WO2014129345A1 - Substrat de verre - Google Patents

Substrat de verre Download PDF

Info

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
Authority
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
English (en)
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Le problème abordé par la présente invention est la formation d'une idée originale d'un substrat de verre qui peut extraire de la lumière vers l'extérieur avec une excellente efficacité même si un film de résine transparent n'est pas fait pour adhérer à la surface du substrat de verre. Ce substrat de verre est un substrat de verre (11) ayant un indice de réfraction (nd) de 1,50 ou plus et est caractérisé en ce qu'il a une surface rendue grossière sur au moins une surface de celui-ci et en ce qu'il a des renfoncements mis en forme de surface incurvée dans la surface rendue grossière.
PCT/JP2014/053030 2013-02-19 2014-02-10 Substrat de verre WO2014129345A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-029622 2013-02-19
JP2013029622A JP2014160543A (ja) 2013-02-19 2013-02-19 ガラス基板

Publications (1)

Publication Number Publication Date
WO2014129345A1 true WO2014129345A1 (fr) 2014-08-28

Family

ID=51391140

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/053030 WO2014129345A1 (fr) 2013-02-19 2014-02-10 Substrat de verre

Country Status (3)

Country Link
JP (1) JP2014160543A (fr)
TW (1) TW201437175A (fr)
WO (1) WO2014129345A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10473829B2 (en) 2016-01-18 2019-11-12 Corning Incorporated Enclosures having an improved tactile surface
CN107708364B (zh) * 2017-10-30 2020-01-14 Oppo广东移动通信有限公司 壳体制作方法、壳体及电子设备

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004079208A (ja) * 2002-08-09 2004-03-11 Senyo Shoji Kk 有機ｅｌ素子封止用ガラス部材及び前記ガラス部材を用いた有機ｅｌパネル
JP2004296438A (ja) * 2003-03-12 2004-10-21 Mitsubishi Chemicals Corp エレクトロルミネッセンス素子
JP2005038767A (ja) * 2003-07-17 2005-02-10 Sony Corp バックライトとその製造方法、及び液晶表示装置
JP2008062349A (ja) * 2006-09-08 2008-03-21 Central Glass Co Ltd ガラス板の洗浄方法
JP2011213568A (ja) * 2009-07-08 2011-10-27 Nippon Electric Glass Co Ltd ガラス板
JP2012144402A (ja) * 2011-01-14 2012-08-02 Central Glass Co Ltd 透明物品及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004079208A (ja) * 2002-08-09 2004-03-11 Senyo Shoji Kk 有機ｅｌ素子封止用ガラス部材及び前記ガラス部材を用いた有機ｅｌパネル
JP2004296438A (ja) * 2003-03-12 2004-10-21 Mitsubishi Chemicals Corp エレクトロルミネッセンス素子
JP2005038767A (ja) * 2003-07-17 2005-02-10 Sony Corp バックライトとその製造方法、及び液晶表示装置
JP2008062349A (ja) * 2006-09-08 2008-03-21 Central Glass Co Ltd ガラス板の洗浄方法
JP2011213568A (ja) * 2009-07-08 2011-10-27 Nippon Electric Glass Co Ltd ガラス板
JP2012144402A (ja) * 2011-01-14 2012-08-02 Central Glass Co Ltd 透明物品及びその製造方法

Also Published As

Publication number Publication date
JP2014160543A (ja) 2014-09-04
TW201437175A (zh) 2014-10-01

Similar Documents

Publication Publication Date Title
JP6269933B2 (ja) ガラス板
KR20160101092A (ko) 디스플레이 응용을 위한 텍스쳐링된 표면
TW200427366A (en) Light-emitting apparatus and method for forming the same
TW201704179A (zh) 包含光提取特徵之玻璃物件以及製造彼之方法
CN102623647A (zh) 有机电致发光器件的制造方法及基板
WO2015186606A1 (fr) Verre à phases séparées, verre à phases séparables, dispositif el organique et procédé de production de verre à phases séparées
WO2014129345A1 (fr) Substrat de verre
WO2015186584A1 (fr) Verre à séparation de phases, procédé de fabrication de verre à séparation de phases et substrat composite utilisant un verre à séparation de phases
WO2015034030A1 (fr) Verre et son procédé de production
JP6249218B2 (ja) ガラスの製造方法及びガラス
JP6103335B2 (ja) ガラス基板及びその製造方法、並びにガラス基板を用いた有機ｅｌデバイス
JP2013109923A (ja) 電子デバイス用基板の製造方法
KR101470293B1 (ko) 유기발광소자용 광추출 기판 제조방법
JP6406571B2 (ja) ガラス
WO2015166708A1 (fr) Substrat de verre, illuminateur électroluminescent (el) organique, et procédé de production de substrat de verre
KR101602470B1 (ko) 디스플레이용 다공성 유리 기판 및 그 제조방법
JP2016064970A (ja) 分相ガラス
JP6331077B2 (ja) 分相ガラス及びこれを用いた複合基板
JP2015105218A (ja) ガラス基板及びその製造方法
JP6090708B2 (ja) 拡散板及びそれを備えた照明装置
JP6331076B2 (ja) ガラスフィルム及びこれを用いた複合基板
JP2015227272A (ja) 分相ガラス及びこれを用いた複合基板
WO2016117406A1 (fr) Verre à phases séparées
JP2016011245A (ja) 分相ガラス
JP2015120614A (ja) ガラス

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14753545

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14753545

Country of ref document: EP

Kind code of ref document: A1