WO2012099002A1 - 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 PDF

Info

Publication number
WO2012099002A1
WO2012099002A1 PCT/JP2012/050559 JP2012050559W WO2012099002A1 WO 2012099002 A1 WO2012099002 A1 WO 2012099002A1 JP 2012050559 W JP2012050559 W JP 2012050559W WO 2012099002 A1 WO2012099002 A1 WO 2012099002A1
Authority
WO
WIPO (PCT)
Prior art keywords
tempered glass
compressive stress
glass
mgo
less
Prior art date
Application number
PCT/JP2012/050559
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
隆 村田
誉子 東條
浩佑 川本
佑輔 冨田
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
Priority to DE112012000047.1T priority Critical patent/DE112012000047B4/de
Priority to CN201280002611.9A priority patent/CN103080029B/zh
Priority to KR1020137004267A priority patent/KR101544744B1/ko
Publication of WO2012099002A1 publication Critical patent/WO2012099002A1/ja

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
    • 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
    • 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
    • C03C3/083—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

Definitions

  • the present invention relates to a tempered glass and a tempered glass plate, and in particular, a tempered glass and a tempered glass plate suitable for a mobile phone, a digital camera, a PDA (portable terminal), a solar cell cover glass, or a glass substrate of a display, particularly a touch panel display.
  • a tempered glass and a tempered glass plate suitable for a mobile phone, a digital camera, a PDA (portable terminal), a solar cell cover glass, or a glass substrate of a display, particularly a touch panel display.
  • tempered glass tempered by ion exchange treatment or the like is used (see Patent Document 1 and Non-Patent Document 1).
  • tempered glass has been used as a protective member for large TV displays.
  • These protective members include (1) high mechanical strength, (2) down-draw method such as overflow down-draw method, slit down-draw method, float method, etc. in order to form large-sized glass plates in large quantities.
  • Characteristics such as (3) having a high-temperature viscosity suitable for molding, (4) being able to perform the strengthening treatment inexpensively and efficiently, and the like are required.
  • KNO 3 molten salt when KNO 3 molten salt is used, a large glass plate can be subjected to ion exchange treatment continuously and in large quantities.
  • KNO 3 molten salt over time KNO 3 molten salt is degraded, there is a problem that must be replaced frequently a KNO 3 molten salt. Since the KNO 3 molten salt bath replacement takes time and expense, the efficiency of the ion exchange treatment is lowered, and the manufacturing cost of the tempered glass is likely to increase.
  • the technical problem of the present invention is that the ion exchange performance and devitrification resistance are high, and the KNO 3 molten salt is resistant to deterioration.
  • the idea is to create a tempered glass and a tempered glass plate that are difficult to generate.
  • 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 3 to 13%, B 2 O 3 in mol%. 0 to 1.5%, Li 2 O 0 to 4%, Na 2 O 7 to 20%, K 2 O 0.5 to 10%, MgO 0.5 to 13%, CaO 0 to 6%, SrO 0 to It is characterized by containing 4.5% and substantially not containing As 2 O 3 , Sb 2 O 3 , PbO, and F.
  • 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 mol%.
  • 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 It indicates that the content of 3 is less than 0.05 mol%.
  • Substantially no PbO means that PbO is not actively added as a glass component, but is allowed to be mixed as an impurity. Specifically, the PbO content is 0.05 mol. It means less than%.
  • substantially no F means that F is not actively added as a glass component but is allowed to be mixed as an impurity. Specifically, the F content is 0.05 mol. It means less than%.
  • the present inventors have obtained the following knowledge.
  • the content (or content ratio) of Al 2 O 3 and MgO is regulated at the same time, the ion exchange performance and devitrification resistance can be improved.
  • the content (or content ratio) of Al 2 O 3 and the alkali metal oxide is simultaneously controlled, devitrification resistance can be improved.
  • the thickness of the compressive stress layer can be increased.
  • the contents (or content ratio) of K 2 O and Na 2 O are simultaneously controlled, the thickness of the compressive stress layer can be increased without reducing the compressive stress value of the compressive stress layer.
  • the glass composition is regulated within the above range, even when using a KNO 3 molten salt deteriorated, the compression stress value and thickness of the compression stress layer is not extremely lowered, the frequency of replacement of KNO 3 molten salt It can be reduced.
  • the tempered glass of the present invention has a glass composition of mol%, SiO 2 50 to 75%, Al 2 O 3 4 to 13%, B 2 O 3 0 to 1.5%, Li 2 O 0. ⁇ 2%, Na 2 O 9-18%, K 2 O 1-8%, MgO 0.5-12%, CaO 0-3.5%, SrO 0-3%, TiO 2 0-0.5% It is preferable to contain.
  • the tempered glass of the present invention has a glass composition of mol%, SiO 2 50-75%, Al 2 O 3 4-12%, B 2 O 3 0-1%, Li 2 O 0-1 %, Na 2 O 10-17%, K 2 O 2-7%, MgO 1.5-12%, CaO 0-3%, SrO 0-1%, TiO 2 0-0.5%. Is preferred.
  • the tempered glass of the present invention has a glass composition of mol%, SiO 2 55-75%, Al 2 O 3 4-11%, B 2 O 3 0-1%, Li 2 O 0-1 %, Na 2 O 10-16%, K 2 O 2-7%, MgO 3-12%, CaO 0-3%, SrO 0-1%, ZrO 2 0.5-10%, TiO 2 0-0 It is preferable to contain 5%.
  • the tempered glass of the present invention has a glass composition of mol%, SiO 2 55-69%, Al 2 O 3 4-11%, B 2 O 3 0-1%, Li 2 O 0-1 %, Na 2 O 11-16%, K 2 O 2-7%, MgO 3-9%, CaO 0-3%, SrO 0-1%, ZrO 2 1-9%, TiO 2 0-0.1 % Is preferably contained.
  • the tempered glass of the present invention has a compressive stress value of the compressive stress layer of 300 MPa or more and a thickness (depth) of the compressive stress layer 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 deterioration coefficient D of 0.01 to 0.6.
  • the deterioration coefficient D indicates a value calculated by the equation of (compressive stress value (new KNO 3 molten salt) ⁇ compressive stress value (deteriorated KNO 3 molten salt)) / compressive stress value (new KNO 3 molten salt).
  • “degraded KNO 3 molten salt” refers to a KNO 3 molten salt containing about 1500 ppm of Na 2 O and about 20 ppm of Li 2 O, and can be prepared by the following method, for example.
  • SiO 2 58.7 wt%, Al 2 O 3 12.8 wt%, Li 2 O 0.1 wt%, Na 2 O 14.0 wt%, K 2 O 6.3 wt%, MgO 2.0 mass %, CaO 2.0% by mass, ZrO 2 4.1% by mass of glass composition is crushed, glass powder passing through a sieve opening of 300 ⁇ m and not passing through a sieve opening of 150 ⁇ m is collected, and the average particle diameter A glass powder of 225 ⁇ m is obtained. Next, 95 g of this glass powder is put into a basket made of a metal mesh having a sieve opening of 100 ⁇ m. Subsequently, the glass powder is immersed in 400 ml of KNO 3 maintained at 440 ° C.
  • new KNO 3 molten salt refers to a KNO 3 molten salt that has not been subjected to ion exchange treatment in the past, Na 2 O content 200ppm or less, Li 2 O content is 3ppm or less of KNO 3 molten Refers to salt.
  • 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 preferably has a temperature at 10 4.0 dPa ⁇ s of 1250 ° C. or lower.
  • 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 density of 2.6 g / cm 3 or less.
  • the “density” can be measured by a known Archimedes method.
  • the tempered glass of the present invention preferably has a Young's modulus of 65 GPa or more.
