出される放射束値）／（光が、入射角０°で、粗面化面が形成されていない表面から空気中に向かって入射された時に、粗面化面が形成されている表面から空気中に取り出される放射束値）の値が０．０１以上、０．１以上、０．１５以上または０．２以上が好ましく、特に０．２５以上が好ましい。このようにすれば、ガラス板内に閉じ込められる光が低減されて、光取り出し効率が向上する。 When one surface of the glass substrate is a surface on which a roughened surface is formed and the other surface is a surface on which no roughened surface is formed, at the interface between the glass substrate and air (light Radiation flux value taken out into the air from the surface where the roughened surface is formed when incident on the surface from the surface where the roughened surface is not formed at an incident angle of 60 ° / (light However, when the incident angle is 0 ° and the light is incident on the air from the surface on which the roughened surface is not formed, the radiant flux value taken into the air from the surface on which the roughened surface is formed). The value is preferably 0.01 or more, 0.1 or more, 0.15 or more, or 0.2 or more, and particularly preferably 0.25 or more. In this way, the light confined in the glass plate is reduced, and the light extraction efficiency is improved.
　以下、実施例に基づいて、本発明を詳細に説明する。なお、以下の実施例は単なる例示である。本発明は、以下の実施例に何ら限定されない。 Hereinafter, the present invention will be described in detail based on examples. The following examples are merely illustrative. The present invention is not limited to the following examples.
＜各試料の作製＞
　まず表１に記載のガラス組成になるように、ガラス原料を調合した後、得られたガラスバッチをガラス溶融炉に供給して１５００～１６００℃で４時間溶融した。次に、得られた溶融ガラスをカーボン板の上に流し出して、板厚０．７ｍｍのガラス基板を成形した後、所定のアニール処理を行った。次に、空気側になるべき面に対して、表１に記載の物理的処理（サンドブラスト処理）を行った後、必要に応じて、物理的処理が行われていない表面にＨＦ溶液に侵食されない保護テープを貼付した上で、表１に記載の化学的処理（ＨＦ処理）を行うことにより、各試料を得た。なお、試料Ｎｏ．１７は、物理的処理と化学的処理が行われていない。サンドブラスト処理は、表１に記載の粒度を有するブラスト材（４ｋｇのＡｌ2Ｏ3を２０Ｌの水に分散させたもの）を用いて、ブラスト材をガラス基板の表面に２ＭＰａで吹きつけることで行った。ＨＦ処理は、各試料を２５℃の１０％ＨＦ溶液に所定時間浸漬することで行った。 <Preparation of each sample>
First, after preparing glass raw materials so as to have the glass composition shown in Table 1, the obtained glass batch was supplied to a glass melting furnace and melted at 1500 to 1600 ° C. for 4 hours. Next, the obtained molten glass was poured onto a carbon plate to form a glass substrate having a thickness of 0.7 mm, and then a predetermined annealing treatment was performed. Next, after the physical treatment (sand blasting treatment) described in Table 1 is performed on the surface to be the air side, the surface not subjected to the physical treatment is not eroded by the HF solution as necessary. Each sample was obtained by applying the chemical treatment (HF treatment) described in Table 1 after applying the protective tape. Sample No. In No. 17, physical treatment and chemical treatment are not performed. The sand blast treatment is performed by spraying the blast material onto the surface of the glass substrate at 2 MPa using a blast material having a particle size shown in Table 1 (4 kg of Al 2 O 3 dispersed in 20 L of water). It was. The HF treatment was performed by immersing each sample in a 10% HF solution at 25 ° C. for a predetermined time.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　屈折率ｎdは、カルニュー社製の屈折率測定器ＫＰＲ－２０００により測定した値である。 Refractive index n d is the value measured by the refractive index measuring instrument KPR-2000 of Kalnew Corporation.
＜表面形状観察＞
　各試料の粗面化面に対して、レーザー顕微鏡（キーエンス社製ＶＫ―Ｘ１００ｓｅｒｒｉｅｓ）により表面形状観察を行った。その結果を表１に示す。 <Surface shape observation>
The surface shape of the roughened surface of each sample was observed with a laser microscope (VK-X100 series manufactured by Keyence Corporation). The results are shown in Table 1.
