[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2021149396A1 - 硫酸塩付きリチウムシリケートガラス板、リチウムシリケートガラス板、及びその製造方法 - Google Patents

硫酸塩付きリチウムシリケートガラス板、リチウムシリケートガラス板、及びその製造方法 Download PDF

Info

Publication number
WO2021149396A1
WO2021149396A1 PCT/JP2020/046495 JP2020046495W WO2021149396A1 WO 2021149396 A1 WO2021149396 A1 WO 2021149396A1 JP 2020046495 W JP2020046495 W JP 2020046495W WO 2021149396 A1 WO2021149396 A1 WO 2021149396A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfate
lithium silicate
glass plate
silicate glass
glass
Prior art date
Application number
PCT/JP2020/046495
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
智 倉田
丈宜 三浦
道教 末原
健二 今北
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to CN202080091856.8A priority Critical patent/CN114929640B/zh
Priority to JP2021573001A priority patent/JP7544070B2/ja
Publication of WO2021149396A1 publication Critical patent/WO2021149396A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • 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

Definitions

  • the present disclosure relates to a lithium silicate glass plate containing sulfate, a lithium silicate glass plate, and a method for producing the same.
  • the method for manufacturing a glass plate includes a molding step of molding molten glass into a plate shape to obtain a glass ribbon, and a slow cooling step of slowly cooling the glass ribbon while transporting it with a plurality of transport rollers.
  • the slow cooling step includes spraying sulfurous acid (SO 2 ) gas onto the main surface of the glass ribbon in contact with the transport roller to form a sulfate film (see, for example, Patent Document 1).
  • the sulfate film is dispersedly arranged on the main surface of the glass ribbon to soften the collision between the glass ribbon and the transport roller and prevent the glass ribbon from being damaged.
  • the glass is soda lime glass, a sulfate containing mainly Na is formed.
  • the sulfate an inorganic compound containing sulfate ions (SO 4 2-).
  • Chemically strengthened glass for chemical strengthening is called chemically strengthened glass.
  • Applications of chemically strengthened glass are, for example, cover glass for image display devices.
  • Chemical strengthening involves ion exchange of alkali metal ions with a small ionic radius contained in the glass surface and alkali metal ions with a large ionic radius contained in the molten salt to form a compressive stress layer on the glass surface.
  • alkali metal include Li, Na and K.
  • the ionic radii of Li, Na, and K increase in this order.
  • Lithium silicate glass contains Li ions with the smallest ionic radius among alkali metal ions. Therefore, as the alkali metal ion of the molten salt, not only K ion but also Na ion having an ionic radius smaller than that of K ion can be selected. The selection range of alkali metal ions in the molten salt is wide, and the control range of chemical strengthening is wide.
  • Lithium silicate glass is chemically strengthened and then mounted on mobile phones, personal digital assistants (PDAs), personal computers, televisions, in-vehicle navigation systems, and the like.
  • PDAs personal digital assistants
  • televisions in-vehicle navigation systems, and the like.
  • the present inventor investigated foreign substances mixed in the lithium silicate glass plate in the past, and found that the cause of the foreign substances mixed was sulfate.
  • the present inventor states that when the sulfate formed on the glass surface adheres to the transport roller and the adhered sulfate melts, the metal transport roller is corroded, rust is generated, and the rust is mixed into the glass plate as a foreign substance. Found.
  • One aspect of the present disclosure provides a technique capable of suppressing foreign matter from being mixed into a lithium silicate glass plate.
  • the lithium silicate glass plate with sulfate includes a lithium silicate glass plate and a sulfate containing an alkali metal ion formed on the main surface of the lithium silicate glass plate.
  • the melting point of the sulfate is 40 ° C. or higher higher than the glass transition point (Tg) of lithium silicate glass.
  • the depth distribution of the Li concentration (unit: mol%) in the glass plate before chemical strengthening is 0 nm to 100 nm in depth from the main surface on which the sulfate is formed.
