WO2012099055A1 - 強化ガラス及び強化ガラス板 - Google Patents
強化ガラス及び強化ガラス板 Download PDFInfo
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- WO2012099055A1 WO2012099055A1 PCT/JP2012/050712 JP2012050712W WO2012099055A1 WO 2012099055 A1 WO2012099055 A1 WO 2012099055A1 JP 2012050712 W JP2012050712 W JP 2012050712W WO 2012099055 A1 WO2012099055 A1 WO 2012099055A1
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- tempered glass
- mgo
- glass
- sro
- bao
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Classifications
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
-
- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- 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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31—Surface property or characteristic of web, sheet or block
- Y10T428/315—Surface modified glass [e.g., tempered, strengthened, etc.]
Definitions
- the present invention relates to a tempered glass and a tempered glass plate, and relates to a tempered glass and a tempered glass plate suitable for a glass substrate of a mobile phone, a digital camera, a PDA (portable terminal), a solar cell or the like, or a display (particularly a touch panel display).
- a mobile phone a digital camera, a PDA (portable terminal), a solar cell or the like, or a display (particularly a touch panel display).
- Devices such as mobile phones, digital cameras, PDAs, touch panel displays, large televisions, and non-contact power supply lamps are becoming increasingly popular.
- Devices such as LCDs and PDPs used in these display units have begun to spread around 2000, and now have already occupied 90% or more of the display market.
- the display In the multi-view 3D display, if the number of pixels on the screen is the same, there is a problem that the resolution of 3D display decreases as the number of viewpoints increases. Under these circumstances, in order to improve the resolution of 3D display, the display is required to have a higher resolution, and with this request, the specifications regarding minute bubbles, defects, etc. in the glass have been tightened. Direction.
- tempered glass is used to protect the display section.
- the tempered glass for this application is required to have characteristics such as (1) having high mechanical strength, (2) being inexpensive and capable of being supplied in large quantities (for example, see Patent Document 1 and Non-Patent Document 1).
- the present invention has a technical problem of creating a tempered glass having a high mechanical strength while being able to use a glass substrate for LCD and PDP as a cullet.
- the present inventors have found that the defects present in the protective member of the display have a smaller influence on the display performance than the defects present in the glass substrate for display, and the glass of tempered glass.
- the tempered glass of the present invention is a tempered glass having a compressive stress layer on the surface, and the glass composition is SiO 2 50 to 75%, Al 2 O 3 5 to 20%, B 2 O 3 in mass%.
- the tempered glass of the present invention has a glass composition of 50% by mass to SiO 2 50 to 70%, Al 2 O 3 7 to 20%, B 2 O 3 0 to 5%, Na 2 O 8 to 20%. %, K 2 O 1-10%, MgO 1.5-12%, SrO + BaO 0.001-3%, and the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is 0.4-1.4. Is preferred.
- the tempered glass of the present invention has a glass composition, in mass%, SiO 2 50 ⁇ 70% , Al 2 O 3 7 ⁇ 18%, B 2 O 3 0 ⁇ 3%, Na 2 O 10 ⁇ 17 %, K 2 O 2 to 9%, MgO 1.5 to 10%, SrO + BaO 0.001 to 3%, and the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is 0.5 to 1.4. Is preferred.
- the tempered glass of the present invention has a glass composition, in mass%, SiO 2 50 ⁇ 70% , Al 2 O 3 8 ⁇ 17%, B 2 O 3 0 ⁇ 1.5%, Na 2 O 11 16%, K 2 O 3-8%, MgO 1.8-9%, SrO + BaO 0.001-1%, and the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is 0.5-0.9. Preferably there is.
- the tempered glass of the present invention has a glass composition of 50% by mass to SiO 2 50 to 65%, Al 2 O 3 8 to 15%, B 2 O 3 0 to 1%, Na 2 O 12 to 15 as a glass composition. %, K 2 O 4-7%, MgO 1.8-5%, SrO + BaO 0.001-0.5%, and the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is 0.5-0.8. Preferably there is.
- the tempered glass of the present invention does not substantially contain As 2 O 3 , Sb 2 O 3 , and PbO.
- “substantially does not contain As 2 O 3 ” means that it does not actively add As 2 O 3 as a glass component, but allows it to be mixed as an impurity. Specifically, It means that the content of As 2 O 3 is less than 0.05% by mass.
- “substantially free of Sb 2 O 3”, but not added actively Sb 2 O 3 as a glass component a purpose to allow the case to be mixed as an impurity, specifically, Sb 2 O The content of 3 is less than 0.05% by mass.
- “Substantially no PbO” means that although PbO is not actively added as a glass component, it is allowed to be mixed as an impurity. Specifically, the PbO content is 0.05 mass. It means less than%.
- the tempered glass of the present invention preferably has a SnO 2 + SO 3 + Cl content of 100 to 3000 ppm (mass).
- SnO 2 + SO 3 + Cl is the total amount of SnO 2 , SO 3 , and Cl.
- the tempered glass of the present invention preferably has a compressive stress layer having a compressive stress value of 200 MPa or more and a compressive stress layer having a thickness (depth) of 10 ⁇ m or more.
- the “compressive stress value of the compressive stress layer” and the “thickness of the compressive stress layer” are observed when the sample is observed using a surface stress meter (for example, FSM-6000 manufactured by Toshiba Corporation). A value calculated from the number of interference fringes and their intervals.