  • the “Young's modulus” can be measured by a known resonance method or the like.
  • the tempered glass sheet of the present invention is characterized by comprising any of the tempered glasses described above.
  • the tempered glass plate of the present invention is preferably formed by a float process.
  • the tempered glass plate of the present invention preferably has a surface polished by 0.5 ⁇ m or more in the thickness direction.
  • the difference ⁇ CS of the compressive stress values of the compressive stress layers on the opposing surfaces is 50 MPa or less.
  • the tempered glass plate of the present invention is a tempered glass plate having a compressive stress on the surface, the length is 500 mm or more, the width is 500 mm or more, the thickness is 0.5 to 1.5 mm, and the Young's modulus is 65 GPa or more, the compressive stress value of the compressive stress layer is 200 MPa or more, the thickness of the compressive stress layer is 20 ⁇ m or more, the deterioration coefficient D is 0.6 or less, and the difference ⁇ CS between the compressive stress layers of the opposing surface compressive stress layers is 50 MPa or less. It is characterized by being.
  • 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.
  • the tempered glass plate of the present invention is a tempered glass plate having a compressive stress on the surface, and has a glass composition of mol%, SiO 2 50 to 75%, Al 2 O 3 4 to 12% , B 2 O 3 0 to 1%, Li 2 O 0 to 1%, Na 2 O 10 to 17%, K 2 O 2 to 7%, MgO 1.5 to 12%, CaO 0 to 3%, SrO 0 -1%, TiO 2 0-0.5%, molar ratio MgO / (MgO + CaO) is 0.5 or more, length is 500 mm or more, width is 500 mm or more, thickness is 0.5 to 1.5 mm, The Young's modulus is 65 GPa or more, the compressive stress value of the compressive stress layer is 400 MPa or more, the thickness of the compressive stress layer is 30 ⁇ m or more, and the degradation coefficient D is 0.4 or less.
  • the tempered glass of the present invention is a tempered glass that is subjected to a tempering treatment, and has a glass composition of mol%, SiO 2 50 to 75%, Al 2 O 3 3 to 13%. , B 2 O 3 0 to 1.5%, Li 2 O 0 to 4%, Na 2 O 7 to 20%, K 2 O 0.5 to 10%, MgO 0.5 to 13%, CaO 0 to 6 %, SrO 0 to 4.5%, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F.
  • the strengthening glass plate of the present invention is a strengthening glass plate subjected to a strengthening process, has a thickness of 1.5 mm or less, and is a planar direction with respect to all planar portions of the strengthening glass plate.
  • the maximum value Fmax of the residual stress is 5 MPa or less.
  • “Fmax” is a grid-like intersection position at a pitch of 10 cm on a glass plate having a dimension of 500 mm ⁇ 500 mm or more (particularly, a dimension of 1 m ⁇ 1 m) using a birefringence measuring machine: ABR-10A manufactured by UNIOPT.
  • R is the optical path difference (nm)
  • L is the distance (cm) through which the polarized wave has passed
  • C is the photoelastic constant (proportional constant).
  • the residual stress in the plane direction includes tensile stress and compressive stress. In the above, the absolute values of both are evaluated.
  • the tempered glass of the present invention has high ion exchange performance, the compressive stress value of the compressive stress layer is increased and the compressive stress value is deeply formed even in a short time ion exchange treatment. For this reason, mechanical strength becomes high and the dispersion
  • the tempered glass of the present invention is excellent in resistance to devitrification, it can be efficiently formed by an overflow down draw method, a float method or the like. In addition, if it is an overflow downdraw method, a float method, etc., a large sized and thin glass plate can be shape
  • the tempered glass of the present invention since deterioration coefficient D is small, even if the ion-exchange treatment for a long time, the compression stress value and thickness of the compression stress layer to be formed since it is difficult to decrease the KNO 3 molten salt It is possible to reduce the exchange frequency.
  • the tempered glass according to an embodiment of the present invention has a compressive stress layer on the surface and has a glass composition of mol%, SiO 2 50 to 75%, Al 2 O 3 3 to 13%, B 2 O 3 0 to 1.5%, Li 2 O 0-4%, Na 2 O 7-20%, K 2 O 0.5-10%, MgO 0.5-13%, CaO 0-6%, SrO 0-4. 5% is contained, and substantially no As 2 O 3 , Sb 2 O 3 , PbO, and F are contained.
  • “%” indicates mol%.
  • the tempered glass of this embodiment is produced by a chemical strengthening method.
  • the chemical strengthening method is a method of introducing alkali ions having a large ion radius to the surface of the 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.
  • SiO 2 is a component that forms a network of glass.
  • the content of SiO 2 is 50 to 75%, preferably 55 to 75%, 55 to 72%, 55 to 69%, particularly 58 to 67%.
  • the thermal expansion coefficient becomes too high, and the thermal shock resistance tends to decrease.
  • the degradation coefficient D tends to increase.
  • the content of SiO 2 is too large, the meltability and the formability tends to decrease.
  • the thermal expansion coefficient becomes too low, making it difficult to match the thermal expansion coefficient of the surrounding material.
  • Al 2 O 3 is a component that enhances the ion exchange performance and is the component that has the highest effect of reducing the degradation coefficient D. It is also a component that increases the strain point and Young's modulus.
  • the content of Al 2 O 3 is 3 to 13%. When the content of Al 2 O 3 is too small, the deterioration coefficient D tends to increase, and there is a possibility that the ion exchange performance cannot be exhibited sufficiently. Therefore, the preferable lower limit range of Al 2 O 3 is 4% or more, 4.5% or more, 5% or more, 5.5% or more, 6% or more, 7% or more, 8.5% or more, 10% or more, In particular, it is 10.5% or more.
  • a suitable upper limit range of Al 2 O 3 is 12.5% or less, particularly 12% 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 1.5%, preferably 0 to 1.3%, 0 to 1.1%, 0 to 1%, 0 to 0.8%, 0 to 0%. 0.5%, especially 0-0.1%.
  • 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 7% 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. Further, the deterioration coefficient D tends to increase.
  • the content of Li 2 O is 0-4%, preferably 0 to 2.5% 0-2% 0 to 1.5% 0 to 1% 0 to 0.5% in particular 0 to 0.3%.
  • 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. When Na 2 O content is too small, or reduced meltability, lowered coefficient of thermal expansion tends to decrease the ion exchange performance. Therefore, the content of Na 2 O is 7% or more, and the preferable lower limit range is 8% or more, 9% or more, 10% or more, 11% or more, 12% or more, particularly 13% or more. On the other hand, when 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.
  • the degradation coefficient D tends to increase. Therefore, the content of Na 2 O is 20% or less, and the preferable upper limit range is 19% or less, 17% or less, and 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 0.5% or more, and a preferable lower limit range is 1% or more, 1.5% or more, and particularly 2% 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 a preferable upper limit range is 9% or less, 8% or less, 7% or less, particularly 6% or less.
  • the preferred content of Li 2 O + Na 2 O + K 2 O is 10-25%, 13-22%, 15-20%, 16-20%, 16.5-20%, especially 18-20%.
