WO2019146379A1 - ガラス基板及びその製造方法 - Google Patents

ガラス基板及びその製造方法 Download PDF

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Publication number
WO2019146379A1
WO2019146379A1 PCT/JP2018/048458 JP2018048458W WO2019146379A1 WO 2019146379 A1 WO2019146379 A1 WO 2019146379A1 JP 2018048458 W JP2018048458 W JP 2018048458W WO 2019146379 A1 WO2019146379 A1 WO 2019146379A1
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Prior art keywords
glass substrate
glass
less
substrate according
content
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PCT/JP2018/048458
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English (en)
French (fr)
Japanese (ja)
Inventor
博通 梅村
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日本電気硝子株式会社
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Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to JP2019567947A priority Critical patent/JP7256473B2/ja
Priority to KR1020207010355A priority patent/KR102516142B1/ko
Priority to CN201880087482.5A priority patent/CN111630010A/zh
Publication of WO2019146379A1 publication Critical patent/WO2019146379A1/ja

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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C03B25/04—Annealing glass products in a continuous way
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C03B25/04—Annealing glass products in a continuous way
    • C03B25/06—Annealing glass products in a continuous way with horizontal displacement of the glass products
    • C03B25/08—Annealing glass products in a continuous way with horizontal displacement of the glass products of glass sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
    • 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

Definitions

  • the present invention relates to a glass substrate suitable for a high definition display, and less likely to cause electrostatic charge even if peeled after contacting with other members, and a method of manufacturing the same.
  • glass is widely used as a substrate for flat panel displays such as liquid crystal displays, hard disks, filters, sensors and the like.
  • flat panel displays such as liquid crystal displays, hard disks, filters, sensors and the like.
  • high definition displays such as low temperature polysilicon TFTs and organic ELs have been actively developed, and some have already been put to practical use.
  • the following characteristics (1) to (5) are particularly required for the glass substrate used for the high definition display.
  • Low thermal shrinkage and excellent thermal stability That is, the glass substrate is heat-treated to several hundred degrees in steps such as film formation and annealing. During the heat treatment, when the glass substrate is thermally shrunk, pattern displacement or the like is likely to occur. For example, in the process of manufacturing a low temperature polysilicon TFT, a heat treatment process at 400 to 600 ° C. is present, and in this heat treatment process, the glass substrate is thermally shrunk to cause dimensional change.
  • Patent Document 1 proposes an alkali-free glass substrate suitable for a high definition display.
  • non-alkali glass substrate which does not contain an alkali metal oxide
  • electrostatic electrification may become a problem.
  • Glass which is originally an insulator, is very likely to be charged, but alkali-free glass is particularly likely to be charged, and static electricity once charged tends to be maintained without escape.
  • charging of the glass substrate is caused in various processes, but in the film forming process etc., the charging caused by peeling after contacting the glass substrate with the metal or insulator plate is peeling It is called electrification.
  • Peeling charging of a glass substrate occurs not only in atmospheric processes under normal pressure, but also in vacuum processes such as a process of etching a thin film on a substrate surface and a film forming process.
  • a discharge occurs.
  • the elements, the electrode lines on the surface of the glass substrate, or the glass substrate itself are destroyed by the discharge (dielectric breakdown or electrostatic breakdown), which causes a display defect.
  • dielectric breakdown or electrostatic breakdown causes a display defect.
  • liquid crystal displays particularly low temperature polysilicon TFT displays have minute semiconductor elements such as thin film transistors and electronic circuits formed on the surface of a glass substrate, but these elements and circuits are particularly problematic because they are very susceptible to electrostatic breakdown. It also attracts dust present in the charged environment and causes contamination of the substrate surface.
  • An object of the present invention is to provide a glass substrate which is suitable as a high definition display substrate due to its low thermal shrinkage and which is less likely to cause peeling charge.
