WO2014175144A1 - 化学強化用ガラス板およびその製造方法 - Google Patents

化学強化用ガラス板およびその製造方法 Download PDF

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Publication number
WO2014175144A1
WO2014175144A1 PCT/JP2014/060869 JP2014060869W WO2014175144A1 WO 2014175144 A1 WO2014175144 A1 WO 2014175144A1 JP 2014060869 W JP2014060869 W JP 2014060869W WO 2014175144 A1 WO2014175144 A1 WO 2014175144A1
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Prior art keywords
glass
glass plate
less
temperature
compaction
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PCT/JP2014/060869
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English (en)
French (fr)
Japanese (ja)
Inventor
学 西沢
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旭硝子株式会社
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Priority to CN201480023702.XA priority Critical patent/CN105189385A/zh
Priority to JP2015513709A priority patent/JPWO2014175144A1/ja
Publication of WO2014175144A1 publication Critical patent/WO2014175144A1/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
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

Definitions

  • the present invention relates to a chemically strengthened glass plate used for various touch panels, various display panels, and the like, and a conductive film or the like is patterned on the glass plate.
  • the glass plate for chemical strengthening uses soda lime silicate glass or alkali aluminosilicate glass, and can be manufactured by various forming methods such as a float method, a roll-out method, and a fusion method.
  • the float method which is a forming method for drawing a glass plate in the horizontal direction, can secure a sufficient length of the slow cooling furnace, whereas the method of forming in the vertical direction such as the fusion method has a restriction on the length of the slow cooling furnace. Cold time is insufficient.
  • the present invention relates to glass molding in heat treatment at a low temperature (150 to 300 ° C.) when manufacturing a TFT panel, a TFT panel with a touch sensor, or a touch sensor (hereinafter collectively referred to as “display member”).
  • a low temperature 150 to 300 ° C.
  • the compaction (C) is small and the patterning patterning accuracy on the glass plate is high (it is difficult for misalignment).
  • the object is to provide a glass plate.
  • the virtual viscosity is 10 12.8 d ⁇ Pa ⁇ s or less
  • In mole percentage display based on the following oxides: 60 to 79% of SiO 2 Al 2 O 3 2.5-18%, 0 to 3% of B 2 O 3 1-15% MgO, 0-1% CaO, 0-1% SrO, BaO 0-1%, 0 to 1% of ZrO 2 7 to 15.5% Na 2 O, 0 to 0.5% of K 2 O, Containing 0 to 2% of Li 2 O, 7 to 15.5% of Na 2 O + K 2 O, Na 2 O / (Na 2 O + K 2 O) is 0.9 to 1, 1 to 18% of MgO + CaO + SrO + BaO, MgO-0.5Al 2 O 3 is 1 to 8, MgO +
  • the glass plate for chemical strengthening of the present invention has a small compaction (C) (20 ppm or less) in the heat treatment at a low temperature (150 to 300 ° C.) in the manufacturing process of the display member, and the positional deviation at the time of film formation patterning on the glass plate is small. Not likely to occur.
  • the glass plate for chemical strengthening of the present invention can be used for increasing the size of the panel, increasing the definition, increasing the speed of the display frame, increasing the weather resistance, increasing the functionality, increasing the reliability, and incorporating IC circuits such as drivers.
  • it can be suitably used as an integrated cover glass chemical strengthening glass plate for a touch panel sensor.
  • the glass plate for chemical strengthening of this invention is a glass plate manufactured with the shaping
  • virtual viscosity is 1012.8 d * Pa * s or less.
  • the glass plate for chemical strengthening of this invention is glass suitable for chemical strengthening, the surface compressive stress after chemical strengthening is high, a surface stress layer is easy to penetrate deeply, and it has high intensity
  • FIG. 1 is a graph showing the relationship between MgO and Al 2 O 3 in the glass plate of the present invention.
  • FIG. 2 is a graph showing the relationship between the virtual viscosity and the compaction of the glass plates of Examples 19 and 22 (Examples) and Example 25 (Comparative Example) of the present invention.
  • 3A to 3D are diagrams conceptually showing an example of the touch sensor plate, FIG. 3A is a plan view, and FIG. 3B is a cross-sectional view taken along the line bb of FIG. 3A.
  • 3C is a cross-sectional view taken along the line cc of FIG. 3A, and FIG. 3D is a cross-section near the end.
  • FIG. 3A to 3D are diagrams conceptually showing an example of the touch sensor plate, FIG. 3A is a plan view, and FIG. 3B is a cross-sectional view taken along the line bb of FIG. 3A. 3C is a cross-sectional view taken along the line cc of
  • FIG. 4 is a conceptual diagram for explaining the configuration of the touch sensor plate shown in FIGS. 3 (A) to 3 (D).
  • FIG. 5 is a flowchart showing an example of a manufacturing method of the touch sensor plate shown in FIGS. 3 (A) to 3 (D).
  • FIG. 6 is a cross-sectional view of a TFT panel or an on-cell touch panel.
  • FIG. 7 is a cross-sectional view of the in-cell touch panel.
  • FIG. 8 is a cross-sectional view of an out-cell (external) touch panel.
  • the glass plate for chemical strengthening of the present invention (hereinafter also referred to as the glass plate of the present invention) has a virtual viscosity of 10 12.8 d ⁇ Pa ⁇ s or less, In mole percentage display based on the following oxides: 60 to 79% of SiO 2 Al 2 O 3 2.5-18%, 0 to 3% of B 2 O 3 1-15% MgO, 0-1% CaO, 0-1% SrO, BaO 0-1%, 0 to 1% of ZrO 2 7 to 15.5% Na 2 O, 0 to 0.5% of K 2 O, Containing 0 to 2% of Li 2 O, 7 to 15.5% of Na 2 O + K 2 O, Na 2 O / (Na 2 O + K 2 O) is 0.9 to 1, 1 to 18% of MgO + CaO + SrO + BaO, MgO-0.5Al 2 O 3 is 1 to 8, MgO + 0.5Al 2 O 3 is 1-20, Glass transition temperature
  • the glass plate of the present invention has a compaction (C) of 20 ppm or less.
