WO2002051767A1 - Verre a glace avec film protecteur et son procede de fabrication - Google Patents

Verre a glace avec film protecteur et son procede de fabrication Download PDF

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Publication number
WO2002051767A1
WO2002051767A1 PCT/JP2001/011331 JP0111331W WO02051767A1 WO 2002051767 A1 WO2002051767 A1 WO 2002051767A1 JP 0111331 W JP0111331 W JP 0111331W WO 02051767 A1 WO02051767 A1 WO 02051767A1
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Prior art keywords
glass
gas
sheet
protective film
nozzle
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Application number
PCT/JP2001/011331
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English (en)
Japanese (ja)
Inventor
Toshiaki Hashimoto
Hiroyasu Fukuda
Hitoshi Takahashi
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Nippon Sheet Glass Co.,Ltd.
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 Nippon Sheet Glass Co.,Ltd. filed Critical Nippon Sheet Glass Co.,Ltd.
Priority to JP2002552872A priority Critical patent/JPWO2002051767A1/ja
Publication of WO2002051767A1 publication Critical patent/WO2002051767A1/fr

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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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass

Definitions

  • the present invention relates to a sheet glass having a protective coating and a method for producing the same.
  • the molten glass is supplied to a molten tin tank called a float bath 1 to reduce the required thickness and width. Molded.
  • the glass passes through the exit part of pass 1 called shield rare "2, and is gradually cooled and cooled in the annealing furnace 3.
  • the glass body 4 becomes a continuous ribbon-shaped glass body 4. The glass body 4 is cut after washing, and the sheet glass is cut. Is manufactured.
  • the metal roller 5 transports the ribbon-shaped glass book 4.
  • Sulfurous acid gas (S 0 2 ) introduced from the nozzle 6 into the annealing furnace 3 smoothes the surface of the roller.
  • the sulfurous acid gas introduced into the annealing furnace 3 reacts with sodium generated from the glass to form a sodium sulfate film on the roller surface.
  • the roller having this coating does not scratch the surface of the glass body 4 when it contacts the glass body 4.
  • a film of sodium sulfate is also formed on the surface of the glass body 4, and this sodium sulfate film is washed and removed in a washing step after the slow cooling.
  • the glass body from which the sodium sulfate coating has been removed may have scratches on the surface of the glass sheet in the transporting and transporting steps, as well as in the subsequent processing steps. Disclosure of the invention
  • An object of the present invention is to prevent a sheet glass from being scratched in a manufacturing process, a subsequent transport, transportation, and a processing process.
  • the glass sheet of the present invention has a glass body, and a protective film formed on the surface of the glass body to prevent the glass body from being scratched.
  • This protective coating is It is formed in a sheet glass manufacturing process for manufacturing sheet glass successively.
  • This protective coating prevents the glass body from being scratched during the manufacturing process and subsequent transport, transport and processing steps.
  • the method for producing a flat glass of the present invention includes a flat glass manufacturing step of continuously producing a flat glass. During manufacturing, a protective film is formed on the surface of the glass body to prevent scratches.
  • the sheet glass is efficiently manufactured because the protective coating is formed during the manufacturing of the sheet glass.
  • FIG. 1 is a schematic plan view showing an embodiment of the method for manufacturing a sheet glass of the present invention.
  • FIG. 2A is a plan view showing an example of a gas blowing nozzle suitable for carrying out the present invention
  • FIG. 2B is a side view of the same.
  • FIG. 3A is a plan view showing another example of a gas blowing nozzle suitable for carrying out the present invention
  • FIG. 3B is a side view of the same.
  • FIG. 4 is a cross-sectional view of the nozzle shown in FIG. 3b, taken along line IV-IV.
  • FIG. 5A is a plan view showing another example of a gas blowing nozzle suitable for carrying out the present invention
  • FIG. 5B is a side view of the same.
  • FIG. 6A is a plan view showing a different example of a gas blowing nozzle suitable for carrying out the present invention
  • FIG. 6B is a side view of the same.
  • FIG. 7 is a schematic cross-sectional view showing an example of the gas heating means.
  • FIG. 8 is a schematic sectional view showing another example of the gas heating means.
  • FIG. 9 is a schematic cross-sectional view showing another embodiment of the method for manufacturing a sheet glass of the present invention.
  • FIG. 10a is a schematic cross-sectional view showing another embodiment of the method for manufacturing a sheet glass of the present invention
  • FIG. 10b is a plan view of the same.