  • the average value of the Li concentration in the region is 88% or less of the average value of the Li concentration in the region having a depth of 400 nm to 600 nm from the main surface.
  • molten glass is formed into a plate shape to obtain a glass ribbon, and the glass ribbon is slowly cooled while being conveyed by a plurality of conveying rollers. Further, in the manufacturing method thereof, sulfur oxide gas is sprayed on the main surface of the glass ribbon in contact with the transport roller to form a sulfate. At the position where the sulfur oxide gas is sprayed, the temperature of the glass ribbon is ⁇ 30 ° C. or higher and lower than 40 ° C. with reference to the glass transition point (Tg) of the lithium silicate glass. The melting point of the sulfate salt is 40 ° C. or higher higher than that of the glass transition point (Tg).
  • FIG. 1 is a side sectional view showing a lithium silicate glass plate manufacturing apparatus according to an embodiment.
  • FIG. 2 is a plan view showing an example of the arrangement of the nozzle and the second transport roller.
  • FIG. 3A is a diagram showing an example of the relationship between M5 and M2 / M1.
  • FIG. 3B is a diagram showing an example of the relationship between M5 and M4 / M3.
  • FIG. 4 is a diagram showing the distribution of Li concentration in the depth direction in the glass plate of Example 3.
  • FIG. 5 is an SEM photograph of the main surface of the glass plate of Example 5 in which the sulfate is formed.
  • FIG. 1 is a side sectional view showing a lithium silicate glass plate manufacturing apparatus according to an embodiment.
  • FIG. 2 is a plan view showing an example of the arrangement of the nozzle and the second transport roller.
  • FIG. 3A is a
  • the same or corresponding configurations may be designated by the same reference numerals and description thereof may be omitted.
  • the X-axis direction, the Y-axis direction, and the Z-axis direction are perpendicular to each other, the X-axis direction and the Y-axis direction are the horizontal direction, and the Z-axis direction is the vertical direction.
  • the X-axis direction is the transport direction of the glass ribbon G, and the Y-axis direction is the width direction of the glass ribbon G.
  • the melting point means the temperature at which the solid begins to melt. When the solidus temperature and the liquidus temperature are present, the melting point means the solidus temperature.
  • the manufacturing apparatus 1 includes a molding apparatus 2 and a heat treatment apparatus 3.
  • the molding apparatus 2 molds the molten glass into a plate shape to obtain a glass ribbon G.
  • the heat treatment apparatus 3 slowly cools the glass ribbon G while transporting the glass ribbon G between the first transport roller 41 and the second transport roller 51. After being taken out from the molding apparatus 2, the glass ribbon G is slowly cooled by the heat treatment apparatus 3, and then cut by a processing apparatus (not shown). As a result, a lithium silicate glass plate is obtained as a product.
  • the lithium silicate glass plate is also simply referred to as a glass plate.
  • the glass plate may be for chemical strengthening.
  • chemical strengthening alkali metal ions having a small ionic radius contained in the glass surface and alkali metal ions having a large ionic radius contained in the molten salt are exchanged with each other to form a compressive stress layer on the glass surface.
  • the alkali metal include Li, Na and K.
  • the ionic radii of Li, Na, and K increase in this order.
  • Lithium silicate glass contains Li ions with the smallest ionic radius among alkali metal ions. Therefore, as the alkali metal ion of the molten salt, not only K ion but also Na ion having an ionic radius smaller than that of K ion can be selected. The selection range of alkali metal ions in the molten salt is wide, and the control range of chemical strengthening is wide.
  • the glass plate After being chemically strengthened, the glass plate will be mounted on mobile phones, personal digital assistants (PDAs), personal computers, televisions, in-vehicle navigation systems, and the like.
  • PDAs personal digital assistants
  • personal computers personal computers
