WO2015115100A1 - ガラス板の製造方法及びガラス板 - Google Patents
ガラス板の製造方法及びガラス板 Download PDFInfo
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- WO2015115100A1 WO2015115100A1 PCT/JP2015/000378 JP2015000378W WO2015115100A1 WO 2015115100 A1 WO2015115100 A1 WO 2015115100A1 JP 2015000378 W JP2015000378 W JP 2015000378W WO 2015115100 A1 WO2015115100 A1 WO 2015115100A1
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- glass plate
- gas
- glass
- heat treatment
- dense structure
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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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B19/00—Arrangements or adaptations of ports, doors, windows, port-holes, or other openings or covers
- B63B19/02—Clear-view screens; Windshields
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/012—Tempering or quenching glass products by heat treatment, e.g. for crystallisation; Heat treatment of glass products before tempering by cooling
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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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/008—Other surface treatment of glass not in the form of fibres or filaments comprising a lixiviation step
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
Definitions
- the present invention relates to a glass plate manufacturing method and a glass plate.
- Patent Document 1 proposes a surface treatment method for obtaining a glass having a dense surface structure by bringing an acidic aqueous solution or vapor generated from the aqueous solution into contact with a glass surface having a temperature equal to or higher than the glass transition point. Has been.
- a glass plate having a dense structure formed by a conventional surface treatment method is subjected to heat treatment, for example, at the air cooling strengthening temperature (about 650 ° C.) of general soda lime glass. It has become clear that there is a problem that the dense structure is not maintained. That is, there has been a problem that the characteristics of the glass plate obtained by the dense structure are greatly changed by the heat treatment.
- an object of the present invention is to provide a glass plate having a dense structure, which can maintain the dense structure even when heat treatment is performed.
- the fact that the dense structure is maintained even by heat treatment may be expressed by the content that the dense structure has heat resistance.
- the present invention A method for producing a glass plate having a modified surface, A gas contact step of bringing hydrogen fluoride (HF) gas, hydrogen chloride (HCl) gas and water vapor into contact with at least one main surface of the glass plate; In the gas containing the hydrogen fluoride (HF) gas used in the gas contact step, the volume ratio of water vapor to the hydrogen fluoride (HF) gas (volume of water vapor / volume of HF gas) is 8 or more.
- a method for producing a glass plate is provided.
- the present invention further provides: A glass plate having a dense structure on at least one main surface,
- the etching rate of the principal surface when 50 ° C. and 0.1% by mass of hydrofluoric acid is used as an etching solution is ER (nm / min) before heat treatment,
- the glass plate was heated for 220 seconds until the temperature of the principal surface was from room temperature to the glass transition point of the glass plate + 95 ° C., and immediately after being naturally cooled at room temperature, 50 ° C. and 0.1% by mass.
- the gas contact step realizes both a treatment for forming a dense structure and a treatment for enhancing the heat resistance of the dense structure on at least one main surface of the glass plate. be able to. Therefore, according to the manufacturing method of the present invention, it is possible to manufacture a glass plate having a dense structure on at least one main surface and capable of maintaining the dense structure even when heat treatment is performed. .
- the glass plate of the present invention has a dense structure on at least one principal surface, and the principal surface has a low etching rate of less than 1.5 nm / min due to the dense structure in a state before being subjected to heat treatment. is doing. Furthermore, the change amount of the etching rate before and after the heat treatment is suppressed to be small on the main surface of the glass plate of the present invention. That is, the glass plate of the present invention can maintain the dense structure provided on the main surface even after heat treatment.
- FIG. 4 is a SEM photograph of the surface of the glass plate of Example 4.
- 10 is a SEM photograph of the surface of a glass plate of Comparative Example 6.
- 10 is a SEM photograph of the surface of a glass plate of Comparative Example 7.
- the manufacturing method of the glass plate of this embodiment is a method of manufacturing a glass plate having a modified surface, and hydrogen fluoride (HF) gas, hydrogen chloride is applied to at least one main surface of the glass plate.
- the gas containing HF gas used in the gas contact process is adjusted so that the volume ratio of water vapor to HF gas (volume of water vapor / volume of HF gas) is 8 or more.
- a smooth dealkalized layer is formed on the main surface of the glass plate in contact with HF gas. Further, in this gas contact step, water vapor having a volume 8 times or more that of HF gas is brought into contact with the main surface of the glass plate together with HF gas. By bringing such a gas having a high volume ratio of water vapor to HF gas into contact with the main surface, a dense structure can be formed in the portion where the dealkalization layer is formed. The mechanism by which the dealkalized layer and the dense structure are formed on the surface of the glass plate by such gas contact will be described later.
- the gas used in the first example of the gas contact step is a mixed gas containing HF gas, HCl gas and water vapor. That is, in the gas contact step, a mixed gas containing HF gas, HCl gas, and water vapor is brought into contact with at least one main surface of the glass plate.
- the mixed gas may be brought into contact with the surface of the glass plate only once, or in a plurality of times.