  • the compaction (C) is more preferably 18 ppm or less, and further preferably 16 ppm or less.
  • misalignment during film-forming patterning on a glass plate hardly occurs during heat treatment at a low temperature (150 to 300 ° C.) in the manufacturing process of the display member.
  • the compaction (C) means a value measured by the method described below.
  • the target glass is melted at 1600 ° C., then the molten glass is poured out, cooled into a plate shape, and then cooled.
  • the obtained glass plate is polished to obtain a sample whose two surfaces are mirror-polished with a thickness of 2 mm and a size of 100 mm ⁇ 20 mm.
  • annealing treatment refers to a process (excluding the chemical strengthening treatment process) in which the raw material is melted, cooled to a temperature below the strain point, and then heated again to a temperature above the strain point.
  • the time required for annealing is preferably within one day of the entire process.
  • chemical strengthening treatment is performed.
  • the compaction (C) is calculated from A and B thus obtained using the following formula. A and B are measured using an optical microscope.
  • the virtual viscosity of the glass plate of the present invention is 10 12.8 d ⁇ Pa ⁇ s or less.
  • the cooling rate after forming the glass plate is preferably set to 20 ° C./min or more.
  • the virtual viscosity of the glass plate is preferably 10 12.6 d ⁇ Pa ⁇ s or less (corresponding to a cooling rate of 30 ° C./min or more), and preferably 10 12.4 d ⁇ Pa ⁇ s or less (corresponding to a cooling rate of 50 ° C./min or more). preferably, 10 12.2 d ⁇ Pa ⁇ s or less (cooling rate 70 ° C. / min or equivalent) is preferred, 10 12.1 d ⁇ Pa ⁇ s or less (cooling rate 100 ° C. / min or equivalent) is preferred, 10 12 0.0 d ⁇ Pa ⁇ s or less (cooling rate equivalent to 120 ° C./min or more) is more preferable.
  • the glass plate of the present invention is particularly preferable because it can achieve the low compaction property even when it is cooled at a rate equivalent to 20 ° C./min or more and has high productivity when producing the glass plate.
  • the virtual viscosity ( ⁇ ) of the glass can be calculated by the following (formula 4) (GW Scherer, Relaxation in Glass and Compositions, Wiley, New York (1986), p. 159).
  • the unit of ⁇ is d ⁇ Pa ⁇ s. q is the cooling rate and the unit is ° C./s.
  • a plurality of glass plate pieces cut out from a single glass plate having a thickness of 1 mm or less, for example, 1 cm square pieces, are separately heat-treated and cooled at various cooling rates q, and the physical properties of each glass piece are measured.
  • the cooling start temperature is preferably a sufficiently high temperature that is not affected by the cooling rate. Typically, it is preferably about Tg + 50 ° C. to + 150 ° C.
  • a calibration curve is created by taking the cooling rate (log 10 ) on the x-axis and taking the physical property values of the glass pieces subjected to the respective heat treatments on the y-axis.
  • the value (q) of the x-axis with respect to the physical property value (y-axis) of the glass piece not subjected to heat treatment indicates the cooling rate of the glass.
  • the present inventor has found that the compaction (C) at a cooling rate of 50 ° C./min can be kept small (to 20 ppm or less) even if chemical strengthening treatment or annealing treatment is performed. It has been found that low compaction properties can be maintained against an increase in the cooling rate during molding, and has led to the present invention.
  • the glass transition temperature (Tg) of the glass plate of this invention is 580 degreeC or more and 720 degrees C or less.
  • the glass transition temperature (Tg) of the glass plate of the present invention is preferably in the above range to reduce the compaction (C), and in the low temperature heat treatment (150 ° C. to 300 ° C.) in the display member manufacturing process,
  • the mobility of alkali ions becomes small, the mobility of IC circuits such as sensors and drivers to transistor elements (sensors, etc.) is low, and performance degradation of the sensors can be suppressed.
  • Tg is preferably 600 ° C. or higher, more preferably 640 ° C. or higher, and further preferably 680 ° C. or higher.
  • SiO 2 SiO 2 is a component that forms a glass skeleton, and maintains the heat resistance and chemical durability of glass, and the density, the average thermal expansion coefficient at 50 to 350 ° C., and the compaction (C) are reduced. 60 mol% (hereinafter simply referred to as “%”) or more. Preferably it is 62% or more, More preferably, it is 63% or more.
  • the content of SiO 2 is set to 79% or less. Preferably it is 77% or less, More preferably, it is 75% or less, More preferably, it is 74% or less.
  • Al 2 O 3 raises the glass transition temperature, improves weatherability (solarization), heat resistance and chemical durability, increases Young's modulus, lowers the average thermal expansion coefficient at 50 to 350 ° C., and compaction (C) , Reducing the photoelastic constant, improving chemical strengthening characteristics, reducing the mobility of alkali ions in the glass, and lowering the mobility of IC circuits such as sensors or drivers to transistor elements (sensors, etc.)
  • the content is set to 2.5% or more in order to suppress performance deterioration of the sensor.
  • it is 4% or more, More preferably, it is 6% or more, More preferably, it is 7% or more.
  • the viscosity at the time of melting the glass is lowered, the deterioration of solubility is suppressed, and the devitrification temperature [surface devitrification temperature (Tc) on the glass surface and internal devitrification temperature (T d ) inside the glass] is reduced, and molding is performed.
  • the content of Al 2 O 3 is set to 18% or less. Preferably it is 16% or less, More preferably, it is 15% or less.
  • B 2 O 3 has the effect of lowering the viscosity at the time of glass melting, accelerating the melting and lowering the devitrification temperature, and may be contained up to 3% in order to improve the strength characteristics.
  • the content is made 3% or less. Preferably it is 1.5% or less. More preferably, it is 0.5% or less, and it is still more preferable not to contain substantially.
  • substantially does not contain means that it is not contained other than inevitable impurities mixed from raw materials or the like, that is, it is not intentionally contained.