- the tempered glass of the present invention preferably has a liquidus temperature of 1075 ° C. or lower.
- the “liquid phase temperature” means that the glass powder that passes through the standard sieve 30 mesh (sieve opening 500 ⁇ m) and remains on the 50 mesh (mesh opening 300 ⁇ m) is placed in a platinum boat and placed in a temperature gradient furnace. It refers to the temperature at which crystals precipitate after holding for a period of time.
- the tempered glass of the present invention preferably has a liquidus viscosity of 10 4.0 dPa ⁇ s or more.
- liquid phase viscosity refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.
- the tempered glass of the present invention it is preferable that the temperature at 10 4.0 dPa ⁇ s is 1250 ° C. or less.
- temperature at 10 4.0 dPa ⁇ s refers to a value measured by a platinum ball pulling method.
- the tempered glass of the present invention preferably has a temperature at 10 2.5 dPa ⁇ s of 1600 ° C. or lower.
- temperature at 10 2.5 dPa ⁇ s refers to a value measured by a platinum ball pulling method.
- the tempered glass of the present invention preferably has a density of 2.6 g / cm 3 or less.
- the “density” can be measured by a known Archimedes method.
- the tempered glass sheet of the present invention is characterized by comprising any of the above tempered glass.
- the tempered glass sheet of the present invention is preferably formed by a float process.
- the tempered glass plate of the present invention is preferably used for a touch panel display.
- the tempered glass plate of the present invention is preferably used for a cover glass of a mobile phone.
- the tempered glass plate of the present invention is preferably used for a cover glass of a solar cell.
- the tempered glass plate of the present invention is preferably used as a protective member for a display.
- a twenty-tempered glass plate of the present invention has a glass composition, in mass%, SiO 2 50 ⁇ 70% , Al 2 O 3 7 ⁇ 20%, B 2 O 3 0 ⁇ 5%, Na 2 O 8 Containing 20 to 20%, K 2 O 1 to 10%, MgO 1.5 to 12%, SrO + BaO 0.001 to 3%, SnO 2 + SO 3 + Cl 100 to 3000 ppm, and mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) Is 0.4 to 1.4, the length is 500 mm or more, the width is 500 mm or more, the thickness is 1.5 mm or less, the Young's modulus is 65 GPa or more, the compressive stress value of the compressive stress layer is 400 MPa or more, and the thickness of the compressive stress layer is It is 30 ⁇ m or more.
- the “Young's modulus” can be measured by a known resonance method or the like.
- the twenty-first, the reinforcing glass of the present invention as a glass composition, in mass%, SiO 2 50 ⁇ 75% , Al 2 O 3 5 ⁇ 20%, B 2 O 3 0 ⁇ 8%, Na 2 O 5 to 20%, K 2 O 0.1 to 10%, MgO 0.1 to 15%, SrO + BaO 0.001 to 5%, and the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is 0.3 to 1 .5.
- the tempered glass of the present invention is less likely to generate fine bubbles and defects in the tempered glass and can secure a sufficient mechanical strength even when a glass substrate for LCD or PDP is used as a cullet.
- the tempered glass according to the embodiment of the present invention has a compressive stress layer on the surface, and has a glass composition of 50% to 75% SiO 2 , 5 to 20% Al 2 O 3 , and B 2 O 3 0 to 0% by mass. 8%, Na 2 O 5-20%, K 2 O 0.1-10%, MgO 0.1-15%, SrO + BaO 0.001-5%, mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) Is 0.3 to 1.5.
- % display points out mass%.
- the tempered glass of this embodiment is produced by a chemical strengthening method.
- the chemical strengthening method is a method in which alkali ions having a large ion radius are introduced into the surface of glass by ion exchange treatment at a temperature below the strain point of the glass. If the compressive stress layer is formed by the chemical strengthening method, the compressive stress layer can be properly formed even when the glass is thin, and even if the tempered glass is cut after forming the compressive stress layer, the air cooling strengthening method is used. The tempered glass does not break easily like the physical tempering method.
- the glass substrate for LCD and PDP contains components such as SiO 2 , Al 2 O 3 , B 2 O 3 , alkali metal oxide, and alkaline earth metal oxide in the glass composition.
- a glass substrate for LCD contains 1 to 8% by mass of SrO + BaO in the glass composition.
- SrO and BaO are mixed in the glass composition, and the ion exchange performance of the tempered glass may be lowered. Therefore, in order to promote recycling of glass substrates for LCD and PDP, it is necessary to design the composition so that excellent ion exchange performance is exhibited even when SrO and BaO are added. Since the glass composition range is regulated as described above, the tempered glass of this embodiment has good ion exchange performance even when SrO and BaO are added to the glass composition.
- SiO 2 is a component that forms a network of glass.
- the content of SiO 2 is 50 to 75%, preferably 50 to 70%, 50 to 68%, 50 to 65%, particularly 55 to 65%. If the content of SiO 2 is too small, vitrification becomes difficult, and the thermal expansion coefficient becomes too high, so that the thermal shock resistance tends to decrease. On the other hand, if the content of SiO 2 is too large, the meltability and moldability tend to be lowered, and the thermal expansion coefficient becomes too low to make it difficult to match the thermal expansion coefficient of the surrounding materials.