  • FIG. 11a is a schematic cross-sectional view showing a conventional method
  • FIG. 11b is a partially enlarged view of a cross section taken along line BB of FIG. 11a.
  • FIG. 12 is a cross-sectional view showing the scratch generation test apparatus used in the examples. Preferred embodiments of the invention
  • the glass sheet having the protective coating of the present invention is preferably a glass sheet on a line at an outlet of a molding furnace for a float glass sheet production line including a glass melting step, a forming step and a slow cooling step, an inlet of a slow cooling furnace or in a slow cooling furnace.
  • a gas for forming a protective film on the body a protective film for preventing the glass body from being scratched is formed.
  • This gas may be sulfurous acid gas.
  • Sulfurous acid gas forms a protective film of sulfate such as sodium sulfate on the surface of the glass body by reacting with the constituents of glass and the like.
  • the sulfate is preferably a sulfate of an Algari metal or an alkaline earth metal, and more preferably a group consisting of sodium sulfate, lithium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, and barium sulfate. At least one species selected from.
  • the film forming gas may be a gas other than the sulfurous acid gas that is reactive with the chemical components in the glass.
  • the carbonate of an alkali metal such as sodium carbonate and the carbonate of an alkaline earth metal can be formed.
  • a protective coating can also be formed.
  • the temperature of the glass body is preferably from 75 ° C to 200 ° C.
  • the inlet of the lehr, or the inside of the lehr the glass body has a temperature of 200 to 75 ° C.
  • the sulfate protective film must have a thickness that does not easily cause scratches in accordance with the hardness of the glass.
  • the amount of the protective film equivalent to sulfate per side of a 30 mm square plate glass (Hereinafter, it may be simply referred to as “the amount of applied protective film”.) The following ranges are preferable.
  • the protective coating weight is 1. Omg or more.
  • the protective film adhesion amount is 0.5 mg or more.
  • the amount of the protective film attached is preferably 0.4 mg or more.
  • the amount of protective coating applied to soda-lime glass is 1.5 mg or more, the amount of protective coating applied to aluminosilicate glass is 0.7 mg or more, and borosilicate glass is used. Is preferably 0.5 mg or more.
  • soda-lime glass does not have high hardness, it is preferable to use a protective coating of 2. Omg or more in order to reliably prevent scratches in the processing process.
  • the amount of sulfate attached becomes saturated as the amount of sulfurous acid gas sprayed increases, and the formation of a protective film of a certain amount or more is excessive and uneconomical to prevent minute scratches.
  • the amount is preferably equal to or less than the upper limit.
  • the amount of film-forming gas such as sulfurous acid gas used was minimized when forming the protective film, thereby preventing waste of raw material gas and protecting the environment. Above, the occurrence of scratches can be reliably prevented.
  • the sulfate coating amount of the sulfate coating formed by spraying sulfurous acid gas usually varies, and the above-mentioned protective coating coating amount is an average value.
  • the variation of each 30 Omm square sample is within ⁇ 40%, especially ⁇ 20% or less, with respect to the above-mentioned average protective coating amount.
  • the protective coating on both sides of the glass sheet.
  • soda lime float glass sheet (thickness 3mm)
  • sulfur dioxide gas was supplied to the inside of the annealing furnace and inside the glass body at 570 ° C and 450 ° C, respectively.
  • a glass sheet having a sulfate film formed with various amounts of adhesion was manufactured.
  • This flaw generation test device lays a sample plate glass 21 on sand 22 of a tray 23 containing sand (silica sand that has been subjected to particle size selection) 22 and shakes the tray 23 with a shaker 24.
  • the purpose of this study is to examine the degree of scratches caused by the friction between the sand 22 and the sheet glass 21. The number of scratches was counted on the front side (non-tin side of float glass) and the back side (tin side of float glass) for a sample measuring 300 mm square, and the results are shown in Table 1. .
  • the amount of sulfate film attached was determined by dissolving the film on the glass surface in pure water, measuring the amount of sulfate ions in the solution using the turbidity method of JIS K103, and determining the amount of sulfate ions in the solution. The amount of sulfate was converted into the amount of sodium and the amount of sulfate attached to the front surface and the back surface of the sample having a size of 30 mm square.
  • the number of scratches and the amount of sulfate attached were all average values of 10 samples.
  • Aluminosilicate glass float glass (thickness 2 mm in Example 8, thickness 1 mm in Example 9)
  • sulfurous acid gas was supplied at 500 ° C and 450 ° C in the same manner as in Example 1.
  • the glass body was sprayed, the amount of sulfate coating was measured and a flaw generation test was performed in the same manner as in Example 1, and the results are shown in Table 2.