  • B 2 When used as TFT panel glass or cell touch panel glass plate, and a low content of B 2 O 3 ratio, to be used in dissolving the glass when the glass plate making, dissolving process, in the refining step and forming step, B 2 The volatilization amount of O 3 is small, and the produced glass plate is excellent in homogeneity and flatness. As a result, when used as a glass panel for a TFT panel that requires a high degree of flatness, the display quality is superior to that of a conventional glass panel for a TFT panel.
  • the content of B 2 O 3 is that less is preferable.
  • cullet containing B 2 O 3 can be used.
  • MgO has the effect of lowering the viscosity at the time of melting the glass, promoting the melting, lowering the devitrification temperature, and improving the weather resistance of the glass plate, so the content is made 1% or more. Preferably it is 3% or more, More preferably, it is 5% or more, More preferably, it is 7% or more.
  • the content is made 15% or less. Preferably it is 13% or less, More preferably, it is 11% or less, More preferably, it is 10% or less.
  • CaO can be contained because it has the effects of lowering the viscosity during glass melting, promoting melting, and lowering the devitrification temperature.
  • the content is made 1% or less. Preferably it is 0.5% or less, More preferably, it does not contain substantially.
  • SrO can be contained because it has the effects of lowering the viscosity during glass melting, promoting melting, lowering the devitrification temperature, and lowering the photoelastic constant.
  • the content of SrO is set to 1% or less. Preferably it is 0.5% or less, More preferably, it does not contain substantially.
  • BaO can be contained because it has the effects of lowering the viscosity during glass melting, promoting melting, lowering the devitrification temperature, and lowering the photoelastic constant.
  • the content is made 1% or less. Preferably it is 0.5% or less, More preferably, it does not contain substantially.
  • ZrO 2 ZrO 2 can be contained because it has the effects of lowering the viscosity during glass melting, promoting melting, and lowering the devitrification temperature.
  • the content is made 1% or less. 0.5% or less is preferable and it is more preferable not to contain substantially.
  • the total amount is 1% or more. It is preferably 3% or more, more preferably 5% or more, and further preferably 7% or more.
  • the total amount is made 18% or less. It is preferably 16% or less, more preferably 12.5% or less, and even more preferably 10% or less.
  • Na 2 O Na 2 O facilitates chemical strengthening, lowers the viscosity during glass melting, promotes melting, and lowers the devitrification temperature, so the content is 7% or more. It is preferably 9% or more, and more preferably 11% or more. More preferably, it is 12% or more.
  • the content of Na 2 O is set to 15.5% or less for the first purpose of minimizing the compaction (C).
  • Compaction (C) preferably 14.5% or less, preferably 13.5% or less in order to suppress an increase in average thermal expansion coefficient at 50 to 350 ° C., chemical durability, and deterioration of weather resistance. More preferred. More preferably, it is 13% or less.
  • K 2 O K 2 O can be contained because it has the effects of lowering the viscosity during glass melting, promoting melting, and lowering the devitrification temperature.
  • the content of K 2 O is set to 0.5% or less. The content is more preferably 0.2% or less, and still more preferably substantially not contained.
  • Li 2 O Li 2 O can be contained because it has the effect of lowering the viscosity at the time of melting the glass, promoting the melting, and lowering the devitrification temperature.
  • the content is made 1% or less. 0.5% or less is more preferable, and it is further more preferable not to contain substantially.
  • (R 2 O) Na 2 O and K 2 O facilitate chemical strengthening, lowering the viscosity during melting of the glass, facilitate dissolution, it has the effect of lowering the liquidus temperature, and to reduce the photoelastic constant, Na 2
  • the total content of O and K 2 O is 7% or more. Preferably it is 9% or more, More preferably, it is 11% or more, More preferably, it is 12% or more.
  • the primary purpose is to keep compaction (C) small, and the improvement of weather resistance is set to 15.5% or less for the second purpose. Preferably it is 15% or less, More preferably, it is 14% or less, More preferably, it is 13% or less.
  • the above (Formula 1) serves as an index for reducing the compaction (C) in the heat treatment at a low temperature (150 to 300 ° C.). From the results of experiment and trial and error, the present inventor has found that when each of the above components satisfies the scope of the present invention and the value obtained by the above (Formula 1) is 0.9 to 1, Tg is 580 to It was found that the compaction (C) satisfies 20 ppm or less while satisfying an average thermal expansion coefficient of 65 ⁇ 10 ⁇ 7 to 85 ⁇ 10 ⁇ 7 at 720 ° C. and 50 to 350 ° C. Preferably, it is 0.95 or more, more preferably 1.
  • MgO and Al 2 O 3 are contained so that the following (Formula 2) satisfies 1 to 8.
  • “Mole%” of MgO and Al 2 O 3 contained in the composition of the glass plate is substituted for “MgO” and “Al 2 O 3 ” in the following (Formula 2).
  • Equation 2 serves as an index for reducing the photoelastic constant and reducing the compaction (C) in the heat treatment at a low temperature (150 to 300 ° C.). From the results of experiments and trial and error, the present inventor has found that each of the above components satisfies the scope of the present invention, and the value obtained by the above (Formula 2) is in the middle of 1 to 8, that is, as the value approaches 4. And found that the compaction (C) can be reduced. Preferably it is 2 or more, more preferably 3 or more. Preferably it is 7.5 or less, More preferably, it is 7 or less, Most preferably, it is 6 or less. Moreover, in order to obtain a low photoelastic constant, it is preferable that it is 2 or more.
  • a portion close to a straight line with an intercept of 5, that is, a portion close to the straight line of MgO-0.5Al 2 O 3 4 within the scope of the present invention in FIG.
  • the above (Formula 3) is for devitrification characteristics in the glass production process, specifically, for satisfying T 4 -T c described later to be ⁇ 50 to 350 ° C. or T 4 -T d satisfying ⁇ 50 to 350 ° C. It becomes an indicator. From the results of experiments and trial and error, the present inventor has found that when each of the above components satisfies the scope of the present invention and the value obtained by the above (Formula 3) is 1 to 20, Tg is 580 to 720. It was found that T 4 -T c or T 4 -T d satisfies the above range while satisfying an average thermal expansion coefficient of 65 ⁇ 10 ⁇ 7 to 85 ⁇ 10 ⁇ 7 / ° C. at 50 ° C. and 50 to 350 ° C.