- the concentration of the HF gas contained in the mixed gas is preferably 0.5 to 6 vol%, more preferably 1 to 5 vol%.
- a substance that becomes HF during the reaction that is, a substance that generates HF as a result can also be used. If the concentration of the HF gas in the mixed gas is too high, formation of the uneven shape on the surface of the glass plate is promoted, and it may be difficult to form a dense structure. On the other hand, if the concentration of HF gas in the mixed gas is too low, dehydration condensation (details will be described later) contributing to the formation of a dense structure may not be sufficiently promoted.
- the concentration of HCl gas contained in the mixed gas is preferably 0.1 to 15 vol%, more preferably 0.2 to 5 vol%, and further preferably 0.25 vol% or more. If the concentration of the HCl gas is too high, handling of the mixed gas may require attention or damage to the equipment. On the other hand, if the concentration of HCl in the mixed gas is too low, it may be difficult to improve heat resistance. As the HCl contained in the mixed gas, a substance that becomes HCl during the reaction, that is, a substance that generates HCl as a result can also be used.
- the mixed gas further contains water vapor.
- the mixed gas needs to contain water vapor so that the volume ratio of water vapor to HF gas (volume of water vapor / volume of HF gas) is 8 or more.
- a mixed gas in which the volume of water vapor is 8 times or more the volume of HF gas a smooth dense structure (densified layer) can be formed without forming an uneven shape on the surface of the glass plate.
- alkali metal ions or alkaline earth metal ions contained in the glass water vapor in the mixed gas and protons (H + ), water (H 2 O) and water caused by moisture in the atmosphere and Ion exchange with oxonium ions (H 3 O + ) and the like is performed.
- the mixed gas all the remainder except the acid gas may be water vapor.
- the mixed gas may contain a gas other than HF gas and HCl gas.
- a gas other than HF gas and HCl gas for example, an inert gas such as N 2 or argon may be included as a dilution gas.
- the inventors of the present invention can form a dense structure on the surface of the glass plate as described above by bringing the mixed gas into contact with the surface of the glass plate, and can enhance the heat resistance of the dense structure. Is considered as follows.
- reaction formulas (1-1) and (1-2) When HF comes into contact with the glass surface, it breaks the Si—O bond, which is the basic structure of glass (the following reaction formulas (1-1) and (1-2)), or causes a dealkalization reaction. (Reaction formulas (2) and (3) below). By this dealkalization reaction, a dealkalization layer is formed on the surface of the glass plate. In these reactions, phenomena such as glass erosion and reprecipitation are also complicated.
- a dehydration condensation reaction (the following reaction formula (4)) in which silanol groups generated in the glass are dehydrated and bonded to each other occurs. Since the mixed gas used in the manufacturing method of the present embodiment includes water vapor having a volume of 8 times or more the volume of HF gas, the glass etching reaction by HF is suppressed, and the formation of the uneven shape is suppressed. The formation of the dense structure becomes dominant, and as a result, the dense structure is formed in the dealkalized layer formed on the glass plate. ⁇ Si-OH + HO-Si ⁇ ⁇ ⁇ Si-O-Si ⁇ + H 2 O (4)
- the dense structure formed on the main surface of the glass plate in this embodiment is referred to as “the glass plate has a dense structure on its main surface from the main surface of the glass plate. It is also possible to specify that the average value of the ratio of protons to Si (proton ratio) is less than 10 in a range up to a depth of 20 nm in the thickness direction (hereinafter, near the main surface).
- the Si—O bond which is the basic structure of glass, is cut by the action of HF, and silanol groups increase near the main surface of the glass plate. As a result, the number of protons near the main surface increases. Conceivable.
- the dense structure is formed by promoting the dehydration condensation of the silanol groups. Therefore, it can be determined that the density is higher as the dehydration condensation near the main surface is accelerated, that is, the proton ratio is smaller. Therefore, it is possible to express the degree of density in terms of proton ratio.
- the average value of the proton ratio in the vicinity of the main surface is less than 10 and that the main surface of the glass plate has a dense structure. The same applies to the following dense structures.
- the average value of proton ratio is calculated
- TOF-SIMS 5 manufactured by ION-TOF can be used.
- Bi 3+ ions are used as primary ions
- Cs + ions are used for sputtering.
- the Cs 2 H + peak area is the proton intensity
- the CsSi + peak area is the silicon intensity.
- the depth is obtained by measuring the depth after sputtering with a stylus profilometer and converting from the sputtering time. Next, an average value from the outermost surface to a depth of 20 nm is obtained from the profile in the depth direction of the ratio of the proton intensity to the silicon intensity.
- the dehydration condensation reaction of the dealkalized layer formed on the surface portion of the glass plate is further promoted to form a strong SiO 2 skeleton. As a result, it is considered that the heat resistance of the surface on which the dense structure of the glass plate is formed is improved.
- the gas contact process includes an HF gas contact process and an HCl gas contact process.