  • 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 deterioration coefficient D becomes 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 material.
  • 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 preferred range of molar ratio (Li 2 O + Na 2 O + K 2 O) / Al 2 O 3 is 1-3. If the molar ratio (Li 2 O + Na 2 O + K 2 O) / Al 2 O 3 is too large, the strain point is lowered, and the ion exchange performance tends to be lowered. Permeability tends to decrease. Further, there is a possibility that the deterioration coefficient D becomes large. However, when the molar ratio (Li 2 O + Na 2 O + K 2 O) / Al 2 O 3 is too small, the viscosity of the glass becomes too high, or decreases bubble quality, lack component balance of the glass composition, denitrification Permeability tends to decrease.
  • the preferred lower limit range of the molar ratio (Li 2 O + Na 2 O + K 2 O) / Al 2 O 3 is 1 or more, 1.2 or more, 1.4 or more, 1.5 or more, 1.7 or more, particularly 1.8 or more.
  • the preferable upper limit range of the molar ratio (Li 2 O + Na 2 O + K 2 O) / Al 2 O 3 is 3 or less, 2.8 or less, 2.6 or less, 2.5 or less, particularly 2.3 or less. .
  • the preferred lower limit range of the molar ratio (Li 2 O + Na 2 O + K 2 O) / Al 2 O 3 is 1 or more, particularly 1.2 or more, and the molar ratio (Li 2 O + Na 2 O + K).
  • the devitrification resistance and the degradation coefficient D can be remarkably improved. .
  • Suitable ranges for the molar ratio K 2 O / Na 2 O are 0.1 to 0.8, 0.2 to 0.8, 0.2 to 0.5, in particular 0.2 to 0.4.
  • the molar ratio K 2 O / Na 2 O decreases, the thickness of the compressive stress layer tends to decrease, and when the molar ratio K 2 O / Na 2 O increases, the compressive stress value decreases or the glass composition component balance is reduced. The lack of glass makes it easy to devitrify the glass.
  • 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 0.5% or more, and a preferable lower limit range is 1% or more, 1.5 or more, 2% or more, 3% or more, 5% or more, particularly 6% or more.
  • the content of MgO is 13% or less
  • a preferable upper limit range is 12% or less, 11% or less, 9% or less, 8% or less, 7% or less, particularly 6.5% or less.
  • a suitable lower limit range of the molar ratio MgO / (MgO + Al 2 O 3 ) is 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, particularly 0.3 or more.
  • the molar ratio MgO / (MgO + Al 2 O 3 ) increases, the devitrification resistance decreases, the density increases, and the thermal expansion coefficient becomes too high.
  • the preferable upper limit range of the molar ratio MgO / (MgO + Al 2 O 3 ) is 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, 0.7 or less, 0.6 or less, particularly 0.5. It is as follows. “MgO + Al 2 O 3 ” is the total amount of MgO and Al 2 O 3 .
  • 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 6%.
  • the preferred content of CaO is 0-5%, 0-4%, 0-3.5%, 0-3%, 0-2%, especially 0-1%.
  • the molar ratio MgO / (MgO + CaO) is 0.5 or more, 0.55 or more, 0.6 or more, 0.7 or more, 0.8 or more, particularly 0.9. It is preferable to restrict to the above.
  • the molar ratio MgO / (MgO + CaO) decreases, the deterioration coefficient D tends to increase and the ion exchange performance tends to decrease.
  • “MgO + CaO” is the total amount of MgO and CaO.
  • SrO is a component that lowers the high-temperature viscosity to improve meltability and moldability, and increase the strain point and Young's modulus.
  • the SrO content is 0 to 6%.
  • the preferred content of SrO is 0 to 4.5%, 0 to 3%, 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to 0.5%, especially 0 to 0.1%. It is.
  • the tempered glass of this embodiment does not substantially contain As 2 O 3 , Sb 2 O 3 , PbO, and F as a glass composition from the environmental consideration.
  • BaO is a component that lowers the high-temperature viscosity to increase meltability and moldability, and increases the strain point and Young's modulus. When the content of BaO is too large, the ion exchange reaction is likely to be inhibited, and in addition, the density and the thermal expansion coefficient are increased, and the glass is easily devitrified.
  • the preferred content of BaO is 0-6%, 0-3%, 0-1.5%, 0-1%, 0-0.5%, especially 0-0.1%.
  • SrO + BaO is the total amount of SrO and BaO.
  • Preferred ranges of molar ratio (CaO + SrO + BaO) / MgO are 0-1, 0-0.9, 0-0.8, 0-0.75, especially 0-0.5.
  • the molar ratio (CaO + SrO + BaO) / MgO increases, the devitrification resistance decreases, the ion exchange performance decreases, the deterioration coefficient D increases, and the density and thermal expansion coefficient increase too much.
  • “CaO + SrO + BaO” is the total amount of CaO, SrO and BaO.
  • the content of MgO + CaO + SrO + BaO is preferably 0.5 to 10%, 0.5 to 8%, 0.5 to 7%, 0.5 to 6%, particularly preferably 0.5 to 4%.
  • 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.
  • MgO + CaO + SrO + BaO is the total amount of MgO, CaO, SrO, and BaO.
  • the mass ratio (MgO + CaO + SrO + BaO) / (Li 2 O + Na 2 O + K 2 O) is preferably 0.5 or less, 0.3 or less, particularly preferably 0.2 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 appears.
  • 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%.
  • 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, a suitable upper limit range of ZrO 2 is 10% or less, 8% or less, 6% or less, 4% or less, 3% or less, particularly 1% or less. In addition, when it is desired to improve the ion exchange performance, a preferable lower limit range of ZrO 2 is 0.01% or more, 0.1% or more, 0.5% or more, 1% or more, particularly 2% or more.
  • 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. However, when the content of ZnO is too large, the glass tends to undergo phase separation, the devitrification resistance decreases, the density increases, or the thickness of the compressive stress layer decreases. Therefore, the content of ZnO is preferably 0 to 6%, 0 to 5%, 0 to 3%, particularly preferably 0 to 1%.
  • 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 , Cl, and SO 3 may be added in an amount of 0 to 3%.
  • the content of SnO 2 + SO 3 + Cl is preferably 0 to 1%, 0.001 to 1%, 0.01 to 0.5%, particularly preferably 0.03 to 0.2%.
  • “SnO 2 + SO 3 + Cl” is the total amount of SnO 2 , Cl, and SO 3 .
  • SnO 2 has an effect of improving ion exchange performance in addition to the clarification effect. Therefore, the addition of SnO 2, it is possible to receive the effect of increasing the clarifying effect and ion exchange performance simultaneously.
  • the SnO 2 content is preferably 0 to 3%, 0.01 to 3%, 0.01 to 3%, particularly preferably 0.1 to 1%.
  • the glass may be colored. Therefore, when it is necessary to obtain a clarification effect while suppressing the coloring of the glass, it is preferable to add SO 3 .
  • the content of SO 3 is 0-3%, in particular 0.001 to 3% is preferred.
  • the Fe 2 O 3 content is preferably less than 1000 ppm (less than 0.1%), less than 800 ppm, less than 600 ppm, less than 400 ppm, and particularly preferably less than 300 ppm. Further, the Fe 2 O 3 content is regulated within the above range, and the molar ratio Fe 2 O 3 / (Fe 2 O 3 + SnO 2 ) is regulated to 0.8 or more, 0.9 or more, particularly 0.95 or more. It is preferable to do. 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 this embodiment preferably contains substantially no Bi 2 O 3 from the environmental consideration.
  • 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, specifically, Bi 2 O It indicates that the content of 3 is less than 0.05 mol%.
  • a suitable content range of each component it is possible to appropriately select a suitable content range of each component to obtain a suitable glass composition range.
