WO2016117406A1 - Verre à phases séparées - Google Patents
Verre à phases séparées Download PDFInfo
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- WO2016117406A1 WO2016117406A1 PCT/JP2016/050634 JP2016050634W WO2016117406A1 WO 2016117406 A1 WO2016117406 A1 WO 2016117406A1 JP 2016050634 W JP2016050634 W JP 2016050634W WO 2016117406 A1 WO2016117406 A1 WO 2016117406A1
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- phase
- glass
- refractive index
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- 239000011521 glass Substances 0.000 title claims abstract description 150
- 239000012071 phase Substances 0.000 claims abstract description 31
- 239000007791 liquid phase Substances 0.000 claims abstract description 15
- 238000005191 phase separation Methods 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 10
- 238000007500 overflow downdraw method Methods 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 abstract description 15
- 230000007423 decrease Effects 0.000 description 27
- 238000004031 devitrification Methods 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 230000001771 impaired effect Effects 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000010583 slow cooling Methods 0.000 description 6
- 238000006124 Pilkington process Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- -1 Gd 2 O 3 Inorganic materials 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000003280 down draw process Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007372 rollout process Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
- C03B17/06—Forming glass sheets
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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
-
- 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
- C03C3/089—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
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- 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
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Definitions
- the present invention relates to a phase-separated glass, and specifically relates to a phase-separated glass having a light scattering function.
- 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.
- the organic EL element includes a glass plate, a transparent conductive film as an anode, an organic EL layer including an organic compound exhibiting electroluminescence that emits light by current injection, and a cathode, and a cathode. It is an element.
- As the organic EL layer used in the organic EL element a low molecular dye material, a conjugated polymer material or the like is used.
- a hole injection layer, a hole transport layer, an electron transport layer, an electron injection A laminated structure with layers and the like is formed.
- An organic EL layer having such a laminated structure is disposed between the anode and the cathode, and by applying an electric field to the anode and the cathode, holes injected from the transparent electrode that is the anode and those injected from the cathode The electrons recombine in the light emitting layer, and the 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.
- An organic EL display using an organic EL element has a light emission efficiency equivalent to that of a thin television such as a liquid crystal display or a plasma display.
- One cause of the decrease in luminance is that light is confined in the glass plate due to the difference in refractive index between the glass plate and air.
- the critical angle is calculated to be 42 ° from Snell's law. Therefore, light having an incident angle greater than the critical angle causes total reflection, is confined in the glass plate, and is not extracted into the air.
- Patent Document 1 a light extraction layer in which a glass frit having a high refractive index is sintered is formed on the surface of a soda glass plate, and a scattering substance is dispersed in the light extraction layer, thereby reducing the light extraction efficiency. It is also described to increase.
- the present invention has been made in view of the above circumstances, and the technical problem thereof is that the light extraction efficiency of the organic EL element can be increased without producing a light extraction layer made of a sintered body, and the production can be achieved.
- the idea is to create an excellent glass.
- phase-separated glass of the present invention i.e., phase-separated glass of the present invention has a phase separation structure comprising at least a first phase and a second phase, the refractive index n d be 1.51 or more
- the liquid phase viscosity is 10 3.5 dPa ⁇ s or more.
- “refractive index n d ” refers to the value of the d-line measured by a refractive index measuring device.
- a rectangular parallelepiped sample of 25 mm ⁇ 25 mm ⁇ about 3 mm is first prepared, and is slowly cooled at a cooling rate of 0.1 ° C./min in the temperature range from (annealing point Ta + 30 ° C.) to (strain point Ps ⁇ 50 ° C.). after, while penetration of immersion the refractive index n d are aligned, it can be measured by the refractive index measuring instrument KPR-2000 manufactured by Shimadzu Corporation.
- “Liquid phase viscosity” refers to the viscosity of the glass at the liquidus temperature.
- Liquid phase temperature is a glass powder that passes through 30 mesh (a sieve opening of 500 ⁇ m) and remains in a 50 mesh (a sieve opening of 300 ⁇ m) in a platinum boat and is kept in a temperature gradient furnace for 24 hours. The value which measured the temperature which precipitates. Note that the phase separation structure including at least the first phase and the second phase can be visually confirmed by light scattering on the surface.