- a first gas that contains HF gas and does not contain acid gas other than HF gas is brought into contact with at least one main surface of the glass plate.
- a second gas containing HCl and not containing an acid gas other than HCl gas is brought into contact with at least one main surface of the glass plate.
- the order of the HF gas contact step and the HCl gas contact step is not particularly limited.
- the HCl gas contact step may be performed after the HF gas contact step, or the HF gas contact step may be performed after the HCl gas contact step.
- count of a HF gas contact process and a HCl gas contact process is not specifically limited, either. Therefore, for example, the HF gas contact step ⁇ the HCl gas contact step ⁇ the HCl gas contact step may be performed in this order.
- a dealkalized layer By bringing the first gas into contact with the surface of the glass plate, a dealkalized layer can be formed on the surface of the glass plate, and the surface part of the dealkalized layer can have a dense structure.
- the mechanism is considered to be the same as in the first example. That is, the reaction of the reaction formulas (1-1), (1-2), (2), (3) and (4), and the phenomenon such as erosion and reprecipitation of the glass complicated in these reactions It is considered that a dealkalized layer having a dense structure is formed on the surface of the plate.
- the concentration of the HF gas contained in the first gas is preferably 0.5 to 6 vol%, more preferably 1 to 5 vol%.
- a substance that becomes HF during the reaction that is, a substance that generates HF as a result can also be used. If the concentration of HF in the first gas is too high, the formation of uneven shapes on the surface of the glass plate is promoted, and it may be difficult to form a dense structure. On the other hand, if the concentration of HF in the first gas is too low, the dealkalization reaction may not proceed sufficiently.
- the first gas further contains water vapor.
- the first gas needs to contain water vapor so that the volume ratio of water vapor to HF gas (water vapor volume / HF gas volume) is 8 or more.
- a smooth dense structure densified layer
- the concentration of water vapor in the first gas is not particularly limited, but if the amount of water vapor is less than 8 times the amount of HF gas, the etching reaction of the glass with HF proceeds, so that irregularities are formed on the surface of the glass plate. May be. If such irregularities are present on the surface of the glass plate, dirt may adhere to the surface of the glass plate, or alkali passivation properties may be reduced, and alkali may easily flow out of the glass plate.
- all of the remaining gas except the acidic gas may be water vapor.
- the reaction that occurs when HF contacts the glass surface is the same as in the first example (the above reaction formulas (1-1), (1-2), (2), and (3)). .
- the first gas may contain a gas other than HF gas and water vapor.
- a gas other than HF gas and water vapor For example, an inert gas such as N 2 or argon may be included as a dilution gas.
- the HCl gas contact process is a process for improving the heat resistance of the dense structure formed in the HF gas contact process.
- the operation of the HCl gas in the second gas will be described. It is assumed that the dense structure formed on the surface of the glass plate in the HF gas contact process has a weak glass skeleton containing a large amount of silanol groups ( ⁇ Si—OH).
- the HCl gas used in the HCl gas contact step performed separately from the HF gas contact step promotes dehydration condensation of the dense structure portion to form a strong SiO 2 skeleton. As a result, the heat resistance of the dense structure is increased. It is thought to improve.
- the surface of the glass plate that is in contact with only the first gas has a glass structure in which many silanol groups remain, in other words, a glass skeleton containing a lot of water. It is conceivable that. It is thought that HCl gas has a catalytic action of dehydration condensation reaction. Therefore, it is considered that by exposing the surface of the glass plate to HCl gas, the dehydration condensation reaction proceeds efficiently in a shorter time and the heat resistance of the dense structure is improved.
- the concentration of the HCl gas contained in the second gas is preferably 0.1 to 15 vol%, more preferably 0.2 to 5 vol%, and even more preferably 0.25 vol% or more. If the concentration of HCl gas is too high, handling of the second gas may require attention or damage to the equipment. On the other hand, if the concentration of HCl in the second gas is too low, it may be difficult to improve heat resistance. As the HCl contained in the second gas, a substance that becomes HCl during the reaction, that is, a substance that generates HCl as a result can also be used.
- the second gas may or may not contain water vapor.
- the haze value may increase depending on the amount of water vapor. Therefore, it is desirable to appropriately adjust the amount of water vapor in the second gas according to characteristics such as a haze value required for the target glass plate.
- the second gas may contain a gas other than HCl gas and water vapor as long as it does not contain an acidic gas other than HCl gas.
- an inert gas such as N 2 or argon may be included as a dilution gas.
- the HCl gas contact step may be performed before or after the HF gas contact step.
- the influence of the HCl gas on the surface of the glass plate in the second gas contacted in the HCl gas contact step is HF. It is thought that it remains even after the dense structure is formed on the surface of the glass plate in the gas contact step. Therefore, even in this case, the heat resistance of the dense structure formed in the HF gas contact step can be improved by the HCl gas contact step.
- the HCl gas contact step is performed before the HF gas contact step, dehydration condensation is started first, so the HCl gas contact step is performed after the HF gas contact step. It is preferable that the HCl gas contact step is performed after the HF gas contact step because a dense structure may be less likely to be formed.