  • the glass substrate of the present invention invented to solve the above-mentioned problems is, by mass percentage, SiO 2 50-70%, Al 2 O 3 10-25%, B 2 O 3 0% or more and less than 3%, MgO 0 ⁇ 10%, CaO 0 to 15%, SrO 0 to 10%, BaO 0 to 15%, Na 2 O 0.005 to 0.3%, ⁇ -OH value less than 0.18 / mm, strain It is characterized in that the point is 735 ° C. or higher.
  • the heat shrinkage rate decreases as the ⁇ -OH value decreases, but the alkali-free glass substrate is significantly easily charged when the ⁇ -OH value is less than 0.18 / mm. .
  • the glass substrate contains 0.005% by mass or more of Na 2 O, which has the effect of reducing the specific resistance of the glass. Can be suppressed.
  • the inclusion of Na 2 O and B 2 O 3 in a large amount of glass containing, B 2 O 3 in the glass during melting tends to volatilize as the sodium compound.
  • B 2 O 3 is regulated to less than 3% by mass, the volatilization of B 2 O 3 at the time of glass melting can be suppressed, and stabilization of the amount of Na 2 O in glass can be achieved. As a result, it is possible to stably obtain a glass substrate which has a low thermal shrinkage and is difficult to be charged.
  • Examples of the method for reducing the ⁇ -OH value of the glass substrate in the present invention include the following methods. (1) A glass batch with a low water content (a glass raw material with a low water content or a glass cullet obtained by finely grinding a glass body with a low water content) is selected. (2) Add components (Cl, SO 3, etc.) having the function of reducing the amount of water in the glass. (3) Decrease the amount of water in the furnace atmosphere. (4) N 2 bubbling is performed in the molten glass. (5) Adopt a small melting furnace. (6) Increase the flow rate of molten glass. (7) Adopt an electric melting furnace.
  • an electric melting furnace using a glass batch with a water content as low as possible from the viewpoint of lowering the ⁇ -OH value.
  • the electric melting furnace is preferably a complete electric melting furnace that does not use a burner, but may be an electric melting furnace equipped with a burner or a heater for performing additional radiant heating at the beginning of melting.
  • the thermal shrinkage of the glass substrate is preferably 20 ppm or less, 15 ppm or less, 12 ppm or less, 10 ppm or less, 9 ppm or less, 8 ppm or less, 7 ppm or less, 6 ppm or less, particularly 5 ppm or less.
  • the thermal contraction rate of a glass substrate 0 ppm it is preferable to be 1 ppm or more, 2 ppm or more, particularly 3 ppm or more, because the productivity is significantly reduced.
  • the variation of the heat shrinkage rate of the glass substrate relative to the target value is preferably ⁇ 1.0 ppm or less, particularly preferably ⁇ 0.5 ppm or less.
  • the thermal contraction rate of the glass substrate is high, display defects of the low temperature polysilicon TFT and the display of the organic EL are easily generated, and when the variation of the thermal contraction rate of the glass substrate is large, the display substrate is stably produced.
  • the water content of the glass material may be adjusted or the cooling rate in the slow cooling process may be adjusted.
  • the method for forming a glass substrate according to the present invention is not particularly limited, but the float method is preferable from the viewpoint of prolonging the slow cooling process, and the surface quality of the glass substrate can be improved or its thickness is small.
  • the downdraw method in particular the overflow downdraw method, is preferred.
  • the overflow down draw method the surfaces to be the front and back surfaces of the glass substrate are not in contact with the molded body, and are molded in the state of free surface. For this reason, the center part of plate thickness direction is an overflow joint surface, and the glass substrate which both surfaces are fire-formed surfaces is obtained.
  • a glass substrate which is not polished and is excellent in surface quality (small surface roughness and waviness) can be manufactured at low cost.
  • the length (height difference) of the annealing furnace is preferably 3 m or more.
  • the slow cooling process is a process for removing the strain of the glass substrate.