  • Table 2
  • the aluminosilicate glass can obtain a good anti-scratch effect with a smaller amount of sulfate attached than the soda lime glass.
  • Porous silicate glass melted with a rutupo was cast, formed into a plate shape, and polished to prepare a sample having a thickness of 1.1 mm and a square of 100 mm.
  • the prepared sample was heated in an electric furnace at 600 ° C. for 30 minutes, and sulfuric acid gas was flowed into the furnace at a rate of 1 L / hr for 5 minutes.
  • the obtained sheet glass was subjected to measurement of the amount of sulfate coating adhered thereon and a flaw generation test in the same manner as in Example 1, and the results are shown in Table 3.
  • a gas spray nozzle is provided above, below or above Z, and a gas reactive with chemical components in the glass, such as sulfurous acid gas, is blown from the gas spray nozzle toward the lipon-like glass body 4.
  • a gas having a gas blowing portion over a length region substantially equal to the width of the ribbon-shaped glass body 4 conveyed by the roller 5 is used.
  • the blowing nozzle 11 extends above and / or below the ribbon-shaped glass body 4 (below in FIG. 1) in the width direction of the ripon-shaped glass body 4, and a gas supply pipe extends from the gas blowing nozzle 11. It is preferable to blow the reactive gas introduced from 10 toward the ribbon-shaped glass body 4.
  • the gas blowing nozzle 11 is provided on the side surface (the surface facing the rifon-like glass body) of the tubular nozzle body 12A. It is possible to use a nozzle 12 having a large number of gas discharge ports 12B arranged at intervals of. To form a more uniform protective coating, as shown in Figure 3a (top view) and Figure 3b (side view), the side of the tubular nozzle body 13A (the side facing the ribbon-shaped glass body) Alternatively, a nozzle 13 provided with a gas discharge slit 13B may be used. As shown in FIGS.
  • the nozzle 12 provided with a large number of gas discharge ports 12B can spray gas relatively uniformly across the width of the ribbon-shaped glass body. However, since the nozzle 12 does not discharge gas from the region between the adjacent gas discharge ports 12 B, the amount of the protective film deposited on the surface of the ribbon-shaped glass body corresponding to this portion is reduced. Tend.
  • a nozzle 13 provided with a slit 13B can blow a curtain-like uniform gas flow onto the ribo glass body, so that a very uniform protective coating is formed. Can be formed.
  • the discharge speed of the gas tends to vary depending on the position of the slit, that is, the distance from the gas supply pipe 10.
  • the nozzle 13 is connected between the outer pipe (nozzle body) 13A and the inner pipe 14A. It is also possible to adopt a double pipe structure and to arrange a plurality of gas discharge ports 14B side by side at 180 ° offset from the slits 13B of the outer pipe 13A on the side of the inner pipe 14A. . With such a nozzle 13, the reactive gas can be more evenly discharged from the slit 13B.
  • a nozzle 13 ′ in which rising walls 15 A and 15 B for rectification are provided at the edge of the slit 13 B of the outer tube 13 A may be used.
  • the amount of reactive gas required for forming the protective film can be reduced, and adverse effects on the facilities such as the annealing furnace due to the reactive gas can be prevented.
  • the amount of reactive gas leaking to the outside can be reduced, and the working environment can be prevented from deteriorating.
  • the reactive gas is blown onto the lipon-like glass body by providing a branch pipe 1OA in the gas supply pipe 10 and supplying an appropriate amount of the reactive gas. It may be diluted with spraying medium gas (hereinafter sometimes referred to as "diluent gas"). In this case, it is possible to increase the pressure of the gas blown onto the lipon-like glass body to increase the reaction efficiency between the reactive gas and the glass, and to form a more uniform protective film with a small amount of the reactive gas.
  • the nozzles shown in Figs. 5a, 5b, 6a, and 6b differ only in that the gas supply pipe 10 is provided with a branch pipe 1OA, as shown in Figs.
  • FIGS. 5a, 5b, 6a, and 6b members having the same functions as those in FIGS. 2a, 2b, 3a, and 3b are denoted by the same reference numerals.
  • air, nitrogen, carbon dioxide or the like can be used as the diluting gas.
  • an inert gas such as nitrogen is used as the dilution gas to prevent tin contamination due to the reaction between the dilution gas and tin in the float bath.
  • a mixed gas of nitrogen and hydrogen supplied in a float bath it is preferable to use.