- the phase separation glass of the present invention has a phase separation structure including at least a first phase and a second phase.
- the light incident on the glass plate from the organic EL layer is scattered at the interface between the first phase and the second phase, so that the light can be easily taken out to the outside.
- the light extraction efficiency can be increased without forming a light extraction layer made of a sintered body.
- the refractive index n d is 1.51 or more.
- the refractive index n d of the transparent conductive film is 1.9 to 2.0, and the refractive index n d of the organic EL layer was 1.8-1.9.
- the refractive index n d of the glass plate was typically about 1.50.
- the refractive index nd is regulated as described above, so that the difference in refractive index between the glass plate and the transparent conductive film is reduced, so that light incident from the organic EL layer is reflected at the interface between the glass plate and the transparent conductive film. Light extraction efficiency can be increased.
- the phase separation glass of the present invention has a liquidus viscosity of 10 3.5 dPa ⁇ s or more. Since the conventional high refractive index phase-separated glass has a low liquidus viscosity, it has been difficult to produce a large number of glass plates. Therefore, if the liquidus viscosity is regulated as described above, the glass becomes difficult to devitrify at the time of molding, and in particular, it becomes easy to mass-produce a plate-shaped phase-separated glass. As a result, the manufacturing cost of the phase separation glass can be reduced.
- phase-separated glass of the present invention preferably has a refractive index n d is less than 1.63.
- the phase-separated glass of the present invention contains, as a glass composition, SiO 2 30 to 75%, Al 2 O 3 0 to 35%, and B 2 O 3 0.1 to 50% by mass. Is preferred. If it does in this way, phase separation property and devitrification resistance can be improved.
- the phase-separated glass of the present invention preferably has a content of SiO 2 + Al 2 O 3 + B 2 O 3 in the glass composition of 55 to 80% by mass. If it does in this way, devitrification resistance can further be improved.
- SiO 2 + Al 2 O 3 + B 2 O 3 refers to the total amount of SiO 2 , Al 2 O 3 and B 2 O 3 .
- the phase-separated glass of the present invention preferably has a content of MgO + CaO + SrO + BaO + ZnO in the glass composition of 15 to 35% by mass.
- MgO + CaO + SrO + BaO + ZnO refers to the total amount of MgO, CaO, SrO, BaO and ZnO.
- the phase-separated glass of the present invention preferably has a P 2 O 5 content of 0.001 to 20% by mass in the glass composition. In this way, it becomes easy to improve the phase separation.
- the content of Li 2 O + Na 2 O + K 2 O in the glass composition is preferably 5% by mass or less.
- 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.
- the phase separation glass of the present invention has a flat plate shape.
- the phase separation glass of the present invention is preferably formed by an overflow downdraw method.
- the phase separation glass of the present invention is preferably used for illumination.
- phase separation glass of the present invention is preferably used for organic EL lighting.
- the organic EL device of the present invention includes the above phase separation glass.
- Phase-separated glass of the present invention has a phase separation structure comprising at least a first phase and a second phase, the content of SiO 2 in the first phase, containing SiO 2 in the second phase More than the amount is preferred. If it does in this way, the refractive index of a 1st phase and a 2nd phase will become easy to differ, and the scattering function of glass can be improved. In addition, if the surface of the sample after being immersed in a 2% by volume hydrofluoric acid solution for 2 minutes is observed with a field emission scanning electron microscope, the details of each phase, particularly the content of SiO 2 in each phase can be confirmed. is there.
- the average particle size of phase-separated particles of at least one phase is preferably 0.01 to 5 ⁇ m, particularly preferably 0.02 to 1 ⁇ m. If the average particle size of the phase-separated particles is small, the light emitted from the organic EL layer is difficult to scatter at the interface between the first phase and the second phase. On the other hand, if the average particle size of the phase-separated particles is large, the scattering intensity becomes too strong and the total light transmittance may be lowered.
- the refractive index n d is 1.51 or more, preferably 1.52 or more, 1.53 or more, 1.54 or more, particularly 1.55 or more.
- the refractive index n d is less than 1.51, it becomes difficult to efficiently extract light by reflection at the interface, such as a glass plate and a transparent conductive film.