  • Formula 3 and molding method As the glass plate forming method of the present invention, a float method and a fusion method (down draw method) can be applied.
  • the above (formula 3) is preferably 14 or less, more preferably 13 or less. More preferably, it is 12 or less.
  • the above (formula 3) is preferably 18 or less, more preferably 16 or less, and further preferably 14 or less. Moreover, in order to obtain a low photoelastic constant, it is preferably 3 or more, more preferably 5 or more, and further preferably 7 or more.
  • the average linear expansion coefficient at 50 to 350 ° C. of the glass plate of the present invention is preferably 85 ⁇ 10 ⁇ 7 / ° C. or less.
  • the glass surface devitrification temperature ( Tc ) of the glass plate of this invention is 1300 degrees C or less. Preferably it is 1275 degrees C or less, More preferably, it is 1250 degrees C or less, Most preferably, it is 1225 degrees C or less. In consideration of the ease of securing other physical properties, the glass surface devitrification temperature (T c ) is 900 ° C. or higher.
  • Glass surface devitrification temperature means that glass particles crushed in a platinum dish are subjected to heat treatment for 17 hours in an electric furnace controlled at a constant temperature, and the glass is observed by optical microscope observation after the heat treatment. This is an average value of the maximum temperature at which crystals are deposited on the surface and the minimum temperature at which crystals are not deposited.
  • the glass plate of the present invention preferably has a glass internal devitrification temperature (T d ) of 1300 ° C. or lower. Preferably it is 1275 degrees C or less, More preferably, it is 1250 degrees C or less, More preferably, it is 1225 degrees C or less, More preferably, it is 1200 degrees C or less. In consideration of the ease of securing other physical properties, the glass internal devitrification temperature (T d ) is 900 ° C. or higher.
  • Glass internal devitrification temperature means that glass particles crushed in a platinum dish are subjected to heat treatment for 17 hours in an electric furnace controlled at a constant temperature, and the glass is observed by optical microscope observation after the heat treatment. Is the average value of the maximum temperature at which crystals are precipitated and the minimum temperature at which crystals are not precipitated.
  • the glass plate of the present invention preferably has a temperature (T 4 ) at which the viscosity is 10 4 d ⁇ Pa ⁇ s is 1350 ° C. or lower. It is preferable that it is 1300 degrees C or less, More preferably, it is 1275 degrees C or less, More preferably, it is 1250 degrees C or less. In consideration of ease of securing other physical properties, the temperature (T 4 ) at which the viscosity is 10 4 d ⁇ Pa ⁇ s is 1100 ° C. or higher.
  • the glass viscosity at Td is 10 4.7 d ⁇ Pa ⁇ s or more. More preferably, it is 10 5.0 d ⁇ Pa ⁇ s or more, more preferably 10 5.3 d ⁇ Pa ⁇ s or more, and particularly preferably 10 5.5 d ⁇ Pa ⁇ s or more.
  • the glass viscosity at T d is preferably 10 7.0 d ⁇ Pa ⁇ s or less.
  • the glass viscosity at T c is preferably 10 3.8 d ⁇ Pa ⁇ s or more, more preferably 10 3.9 d ⁇ Pa ⁇ s or more, and even more preferably 10 4.0 d ⁇ Pa ⁇ s or more.
  • the glass viscosity at T c is preferably 10 7.0 d ⁇ Pa ⁇ s or less in the float method.
  • T 4 ⁇ T d is preferably 100 to 350 ° C., preferably satisfies T 4 ⁇ T d ⁇ 50 ° C., more preferably satisfies T 4 ⁇ T d ⁇ 150 ° C., and T 4 ⁇ T d ⁇ 200 ° C. It is more preferable to satisfy.
  • T 4 -T c is preferably ⁇ 50 to 350 ° C., T 4 ⁇ T c ⁇ ⁇ 20 ° C. is preferable, and T 4 ⁇ T c ⁇ ⁇ 10 ° C. is satisfied. It is more preferable that T 4 ⁇ T c ⁇ 0 ° C. is further satisfied.
  • the temperature (T 2 ) at which the viscosity becomes 10 2 d ⁇ Pa ⁇ s is preferably 1850 ° C. or less, more preferably 1800 ° C. or less, more preferably 1750 ° C. or less. Yes, more preferably 1700 ° C. or lower, and further preferably 1650 ° C. or lower.
  • the glass plate of the present invention preferably has a density of 2.50 g / cm 3 or less for reducing the weight of the display member, more preferably 2.45 g / cm 3 or less, and still more preferably 2.43 g / cm 3. It is cm 3 or less, particularly preferably 2.41 g / cm 3 or less.
  • the glass plate of the present invention preferably has a density of 2.35 g / cm 3 or more in consideration of the ease of securing other physical properties.
  • the glass plate of the present invention preferably has a photoelastic constant of 33 nm / MPa / cm or less, more preferably 31 nm / MPa / cm or less, still more preferably 30 nm / MPa / cm or less, particularly preferably. It is 29 nm / MPa / cm or less.
  • the glass plate of the present invention preferably has a photoelastic constant of 27 nm / MPa / cm or more in consideration of ease of securing other physical properties.
  • the photoelastic constant can be measured by a disk compression method.
  • the glass plate of the present invention preferably has a Young's modulus of 66 GPa or more, more preferably 70 GPa or more, and further preferably 74 GPa or more.
  • the glass plate of the present invention preferably has a Young's modulus of 80 GPa or less.
  • the amount of deflection at the center when holding the two ends is small, preventing problems such as contact between the glass plates, and the space between the glass plates Since it can be made smaller, there are advantages such as an increase in the number of processed sheets at a time and an increase in productivity.
  • a high Young's modulus contributes to improving the mechanical properties of the glass plate and improving the durability against cracking.
  • the glass plate of the present invention preferably consists essentially of the above mother composition, but may contain other components as long as the object of the present invention is not impaired.
