WO2015080171A1 - 無アルカリガラス基板、および、無アルカリガラス基板の薄板化方法 - Google Patents
無アルカリガラス基板、および、無アルカリガラス基板の薄板化方法 Download PDFInfo
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- WO2015080171A1 WO2015080171A1 PCT/JP2014/081293 JP2014081293W WO2015080171A1 WO 2015080171 A1 WO2015080171 A1 WO 2015080171A1 JP 2014081293 W JP2014081293 W JP 2014081293W WO 2015080171 A1 WO2015080171 A1 WO 2015080171A1
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- alkali
- glass substrate
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- free glass
- cao
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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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133302—Rigid substrates, e.g. inorganic substrates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention is a non-alkali glass substrate which is suitable for various display glass substrates and photomask glass substrates and which is made thin by etching using hydrofluoric acid (HF) and substantially does not contain an alkali metal oxide, and
- HF hydrofluoric acid
- the present invention relates to a method for thinning an alkali-free glass substrate.
- the following characteristics have been required for various display glass substrates, particularly those in which a metal or oxide thin film is formed on the surface.
- alkali metal oxide When an alkali metal oxide is contained, alkali metal ions diffuse into the thin film and deteriorate the film characteristics, so that the alkali metal ions are not substantially contained.
- the strain point When exposed to a high temperature in the thin film forming process, the strain point is high so that the deformation (thermal shrinkage) associated with glass deformation and glass structural stabilization can be minimized.
- BHF buffered hydrofluoric acid
- ITO various acids used for etching metal electrodes
- ITO various acids used for etching metal electrodes
- resistant to alkali of resist stripping solution Resistant to alkali of resist stripping solution.
- a-Si amorphous silicon
- p-Si polycrystalline silicon
- a glass having a small average thermal expansion coefficient is required to increase productivity and thermal shock resistance by increasing the temperature raising / lowering rate of the heat treatment for producing a liquid crystal display.
- Patent Document 1 discloses a glass containing 0 to 5 mol% of B 2 O 3 , but the average coefficient of thermal expansion at 50 to 350 ° C. exceeds 50 ⁇ 10 ⁇ 7 / ° C.
- the alkali-free glass described in Patent Document 2 has a high strain point and can be molded by a float process, and is said to be suitable for applications such as a display substrate and a photomask substrate.
- a process of thinning (thinning) the plate thickness by applying an etching process to the glass substrate surface after the array / color filter bonding step is widely employed.
- the surface of a glass substrate having a plate thickness of 0.4 mm to 0.7 mm is etched with an etching solution containing hydrofluoric acid (HF) (hereinafter referred to as “hydrofluoric acid etching process”) to obtain a plate thickness of 0.
- HF hydrofluoric acid
- the object of the present invention is to solve the above disadvantages, to have a high strain point, a low viscosity, particularly a low temperature T 4 at which the glass viscosity is 10 4 dPa ⁇ s, a high etching rate during the hydrofluoric acid etching treatment, and a hydrofluoric acid
- the present invention provides an alkali-free glass substrate and a method for thinning an alkali-free glass substrate, which have high strength after etching, are hardly bent even when they are thin, and hardly cause problems such as color unevenness even when stress is applied.
- the present invention relates to a non-alkali glass substrate having a thickness of 0.4 mm or less that has been thinned by a hydrofluoric acid (HF) etching process to a thickness of 5 ⁇ m or more, and the non-alkali glass substrate is the following non-alkali glass, and is made thin.
- HF hydrofluoric acid
- an alkali-free glass substrate having a specific elastic modulus of 31 MNm / kg or more and a photoelastic constant of 30 nm / MPa / cm or less in the later alkali-free glass substrate. Temperature at which the strain point is 680 to 735 ° C., the average coefficient of thermal expansion at 50 to 350 ° C.
- the temperature T 4 at which T 2 is 1710 ° C. or lower and the glass viscosity is 10 4 dPa ⁇ s is 1310 ° C.
- MgO + CaO + SrO + BaO 2 is 15.5-21
- the alkali-free glass substrate of the present invention has an average breaking load measured by a ball-on-ring (BOR) method using a ring having a diameter of 30 mm, R of 2.5 mm, and a ball of 10 mm in diameter of 300 N in terms of a plate thickness of 0.4 mm.
- BOR ball-on-ring
- the present invention is a method for thinning an alkali-free glass substrate
- the alkali-free glass substrate is the following alkali-free glass, and at least one main surface of the alkali-free glass substrate is immersed in an etching solution (25 ° C., 5% HF aqueous solution) containing hydrofluoric acid (HF).
- etching solution 25 ° C., 5% HF aqueous solution
- HF hydrofluoric acid
- the strain point is 680 to 735 ° C.
- the average coefficient of thermal expansion at 50 to 350 ° C. is 30 ⁇ 10 ⁇ 7 to 43 ⁇ 10 ⁇ 7 / ° C.
- the glass viscosity is 10 2 dPa ⁇ s.
- the temperature T 4 at which T 2 is 1710 ° C. or lower and the glass viscosity is 10 4 dPa ⁇ s is 1310 ° C.
- MgO + CaO + SrO + BaO 2 is 15.5-21
- the alkali-free glass substrate of the present invention has a high strain point, a low temperature T 4 at which the glass viscosity becomes 10 4 dPa ⁇ s, a high etching rate during the hydrofluoric acid etching treatment, and a high strength after the hydrofluoric acid etching treatment. Because it is difficult to bend even if it is thin and it is difficult to cause problems such as color unevenness even when stress is applied, it is used in the field of portable displays such as small and medium-sized LCDs and OLEDs, especially mobiles, digital cameras and mobile phones. It is suitable as a thin glass substrate having a plate thickness of 0.4 mm or less.
