WO2017115765A1 - 化学強化ガラスの製造方法 - Google Patents
化学強化ガラスの製造方法 Download PDFInfo
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- WO2017115765A1 WO2017115765A1 PCT/JP2016/088788 JP2016088788W WO2017115765A1 WO 2017115765 A1 WO2017115765 A1 WO 2017115765A1 JP 2016088788 W JP2016088788 W JP 2016088788W WO 2017115765 A1 WO2017115765 A1 WO 2017115765A1
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- glass
- glass plate
- producing chemically
- water vapor
- alkali
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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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
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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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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
-
- 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
- C03C23/0075—Cleaning of glass
Definitions
- the present invention relates to a method for producing chemically strengthened glass.
- Patent Document 1 describes that the surface strength of glass is dramatically improved without subjecting the glass surface after chemical strengthening treatment to etching treatment using polishing or hydrofluoric acid.
- Patent Document 1 a removal amount larger than the surface removal amount described in Patent Document 1 may be desired.
- an object of the present invention is to provide a method for producing chemically tempered glass capable of improving the amount of surface removal as compared with the prior art.
- the present inventors have found that the amount of glass removed can be dramatically improved by controlling the amount of water vapor during the chemical strengthening treatment, and the present invention has been completed.
- the present invention relates to the following ⁇ 1> to ⁇ 19>.
- ⁇ 1> preparing a glass plate containing alkali ions; Preparing an inorganic salt containing other alkali ions larger than the ionic radius of the alkali ions; A step of performing ion exchange between the alkali ions of the glass plate and the other alkali ions of the inorganic salt in an atmosphere having a dew point temperature of 20 ° C. or higher; Removing a portion of the surface of the ion-exchanged glass plate;
- the manufacturing method of the chemically strengthened glass characterized by including.
- ⁇ 2> The method for producing chemically tempered glass according to ⁇ 1>, wherein the ion exchange step is performed in an atmosphere having a dew point temperature of 30 ° C. or higher.
- ⁇ 3> The method for producing chemically tempered glass according to ⁇ 1> or ⁇ 2>, wherein the ion exchange step is performed in an atmosphere having a dew point temperature of 40 ° C. or higher.
- ⁇ 4> The method for producing chemically tempered glass according to any one of ⁇ 1> to ⁇ 3>, wherein the ion exchange step is performed in an atmosphere having a dew point temperature of 50 ° C. or higher. .
- ⁇ 5> The chemically tempered glass according to any one of ⁇ 1> to ⁇ 4>, wherein the ion exchange step is performed in an atmosphere in which the dew point temperature is equal to or lower than the temperature of the inorganic salt.
- ⁇ 6> The atmosphere in the ion exchange step is formed by introducing a gas containing water vapor from a water vapor supply unit into the space above the inorganic salt, and the amount of the gas containing water vapor is about 1 cm 3.
- the atmosphere in the ion exchange step is formed by introducing a gas containing water vapor into the inorganic salt from a bubbling portion, and the amount of the gas containing water vapor is supplied as water vapor per 1 cm 3.
- the step of preparing the inorganic salt includes K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO 3, Li 2 CO 3 , Rb 2 CO 3 , Cs 2 CO 3 , MgCO 3 , CaCO 3 , and The method for producing chemically tempered glass according to any one of ⁇ 1> to ⁇ 7>, wherein an inorganic salt containing at least one salt selected from the group consisting of BaCO 3 and potassium nitrate is prepared.
- the step of removing a part of the surface of the glass plate includes a step of bringing the ion-exchanged glass plate into contact with an acid.
- any one of the above items ⁇ 1> to ⁇ 8> The manufacturing method of the chemically strengthened glass as described in one.
- the step of removing a part of the surface of the glass plate further includes a step of bringing the glass plate into contact with an alkali after the step of bringing into contact with the acid.
- the method for producing chemically tempered glass according to ⁇ 10>, further comprising a step of washing the glass plate between the step of contacting with the acid and the step of contacting with the alkali. . ⁇ 12> The step ⁇ 1> to ⁇ 11>, further comprising a step of washing the glass plate between the step of ion exchange and the step of removing a part of the surface of the glass plate.
- the manufacturing method of the chemically strengthened glass as described in any one of these. ⁇ 13> The method for producing chemically tempered glass according to any one of ⁇ 10> to ⁇ 12>, further comprising a step of washing the glass plate after the step of contacting with the alkali. . ⁇ 14>
- the method for producing chemically tempered glass according to any one of ⁇ 9> to ⁇ 13>, wherein the step of contacting with the acid uses a solution having a pH of less than 7.
- ⁇ 16> The method for producing chemically tempered glass according to ⁇ 14>, wherein the solution having a pH of less than 7 is a strong acid.
- ⁇ 17> The method for producing chemically tempered glass according to any one of ⁇ 10> to ⁇ 16>, wherein the step of contacting with the alkali uses a solution having a pH of more than 7.
- ⁇ 18> The method for producing chemically tempered glass according to ⁇ 17>, wherein the solution having a pH exceeding 7 is a weak base.
- ⁇ 19> The method for producing chemically tempered glass according to ⁇ 17>, wherein the solution having a pH exceeding 7 is a strong base.
- FIG. 1 is a schematic diagram for explaining a ball-on-ring test method.
- FIG. 2 is a schematic view showing a process for producing chemically strengthened glass according to the present invention.
- FIG. 3 is a schematic diagram of an experimental system for forming an atmosphere in an ion exchange process.