- the refractive index n d is too high, since the introduction of the components to improve the devitrification resistance is limited, it is difficult to increase the liquidus viscosity. Further, the reflectance at the interface between the glass plate and the air becomes high, and it becomes difficult to extract light to the outside.
- the refractive index n d is preferably 2.30 or less, 2.00 or less, 1.80 or less, 1.70 or less, 1.65 or less, less than 1.63, 1.62 or less, 1.61 or less, 1.60 or less, 1.59 or less, particularly 1.58 or less.
- the liquidus viscosity is 10 3.5 dPa ⁇ s or more, preferably 10 3.5 dPa ⁇ s or more, 10 3.8 dPa ⁇ s or more, 10 4.0 dPa ⁇ s.
- Phase-separated glass of the present invention has a glass composition, in mass%, SiO 2 30 ⁇ 75% , Al 2 O 3 0 ⁇ 35%, preferably contains 2 O 3 0.1 ⁇ 50% B .
- % display means the mass%.
- the preferable upper limit range of SiO 2 is 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, and particularly 48% or less.
- the preferable lower limit range of SiO 2 is 30% or more, 35% or more, 40% or more, 42% or more, 44% or more, particularly 46% or more.
- Al 2 O 3 is a component that enhances devitrification resistance.
- the preferable upper limit range of Al 2 O 3 is 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 12% or less, 10% or less, particularly 9% or less.
- the range is 0.1% or more, 3% or more, 4% or more, particularly 5% or more.
- B 2 O 3 is a component that enhances phase separation, but if the content of B 2 O 3 is too large, the component balance of the glass composition is impaired, and devitrification resistance is likely to decrease.
- the acid resistance tends to decrease. Therefore, the preferable upper limit range of B 2 O 3 is 50% or less, 40% or less, 30% or less, 25% or less, 20% or less, 17% or less, particularly 15% or less. 1% or more, 0.5% or more, 1% or more, 4% or more, 7% or more, 9% or more, 10% or more, 11% or more, particularly 12% or more.
- the content of SiO 2 + Al 2 O 3 + B 2 O 3 is preferably 55 to 80%, 58 to 75%, 60 to 70%, particularly 64 to 68% from the viewpoint of refractive index and devitrification resistance. .
- Li 2 O, Na 2 O, and K 2 O are components that lower the high-temperature viscosity while increasing the phase separation, but if the content of Li 2 O + Na 2 O + K 2 O is too large, the liquid phase viscosity decreases. It becomes easy and a strain point falls easily. Furthermore, the alkali component is easily eluted in the acid etching step. Therefore, a suitable upper limit range of Li 2 O + Na 2 O + K 2 O is 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, 0.5% or less, particularly less than 0.1%.
- Li 2 O is a component that enhances phase separation. However, if the content of Li 2 O is too large, the liquid phase viscosity tends to decrease and the strain point tends to decrease. Furthermore, the alkali component is easily eluted in the acid etching step. Therefore, the preferable upper limit range of Li 2 O is 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, 0.5% or less, particularly less than 0.1%.
- Na 2 O is a component that lowers the high temperature viscosity.
- a preferable upper limit range of Na 2 O is 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, 0.5% or less, particularly less than 0.1%.
- K 2 O is a component that enhances phase separation.
- the preferable upper limit range of K 2 O is 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, 0.5% or less, particularly less than 0.1%.
- MgO is a component that raises the refractive index, Young's modulus, and strain point and lowers the high-temperature viscosity.
- the preferable upper limit range of MgO is 30% or less, 20% or less, 10% or less, 5% or less, and particularly less than 1%.
- a suitable lower limit range is 0% or more, 0.1% or more, 0.2% or more, especially 0.5% or more.
- CaO is a component that lowers the high-temperature viscosity.
- the preferable upper limit range of CaO is 30% or less, 20% or less, 10% or less, 8% or less, 5% or less, 3% or less, 2% or less, particularly 1% or less. % Or more, 0.1% or more, particularly 0.5% or more.
- the preferred upper limit range of SrO is 30% or less, 25% or less, 20% or less, 15% or less, particularly 10% or less
- the preferred lower limit range is 0% or more, 1% or more, 3% or more, 5% or less. % Or more, 7% or more, particularly 8% or more.