- the alkali-free glass substrate of the present invention can also be used as a glass substrate for a magnetic disk.
- an alkali-free glass substrate using a glass raw material prepared to have the following glass composition is used.
- the temperature T 4 at which T 2 is 1710 ° C. or lower and the glass viscosity is 10 4 dPa ⁇ s is 1310 ° C.
- MgO + CaO + SrO + BaO 2 is 15.5-21
- the composition range of each component will be described. If the SiO 2 content is less than 63% (mol%, the same unless otherwise specified), the strain point is not sufficiently increased, the thermal expansion coefficient is increased, and the density is increased. It is preferably 64% or more, more preferably 65% or more, further preferably 66% or more, and particularly preferably 66.5% or more. Preferably it is 66.5% or more, more preferably 67% or more. If it exceeds 74%, the etching rate decreases, the glass solubility decreases, and the devitrification temperature increases. 70% or less is preferable, 69% or less is more preferable, and 68% or less is more preferable.
- Al 2 O 3 increases Young's modulus to suppress deflection after thinning, suppresses phase separation of glass, lowers thermal expansion coefficient, increases strain point, increases fracture toughness value and increases glass strength. If it is less than 11.5%, this effect does not appear, and other components that increase the expansion are increased, resulting in an increase in thermal expansion. It is preferably 12% or more, 12.5% or more, and more preferably 13% or more. If it exceeds 16%, the solubility of the glass may be deteriorated, or the devitrification temperature may be increased. It is preferably 15% or less, more preferably 14% or less, and further preferably 13.5% or less.
- B 2 O 3 improves the melting reactivity of the glass, lowers the devitrification temperature, and improves the BHF resistance, but this effect is not sufficiently exhibited at 1.5% or less, and the strain point is excessive. It tends to increase or become a haze problem after treatment with BHF. 2% or more is preferable, and 3% or more is more preferable. However, if the amount is too large, the photoelastic constant increases, and problems such as color unevenness are likely to occur when stress is applied. On the other hand, if B 2 O 3 exceeds 5%, the surface roughness after thinning becomes large, and the strength after thinning becomes low. In addition, the strain point decreases and the Young's modulus decreases. 4.5% or less is preferable and 4% or less is more preferable.
- MgO increases the Young's modulus without increasing the specific gravity, so the problem of deflection can be reduced by increasing the specific modulus.
- the alkaline earth has the characteristics that the expansion is not increased and the strain point is not excessively lowered, and the solubility is improved. Further, the fracture toughness value is improved to increase the glass strength. However, if the content is less than 5.5%, this effect is not sufficiently exhibited, and the density is increased because the ratio of other alkaline earths is increased. 6% or more, more preferably 7% or more, 7.5% or more, 8% or more, more preferably more than 8%, more preferably 8.1% or more, more preferably 8.3% or more, and particularly preferably 8.5% or more preferable. If it exceeds 13%, the devitrification temperature may increase. It is preferably 12% or less, more preferably 11% or less, and particularly preferably 10% or less.
- CaO has the characteristics that the specific elastic modulus is increased next to MgO in alkaline earth, the expansion is not increased, the density is kept low, and the strain point is not excessively lowered, and the solubility is improved. If it is less than 1.5%, the above-described effect due to the addition of CaO is not sufficiently exhibited. It is preferably 2% or more, more preferably 3% or more, further preferably 3.5% or more, and particularly preferably 4% or more. However, if it exceeds 12%, the devitrification temperature may increase, or a large amount of phosphorus, which is an impurity in limestone (CaCO 3 ), which is a CaO raw material, may be mixed. It is preferably 10% or less, more preferably 9% or less, further preferably 8% or less, and particularly preferably 7% or less.
- SrO improves the solubility without increasing the devitrification temperature of the glass, but if it is less than 1.5%, this effect does not appear sufficiently. 2% or more is preferable, 2.5% or more is more preferable, and 3% or more is more preferable. However, if it exceeds 9%, the expansion coefficient may increase. It is preferably 7% or less, more preferably 6% or less and 5% or less.
- BaO is not essential, but can be contained to improve solubility. However, if the amount is too large, the expansion and density of the glass are excessively increased, so the content is made 1% or less. Less than 1% is preferable, 0.5% or less is more preferable, and it is preferable not to contain substantially. “Substantially not contained” means not containing any inevitable impurities.
- ZrO 2 may be incorporated up to 2% in order to increase the Young's modulus, to lower the glass melting temperature, or to promote crystal precipitation during firing. If it exceeds 2%, the glass becomes unstable or the relative dielectric constant ⁇ of the glass increases. Preferably it is 1.5% or less, More preferably, it is 1.0% or less, More preferably, it is 0.5% or less, and it is especially preferable not to contain substantially.
- MgO / (MgO + CaO + SrO + BaO) is 0.35 or more, preferably 0.37 or more, and more preferably 0.4 or more.
- CaO / (MgO + CaO + SrO + BaO) is 0.50 or less, preferably 0.48 or less, and more preferably 0.45 or less.
- SrO / (MgO + CaO + SrO + BaO) is 0.50 or less, preferably 0.40 or less, more preferably 0.30 or less, more preferably 0.27 or less, and further preferably 0.25 or less.