- Al 2 O 3 is a component that improves ion exchange performance, and is a component that increases the strain point and Young's modulus.
- the content of Al 2 O 3 is 5 to 20%.
- the preferable lower limit range of Al 2 O 3 is 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, particularly 12% or more.
- the content of Al 2 O 3 is too large, devitrification crystal glass becomes easy to precipitate, and it becomes difficult to mold the glass sheet by a float process and an overflow down draw method and the like.
- the preferable upper limit range of Al 2 O 3 is 19% or less, 17% or less, 16% or less, and particularly 15% or less.
- B 2 O 3 is a component that lowers the high temperature viscosity and density, stabilizes the glass, makes it difficult to precipitate crystals, and lowers the liquidus temperature.
- the content of B 2 O 3 is 0 to 8%, preferably 0 to 5%, 0 to 3%, 0 to 1.8%, 0 to 0.9%, 0 to 0.5%, In particular, it is 0 to 0.1%.
- Na 2 O is an ion exchange component, and is a component that lowers the high temperature viscosity and improves the meltability and moldability. Na 2 O is also a component that improves devitrification resistance.
- the content of Na 2 O is 5 to 20%.
- a preferable lower limit range of Na 2 O is 8% or more, 9% or more, 10% or more, 11% or more, 12% or more, particularly 13% or more.
- the content of Na 2 O is too large, the thermal expansion coefficient becomes too high, the thermal shock resistance is lowered, and it becomes difficult to match the thermal expansion coefficient of the surrounding materials.
- the strain point may be excessively lowered or the component balance of the glass composition may be lost, and the devitrification resistance may be deteriorated. Therefore, the preferable upper limit range of Na 2 O is 19% or less, 17% or less, particularly 16% or less.
- K 2 O is a component that promotes ion exchange, and among alkali metal oxides, it is a component that tends to increase the thickness of the compressive stress layer. Moreover, it is a component which reduces high temperature viscosity and improves a meltability and a moldability. Furthermore, it is also a component that improves devitrification resistance. Therefore, the content of K 2 O is 0.1% or more, and a preferable lower limit range is 1% or more, 1.5% or more, 2% or more, 3% or more, particularly 4% or more. However, if the content of K 2 O is too large, the thermal expansion coefficient becomes too high, and the thermal shock resistance is lowered or it is difficult to match the thermal expansion coefficient of the surrounding materials.
- the content of K 2 O is 10% or less, and the preferable upper limit range is 8% or less, 7% or less, and particularly 6% or less.
- MgO is a component that lowers the viscosity at high temperature, increases meltability and moldability, and increases the strain point and Young's modulus.
- MgO is a component that has a large effect of improving ion exchange performance. is there. Therefore, the content of MgO is 0.1% or more, and a preferable lower limit range is 0.5% or more, 1% or more, 1.5 or more, 1.8% or more, particularly 2% or more.
- the content of MgO is 15% or less, and a preferable upper limit range is 12% or less, 10% or less, 8% or less, 4% or less, 3.5% or less, particularly 2.8% or less.
- CaO compared with other components, has a great effect of lowering the high-temperature viscosity without increasing devitrification resistance, improving meltability and moldability, and increasing the strain point and Young's modulus.
- the content of CaO is 0 to 10%.
- the preferred content of CaO is 0-5%, 0-4%, 0-3.5%, 0-3%, 0-2%, especially 0-1%.
- SrO + BaO is a component that lowers the high-temperature viscosity without increasing devitrification resistance, thereby increasing meltability and moldability, and increasing the strain point and Young's modulus.
- the content of SrO + BaO is 0.001 to 5%. When there is too little content of SrO + BaO, it will become difficult to acquire the said effect and it will become difficult to promote recycling of the glass substrate for LCD and PDP.
- a suitable lower limit range of SrO + BaO is 0.05% or more, 0.1% or more, and particularly 0.3% or more.
- SrO + BaO when the content of SrO + BaO is too large, the density and the thermal expansion coefficient are increased, the ion exchange performance is lowered, the component balance of the glass composition is lacking, and the glass is liable to devitrify.
- a preferable upper limit range of SrO + BaO is 4% or less, 2% or less, particularly 1% or less.
- SrO raw material or BaO raw material may be used as a raw material for introducing SrO and BaO, it is preferable to use a cullet of a glass substrate for LCD or PDP.
- SrO is a component that lowers the high-temperature viscosity without increasing devitrification resistance, thereby improving meltability and moldability, and increasing the strain point and Young's modulus.
- the SrO content is 0 to 5%.
- a preferable upper limit range of SrO is 4% or less, 2% or less, particularly 1% or less.
- a suitable lower limit range of SrO is 0.001% or more, 0.05% or more, 0.1% or more, and particularly 0.3% or more.
- BaO is a component that lowers the high-temperature viscosity without increasing devitrification resistance, thereby increasing meltability and moldability, and increasing the strain point and Young's modulus.
- the BaO content is 0 to 5%.
- a preferable upper limit range of BaO is 4% or less, 2% or less, particularly 1% or less.
- a suitable lower limit range of BaO is 0.001% or more, 0.05% or more, 0.1% or more, and particularly 0.3% or more.
- the content of MgO + CaO + SrO + BaO is preferably 0.101 to 16%, 0.2 to 11%, 0.5 to 9%, 1 to 5%, particularly 2 to 4%.