- the temperature of the glass plate to which the HF gas and the HCl gas are brought into contact is preferably in the range of glass transition point +40 to glass transition point + 120 ° C. More preferably, it is within the range of transition point +70 to glass transition point + 100 ° C.
- the contact time between the gas and the glass material is not particularly limited, but is preferably 2 to 8 seconds, for example, and more preferably 3 to 6 seconds.
- the contact time is too long, the formation of the uneven shape on the surface of the glass plate is promoted by the HF gas contained in the mixed gas or the first gas, and it may be difficult to form a dense structure.
- the contact time is too short, the dealkalization reaction with HF gas is insufficient, or the promotion of dehydration condensation with HCl gas is insufficient, which may result in insufficient formation of a dense structure. . Therefore, it is desirable to determine the contact time between the gas and the glass material in consideration of these circumstances. For example, when the mixed gas is divided into a plurality of times and brought into contact with the surface of the glass plate, the total processing time may be set within the above time range, for example.
- a glass plate can be obtained by cooling the glass plate which passed through the gas contact process.
- the cooling method is not particularly limited, and a cooling method implemented by a known glass plate manufacturing method can be used.
- the glass plate manufactured by the manufacturing method of this embodiment has both a dense structure and high heat resistance. Therefore, even when the manufactured glass plate is subjected to further heat treatment, the dense structure is maintained.
- the method for producing a glass plate of the present embodiment can be applied to the production of a glass plate by a float method, for example. That is, even if the gas contact process of the manufacturing method of the glass plate of this embodiment is implemented by making gas contact with at least one of the main surfaces of the glass plate in the state shape
- the glass material (molten glass) melted in the float kiln 11 flows out from the float kiln 11 to the float bath 12, and is a glass ribbon (glass material is formed into a plate shape.
- the glass ribbon solidified in the slow cooling furnace 13 is cut into a glass plate of a predetermined size by a cutting device (not shown).
- a predetermined number of spraying parts 16 are arranged in the float bath 12 at a predetermined distance from the surface of the glass ribbon 10 in a high temperature state on the molten tin 15. ing.
- a gas (a mixed gas containing HF gas and HCl gas, a first gas containing HF gas, or a first gas containing HCl gas) is continuously formed on the glass ribbon 10 from at least one of the blowing parts 16a to 16c. 2 gas) is supplied.
- the temperature of the glass ribbon 10 on the molten tin 15 passing through the vicinity of the spraying portions 16a to 16c is set within a range of 450 to 630 ° C.
- the step of cooling the glass plate is performed in the slow cooling furnace 13.
- the glass plate a known glass material having a glass composition to which the float method can be applied can be used.
- general soda lime glass and aluminosilicate glass can be used, and sodium is generally contained as a component.
- general clear glass or low iron glass can be used.
- molded is suitably determined according to the thickness of the glass plate to manufacture, it is not specifically limited.
- the thickness of the finally obtained glass plate is not particularly limited, but can be, for example, 0.3 to 25 mm.
- the surface of the glass plate is provided with the dealkalized layer having a dense structure with improved heat resistance only by performing a very simple treatment of bringing a specific gas into contact.
- a glass plate can be manufactured.
- the manufacturing method of this embodiment can also be implemented using the manufacturing line of the float process which is a continuous manufacturing method of a glass plate as above-mentioned.
- a glass plate provided with an alkali layer can be provided.
- the gas contact process is performed on one main surface of the glass plate.
- the present invention is not limited to this, and the gas contact process may be performed on both surfaces of the glass plate. Good. In this case, it is possible to produce a glass plate having a dense structure on both main surfaces and capable of maintaining the dense structure even when heat treatment is performed.
- the glass plate of this embodiment has a dense structure on at least one main surface.
- This dense structure is a structure that can be formed on the surface of a glass plate by the manufacturing method of Embodiment 1, for example, and has high heat resistance. Therefore, a dense structure can be maintained even when heat treatment is performed for the purpose of, for example, air cooling strengthening. Note that the dense structure, the mechanism by which it is formed, and the specification of the dense structure are as described in the first embodiment, and thus detailed description thereof is omitted here.
- the etching rate of the main surface in the case of using 0.1% by mass of hydrofluoric acid at 50 ° C. is defined as ER (nm / min) before heat treatment. Further, the glass plate of the present embodiment was heated for 220 seconds until the temperature of the main surface was from room temperature to the glass transition point of the glass plate + 95 ° C, and immediately after that, naturally cooled at room temperature, The etching rate of the main surface when 0.1% by mass of hydrofluoric acid is used as an etching solution is defined as ER (nm / min) after heat treatment. Further, the amount of change in the etching rate of the main surface by heat treatment is ⁇ ER (nm / min).
- a conventional glass plate having a dense structure formed on the surface by a conventional method cannot maintain the dense structure when exposed to a high temperature by a heat treatment or the like applied thereafter.