- the method for producing chemically strengthened glass according to the present invention includes: (A) preparing a glass plate containing alkali ions; (B) preparing an inorganic salt containing another alkali ion larger than the ion radius of the alkali ion; (C) performing an ion exchange between the alkali ions of the glass plate and the other alkali ions of the inorganic salt in an atmosphere having a dew point temperature of 20 ° C. or higher; (D) removing a part of the surface of the ion-exchanged glass plate; It is characterized by including.
- Glass composition The glass used in the present invention only needs to contain alkali ions, and glass having various compositions can be used as long as it has a composition that can be strengthened by molding and chemical strengthening treatment. Among them, it is preferable to contain sodium, and specific examples include aluminosilicate glass, soda lime glass, borosilicate glass, lead glass, alkali barium glass, aluminoborosilicate glass, and the like.
- the method for producing the glass is not particularly limited, and a desired glass raw material is charged into a continuous melting furnace, and the glass raw material is heated and melted preferably at 1500 to 1600 ° C., clarified, and then supplied to a molding apparatus. It can be manufactured by forming into a plate shape and slowly cooling.
- various methods can be employed for forming the glass.
- various forming methods such as a down draw method (for example, an overflow down draw method, a slot down method and a redraw method), a float method, a roll-out method, and a press method can be employed.
- the float method is preferred in that cracks are likely to occur on at least a part of the glass surface, and the effects of the present invention are more prominent.
- the thickness of the glass is not particularly limited, but is usually preferably 5 mm or less, more preferably 3 mm or less, and even more preferably 1 mm or less for effective chemical strengthening treatment. Preferably, 0.7 mm or less is particularly preferable.
- the shape of the glass used in the present invention is not particularly limited.
- various shapes of glass such as a flat plate shape having a uniform plate thickness, a shape having a curved surface on at least one of the front surface and the back surface, and a three-dimensional shape having a bent portion can be employed.
- the composition expressed by mol% on the basis of oxide is SiO 2 2 to 50 to 74%, Al 2 O 3 to 1 to 10%, Na 2 O to 6 to 14%, K 2 O to 3 to 11%, MgO to 2 to 15%, CaO to 0 to 6% and ZrO 2 to 5%
- the total content of SiO 2 and Al 2 O 3 is 75% or less
- the total content of Na 2 O and K 2 O is 12 to 25%
- the content of MgO and CaO total the composition viewed in mole% of the glass (3) oxide basis is 7-15%
- the chemically strengthened glass of the present invention has an ion-exchanged compressive stress layer on the glass surface.
- the surface of glass is ion exchanged to form a surface layer in which compressive stress remains.
- alkali metal ions Li ions and / or Na ions
- other alkali ions Na ions and / or Na ions
- compressive stress remains on the surface of the glass, and the strength of the glass is improved.
- the chemical strengthening treatment is performed by bringing the glass containing an alkali ion into contact with the inorganic salt containing another alkali ion larger than the ion radius of the alkali ion contained in the glass to perform ion exchange. Is done. That is, the alkali ions contained in the glass are ion-exchanged with other alkali ions contained in the inorganic salt.
- the inorganic salt is an inorganic salt containing potassium nitrate (KNO 3 ), and further includes K 2 CO 3 , Na 2 CO 3 , KHCO 3, NaHCO 3, Li It is more preferable to contain at least one salt selected from the group consisting of 2 CO 3 , Rb 2 CO 3 , Cs 2 CO 3 , MgCO 3 , CaCO 3 , and BaCO 3 .
- the melting point of potassium nitrate is 330 ° C., and the melting point is below the strain point (usually 500 to 600 ° C.) of the glass to be chemically strengthened.
- salts excluding potassium nitrate (hereinafter sometimes referred to as “flux”) have a property of cutting a glass network represented by Si—O—Si bonds. Since the temperature at which the chemical strengthening treatment is performed is as high as several hundred degrees Celsius, the covalent bond between Si—O of the glass is appropriately broken at that temperature, and the density reduction treatment described later easily proceeds.
- the degree of breaking the covalent bond varies depending on the chemical composition treatment conditions such as the glass composition, the type of salt (flux) used, the temperature and time for the chemical strengthening treatment, but the four covalent bonds extending from Si. Of these, it is considered preferable to select conditions that are sufficient to break one or two bonds.
- a high-density compressive stress layer is formed by ion exchange between Na ions (or Li ions) on the glass surface and K ions (or Na ions) in the inorganic salt.
- Examples of the method of bringing the glass into contact with the inorganic salt include a method of applying a paste-like inorganic salt, a method of spraying an aqueous solution of an inorganic salt onto the glass, a method of immersing the glass in a salt bath of a molten salt heated to a melting point or higher Although possible, among these, the method of immersing in molten salt is desirable.
- the amount of the flux added is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, further preferably 1 mol% or more, and particularly preferably 2 mol% or more. Further, from the viewpoint of productivity, the saturation solubility or less of each salt is preferable. Addition in excess may lead to glass corrosion. For example, when K 2 CO 3 is used as the flux, it is preferably 24 mol% or less, more preferably 12 mol% or less, and particularly preferably 8 mol% or less.
- the inorganic salt may contain other chemical species as long as the effects of the present invention are not impaired.
- alkali salts such as sodium chloride, potassium chloride, sodium borate, potassium borate, etc.
- Examples include chlorides and alkali borates. These may be added alone or in combination of two or more.
- the molten salt can be produced by a known process.
- the inorganic salt is a molten salt containing potassium nitrate and a flux
- it can be obtained by preparing a potassium nitrate molten salt and then adding the flux to the potassium nitrate molten salt.
- it can be obtained by mixing potassium nitrate and a flux and then melting a mixed salt of the potassium nitrate and the flux.
- the molten salt used in the production method of the present invention preferably has a Na concentration of 500 ppm by weight or more, more preferably 1000 ppm by weight or more. It is more preferable that the Na concentration in the molten salt is 2000 ppm by weight or more because the low-density layer is easily deepened by the acid treatment step described later.