- MgO + CaO + SrO + BaO When there is too little content of MgO + CaO + SrO + BaO, it will become difficult to improve a meltability and a moldability.
- the content of MgO + CaO + SrO + BaO is too large, the density and thermal expansion coefficient increase and the devitrification resistance tends to decrease, and the ion exchange performance tends to decrease.
- ZrO 2 is a component that remarkably improves the ion exchange performance, and is a component that increases the viscosity and strain point near the liquid phase viscosity. However, if its content is too large, the devitrification resistance may be significantly reduced. There is also a possibility that the density becomes too high. Therefore, the preferable upper limit range of ZrO 2 is 10% or less, 8% or less, 6% or less, 4% or less, particularly 3% or less. In addition, when improving ion exchange performance, it is preferable to add ZrO 2 in the glass composition, and in that case, a suitable lower limit range of ZrO 2 is 0.01% or more, 0.1% or more, 0.5% Above 1% or more, especially 2% or more.
- the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is 0.3 to 1.5. If the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is too large, the devitrification resistance is lowered, the ion exchange performance is lowered, and the density and the thermal expansion coefficient are too high. On the other hand, if the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is too small, the liquidus temperature rises rapidly and the liquidus viscosity tends to decrease.
- the preferable upper limit range of the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is 1.45 or less, 1.4 or less, 1.2 or less, 1.0 or less, 0.9 or less, particularly 0.8 or less.
- the preferable lower limit range is 0.4 or more, 0.5 or more, 0.55 or more, particularly 0.6 or more.
- Li 2 O is an ion exchange component, and is a component that lowers the high-temperature viscosity to increase the meltability and moldability, and also increases the Young's modulus. Furthermore, Li 2 O has a large effect of increasing the compressive stress value among alkali metal oxides. However, in a glass system containing 5% or more of Na 2 O, if the Li 2 O content is extremely increased, the compressive stress is rather increased. The value tends to decrease. Further, when the content of Li 2 O is too large, and decreases the liquidus viscosity, in addition to the glass tends to be devitrified, the thermal expansion coefficient becomes too high, the thermal shock resistance may decrease, It becomes difficult to match the thermal expansion coefficient of the surrounding material.
- the low-temperature viscosity decreases too much, and stress relaxation is likely to occur, and the compressive stress value may decrease instead. Therefore, the content of Li 2 O is 0-12%, 0-6%, 0-2%, 0-1%, 0-0.5%, 0-0.3%, especially 0-0.1%. Is preferred.
- Suitable ranges for the mass ratio K 2 O / Na 2 O are 0.1 to 0.8, 0.2 to 0.8, 0.2 to 0.7, in particular 0.3 to 0.6.
- the mass ratio K 2 O / Na 2 O is small, the thickness of the compressive stress layer is likely to be small, and when the mass ratio K 2 O / Na 2 O is large, the compressive stress value is decreased or the component balance of the glass composition is reduced. The lack of glass makes it easy to devitrify the glass.
- the preferred content of Li 2 O + Na 2 O + K 2 O is 5.1-25%, 8-22%, 12-20%, in particular 16.5-20%.
- Li 2 O + Na 2 O + K content of 2 O is too small, the ion exchange performance and meltability is liable to decrease.
- the content of Li 2 O + Na 2 O + K 2 O is too large, the glass tends to be devitrified, the thermal expansion coefficient becomes too high, the thermal shock resistance decreases, and the heat of the surrounding materials It becomes difficult to match the expansion coefficient.
- the strain point may be excessively lowered, making it difficult to obtain a high compressive stress value.
- the viscosity near the liquidus temperature may decrease, making it difficult to ensure a high liquidus viscosity.
- “Li 2 O + Na 2 O + K 2 O” is the total amount of Li 2 O, Na 2 O, and K 2 O.
- the mass ratio (MgO + CaO + SrO + BaO) / (Li 2 O + Na 2 O + K 2 O) is preferably 0.5 or less, 0.35 or less, 0.3 or less, and particularly preferably 0.25 or less.
- the mass ratio (MgO + CaO + SrO + BaO) / (Li 2 O + Na 2 O + K 2 O) increases, the tendency of devitrification resistance to decrease and the density to increase appear.
- TiO 2 is a component that enhances ion exchange performance and a component that lowers the high-temperature viscosity. However, if its content is too large, the glass tends to be colored or devitrified. Therefore, the content of TiO 2 is preferably 0 to 3%, 0 to 1%, 0 to 0.8%, 0 to 0.5%, particularly preferably 0 to 0.1%.
- ZnO is a component that enhances ion exchange performance, and is a component that is particularly effective in increasing the compressive stress value. Moreover, it is a component which reduces high temperature viscosity, without reducing low temperature viscosity.
- the content of ZnO is preferably 0 to 6%, 0 to 5%, 0 to 3%, 0 to 1%, particularly preferably 0 to 0.5%.
- P 2 O 5 is a component that enhances ion exchange performance, and in particular, a component that increases the thickness of the compressive stress layer.
- the content of P 2 O 5 is preferably 0 to 10%, 0 to 3%, 0 to 1%, particularly preferably 0 to 0.5%.
- one or two or more selected from the group of CeO 2 , SnO 2 , SO 3 and Cl may be added in an amount of 0 to 3%.