  • televisions in-vehicle navigation systems, and the like.
  • Lithium silicate glass is, for example, in terms of oxide-based mol%, SiO 2 is 50 to 75%, Al 2 O 3 is 2 to 25%, Li 2 O is 5 to 20%, and Na 2 O + K 2 O is 0. Contains 5 to 15%.
  • SiO 2 is 55 to 75%
  • Al 2 O 3 is 8 to 25%
  • Li 2 O is 5 to 20%
  • Na 2 O + K 2 O is 0.5 to 15. %contains.
  • Lithium silicate glass is expressed in molar% based on oxides, SiO 2 is 60 to 73%, Al 2 O 3 is 8 to 22%, Li 2 O is 9 to 15%, and K 2 O is 1.2 to 3. It is more preferable to contain 0.0% and 0.5 to 10% of Na 2 O + K 2 O.
  • the glass transition point Tg of lithium silicate glass is, for example, 510 ° C. or higher, preferably 540 ° C. or higher.
  • the glass transition point Tg of the lithium silicate glass is, for example, 650 ° C. or lower, preferably 630 ° C. or lower, and more preferably 600 ° C. or lower.
  • the molding apparatus 2 obtains a glass ribbon G by, for example, a float method.
  • molten glass is continuously supplied on the liquid surface of the molten metal M, and the supplied molten glass flows on the liquid surface of the molten metal M from the negative side in the X-axis direction to the positive side in the X-axis direction.
  • it is molded into a strip shape.
  • the molding apparatus 2 has a bathtub 21 for storing the molten metal M.
  • the molten metal M for example, molten tin or a molten tin alloy is used.
  • the inside of the molding apparatus 2 is filled with a reducing atmosphere in order to suppress the oxidation of the molten metal M.
  • the reducing atmosphere includes, for example, nitrogen gas and hydrogen gas. Further, the inside of the molding apparatus 2 is maintained at a positive pressure higher than the atmospheric pressure in order to suppress the mixing of air from the outside of the molding apparatus 2.
  • the molding apparatus 2 uses the liquid level of the molten metal M to obtain a plate-shaped glass ribbon G.
  • the glass ribbon G is gradually cooled and hardened while flowing on the liquid surface of the molten metal M.
  • the glass ribbon G is pulled up from the molten metal M in the downstream region of the bathtub 21 and carried out from the outlet 22 of the molding apparatus 2.
  • the temperature of the glass ribbon G at the outlet 22 is lower than the first temperature T1.
  • the heat treatment apparatus 3 is adjacent to the outlet 22 of the molding apparatus 2.
  • the heat treatment apparatus 3 has a dross box 4 and a slow cooling furnace 5 provided on the downstream side in the transport direction with respect to the dross box 4. Inside the heat treatment apparatus 3, the temperature of the glass ribbon G becomes lower from the upstream side in the transport direction to the downstream side in the transport direction.
  • the heat treatment apparatus 3 has a first metal transport roller 41 inside the dross box 4.
  • the first transport roller 41 pulls the glass ribbon G diagonally upward from the liquid surface of the molten metal M, and transports the glass ribbon G from the molding apparatus 2 to the dross box 4.
  • a plurality of first transport rollers 41 are provided at intervals in the transport direction of the glass ribbon G.
  • the first transfer roller 41 contacts the lower surface of the glass ribbon G and rotates to convey the glass ribbon G.
  • the heat treatment apparatus 3 further has a carbon block 42 inside the dross box 4.
  • the carbon block 42 is provided for each first transport roller 41 and comes into contact with the first transport roller 41 from below to form a carbon protective film on the outer peripheral surface of the first transport roller 41. Since the carbon protective film functions as a cushioning material for softening the collision between the first transport roller 41 and the glass ribbon G, it is possible to prevent the glass ribbon G from being damaged.
  • the inside of the dross box 4 is filled with a reducing atmosphere that flows in from the outlet 22 of the molding apparatus 2 in order to suppress burning of the carbon block 42 due to oxidation. Further, in order to suppress the mixing of the atmosphere from the outside of the dross box 4, the inside of the dross box 4 is maintained at a positive pressure higher than the atmospheric pressure by introducing nitrogen gas or the like.