  • particularly preferable glass composition ranges are as follows. (1) As a glass composition, in mol%, SiO 2 50 to 75%, Al 2 O 3 4 to 12%, B 2 O 3 0 to 1%, Li 2 O 0 to 1%, Na 2 O 10 to 17 %, K 2 O 2-7%, MgO 1.5-12%, CaO 0-3%, SrO 0-1%, TiO 2 0-0.5%, and the molar ratio MgO / (MgO + CaO) is 0.5-1 (2) As a glass composition, mol%, SiO 2 50 to 75%, Al 2 O 3 4 to 12%, B 2 O 3 0 to 1%, Li 2 O 0 to 1%, Na 2 O 10 to 17 %, K 2 O 2-7%, MgO 1.5-12%, CaO 0-3%, SrO 0-1%, TiO 2 0-0.5%, and the
  • the following glass composition ranges are preferable.
  • mol%, SiO 2 55 to 75%, Al 2 O 3 10 to 13%, B 2 O 3 0 to 1.5%, Li 2 O 0 to 2%, Na 2 O 13 -20%, K 2 O 1-8%, MgO 6-12%, CaO 0-6%, SrO 0-6%, ZrO 2 0-1%, and the molar ratio MgO / (MgO + CaO) is 0.
  • molar ratio MgO / (MgO + Al 2 O 3 ) is 0.1 to 0.9
  • molar ratio (CaO + SrO + BaO) / MgO is 0 to 0.75
  • the molar ratio MgO / (MgO + CaO) is 0.
  • molar ratio MgO / (MgO + Al 2 O 3 ) is 0.25 to 0.6
  • molar ratio (CaO + SrO + BaO) / MgO is 0 to 0.5
  • (10) As a glass composition, mol%, SiO 2 55 to 75%, Al 2 O 3 10 to 13%, B 2 O 3 0 to 1%, Li 2 O 0 to 2%, Na 2 O 13 to 20 %, K 2 O 1-8%, MgO 6-12%, CaO 0-6%, SrO 0-6%, ZrO 2 0-1%, and a molar ratio MgO / (MgO + CaO) of 0.7- 1, molar ratio MgO / (MgO + Al 2 O 3 ) is 0.25 to 0.6, molar ratio (CaO + SrO + BaO) / MgO is 0 to 0.5, (11) as a glass composition, in mol%, SiO 2 55 ⁇ 70% , Al 2 O 3 10
  • 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, particularly 900 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 2000 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. If the content of K 2 O or P 2 O 5 in the glass composition is increased or the content of SrO or BaO is decreased, 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, 2.55 g / cm 3 or less, 2.50 g / cm 3 or less, particularly preferably 2.48 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, 530 ° C. or higher, particularly 540 ° 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, particularly 870 ° 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 3 dPa ⁇ s or more, 10 5.5 dPa ⁇ s or more, 10 5.7 dPa ⁇ s or more, 10 5.8 dPa ⁇ s or more, and particularly preferably 10 6.0 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 deterioration coefficient D is preferably 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, particularly 0.05 or less.
  • the smaller the degradation coefficient D the lower the compression stress value obtained even when ion exchange treatment is performed in an aged KNO 3 molten salt. As a result, the production cost of tempered glass can be easily reduced.
  • the tempered glass plate according to the embodiment of the present invention is characterized by comprising the tempered glass of the above-described embodiment. 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 difference ⁇ CS of the compressive stress values of the compressive stress layers on the opposing surfaces is preferably 50 MPa or less, 30 MPa or less, 20 MPa or less, 10 MPa or less, particularly 5 MPa or less.
  • ⁇ CS becomes large, the tempered glass plate is likely to warp after the ion exchange treatment of the large glass plate.
  • the average surface roughness (Ra) of the surface is preferably 10 mm or less, 8 mm or less, 6 mm or less, 4 mm or less, 3 mm or less, particularly 2 mm or less.
  • the mechanical strength of a tempered glass board to fall, so that average surface roughness (Ra) is large.
  • the average surface roughness (Ra) refers to a value measured by a method based on SEMI D7-97 “Measurement method of surface roughness of FPD glass substrate”.
  • the length is preferably 500 mm or more, 700 mm or more, particularly 1000 mm or more
  • the width is preferably 500 mm or more, 700 mm or more, particularly 1000 mm or more.
  • 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, 0.4 mm or more, particularly 0.5 mm or more.
  • the tempered glass according to the embodiment of the present invention is a tempered glass subjected to an ion exchange treatment, and has a glass composition of mol%, SiO 2 50 to 75%, Al 2 O 3 3 to 13%, B 2 O 3 0 to 1.5%, Li 2 O 0 to 4%, Na 2 O 7 to 20%, K 2 O 0.5 to 10%, MgO 0.5 to 13%, CaO 0 to 6% , SrO 0 to 4.5%, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F.
  • the technical features of the tempered glass of the present embodiment are the same as the technical features of the tempered glass and 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 600 MPa or more and the thickness of the compressive stress layer is 50 ⁇ m or more, and the surface compressive stress is 700 MPa or more and the thickness of the compressive stress layer is preferably 50 ⁇ m or more.
  • the temperature of the KNO 3 molten salt is preferably 360 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 maximum value Fmax of the residual stress in the plane direction with respect to the entire plane portion of the glass plate is preferably 5 MPa or less, 3 MPa or less, 1 MPa or less, 0.5 MPa or less, particularly preferably 0.1 MPa or less.
  • the warp of the tempered glass plate may increase when the large glass plate is tempered.
  • Reinforcing glass plate of the present embodiment SiO 2, TiO 2 on the surface, NESA, ITO, it is preferable formed by forming a film of the AR and the like. If it does in this way, even if it does not grind
  • the film forming method include CVD, sputtering, and spin coating.
  • the film thickness is preferably 1 nm or more, 5 nm or more, 10 nm or more, 30 nm or more, particularly 50 nm or more.
  • the film thickness is too thick, the compressive stress value of the compressive stress layer on the film surface may be too low.
  • a preferable upper limit range of the film thickness is 1000 nm or less, 800 nm or less, 500 nm or less, and particularly 300 nm or less. Note that it is preferable to form a film in a portion where warpage is likely to occur after the strengthening treatment.
  • the tempered glass plate of the present embodiment is preferably formed by forming a film of SiO 2 , TiO 2 , Nesa, ITO, AR, etc. on the surface before the tempering treatment.
  • 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 method is a method that can produce a glass plate in a large amount at a low cost, and is a method that 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 to 5 show examples of the present invention (sample Nos. 1 to 24). 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.
  • Liquid phase viscosity is a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.
  • sample No. Nos. 1 to 24 had a density of 2.54 g / cm 3 or less and a thermal expansion coefficient of 87 to 107 ⁇ 10 ⁇ 7 / ° C., and were suitable as a tempered glass material, that is, a tempered glass.
  • the liquid phase viscosity is 10 4.5 dPa ⁇ s or more, it can be formed into a plate shape by a float process, and the temperature at 10 2.5 dPa ⁇ s is 1622 ° C. or less, so that productivity is high. It is considered that a large amount of glass plates can be produced at low cost.
  • 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 deterioration coefficient D was calculated as follows. First, SiO 2 58.7 mass%, Al 2 O 3 12.8 mass%, Li 2 O 0.1 mass%, Na 2 O 14.0 mass%, K 2 O 6.3 mass%, MgO 2.0 A glass having a glass composition of mass%, CaO 2.0 mass%, and ZrO 2 4.1 mass% was produced. Next, this glass was pulverized, and glass powder that passed through a sieve opening of 300 ⁇ m and did not pass through a sieve opening of 150 ⁇ m was collected to obtain a glass powder having an average particle diameter of 225 ⁇ m. Subsequently, the glass powder was immersed in 400 ml of KNO 3 maintained at 440 ° C.