- concentration It is permissible until a desired surface compressive stress (CS) is obtained.
- the molten salt that has been subjected to the chemical strengthening treatment one or more times contains sodium eluted from the glass. Therefore, if the Na concentration is already within the above range, glass-derived sodium may be used as it is as the Na source. If the Na concentration is not sufficient, or if a molten salt not used for chemical strengthening is used, nitric acid is used. It can adjust by adding inorganic sodium salts, such as sodium.
- the density of the chemically strengthened glass gradually increases from the outer edge of the intermediate layer 30 (bulk) existing in the center of the glass toward the surface of the compressive stress layer. There is no clear boundary between 20 and 20 where the density changes rapidly.
- the intermediate layer is a layer present in the center of the glass and sandwiched between the compressive stress layers. Unlike the compressive stress layer, this intermediate layer is a layer that is not ion-exchanged.
- the chemical strengthening treatment (ion exchange step) in the present invention can be performed by the following procedure.
- the glass is preheated, and the above-mentioned molten salt is adjusted to a temperature at which chemical strengthening is performed.
- the preheated glass is immersed in the molten salt in the molten salt tank 27 for a predetermined time, the glass is pulled out of the molten salt and allowed to cool.
- shape processing according to a use, for example, mechanical processing, such as a cutting
- the preheating temperature of glass depends on the temperature immersed in the molten salt, but is generally preferably 100 ° C. or higher.
- the chemical strengthening temperature is preferably not more than the strain point of the glass to be tempered (usually 500 to 600 ° C.), particularly preferably 350 ° C. or more in order to obtain a higher compressive stress layer depth, shortening the processing time and forming a low density layer.
- 400 degreeC or more is more preferable, and 430 degreeC or more is further more preferable.
- the immersion time of the glass in the molten salt is preferably 1 minute to 10 hours, more preferably 5 minutes to 8 hours, and even more preferably 10 minutes to 4 hours. In such a range, a chemically strengthened glass excellent in the balance between strength and depth of the compressive stress layer can be obtained, which is preferable.
- the low-density layer formed in the step of contacting with an acid described later can be thickened.
- the low density layer can be removed. Therefore, by setting the thickness of the low density layer to be equal to or greater than the average depth of cracks and latent scratches existing on the glass surface, The cracks and latent scratches can be removed along with the removal. Therefore, the excellent surface strength of chemically strengthened glass can be achieved.
- the ion exchange process is performed in an atmosphere with a dew point temperature of 20 ° C or higher.
- the dew point is preferably 30 ° C or higher, more preferably 40 ° C or higher, further preferably 50 ° C or higher, and further preferably 60 ° C or higher.
- the dew point temperature (hereinafter, sometimes simply referred to as “dew point”) may be such that the dew point temperature at least near the interface of the molten salt is within the above range, and the vicinity of the interface is a region of 200 mm or less from the interface of the molten salt. Means the atmosphere.
- the dew point can be measured with a Vaisala DRYCAP® DMT346 dew point converter.
- the dew point in this specification is a value when it is considered that an equilibrium is established between the molten salt and the atmosphere in the vicinity of the molten salt interface.
- the dew point can be achieved by introducing water vapor into the molten salt and / or the atmosphere in the vicinity of the molten salt interface before and / or simultaneously with the ion exchange step.
- water vapor can be introduced into the atmosphere near the interface between the molten salt and / or the molten salt by adding a water vapor supply unit to the molten salt tank.
- water vapor itself supplied from the water vapor supply unit to the molten salt, a gas containing water vapor, and water (liquid) may be directly bubbled, and a gas containing water vapor or water vapor is introduced into the space above the molten salt. May be.
- water (liquid) itself dropwise onto the molten salt as long as no steam explosion occurs.
- the molten salt When introducing water vapor or a gas containing water vapor or water (liquid) (hereinafter, simply referred to as “water vapor”), the molten salt may or may not be stirred. Stirring is preferable in terms of shortening.
- the time from the introduction of water vapor, etc. until equilibrium is reached varies depending on the amount of gas or liquid to be introduced, the water vapor concentration, the method of introduction, etc., but it cannot be generally stated, but the dew point of the above atmosphere is stable and constant. Can be judged as having reached equilibrium.
- a gas that does not affect the chemical strengthening treatment can be used.
- a dry gas A such as air, nitrogen gas, carbon dioxide gas or the like is introduced into heated water 24.
- the gas B gas containing water vapor
- steam with high humidity.
- the water 24 used as a water vapor supply source it is preferable to use pure water such as ion-exchanged water from the viewpoint of suppressing scale accumulation on piping and the like.
- the water 24 is heated by, for example, a water bath using a water tank 25.
- steam can also be generated by heating water 24 itself with a boiler etc., for example.
- examples thereof include introducing gas B containing water vapor into (molten salt 26), or (3) introducing water (liquid) directly into inorganic salt (molten salt 26).
- the gas B containing water vapor into the space above the inorganic salt for example, water vapor supplied from a water vapor supply unit is sprayed on the inorganic salt or near the interface of the inorganic salt by spraying. There is a way to do it. It is preferable to introduce water vapor or the like by spraying because the water vapor concentration in the space above the inorganic salt can be controlled almost uniformly.
- a water vapor supply unit, a bubbling unit, an introduction unit for introducing water (liquid) or a spray may be appropriately provided according to the apparatus, and is not particularly limited.
- the spray may be singular or plural.
- spraying water vapor or the like with a plurality of sprays makes it easier to control the water vapor concentration in the space above the inorganic salt substantially uniformly.