- the content of SnO 2 + SO 3 + Cl is preferably 0 to 1%, 100 to 3000 ppm, 300 to 2500 ppm, particularly 500 to 2500 ppm.
- the content of SnO 2 + SO 3 + Cl is too much, devitrification resistance is liable to decrease.
- the content of SnO 2 + SO 3 + Cl is less than 100 ppm, it becomes difficult to enjoy the fining effect.
- the preferable content range of SnO 2 is 0 to 5000 ppm, 0 to 3000 ppm, and 0 to 2000 ppm.
- the preferred content range of SO 3 is 0 to 1000 ppm, 0 to 800 ppm, especially 0 to 500 ppm.
- the preferred content range of Cl is 0 to 1500 ppm, 0 to 1200 ppm, 0 to 800 ppm, 0 to 500 ppm, especially 0 to 300 ppm.
- the content of Fe 2 O 3 is preferably less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, and particularly preferably less than 150 ppm. In this way, the transmittance (400 nm to 770 nm) of glass at a plate thickness of 1 mm can be easily improved (for example, 90% or more).
- Rare earth oxides such as Nb 2 O 5 and La 2 O 3 are components that increase the Young's modulus. However, the cost of the raw material itself is high, and when it is added in a large amount, the devitrification resistance tends to be lowered. Therefore, the rare earth oxide content is preferably 3% or less, 2% or less, 1% or less, 0.5% or less, and particularly preferably 0.1% or less.
- Transition metal elements that strongly color the glass may reduce the transmittance of the glass.
- the glass raw material including cullet
- the content of the transition metal oxide is 0.5% or less, 0.1% or less, particularly 0.05% or less.
- the tempered glass of the present embodiment does not substantially contain As 2 O 3 , Sb 2 O 3 , and PbO as a glass composition from the environmental consideration. Moreover, it is also preferable not to contain F substantially.
- “substantially does not contain F” means that F is not actively added as a glass component but is allowed to be mixed as an impurity. Specifically, the content of F is 0. 0.05% by mass or less.
- “substantially free of Bi 2 O 3” but not added actively Bi 2 O 3 as a glass component, a purpose to allow the case to be mixed as an impurity, in particular, It indicates that the content of Bi 2 O 3 is less than 0.05% by mass.
- the tempered glass of the present embodiment preferably has the following characteristics.
- the tempered glass of this embodiment has a compressive stress layer on the surface.
- the compressive stress value of the compressive stress layer is preferably 300 MPa or more, 400 MPa or more, 500 MPa or more, 600 MPa or more, 700 MPa or more, particularly 800 MPa or more.
- the greater the compressive stress value the higher the mechanical strength of the tempered glass.
- microcracks may be generated on the surface, which may reduce the mechanical strength of the tempered glass.
- the compressive stress value of the compressive stress layer is preferably 1500 MPa or less.
- the compressive stress value tends to increase. Further, if the ion exchange time is shortened or the temperature of the ion exchange solution is lowered, the compressive stress value tends to increase.
- the thickness of the compressive stress layer is preferably 10 ⁇ m or more, 15 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, particularly 40 ⁇ m or more.
- the thickness of the compressive stress layer is preferably 500 ⁇ m or less, 200 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, particularly preferably 80 ⁇ m or less.
- the thickness of the compressive stress layer tends to increase. Moreover, if the ion exchange time is lengthened or the temperature of the ion exchange solution is increased, the thickness of the compressive stress layer tends to increase.
- the tempered glass of the present embodiment the density is 2.6 g / cm 3 or less, particularly preferably 2.55 g / cm 3 or less. The smaller the density, the lighter the tempered glass.
- the content of SiO 2 , B 2 O 3 , P 2 O 5 in the glass composition is increased, or the content of alkali metal oxide, alkaline earth metal oxide, ZnO, ZrO 2 , TiO 2 is decreased. As a result, the density tends to decrease.
- the thermal expansion coefficient in the temperature range of 30 to 380 ° C. is 80 to 120 ⁇ 10 ⁇ 7 / ° C., 85 to 110 ⁇ 10 ⁇ 7 / ° C., 90 to 110 ⁇ 10 ⁇ 7 / ° C., In particular, 90 to 105 ⁇ 10 ⁇ 7 / ° C. is preferable. If the thermal expansion coefficient is regulated within the above range, it becomes easy to match the thermal expansion coefficient of a member such as a metal or an organic adhesive, and it becomes easy to prevent peeling of a member such as a metal or an organic adhesive.
- thermal expansion coefficient in a temperature range of 30 to 380 ° C.” refers to a value obtained by measuring an average thermal expansion coefficient using a dilatometer. If the content of alkali metal oxides and alkaline earth metal oxides in the glass composition is increased, the coefficient of thermal expansion tends to increase, and conversely the content of alkali metal oxides and alkaline earth metal oxides is reduced. If it decreases, the thermal expansion coefficient tends to decrease.
- the strain point is preferably 500 ° C. or higher, 520 ° C. or higher, and particularly preferably 530 ° C. or higher.
- the higher the strain point the better the heat resistance.
- the compressive stress layer is less likely to disappear.
- the higher the strain point the less the stress relaxation occurs during the ion exchange treatment, and the easier it is to maintain the compressive stress value. If the content of alkaline earth metal oxide, Al 2 O 3 , ZrO 2 , P 2 O 5 in the glass composition is increased or the content of alkali metal oxide is reduced, the strain point becomes higher. easy.