  • the other components may be contained in a total of 2% or less, preferably 1% or less, more preferably 0.5% or less.
  • ZnO Li for the purpose of improving weather resistance, solubility, devitrification, ultraviolet shielding, infrared shielding, ultraviolet transmission, infrared transmission, etc., or contamination by impurities using cullet by recycling display panels after use 2 O, a WO 3, Nb 2 O 5, V 2 O 5, Bi 2 O 3, MoO 3, P 2 O 5, Ga 2 O 3, I 2 O 5, In 2 O 5, Ge 2 O 5 , etc. You may contain.
  • the glass plate of the present invention contains these raw materials as matrix composition raw materials so that the total amount of SO 3 , F, Cl, SnO 2 is 2% or less in the glass. You may add to.
  • ZrO 2 , Y 2 O 3 , La 2 O 3 , TiO 2 , SnO 2 may be contained in the glass in a total amount of 2% or less, preferably 1%. Below, more preferably 0.5% or less.
  • Y 2 O 3 , La 2 O 3 and TiO 2 contribute to the improvement of the Young's modulus of the glass.
  • the glass plate of the present invention may contain a colorant such as Fe 2 O 3 or CeO 2 in the glass in order to adjust the color tone of the glass.
  • a colorant such as Fe 2 O 3 or CeO 2 in the glass in order to adjust the color tone of the glass.
  • the total content of such colorants is preferably 1% or less.
  • the glass plate of the present invention preferably contains substantially no As 2 O 3 or Sb 2 O 3 in consideration of environmental load. In consideration of stable float forming, it is preferable that ZnO is not substantially contained. However, the glass plate of the present invention is more effective when applied to thin glass with a high glass pull-out speed or by molding by the fusion method.
  • the glass plate of this invention can be used suitably as a glass plate for chemical strengthening suitable for a display member. This will be described in detail below.
  • Glass plate manufacturing method When manufacturing the glass plate in this invention, it melt
  • raw materials are prepared so as to have the composition of the obtained glass plate, and the raw materials are continuously charged into a melting furnace, and preferably heated to about 1450 to 1650 ° C. to obtain molten glass.
  • Oxides, carbonates, hydroxides, and in some cases halides such as chlorides can be used as raw materials. From raw materials with a large particle size of several hundred microns that do not cause undissolved raw material particle size, to materials with a small particle size of about several microns that do not scatter during transportation of the raw material and do not agglomerate as secondary particles it can. The use of granules is also possible.
  • the water content, ⁇ -OH, the redox degree of Fe, or the dissolution conditions such as redox [Fe 2+ / (Fe 2+ + Fe 3+ )] can be appropriately adjusted and used.
  • the glass plate of the present invention are the alkali glass plate containing an alkali metal oxide (Na 2 O, K 2 O ), can be used SO 3 effectively as a fining agent. Further, a defoaming method using reduced pressure may be applied. Halogens such as Cl and F are preferably used as the clarifying agent in the defoaming method using reduced pressure.
  • the glass ribbon is obtained by applying the float method and fusion method (down draw method) as the molding process.
  • the glass ribbon is preferably cooled to room temperature at a cooling rate of 20 ° C./min or more, and after cutting, a glass plate is obtained.
  • the thickness of the glass plate in the present invention is preferably 2 mm or less. If the thickness of the glass plate is 2 mm or less, it can contribute to the reduction in thickness and weight of a product equipped with a display or sensor integrated cover glass. Preferably it is 1.5 mm or less, More preferably, it is 1.0 mm or less, More preferably, it is 0.5 mm or less, More preferably, it is 0.3 mm or less.
  • the method for chemically strengthening the glass plate in the present invention is not particularly limited as long as it can ion-exchange Na ions on the glass surface layer and K ions in the molten salt, but for example, heated potassium nitrate (KNO 3 ).
  • KNO 3 heated potassium nitrate
  • the method of immersing glass in molten salt is mentioned.
  • the chemical strengthening treatment conditions for forming a chemically strengthened layer (compressive stress layer) having a desired surface compressive stress on the glass vary depending on the thickness of the glass plate, but the KNO 3 molten salt at 350 to 550 ° C.
  • the glass plate is typically immersed for 2 to 20 hours. From an economical point of view, it is preferable to immerse under conditions of 350 to 500 ° C. and 2 to 16 hours, and a more preferable immersion time is 2 to 10 hours.
  • Etching, polishing or annealing may be performed before or after chemical strengthening.
  • the order of each process and the number of processing are not particularly limited.
  • the glass may be cut once or a plurality of times at any stage before or after the touch panel fabrication described below.
  • the method for cutting the glass is not particularly specified and can be carried out by a known method.
  • the surface compressive stress (CS) of the glass plate after performing the chemical strengthening treatment on the glass plate of the present invention, or after performing etching, polishing and annealing before or after the chemical strengthening treatment is usually 550 MPa or more. Typically, it is 650 MPa or more.
  • the surface compressive stress is preferably 1400 MPa or less. If it exceeds 1400 MPa, the internal tensile stress (CT) may be too large. More preferably, it is 1300 MPa or less, typically 1200 MPa or less.
  • the thickness (DOL) of the surface compressive stress layer of the glass plate after performing the chemical strengthening treatment on the glass plate of the present invention, or after performing etching, polishing and annealing before or after the chemical strengthening treatment is usually 10 ⁇ m. It is preferably greater than, more preferably greater than 15 ⁇ m, typically greater than 20 ⁇ m.
  • the thickness of the surface compressive stress layer is preferably 90 ⁇ m or less. If it exceeds 90 ⁇ m, the internal tensile stress (CT) may be too large. More preferably, it is 80 ⁇ m or less, and typically 70 ⁇ m or less.
  • CT internal tensile stress
  • CT Internal tensile stress
  • CT internal tensile stress
  • the glass plate of this invention can be used suitably for a TFT panel or an in-cell type touch panel (henceforth "mode 1").
  • a cross-sectional view of aspect 1 is shown in FIG. The upper part is the touch surface and the viewing side of the display.