  • the heat treatment apparatus 3 has a metal second transfer roller 51 inside the slow cooling furnace 5.
  • the second transfer roller 51 horizontally conveys the glass ribbon G from the inlet 52 of the slow cooling furnace 5 toward the outlet 53.
  • a plurality of second transport rollers 51 are provided at intervals in the transport direction of the glass ribbon G.
  • the second transfer roller 51 contacts the lower surface of the glass ribbon G and rotates to convey the glass ribbon G.
  • the heat treatment apparatus 3 has a nozzle 54 inside the slow cooling furnace 5.
  • Nozzle 54 the lower surface of the glass ribbon G blowing sulfur oxide gas (SO X gas), to form a sulfate.
  • SO X gas is at least one selected from SO 2 gas and SO 3 gas.
  • the sulfate meant an inorganic compound containing sulfate ions (SO 4 2-). Since the sulfate functions as a cushioning material for softening the collision between the second transport roller 51 and the glass ribbon G, it is possible to prevent the glass ribbon G from being damaged.
  • the nozzle 54 is arranged near the inlet 52 of the slow cooling furnace 5 in order to prevent the glass ribbon G from being damaged as much as possible.
  • the position of the nozzle 54 is not limited to the vicinity of the inlet 52 of the slow cooling furnace 5.
  • the number of nozzles 54 is one in the present embodiment, but may be plural.
  • a plurality of nozzles 54 are provided at intervals in the transport direction of the glass ribbon G.
  • Nozzle 54 has a discharge port 541 for discharging the SO X gas. As shown in FIG. 2, a plurality of discharge ports 541 are arranged at intervals in the Y-axis direction in order to form sulfate over the entire width direction of the glass ribbon G. The plurality of discharge ports 541 are formed in the horizontal pipe 542 parallel to the Y-axis direction.
  • the nozzle 54 is connected to the first gas supply source 64 via a first pipe 63 in which a first on-off valve 61 and a first flow rate control valve 62 are provided in the middle.
  • the first on-off valve 61 opens the flow path of the first pipe 63
  • the first gas supply source 64 supplies the SO X gas to the nozzle 54
  • the nozzle 54 ejects SO X gas.
  • the flow rate of the SO X gas is controlled by the first flow control valve 62.
  • the first on-off valve 61 closes the flow path of the first pipe 63, the supply of the SO X gas from the first gas supply source 64 to the nozzle 54 is stopped, the nozzle 54 stops discharging the SO X Gas ..
  • SO 2 gas becomes SO 3 gas is oxidized within the lehr 5. Since SO 3 gas is estimated to contribute to the generation of crystals of sulfate, internal lehr 5 as SO 3 gas can stably be present is an oxidizing atmosphere.
  • the oxidizing atmosphere is formed by the atmosphere flowing in from the outlet 53 of the slow cooling furnace 5. Therefore, the oxygen gas concentration in the internal atmosphere of the slow cooling furnace 5 becomes lower from the outlet 53 to the inlet 52 of the slow cooling furnace 5.
  • the nozzle 54 is arranged near the inlet 52 of the slow cooling furnace 5. Therefore, the nozzle 54 may discharge the oxygen-containing gas in order to increase the oxygen gas concentration.
  • the oxygen-containing gas may be any gas containing oxygen gas and may be pure oxygen gas, but in the present embodiment, it is air. Air may be discharged simultaneously with the SO X gas may be alternately discharged and SO X gas.
  • the nozzle 54 is connected to the second gas supply source 74 via a second pipe 73 in which the second on-off valve 71 and the second flow rate control valve 72 are provided in the middle.
  • the second on-off valve 71 opens the flow path of the second pipe 73
  • the second gas supply source 74 supplies air to the nozzle 54
  • the nozzle 54 discharges air.
  • the flow rate of air is controlled by the second flow rate control valve 72.
  • the second on-off valve 71 closes the flow path of the second pipe 73, the supply of air from the second gas supply source 74 to the nozzle 54 is stopped, and the nozzle 54 stops the discharge of air.
  • one nozzle 54 in the present embodiment ejects both SO X gas and air
  • a nozzle for SO X gas, a nozzle for air may be provided separately.