- the amount of water vapor supplied in the gas introduced per 1 cm 3 is preferably 0.01 mg / min or more, and more preferably 0.02 mg / min or more.
- the flow rate of water introduced per 1 cm 3 is preferably 0.01 mg / min or more, and more preferably 0.02 mg / min or more.
- the amount of water vapor supplied in the gas introduced per 1 cm 3 is preferably 0.01 mg / min or more, and 0.02 mg / min or more. Is more preferable.
- hydroxide ions are ions that promote cutting of the glass network, it is considered that formation of a low density layer on the glass surface is promoted by generating more hydroxide ions.
- the sum of the carbonate anion concentration and the hydrogen carbonate anion concentration obtained by the following formula in the inorganic salt is preferably 4 mol% or more, more preferably 6 mol% or more. It is preferable that the concentration is 4 mol% or more because the low-density layer forming reaction on the glass surface can be promoted.
- ⁇ (Carbonate anion concentration) + (hydrogen carbonate anion concentration) ⁇ (mol%) ⁇ (amount of carbonate anion in inorganic salt) + (amount of hydrogen carbonate anion in inorganic salt) ⁇ (mol) / (in inorganic salt) Total anion) (mol) x 100
- the sum of the carbonate anion concentration and the bicarbonate anion concentration is less than or equal to the sum of the saturated carbonate anion concentration and the saturated bicarbonate anion concentration.
- the low-density layer is formed in the step of contacting the acid among the steps of removing a part of the surface of the glass plate described later, but the thickness is 100 to 200 nm in the conventional ion exchange step without introducing water vapor. On the other hand, the thickness can be increased to 300 nm or more by introducing water vapor and performing ion exchange in an atmosphere having a dew point temperature of 20 ° C. or higher.
- the thickness of the low density layer is more preferably 500 nm or more, and 600 nm or more. Is more preferable.
- the formed low density layer can be removed by a step of contacting with an alkali described later in the step of removing a part of the surface of the glass plate. Therefore, if the depths of the cracks and latent scratches on the glass surface are all shallower than the thickness of the low-density layer, all the cracks and latent scratches can be removed in the step of contacting with alkali.
- the surface strength of the chemically strengthened glass can be increased by removing cracks and latent scratches on the glass surface that cause a decrease in strength in the chemically strengthened glass.
- the manufacturing method according to the present invention preferably further includes a step of washing the glass plate between the step of ion exchange and the step of removing a part of the surface of the glass plate.
- the glass is cleaned using industrial water, ion-exchanged water or the like. Use the treated water if necessary. Of these, ion-exchanged water is preferred.
- washing conditions vary depending on the washing solution used, but when ion-exchanged water is used, washing at 0 to 100 ° C. is preferable from the viewpoint of completely removing the attached salt.
- various methods such as a method of immersing chemically tempered glass in a water tank containing ion-exchanged water, a method of exposing the glass surface to running water, a method of spraying a cleaning liquid toward the glass surface by a shower, etc. Can be used.
- Step of removing part of the surface of the glass plate The ion exchanged glass plate is subjected to a step of removing a part of the surface of the glass plate.
- the step of removing a part of the surface of the glass plate preferably includes a step of bringing the glass plate into contact with an acid, and further includes a step of bringing the glass plate into contact with an alkali after the step of contacting the acid. preferable.
- Step of contacting with acid In the production method according to the present invention, after the ion exchange step or the washing step, as a step of removing a part of the surface of the glass plate, a step of bringing the glass into contact with an acid (acid treatment step) is performed. preferable.
- the acid treatment of glass is performed by immersing chemically tempered glass in an acidic solution, whereby Na and / or K on the surface of chemically tempered glass can be replaced with H. That is, the surface of the glass further has a low-density layer in which the surface layer of the compressive stress layer is altered, specifically, the density is reduced.
- the solution is not particularly limited as long as it is acidic, and may be less than pH 7.
- the acid used may be a weak acid or a strong acid.
- acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid and citric acid are preferred. These acids may be used alone or in combination.
- the temperature at which the acid treatment is performed varies depending on the type, concentration, and time of the acid used, but is preferably 100 ° C. or less.
- the acid treatment time varies depending on the type, concentration, and temperature of the acid used, but is preferably 10 seconds to 5 hours from the viewpoint of productivity, and more preferably 1 minute to 2 hours.
- the concentration of the solution used for the acid treatment varies depending on the type of acid used, the time, and the temperature, but is preferably a concentration at which there is little concern about container corrosion, and specifically 0.1 to 20% by weight.
- the glass surface is more easily removed as the low density layer is thicker.
- the thickness of the low density layer is as described above, it is preferably 300 nm or more, more preferably 500 nm or more, and further preferably 600 nm or more from the viewpoint of the glass surface removal amount.
- the density of the low density layer is preferably lower than the density of the region (bulk) deeper than the ion-exchanged compressive stress layer from the viewpoint of glass surface removability.
- the thickness of the low density layer can be determined from the period ( ⁇ ) measured by the X-ray reflectivity method (X-ray-Reflectometry: XRR).
- the density of the low density layer can be determined from the critical angle ( ⁇ c) measured by XRR.
- Step of contacting with alkali In the production method of the present invention, it is preferable to further perform a step of contacting with an alkali (alkali treatment step) after a step of contacting with an acid. More preferably, after the step of contacting with an acid, before the step of contacting with an alkali, a step of washing the same glass plate as the step of washing described above is performed.
- Alkali treatment is performed by immersing chemically tempered glass in a basic solution, whereby a part or all of the low density layer formed in the step of contacting with the acid can be removed.
- the solution is not particularly limited as long as it is basic, and may have a pH exceeding 7, and a weak base or a strong base may be used.