　曲面状凹部の評価は、粗面化面全体に亘って、曲面状凹部が形成されていたものを「○」、部分的に曲面状凹部が形成されていたものを「△」、曲面状凹部が形成されておらず、破砕形状のみであったものを「×」として評価した。なお、試料Ｎｏ．１～１６の粗面化面の顕微鏡写真を図２～１７にそれぞれ示す。詳述すると、図２は資料Ｎｏ．１の粗面化面、図３は資料Ｎｏ．２の粗面化面、図４は資料Ｎｏ．３の粗面化面、図５は資料Ｎｏ．４の粗面化面、図６は資料Ｎｏ．５の粗面化面、図７は資料Ｎｏ．６の粗面化面、図８は資料Ｎｏ．７の粗面化面、図９は資料Ｎｏ．８の粗面化面、図１０は資料Ｎｏ．９の粗面化面、図１１は資料Ｎｏ．１０の粗面化面、図１２は資料Ｎｏ．１１の粗面化面、図１３は資料Ｎｏ．１２の粗面化面、図１４は資料Ｎｏ．１３の粗面化面、図１５は資料Ｎｏ．１４の粗面化面、図１６は資料Ｎｏ．１５の粗面化面、図１７は資料Ｎｏ．１６の粗面化面、をそれぞれ示す顕微鏡写真である。 The evaluation of the curved concave portion is “◯” when the curved concave portion is formed over the entire roughened surface, “△” when the curved concave portion is partially formed, and the curved concave portion. Was not formed, and only the crushed shape was evaluated as “x”. Sample No. Photomicrographs of roughened surfaces 1 to 16 are shown in FIGS. 2 to 17, respectively. Specifically, FIG. No. 1 roughened surface, FIG. 2 roughened surface, FIG. 3 roughened surface, FIG. 4 is a roughened surface, FIG. No. 5 roughened surface, FIG. 6 is a roughened surface, FIG. 7 is a roughened surface, FIG. No. 8 roughened surface, FIG. 9 is a roughened surface, FIG. No. 10 roughened surface, FIG. 11 is a roughened surface, FIG. 12 roughened surface, FIG. 13 is a roughened surface, FIG. 14 is a roughened surface, FIG. 15 roughened surface, FIG. It is a microscope picture which shows 16 roughening surfaces, respectively.
　曲面状凹部について、画像解析により、平均半径、深さを算出した。算出に際して、任意の１０個の曲面状凹部を抽出し、その平均値を求めた。なお、本実施例では、実験の便宜上、画像解析により平均半径、深さを算出したが、画像解析以外の方法でも算出可能である。なお、図１８は、曲面状凹部の平均半径と深さを模式的に示す概略断面図である。図１８において、ａが平均半径を示し、ｂが深さを示している。 The average radius and depth of the curved concave portion were calculated by image analysis. In the calculation, arbitrary 10 curved concave portions were extracted, and the average value was obtained. In the present embodiment, the average radius and depth are calculated by image analysis for convenience of experiment, but can be calculated by methods other than image analysis. FIG. 18 is a schematic cross-sectional view schematically showing the average radius and depth of the curved concave portion. In FIG. 18, a indicates the average radius and b indicates the depth.
　図１９は、試料Ｎｏ．８の粗面化面について、サーフコーダによる断面形状を測定したデータである。図９及び図１９から、試料Ｎｏ．８の粗面化面に曲面状凹部が非周期的に形成されていることが分かる。 FIG. 19 shows sample no. 8 is data obtained by measuring a cross-sectional shape of a roughened surface of 8 using a surf coder. From FIG. 9 and FIG. It can be seen that curved concave portions are formed aperiodically on the roughened surface 8.
＜光散乱機能の評価＞
　続いて、各試料について、光散乱機能を評価した。図２０を参酌しながら、光散乱機能の評価方法を詳細に説明する。図２０は、光散乱機能の評価方法を示す概略断面図である。まずガラス基板２１の一方の表面（粗面化面が形成されていない表面）上に浸液を用いて屈折率ｎd１．７４の半球レンズ２２を設置し、半球レンズ２２の中心に向かって、光源２４から光を入射させた。次に、ガラス基板２１の内部を通って、ガラス基板２１の他方の表面（粗面化面が形成されている表面）から取り出される光を積分球２３により検出した。更に、ガラス基板２１の表面に垂直な面からの傾きをθとし、入射角θを変化させて同様の実験を繰り返し、それぞれの入射角において取り出される光を積分球２３により検出した。その測定結果を表１に示す。ここで、積分球２３と分光器を接続する光ファイバには、オーシャンオプティクス製Ｐ５０－２－ＵＶ－ＶＩＳを用いた。また、光源２４には、モリテックス製赤色レーザーＳＮＦ－６６０－５、分光器には、オーシャンフォトニクス製ファイバマルチチャンネル分光器ＵＳＢ４０００、ソフトウェアには、オーシャンフォトニクス製ＯＰＷａｖｅを用いた。 <Evaluation of light scattering function>
Subsequently, the light scattering function was evaluated for each sample. The light scattering function evaluation method will be described in detail with reference to FIG. FIG. 20 is a schematic cross-sectional view showing a method for evaluating the light scattering function. First, a hemispherical lens 22 having a refractive index n d 1.74 is installed on one surface of the glass substrate 21 (a surface on which a roughened surface is not formed) using an immersion liquid, and toward the center of the hemispherical lens 22. Then, light was incident from the light source 24. Next, the light extracted from the other surface (the surface on which the roughened surface is formed) of the glass substrate 21 through the inside of the glass substrate 21 was detected by the integrating sphere 23. Further, the inclination from a plane perpendicular to the surface of the glass substrate 21 was θ, and the same experiment was repeated while changing the incident angle θ, and the light extracted at each incident angle was detected by the integrating sphere 23. The measurement results are shown in Table 1. Here, P50-2-UV-VIS manufactured by Ocean Optics was used as the optical fiber connecting the integrating sphere 23 and the spectroscope. In addition, a red laser SNF-660-5 manufactured by Moritex was used as the light source 24, a fiber multichannel spectrometer USB4000 manufactured by Ocean Photonics was used as the spectrometer, and OPWave manufactured by Ocean Photonics was used as the software.