  • the diluent gas When diluting a reactive gas with a diluent gas, if the amount of the diluent gas used is too small relative to the reactive gas, the effect of increasing the blowing gas pressure due to the use of the diluent gas cannot be sufficiently obtained. However, the concentration of the reactive gas becomes too low, and the reaction efficiency decreases. Therefore, it is preferable to use the diluent gas in a volume ratio of about 0.2 to 1.0 times the volume of the reactive gas.
  • the gas (reaction It is desirable that at least a portion of the neutralizing gas and / or the diluting gas be heated to a predetermined temperature in advance to prevent the ribbon-like glass body and the rollers from cooling.
  • the reactive gas and dilution gas are passed through a heater 17 containing a heating medium such as a heater 16 and then heated, and then sent to a gas spray nozzle. May be.
  • the reactive gas and the diluent gas are passed through the annealing furnace 3, the reactive gas and the diluting gas are heat-exchanged and heated in the annealing furnace 3, and then sent to the gas spray nozzle. Is also good.
  • the annealing furnace 3 is usually provided with a heating means and a cooling means for adjusting the temperature of the ripon glass body 4 conveyed by the rollers 5, for example, a reactive gas and a dilution gas are supplied to the cooling means. Heating can be performed by introducing and exchanging heat. In both cases shown in Figs. 7 and 8, the heated gas is sent to the gas spray nozzle through a pipe with heat retaining means to prevent the temperature of the heated gas from reaching the gas spray nozzle. You may.
  • the preheating temperature of such a blowing gas is appropriately determined depending on the location at which the gas is blown, that is, the temperature of the Ripon glass body to which the gas is blown.
  • the preheating temperature of the blowing gas is 600 to 500 ° C when the gas is blown onto the ribbon-like glass body in the shield layer, and when the gas is blown onto the ripon-like glass body at the entrance of the lehr.
  • the temperature is preferably 500 to 400 ° C., and 400 to 300 ° C. when spraying the ripon glass body at an intermediate position of the annealing furnace.
  • Preheating of such gas reduces the adverse effects of a drop in the temperature of the ribbon glass body when a reactive gas or reactive gas or diluent gas is blown in a shield layer where the temperature of the ribbon glass body is high. can do.
  • only one gas blowing nozzle may be provided, and a reactive gas or a reactive gas and a diluent gas may be blown from only one location onto the ribbon-like glass body.
  • a plurality of gas spray nozzles may be provided, and a reactive gas or a reactive gas and a diluent gas may be sprayed on a plurality of portions of the ribbon-shaped glass body.
  • a uniform protective coating can be formed with a small amount of reactive gas.
  • the number of gas blowing nozzles is not particularly limited, but it is not economically feasible to increase the number excessively. It is preferable to set the following.
  • the gas blowing nozzle is usually provided at a position of 5 to 30 cm above the rifon-like glass body or at a position of 5 to 50 cm below the ripon-like glass body.
  • the partition wall (the rising wall 18A, the rising wall 18A, 18 and a hanging wall 18 8, 18 B) are provided so as to avoid the lipon-like glass body 4 to be conveyed, and a gas blowing nozzle 19 is provided in the protective film forming area H defined by the partition wall.
  • a plurality of the protective films may be provided so that the protective film forming region H is filled with a reactive gas.
  • the reactive gas concentration in the protective film forming region H is increased, the reaction efficiency between the glass and the reactive gas is increased, and the reaction time between the reactive gas and the glass is increased.
  • the protective coating can be efficiently formed on both surfaces of the ribbon-shaped glass body 4.
  • the lipon-like glass body 4 is naturally gradually cooled in the insulated region H.
  • the annealing furnace of the float method is equipped with a heating means 3A and a cooling means 3B (a heat exchanger using cooling air) in the temperature range M where the glass on the upstream side is cooled from the strain point to the annealing point.
  • the glass body 4 is maintained at an appropriate temperature. After the strain point, the surface stress of the glass body 4 only needs to be smaller than the stress that breaks the glass body 4, and there is no particular problem even if such a partition wall is provided.
  • Fig. 10a cross-sectional view
  • Fig. 10b plane view, however, the Ripon-shaped glass body is not shown
  • a gas suction nozzle 21 is provided, and of the gas blown out from the gas blowing nozzle 20, the excess gas that does not reach the lipon-shaped glass body 4 is sucked by the gas suction nozzle 21 and discharged out of the system. May be.
  • the flow of reactive gas from the shield layer 2 to the float path 1 can also be prevented by setting the atmospheric pressure in the float bath 1 to be slightly higher than the atmospheric pressure in the shield layer 2. .