- the glass plate of this embodiment has high heat resistance to such an extent that the dense structure formed on the surface can be maintained. Therefore, since the glass plate of this embodiment can be used as a glass plate for heat treatment to be subjected to heat treatment, its application is wide.
- the heat treatment here may be, for example, a heat treatment for strengthening air cooling.
- the glass plate of this embodiment can be applied to various uses.
- glass plate for chemical strengthening glass plate subjected to chemical strengthening treatment
- high weather resistance glass plate glass plate for functional film generation (glass plate on which functional film is generated)
- glass plate for shower booth It can be applied to glass plates for ships.
- a glass plate for chemical strengthening is required to suppress warpage caused by chemical strengthening treatment by alkali ion substitution.
- the glass plate of this embodiment can suppress the generation
- the glass plate for these uses has a dense structure formed on the surface of the glass plate. It is preferable that the amount of alkali elution is smaller than that of the glass plate of the present embodiment, which has the same thickness and the same composition and has no dense structure on the surface. Moreover, since such a glass plate has little alkali elution amount, it is suitable also as a glass plate for functional film production
- generation of a functional film is not specifically limited, It can produce
- Examples of functional films that can be generated using this method include a low radiation film, heat ray reflective film, photocatalyst film, low reflective film, transparent conductive film, radio wave shielding film and ultraviolet / infrared cut film on the main surface of the glass plate. Can be generated.
- the functional film the low radiation film can reinforce the glass plate. Therefore, the glass plate on which such a functional film is generated is used for, for example, a glass plate for building provided with a strengthening standard. be able to.
- the strengthened low-emission film is produced, for example, by heating at a temperature in the vicinity of 700 ° C. for 3 to 5 minutes and then rapidly cooling at room temperature.
- Glass plate manufacturing method (Examples 1 to 4) A glass plate having a thickness of 4 mm was produced by the float process. First, the main glass composition is mass%, SiO 2 : 70.4%, Al 2 O 3 : 2.0%, CaO: 8.6%, MgO: 3.9%, Na 2 O: 13. The glass material prepared to be 6% and K 2 O: 1.2% was melted, and the glass material melted on the molten tin in the float bath was formed into a glass ribbon. The glass transition point of this glass material was 555 ° C.
- the surface of the glass plate is separately supplied with HF gas and HCl gas separately from the glass plate production line with respect to one main surface of the glass plate having a thickness of 4 mm obtained by cutting the glass ribbon. Sprayed on. That is, the first gas containing HF gas and water vapor and not containing HCl gas and the second gas containing HCl gas and no HF gas were separately sprayed on the glass plate offline.
- the order of gas spraying was the order of the first gas ⁇ the second gas.
- a transport mechanism 21 that transports the glass plate and a spraying unit 23 that can spray the gas onto the surface of the glass plate 22 being transported.
- the equipped apparatus 20 was used.
- the apparatus 20 was provided with a heating mechanism (not shown) that can heat the glass plate 22 to be conveyed.
- the glass plate 22 was in contact with a gas heated to 180 ° C. for a predetermined time while being heated to a predetermined temperature (within a range of 630 to 660 ° C.).
- Table 1 shows the processing conditions (components of the sprayed gas) in Examples 1 to 4, the volume ratio of water vapor to HF gas (H 2 O / HF), the temperature of the glass plate during gas contact, and the gas contact time. . Note that each gas blown, N 2 gas was used as a diluent gas. That is, the remainder other than the gas components shown in Table 1 was all N 2 gas.
- As the HCl gas 99.99% HCl gas was used.
- the HF gas was obtained by vaporizing 55% by mass of hydrofluoric acid.
- Example 5 to 11 The same apparatus 20 was used to spray a gas on a glass plate produced by the same method as in Examples 1 to 4. However, in Examples 5 to 11, instead of the first gas and the second gas, a mixed gas containing HF gas, HCl gas and water vapor was sprayed. Note that each gas blown, N 2 gas was used as a diluent gas. That is, the remainder other than the gas components shown in Table 1 was all N 2 gas. As the HCl gas, 99.99% HCl gas was used. The HF gas was obtained by vaporizing 55% by mass of hydrofluoric acid.
- etching rate of the main surface of the glass plate 50 degreeC and 0.1 mass% hydrofluoric acid were used as etching liquid.
- the glass plate was immersed in this etching solution, and the etching depth was measured every 5 minutes.
- the time for passing through the etching depth of 20 nm was determined by interpolation of the etching depth data at two points before and after.
- the etching rate (nm / min) when reaching 20 nm was calculated by dividing 20 nm by the determined time. The measurement of this etching rate was implemented with respect to the main surface of both the glass plate before heat processing, and the glass plate after heat processing.
- the etching amount was measured by applying a hydrofluoric acid-resistant mask agent to a part of the glass plate before etching and measuring the step formed after the etching.
- a film thickness meter manufactured by KLA Tencor, “Alpha Step 500” was used for measuring the level difference.