  • the longer the slow cooling furnace the easier it is to adjust the cooling rate of the sheet glass and the smaller the thermal contraction rate of the glass substrate. Therefore, the length of the lehr is preferably 5 m or more, 6 m or more, 7 m or more, 8 m or more, 9 m or more, particularly 10 m or more.
  • the cooling rate of the sheet glass in the slow cooling step is 50 to 1000 ° C./min, 100 to 1000 ° C./min, 100 to 800 ° C. in the temperature range from the slow cooling point (slow cooling point -100 ° C.). It is preferable that the cooling rate per minute be 300 ° C./min to 800 ° C./min.
  • the thermal contraction rate of the glass substrate also fluctuates at the cooling rate when the plate glass is gradually cooled. That is, the glass substrate cooled rapidly has a high thermal contraction rate, and the glass substrate cooled slowly has a low thermal contraction rate.
  • the slowly cooled plate glass is subjected to a cutting process. That is, the formed plate-like glass (glass ribbon) is cut into a predetermined size. Thereafter, in order to prevent damage from the end face, end face grinding or end face polishing may be performed. It is preferable that the short side of the glass substrate thus obtained is 1500 mm or more and the long side is 1850 mm or more.
  • the short side is preferably 1950 mm or more, 2200 mm or more, 2800 mm or more, particularly 2950 mm or more
  • the long side is 2250 mm or more, 2500 mm or more, 3000 mm or more And particularly preferably 3400 mm or more.
  • the thickness of the glass substrate is preferably 0.7 mm or less, 0.6 mm or less, 0.5 mm or less, and particularly 0.4 mm or less.
  • the thickness is reduced, the weight of the glass substrate can be reduced, which is suitable for a mobile display substrate.
  • the thickness of the glass substrate is too small, it is likely to be damaged by peeling charge, and it is preferably 0.1 mm or more, more preferably 0.2 mm or more.
  • At least one surface is a fine uneven surface.
  • the surface roughness Ra may be 0.1 to 10 nm as the surface shape of the fine uneven surface.
  • a method for making the surface of the glass substrate a fine uneven surface physical etching using a polishing apparatus or chemical etching in which an etching solution is applied to the glass substrate or an etching gas is sprayed may be adopted. good. It is preferable to use the latter chemical etching because glass powder and the like are less likely to adhere to the glass substrate and the surface can be cleaned. Since the glass substrate of the present invention is originally unlikely to cause peeling charge, even when fine irregularities are formed on the surface, the processing time can be shortened and productivity can be improved.
  • the present invention it is possible to stably obtain a glass substrate which is suitable as a high definition display substrate due to its low thermal shrinkage and which is less likely to cause peeling charge.
  • a numerical range indicated using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the glass substrate of the present invention is, by mass percentage, 50 to 70% SiO 2 , 10 to 25% Al 2 O 3 , 0 to 3% B 2 O 3 , 0 to 10% MgO, 0 to 15% CaO, It contains 0 to 10% of SrO, 0 to 15% of BaO, and 0.005 to 0.3% of Na 2 O.
  • the reason for restricting the content of each glass component as described above will be described below.
  • % indication of the following each component points to the mass% unless there is particular notice.
  • the chemical resistance in particular, the acid resistance tends to decrease, and the strain point tends to decrease.
  • the density is increased, which makes it difficult to reduce the weight of the glass substrate.
  • the density of the glass is preferably less than 2.70 g / cm 3 and even less than 2.65 g / cm 3 .
  • SiO 2 -based crystals in particular cristobalite, precipitate and the liquidus viscosity decreases, that is, the devitrification resistance tends to decrease.
  • SiO 2 is 50% or more, 55% or more, 58% or more, 60.5% or more, more preferably 61% or more, 70% or less, 65% or less, 64% or less, 63.5% or less, 63 % Or less, 62.5% or less, and more preferably 62% or less.
  • Al 2 O 3 is 10% or more, 13% or more, 15% or more, 16% or more, 17% or more, 17.5% or more, preferably 18% or more, and 25% or less, 23% or less, 21 % Or less, 20% or less, 19% or less, 19.7% or less, and further preferably 19.5% or less.