- BaO is a component that increases the refractive index of alkaline earth metal oxides without extremely reducing the viscosity of the glass. If the content of BaO increases, the refractive index tends to increase, and if the content of BaO is too large, the density tends to increase, and the balance of the components of the glass composition is impaired, resulting in a decrease in devitrification resistance. It becomes easy. Therefore, the preferable upper limit range of BaO is 40% or less, 30% or less, 26% or less, 24% or less, 22% or less, particularly 20% or less, and the preferable lower limit range is 0% or more, 1% or more, 5 % Or more, 7% or more, 10% or more, 12% or more, 14% or more, particularly 15% or more.
- the preferable upper limit range of ZnO is 20% or less, 10% or less, 7% or less, 5% or less, particularly 4% or less, and the preferable lower limit range is 0% or more, 0.1% or more, 0.5% or less. % Or more, 1% or more, 1.5% or more, particularly 2% or more.
- the content of MgO + CaO + SrO + BaO + ZnO is preferably 15 to 35%, 20 to 34%, 22 to 33%, 24 to 32%, particularly 26 to 31% from the viewpoint of achieving both refractive index and devitrification resistance.
- the mass ratio (SiO 2 + Al 2 O 3 + B 2 O 3 ) / (MgO + CaO + SrO + BaO + ZnO) is preferably 1.8 to 4.0, 2.0 to 3.3 from the viewpoint of achieving both refractive index and devitrification resistance. 2, 2.1 to 3.0, 2.2 to 2.9, particularly 2.3 to 2.8.
- (SiO 2 + Al 2 O 3 + B 2 O 3 ) / (MgO + CaO + SrO + BaO + ZnO) is a value obtained by dividing the content of SiO 2 + Al 2 O 3 + B 2 O 3 by the content of MgO + CaO + SrO + BaO + ZnO.
- TiO 2 is a component that increases the refractive index. However, when the content of TiO 2 increases, the component balance of the glass composition is impaired, and the devitrification resistance is likely to decrease. Therefore, the preferable upper limit range of TiO 2 is 20% or less, 15% or less, 10% or less, 5% or less, particularly 3% or less, and the preferable lower limit range is 0% or more, 0.001% or more, 0. 01% or more, 0.1% or more, 1% or more, 1.5% or more, particularly 2% or more.
- ZrO 2 is a component that increases the refractive index. However, when the content of ZrO 2 increases, the component balance of the glass composition is impaired, and the devitrification resistance is likely to decrease. Therefore, the preferable upper limit range of ZrO 2 is 20% or less, 10% or less, 6% or less, 4% or less, 3% or less, particularly 2% or less, and the preferable lower limit range is 0% or more and 0.001%. Above, 0.01% or more, 0.1% or more, 0.5% or more, particularly 1% or more.
- P 2 O 5 is a component that improves phase separation.
- a suitable upper limit range of P 2 O 5 is 20% or less, 15% or less, 10% or less, 7% or less, 4% or less, 3% or less, particularly 2.5% or less. It is 0% or more, 0.001% or more, 0.01% or more, 0.1% or more, 0.5% or more, 1% or more, 1.2% or more, particularly 1.4% or more.
- La 2 O 3 is a component that increases the refractive index.
- a suitable upper limit range of La 2 O 3 is 10% or less, 5% or less, 3% or less, 1% or less, 0.5% or less, particularly 0.1% or less.
- Nb 2 O 5 is a component that increases the refractive index, but as the content of Nb 2 O 5 increases, the density tends to increase and the devitrification resistance tends to decrease. Furthermore, the raw material cost rises, and the manufacturing cost of the glass plate is likely to rise. Therefore, the preferable upper limit range of Nb 2 O 5 is 10% or less, 5% or less, 3% or less, 1% or less, 0.5% or less, particularly 0.1% or less.
- Gd 2 O 3 is a component that increases the refractive index. However, if the content of Gd 2 O 3 increases, the density becomes too high, or the balance of the glass composition component is lost, resulting in a decrease in devitrification resistance. The high-temperature viscosity is too low, and it becomes difficult to ensure a high liquid phase viscosity. Therefore, a suitable upper limit range of Gd 2 O 3 is 10% or less, 5% or less, 3% or less, 1% or less, 0.5% or less, particularly 0.1% or less.