- the glass plates manufactured by the manufacturing methods of Examples 1 to 11 that satisfy all the conditions of the manufacturing method of the present invention have a low etching rate of less than 1.5 nm / min before heat treatment, and a dense structure is formed on the surface. It was. About the glass plate of Example 1 and 4, the SEM photograph (FIG. 3: glass plate of Example 1, FIG. 4: glass plate of Example 4) also has the dense structure where the surface is smooth. It was confirmed. Furthermore, the glass plates of Examples 1 to 11 were able to keep the amount of change in the etching rate due to the heat treatment as small as less than 4.0 nm / min.
- the glass plate produced by the production methods of Examples 1 to 11 was a glass plate having a dense structure and capable of maintaining the dense structure even after heat treatment.
- the average value of the proton ratio in the vicinity of the main surface was measured by the method described in Embodiment 1, the average value of the proton ratio was less than 10.
- the glass plates manufactured by the manufacturing methods of Comparative Examples 1 to 12 that do not satisfy the conditions of the manufacturing method of the present invention are glass plates that do not have a dense structure on the main surface, or dense on the main surface before heat treatment. Although it had a structure, it was a glass plate whose dense structure was not maintained by heat treatment.
- Example 1 and Comparative Example 1, Example 4 and Comparative Example 2 were all under the same conditions except for the presence or absence of HCl gas contact with the glass plate.
- the etching rate after the heat treatment increased more than that before the heat treatment, compared with the glass plates of Examples 1 and 4. This is presumably because the heat resistance of the dense structure could not be improved because the HCl gas was not contacted.
- the same can be confirmed by comparing the glass plates of Examples 6 and 7 with the glass plate of Comparative Example 8 and comparing the glass plate of Example 8 and the glass plate of Comparative Example 9.
- Example 2 the concentration of HCl gas to be contacted was lower than that of Example 1, but the amount of change in the etching rate was almost the same as Example 1, and the heat resistance of the dense structure was realized. Moreover, according to the comparison between Example 1 and Example 3, it is considered that the presence or absence of water vapor in the gas containing HCl gas does not significantly affect the heat resistance of the glass plate.
- the higher temperature of the glass plate at the time of gas contact is desirable. This is because the glass plate of Example 6 in which a gas is brought into contact with a glass plate at 660 ° C. has a smaller etching rate change than the glass plate of Example 8 in which a gas is brought into contact with a glass plate at 630 ° C. I understand that. Further, the glass plate of Example 8 in which the temperature of the glass plate satisfies the range of glass transition point + 40 to glass transition point + 120 ° C. has a change in etching rate as compared with the glass plate of Example 9 that does not satisfy the temperature range. The amount was small.
- Comparative Examples 6 and 7 in the gas containing HF gas, the volume of water vapor was less than 8 times the volume of HF gas. As a result, the glass plates of Comparative Examples 6 and 7 were smooth so as to be confirmed from the SEM photographs shown in FIGS. 5 and 6 (FIG. 5: Glass plate of Comparative Example 6 and FIG. 6: Glass plate of Comparative Example 7). The glass plate of Comparative Example 7 also had a high haze ratio. In addition, about the glass plate of the comparative examples 6 and 7, since it did not have a smooth surface, the measurement of the etching rate was not implemented.
- the glass plate of the present invention can maintain a dense structure provided on its main surface even after heat treatment.
- the glass plate of this invention can be used for various uses, such as a glass plate for chemical strengthening, a weather-resistant glass plate, a glass plate for functional film production
- the glass plate of this invention is suitable also as a glass plate for heat processing to which heat processing is performed, for example, for the purpose of air-cooling strengthening.