  • a tensile stress is generated on the back surfaces of the color filter substrate 110 and the array substrate 130, 110b and 130b, respectively, by the force pressed from above.
  • the surface 110 a of the color filter substrate 110 has a destructive effect against the indentation stress caused by the particle particles sandwiched between the polarizing plate 100 and the color filter substrate 110.
  • the array substrate surface 130 a has a destructive effect against the indentation stress of the spacer 140.
  • TFT and in-cell type Method for manufacturing array substrate, etc.
  • array substrate or the like an array substrate
  • the manufacturing method of aspect 1 which comprises the film-forming process which forms a gate insulating film in the surface of the glass plate which gave this is demonstrated.
  • the film formation region on the surface of the glass plate chemically strengthened on the glass plate of the present invention is within the range of 150 to 300 ° C.
  • a film forming step of forming the array substrate gate insulating film in the film forming region by raising the temperature to the temperature (hereinafter referred to as film forming temperature) and holding the film at the film forming temperature for 5 to 60 minutes. If it is a thing, it will not specifically limit.
  • the film formation temperature is preferably 150 to 250 ° C., more preferably 150 to 230 ° C., and further preferably 150 to 200 ° C.
  • the time for maintaining the film forming temperature is preferably 5 to 30 minutes, more preferably 5 to 20 minutes, and further preferably 5 to 15 minutes.
  • the glass plate Since the gate insulating film is formed within the range of the film forming temperature and the holding time as described above, the glass plate is thermally shrunk during this time. Since the glass plate obtained by chemically strengthening the glass plate of the present invention has a small compaction (C), it is difficult for the film formation pattern to shift.
  • the film formation in the film formation step can be achieved by, for example, a conventionally known CVD method.
  • TFT and in-cell type Assembly method to panel
  • TFT and in-cell type Assembly method to panel
  • it can manufacture using the said array substrate etc. and a well-known color filter substrate.
  • an alignment film is formed on each color filter substrate, such as the array substrate, and an alignment treatment process for rubbing, a normal spherical spacer is used for the TFT array substrate and the color filter substrate, and a predetermined gap between the substrates is maintained.
  • a series of steps including a bonding process for bonding with high accuracy, a dividing process for dividing the cell into a predetermined size from the substrate, an injection process for injecting liquid crystal into the divided cell, and a polarizing plate attaching process for attaching a polarizing plate to the cell.
  • a TFT panel or the like can be manufactured by this process.
  • a touch sensor array may be fabricated on the color filter substrate.
  • the glass plate of the present invention may or may not be used for the color filter substrate. In order to impart high strength, it is preferable to use the plate of the present invention.
  • the glass plate of this invention can be used suitably for an on-cell type touch panel (henceforth "mode 2").
  • mode 2 On-cell type touch panel
  • a cross-sectional view of aspect 2 is shown in FIG.
  • the glass plate of the present invention is used for at least one of the three glass plates.
  • the upper part is the touch surface and the viewing side of the display.
  • the touch sensor plate 160 is inserted inside the polarizing plate 100. Due to the force stamped from above, tensile stresses are generated on the back surfaces of the touch sensor plate 160, the color filter substrate 110, and the array substrate 130, respectively 160b, 110b, and 130b. Therefore, if a compressive stress is applied to this surface due to chemical strengthening, there is a great effect in improving the panel strength.
  • each surface opposite surface opposite to the back surface
  • compressive stress due to chemical strengthening it has a great effect on improving the strength against breakage of the substrate due to indentation stress by particles or spacers.
  • the surface 160 a of the touch sensor plate 160 has a destructive effect against the indentation stress caused by the particle particles sandwiched between the polarizing plate 100 and the touch sensor plate 160.
  • On the surface 110 a of the color filter substrate 110 there is an effect of suppressing destruction against indentation stress caused by particle particles sandwiched between the touch sensor plate 160.
  • the array substrate surface 130 a has a destructive effect against the indentation stress of the spacer 140.
  • the glass plate of this invention can be used suitably for an out-cell type touch panel (henceforth "mode 3").
  • mode 3 An out-cell type touch panel
  • mode 1 two glass plates are used, but in mode 3, another “touch sensor plate” is used.
  • the glass plate of the present invention is used for at least one of the three glass plates.
  • the upper part is the touch surface and the viewing side of the display.
  • the touch sensor plate 160 is inserted outside the polarizing plate 100. Due to the force stamped from above, tensile stresses are generated on the back surfaces of the touch sensor plate 160, the color filter substrate 110, and the array substrate 130, respectively 160b, 110b, and 130b. Therefore, if a compressive stress is applied to this surface due to chemical strengthening, there is a great effect in improving the panel strength.
  • each surface opposite surface opposite to the back surface
  • compressive stress due to chemical strengthening it has a great effect on improving the strength against breakage of the substrate due to indentation stress by particles or spacers. That is, the surface 160a of the touch sensor plate 160 has a destructive deterrent effect against indentation stress due to particle particles, sand, fibers, etc. existing in the daily life space on the surface of the touch sensor.
  • the surface 110 a of the color filter substrate 110 has an effect of inhibiting destruction against indentation stress caused by particle particles sandwiched between the polarizing plate 100.
  • the array substrate surface 130 a has a destructive effect against the indentation stress of the spacer 140.
  • the first transparent conductive film 14 extends in the x direction in the drawing, and a plurality of first transparent conductive films 14 are arranged in the y direction orthogonal to the x direction.
  • the second transparent conductive film 16 extends in the y direction in the drawing, and a plurality of the second transparent conductive films 16 are arranged in the x direction.
  • the large area part 14a and the large area part 16a are arranged so as to be spaced apart from each other and alternately in the x direction and the y direction, and are provided to improve input position detection. Accordingly, the first transparent conductive film 14 and the second transparent conductive film 16 are formed so as to intersect at the connection portion 14b and the connection portion 16b.
  • the first transparent conductive film 14 is formed on the intersection insulating film 28 so as to straddle the intersection insulating film 28 and the second transparent conductive film 16 in the x direction.