  • B 2 O 3 is a component that acts as a flux and reduces the viscosity to improve the meltability.
  • the content of B 2 O 3 increases, the molten glass is volatilized and the glass component tends to fluctuate. Further, as the content of B 2 O 3 increases, the strain point is lowered, and the heat resistance and the acid resistance are also easily lowered. Furthermore, the Young's modulus is lowered, and the deflection of the glass substrate tends to be large. Therefore, it is preferable that B 2 O 3 is not contained substantially less than 3%, 2% or less, 1.7% or less, 1.5% or less, 1.4% or less, 1% or less. However, B 2 O 3 is 0.1% or more, 0.2% or more, 0.3% or more, 0.4% or more from the viewpoint of improving the meltability and preventing the decrease in BHF resistance and crack resistance. Furthermore, 0.5% or more may be contained.
  • the ⁇ -OH value of the glass is susceptible to the moisture contained in the glass batch charged into the glass melting furnace, and in particular, the glass material serving as the boron source is hygroscopic and contains crystal water. Because there is also, it is easy to bring moisture into the glass. Therefore, as the content of B 2 O 3 in the glass decreases, the ⁇ -OH value of the glass tends to decrease. Further, as the ⁇ -OH value decreases, the strain point of the glass becomes higher, and it becomes easier to reduce the heat shrinkage of the glass substrate. From the above reasons, in the present invention, it is preferable to reduce B 2 O 3 as much as possible, and it is desirable not to substantially contain B 2 O 3 .
  • the substantially free of B 2 O 3, a means that does not contain B 2 O 3 as intentionally raw material, does not exclude the contamination from impurities. Specifically, it means that the content of B 2 O 3 is 0.1% or less.
  • MgO is a component that lowers the viscosity at high temperature to enhance the meltability, and among alkaline earth metal oxides is a component that significantly increases the Young's modulus, but when introduced in excess, SiO 2 -based crystals, especially cristobalite It precipitates and the liquidus viscosity tends to decrease. Furthermore, MgO is a component that easily reacts with BHF to form a product. When the content of MgO is reduced, it is difficult to receive the above effect, and when the content of MgO is increased, the devitrification resistance and the strain point are easily reduced.
  • the content of MgO is preferably 10% or less, 9% or less, 8% or less, 6% or less, 5% or less, 4% or less, 3.5% or less, particularly 3% or less. Further, it is preferably 1% or more and 1.5% or more, particularly 2% or more.
  • CaO is a component that lowers the high temperature viscosity and significantly enhances the meltability without reducing the strain point. Further, among the alkaline earth metal oxides, since the introduced material is relatively inexpensive, it is a component that reduces the cost of the material. When the content of CaO decreases, it becomes difficult to receive the above effects. On the other hand, when the content of CaO is too large, the glass is likely to be devitrified and the thermal expansion coefficient tends to be high. Therefore, the content of CaO is preferably 15% or less, 12% or less, 11% or less, 8% or less, particularly 6% or less. Further, it is preferably 1% or more, 2% or more, 3% or more, 4% or more, particularly 5% or more.
  • SrO is a component that suppresses the phase separation of glass and enhances the devitrification resistance. Furthermore, it is a component which suppresses the rise of liquidus temperature while lowering the high temperature viscosity and reducing the melting point without lowering the strain point.
  • the content of SrO decreases, it is difficult to receive the above effects.
  • the content of SrO is preferably 10% or less, 7% or less, 5% or less, 4% or less, particularly 3% or less. Further, 0.1% or more, 0.2% or more, 0.3% or more, 0.5% or more, 1.0% or more, particularly preferably 1.5% or more.
  • BaO is a component that significantly enhances the devitrification resistance.
  • the content of BaO decreases, it becomes difficult to receive the above effects.
  • the content of BaO increases, the density becomes too high and the meltability tends to be reduced.