- bases such as sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate are preferred. These bases may be used alone or in combination.
- the temperature at which the alkali treatment is performed varies depending on the type, concentration and time of the base used, but is preferably 0 to 100 ° C, more preferably 10 to 80 ° C, and particularly preferably 20 to 60 ° C. If it is this temperature range, there is no possibility that glass will corrode and it is preferable.
- the alkali treatment time varies depending on the type, concentration and temperature of the base used, it is preferably 10 seconds to 5 hours from the viewpoint of productivity, and more preferably 1 minute to 2 hours.
- the concentration of the solution used for the alkali treatment varies depending on the type of base used, the time, and the temperature, but is preferably 0.1% by weight to 20% by weight from the viewpoint of glass surface removability.
- the alkali treatment a part or all of the low density layer into which H has invaded is removed, whereby a chemically strengthened glass having improved surface strength can be obtained.
- the thickness of the low density layer can be made deeper than the depth of cracks and latent scratches existing on the glass surface. Therefore, it is considered that cracks and latent scratches existing on the glass surface can be removed together with the low-density layer, and the glass surface strength is further improved.
- the method for producing chemically tempered glass according to the present invention since the low density layer can be formed deeper than the conventional chemical tempering treatment, the surface layer of the chemically tempered glass obtained after removing the low density layer is used. Less cracks and latent damage. Therefore, the chemically strengthened glass obtained by the present invention has a very high surface strength.
- Glass surface strength The surface strength of chemically strengthened glass can be evaluated by a ball-on-ring test.
- Chemically tempered glass is a state in which a glass plate is placed on a ring made of stainless steel having a diameter of 30 mm and a contact portion having a radius of curvature of 2.5 mm, and a sphere made of steel having a diameter of 10 mm is in contact with the glass plate,
- the sphere is evaluated by a BoR surface strength F (N) measured by a Ball on Ring (BoR) test in which the sphere is loaded at the center of the ring under a static load condition.
- the strengths of the first main surface and the second main surface both preferably satisfy F ⁇ 1500 ⁇ t 2 , more preferably F ⁇ 1800 ⁇ t 2 , and F ⁇ 2000 ⁇ t 2 More preferably, F is the BoR surface strength (N) measured by a ball-on-ring test, and t is the plate thickness (mm) of the glass substrate. ].
- F is the BoR surface strength (N) measured by a ball-on-ring test
- t is the plate thickness (mm) of the glass substrate.
- the BoR test can be performed by the method described in Examples described later.
- the compressive stress value of the compressive stress layer and the depth of the compressive stress layer of the chemically tempered glass can be measured using an EPMA (electron probe micro analyzer) or a surface stress meter (for example, FSM-6000 manufactured by Orihara Seisakusho). .
- EPMA electron probe micro analyzer
- surface stress meter for example, FSM-6000 manufactured by Orihara Seisakusho.
- the removal amount (thickness) of the glass surface (low-density layer) after the alkali treatment can be obtained by measuring the weight before and after the chemical treatment using an analytical electronic balance and converting the thickness using the following formula.
- (Removed thickness per side) [(weight before treatment) ⁇ (weight after treatment)] / (glass specific gravity) / treated area / 2 In this case, to calculate the glass density as 2.48 (g / cm 3).
- FIG. 1 is a schematic diagram for explaining the ball-on-ring test used in the present invention. With the glass plate 1 placed horizontally, the glass plate was pressed using a pressurizing jig 2 (hardened steel, diameter 10 mm, mirror finish) made of SUS304, and the surface strength of the glass plate was measured.
- a pressurizing jig 2 hardened steel, diameter 10 mm, mirror finish
- a glass plate as a sample is horizontally installed on a receiving jig 3 made of SUS304 (diameter 30 mm, contact portion curvature R2.5 mm, contact portion is hardened steel, mirror finish). Above the glass plate, a pressing jig for pressing the glass plate is installed.
- region of the glass plate was pressurized from the upper direction of the obtained glass plate.
- the test conditions are as follows. Pressure jig descending speed: 1.0 (mm / min)
- the breaking load (unit N) when the glass was broken was defined as the BoR surface strength
- the average value of 20 measurements was defined as the BoR average surface strength.
- the fracture start point of the glass plate was 2 mm or more away from the ball pressing position, it was excluded from the data for calculating the average value.
- the surface compressive stress value (CS, unit: MPa) of glass and the depth (DOL, unit: ⁇ m) of the compressive stress layer were measured using a surface stress meter (FSM-6000) manufactured by Orihara Seisakusho.
- the glass removal amount thickness was determined by measuring the weight before and after the chemical treatment with an analytical electronic balance (HR-202i; manufactured by AND) and converting the thickness using the following formula.
- (Removed thickness per side) [(weight before treatment) ⁇ (weight after treatment)] / (glass specific gravity) / treated area / 2 At this time, the glass specific gravity was calculated as 2.48 (g / cm 3 ).
- Example 1 (Ion-exchange process) Potassium nitrate 8454 g, potassium carbonate 1324 g, and sodium nitrate 222 g were added to a stainless steel (SUS) pot, and heated to 490 ° C. with a mantle heater to prepare a molten salt of 10 mol% potassium carbonate and 6000 ppm by weight sodium. Water vapor was included in the molten salt by flowing air introduced into water heated to 55 ° C. in an atmosphere near the interface of the molten salt.
- SUS stainless steel
- air is used as the dried gas A, and the air is humidified by passing the air through the water 24 heated to 55 ° C. by the water tank 25, and contains humidified water vapor.
- Gas (air) B was used.