  • Na 2 O contained in the deterioration KNO 3 molten salt prepared in this condition was 1000 ppm (mol) or more.
  • the compressive stress value of the compressive stress layer on the surface is determined from the number of interference fringes observed using a surface stress meter (FSM-6000 manufactured by Toshiba Corporation) and the distance between them. And the thickness was calculated. Further, after polishing both surfaces of the glass plate by 10 ⁇ m, the compressive stress value and thickness of the compressive stress layer on the surface are determined from the number of interference fringes observed using a surface stress meter (FSM-6000 manufactured by Toshiba Corporation) and the distance between them. Was calculated. In the calculation, the refractive index of the glass plate was 1.52, and the optical elastic constant was 28 [(nm / cm) / MPa].
  • the difference ⁇ CS between the compressive stress values of the compressive stress layer on the front surface (front surface) and the back surface is 40 MPa, and when both surfaces are polished by 0.2 ⁇ m, the surface (front surface)
  • the difference ⁇ CS between the compression stress values of the compression stress layer on the back surface and the back surface is 20 MPa.
  • both surfaces are polished by 10 ⁇ m, the difference ⁇ CS between the compression stress values on the surface (front surface) and the compression stress layer on the back surface is not recognized. It was.
  • sample No. A glass raw material was prepared so that the glass composition described in 1 was obtained. After the obtained glass batch was melted, a glass plate having a thickness of 1 mm was formed by a float process. At that time, the temperature was set so that the temperature near the entrance of the tin bath was 1200 ° C and the temperature near the exit was about 700 ° C. Subsequently, the glass plate exiting the tin bath was passed through the slow cooling furnace. The temperature is set so that the temperature near the inlet of the slow cooling furnace is about 700 ° C and the temperature near the outlet is about 100 ° C.
  • the temperature distribution in the plate width direction is ⁇ 2% or less, and the temperature difference between the front and back surfaces of the glass plate in the slow cooling furnace was gradually cooled while controlling the temperature so that the value became ⁇ 1% or less.
  • a 1 m ⁇ 1 m glass plate was cut out from the obtained glass plate, and the glass plate was used with a birefringence measuring machine manufactured by UNIOPT Co., Ltd .: ABR-10A. Residual stress values were measured. The data is shown in FIG. As a result, the maximum value Fmax of the residual stress in the plane direction of the glass plate was 0.25 MPa. Furthermore, when this glass plate was immersed in 440 ° C.
  • the warped amount of the tempered glass plate was 0.1%. there were. From this result, it can be seen that if the distribution of residual stress in the plane direction is regulated, the amount of warpage of the tempered glass plate can be reduced without polishing.
  • the curvature amount of a tempered glass board is the value which measured the straightness per long side dimension using the laser interferometer.
  • Sample No. A glass raw material was prepared so that the glass composition described in 1 was obtained. After the obtained glass batch was melted, a glass plate having a thickness of 1 mm was formed by a float process. At that time, the temperature was set so that the temperature near the entrance of the tin bath was 1200 ° C and the temperature near the exit was about 700 ° C. Subsequently, the glass plate exiting the tin bath was passed through the slow cooling furnace. The temperature is set so that the temperature near the inlet of the slow cooling furnace is about 700 ° C and the temperature near the outlet is about 100 ° C. The temperature distribution in the width direction of the plate is ⁇ 2% or less. Was gradually cooled while controlling the temperature so that the value became ⁇ 1% or less.
  • Example 3 and [Example 4] have different slow cooling rates.
  • a 1 m ⁇ 1 m glass plate was cut out from the obtained glass plate, and the glass plate was used with a birefringence measuring machine manufactured by UNIOPT Co., Ltd .: ABR-10A. Residual stress values were measured. The data is shown in FIG. As a result, the maximum value Fmax of the residual stress in the plane direction of the glass plate was 0.80 MPa. Furthermore, when this glass plate was immersed in 440 ° C. KNO 3 molten salt (new KNO 3 molten salt) for 6 hours to perform ion exchange treatment, the warped amount of the tempered glass plate was 0.1%. there were.
  • the curvature amount of a tempered glass board is the value which measured the straightness per long side dimension using the laser interferometer.
  • the glass exiting the tin bath is not damage by subsequent roller conveyor, near the exit of the tin bath, preferably by blowing SO 2 gas from above and below.
  • SO 2 gas adheres to the glass, it has an effect of eluting Na in the glass.
  • SO 2 gas becomes constant at the upper and lower glass, and it is preferred to be constant even in the upper and lower respectively in the width direction. Therefore, a slit-like gas outlet extending in the width direction is provided on each of the upper and lower sides of the glass, and a slit-like gas exhaust outlet extending in the width direction is provided immediately behind the gas outlet to supply SO 2 gas. It is preferable.
  • the flow rate of the SO 2 gas is set to 1 liter / min, for example.
  • sample No. A glass raw material was prepared so that the glass composition described in 1 was obtained. After the obtained glass batch was melted, a glass plate having a thickness of 1 mm was formed by a float process. At that time, the temperature was set so that the temperature near the entrance of the tin bath was 1200 ° C and the temperature near the exit was about 700 ° C. Subsequently, the glass plate exiting the tin bath was passed through the slow cooling furnace. The temperature is set so that the temperature near the inlet of the slow cooling furnace is about 700 ° C.
  • the temperature distribution in the width direction of the plate is controlled to ⁇ 2% or less, and the glass plate in the slow cooling furnace was slowly cooled while controlling the temperature so that the temperature difference between the front and back surfaces (over ⁇ 2% ⁇ 10% or less) was large.
  • KNO 3 new KNO 3 molten salt
  • the tempered glass plate warps convexly by about 1% in the top surface direction (direction not in contact with the tin bath). .
  • the compressive stress value of the compressive stress layer on the top surface side was 15 MPa higher than the bottom surface (tin bath contact surface) side.
  • the thickness of the compressive stress layer was the same on the top surface and the bottom surface. Therefore, the obtained glass plate where, after forming a SiO 2 film having a thickness of 100nm on top surface by sputtering, was immersed for 6 hours in 440 ° C. KNO 3 (new KNO 3 molten salt), top
  • KNO 3 new KNO 3 molten salt
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Photovoltaic Devices (AREA)
  • Liquid Crystal (AREA)
  • Position Input By Displaying (AREA)
PCT/JP2012/050559 2011-01-18 2012-01-13 強化ガラス及び強化ガラス板 WO2012099002A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE112012000047.1T DE112012000047B4 (de) 2011-01-18 2012-01-13 Zu härtende Glasplatte
CN201280002611.9A CN103080029B (zh) 2011-01-18 2012-01-13 强化玻璃及强化玻璃板
KR1020137004267A KR101544744B1 (ko) 2011-01-18 2012-01-13 강화 유리 및 강화 유리판