　表１から明らかなように、試料Ｎｏ．２～４、６～８、１０～１２、１４～１６は、０°の入射角で高い放射束値が得られると共に、４０°以上の入射角でも、高い放射束値が得られた。そして、試料Ｎｏ．２～４、６～８、１０～１２、１４～１６には、曲面状凹部が形成されているため、面内強度が高いと推測される。 As is clear from Table 1, sample No. For 2-4, 6-8, 10-12, and 14-16, high radiant flux values were obtained at an incident angle of 0 °, and high radiant flux values were also obtained at an incident angle of 40 ° or more. And sample no. In 2-4, 6-8, 10-12, and 14-16, since the curved concave portions are formed, it is estimated that the in-plane strength is high.
１　　有機ＥＬ照明
１１　ガラス基板
１２　陽極
１３　有機ＥＬ層
１４　陰極
２１　ガラス基板
２２　半球レンズ
２３　積分球
２４　光源 DESCRIPTION OF SYMBOLS 1 Organic EL illumination 11 Glass substrate 12 Anode 13 Organic EL layer 14 Cathode 21 Glass substrate 22 Hemispherical lens 23 Integrating sphere 24 Light source

Claims (13)

  1. 　屈折率ｎdが１．５０以上のガラス基板であって、少なくとも一方の表面に粗面化面を有し、該粗面化面に曲面状凹部を有することを特徴とするガラス基板。 A glass substrate of 1.50 or more refractive index n d has a roughened surface on at least one surface, a glass substrate and having a curved recess in the crude surface treatment side.
  2. 　粗面化面に曲面状凹部が非周期的に形成されていることを特徴とする請求項１に記載のガラス基板。 2. The glass substrate according to claim 1, wherein a curved concave portion is aperiodically formed on the roughened surface.
  3. 　曲面状凹部が、物理的処理後に化学的処理を行うことにより形成されていることを特徴とする請求項１又は２に記載のガラス基板。 The glass substrate according to claim 1 or 2, wherein the curved concave portion is formed by performing chemical treatment after physical treatment.
  4. 　物理的処理がサンドブラスト処理であることを特徴とする請求項３に記載のガラス基板。 4. The glass substrate according to claim 3, wherein the physical treatment is sandblast treatment.
  5. 　化学的処理が酸による薬液処理であることを特徴とする請求項３又は４に記載のガラス基板。 The glass substrate according to claim 3 or 4, wherein the chemical treatment is a chemical treatment with an acid.
  6. 　曲面状凹部の平均半径が０．１～１００μｍであることを特徴とする請求項１～５の何れかに記載のガラス基板。 6. The glass substrate according to claim 1, wherein an average radius of the curved concave portion is 0.1 to 100 μm.
  7. 　曲面状凹部の深さが０．１～１００μｍであることを特徴とする請求項１～６の何れかに記載のガラス基板。 7. The glass substrate according to claim 1, wherein the depth of the curved concave portion is 0.1 to 100 μm.
  8. 　（曲面状凹部の深さ）／（曲面状凹部の平均半径）が０．０１～１０であることを特徴とする請求項１～７の何れかに記載のガラス基板。 The glass substrate according to any one of claims 1 to 7, wherein (depth of curved concave portion) / (average radius of curved concave portion) is 0.01 to 10.
  9. 　一方の表面に平滑面を有し、平滑面の表面粗さＲｔが１０ｎｍ以下であることを特徴とする請求項１～８の何れかに記載のガラス基板。 9. The glass substrate according to claim 1, wherein the glass substrate has a smooth surface on one surface, and the surface roughness Rt of the smooth surface is 10 nm or less.
  10. 　ガラス組成として、ＳｉＯ2を３０～７０質量％含むことを特徴とする請求項１～９の何れかに記載のガラス基板。 The glass substrate according to any one of claims 1 to 9, wherein the glass composition contains 30 to 70 mass% of SiO 2 .
  11. 　ガラス基板内部から空気中へ進行する光が、臨界角以上でも全反射せずに、粗面化面から空気中に取り出される性質を有することを特徴とする請求項１～１０の何れかに記載のガラス基板。 11. The light traveling from the inside of the glass substrate into the air has a property of being taken out into the air from the roughened surface without being totally reflected even at a critical angle or more. Glass substrate.
  12. 　有機ＥＬデバイスに用いることを特徴とする請求項１～１１の何れかに記載のガラス基板。 The glass substrate according to any one of claims 1 to 11, which is used for an organic EL device.
  13. 　照明に用いることを特徴とする請求項１～１２の何れかに記載のガラス基板。 The glass substrate according to any one of claims 1 to 12, wherein the glass substrate is used for illumination.
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JP2005038767A (en) * 2003-07-17 2005-02-10 Sony Corp Backlight and its manufacturing method, and liquid crystal display
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