  • devitrified crystals containing BaO are easily precipitated, and the liquidus temperature tends to rise. Therefore, the content of BaO is 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10.5% or less, 10% or less, 9.5% or less, particularly 9% or less Is preferred. Further, it is preferably 1% or more, 3% or more, 4% or more, 5% or more, 6% or more, particularly 7% or more.
  • Na 2 O is a component that reduces the specific resistance of glass. When the content of Na 2 O decreases, it is difficult to receive the above effects. On the other hand, when the content of Na 2 O is increased, alkali ions are diffused into the formed semiconductor substance at the time of heat treatment, resulting in deterioration of film properties. Therefore, Na 2 O is 0.005% or more, 0.008% or more, 0.01% or more, 0.02% or more, 0.025% or more, 0.03% or more, or 0.05% or more. Preferably, it is 0.3% or less, more preferably 0.2% or less.
  • K 2 O may be added as an alkali metal oxide other than Na 2 O.
  • K 2 O is also a component that reduces the specific resistance of glass. As the content of K 2 O decreases, it becomes difficult to receive the above effects. On the other hand, when the content of K 2 O is increased, alkali ions are diffused into the formed semiconductor substance during heat treatment, resulting in deterioration of film properties. Therefore, K 2 O is 0.001% or more, 0.002% or more, 0.005% or more, 0.01% or more, 0.02% or more, 0.025% or more, 0.035% or more, or more. 0.05% or more is preferable, 0.3% or less, further 0.2% or less is preferable. K 2 O can be contained more than Na 2 O.
  • the total amount of alkali metal oxides (Na 2 O, Li 2 The total amount of O and K 2 O) is preferably 0.4% or less.
  • the glass substrate of the present invention preferably contains 0.005 to 0.1% of Fe 2 O 3 .
  • Fe 2 O 3 is a component having the function of reducing the specific resistance of glass, and the effect of suppressing charging of the glass substrate is further enhanced by containing Fe 2 O 3 in a certain amount or more.
  • the Fe 2 O 3 content is preferably 0.005% or more, 0.008% or more, and particularly preferably 0.01% or more.
  • the content of Fe 2 O 3 is preferably 0.1% or less.
  • the glass substrate of the present invention preferably contains 0.001 to 0.5% of SnO 2 .
  • SnO 2 is a component that has a good fining action in the high temperature range, and increases the strain point and reduces the high temperature viscosity. In the case of an electric melting furnace using a molybdenum electrode, there is an advantage that the electrode is not corroded.
  • the content of SnO 2 increases, devitrified crystals of SnO 2 easily precipitate and it becomes easy to promote the precipitation of devitrified crystals of ZrO 2 . Therefore, the content of SnO 2 is 0.001 to 0.5%, 0.001 to 0.45%, 0.001 to 0.4%, 0.01 to 0.35%, 0.1 to 0. It is preferably 3%, particularly 0.15 to 0.3%.
  • ZnO is a component that enhances the meltability. However, when the content of ZnO is increased, the glass is likely to be devitrified and the strain point is easily reduced.
  • the content of ZnO is preferably 0 to 5%, 0 to 4%, 0 to 3%, particularly 0 to 2%.
  • ZrO 2 is a component that enhances chemical durability, but when the content of ZrO 2 is large, devitrification of ZrSiO 4 tends to occur.
  • the content of ZrO 2 is preferably 0 to 5%, 0 to 4%, 0 to 3%, particularly 0.01 to 2%.
  • TiO 2 is a component that lowers high-temperature viscosity to enhance meltability and suppresses coloring due to solarization, but if the content of TiO 2 is large, the glass becomes colored and the transmittance tends to be reduced.
  • the content of TiO 2 is preferably 0 to 5%, 0 to 4%, 0 to 3%, 0 to 2%, particularly 0 to 0.1%.
  • P 2 O 5 is a component that enhances the strain point and suppresses the precipitation of devitrified crystals of an alkaline earth aluminosilicate system such as anorthite. However, when a large amount of P 2 O 5 is contained, the phase separation of the glass is facilitated.