  • a temperature gradient in the transport direction of the ribbon-shaped glass body is usually set inside the annealing furnace. It is effective to combine the air flow that flows from the downstream to the upstream generated by the above, and eject the reactive gas near the surface of the ribbon-shaped glass body.
  • Such a method of the present invention can be applied to soda lime glass, PDP glass having a slower cooling region at a higher temperature, and the like.
  • This sulfate protective film specifically includes sodium sulfate, lithium sulfate, and sulfuric acid. It is formed of one or more of potassium, magnesium sulfate, calcium sulfate, strontium sulfate, and barium sulfate.
  • the protective film formed in the present invention is not limited to a sulfate film, and a protective film of a carbonate such as sodium carbonate is formed using a gas having a reactivity with a chemical component in glass, for example, carbon dioxide. You can also.
  • the nozzle used was 3 cm in diameter and 500 cm in length, and 100 gas outlets with a diameter of 2 mm were provided at equal intervals over the widthwise region of the rifon-like glass body. .
  • the amount of the protective coating (sulfate) deposited on the obtained glass sheet was examined. The results are shown in Table 4.
  • the amount of sulfate protective coating can be determined by dissolving the coating on the glass surface
  • the amount of sulfate ions in the solution was measured using the turbidimetric method of 103, and the amount of sulfate ions was converted to the amount of sodium sulfate.
  • the amount of salt adhered was used.
  • the amount of adhesion was an average value of 10 samples. Comparative Example 3
  • a protective coating was formed in the same manner as in Example 10 except that the conventional nozzle shown in Fig. 11 was used as the sulfurous acid gas spray nozzle, the amount of sulfate attached was examined in the same manner, and the results are shown in Table 4. Indicated.
  • the nozzle used had a diameter of 3.4 cm and a length of 350 cm, and its tip was located at the approximate center of the ribbon-shaped glass body in the width direction. Is discharged.
  • Table 4 shows that the present invention can form a protective film more efficiently than the conventional method.
  • the gas spray nozzle shown in Fig. 5 was used to supply sulfurous acid gas at the entrance to the lehr, 450 ° C from the position 20 cm above the ribbon-like glass body and 50 cm below the ribbon-like glass body. 100 NL / hr, respectively, for a total of 200 NL / hr.
  • the nozzle used had a diameter of 3.4 cm and a length of 500 cm, and 100 gas discharge ports of 2 mm in diameter were provided over the area in the width direction of the ribbon-shaped glass body. It is configured so that air is introduced as gas. The amount of air introduced was 30 NL / hr for 100 NL / hr for sulfurous acid gas per nozzle. With respect to the obtained plate glass, the amount of sulfate attached on the front surface (upper surface) and the back surface (lower surface) was examined in the same manner as in Example 10 and the results are shown in Table 5.
  • Table 5 shows that by diluting sulfurous acid gas with air, it is possible to form a protective film more efficiently.
  • the nozzle used had a diameter of 3.4 cm and a length of 500 cm, and 100 gas outlets with a diameter of 2 mm were provided at equal intervals across the width of the ribbon-shaped glass body. It is configured so that air is introduced from the branch pipe as dilution gas at the flow rate shown in Table 6.
  • the amount of sulfate attached on the back surface (lower surface) was examined in the same manner as in Example 10, and the maximum value and the minimum value of the amount of sulfate attached and the difference were determined. The results are shown in Table 6. .
  • the obtained plate glass was treated with 1% hydrofluoric acid, the appearance after the treatment was observed, and the results are shown in Table 6.
  • This sheet glass was treated in a hydrofluoric acid solution to perform AR (anti-reflection) processing by a liquid layer deposition method that forms a silica film on the surface. At this time, samples were collected three times every 8 hours, and the AR processing yield was checked for each time (300 samples). The results are shown in Table 6. Comparative Example 4
  • Sheet glass was manufactured in the same manner as in Example 12 except that the conventional nozzle shown in Fig. 11 was used as the gas spray nozzle, and the spray amount of sulfurous acid gas and diluent gas was set to the amount shown in Table 6.
  • Table 6 shows the variation in the amount of sulfate attached, the resistance to hydrofluoric acid due to hydrofluoric acid treatment, and the yield of AR processing.
  • the nozzles used were the same as those used in Comparative Example 3.
  • a gas blowing nozzle shown in Fig. 6 was used to supply sulfurous acid gas at the entrance of the lehr, and a repong-like glass body at 580 ° C from a position 5 cm below the ribbon-like glass body
  • the amount of spray shown in Table 7 was sprayed toward.