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-007516 2011-01-18
JP2011007516 2011-01-18
JP2011238630 2011-10-31
JP2011-238630 2011-10-31

Publications (1)

Publication Number Publication Date
WO2012099002A1 true WO2012099002A1 (ja) 2012-07-26

Family

ID=46515630

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/050559 WO2012099002A1 (ja) 2011-01-18 2012-01-13 強化ガラス及び強化ガラス板

Country Status (6)

Country Link
JP (4) JP5896338B2 (zh)
KR (1) KR101544744B1 (zh)
CN (1) CN103080029B (zh)
DE (1) DE112012000047B4 (zh)
TW (1) TWI522327B (zh)
WO (1) WO2012099002A1 (zh)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014025068A2 (ja) * 2012-08-09 2014-02-13 日本電気硝子株式会社 強化ガラスの製造方法及び強化ガラス基板
WO2014148046A1 (ja) * 2013-03-19 2014-09-25 日本板硝子株式会社 ガラス板及びガラス板の製造方法
WO2014167842A1 (ja) * 2013-04-08 2014-10-16 日本板硝子株式会社 ガラス板及びガラス板の製造方法
JP2014208565A (ja) * 2013-03-26 2014-11-06 日本電気硝子株式会社 ガラス基板製造方法、ガラス基板製造装置、及びガラス基板
WO2014185486A1 (ja) * 2013-05-15 2014-11-20 日本電気硝子株式会社 強化用ガラス板、強化ガラス板及び強化ガラス板の製造方法
JP2015051882A (ja) * 2012-08-09 2015-03-19 日本電気硝子株式会社 強化ガラスの製造方法及び強化ガラス基板
WO2015079768A1 (ja) * 2013-11-29 2015-06-04 日本電気硝子株式会社 強化ガラス板およびその製造方法
US9187365B2 (en) 2013-02-25 2015-11-17 Corning Incorporated Methods for measuring the asymmetry of a glass-sheet manufacturing process
US9308616B2 (en) 2013-01-21 2016-04-12 Innovative Finishes LLC Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device
US20220206332A1 (en) * 2020-11-20 2022-06-30 Fujian Tianquan Education Technology Limited Double-screen Tablet Computer for Students
WO2022190651A1 (ja) * 2021-03-11 2022-09-15 日本電気硝子株式会社 強化ガラス及びその製造方法