  • Sulfates are usually an alkali metal contained in the glass ribbon G, it is formed by the reaction of SO 3 gas. Therefore, the sulfate contains alkali metal ions.
  • sulfates, and alkaline earth metals contained in the glass ribbon G, and can also be formed by the reaction of SO 3 gas can further also comprise alkaline earth metal ions.
  • lithium silicate glass contains Li
  • sulfate also contains Li.
  • the sulfate may further contain any one or more of Na and K.
  • Li (1-A-B ), Na A, K B the melting point of 2 SO 4 depends on the A and B.
  • A is 0-1 and B is also 0-1.
  • the solidus temperature of (Li 0.9 , Na 0.1 ) 2 SO 4 is 732 ° C, but there are combinations of A and B having a solidus temperature of 530 ° C or less.
  • the present inventor investigated foreign substances mixed in the lithium silicate glass plate in the past, and found that the cause of the foreign substances mixed was sulfate.
  • the present inventor has found that when the sulfate melts, the metal second transport roller 51 is corroded and rust is generated, and the rust is mixed into the glass plate as a foreign substance. Further, the present inventor has found that when the sulfate melts or softens without melting, the sulfate loses its function as a cushioning material and the glass ribbon G is damaged more.
  • the temperature of the glass ribbon G is lower than the first temperature T1 at the outlet 22 of the molding apparatus 2, so that it is lower than the first temperature T1 at the inlet 52 of the slow cooling furnace 5 and exits from the inlet 52 of the slow cooling furnace 5. It is lower toward 53.
  • the melting point T M of sulfate high 40 ° C. or more as compared with the Tg (T M ⁇ Tg + 40 ), preferably greater than 50 ° C. as compared to Tg (T M ⁇ Tg + 50 ).
  • Melting point T M of the sulfate for example, 550 ° C. or higher, preferably 580 ° C. or higher, more preferably 600 ° C. or higher.
  • the melting point T M of sulfates for example 860 ° C. or less, preferably 720 ° C. or less.
  • the ratio (M2 / M1) is less than 0.1 and the ratio (M4 / M3) is 0.018 or less, the ratio of Li ions to the alkali metal ions is high, and (Li (1-AB). ), Na a, the solidus temperature of the K B) 2 SO 4 is more than 600 ° C.. In this case, if the temperature of the glass ribbon G inside the slow cooling furnace 5 is 600 ° C. or lower, melting of the sulfate can be suppressed.
  • the present inventor has a same glass composition of the lithium silicate glass, and the amount of glass when the temperature T2 of the ribbon G is the same, a unit area (1 m 2) sulfate per at blowing position of SO X Gas It was found in the experiment that both the ratio (M2 / M1) and the ratio (M4 / M3) became smaller as the ratio (M2 / M1) increased.
  • the amount of sulfate per unit area is represented by the number of moles of sulfur M5 per unit area.
  • the relationship between M5 and M2 / M1 is shown in FIG. 3A, and the relationship between M5 and M4 / M3 is shown in FIG. 3B. As shown in FIG. 3A, as M5 increases, M2 / M1 becomes smaller. Further, as shown in FIG. 3B, as M5 increases, M4 / M3 becomes smaller.
  • both M2 / M1 and M4 / M3 become smaller.
  • M2 / M1 and that both the M4 / M3 becomes small means that the ratio of Li to total alkali metal in the sulphate is increased, which means that the higher the melting point T M of sulfate.
  • M5 is, for example, 5.1 ⁇ 10-5 mol or more, preferably 6.0 ⁇ 10-5 mol or more, and more preferably 7.5 ⁇ 10-5 mol or more. If M5 is 5.1 ⁇ 10 -5 mol or more, high percentage of Li occupying the alkali metal in the sulphate, because of the high melting point T M of sulphate, it is possible to suppress the melting of the sulfate salt. M5 is preferably 15 ⁇ 10-5 mol or less.
  • the main surface (30 cm ⁇ 30 cm) of the glass plate with sulfate was scrubbed with 20 ml of a 1-defined hydrochloric acid aqueous solution, and further washed with warm water. The 100 ml liquid obtained was analyzed and measured.
  • M2 / M1 and M4 / M3 were measured by atomic absorption spectrometry.
  • a polarized Zeeman atomic absorption spectrophotometer (Z-2310) manufactured by Hitachi High-Tech Science was used for the measurement.
  • ICP emission spectroscopic analyzer ICP-OES SPS3100HV UV
  • Hitachi High-Tech Science The quantification of each element was performed using the calibration curve method.