  • the nozzle used has an outer tube diameter of 3.4 cm, an inner tube diameter of 2.1 cm, and a length of 500 cm, and a gas discharge slit of lmm in width and 460 cm in length in the width direction of the ripon glass body.
  • the inner pipe is provided with 100 gas discharge ports having a diameter of 2 mm at regular intervals on the side of the outer pipe opposite to the side on which the slit is formed. It is configured so that air is introduced as a dilution gas from the branch pipe at the flow rate shown in Table 7.
  • both the sulfurous acid gas supplied to the gas spraying nozzle and the air as the diluting gas were previously heated to 460 ° C. by a heating means as shown in FIG.
  • the conventional nozzle shown in FIG. 11 was used as the sulfurous acid gas spray nozzle, and a protective film was formed in the same manner as in Example 13 except that the sulfuric acid gas was not preheated.
  • the results are shown in Table 7.
  • the nozzle used was 3.4 cm in diameter and 350 cm in length. The tip was located at the approximate center in the width direction of the rifon-like glass body, and the sulfur dioxide gas was passed through the 27 mm diameter opening at the tip. Is discharged.
  • Example 13 and Comparative Example 5 the gas was blown at 50 NL / hr at the inlet of the lehr, and the remaining gas was blown in the region where the temperature of the ribbon glass body in the lehr was 450 ° C. , Sulfurous acid gas spray amount, dilution gas spray amount and preheating temperature The conditions were as shown in Table 8, and the nozzle position was 50 cm below the ribbon-shaped glass body. Otherwise, a protective film was formed in the same manner as in Example 13 and Comparative Example 5, respectively. The sulfated amount of the obtained plate glass was measured in the same manner as in Example 10, and the results are shown in Table 8.
  • Tables 7 and 8 show that preheating the reactive gas allows the protective film to be formed more efficiently.
  • Example 14 a protective coating was formed in the same manner as in Example 14, except that a plurality of gas spray nozzles were provided in the lehr and the gas preheating temperature was set at 350 ° C. The obtained plate glass was examined for sulfate attachment amount in the same manner as in Example 10, and the results are shown in Table 9.
  • the gas blowing nozzles used were the same as those used in Example 14, and the installation positions of the nozzles were as shown in Table 9.
  • Table 9 shows that more efficient formation of the protective film can be achieved by increasing the number of gas spray nozzles in the ribbon glass body and dispersing the sulphite gas spray locations.
  • the nozzle used has an outer pipe diameter of 3.4 cm, an inner pipe diameter of 2.1 cm, and a length of 500 cm. It is provided over the region in the width direction of the glass body.
  • a gas discharge port having a diameter of 2 mm is provided at equal intervals on the side surface of the outer tube of the nozzle opposite to the slit forming side of the outer tube at 100 holes. This nozzle is configured so that dilution gas is introduced from the branch pipe.
  • both the sulfurous acid gas and the diluent gas supplied to the gas spray nozzle were heated to 530 ° C. in advance by a heating means as shown in FIG.
  • the pressure in the atmosphere in the float bath was 24.5 Pa, and the pressure in the shield layer was 17.6 Pa.
  • the obtained plate glass was examined for the amount of sulfate attached in the same manner as in Example 10, and the results are shown in Table 10.
  • Example 17 two conventional nozzles shown in FIG. 11 were used as gas blowing nozzles, and the temperature of the ribbon-like glass body was 60 cm, and the position 50 cm below the ripon-like glass body. Then, a protective film was formed in the same manner as in Example 8 except that two nozzles were arranged facing each other so as to protrude from a side portion of the ripon glass body, and only sulfuric acid gas at room temperature was sprayed from these nozzles. The obtained plate glass was examined for the amount of sulfate attached and the condition in the float path in the same manner as in Example 17, and the results are shown in Table 10.
  • the nozzle used had a diameter of 3.4 cm and a length of 150 cm. The tip of each nozzle was located at approximately one-third in the width direction of the rifon-like glass body. Sulfurous acid gas is discharged from the opening of mm.
  • a thin solid layer mainly composed of soot oxide suspended in water As is clear from Table 10, according to the present invention, tin contamination in the float path can be prevented, and an effective protective film can be formed.
  • the nozzle used had an outer tube diameter of 3.4 cm, an inner tube diameter of 2.1 cm, and a length of 500 cm, and a 1 ram wide, 460 cm long gas discharge slit with a ribbon-like glass body width. It is provided over the region in the direction.