- the temperature at 10 4.0 dPa ⁇ s is preferably 1250 ° C. or lower, 1230 ° C. or lower, 1200 ° C. or lower, 1180 ° C. or lower, particularly 1160 ° C. or lower.
- the temperature at 10 2.5 dPa ⁇ s is preferably 1600 ° C. or lower, 1550 ° C. or lower, 1530 ° C. or lower, 1500 ° C. or lower, particularly 1450 ° C. or lower.
- the lower the temperature at 10 2.5 dPa ⁇ s the lower the temperature melting becomes possible, and the burden on glass production equipment such as a melting kiln is reduced, and the bubble quality is easily improved. That is, the lower the temperature at 10 2.5 dPa ⁇ s, the easier it is to reduce the manufacturing cost of tempered glass.
- the temperature at 10 2.5 dPa ⁇ s corresponds to the melting temperature.
- the liquidus temperature is preferably 1075 ° C. or lower, 1050 ° C. or lower, 1030 ° C. or lower, 1010 ° C. or lower, 1000 ° C. or lower, 950 ° C. or lower, 900 ° C. or lower, and particularly 880 ° C. or lower.
- devitrification resistance and a moldability improve, so that liquidus temperature is low.
- the liquid phase viscosity is 10 4.0 dPa ⁇ s or more, 10 4.4 dPa ⁇ s or more, 10 4.8 dPa ⁇ s or more, 10 5.0 dPa ⁇ s or more, 10 5 0.5 dPa ⁇ s or more, 10 5.8 dPa ⁇ s or more, 10 6.0 dPa ⁇ s or more, 10 6.2 dPa ⁇ s or more, and particularly preferably 10 6.3 dPa ⁇ s or more.
- devitrification resistance and a moldability improve, so that liquid phase viscosity is high.
- the Young's modulus is preferably 65 GPa or more, 69 GPa or more, 71 GPa or more, 75 GPa or more, particularly 77 GPa or more.
- the higher the Young's modulus the harder the tempered glass bends.
- the tempered glass plate according to the embodiment of the present invention is characterized by comprising the tempered glass of the present embodiment already described. Therefore, the technical characteristics and suitable range of the tempered glass sheet of the present embodiment are the same as the technical characteristics of the tempered glass of the present embodiment. Here, the description is omitted for convenience.
- the length is 500 mm or more, 700 mm or more, particularly 1000 mm or more
- the width is 500 mm or more, 700 mm or more, particularly 1000 mm or more. If the size of the tempered glass plate is increased, it can be used as a cover glass for the display part of a display such as a large TV, and as the amount of glass increases due to the increase in size, it is easy to promote recycling of glass substrates for LCD and PDP. Become.
- the plate thickness is 3.0 mm or less, 2.0 mm or less, 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 1.0 mm or less, 0.8 mm or less, 7 mm or less is preferable.
- the plate thickness is preferably 0.1 mm or more, 0.2 mm or more, 0.3 mm or more, particularly 0.4 mm or more.
- Reinforcing glass according to an embodiment of the present invention has a glass composition, in mass%, SiO 2 50 ⁇ 75% , Al 2 O 3 5 ⁇ 20%, B 2 O 3 0 ⁇ 8%, Na 2 O 5 ⁇ 20%, K 2 O 0.1 to 10%, MgO 0.1 to 15%, SrO + BaO 0.001 to 5%, and the mass ratio (MgO + CaO + SrO + BaO) / (MgO + ZrO 2 ) is 0.3 to 1.5. It is characterized by being.
- the technical characteristics of the tempered glass of the present embodiment are the same as the technical characteristics of the tempered glass and the tempered glass plate of the present embodiment. Here, the description is omitted for convenience.
- the compressive stress value of the surface compressive stress layer may be 300 MPa or more and the thickness of the compressive stress layer may be 10 ⁇ m or more.
- the surface compressive stress is 500 MPa or more and the thickness of the compressive stress layer is 30 ⁇ m or more, and the surface compressive stress is 600 MPa or more and the thickness of the compressive stress layer is preferably 40 ⁇ m or more.
- the temperature of the KNO 3 molten salt is preferably 400 to 550 ° C., and the ion exchange time is preferably 2 to 10 hours, particularly 4 to 8 hours. If it does in this way, it will become easy to form a compressive stress layer appropriately.
- the reinforcing glass of the present embodiment has a glass composition described above, without using a mixture of KNO 3 molten salt and NaNO 3 molten salt, to increase the compressive stress value and thickness of the compression stress layer It becomes possible. Further, even when a deteriorated KNO 3 molten salt is used, the compressive stress value and thickness of the compressive stress layer are not extremely reduced.
- the tempering glass, tempered glass, and tempered glass plate of this embodiment can be produced.
- the glass raw material prepared so as to have the above glass composition is put into a continuous melting furnace, heated and melted at 1500 to 1600 ° C., clarified, fed into a molding apparatus, shaped into a plate shape, etc. By cooling, a plate-like glass can be produced.
- the float process is a method that can produce a large number of glass plates at low cost, and can easily produce a large glass plate.
- various molding methods can be employed.
- an overflow downdraw method a downdraw method (slot down method, redraw method, etc.), a rollout method, a press method, or the like can be employed.