- Al 2 O 3 ⁇ (MgO / (MgO + CaO + SrO + BaO)) is preferably 4.3 or more because the Young's modulus can be increased. 4.5 or more is preferable, 4.7 or more is more preferable, and 5.0 or more is further more preferable.
- Alkali metal oxides such as Na 2 O and K 2 O may be added for the purpose of heating an electric booster.
- the content of the alkali metal oxide is increased, alkali metal ions diffuse into the thin film and deteriorate the film characteristics. This causes a problem when used as a substrate glass for various displays, but the alkali metal oxide in the glass composition. Is less than 2000 mol ppm, it is difficult to cause such a problem. More preferably, it is 1500 mol ppm or less, 1300 mol ppm or less, and 1000 mol ppm or less.
- the glass raw material preferably does not substantially contain P 2 O 5 .
- the amount of impurities as impurities is preferably 23 mol ppm or less, more preferably 18 mol ppm or less, further preferably 11 mol ppm or less, and particularly preferably 5 mol ppm or less.
- the glass raw material does not substantially contain PbO, As 2 O 3 , or Sb 2 O 3 .
- ZnO, Fe 2 O 3 , SO 3 , F, Cl, SnO 2 in total amount is 1% or less, preferably 0.5% or less, more preferably 0 .3% or less, more preferably 0.15% or less, and particularly preferably 0.1% or less. It is preferable that ZnO is not substantially contained.
- the production of the alkali-free glass substrate of the present invention is performed, for example, according to the following procedure.
- the raw materials of each component are prepared so as to become target components, which are continuously charged into a melting furnace, heated to 1500-1800 ° C. and melted.
- the molten glass is formed into a plate-like glass ribbon having a predetermined plate thickness by a forming apparatus, and the glass ribbon is gradually cooled and then cut to obtain an alkali-free glass substrate.
- an alkali-free glass substrate of the present invention at least one of the two principal surfaces of the alkali-free glass substrate is subjected to hydrofluoric acid (HF) etching treatment so that the alkali-free glass substrate is 5 ⁇ m or more. Thinned.
- HF hydrofluoric acid
- the thickness of the display using the alkali-free glass substrate can be reduced, and the display can be reduced in weight. If a thin plate, that is, a non-alkali glass substrate with a small plate thickness is used from the beginning without being thinned by the etching process, it is necessary to handle a large thin plate in the device manufacturing process, etc. performed during display manufacturing.
- the thickness is preferably 10 ⁇ m or more, more preferably 100 ⁇ m or more, and particularly preferably 200 ⁇ m or more.
- the thickness of the alkali-free glass substrate after thinning is 0.4 mm or less. If it exceeds 0.4 mm, the effect of reducing the weight and thickness of the display cannot be obtained. More preferably, it is 0.35 mm or less, More preferably, it is 0.25 mm or less.
- the plate thickness of the alkali-free glass substrate before being thinned is preferably 0.3 mm or more.
- the thickness is less than 0.3 mm, it is necessary to handle a large thin plate in the device manufacturing process and the like, and problems such as conveyance trouble and cracking due to self-weight deflection are likely to occur.
- it is 0.4 mm or more, Most preferably, it is 0.45 mm or more.
- it exceeds 0.75 mm, the time required for thinning the display for lightening and thinning may become too long. More preferably, it is 0.65 mm or less, More preferably, it is 0.55 mm or less.
- a chemical solution containing hydrofluoric acid is used as the chemical solution for the etching process. Etching can be performed with an alkaline chemical solution, but a chemical solution containing hydrofluoric acid has a higher etching rate and can be etched smoothly.
- the concentration of hydrofluoric acid contained in the chemical solution is more preferably 1% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more.
- an acid other than hydrofluoric acid such as hydrochloric acid, nitric acid or sulfuric acid to the chemical solution.
- At the time of etching at least one main surface of the alkali-free glass substrate is immersed in a chemical solution containing hydrofluoric acid. Depending on the fluorine concentration in the chemical solution, the alkali-free glass substrate is thinned by a predetermined amount by being immersed for a predetermined time.
- the chemical liquid is fluidized by at least one of stirring, bubbling, ultrasonic waves, and showering. Instead of flowing the chemical solution, the alkali-free glass substrate may be moved by at least one method of rocking and rotating.
- the elution amount per unit area and unit time which is an index of the etching rate, is 0.00.
- Etching is performed under conditions of 17 (mg / cm 2 ) / min or more. If it is less than 0.17 (mg / cm 2 ) / min, the time required for thinning may be too long. More preferably, it is 0.18 (mg / cm 2 ) / min or more.
- the alkali-free glass substrate thinned by the method of the present invention has high strength after thinning.
- the main surface on the etched side of the non-alkali glass substrate after thinning is a ring having a diameter of 30 mm and R of 2.5 mm (the cross section of the ring is a circle) R is the radius of the circle) and a ball with a diameter of 10 mm
- the average breaking load measured by the ball-on-ring (BOR) method (with the surface to be evaluated facing down on the ring) is the thickness of the plate It is preferable that it is 300 N or more in terms of 0.4 mm.
- the diameter of the ring is a diameter of a circle passing through the center of the cross section.
- the outermost diameter of the ring is 35 mm and the innermost diameter is 25 mm.
- the average breaking load means the average value of the measurement results obtained by measuring the breaking load by the BOR method a plurality of times. In the examples described later, the measurement of the breaking load by the BOR method was carried out five times, and the average value of the measurement results was taken as the average breaking load.