  • the content of P 2 O 5 is preferably 0 to less than 0.15%, 0 to 1%, or 0 to 0.1%, and in particular, does not substantially contain it in terms of facilitating glass recycling. Specifically, it is desirable to be less than 0.01%.
  • Metal powders such as Cl, F, SO 3 , C, CeO 2 or Al, Si can be contained up to 3% in total.
  • As 2 O 3 and Sb 2 O 3 are useful as a fining agent, but it is desirable not to contain substantially from the viewpoint of preventing the environment and erosion of the electrode.
  • “not substantially contained” means that the total amount of As 2 O 3 and Sb 2 O 3 is 0.1% or less.
  • the glass substrate of the present invention has a ⁇ -OH value of less than 0.18 / mm.
  • the ⁇ -OH value is preferably 0.01 / mm or more, 0.02 / mm or more, and particularly preferably 0.03 / mm or more.
  • the strain point of the glass substrate of the present invention is 735 ° C. or more.
  • the strain point is preferably 800 ° C. or less.
  • the glass substrate of the present invention preferably has an annealing point of 780 ° C. or more, 790 ° C. or more, 800 ° C. or more, 810 ° C. or more, particularly 820 ° C. or more, for the same reason as the strain point.
  • the annealing temperature is preferably 850 ° C. or less, more preferably 840 ° C. or less .
  • the glass substrate of the present invention preferably has a Young's modulus of 80 GPa or more.
  • the Young's modulus is preferably 81 GPa or more, 82 GPa or more, 83 GPa or more, 84 GPa or more, and more preferably 85 GPa or more.
  • the glass substrate of the present invention preferably has a temperature corresponding to 10 4.5 dPa ⁇ s of 1330 ° C. or less, 1320 ° C. or less, and particularly 1310 ° C. or less.
  • a temperature corresponding to 10 4.5 dPa ⁇ s becomes high, the temperature at the time of molding becomes too high, and the production yield tends to be lowered.
  • the glass substrate of the present invention preferably has a temperature corresponding to 10 2.5 dPa ⁇ s of 1670 ° C. or less, 1660 ° C. or less, particularly 1650 ° C. or less.
  • a temperature corresponding to 10 2.5 dPa ⁇ s becomes high, the glass becomes difficult to melt, defects such as bubbles increase, and the production yield tends to decrease.
  • the glass substrate of the present invention preferably has a liquidus temperature of less than 1250 ° C., less than 1240 ° C., less than 1230 ° C., and particularly less than 1220 ° C.
  • a liquidus temperature of less than 1250 ° C., less than 1240 ° C., less than 1230 ° C., and particularly less than 1220 ° C.
  • the glass substrate of the present invention has a viscosity at a liquidus temperature of 10 4.9 dPa ⁇ s or more, 10 5.0 dPa ⁇ s 10 5.1 dPa ⁇ s or more, 10 5.2 dPa ⁇ s or more, in particular 10 5. It is preferably 3 dPa ⁇ s or more. In this way, devitrification is less likely to occur at the time of glass forming, so it becomes easy to form in a plate shape by the overflow down draw method, and the surface quality of the glass substrate can be improved.
  • the viscosity at the liquidus temperature is an index of formability, and the formability improves as the viscosity at the liquidus temperature is higher.
  • Example 1 Tables 1 and 2 show example glasses of the present invention (samples No. 1 to 9) and conventional glasses (sample No. 10). The contents of the components other than Na 2 O, K 2 O, Fe 2 O 3 , and ZrO 2 in the table are rounded off to one decimal place.
  • the glass samples in Tables 1 and 2 were prepared as follows. First, a glass batch prepared by preparing glass raw materials to have the composition shown in the table was put into a platinum crucible and melted at 1600 to 1650 ° C. for 24 hours. In melting the glass batch, it was stirred using a platinum stirrer and homogenized. Next, the molten glass was poured out on a carbon plate and formed into a plate, and then annealed for 30 minutes at a temperature near the annealing point.