  • sulfate as described above, and the alkali metal contained in the glass ribbon G, are formed by the reaction of SO 3 gas. At that time, the alkali metal escapes from the glass ribbon G and forms a sulfate on the main surface of the glass plate. As shown in FIG. 4, the shallower the depth from the glass surface, the smaller the Li concentration (unit: mol%) in the glass.
  • the average value of the Li concentration in the region of 0 nm to 100 nm in depth from the main surface of the glass plate is described as D1
  • the average value of the Li concentration in the region of depth of 400 nm to 600 nm from the main surface of the glass plate is described as D2.
  • the main surface of the glass plate is the main surface on which the sulfate is formed.
  • D1 is, for example, 88% or less of D2, preferably 86% or less of D2.
  • D1 is preferably 65% or more of D2.
  • the amount of Li ions is proportional to the amount of sulfate formed on the lithium silicate glass and is proportional to M5. More M5 increases, as described above, the melting point T M of sulphate increases. Therefore, it D1 / D2 is small, it means that higher melting point T M of sulfate.
  • D1 / D2 is also dependent on the temperature T2 of the glass ribbon G in the glass composition, and spraying position of SO X gas lithium silicate glass.
  • the temperature T2 is ⁇ 30 ° C. or higher and lower than 40 ° C. with reference to the glass transition point (Tg) (Tg-30 ⁇ T2 ⁇ Tg + 40).
  • D1 / D2 is measured with an unreinforced glass plate. This is because the distribution of Li concentration in the depth direction also changes due to chemical strengthening.
  • the depth distribution of the Li concentration on the glass plate was measured by X-ray photoelectron spectroscopy (XPS) using C60 ion sputtering in the examples described later.
  • XPS X-ray photoelectron spectroscopy
  • ESCA5500 manufactured by ULVAC-PHI was used.
  • the abundance ratio of each element contained in glass is Si (2p), Al (2p), Na (2s), K (2p), Li (1s), Ca (2s), Mg (2s), Zr (3d). , Sn (3d5), O (1s) peaks.
  • the peak measurement conditions were a path energy of 117.4 eV, an energy step of 0.5 eV / step, and a detection angle (angle formed by the sample surface and the detector) of 75 °.
  • the analysis software MultiPak was used for the analysis of the spectrum. The background of the spectrum was removed by the Shirley method.
  • Examples 1 to 5 will be described. Examples 1 to 4 are examples, and example 5 is a comparative example.
  • Example 1 molding the molten glass into a plate shape by a float process, after obtaining the glass ribbon G, blowing SO X gas near the inlet 52 of the annealing furnace 5, to form a sulfate on the lower surface of the glass ribbon G.
  • Temperature T2 of the glass ribbon G at blowing position of SO X gas was 540 ° C.. After slow cooling, a glass plate was cut out from the glass ribbon G.
  • the glass of the glass plate is lithium silicate glass, which is expressed in mole% based on oxides, SiO 2 is 66.2%, Al 2 O 3 is 11.2%, Li 2 O is 10.4%, and Na 2 is used. O 5.6% of K 2 O 1.5% and MgO 3.1% 0.2% to CaO, the ZrO 2 1.3% glass containing Y 2 O 3 0.5% Met. This glass had a glass transition point Tg of 558 ° C and a slow cooling point of 552 ° C. The glass composition was measured at the center of the glass plate in the plate thickness direction.
  • the alkali metal ions of the sulfate were 0.09 for M2 / M1 and 0.0178 for M4 / M3.
  • the number of moles of sulfur M5 per unit area was 5.1 ⁇ 10-5 moles.
  • Melting point T M of sulfate was 600 ° C. or higher.
  • D1 was 88% of D2.
  • Example 2 In Example 2, to increase the amount of sulfate per unit area, except for increasing the flow rate of the SO X gas, to produce the glass plate under the same conditions as Example 1. Temperature T2 of the glass ribbon G at blowing position of SO X gas was 540 ° C.. The obtained glass had a glass transition point Tg of 558 ° C and a slow cooling point of 552 ° C.
  • the alkali metal ions of the sulfate were 0.08 for M2 / M1 and 0.0156 for M4 / M3.
  • the number of moles of sulfur M5 per unit area was 5.8 ⁇ 10-5 moles.
  • Melting point T M of sulfate was 600 ° C. or higher.
  • D1 was 86% of D2.