- the average breaking load measured by the BOR method is less than 300 N in terms of a plate thickness of 0.4 mm, the surface strength of the alkali-free glass substrate is low, and the glass substrate breaks during handling during display manufacturing (for example, support pins, etc.) Thus, the glass substrate is broken in a process of lifting the alkali-free glass substrate after device fabrication), and the strength after thinning may be a problem. More preferably, it is 350 N or more.
- Sheet thickness conversion by the BOR method is performed according to the following procedure.
- the breaking load W (N) in terms of the plate thickness of 0.4 mm is set to t (mm), and the BOR method is used.
- the obtained breaking load is w (N)
- it can be obtained from the relational expression of W w ⁇ 0.16 / t 2 .
- the alkali-free glass substrate thinned by the method of the present invention has a surface strength of 500 MPa or more by three-point bending of the etched main surface (surface to be evaluated) of the alkali-free glass substrate after thinning. Preferably there is. If the pressure is less than 500 MPa, a display using a thin alkali-free glass substrate may easily cause problems such as cracking when used as a portable display. More preferably, it is 800 MPa or more, More preferably, it is 1000 MPa or more, Especially preferably, it is 1200 MPa or more, Most preferably, it is 1500 MPa or more.
- the surface strength by three-point bending of the main surface on the etched side of the alkali-free glass substrate after thinning is measured as follows. With the evaluation surface protected with a seal, the glass substrate is scribed with a point scriber, cut, and then the evaluation surface is peeled off so that the non-scribe side faces down and a 3-point bending jig with a span of 10 mm and R1.5 mm Install on top. The surface strength by three-point bending is calculated from the breaking load when the jig is pushed with a R1.5 mm jig from the scribe side of the upper surface. When scratches enter the evaluation surface, the strength becomes low.
- the environment in which the average breaking load is measured by the BOR method or by three-point bending is a temperature of 22 ⁇ 2 ° C. and a humidity of 40 ⁇ 10%.
- the surface roughness of the main surface on the etched side of the alkali-free glass substrate after thinning is 1 ⁇ m square Ra in AFM measurement is 0.75 nm or less. It is preferable that If it exceeds 0.75 nm, the strength of the alkali-free glass substrate may be lowered. More preferably, it is 0.7 nm or less.
- the alkali-free glass substrate of the present invention has a strain point of 680 ° C. or higher and 735 ° C. or lower. Since the alkali-free glass substrate of the present invention has a strain point of 680 ° C. or higher, thermal shrinkage during panel production can be suppressed. Further, a laser annealing method can be applied as a method for manufacturing the p-Si TFT. 685 degreeC or more is more preferable, and 690 degreeC or more is further more preferable. In addition, since the alkali-free glass substrate of the present invention has a strain point of 680 ° C.
- a high strain point application for example, a plate thickness of 0.7 mm or less, preferably 0.5 mm or less, more preferably 0.3 mm or less. It is suitable for a display substrate or an illumination substrate for organic EL, or a thin display substrate or illumination substrate having a thickness of 0.3 mm or less, preferably 0.1 mm or less.
- a sheet glass having a plate thickness of 0.7 mm or less, further 0.5 mm or less, further 0.3 mm or less, and further 0.1 mm or less the drawing speed at the time of forming tends to increase. Rises and the compaction of the glass tends to increase. In this case, compaction can be suppressed when the glass is a high strain point glass.
- the strain point is 735 ° C. or lower, it is not necessary to raise the temperature of the float bath and the exit of the float bath so much that it affects the life of the metal member located in the float bath and on the downstream side of the float bath. Few. 725 ° C or lower is more preferable, 715 ° C or lower is further preferable, and 710 ° C or lower is particularly preferable. Moreover, in order to improve the plane strain of the glass, it is necessary to increase the temperature at the portion entering the annealing furnace from the float bath outlet, but it is not necessary to increase the temperature at this time. For this reason, a load is not applied to the heater used for heating, and the life of the heater is hardly affected.
- the alkali-free glass substrate of the present invention has a glass transition point of preferably 730 ° C. or higher, more preferably 740 ° C. or higher, and further preferably 750 ° C. or higher for the same reason as the strain point. Moreover, 780 degrees C or less is preferable, 775 degrees C or less is more preferable, and 770 degrees C or less is especially preferable.
- the alkali-free glass substrate of the present invention has an average thermal expansion coefficient at 50 to 350 ° C. of 30 ⁇ 10 ⁇ 7 to 43 ⁇ 10 ⁇ 7 / ° C., has high thermal shock resistance, and increases productivity during panel manufacture. Can be high.
- the average coefficient of thermal expansion at 50 to 350 ° C. is preferably 35 ⁇ 10 ⁇ 7 / ° C. or more.
- the average thermal expansion coefficient at 50 to 350 ° C. is preferably 42 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 41 ⁇ 10 ⁇ 7 / ° C. or less, and further preferably 40 ⁇ 10 ⁇ 7 / ° C. or less.
- the non-alkali glass substrate of the present invention preferably has a specific gravity of 2.62 or less, more preferably 2.60 or less, and even more preferably 2.58 or less.
- the temperature T 2 at which the viscosity ⁇ becomes 10 2 poise is 1710 ° C. or less, more preferably 1700 ° C. or less, still more preferably 1690 ° C. or less, particularly preferably Since it is 1680 ° C. or lower and 1670 ° C. or lower, dissolution is relatively easy.