- Rare metal oxide is a component that increases the refractive index, but as the content of these components increases, the density and thermal expansion coefficient tend to increase, and devitrification resistance decreases, ensuring high liquid phase viscosity. It becomes difficult to do. Furthermore, the raw material cost rises, and the manufacturing cost of the glass plate is likely to rise. Therefore, a preferable upper limit range of the rare metal oxide is 10% or less, 5% or less, 3% or less, 1% or less, 0.5% or less, particularly 0.1% or less.
- the “rare metal oxide” as used in the present invention is a rare earth oxide such as La 2 O 3 , Nd 2 O 3 , Gd 2 O 3 , CeO 2 , Y 2 O 3 , Nb 2 O 5 , Ta 2 O 5. Point to.
- the following oxide conversion means that an oxide having a valence different from the indicated oxide is handled after being converted to the indicated oxide.
- the content of SnO 2 is preferably 0 to 1%, 0.001 to 1%, particularly 0.01 to 0.5%.
- the content of Fe 2 O 3 is preferably 0.05% or less, 0.04% or less, 0.03% or less, and particularly 0.001 to 0.02%.
- the CeO 2 content is preferably 0 to 6%.
- the preferable upper limit range of CeO 2 is 6% or less, 5% or less, 3% or less, 2% or less, 1% or less, particularly 0.1% or less.
- a suitable lower limit range of CeO 2 is 0.001% or more, particularly 0.01% or more.
- PbO is a component that lowers the high temperature viscosity, but it is preferable to refrain from using it as much as possible from an environmental point of view.
- the PbO content is preferably 0.5% or less, particularly preferably less than 0.1%.
- other components may be introduced in a total amount of preferably 10% (desirably 5%, more desirably 2%).
- the phase-separated glass of the present invention preferably has the following characteristics.
- the strain point is preferably 450 ° C. or higher, 500 ° C. or higher, 550 ° C. or higher, particularly 600 ° C. or higher.
- the higher the temperature of the transparent conductive film the higher the transparency and the lower the electrical resistance.
- the conventional glass plate has insufficient heat resistance, it has been difficult to form a transparent conductive film at a high temperature. Therefore, if the strain point is in the above range, the heat resistance is improved, so that both transparency of the transparent conductive film and low electrical resistance can be achieved. Further, in the organic device manufacturing process, the glass plate is heated by heat treatment. It becomes difficult to shrink.
- the temperature at 10 2.5 dPa ⁇ s is preferably 1450 ° C. or lower, 1400 ° C. or lower, 1380 ° C. or lower, particularly 1360 ° C. or lower. If it does in this way, since a meltability will improve, productivity of a glass plate will improve.
- the liquidus temperature is preferably 1200 ° C. or lower, 1150 ° C. or lower, 1100 ° C. or lower, particularly 1060 ° C. or lower. If it does in this way, it will become difficult to devitrify glass at the time of shaping
- the phase separation temperature is preferably 800 ° C. or higher, 850 ° C. or higher, 900 ° C. or higher, 950 ° C. or higher, 1000 ° C. or higher, particularly 1100 ° C. or higher.
- the phase separation viscosity is preferably 10 9.0 dPa ⁇ s or less, 10 8.0 dPa ⁇ s or less, 10 7.0 dPa ⁇ s or less, particularly 10 3.5 to 10 6.0 dPa ⁇ s. is there.
- phase separation temperature indicates that clear cloudiness is observed when a glass piece is placed in a platinum boat and remelted at 1400 ° C., then the platinum boat is transferred to a temperature gradient furnace and held in the temperature gradient furnace for 30 minutes. Temperature.
- Phase separation viscosity refers to a value obtained by measuring the viscosity of glass at the phase separation temperature by the platinum pulling method.
- the glass is preferably phase-separated in the forming step and / or the slow cooling step, but the glass may be phase-separated other than these steps, for example, in the melting step.
- the thickness (in the case of a flat plate) is preferably 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 0.8 mm or less, 0.7 mm or less, 0.5 mm or less, 0.3 mm or less, 0 .2 mm or less, particularly 0.1 mm or less.
- the smaller the thickness the higher the flexibility and the easier it is to improve the design of organic EL lighting.
- the thickness is preferably 10 ⁇ m or more, particularly 30 ⁇ m or more.