  • Example 3 In Example 3, to increase the amount of sulfate per unit area, except for increasing the flow rate of the SO X gas, to produce the glass plate under the same conditions as Example 1. Temperature T2 of the glass ribbon G at blowing position of SO X gas was 540 ° C.. The obtained glass had a glass transition point Tg of 558 ° C and a slow cooling point of 552 ° C.
  • the alkali metal ions of the sulfate were 0.03 for M2 / M1 and 0.0070 for M4 / M3.
  • the number of moles of sulfur M5 per unit area was 12.9 ⁇ 10-5 moles.
  • Melting point T M of sulfate was 600 ° C. or higher.
  • the distribution of the Li concentration of the glass plate obtained in Example 3 in the depth direction is shown in FIG. D1 was 69% of D2.
  • Example 4 a glass raw material having a different compounding ratio from that of Examples 1 to 3 is melted to obtain molten glass, and then the molten glass is formed into a plate shape by a float method in the same manner as in Examples 1 to 3, and a glass ribbon is formed. I got a G. Thereafter, it is blown SO X gas near the inlet 52 of the annealing furnace 5, to form a sulfate on the lower surface of the glass ribbon G. Temperature T2 of the glass ribbon G at blowing position of SO X gas was 570 ° C.. After slow cooling, a glass plate was cut out from the glass ribbon G.
  • the glass of the glass plate is lithium silicate glass, which is expressed in mole% based on oxides, SiO 2 is 70.0%, Al 2 O 3 is 7.5%, Li 2 O is 8.0%, and Na 2 is used. O 5.3% of K 2 O 1.0% and MgO 7.0% 0.2% a CaO, and a glass containing ZrO 2 1.0%. This glass had a glass transition point Tg of 548 ° C and a slow cooling point of 542 ° C. The glass composition was measured at the center of the glass plate in the plate thickness direction.
  • the alkali metal ions of the sulfate were 0.08 for M2 / M1 and 0.0120 for M4 / M3.
  • the number of moles of sulfur M5 per unit area was 5.2 ⁇ 10-5 moles.
  • Melting point T M of sulfate was 600 ° C. or higher.
  • D1 was 78% of D2.
  • Example 5 In Example 5, except that the temperature T2 of the glass ribbon G at blowing position of SO X gas from 540 ° C. to 560 ° C., to produce a glass plate as in Example 1. Temperature T2 of the glass ribbon G at blowing position of SO X gas was 560 ° C.. The obtained glass had a glass transition point Tg of 558 ° C and a slow cooling point of 552 ° C.
  • the alkali metal ions of the sulfate were 0.12 for M2 / M1 and 0.0244 for M4 / M3.
  • the number of moles of sulfur M5 per unit area was 4.2 ⁇ 10-5 moles.
  • Melting point T M of sulphate was 557 ° C..
  • D1 was 91% of D2.
  • the foreign matter C contained sulfur and iron. Therefore, it is presumed that the sulfate is melted, the second transport roller 51 made of stainless steel is corroded, rust is generated, and the rust is mixed as foreign matter C.
  • the glass of Example 1 has a higher potassium concentration than the glass of Example 4.
  • the higher the potassium concentration in the glass the larger the amount of potassium that escapes from the glass, the higher the potassium concentration of the sulfate, and the easier it is for the sulfate to dissolve. Therefore, like the glass of Example 1, SiO 2 is 60 to 73%, Al 2 O 3 is 8 to 22%, Li 2 O is 9 to 15%, and K 2 O is 1 in the oxide-based molar% representation.
  • the technical significance of applying the present invention to glass containing 2 to 3.0% and 0.5 to 10% of Na 2 O + K 2 O is great.
  • the region indicated by the dot pattern is the region where the liquid phase is generated.
  • the lithium silicate glass plate with sulfate, the lithium silicate glass plate, and the manufacturing method thereof according to the present disclosure have been described above, but the present disclosure is not limited to the above-described embodiment and the like.
  • various changes, modifications, replacements, additions, deletions, and combinations are possible. Of course, they also belong to the technical scope of the present disclosure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
PCT/JP2020/046495 2020-01-20 2020-12-14 硫酸塩付きリチウムシリケートガラス板、リチウムシリケートガラス板、及びその製造方法 WO2021149396A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202080091856.8A CN114929640B (zh) 2020-01-20 2020-12-14 带有硫酸盐的锂硅酸盐玻璃板、锂硅酸盐玻璃板及其制造方法
JP2021573001A JP7544070B2 (ja) 2020-01-20 2020-12-14 硫酸塩付きリチウムシリケートガラス板、リチウムシリケートガラス板、及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020007091 2020-01-20
JP2020-007091 2020-01-20