  • a jumper portion that intersects the first transparent conductive film 14 and the second transparent conductive film 16 in an insulating state is formed, and the first transparent conductive film 14 and the second transparent film 14 that intersect each other are formed. The insulation state with the transparent conductive film 16 is maintained.
  • the transparent conductive films 14 and 16 are made of a known transparent (light transmissive) conductive material used for forming a sensor portion in a capacitive touch sensor. Various materials can be used.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • ITO is preferably used.
  • various known transparent insulating materials can be used. Specifically, various photoresists such as acrylic and polyimide are exemplified.
  • FIG. 4 is a plan view conceptually showing the touch sensor plate 10.
  • the light shielding film 18 is an insulating film formed on the outer peripheral portion of the sensor surface of the glass plate 12 and having a light shielding property.
  • the light shielding film 18 is provided for shielding light leaked from the display combined with the touch sensor plate 10, concealing the metal wiring 20 and the IC for driving the touch sensor, and the like.
  • a metal wiring 20 is formed on the light shielding film 18 (sensor surface 12b).
  • a plurality of metal wirings 20 are formed according to the number of the first transparent conductive film 14 and the second transparent conductive film 16, and one end of each metal wiring 20 is the first transparent conductive film 14 or the second transparent conductive film 14. Connected to the transparent conductive film 16.
  • each metal wiring 20 is combined with the touch sensor driving IC on the same substrate when the touch sensor driving IC is manufactured on the same substrate, and is combined with the touch sensor plate 10 when the driving IC is not manufactured on the same substrate.
  • various metal materials can be used for the metal wiring 20.
  • a three-layer metal material (MAM) of Mo / Al / Mo a three-layer metal material of Mo—Nb alloy / Al / Mo—Nb alloy, Mo—Nb alloy / Al—Nb alloy / Mo— Examples of the metal material include three layers of Nb alloy.
  • the glass plate of this invention can be used suitably for the glass plate for chemical strengthening for the sensor plate for an on-cell type or an out-cell type touch panel.
  • a light shielding film 18 is printed on the glass plate 12 so as to surround a region to be the active area A (see FIG. 4) on the surface of the glass plate obtained by chemically strengthening the glass plate of the present invention.
  • heat treatment thermal process 1 is performed.
  • the light shielding film 18 may be printed by a known method used in the manufacture of touch panels.
  • ITO or the like that will become the intersection transparent conductive film 16b that will later become a part of the second transparent conductive film 16 is formed on the entire surface.
  • the ITO film may be formed by a known method such as sputtering.
  • the glass plate is heat-treated at 150 to 300 ° C. for 5 to 60 minutes (thermal process 2).
  • patterning is performed. Patterning may be performed by a known method such as a method using photolithography.
  • Method 5 for manufacturing touch sensor plate transparent conductive film
  • the first transparent conductive film 14 and ITO or the like to be the second transparent conductive film 16 excluding the intersection transparent conductive film 16b are formed on the entire surface.
  • the glass plate is heat-treated at 150 to 300 ° C. for 5 to 60 minutes (thermal process 4). Subsequently, the transparent sensor wiring portion is completed by patterning.
  • the transparent conductive film 16 excluding the crossing transparent conductive film 16b and the crossing transparent conductive film 16b may be disconnected, or the first transparent conductive film 14 may be disconnected.
  • the second transparent conductive film 16 may be short-circuited beyond the intersection insulating film 28.
  • film formation of ITO or the like may be performed by a known method such as sputtering, and patterning may be performed by a known method. Further, a metal wiring 20 is formed on the light shielding film 18 and patterned.
  • a protective insulating film 24 is formed so as to cover the entire sensor surface 12ba of the glass plate 12, and patterning is performed so that necessary portions such as the metal wiring 20 and the IC portion are exposed to drive the touch panel sensor. I do.
  • the film forming method and patterning may be performed by a known method corresponding to the material for forming the protective insulating film 24.
  • Examples of the glass plate of the present invention (Examples 1 to 13, 18 to 22) and comparative examples (Examples 14 to 17 and 23 to 25) are shown.
  • the parentheses in the table are calculated values.
  • the raw materials of the respective components for the glass plate were prepared so that the compositions shown in Tables 1 to 4 were obtained, and 0.1 part by mass of sulfate was converted to SO 3 with respect to 100 parts by mass of the raw material for the glass plate component. It added to the raw material, and it melt
  • the average thermal expansion coefficient (unit: ⁇ 10 -7 / ° C), glass transition temperature (Tg) (unit: ° C), density, T 4 , compaction (C), photoelasticity of the glass thus obtained at 50 to 350 ° C. Constant, Young's modulus, devitrification temperature (glass surface devitrification temperature (T c ), glass internal devitrification temperature (T d )), glass viscosity (unit: dPa ⁇ s) at T 4 and T d , , T 4 -T c and T 4 -T d were calculated and shown in Tables 1 to 3. The measuring method of each physical property is shown below.
  • Tg Tg is a value measured using TMA, and was determined according to JIS R3103-3 (fiscal 2001).
  • Density About 20 g of glass plate not containing bubbles was measured by Archimedes method.
  • T 4 Viscosity was measured using a rotational viscometer, and a temperature T 4 (° C.) at 10 4 dPa ⁇ s was measured. Further, the coefficient of Fruchar's formula is obtained from the measurement result of the glass viscosity at a high temperature (1000 to 1600 ° C.) of the molten glass, and the glass viscosity at the glass internal devitrification temperature (T d ) is obtained by the Frucher's formula using the coefficient. Asked. (4) Compaction (C): Measured by the measurement method for compaction (C) described above.
  • Devitrification temperature Glass surface devitrification temperature (T c ) and glass internal devitrification temperature (T d )]: Glass particles crushed in a platinum dish and placed in an electric furnace controlled at a constant temperature Heat treatment is performed for 17 hours, and the average value of the maximum temperature at which crystals are deposited on the surface of the glass and the minimum temperature at which crystals are not precipitated is determined by observation with an optical microscope after the heat treatment, and the glass surface devitrification temperature T c (° C.) The average value of the maximum temperature at which crystals precipitate inside and the minimum temperature at which crystals do not precipitate is defined as the glass internal devitrification temperature T d (° C.).