- the phase-separated glass of the present invention preferably has a flat plate shape, that is, a glass plate. If it does in this way, it will become easy to apply to an organic EL device.
- a flat plate shape it is preferable to have an unpolished surface on at least one surface (in particular, the entire effective surface of at least one surface is an unpolished surface).
- the theoretical strength of glass is very high, but breakage often occurs even at a stress much lower than the theoretical strength. This is because a small defect called Griffith flow occurs on the surface of the glass plate in a post-molding process such as a polishing process. Therefore, if the surface of the glass plate is unpolished, the original mechanical strength is hardly lost, and thus the glass plate is difficult to break. Further, since the polishing step can be simplified or omitted, the manufacturing cost of the glass plate can be reduced.
- the surface roughness Ra of at least one surface is preferably 0.01 to 1 ⁇ m.
- surface roughness Ra is large, when forming a transparent conductive film etc. on the surface, the quality of a transparent conductive film falls and it becomes difficult to obtain uniform light emission.
- Suitable upper limit ranges of the surface roughness Ra are 1 ⁇ m or less, 0.8 ⁇ m or less, 0.5 ⁇ m or less, 0.3 ⁇ m or less, 0.1 ⁇ m or less, 0.07 ⁇ m or less, 0.05 ⁇ m or less, 0.03 ⁇ m or less, particularly 10 nm. It is as follows.
- the phase-separated glass of the present invention is preferably formed by a downdraw method, particularly an overflow downdraw method.
- a downdraw method particularly an overflow downdraw method.
- the overflow down draw method the surface to be the surface is not in contact with the bowl-shaped refractory and is molded in a free surface state.
- a slot downdraw method can be employed. If it does in this way, it will become easy to produce a thin glass plate.
- a redraw method for example, a float method, a roll-out method, etc.
- a redraw method for example, a float method, a roll-out method, etc.
- a large glass plate can be efficiently formed.
- the phase-separated glass of the present invention is preferably not subjected to a heat treatment step for phase-separating the glass after the cutting step, and the glass is phase-separated in the molding step, or a slow cooling (cooling) step immediately after molding. It is preferable that the glass is phase-separated.
- a phase separation phenomenon may occur in the bowl-shaped structure, or a phase separation phenomenon may occur during stretch molding or slow cooling. If it does in this way, the number of manufacturing processes will decrease and the productivity of phase separation glass can be raised.
- the phase separation phenomenon can be controlled by the glass composition, molding conditions, slow cooling conditions, and the like.
- At least one surface may be a roughened surface. If the roughened surface is arranged on the side in contact with air such as organic EL lighting, in addition to the scattering effect of the glass plate, the non-reflective structure of the roughened surface allows light emitted from the organic EL layer to be within the organic EL layer. As a result, the light extraction efficiency can be increased.
- the surface roughness Ra of the roughened surface is preferably 10 mm or more, 20 mm or more, 30 mm or more, particularly 50 mm or more.
- the roughened surface can be formed by HF etching, sandblasting, or the like.
- the roughened surface can be formed by an atmospheric pressure plasma process. If it does in this way, while maintaining the smooth surface state of one surface of a glass plate, a roughening process can be uniformly performed with respect to the other surface. Moreover, it is preferable to use a gas containing F (for example, SF 6 , CF 4 ) as a source of the atmospheric pressure plasma process. In this way, since plasma containing HF gas is generated, the roughened surface can be formed efficiently.
- a gas containing F for example, SF 6 , CF 4
- a roughened surface can be formed on at least one surface during molding of the glass plate. This eliminates the need for a separate roughening process and improves the efficiency of the roughening process.
- the uneven surface roughness Ra is preferably 10 mm or more, 20 mm or more, 30 mm or more, particularly 50 mm or more.
- Tables 1 to 3 show sample numbers. 1 to 32 are shown.
- the obtained glass batch was supplied to a glass melting furnace and melted at 1400 ° C. for 7 hours.
- a slow cooling treatment was performed from the strain point to room temperature over 10 hours.
- the obtained glass plate was processed as necessary to evaluate various properties.
- the obtained glass plate has a phase separation structure including at least a first phase and a second phase, that is, exhibits phase separation, and the sample surface after being immersed in a 2% by volume hydrofluoric acid solution for 2 minutes. was observed with a field emission scanning electron microscope.