- the alkali-free glass substrate of the present invention has a temperature T 4 at which the viscosity ⁇ becomes 10 4 poise is 1310 ° C. or less, preferably 1305 ° C. or less, more preferably 1300 ° C. or less, further preferably less than 1300 ° C., 1295 ° C. or less, It is 1290 ° C. or lower and is suitable for float forming.
- the alkali-free glass substrate of the present invention preferably has a devitrification temperature of 1315 ° C. or less because it is easy to form by the float process. Preferably they are 1300 degrees C or less, 1300 degrees C or less, 1290 degrees C or less, More preferably, it is 1280 degrees C or less.
- the difference between the temperature T 4 (temperature at which the glass viscosity ⁇ becomes 10 4 poise, unit: ° C.) and the devitrification temperature (T 4 ⁇ devitrification temperature), which is a standard of float moldability and fusion moldability, is preferably Is ⁇ 20 ° C. or higher, ⁇ 10 ° C. or higher, further 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, and particularly preferably 30 ° C. or higher.
- the devitrification temperature is obtained by putting crushed glass particles in a platinum dish and performing heat treatment for 17 hours in an electric furnace controlled at a constant temperature. It is an average value of the maximum temperature at which crystals are deposited inside and the minimum temperature at which crystals are not deposited.
- the alkali-free glass substrate of the present invention has a specific modulus of 31 MNm / kg or more. If it is less than 31 MNm / kg, problems such as conveyance troubles and cracks due to self-weight deflection are likely to occur. Preferably it is 32 MNm / kg or more, more preferably 33 MNm / kg or more.
- the alkali-free glass substrate of the present invention has a Young's modulus of preferably 78 GPa or more, 79 GPa or more, 80 GPa or more, more preferably 81 GPa or more, and further preferably 82 GPa or more.
- the alkali-free glass substrate of the present invention preferably has a photoelastic constant of 30 nm / MPa / cm or less. Due to the birefringence of the glass substrate due to stress generated during the manufacturing process of the liquid crystal display panel and the liquid crystal display device, a phenomenon in which the black display becomes gray and the contrast of the liquid crystal display decreases may be observed. By setting the photoelastic constant to 30 nm / MPa / cm or less, this phenomenon can be suppressed small. Preferably it is 29 nm / MPa / cm or less, More preferably, it is 28.5 nm / MPa / cm or less, More preferably, it is 28 nm / MPa / cm or less.
- the alkali-free glass substrate of the present invention has a photoelastic constant of preferably 23 nm / MPa / cm or more, more preferably 25 nm / MPa / cm or more, considering the ease of securing other physical properties.
- the photoelastic constant can be measured by a disk compression method at a measurement wavelength of 546 nm.
- the alkali-free glass substrate of the present invention preferably has a relative dielectric constant of 5.6 or more.
- the sensing sensitivity of the touch sensor is improved, the driving voltage is reduced, From the viewpoint of power saving, it is better that the glass substrate has a higher relative dielectric constant.
- the relative dielectric constant is 5.8 or more, More preferably, it is 6.0 or more, More preferably, it is 6.2 or more, Most preferably, it is 6.4 or more.
- the relative dielectric constant can be measured by the method described in JIS C-2141.
- the alkali-free glass substrate of the present invention preferably has a small amount of shrinkage during heat treatment.
- the heat treatment process is different between the array side and the color filter side. Therefore, particularly in a high-definition panel, when the thermal shrinkage rate of glass is large, there is a problem in that dot displacement occurs during fitting.
- the evaluation of the heat shrinkage rate can be measured by the following procedure. The sample is held at a temperature of glass transition point + 100 ° C. for 10 minutes and then cooled to room temperature at 40 ° C. per minute. Here measuring the total length of the sample (the L 0). Next, it is heated to 600 ° C. at 100 ° C./hour, held at 600 ° C.
- the heat shrinkage rate is preferably 100 ppm or less, more preferably 80 ppm or less, further preferably 60 ppm or less, further 55 ppm or less, and particularly preferably 50 ppm or less.
- Examples 1 to 6, Comparative Examples 1 and 2 The raw material of each component was prepared so that it might become the target composition shown in Table 1, and it melt
- the obtained glass substrate is mirror-polished and then etched on one side of the glass substrate so that the plate thickness is 0.7 mm to 0.4 mm while bubbling with a mixed acid of 8% by mass hydrofluoric acid and 10% by mass hydrochloric acid. And thinned.
- Table 2 shows the average breaking load in terms of the plate thickness of 0.4 mm obtained from the measurement results. Further, in the same procedure as described above, the surface roughness on the etched surface when the plate thickness was etched by 30 ⁇ m was determined by the following method. The results are shown in Table 2 below.