- tempered glass can be produced by tempering the obtained glass.
- the time when the tempered glass is cut into a predetermined dimension may be before the tempering treatment, but it is advantageous from the viewpoint of cost to carry out after the tempering treatment.
- an ion exchange treatment is preferable.
- the conditions for the ion exchange treatment are not particularly limited, and the optimum conditions may be selected in consideration of the viscosity characteristics, application, thickness, internal tensile stress, and the like of the glass.
- the ion exchange treatment can be performed by immersing the glass in KNO 3 molten salt at 400 to 550 ° C. for 1 to 8 hours.
- K ions in the KNO 3 molten salt are ion-exchanged with Na components in the glass, a compressive stress layer can be efficiently formed on the surface of the glass.
- Tables 1 and 2 show examples of the present invention (sample Nos. 1 to 11). In the table, “not yet” means unmeasured.
- Each sample in the table was prepared as follows. First, glass raw materials were prepared so as to have the glass composition in the table, and were melted at 1580 ° C. for 8 hours using a platinum pot. Thereafter, the obtained molten glass was poured out on a carbon plate and formed into a plate shape. Various characteristics were evaluated about the obtained glass plate.
- the density ⁇ is a value measured by the well-known Archimedes method.
- the thermal expansion coefficient ⁇ is a value obtained by measuring an average thermal expansion coefficient in a temperature range of 30 to 380 ° C. using a dilatometer.
- strain point Ps and the annealing point Ta are values measured based on the method of ASTM C336.
- the softening point Ts is a value measured based on the method of ASTM C338.
- the temperature at a high temperature viscosity of 10 4.0 dPa ⁇ s, 10 3.0 dPa ⁇ s, and 10 2.5 dPa ⁇ s is a value measured by a platinum ball pulling method.
- the liquid phase temperature TL passes through a standard sieve 30 mesh (a sieve opening of 500 ⁇ m), and glass powder remaining in a 50 mesh (a sieve opening of 300 ⁇ m) is put in a platinum boat, and then held in a temperature gradient furnace for 24 hours. This is a value obtained by measuring the temperature at which crystals are deposited.
- the liquidus viscosity log 10 ⁇ TL is a value obtained by measuring the viscosity of the glass at the liquidus temperature by a platinum ball pulling method.
- Sample No. Nos. 1 to 11 had a density of 2.56 g / cm 3 or less and a thermal expansion coefficient of 99 to 107 ⁇ 10 ⁇ 7 / ° C., and were suitable as a tempered glass material, that is, a tempered glass. Further, since the liquid phase viscosity is 10 5.5 dPa ⁇ s or more, it can be formed into a plate shape by the float process, and the temperature at 10 4.0 dPa ⁇ s is 1156 ° C. or less, so the burden on the forming equipment However, since the temperature at 10 2.5 dPa ⁇ s is 1528 ° C.
- the glass composition in the surface layer of glass differs microscopically before and after the tempering treatment, the glass composition is not substantially different when viewed as the whole glass.
- the tempered glass and the tempered glass plate of the present invention are suitable as a glass substrate for a mobile phone, a digital camera, a cover glass such as a PDA, or a touch panel display. Further, the tempered glass and the tempered glass plate of the present invention are used for applications requiring high mechanical strength in addition to these uses, such as window glass, substrates for magnetic disks, substrates for flat panel displays, and cover glasses for solar cells. Application to cover glass for solid-state imaging devices and tableware can be expected.
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Abstract
Description
Claims (21)
- 表面に圧縮応力層を有する強化ガラスであって、ガラス組成として、質量%で、SiO2 50~75%、Al2O3 5~20%、B2O3 0~8%、Na2O 5~20%、K2O 0.1~10%、MgO 0.1~15%、SrO+BaO 0.001~5%を含有し、質量比(MgO+CaO+SrO+BaO)/(MgO+ZrO2)が0.3~1.5であることを特徴とする強化ガラス。