  • Photoelastic constant Measured by a disk compression method using 546 nm light as a light source.
  • Young's modulus Glass having a thickness of 7 to 10 mm was measured by an ultrasonic pulse method.
  • the residual amount of SO 3 in the glass was 100 to 500 ppm.
  • the glass of Examples has a high glass transition temperature Tg.
  • the glass of the example has an average coefficient of thermal expansion at 50 to 350 ° C. of 65 ⁇ 10 ⁇ 7 to 85 ⁇ 10 ⁇ 7 / ° C., there is little dimensional change in the display member manufacturing process, and the color filter and the array plate Pattern matching at the time of matching becomes easy.
  • the influence on the quality by the thermal stress at the time of panel use is small, it is particularly preferable in terms of display quality.
  • the compaction (C) is 20 ppm or less, it is difficult to cause a position shift at the time of film formation patterning on the glass plate. Therefore, it can be suitably used as a glass plate for producing a large display member, for example, a mother glass having a side length of 2 m or more, corresponding to the recent low temperature heat treatment.
  • T 4 -T c satisfies ⁇ 50 to 350 ° C. or T 4 -T d satisfies ⁇ 50 to 350 ° C., and thus devitrification during sheet glass forming can be suppressed.
  • T 4 -T d is 100 to 350 ° C.
  • the glass viscosity at T d is 10 4.7 d ⁇ Pa ⁇ s or more, which is suitable for molding by the fusion method. ing.
  • each physical property value (T c , T d , T 4 , T 4 -T c , T 4 -T d , photoelastic constant, Young's modulus) satisfies the scope of the present invention.
  • Example 14 the compaction (C) is larger than 20 ppm, the dimensional change in the display member manufacturing process is large, and it is difficult to align the pattern when the color filter and the array plate are aligned. Is likely to occur.
  • Examples 16 and 17 have a glass transition temperature of less than 580 ° C., which may cause an increase in alkali mobility and heat resistance.
  • the glass compaction (C) shown in Tables 1 to 3 shows the compaction value of the glass plate cooled at 50 ° C./min.
  • Table 4 shows the compaction values of glass plates cooled at respective cooling rates of 50 ° C./min, 70 ° C./min, 150 ° C./min, and 300 ° C./min. Further, the compaction values according to the presence or absence of annealing treatment (holding at 630 to 650 ° C. for 1 h, then cooling at 30 ° C./h) or chemical strengthening treatment (435 ° C. for 4 h) are shown.
  • Example 19 a glass plate having the composition shown in Example 19 was heated to a transition temperature Tg + 50 ° C., held at this temperature for 1 minute, and then 50 ° C./min, 70 ° C./min, 150 ° C./min, 300 ° C./min.
  • the respective compactions (C) of the chemically strengthened glass plates were shown after cooling to room temperature at each cooling rate of minutes.
  • Example 20 the glass plate having the composition shown in Example 20 was heated to a transition temperature Tg + 50 ° C., held at this temperature for 1 minute, and then cooled to room temperature at a cooling rate of 50 ° C./min. )showed that.
  • Example 21 a glass plate having the composition shown in Example 21 was heated to a transition temperature Tg + 50 ° C., held at this temperature for 1 minute, cooled to room temperature at a cooling rate of 50 ° C./minute, and then annealed. Each compaction (C) of the glass plate that was carried out and then chemically strengthened was shown.
  • Example 22 a glass plate having the composition shown in Example 22 was heated to a transition temperature Tg + 50 ° C., held at this temperature for 1 minute, and then 50 ° C./min, 70 ° C./min, 150 ° C./min, 300 ° C./min.
  • the respective compactions (C) of the chemically strengthened glass plates were shown after cooling to room temperature at each cooling rate of minutes.
  • Example 23 the glass plate having the composition shown in Example 23 was heated to the transition temperature Tg + 50 ° C., held at this temperature for 1 minute, and then cooled to room temperature at a cooling rate of 50 ° C./min. )showed that.
  • Example 24 a glass plate having the composition shown in Example 24 was heated to a transition temperature Tg + 50 ° C., held at this temperature for 1 minute, cooled to room temperature at a cooling rate of 50 ° C./min, and then annealed. Each compaction (C) of the glass plate that was carried out and then chemically strengthened was shown.
  • Example 25 a glass plate having the composition shown in Example 25 was heated to a transition temperature Tg + 50 ° C., held at this temperature for 1 minute, then 50 ° C./min, 70 ° C./min, 150 ° C./min, 300 ° C./min.
  • the respective compactions (C) of the chemically strengthened glass plates were shown after cooling to room temperature at each cooling rate of minutes.
  • Examples 21 to 23 and Examples 24 to 25 show the effects of the two glass compositions on the compaction (C) of the annealing treatment and the chemical strengthening treatment.
  • compaction (C) In contrast to compaction (C), annealing treatment and chemical strengthening treatment had no improvement effect, but rather showed an increasing tendency.
  • Examples 19, 22, 25 and FIG. 2 show the effect of the three glass compositions on the compaction (C) for the virtual viscosity of the chemical strengthening treatment.
  • the glass plate of the present invention is suitable as a glass plate for a liquid crystal display member having a touch panel sensor, but for other display plates having a touch panel sensor, such as a plasma display panel (PDP), an inorganic electroluminescence display, and the like. Can be used.
  • PDP plasma display panel
  • inorganic electroluminescence display and the like. Can be used.

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US10579106B2 (en) 2015-07-21 2020-03-03 Corning Incorporated Glass articles exhibiting improved fracture performance
US11878936B2 (en) 2015-12-11 2024-01-23 Corning Incorporated Fusion-formable glass-based articles including a metal oxide concentration gradient
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JP7310791B2 (ja) 2018-02-16 2023-07-19 Ａｇｃ株式会社 カバーガラス、およびインセル型液晶表示装置
JPWO2019159983A1 (ja) * 2018-02-16 2021-02-04 Ａｇｃ株式会社 カバーガラス、およびインセル型液晶表示装置

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