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Abstract
Description
(1)アルカリ金属酸化物を含有していると、アルカリ金属イオンが薄膜中に拡散して膜特性を劣化させるため、実質的にアルカリ金属イオンを含まないこと。
(2)薄膜形成工程で高温にさらされる際に、ガラスの変形およびガラスの構造安定化に伴う収縮(熱収縮)を最小限に抑えうるように、歪点が高いこと。
(4)内部および表面に欠点(泡、脈理、インクルージョン、ピット、キズ等)がないこと。
(5)ディスプレイの軽量化が要求され、ガラス自身も密度の小さいガラスが望まれる。
(6)ディスプレイの軽量化が要求され、ガラス基板の薄板化が望まれる。
(8)液晶ディスプレイ作製熱処理の昇降温速度を速くして、生産性を上げたり耐熱衝撃性を上げるために、ガラスの平均熱膨張係数の小さいガラスが求められる。
また、ガラス製造プロセス、特に溶解、成形における要請から、ガラスの粘性、特にガラス粘度が104dPa・sとなる温度T4を低くすることが求められている。
歪点が680~735℃であって、50~350℃での平均熱膨張係数が30×10-7~43×10-7/℃であって、ガラス粘度が102dPa・sとなる温度T2が1710℃以下であって、ガラス粘度が104dPa・sとなる温度T4が1310℃以下であって、酸化物基準のモル%表示で
SiO2 63~74、
Al2O3 11.5~16、
B2O3 1.5超5以下、
MgO 5.5~13、
CaO 1.5~12、
SrO 1.5~9、
BaO 0~1、
ZrO2 0~2を含有し
MgO+CaO+SrO+BaO が15.5~21であり、
MgO/(MgO+CaO+SrO+BaO)が0.35以上であり、CaO/(MgO+CaO+SrO+BaO)が0.50以下であり、SrO/(MgO+CaO+SrO+BaO)が0.50以下である無アルカリガラス。
前記無アルカリガラス基板が下記の無アルカリガラスであり、前記無アルカリガラス基板の少なくとも一方の主面を、フッ酸(HF)を含有するエッチング液(25℃、5%HF水溶液)に浸漬して、単位面積および単位時間当たりの溶出量が、0.17(mg/cm2)/分以上となる条件で、前記無アルカリガラス基板を5μm以上薄板化する、無アルカリガラス基板の薄板化方法を提供する。
歪点が680~735℃であって、50~350℃での平均熱膨張係数が30×10-7~43×10-7/℃であって、ガラス粘度が102dPa・sとなる温度T2が1710℃以下であって、ガラス粘度が104dPa・sとなる温度T4が1310℃以下であって、酸化物基準のモル%表示で
SiO2 63~74、
Al2O3 11.5~16、
B2O3 1.5超5以下、
MgO 5.5~13、
CaO 1.5~12、
SrO 1.5~9、
BaO 0~1、
ZrO2 0~2を含有し
MgO+CaO+SrO+BaO が15.5~21であり、
MgO/(MgO+CaO+SrO+BaO)が0.35以上であり、CaO/(MgO+CaO+SrO+BaO)が0.50以下であり、SrO/(MgO+CaO+SrO+BaO)が0.50以下である無アルカリガラス。
本発明の無アルカリガラス基板の薄板化方法では、下記ガラス組成となるように調合したガラス原料を用いた無アルカリガラス基板を使用する。
歪点が680~735℃であって、50~350℃での平均熱膨張係数が30×10-7~43×10-7/℃であって、ガラス粘度が102dPa・sとなる温度T2が1710℃以下であって、ガラス粘度が104dPa・sとなる温度T4が1310℃以下であって、酸化物基準のモル%表示で
SiO2 63~74、
Al2O3 11.5~16、
B2O3 1.5超5以下、
MgO 5.5~13、
CaO 1.5~12、
SrO 1.5~9、
BaO 0~1、
ZrO2 0~2を含有し
MgO+CaO+SrO+BaO が15.5~21であり、
MgO/(MgO+CaO+SrO+BaO)が0.35以上であり、CaO/(MgO+CaO+SrO+BaO)が0.50以下であり、SrO/(MgO+CaO+SrO+BaO)が0.50以下である無アルカリガラス。
MgO/(MgO+CaO+SrO+BaO)が0.35以上であり、0.37以上が好ましく、0.4以上がより好ましい。
CaO/(MgO+CaO+SrO+BaO)が0.50以下であり、0.48以下が好ましく、0.45以下がより好ましい。
SrO/(MgO+CaO+SrO+BaO)が0.50以下であり、0.40以下が好ましく、0.30以下がより好ましく、0.27以下がより好ましく、0.25以下がさらに好ましい。
なお、本発明の無アルカリガラス基板を用いたディスプレイ製造時にガラス表面に設ける金属ないし酸化物薄膜の特性劣化を生じさせないために、ガラス原料はP2O5を実質的に含有しないことが好ましい。不純物としての混入量は23モルppm以下が好ましく、18モルppm以下がより好ましく、11モルppm以下がさらに好ましく、5モルppm以下が特に好ましい。さらに、ガラスのリサイクルを容易にするため、ガラス原料はPbO、As2O3、Sb2O3は実質的に含有しないことが好ましい。
各成分の原料を目標成分になるように調合し、これを溶解炉に連続的に投入し、1500~1800℃に加熱して溶融する。この溶融ガラスを成形装置にて、所定の板厚の板状のガラスリボンに成形し、このガラスリボンを徐冷後切断することによって、無アルカリガラス基板を得ることができる。
本発明では、フロート法にて板状のガラスリボンに成形することが好ましい。