  • strain point For each sample thus obtained, strain point, annealing point, density, Young's modulus, temperature corresponding to 10 4.5 dPa ⁇ s, temperature corresponding to 10 2.5 dPa ⁇ s, liquidus temperature TL, liquid Log 10 ⁇ TL was measured for viscosity TL TL (dPa ⁇ s) at the phase temperature.
  • strain points and annealing points in Tables 1 and 2 were measured by the method of ASTM C336.
  • the density was measured by Archimedes method according to ASTM C693.
  • Young's modulus was measured by a bending resonance method according to JIS R1602.
  • the temperatures corresponding to 10 4.5 dPa ⁇ s and 10 2.5 dPa ⁇ s were measured by a platinum ball pulling method.
  • the liquidus temperature TL passes through a standard sieve of 30 mesh (500 ⁇ m), and the glass powder remaining on 50 mesh (300 ⁇ m) is charged into a platinum boat and held for 24 hours in a temperature gradient furnace set at 1100 ° C. to 1350 ° C. After that, the platinum boat was taken out, and the temperature at which devitrification (crystal foreign matter) was observed in the glass was measured.
  • the viscosity Log 10 ⁇ TL at the liquidus temperature was measured by measuring the viscosity ⁇ TL of the glass at the liquidus temperature by a platinum ball pulling method, and the Log 10 ⁇ TL was calculated.
  • ⁇ -OH value (1 / X) log (T1 / T2)
  • X Glass thickness (mm)
  • T1 transmittance at a reference wavelength 3846 cm -1 (%)
  • T2 Minimum transmittance in the vicinity of the hydroxyl group absorption wavelength 3600 cm -1 (%)
  • each of the samples No. 1 to No. 9 is a glass which tends to have a thermal shrinkage of 20 ppm or less because the strain point is 735 ° C. or more and the slow cooling point is 785 ° C. or more. Further, since the Young's modulus is 80.4 GPa or more, it is difficult to bend, and since the liquid phase temperature TL is 1246 ° C. or less and the viscosity TLTL at the liquid phase temperature is 10 4.9 dPa ⁇ s or more, devitrification hardly occurs during molding. . In particular, no. Each of the samples 1, 2 and 7 to 9 was suitable for the overflow down draw method because the viscosity ⁇ TL at the liquidus temperature was 10 5.2 dPa ⁇ s or more.
  • Example 2 Sample No. in Table 2 Glass batches were prepared to be 8 and 10 glasses. Next, the glass batch was put into an electric melting furnace, melted at 1600 to 1650 ° C., and then the molten glass was clarified and homogenized in a clarification tank and a homogenization tank, and then adjusted to a viscosity suitable for molding in a pot. . Next, the molten glass is formed into a plate shape by an overflow downdraw apparatus, and the average cooling rate in the temperature range from the annealing point to (annealing point -100 ° C) is set to 385 ° C / min in a 5-m long annealing furnace. Then it was slowly cooled. Thereafter, the plate-like glass was cut and edge-processed to prepare a glass substrate having dimensions of 1500 ⁇ 1850 ⁇ 0.7 mm.
  • the ⁇ -OH value and the thermal contraction rate of each glass substrate thus obtained were measured.
  • the ⁇ -OH value of the glass substrate of No. 8 was 0.1 / mm, and the thermal shrinkage was 10 ppm.
  • the ⁇ -OH value of the 10 glass substrates was 0.3 / mm, and the thermal shrinkage was 25 ppm.
  • the thermal contraction rate of the glass substrate was measured by the following method. First, as shown in FIG. 1A, a strip-shaped sample G of 160 mm ⁇ 30 mm was prepared as a sample of a glass substrate. A marking M was formed on each of both ends in the long side direction of the strip-like sample G using a water-resistant abrasive paper of # 1000 at a distance of 20 to 40 mm from the edge. Thereafter, as shown in FIG. 1B, the strip-like sample G on which the marking M was formed was broken into two along the direction orthogonal to the marking M to produce sample pieces Ga and Gb. Then, only one of the sample pieces Gb was heated from normal temperature (25 ° C.) to 500 ° C.