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5896338B2 (ja) * 2011-01-18 2016-03-30 日本電気硝子株式会社 強化用ガラスの製造方法及び強化ガラス板の製造方法
TWI591039B (zh) * 2011-07-01 2017-07-11 康寧公司 具高壓縮應力的離子可交換玻璃
KR101468669B1 (ko) * 2012-05-15 2014-12-04 주식회사 엘지화학 알칼리 유리 및 그 제조 방법
JP6597950B2 (ja) * 2013-07-24 2019-10-30 日本電気硝子株式会社 強化ガラス及び強化用ガラス
US10941071B2 (en) * 2013-08-02 2021-03-09 Corning Incorporated Hybrid soda-lime silicate and aluminosilicate glass articles
JP6131154B2 (ja) * 2013-09-11 2017-05-17 Hoya株式会社 磁気記録媒体基板用ガラスおよび磁気記録媒体基板
US9902644B2 (en) * 2014-06-19 2018-02-27 Corning Incorporated Aluminosilicate glasses
JP6627388B2 (ja) * 2014-12-16 2020-01-08 日本電気硝子株式会社 支持ガラス基板及びこれを用いた積層体
WO2016098499A1 (ja) * 2014-12-16 2016-06-23 日本電気硝子株式会社 支持ガラス基板及びこれを用いた積層体
US10315949B2 (en) * 2015-02-26 2019-06-11 Corning Incorporated Fast ion-exchangeable boron-free glasses with low softening point
JP6774614B2 (ja) * 2015-07-01 2020-10-28 日本電気硝子株式会社 強化用ガラス及び強化ガラス
CN109219583A (zh) * 2016-06-03 2019-01-15 Ａｇｃ株式会社 化学强化用玻璃和化学强化玻璃
CN106865982B (zh) * 2017-03-03 2019-05-24 四川旭虹光电科技有限公司 电容式触控系统保护用玻璃
JP7280546B2 (ja) * 2017-11-09 2023-05-24 日本電気硝子株式会社 ガラス板及びこれを用いた波長変換パッケージ
CN107915890A (zh) * 2017-12-21 2018-04-17 安徽省凯丽方化工有限公司 一种高强度钢化玻璃手机贴膜
CN109052934B (zh) * 2018-10-16 2020-06-19 四川旭虹光电科技有限公司 具有抗冲击应力特性的保护玻璃板
CN114845965A (zh) * 2020-02-25 2022-08-02 日本电气硝子株式会社 强化玻璃板及强化用玻璃板
JP6991416B1 (ja) * 2020-06-26 2022-01-13 日本板硝子株式会社 表示装置
CN114988698B (zh) * 2022-05-30 2024-03-22 河北光兴半导体技术有限公司 用于制备铝硅酸盐玻璃的组合物、铝硅酸盐玻璃及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010059038A (ja) * 2008-08-04 2010-03-18 Nippon Electric Glass Co Ltd 強化ガラスおよびその製造方法
JP2010168233A (ja) * 2009-01-21 2010-08-05 Nippon Electric Glass Co Ltd 強化ガラスおよびガラス

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6022662B2 (ja) * 1978-10-20 1985-06-03 石塚硝子株式会社 安定した化学的耐久性・機械的強度を有する軽量びんの製造方法
JPS58115043A (ja) * 1981-12-28 1983-07-08 Konishiroku Photo Ind Co Ltd 板ガラスのイオン交換方法
JPH0660038B2 (ja) * 1986-05-23 1994-08-10 セントラル硝子株式会社 研磨されたガラスの化学強化方法
JPH07223843A (ja) * 1994-02-15 1995-08-22 Nippon Sheet Glass Co Ltd 化学強化ガラスの製造方法
JPH10162354A (ja) * 1996-11-27 1998-06-19 Nippon Sheet Glass Co Ltd ガラス基板を用いた磁気ディスク媒体の製造方法
JP4006747B2 (ja) * 1998-06-29 2007-11-14 日本電気硝子株式会社 ディスプレイ基板の製造方法
JP4497591B2 (ja) * 1998-09-11 2010-07-07 Ｈｏｙａ株式会社 ガラス組成物、それを用いた情報記録媒体用基板および情報記録媒体
JP4785274B2 (ja) 2001-05-29 2011-10-05 日本板硝子株式会社 ガラス物品およびそれを用いた磁気記録媒体用ガラス基板
JP2003187424A (ja) * 2001-12-17 2003-07-04 Nippon Sheet Glass Co Ltd 情報記録媒体用ガラス基板の製造方法及び情報記録媒体用ガラス基板
JP4446683B2 (ja) * 2002-05-24 2010-04-07 Ｈｏｙａ株式会社 磁気記録媒体用ガラス基板
JP4656863B2 (ja) * 2003-06-06 2011-03-23 Ｈｏｙａ株式会社 ジルコニウムを含むガラス組成物、化学強化ガラス物品、磁気記録媒体用ガラス基板、およびガラス板の製造方法
JP4209316B2 (ja) * 2003-12-12 2009-01-14 Ｈｏｙａ株式会社 情報記録媒体用ガラス基板の製造方法
JP2006083045A (ja) 2004-09-17 2006-03-30 Hitachi Ltd ガラス部材
CN101542603B (zh) * 2006-11-22 2011-08-24 柯尼卡美能达精密光学株式会社 信息记录媒体用玻璃基板、信息记录媒体用玻璃基板的制造方法及信息记录媒体
US20090070237A1 (en) * 2007-09-11 2009-03-12 Goldman Sachs& Co. Data reconciliation
JP5743125B2 (ja) 2007-09-27 2015-07-01 日本電気硝子株式会社 強化ガラス及び強化ガラス基板
JP4930336B2 (ja) * 2007-11-09 2012-05-16 日本電気硝子株式会社 ガラス基板の反り検査方法および製造方法
WO2009063756A1 (ja) * 2007-11-12 2009-05-22 Asahi Glass Company, Limited ガラス板の製造方法およびガラス物品の残留応力測定方法
EP3392220A1 (en) * 2007-11-29 2018-10-24 Corning Incorporated Glasses having improved toughness and scratch resistance
JP2009155148A (ja) * 2007-12-26 2009-07-16 Central Glass Co Ltd ガラス組成物
DE202009018699U1 (de) * 2008-02-26 2012-11-20 Corning Incorporated Läutermittel für Silikatgläser
JP2011527661A (ja) 2008-07-11 2011-11-04 コーニング インコーポレイテッド 民生用途のための圧縮面を有するガラス
EP2334613A1 (en) * 2008-08-21 2011-06-22 Corning Inc. Durable glass housings/enclosures for electronic devices
JP5668477B2 (ja) * 2008-12-25 2015-02-12 旭硝子株式会社 ガラス基板及びその製造方法
JP5350853B2 (ja) * 2009-03-26 2013-11-27 Ｈｏｙａ株式会社 ガラス基板の製造方法、及び磁気記録媒体の製造方法
JP5115545B2 (ja) * 2009-09-18 2013-01-09 旭硝子株式会社 ガラスおよび化学強化ガラス
JP5689075B2 (ja) * 2009-11-25 2015-03-25 旭硝子株式会社 ディスプレイカバーガラス用ガラス基板及びその製造方法
TWI401219B (zh) * 2009-12-24 2013-07-11 Avanstrate Inc Glass plate manufacturing method and glass plate manufacturing apparatus
JP2010202514A (ja) * 2010-06-10 2010-09-16 Hoya Corp 携帯型液晶ディスプレイ用のガラス基板及びその製造方法並びにこれを用いた携帯型液晶ディスプレイ
JP5459122B2 (ja) * 2010-07-15 2014-04-02 旭硝子株式会社 ディスプレイ装置
JP2012126615A (ja) * 2010-12-16 2012-07-05 Asahi Glass Co Ltd フラットパネルディスプレイ用カバーガラス
JP5896338B2 (ja) * 2011-01-18 2016-03-30 日本電気硝子株式会社 強化用ガラスの製造方法及び強化ガラス板の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010059038A (ja) * 2008-08-04 2010-03-18 Nippon Electric Glass Co Ltd 強化ガラスおよびその製造方法
JP2010168233A (ja) * 2009-01-21 2010-08-05 Nippon Electric Glass Co Ltd 強化ガラスおよびガラス