エッチング処理により薄板化せずに、最初から薄板、すなわち、板厚が小さい無アルカリガラス基板を使用すると、ディスプレイ製造時に実施されるデバイス作製工程などで、大きな薄板をハンドリングする必要があるため、自重たわみによる搬送トラブル(例えば、搬送時の接触による基板へのキズの発生等。以下、同様)や基板の割れなどの問題が生じやすい。好ましくは10μm以上、さらに好ましくは100μm以上、特に好ましくは200μm以上薄板化される。
エッチング処理時には、無アルカリガラス基板の少なくとも一方の主面を、フッ酸を含む薬液に浸漬させる。薬液中のフッ素濃度に応じて、所定時間浸漬させることで、無アルカリガラス基板が所定量薄板化される。
エッチング処理において、薬液が撹拌、バブリング、超音波、シャワー、のうち少なくともいずれか1種類以上の方法で流動されていることが好ましい。薬液を流動する代わりに、無アルカリガラス基板を揺動、回転、のうち少なくともいずれか1種類以上の方法で移動させてもよい。
また、平均破壊荷重とは、BOR法による破壊荷重の測定を複数回実施し、それらによって得られた測定結果の平均値を意味する。なお、後述する実施例では、BOR法による破壊荷重の測定を5回実施し、それらの測定結果の平均値を平均破壊荷重とした。
BOR法で測定した平均破壊荷重が板厚0.4mm換算で300N未満だと、無アルカリガラス基板の表面強度が低く、ディスプレイ製造時におけるハンドリング時等にガラス基板が割れるなど(例えば、支持ピン等で、デバイス作製後の無アルカリガラス基板を持ち上げるような工程でガラス基板が割れるなど)、薄板化後の強度が問題となるおそれがある。より好ましくは350N以上である。
BOR法ではガラス基板表面に発生する応力は板厚の二乗に反比例するため、板厚0.4mm換算の破壊荷重W(N)は、ガラス基板の板厚をt(mm)とし、BOR法により得られる破壊荷重をw(N)とするとき、W=w×0.16/t2の関係式より求めることができる。
薄板化後の無アルカリガラス基板のエッチング処理された側の主面(評価したい側の面)の3点曲げによる面強度は以下のように測定する。評価面をシールで保護した状態で、ガラス基板をポイントスクライバーにてスクライブし、切断した後、評価面のシールをはがして非スクライブ側が下になるようにスパン10mm、R1.5mmの3点曲げジグの上に設置する。上面のスクライブ側からR1.5mmのジグにて押した際の破壊荷重から、3点曲げによる面強度を算出する。
評価面にキズが入ると低強度となるので、薄板後は評価面にはさわらない状態で維持する必要がある。曲げ試験において、端面に破壊起点がある場合は面強度ではなく端面強度を測定していることになるため、起点が面内にある場合の試験結果のみを採用し、平均破壊荷重を求める。
本発明の無アルカリガラス基板は、歪点が680℃以上であるため、パネル製造時の熱収縮を抑えられる。また、p-Si TFTの製造方法としてレーザーアニールによる方法を適用することができる。685℃以上がより好ましく、690℃以上がさらに好ましい。
また、本発明の無アルカリガラス基板は、歪点が680℃以上であるため、高歪点用途(例えば、板厚0.7mm以下、好ましくは0.5mm以下、より好ましくは0.3mm以下の有機EL用のディスプレイ用基板または照明用基板、あるいは板厚0.3mm以下、好ましくは0.1mm以下の薄板のディスプレイ用基板または照明用基板)に適している。
板厚0.7mm以下、さらには0.5mm以下、さらには0.3mm以下、さらには0.1mm以下の板ガラスの成形では、成形時の引き出し速度が速くなる傾向があるため、ガラスの仮想温度が上昇し、ガラスのコンパクションが増大しやすい。この場合、高歪点ガラスであると、コンパクションを抑制することができる。
一方、歪点が735℃以下であるため、フロートバス内及びフロートバス出口の温度をあまり高くする必要が無く、フロートバス内及びフロートバス下流側に位置する金属部材の寿命に影響を及ぼすことが少ない。725℃以下がより好ましく、715℃以下がさらに好ましく、710℃以下が特に好ましい。
また、ガラスの平面歪が改善するため、フロートバス出口から徐冷炉に入る部分で温度を高くする必要があるが、この際の温度をあまり高くする必要がない。このため、加熱に使用するヒータに負荷がかかることがなく、ヒータの寿命に影響を及ぼすことが少ない。
また、本発明の無アルカリガラス基板は失透温度が、1315℃以下であることがフロート法による成形が容易となることから好ましい。好ましくは1300℃以下、1300℃未満、1290℃以下、より好ましくは1280℃以下である。また、フロート成形性やフュージョン成形性の目安となる温度T4(ガラス粘度ηが104ポイズとなる温度、単位:℃)と失透温度との差(T4-失透温度)は、好ましくは-20℃以上、-10℃以上、さらには0℃以上、より好ましくは10℃以上、さらに好ましくは20℃以上、特に好ましくは30℃以上である。
本明細書における失透温度は、白金製の皿に粉砕されたガラス粒子を入れ、一定温度に制御された電気炉中で17時間熱処理を行い、熱処理後の光学顕微鏡観察によって、ガラスの表面及び内部に結晶が析出する最高温度と結晶が析出しない最低温度との平均値である。
液晶ディスプレイパネル製造工程や液晶ディスプレイ装置使用時に発生した応力によってガラス基板が複屈折性を有することにより、黒の表示がグレーになり、液晶ディスプレイのコントラストが低下する現象が認められることがある。光弾性定数を30nm/MPa/cm以下とすることにより、この現象を小さく抑えることができる。好ましくは29nm/MPa/cm以下、より好ましくは28.5nm/MPa/cm以下、さらに好ましくは28nm/MPa/cm以下である。