  • the support base 1 of the glass substrate G is provided with pads 2 made of Teflon (registered trademark) for supporting the four corners of the glass substrate G.
  • the support base 1 is provided with a table 3 made of metal aluminum which can be moved up and down, and after bringing the table 3 into contact with the glass substrate G by moving the table 3 up and down as shown in FIG. By peeling the glass substrate G, the glass substrate G can be charged.
  • the table 3 is grounded. Further, one or more holes (not shown) are formed in the table 3, and the holes are connected to a diamond-shaped vacuum pump (not shown). When the vacuum pump is driven, air is sucked from the holes of the table 3, whereby the glass substrate G can be vacuum adsorbed to the table 3.
  • a surface voltmeter 4 is installed at a position 10 mm above the glass substrate G, by which the amount of charge generated at the central portion of the glass substrate G is continuously measured.
  • an air gun 5 with an ionizer is installed above the glass substrate G, whereby the charging of the glass substrate G can be eliminated.
  • the peeling charge of the glass substrate was measured in the next step using this apparatus.
  • the experiment was conducted in a clean booth at a temperature of 25 ° C. and a humidity of 40%. Since the amount of charge changes greatly under the influence of the atmosphere, particularly the humidity in the atmosphere, it is particularly necessary to adjust the humidity.
  • the glass substrate G is placed on the support pad 2 of the support 1.
  • the glass substrate G is discharged by an air gun 5 with an ionizer.
  • the table 3 is raised and brought into contact with the glass substrate G, and vacuum suction is carried out to bring the table 3 and the glass substrate G into close contact for 20 seconds.
  • the table 3 is lowered to separate the glass substrate G from the table 3, and the amount of charge generated at the central portion of the glass substrate G is continuously measured by the surface voltmeter 4.
  • a total of five peel evaluations are continuously performed by repeating the steps (3) and (4). The maximum charge amount in each measurement is determined, and these are integrated to obtain a peeling charge amount.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Mechanical Engineering (AREA)
  • Glass Compositions (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Surface Treatment Of Glass (AREA)
PCT/JP2018/048458 2018-01-23 2018-12-28 ガラス基板及びその製造方法 WO2019146379A1 (ja)

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WO2021131668A1 (ja) * 2019-12-23 2021-07-01 日本電気硝子株式会社 ガラス基板の製造方法及びガラス基板
CN114080369A (zh) * 2019-08-14 2022-02-22 日本电气硝子株式会社 玻璃基板
WO2022038976A1 (ja) * 2020-08-19 2022-02-24 日本電気硝子株式会社 ガラス板の製造方法
JP7392909B2 (ja) 2019-11-25 2023-12-06 日本電気硝子株式会社 磁気記録媒体用ガラス基板及びそれを用いた磁気記録装置

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WO2016185976A1 (ja) * 2015-05-18 2016-11-24 日本電気硝子株式会社 無アルカリガラス基板
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CN114080369A (zh) * 2019-08-14 2022-02-22 日本电气硝子株式会社 玻璃基板
CN114080369B (zh) * 2019-08-14 2024-01-05 日本电气硝子株式会社 玻璃基板
JP7392909B2 (ja) 2019-11-25 2023-12-06 日本電気硝子株式会社 磁気記録媒体用ガラス基板及びそれを用いた磁気記録装置
WO2021131668A1 (ja) * 2019-12-23 2021-07-01 日本電気硝子株式会社 ガラス基板の製造方法及びガラス基板
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WO2022038976A1 (ja) * 2020-08-19 2022-02-24 日本電気硝子株式会社 ガラス板の製造方法

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TWI758576B (zh) 2022-03-21
JP7256473B2 (ja) 2023-04-12
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