Publications (1)

Publication Number Publication Date
WO2021149396A1 true WO2021149396A1 (ja) 2021-07-29

Family

ID=76992335

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/046495 WO2021149396A1 (ja) 2020-01-20 2020-12-14 硫酸塩付きリチウムシリケートガラス板、リチウムシリケートガラス板、及びその製造方法

Country Status (3)

Country Link
JP (1) JP7544070B2 (zh)
CN (1) CN114929640B (zh)
WO (1) WO2021149396A1 (zh)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002051767A1 (fr) * 2000-12-26 2002-07-04 Nippon Sheet Glass Co.,Ltd. Verre a glace avec film protecteur et son procede de fabrication
WO2008004481A1 (fr) * 2006-07-07 2008-01-10 Asahi Glass Co., Ltd. Procédé de production de substrat de verre destiné à du verre de type panneaux plats
WO2015194569A1 (ja) * 2014-06-20 2015-12-23 旭硝子株式会社 ガラス板及びその製造方法
JP2019137562A (ja) * 2018-02-06 2019-08-22 Ａｇｃ株式会社 フロートガラス製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6044772B2 (ja) * 2013-01-18 2016-12-14 日本電気硝子株式会社 保護膜付きガラス基材
CN108863050A (zh) * 2018-06-20 2018-11-23 醴陵旗滨电子玻璃有限公司 锂铝硅酸盐玻璃及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002051767A1 (fr) * 2000-12-26 2002-07-04 Nippon Sheet Glass Co.,Ltd. Verre a glace avec film protecteur et son procede de fabrication
WO2008004481A1 (fr) * 2006-07-07 2008-01-10 Asahi Glass Co., Ltd. Procédé de production de substrat de verre destiné à du verre de type panneaux plats
WO2015194569A1 (ja) * 2014-06-20 2015-12-23 旭硝子株式会社 ガラス板及びその製造方法
JP2019137562A (ja) * 2018-02-06 2019-08-22 Ａｇｃ株式会社 フロートガラス製造方法

Also Published As

Publication number Publication date
CN114929640B (zh) 2024-03-08
JP7544070B2 (ja) 2024-09-03
JPWO2021149396A1 (zh) 2021-07-29
CN114929640A (zh) 2022-08-19

Similar Documents

Publication Publication Date Title
JP6023791B2 (ja) 化学強化ガラス板およびフラットパネルディスプレイ装置
CN104884399B (zh) 能够减小化学强化时的翘曲的玻璃板的制造方法及玻璃板
CN101489946B (zh) 无碱玻璃基板的制造方法
TWI473770B (zh) Glass substrate for flat panel displays
WO2002051767A1 (fr) Verre a glace avec film protecteur et son procede de fabrication
CN105579408B (zh) 玻璃板的制造方法
CN107406309A (zh) 玻璃板
TW201331141A (zh) 化學強化用玻璃基板及其製造方法
WO2021149396A1 (ja) 硫酸塩付きリチウムシリケートガラス板、リチウムシリケートガラス板、及びその製造方法
TW201514119A (zh) 玻璃板
TWI666179B (zh) Glass plate and manufacturing method thereof
JP2019137562A (ja) フロートガラス製造方法
WO2014123089A1 (ja) ガラス製造方法
KR101404060B1 (ko) 유리 표면 윤활층 형성 방법 및 이를 이용하는 유리 제조 방법
CN112745017B (zh) 保护玻璃的制造方法和保护玻璃
TW201247571A (en) Apparatus for forming lubricant layer on surface of glass and annealing furnace and glass manufacturing apparatus including the same
TW201514104A (zh) 浮式玻璃之製造方法
JP2023108776A (ja) ガラス製造装置、及びガラス製造方法
JP2024030123A (ja) ステンレスロール、ガラス製造装置およびガラス製造方法
JP2016147763A (ja) ガラス板、発光モジュールおよびガラス板製造方法
WO2014013913A1 (ja) ガラス板の製造方法、及びガラス板

Legal Events

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

Ref document number: 20914907

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021573001

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20914907

Country of ref document: EP

Kind code of ref document: A1