- this gas B containing water vapor By introducing this gas B containing water vapor into the space above the inorganic salt (molten salt) 26 of the tank that performs the chemical strengthening treatment through the route heated by the ribbon heater, the dew point was controlled in the ion exchange process. . At this time, the amount of water vapor supplied per cm 3 was 0.02 mg / min, and the dew point near the interface of the molten salt was 38 ° C.
- Glass composition of glass plate A (expressed as mol% based on oxide): SiO 2 64.2%, Al 2 O 3 8.0%, Na 2 O 12.5%, K 2 O 4.0%, MgO 10 0.5%, CaO 0.1%, SrO 0.1%, BaO 0.1%, ZrO 2 0.5%
- Step of removing part of surface 1 step of contacting with acid
- 6.0% by weight of nitric acid nitric acid 1.38 (manufactured by Kanto Chemical Co., Inc.) was diluted with ion-exchanged water
- the glass obtained in the chemical strengthening step was immersed in the prepared nitric acid for 120 seconds to perform acid treatment. Thereafter, the glass was washed with water and subjected to the next step.
- Step 2 removing part of the surface: contacting with alkali
- a 4.0 wt% sodium hydroxide aqueous solution (48% sodium hydroxide solution (manufactured by Kanto Chemical Co., Inc.) was diluted with ion-exchanged water) was prepared in a beaker, and the temperature was adjusted to 40 ° C. using a water bath.
- the glass washed after the step of contacting with an acid was immersed in the prepared aqueous sodium hydroxide solution for 120 seconds to perform alkali treatment. Thereafter, the glass was washed with water to remove alkali on the glass surface. Then, it dried by air blow.
- the chemically strengthened glass of Example 1 was obtained. The presence of cracks and latent scratches was not confirmed in the obtained chemically strengthened glass.
- Example 2 Chemically strengthened glass as in Example 1, except that the potassium carbonate concentration of the molten salt in the ion exchange step was 8 mol%, the dew point near the interface of the molten salt was 71 ° C., and the chemical strengthening treatment condition was 450 ° C. for 2 hours. Manufactured. In addition, when the gas containing water vapor
- ⁇ Comparative Example 1> A chemically strengthened glass was produced in the same manner as in Example 2 except that the dew point in the vicinity of the interface of the molten salt in the ion exchange step was 9 ° C. In addition, the gas containing water vapor for dew point control was not introduced. The presence of cracks and latent scratches was not confirmed in the obtained chemically strengthened glass.
- ⁇ Comparative Example 2> A chemically tempered glass was produced in the same manner as in Comparative Example 1 except that potassium carbonate was not added to the molten salt in the ion exchange step, the sodium was 2000 ppm by weight, and no acid treatment and alkali treatment were performed. The presence of cracks and latent scratches was not confirmed in the obtained glass.
- Example 3> A chemically strengthened glass was produced under the same conditions as in Example 1 except that the glass plate B was used. The presence of cracks and latent scratches was not confirmed in the obtained chemically strengthened glass.
- a chemically strengthened glass was produced under the same conditions as in Example 2 except that the same glass as in Example 3 was used. The presence of cracks and latent scratches was not confirmed in the obtained chemically strengthened glass.
- ⁇ Comparative Example 3> A chemically strengthened glass was produced under the same conditions as in Comparative Example 1 except that the same glass as in Example 3 was used.
- Example 5 (Ion-exchange process) A chemically strengthened glass was produced under the same conditions as in Example 2 except that the glass plate C having a thickness of 0.55 mmt was used and the dew point near the interface of the molten salt was 66 ° C. The presence of cracks and latent scratches was not confirmed in the obtained chemically strengthened glass.
- Glass composition of glass plate C (expressed as mol% based on oxide): SiO 2 67%, B 2 O 3 4%, Al 2 O 3 13%, Na 2 O 14%, K 2 O ⁇ 1%, MgO 2 %, CaO ⁇ 1%
- Table 1 shows the processing conditions and evaluation results of the glass.
- the BoR average surface strength is shown as the BoR surface strength.
- Examples 1 to 5 and Comparative Examples 1 to 5 when a visual inspection was performed under a light source with an illuminance of 1500 Lux, the presence of cracks and latent scratches was not confirmed. However, as shown in Table 1, Examples 1 to 5 showed higher BoR surface strength F (N) than Comparative Examples 1 to 5.
- the step of removing a part of the surface of the ion-exchanged glass plate, together with the removal of the low-density layer, can sufficiently remove or reduce the number of cracks and latent scratches, and has a high BoR.
- the surface strength F (N) can be realized.
- chemically tempered glass having very high surface strength can be obtained without chemical etching and etching treatment using polishing or hydrofluoric acid. That is, it is possible to obtain a chemically strengthened glass excellent in surface strength that is free from appearance defects due to expansion of latent scratches due to etching treatment with hydrofluoric acid or the like and polishing scratches associated with polishing.