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Abstract
Description
改質された表面を有するガラス板を製造する方法であって、
ガラス板の少なくとも一方の主面に対して、フッ化水素(HF)ガス、塩化水素(HCl)ガス及び水蒸気を接触させるガス接触工程を含み、
前記ガス接触工程で使用される前記フッ化水素(HF)ガスを含むガスにおいて、フッ化水素(HF)ガスに対する水蒸気の体積比(水蒸気の体積/HFガスの体積)が8以上である、
ガラス板の製造方法を提供する。
少なくとも一方の主面に緻密構造を有するガラス板であって、
50℃、0.1質量%のフッ化水素酸をエッチング液として用いた場合の前記主面のエッチングレートを熱処理前ER(nm/min)とし、
前記ガラス板を、前記主面の温度が室温から前記ガラス板のガラス転移点+95℃になるまで220秒間かけて加熱し、その直後に室温で自然冷却した後に、50℃、0.1質量%のフッ化水素酸をエッチング液として用いた場合の前記主面のエッチングレートを熱処理後ER(nm/min)とし、かつ、
熱処理による前記主面のエッチングレートの変化量をΔER(nm/min)とした場合に、
熱処理前ER<1.5(nm/min)、及び
ΔER=熱処理後ER-熱処理前ER<4.0(nm/min)
を満たす、ガラス板を提供する。
本発明のガラス板の製造方法の実施形態について説明する。本実施形態のガラス板の製造方法は、改質された表面を有するガラス板を製造する方法であって、ガラス板の少なくとも一方の主面に対して、フッ化水素(HF)ガス、塩化水素(HCl)ガス及び水蒸気を接触させるガス接触工程を含む。なお、ガス接触工程で使用されるHFガスを含むガスは、HFガスに対する水蒸気の体積比(水蒸気の体積/HFガスの体積)が8以上となるように調整されている。
≡Si-O-Si≡ + HF ⇔ ≡Si-OH + F-Si≡ (1-1)
4HF + SiO2(glass) ⇔ SiF4↑ + 2H2O (1-2)
HF + H2O ⇔ H3O+ + F- (2)
≡Si-O-Na++ H3O++ F- ⇔ ≡Si-OH + H2O + NaF (3)
≡Si-OH + HO-Si≡ ⇒ ≡Si-O-Si≡ + H2O (4)
本発明のガラス板の実施形態について説明する。本実施形態のガラス板は、少なくとも一方の主面に緻密構造を有している。この緻密構造は、例えば、実施形態1の製造方法によってガラス板の表面に形成され得る構造であり、高い耐熱性を有する。したがって、例えば風冷強化等の目的で熱処理が施される場合でも、緻密構造を維持できる。なお、緻密構造及びそれが形成されるメカニズム、さらには緻密構造の特定については、実施形態1で説明したとおりであるため、ここでは詳細な説明を省略する。
熱処理前ER<1.5(nm/min)、及び、
ΔER=熱処理後ER-熱処理前ER<4.0(nm/min)
を満たす。すなわち、本実施形態のガラス板は、熱処理が施された後でもエッチングレートが低い表面状態、すなわち緻密構造を維持する。
(実施例1~4)
フロート法によって、厚さ4mmのガラス板を製造した。まず、主なガラス組成が、質量%で、SiO2:70.4%、Al2O3:2.0%、CaO:8.6%、MgO:3.9%、Na2O:13.6%、K2O:1.2%、となるように調合したガラス材料を溶融し、フロートバスの溶融錫上で溶融したガラス材料をガラスリボンへと成形した。なお、このガラス材料のガラス転移点は555℃であった。本実施例では、ガラスリボンを切断して得た厚さ4mmのガラス板の一方の主面に対し、ガラス板製造ラインとは別のラインで、HFガス及びHClガスを別々にガラス板の表面に吹付けた。すなわち、HFガス及び水蒸気を含みかつHClガスを含まない第1ガスと、HClガスを含みかつHFガスを含まない第2ガスとを別々に、オフラインでガラス板に吹付けた。ガスの吹付け順は、第1ガス→第2ガスの順であった。本実施例におけるガスの吹付けには、図2に示すような、ガラス板を搬送する搬送機構21と、搬送されているガラス板22の表面にガスを吹付けることができる吹付部23とを備えた装置20を用いた。装置20には、搬送されるガラス板22を加熱できる加熱機構(図示せず)が設けられていた。ガラス板22は、所定の温度(630~660℃の範囲内)に加熱された状態で、180℃に暖められたガスと所定の時間接触した。実施例1~4における処理条件(吹付けたガスの成分)、HFガスに対する水蒸気の体積比(H2O/HF)、ガス接触時のガラス板の温度、ガスの接触時間を表1に示す。なお、吹付けた各ガスには、希釈ガスとしてN2ガスが用いられた。すなわち、表1に示したガスの成分以外の残部は、全てN2ガスであった。HClガスには99.99%のHClガスを用いた。HFガスは、55質量%のフッ化水素酸を気化させたものであった。
実施例1~4と同じ方法で作製したガラス板に対して、同じ装置20を用いてガスの吹付けを行った。ただし、実施例5~11では、第1ガス及び第2ガスではなく、HFガス、HClガス及び水蒸気を含む混合ガスを吹付けた。なお、吹付けた各ガスには、希釈ガスとしてN2ガスが用いられた。すなわち、表1に示したガスの成分以外の残部は、全てN2ガスであった。HClガスには99.99%のHClガスを用いた。HFガスは、55質量%のフッ化水素酸を気化させたものであった。