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015051882A (ja) * 2012-08-09 2015-03-19 日本電気硝子株式会社 強化ガラスの製造方法及び強化ガラス基板
WO2014025068A3 (ja) * 2012-08-09 2014-04-17 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
WO2014025068A2 (ja) * 2012-08-09 2014-02-13 日本電気硝子株式会社 強化ガラスの製造方法及び強化ガラス基板
CN104487396A (zh) * 2012-08-09 2015-04-01 日本电气硝子株式会社 强化玻璃的制造方法及强化玻璃基板
US9308616B2 (en) 2013-01-21 2016-04-12 Innovative Finishes LLC Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device
US9840436B2 (en) 2013-02-25 2017-12-12 Corning Incorporated Methods for measuring the asymmetry of a glass-sheet manufacturing process
US9187365B2 (en) 2013-02-25 2015-11-17 Corning Incorporated Methods for measuring the asymmetry of a glass-sheet manufacturing process
CN105189396A (zh) * 2013-03-19 2015-12-23 日本板硝子株式会社 玻璃板及玻璃板的制造方法
CN105189396B (zh) * 2013-03-19 2019-10-22 日本板硝子株式会社 玻璃板及玻璃板的制造方法
US10399894B2 (en) 2013-03-19 2019-09-03 Nippon Sheet Glass Company, Limited Glass sheet and method for producing glass sheet
US20160023946A1 (en) * 2013-03-19 2016-01-28 Nippon Sheet Glass Company, Limited Glass sheet and method for producing glass sheet
WO2014148046A1 (ja) * 2013-03-19 2014-09-25 日本板硝子株式会社 ガラス板及びガラス板の製造方法
JPWO2014148046A1 (ja) * 2013-03-19 2017-02-16 日本板硝子株式会社 ガラス板及びガラス板の製造方法
JP2014208565A (ja) * 2013-03-26 2014-11-06 日本電気硝子株式会社 ガラス基板製造方法、ガラス基板製造装置、及びガラス基板
CN105102394A (zh) * 2013-04-08 2015-11-25 日本板硝子株式会社 玻璃板及玻璃板的制造方法
JPWO2014167842A1 (ja) * 2013-04-08 2017-02-16 日本板硝子株式会社 ガラス板及びガラス板の製造方法
WO2014167842A1 (ja) * 2013-04-08 2014-10-16 日本板硝子株式会社 ガラス板及びガラス板の製造方法
WO2014185486A1 (ja) * 2013-05-15 2014-11-20 日本電気硝子株式会社 強化用ガラス板、強化ガラス板及び強化ガラス板の製造方法
US20160115074A1 (en) * 2013-05-15 2016-04-28 Nippon Electric Glass Co., Ltd. Glass plate for tempering, tempered glass plate, and method for manufacturing tempered glass plate
JP2014240346A (ja) * 2013-05-15 2014-12-25 日本電気硝子株式会社 強化用ガラス板及び強化ガラス板
WO2015079768A1 (ja) * 2013-11-29 2015-06-04 日本電気硝子株式会社 強化ガラス板およびその製造方法
US20220206332A1 (en) * 2020-11-20 2022-06-30 Fujian Tianquan Education Technology Limited Double-screen Tablet Computer for Students
WO2022190651A1 (ja) * 2021-03-11 2022-09-15 日本電気硝子株式会社 強化ガラス及びその製造方法

Also Published As

Publication number Publication date
KR101544744B1 (ko) 2015-08-17
JP5896338B2 (ja) 2016-03-30
JP6075661B2 (ja) 2017-02-08
JP5721065B2 (ja) 2015-05-20
CN103080029B (zh) 2017-03-01
JP2016026996A (ja) 2016-02-18
TWI522327B (zh) 2016-02-21
JP2015038021A (ja) 2015-02-26
JP5721066B2 (ja) 2015-05-20
TW201231428A (en) 2012-08-01
CN103080029A (zh) 2013-05-01
JP2013116846A (ja) 2013-06-13
KR20130056289A (ko) 2013-05-29
DE112012000047B4 (de) 2018-08-23
DE112012000047T5 (de) 2013-05-16
JP2015024951A (ja) 2015-02-05

Similar Documents

Publication Publication Date Title
JP6075661B2 (ja) 強化用ガラス板の製造方法及び強化ガラス板の製造方法
US8835007B2 (en) Tempered glass and tempered glass sheet
JP6136599B2 (ja) 強化ガラス及び強化ガラス板並びに強化用ガラス
US20120196110A1 (en) Tempered glass and tempered glass sheet
JP5743125B2 (ja) 強化ガラス及び強化ガラス基板
JP5365974B2 (ja) 強化ガラス基板及びその製造方法
US8652979B2 (en) Tempered glass substrate
JP5839338B2 (ja) 強化ガラス板の製造方法
JP4974066B2 (ja) 強化ガラス基板及びその製造方法
US20160137550A1 (en) Tempered glass and glass for tempering
US20130045386A1 (en) Tempered glass and manufacturing method for the same
WO2012099053A1 (ja) 強化ガラス及び強化ガラス板
US20150329418A1 (en) Reinforced glass substrate and method for producing same
WO2015125584A1 (ja) 強化ガラスの製造方法及び強化ガラス
JP2009084075A (ja) 強化ガラス基板及びガラス並びに強化ガラス基板の製造方法
WO2013031855A1 (ja) 強化ガラス基板及びその製造方法
WO2013125507A1 (ja) 強化ガラス
JP5796905B2 (ja) 強化ガラス基板及びガラス並びに強化ガラス基板の製造方法
JP5413817B2 (ja) 強化ガラス基板及びガラス並びに強化ガラス基板の製造方法
WO2014185486A1 (ja) 強化用ガラス板、強化ガラス板及び強化ガラス板の製造方法
WO2021171761A1 (ja) 強化ガラス板及び強化用ガラス板

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201280002611.9

Country of ref document: CN

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

Ref document number: 12736531

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 1120120000471

Country of ref document: DE

Ref document number: 112012000047

Country of ref document: DE

ENP Entry into the national phase

Ref document number: 20137004267

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 12736531

Country of ref document: EP

Kind code of ref document: A1