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Abstract
Description
<1>アルカリイオンを含むガラス板を準備する工程と、
前記アルカリイオンのイオン半径よりも大きい他のアルカリイオンを含む無機塩を準備する工程と、
露点温度が20℃以上の雰囲気で、前記ガラス板の前記アルカリイオンと前記無機塩の前記他のアルカリイオンとのイオン交換をする工程と、
前記イオン交換された前記ガラス板の表面の一部を除去する工程と、
を含むことを特徴とする化学強化ガラスの製造方法。
<2>前記イオン交換をする工程は、前記露点温度が30℃以上の雰囲気で行われることを特徴とする前記<1>に記載の化学強化ガラスの製造方法。
<3>前記イオン交換をする工程は、前記露点温度が40℃以上の雰囲気で行われることを特徴とする前記<1>または<2>に記載の化学強化ガラスの製造方法。
<4>前記イオン交換をする工程は、前記露点温度が50℃以上の雰囲気で行われることを特徴とする前記<1>~<3>のいずれか一つに記載の化学強化ガラスの製造方法。
<5>前記イオン交換をする工程は、前記露点温度が前記無機塩の温度以下の雰囲気で行われることを特徴とする前記<1>~<4>のいずれか一つに記載の化学強化ガラスの製造方法。
<6>前記イオン交換する工程における雰囲気は、水蒸気供給部から前記無機塩の上部の空間に水蒸気を含む気体が導入されることで形成され、前記水蒸気を含む気体の導入量は、1cm3あたりの水蒸気供給量が0.01mg/分以上であることを特徴とする前記<1>~<5>のいずれか一つに記載の化学強化ガラスの製造方法。
<7>前記イオン交換する工程における雰囲気は、バブリング部から前記無機塩の中に水蒸気を含む気体が導入されることで形成され、前記水蒸気を含む気体の導入量は、1cm3あたりの水蒸気供給量が0.01mg/分以上であることを特徴とする前記<1>~<5>のいずれか一つに記載の化学強化ガラスの製造方法。
<8>前記無機塩を準備する工程は、K2CO3、Na2CO3、KHCO3、NaHCO3、Li2CO3、Rb2CO3、Cs2CO3、MgCO3、CaCO3、及びBaCO3からなる群より選ばれる少なくとも一種の塩と硝酸カリウムとを含む無機塩を準備することを特徴する前記<1>~<7>のいずれか一つに記載の化学強化ガラスの製造方法。
<9>前記ガラス板の表面の一部を除去する工程は、前記イオン交換された前記ガラス板を酸に接触させる工程を含むことを特徴とする前記<1>~<8>のいずれか一つに記載の化学強化ガラスの製造方法。
<10>前記ガラス板の表面の一部を除去する工程は、前記酸に接触させる工程の後に前記ガラス板をアルカリに接触させる工程をさらに含むことを特徴とする前記<9>に記載の化学強化ガラスの製造方法。
<11>前記酸に接触させる工程と前記アルカリに接触させる工程との間に、前記ガラス板を洗浄する工程、をさらに含むことを特徴とする前記<10>に記載の化学強化ガラスの製造方法。
<12>前記イオン交換する工程と前記ガラス板の表面の一部を除去する工程との間に、前記ガラス板を洗浄する工程、をさらに含むことを特徴とする前記<1>~<11>のいずれか一つに記載の化学強化ガラスの製造方法。
<13>前記アルカリに接触させる工程の後に、前記ガラス板を洗浄する工程、を更に含むことを特徴とする前記<10>~<12>のいずれか一つに記載の化学強化ガラスの製造方法。
<14>前記酸に接触させる工程は、pH7未満である溶液を用いることを特徴とする前記<9>~<13>のいずれか一つに記載の化学強化ガラスの製造方法。
<15>前記pH7未満である溶液は、弱酸であることを特徴とする前記<14>に記載の化学強化ガラスの製造方法。
<16>前記pH7未満である溶液は、強酸であることを特徴とする前記<14>に記載の化学強化ガラスの製造方法。
<17>前記アルカリに接触させる工程は、pH7超である溶液を用いることを特徴とする前記<10>~<16>いずれか一つに記載の化学強化ガラスの製造方法。
<18>前記pH7超である溶液は、弱塩基であることを特徴とする前記<17>に記載の化学強化ガラスの製造方法。
<19>前記pH7超である溶液は、強塩基であることを特徴とする前記<17>に記載の化学強化ガラスの製造方法。
本発明に係る化学強化ガラスの製造方法は、
(a)アルカリイオンを含むガラス板を準備する工程と、
(b)前記アルカリイオンのイオン半径よりも大きい他のアルカリイオンを含む無機塩を準備する工程と、
(c)露点温度が20℃以上の雰囲気で、前記ガラス板の前記アルカリイオンと前記無機塩の前記他のアルカリイオンとのイオン交換をする工程と、
(d)前記イオン交換された前記ガラス板の表面の一部を除去する工程と、
を含むことを特徴とする。
本発明で使用されるガラスはアルカリイオンを含んでいればよく、成形、化学強化処理による強化が可能な組成を有するものである限り、種々の組成のものを使用することができる。中でもナトリウムを含んでいることが好ましく、具体的には、例えば、アルミノシリケートガラス、ソーダライムガラス、ボロシリケートガラス、鉛ガラス、アルカリバリウムガラス、アルミノボロシリケートガラス等が挙げられる。
(1)酸化物基準のモル%で表示した組成で、SiO2を50~80%、Al2O3を2~25%、Li2Oを0~10%、Na2Oを0~18%、K2Oを0~10%、MgOを0~15%、CaOを0~5%およびZrO2を0~5%を含むガラス
(2)酸化物基準のモル%で表示した組成が、SiO2を50~74%、Al2O3を1~10%、Na2Oを6~14%、K2Oを3~11%、MgOを2~15%、CaOを0~6%およびZrO2を0~5%含有し、SiO2およびAl2O3の含有量の合計が75%以下、Na2OおよびK2Oの含有量の合計が12~25%、MgOおよびCaOの含有量の合計が7~15%であるガラス