実施例1~11と同じ方法で作製したガラス板に対して、同じ装置20を用いてガスの吹付けを行った。ただし、比較例12のガラス板にはガスの吹付けを行わなかった。実施例1~11と同様に、ガスの吹付けが行われた。各比較例における処理条件(吹付けたガスの成分)、HFガスに対する水蒸気の体積比(H2O/HF)、ガス接触時のガラス板の温度、ガスの接触時間を表1に示す。なお、吹付けた各ガスには、希釈ガスとしてN2ガスが用いられた。すなわち、表1に示したガスの成分以外の残部は、全てN2ガスであった。HClガスには99.99%のHClガスを用いた。HFガスは、55質量%のフッ化水素酸を気化させたものであった。
(熱処理前後のエッチングレートの測定)
実施例1~11と、比較例1~5及び8~12のガラス板について熱処理を実施し、熱処理前後のエッチングレート(熱処理前ER(nm/min)及び熱処理後ER(nm/min))を測定し、エッチングレートの変化量(ΔER(nm/min))を算出した。結果を表1に示す。ガラス板に対して実施した熱処理の方法、及び、エッチングレートの測定方法は、以下のとおりである。
実施例1~11及び比較例1~12のガラス板について、熱処理前に、ガードナー社製「ヘイズガードプラス」を用い、C光源を用いてヘイズ率を測定した。結果を表1に示す。
Claims (12)
- 改質された表面を有するガラス板を製造する方法であって、
ガラス板の少なくとも一方の主面に対して、フッ化水素(HF)ガス、塩化水素(HCl)ガス及び水蒸気を接触させるガス接触工程を含み、
前記ガス接触工程で使用される前記フッ化水素(HF)ガスを含むガスにおいて、フッ化水素(HF)ガスに対する水蒸気の体積比(水蒸気の体積/HFガスの体積)が8以上である、
ガラス板の製造方法。 - 前記ガス接触工程は、ガラス転移点+40~ガラス転移点+120℃の範囲内の温度を有するガラス板に対して実施される、
請求項1に記載のガラス板の製造方法。 - 前記ガス接触工程において、前記ガラス板の少なくとも前記一方の主面に対して、フッ化水素(HF)ガス、塩化水素(HCl)ガス及び水蒸気を含む混合ガスを接触させる、請求項1に記載のガラス板の製造方法。
- 前記ガス接触工程が、フッ化水素(HF)ガス接触工程と、塩化水素(HCl)ガス接触工程とを含み、
前記フッ化水素(HF)ガス接触工程では、フッ化水素(HF)ガス及び水蒸気を含みかつフッ化水素(HF)ガス以外の酸性ガスを含まない第1ガスを、前記ガラス板の少なくとも前記一方の主面に対して接触させ、
前記塩化水素(HCl)ガス接触工程では、塩化水素(HCl)ガスを含みかつ塩化水素(HCl)ガス以外の酸性ガスを含まない第2ガスを、前記ガラス板の少なくとも前記一方の主面に対して接触させる、
請求項1に記載のガラス板の製造方法。 - 少なくとも一方の主面に緻密構造を有するガラス板であって、
50℃、0.1質量%のフッ化水素酸をエッチング液として用いた場合の前記主面のエッチングレートを熱処理前ER(nm/min)とし、
前記ガラス板を、前記主面の温度が室温から前記ガラス板のガラス転移点+95℃になるまで220秒間かけて加熱し、その直後に室温で自然冷却した後に、50℃、0.1質量%のフッ化水素酸をエッチング液として用いた場合の前記主面のエッチングレートを熱処理後ER(nm/min)とし、かつ、
熱処理による前記主面のエッチングレートの変化量をΔER(nm/min)とした場合に、
熱処理前ER<1.5(nm/min)、及び
ΔER=熱処理後ER-熱処理前ER<4.0(nm/min)
を満たす、ガラス板。 - 前記ガラス板は、熱処理が施される熱処理用ガラス板であり、
前記熱処理が風冷強化のための熱処理である、
請求項5に記載のガラス板。 - 前記ガラス板は、化学強化処理が施される化学強化用ガラス板であり、
前記ガラス板の少なくとも前記主面に脱アルカリ層が形成されており、
前記脱アルカリ層の表面に前記緻密構造が形成されている、
請求項5に記載のガラス板。 - 前記ガラス板は、高耐候性ガラス板であり、
同一厚さ及び同一組成を有しかつ表面に緻密構造が形成されていないガラス板と比較してアルカリ溶出量が少ない、
請求項5に記載のガラス板。 - 前記ガラス板は、前記主面上に機能膜が生成される機能膜生成用ガラス板であり、
同一厚さ及び同一組成を有しかつ表面に緻密構造が形成されていないガラス板と比較してアルカリ溶出量が少ない、
請求項5に記載のガラス板。 - 前記機能膜は、スパッタリング法又は熱CVD法により生成される、
請求項9に記載のガラス板。 - 前記ガラス板は、シャワーブース用ガラス板であり、
同一厚さ及び同一組成を有しかつ表面に緻密構造が形成されていないガラス板と比較してアルカリ溶出量が少ない、
請求項5に記載のガラス板。 - 前記ガラス板は、船舶用ガラス板であり、
同一厚さ及び同一組成を有しかつ表面に緻密構造が形成されていないガラス板と比較してアルカリ溶出量が少ない、
請求項5に記載のガラス板。
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JPWO2016152848A1 (ja) * | 2015-03-25 | 2018-01-18 | 旭硝子株式会社 | ガラス板 |
CN109052977A (zh) * | 2018-08-13 | 2018-12-21 | 中国人民解放军陆军防化学院 | 一种微纳米缺陷玻璃表面的构建方法 |
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