また、本発明の無アルカリガラス基板は、他の物性確保の容易性を考慮すると、光弾性定数が好ましくは23nm/MPa/cm以上、より好ましくは25nm/MPa/cm以上である。
なお、光弾性定数は円盤圧縮法により測定波長546nmにて測定できる。
日本国特開2011-70092号公報に記載されているような、インセル型のタッチパネル(液晶ディスプレイパネル内にタッチセンサを内蔵したもの)の場合、タッチセンサのセンシング感度の向上、駆動電圧の低下、省電力化の観点から、ガラス基板の比誘電率が高いほうがよい。比誘電率を5.6以上とすることにより、タッチセンサのセンシング感度が向上する。好ましくは5.8以上、より好ましくは6.0以上、さらに好ましくは6.2以上、特に好ましくは6.4以上である。
なお、比誘電率はJIS C-2141に記載の方法で測定できる。
各成分の原料を、表1に示す目標組成になるように調合し、連続溶融窯にて溶解を行い、フロート法にて板成形を行い、無アルカリガラス基板を得た。
得られたガラス基板を鏡面研磨後、8質量%フッ酸、10質量%塩酸による混酸にて、バブリングを行いながら板厚が0.7mmから0.4mmになるよう、ガラス基板の片面のエッチング処理を行い、薄板化を行った。
薄板化後のガラス基板を用いて、直径30mm、R=2.5mmのSUS製リングと直径10mmのSUS製ボールとを用いたボールオンリング(BOR)法にて破壊荷重の測定を5回実施し、それらの測定結果から得られた板厚0.4mm換算の平均破壊荷重を表2に示す。
また、上記と同様の手順で、板厚を30μmエッチング処理した場合の、エッチング処理面における表面粗さを下記手法で求めた。結果を下記表2に示す。
ガラス基板のエッチング処理面について、Park Systems社製XE-HDMにて、スキャンレートを1Hzとし、1μm四方の表面粗さRaを求める。
さらに、フッ酸エッチング処理時のエッチング速度の指標として、25℃、5質量%のフッ酸水溶液に無アルカリガラス基板を浸漬した際の、単位面積および単位時間当たりの溶出量を下記手順で評価した。結果を表2に示す。かっこは計算値を示す。
鏡面研磨された40mm四方に切断した無アルカリガラス基板を洗浄後、質量を測定する。25℃の5質量%フッ酸に20分間浸漬し、浸漬後の質量を測定する。サンプル寸法から表面積を算出し、質量減少量を表面積で割ったのち、さらに浸漬時間で割ることで、単位面積および単位時間当たりの溶出量を求める。
なお、上記の手順で得られた無アルカリガラス基板については、歪点、ヤング率、比弾性率、光弾性定数、比誘電率も測定した。結果を表2に示す。
本出願は、2013年11月28日出願の日本特許出願2013-246801に基づくものであり、その内容はここに参照として取り込まれる。
Claims (3)
- フッ酸(HF)エッチング処理により5μm以上薄板化された、板厚0.4mm以下の無アルカリガラス基板であって、前記無アルカリガラス基板が下記の無アルカリガラスであり、薄板化後の前記無アルカリガラス基板における、比弾性率が31MNm/kg以上であり、光弾性定数が30nm/MPa/cm以下である、無アルカリガラス基板。
歪点が680~735℃であって、50~350℃での平均熱膨張係数が30×10-7~43×10-7/℃であって、ガラス粘度が102dPa・sとなる温度T2が1710℃以下であって、ガラス粘度が104dPa・sとなる温度T4が1310℃以下であって、酸化物基準のモル%表示で
SiO2 63~74、
Al2O3 11.5~16、
B2O3 1.5超5以下、
MgO 5.5~13、
CaO 1.5~12、
SrO 1.5~9、
BaO 0~1、
ZrO2 0~2を含有し
MgO+CaO+SrO+BaO が15.5~21であり、
MgO/(MgO+CaO+SrO+BaO)が0.35以上であり、CaO/(MgO+CaO+SrO+BaO)が0.50以下であり、SrO/(MgO+CaO+SrO+BaO)が0.50以下である無アルカリガラス。 - 前記無アルカリガラス基板は、直径が30mmでRが2.5mmのリングと直径10mmのボールを用いたボールオンリング(BOR)法で測定した平均破壊荷重が板厚0.4mm換算で300N以上である、請求項1に記載の無アルカリガラス基板。
- 無アルカリガラス基板の薄板化方法であって、
前記無アルカリガラス基板が下記の無アルカリガラスであり、前記無アルカリガラス基板の少なくとも一方の主面を、フッ酸(HF)を含有するエッチング液(25℃、5%HF水溶液)に浸漬して、単位面積および単位時間当たりの溶出量が、0.17(mg/cm2)/分以上となる条件で、前記無アルカリガラス基板を5μm以上薄板化する、無アルカリガラス基板の薄板化方法。
歪点が680~735℃であって、50~350℃での平均熱膨張係数が30×10-7~43×10-7/℃であって、ガラス粘度が102dPa・sとなる温度T2が1710℃以下であって、ガラス粘度が104dPa・sとなる温度T4が1310℃以下であって、酸化物基準のモル%表示で
SiO2 63~74、
Al2O3 11.5~16、
B2O3 1.5超5以下、
MgO 5.5~13、
CaO 1.5~12、
SrO 1.5~9、
BaO 0~1、
ZrO2 0~2を含有し
MgO+CaO+SrO+BaO が15.5~21であり、
MgO/(MgO+CaO+SrO+BaO)が0.35以上であり、CaO/(MgO+CaO+SrO+BaO)が0.50以下であり、SrO/(MgO+CaO+SrO+BaO)が0.50以下である無アルカリガラス。
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