- the content of SiO 2 in the first phase was higher than the content of SiO 2 in the second phase.
- the strain point Ps is a value measured by the method described in ASTM C336-71. In addition, heat resistance becomes high, so that the strain point Ps is high.
- the annealing point Ta and the softening point Ts are values measured by the method described in ASTM C338-93.
- the temperatures at high temperature viscosities of 10 4.0 dPa ⁇ s, 10 3.0 dPa ⁇ s, 10 2.5 dPa ⁇ s, and 10 2.0 dPa ⁇ s are values measured by the platinum ball pulling method. In addition, it is excellent in a meltability, so that high temperature viscosity is low.
- the liquidus temperature passes through 30 mesh (500 ⁇ m sieve opening), and the glass powder remaining in 50 mesh (300 ⁇ m sieve opening) is placed in a platinum boat and held in a temperature gradient furnace for 24 hours, followed by crystal precipitation. Measured temperature.
- the liquid phase viscosity is a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.
- the phase separation temperature was measured at a temperature at which clear white turbidity was observed when a glass piece was put in a platinum boat and remelted at 1400 ° C., and then the platinum boat was transferred to a temperature gradient furnace and held in the temperature gradient furnace for 30 minutes. Is.
- the phase separation viscosity is a value obtained by measuring the viscosity of the glass at the phase separation temperature by a platinum ball pulling method.
- Refractive index n d is the value of the d-line as determined by the refractive index measuring instrument KPR-2000 manufactured by Shimadzu Corporation. Specifically, first, a rectangular parallelepiped sample of 25 mm ⁇ 25 mm ⁇ about 3 mm is prepared, and the temperature range from (annealing point Ta + 30 ° C.) to (strain point Ps ⁇ 50 ° C.) is set at a cooling rate of 0.1 ° C./min. It is a value measured by infiltrating an immersion liquid having a matching refractive index n d after annealing.
- Sample No. 1 to 32 have a phase separation structure including at least a first phase and a second phase, a liquid phase viscosity of 10 3.5 dPa ⁇ s or more, and a refractive index nd of 1.550 or more. there were. Therefore, sample no. Nos. 1 to 32 can be suitably used as glass plates used for organic EL lighting.
Abstract
La présente invention aborde le problème technique qui consiste à fournir un verre permettant d'obtenir une excellente productivité et qui est susceptible d'améliorer l'efficacité d'extraction de lumière d'un élément EL organique, même si une couche d'extraction de lumière comprenant un corps fritté n'est pas formée. Le verre à phases séparées de l'invention est caractérisé en ce que : il est pourvu d'une structure à phases séparées comprenant au moins une première phase et une seconde phase; il a un indice de réfraction (nd) d'au moins 1,51; et il a une viscosité en phase liquide d'au moins 103,5 dPa∙s.
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JP2004075494A (ja) * | 2002-08-22 | 2004-03-11 | Nippon Electric Glass Co Ltd | ガラス基板及びその製造方法 |
JP2014144907A (ja) * | 2013-01-04 | 2014-08-14 | Nippon Electric Glass Co Ltd | ガラス板 |
WO2015034030A1 (fr) * | 2013-09-03 | 2015-03-12 | 日本電気硝子株式会社 | Verre et son procédé de production |
WO2015186606A1 (fr) * | 2014-06-02 | 2015-12-10 | 日本電気硝子株式会社 | Verre à phases séparées, verre à phases séparables, dispositif el organique et procédé de production de verre à phases séparées |
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JP2004075494A (ja) * | 2002-08-22 | 2004-03-11 | Nippon Electric Glass Co Ltd | ガラス基板及びその製造方法 |
JP2014144907A (ja) * | 2013-01-04 | 2014-08-14 | Nippon Electric Glass Co Ltd | ガラス板 |
WO2015034030A1 (fr) * | 2013-09-03 | 2015-03-12 | 日本電気硝子株式会社 | Verre et son procédé de production |
WO2015186606A1 (fr) * | 2014-06-02 | 2015-12-10 | 日本電気硝子株式会社 | Verre à phases séparées, verre à phases séparables, dispositif el organique et procédé de production de verre à phases séparées |
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