  • the inner pipe of this nozzle has 100 gas outlets with a diameter of 2 mm at equal intervals on the side opposite to the slit forming side of the outer pipe. It is provided in.
  • This nozzle is configured so that air is introduced as dilution gas from the branch pipe.
  • the position of the ribbon glass body at 15 cm above the ribbon glass body at 480 ° C The temperature of the ribbon glass body at 15 cm above the ribbon glass body at the temperature of 430 ° C Ribbon
  • the position of the ribbon glass body 15 cm above the glass body at a temperature of 380 ° C The position of the ribbon glass body 30 cm below the ribbon glass body at a temperature of 480 ° C Ribbon glass body
  • the temperature of the ribbon-shaped glass body 30 cm below the lipon-shaped glass body is at a position of 4300 ° C.
  • the amount of sulfate attached on the front surface (upper surface) and the back surface (lower surface) and the variation thereof were examined. The results are shown in Table 11.
  • Example 18 a protective coating was formed in the same manner as in Example 1S, except that the gas blowing nozzle shown in FIG. 6 was used and the amount of the diluted gas sprayed was as shown in Table 11. .
  • the amount of attached nitrate and its variation were examined in the same manner as in Example 10, and the results are shown in Table 11.
  • a protective film was formed in the same manner as in Example 18 except that the conventional method was used as the protective film forming region in Example 18.
  • the obtained plate glass was examined for sulfate attachment amount and its variation in the same manner as in Example 10, and the results are shown in Table 11.
  • ADVANTAGE OF THE INVENTION According to this invention, generation
  • the present invention is suitable for flat glass products such as glass for liquid crystals, glass for disks, glass for solar cells, and glass for PDP (plasma display), which are not allowed to have fine defects on the glass surface. Can effectively prevent scratches and provide products with high commercial value with good yield.

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Abstract

Cette invention concerne un procédé de fabrication de verre à glace. Ce procédé de fabrication en continu consiste à vaporiser un gaz réactif sur la surface d'un corps de verre en cours de production pour y faire adhérer un film protecteur, lequel film protège efficacement le verre à glace contre les rayures lors des procédés de fabrication en continu, de transfert, de transport et de façonnage.
PCT/JP2001/011331 2000-12-26 2001-12-25 Verre a glace avec film protecteur et son procede de fabrication WO2002051767A1 (fr)

Priority Applications (1)

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JP2002552872A JPWO2002051767A1 (ja) 2000-12-26 2001-12-25 保護被膜を有する板ガラス及びその製造方法

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JP2000395406 2000-12-26
JP2000-395406 2000-12-26

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JP2007204295A (ja) * 2006-01-31 2007-08-16 Asahi Glass Co Ltd ディスプレイ基板用ガラス板及びその製造方法
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
WO2008004480A1 (fr) * 2006-07-07 2008-01-10 Asahi Glass Co., Ltd. Procédés destinés à produire un substrat de verre sans alcali
WO2008120535A1 (fr) * 2007-04-03 2008-10-09 Asahi Glass Company, Limited Procédé de production de verre plat, appareil servant à former une couche tampon de verre plat et équipement de production de verre plat
WO2009148141A1 (fr) * 2008-06-06 2009-12-10 旭硝子株式会社 Appareil et procédé de fabrication de glace
CN102092921A (zh) * 2009-12-14 2011-06-15 旭硝子株式会社 浮法玻璃的制造方法和制造装置
JP2011251893A (ja) * 2010-05-31 2011-12-15 Lg Chem Ltd フロートガラスのための徐冷装置及び方法
JP2012091952A (ja) * 2010-10-26 2012-05-17 Hoya Corp ガラスの表面処理法、ガラスの研磨方法および光学素子の製造方法。
JP2013063880A (ja) * 2011-09-20 2013-04-11 Nippon Electric Glass Co Ltd ガラス板
KR101305592B1 (ko) * 2011-07-20 2013-09-09 아사히 가라스 가부시키가이샤 플로트 유리의 제조 방법
WO2013172307A1 (fr) * 2012-05-16 2013-11-21 旭硝子株式会社 Procédé de production de verre à glace
WO2014077371A1 (fr) 2012-11-16 2014-05-22 旭硝子株式会社 Procédé de production de verre et appareil de production de verre
JP2014097916A (ja) * 2012-11-16 2014-05-29 Nippon Electric Glass Co Ltd 薄膜太陽電池用ガラス板及びその製造方法
KR101422162B1 (ko) 2010-06-29 2014-07-22 주식회사 엘지화학 플로트 유리 제조 장치 및 방법
WO2014157004A1 (fr) * 2013-03-26 2014-10-02 旭硝子株式会社 Procédé de production d'un produit de verre
WO2014167842A1 (fr) * 2013-04-08 2014-10-16 日本板硝子株式会社 Plaque de verre et son procédé de fabrication
JP2015160804A (ja) * 2014-02-27 2015-09-07 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ フロート板ガラスを製造するためのフロート法及びフロート板ガラス
WO2015174324A1 (fr) * 2014-05-12 2015-11-19 旭硝子株式会社 Rouleau de transport pour transporter du verre, procédé de fabrication de verre l'utilisant et dispositif de fabrication de verre.