- ガラス組成として、質量%で、SiO2 50~70%、Al2O3 7~20%、B2O3 0~5%、Na2O 8~20%、K2O 1~10%、MgO 1.5~12%、SrO+BaO 0.001~3%を含有し、質量比(MgO+CaO+SrO+BaO)/(MgO+ZrO2)が0.4~1.4であることを特徴とする請求項1に記載の強化ガラス。
- ガラス組成として、質量%で、SiO2 50~70%、Al2O3 7~18%、B2O3 0~3%、Na2O 10~17%、K2O 2~9%、MgO 1.5~10%、SrO+BaO 0.001~3%を含有し、質量比(MgO+CaO+SrO+BaO)/(MgO+ZrO2)が0.5~1.4であることを特徴とする請求項1又は2に記載の強化ガラス。
- ガラス組成として、質量%で、SiO2 50~70%、Al2O3 8~17%、B2O3 0~1.5%、Na2O 11~16%、K2O 3~8%、MgO 1.8~9%、SrO+BaO 0.001~1%を含有し、質量比(MgO+CaO+SrO+BaO)/(MgO+ZrO2)が0.5~0.9であることを特徴とする請求項1~3のいずれか一項に記載の強化ガラス。
- ガラス組成として、質量%で、SiO2 50~65%、Al2O3 8~15%、B2O3 0~1%、Na2O 12~15%、K2O 4~7%、MgO 1.8~5%、SrO+BaO 0.001~0.5%を含有し、質量比(MgO+CaO+SrO+BaO)/(MgO+ZrO2)が0.5~0.8であることを特徴とする請求項1~4のいずれか一項に記載の強化ガラス。
- 実質的にAs2O3、Sb2O3、及びPbOを含有しないことを特徴とする請求項1~5のいずれか一項に記載の強化ガラス。
- SnO2+SO3+Clの含有量が100~3000ppmであることを特徴とする請求項1~6のいずれか一項に記載の強化ガラス。
- 圧縮応力層の圧縮応力値が200MPa以上、且つ圧縮応力層の厚みが10μm以上であることを特徴とする請求項1~7のいずれか一項に記載の強化ガラス。
- 液相温度が1075℃以下であることを特徴とする請求項1~8のいずれか一項に記載の強化ガラス。
- 液相粘度が104.0dPa・s以上であることを特徴とする請求項1~9のいずれか一項に記載の強化ガラス。
- 104.0dPa・sにおける温度が1250℃以下であることを特徴とする請求項1~10のいずれか一項に記載の強化ガラス。
- 102.5dPa・sにおける温度が1600℃以下であることを特徴とする請求項1~11のいずれか一項に記載の強化ガラス。
- 密度が2.6g/cm3以下であることを特徴とする請求項1~12のいずれか一項に記載の強化ガラス。
- 請求項1~13のいずれか一項に記載の強化ガラスからなることを特徴とする強化ガラス板。
- フロート法で成形されてなることを特徴とする請求項14に記載の強化ガラス板。
- タッチパネルディスプレイに用いることを特徴とする請求項14に記載の強化ガラス板。
- 携帯電話のカバーガラスに用いることを特徴とする請求項14に記載の強化ガラス板。
- 太陽電池のカバーガラスに用いることを特徴とする請求項14に記載の強化ガラス板。
- ディスプレイの保護部材に用いることを特徴とする請求項14に記載の強化ガラス板。
- ガラス組成として、質量%で、SiO2 50~70%、Al2O3 7~20%、B2O3 0~5%、Na2O 8~20%、K2O 1~10%、MgO 1.5~12%、SrO+BaO 0.001~3%、SnO2+SO3+Cl 100ppm~3000ppmを含有し、質量比(MgO+CaO+SrO+BaO)/(MgO+ZrO2)が0.4~1.4であって、長さ500mm以上、幅500mm以上、厚み1.5mm以下、ヤング率が65GPa以上、圧縮応力層の圧縮応力値が400MPa以上、圧縮応力層の厚みが30μm以上であることを特徴とする強化ガラス板。
- ガラス組成として、質量%で、SiO2 50~75%、Al2O3 5~20%、B2O3 0~8%、Na2O 5~20%、K2O 0.1~10%、MgO 0.1~15%、SrO+BaO 0.001~5%を含有し、質量比(MgO+CaO+SrO+BaO)/(MgO+ZrO2)が0.3~1.5であることを特徴とする強化用ガラス。
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EP12736075.8A EP2666756A1 (en) | 2011-01-18 | 2012-01-16 | Tempered glass, and tempered glass plate |
KR1020137012710A KR101487785B1 (ko) | 2011-01-18 | 2012-01-16 | 강화 유리 및 강화 유리판 |
CN2012800038597A CN103228590A (zh) | 2011-01-18 | 2012-01-16 | 强化玻璃及强化玻璃板 |
US13/979,273 US20130295366A1 (en) | 2011-01-18 | 2012-01-16 | Tempered glass, and tempered glass plate |
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JP2011007410A JP5839338B2 (ja) | 2011-01-18 | 2011-01-18 | 強化ガラス板の製造方法 |
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JP5467490B2 (ja) * | 2007-08-03 | 2014-04-09 | 日本電気硝子株式会社 | 強化ガラス基板の製造方法及び強化ガラス基板 |
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2011
- 2011-01-18 JP JP2011007410A patent/JP5839338B2/ja active Active
-
2012
- 2012-01-16 KR KR1020137012710A patent/KR101487785B1/ko active IP Right Grant
- 2012-01-16 EP EP12736075.8A patent/EP2666756A1/en not_active Withdrawn
- 2012-01-16 CN CN2012800038597A patent/CN103228590A/zh active Pending
- 2012-01-16 WO PCT/JP2012/050712 patent/WO2012099055A1/ja active Application Filing
- 2012-01-16 US US13/979,273 patent/US20130295366A1/en not_active Abandoned
- 2012-01-17 TW TW101101772A patent/TWI522329B/zh active
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TETSURO IZUMITANI ET AL.: "New glass and physical properties thereof", 20 August 1984, MANAGEMENT SYSTEM LABORATORY. CO., LTD., pages: 451 - 498 |
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Also Published As
Publication number | Publication date |
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EP2666756A4 (en) | 2013-11-27 |
US20130295366A1 (en) | 2013-11-07 |
CN103228590A (zh) | 2013-07-31 |
KR101487785B1 (ko) | 2015-01-29 |
JP5839338B2 (ja) | 2016-01-06 |
TWI522329B (zh) | 2016-02-21 |
EP2666756A1 (en) | 2013-11-27 |
KR20130101095A (ko) | 2013-09-12 |
JP2012148908A (ja) | 2012-08-09 |
TW201233654A (en) | 2012-08-16 |
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