WO2015194569A1 (fr) * 2014-06-20 2015-12-23 旭硝子株式会社 Plaque de verre et procédé de fabrication correspondant
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US10399894B2 (en) 2013-03-19 2019-09-03 Nippon Sheet Glass Company, Limited Glass sheet and method for producing glass sheet
KR20200130266A (ko) 2018-03-09 2020-11-18 에이지씨 가부시키가이샤 무알칼리 유리 기판
KR20200136263A (ko) * 2019-05-27 2020-12-07 주식회사 엘지화학 판유리 제조 장치
KR20200136262A (ko) * 2019-05-27 2020-12-07 주식회사 엘지화학 판유리 제조 장치
KR20200136264A (ko) * 2019-05-27 2020-12-07 주식회사 엘지화학 판유리 제조 장치
CN112830686A (zh) * 2021-01-21 2021-05-25 四川虹科创新科技有限公司 一种浮法玻璃表面硫膜控制装置及方法
WO2021149396A1 (fr) * 2020-01-20 2021-07-29 Ａｇｃ株式会社 Plaque de verre de silicate de lithium dotée de sulfate, plaque de verre de silicate de lithium et son procédé de production

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JP2007204295A (ja) * 2006-01-31 2007-08-16 Asahi Glass Co Ltd ディスプレイ基板用ガラス板及びその製造方法
KR101107369B1 (ko) * 2006-07-07 2012-01-19 아사히 가라스 가부시키가이샤 무알칼리 유리 기판의 제조 방법
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
WO2008004480A1 (fr) * 2006-07-07 2008-01-10 Asahi Glass Co., Ltd. Procédés destinés à produire un substrat de verre sans alcali
JP5239859B2 (ja) * 2006-07-07 2013-07-17 旭硝子株式会社 無アルカリガラス基板の製造方法
JP5157904B2 (ja) * 2006-07-07 2013-03-06 旭硝子株式会社 フラットパネルディスプレイ用ガラス基板の製造方法
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CN102351418A (zh) * 2006-07-07 2012-02-15 旭硝子株式会社 平板玻璃用玻璃基板
JP5223861B2 (ja) * 2007-04-03 2013-06-26 旭硝子株式会社 板ガラスの製造方法、板ガラスの緩衝層形成装置及び板ガラスの製造設備
WO2008120535A1 (fr) * 2007-04-03 2008-10-09 Asahi Glass Company, Limited Procédé de production de verre plat, appareil servant à former une couche tampon de verre plat et équipement de production de verre plat
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KR101503964B1 (ko) 2008-06-06 2015-03-18 아사히 가라스 가부시키가이샤 판유리의 제조 장치 및 판유리의 제조 방법
WO2009148141A1 (fr) * 2008-06-06 2009-12-10 旭硝子株式会社 Appareil et procédé de fabrication de glace
JP5387920B2 (ja) * 2008-06-06 2014-01-15 旭硝子株式会社 板ガラスの製造装置及び板ガラスの製造方法
CN102092921A (zh) * 2009-12-14 2011-06-15 旭硝子株式会社 浮法玻璃的制造方法和制造装置
TWI480238B (zh) * 2009-12-14 2015-04-11 Asahi Glass Co Ltd Production method and manufacturing apparatus of floating glass
JP2011121834A (ja) * 2009-12-14 2011-06-23 Asahi Glass Co Ltd フロートガラスの製造方法および製造装置
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US8769994B2 (en) 2010-05-31 2014-07-08 Lg Chem, Ltd. Annealing apparatus and method for float glass
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JP2013063880A (ja) * 2011-09-20 2013-04-11 Nippon Electric Glass Co Ltd ガラス板
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CN107543032A (zh) * 2017-10-18 2018-01-05 蚌埠中建材信息显示材料有限公司 一种超薄玻璃防划伤装置
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