(3)酸化物基準のモル%で表示した組成が、SiO2を68~80%、Al2O3を4~10%、Na2Oを5~15%、K2Oを0~1%、MgOを4~15%およびZrO2を0~1%含有するガラス
(4)酸化物基準のモル%で表示した組成が、SiO2を67~75%、Al2O3を0~4%、Na2Oを7~15%、K2Oを1~9%、MgOを6~14%およびZrO2を0~1.5%含有し、SiO2およびAl2O3の含有量の合計が71~75%、Na2OおよびK2Oの含有量の合計が12~20%であり、CaOを含有する場合その含有量が1%未満であるガラス
(5)酸化物基準の質量%で表示した組成が、SiO2を65~75%、Al2O3を0.1~5%、MgOを1~6%、CaOを1~15%含有し、Na2O+K2Oが10~18%であるガラス
(6)酸化物基準の質量%で表示した組成が、SiO2を60~72%、Al2O3を1~10%、MgOを5~12%、CaOを0.1~5%、Na2Oを13~19%、K2Oを0~5%含有し、RO/(RO+R2O)が0.20以上、0.42以下(式中、ROとはアルカリ土類金属酸化物、R2Oはアルカリ金属酸化物を示す。)であるガラス
(7)酸化物基準のモル%で表示した組成が、SiO2を55.5~80%、Al2O3を12~20%、Na2Oを8~25%、P2O5を2.5%以上、アルカリ土類金属RO(ROはMgO+CaO+SrO+BaOである)を1%以上含有するガラス
(8)酸化物基準のモル%で表示した組成が、SiO2を57~76.5%、Al2O3を12~18%、Na2Oを8~25%、P2O5を2.5~10%、アルカリ土類金属ROを1%以上含有するガラス
(9)酸化物基準のモル%で表示した組成が、SiO2を56~72%、Al2O3を8~20%、B2O3を3~20%、Na2Oを8~25%、K2Oを0~5%、MgOを0~15%、CaOを0~15%、SrO2を0~15%、BaOを0~15%およびZrO2を0~8%含有するガラス
溶融塩は公知の工程により製造することができる。例えば無機塩が硝酸カリウムと融剤を含む溶融塩である場合、硝酸カリウム溶融塩を調製し、次いで該硝酸カリウム溶融塩へ融剤を添加することで得ることができる。また、別の方法として、硝酸カリウムと融剤を混合し、次いで該硝酸カリウムと融剤との混合塩を溶融することで得ることができる。
次に、調製した溶融塩を用いて化学強化処理を行う。化学強化処理は、ガラスを溶融塩に浸漬し、ガラス中のアルカリイオン(LiイオンまたはNaイオン)を、溶融塩中のイオン半径の大きい他のアルカリイオン(NaイオンまたはKイオン)とイオン交換(置換)することで行われる。このイオン交換によってガラス表面の組成を変化させ、ガラス表面が高密度化した圧縮応力層20を形成することができる[図2(a)~(b)]。このガラス表面の高密度化によって圧縮応力が発生することから、ガラスを強化することができる。
{(炭酸アニオン濃度)+(炭酸水素アニオン濃度)}(mol%)={(無機塩中の炭酸アニオン量)+(無機塩中の炭酸水素アニオン量)}(mol)/(無機塩中の全アニオン量)(mol)×100
本発明に係る製造方法では、イオン交換する工程とガラス板の表面の一部を除去する工程との間にガラス板を洗浄する工程をさらに含むことが好ましい。洗浄する工程では工水、イオン交換水等を用いてガラスの洗浄を行う。工水は必要に応じて処理したものを用いる。中でもイオン交換水が好ましい。
イオン交換されたガラス板は、該ガラス板の表面の一部を除去する工程に供される。ガラス板の表面の一部を除去する工程は、ガラス板を酸に接触させる工程を含むことが好ましく、前記酸に接触させる工程の後に、ガラス板をアルカリに接触させる工程をさらに含むことがより好ましい。
本発明に係る製造方法では、前記イオン交換する工程または前記洗浄する工程の後に、ガラス板の表面の一部を除去する工程として、ガラスを酸に接触させる工程(酸処理工程)を行うことが好ましい。
本発明の製造方法では、酸に接触させる工程を経た後、アルカリに接触させる工程(アルカリ処理工程)をさらに行うことが好ましい。酸に接触させる工程の後、アルカリに接触させる工程の前に、先述した洗浄する工程と同様のガラス板を洗浄する工程を経ることがより好ましい。
本発明に係る化学強化ガラスの製造方法によれば、従来の化学強化処理と比べて、低密度層をより深く形成できることから、該低密度層を除去した後に得られる化学強化ガラスの表層にはクラックや潜傷がより少ない。そのため、本発明により得られる化学強化ガラスは、非常に高い面強度を有する。
化学強化ガラスの面強度は、ボールオンリング試験により評価することができる。
化学強化ガラスは、ガラス板を直径30mm、接触部が曲率半径2.5mmの丸みを持つステンレスからなるリング上に配置し、該ガラス板に直径10mmの鋼からなる球体を接触させた状態で、該球体を静的荷重条件下で該リングの中心に荷重するボールオンリング(Ball on Ring;BoR)試験により測定したBoR面強度F(N)で評価する。
化学強化ガラスの圧縮応力層の圧縮応力値および圧縮応力層の深さは、EPMA(electron probe micro analyzer)または表面応力計(例えば、折原製作所製FSM-6000)等を用いて測定することができる。
アルカリ処理後のガラス表面(低密度層)の除去量(厚み)は、薬液処理前後の重量を分析用電子天秤により測定し、次の式を用いて厚み換算することにより求めることができる。
(片面あたりの除去量厚み)=[(処理前重量)-(処理後重量)]/(ガラス比重)/処理面積/2
このとき、ガラス比重を2.48(g/cm3)として計算する。
本実施例における各種評価は以下に示す分析方法により行った。
(ガラスの評価:面強度)
ガラス面強度はボールオンリング(Ball on Ring;BoR)試験により測定した。図1に、本発明で用いたボールオンリング試験を説明するための概略図を示す。ガラス板1を水平に載置した状態で、SUS304製の加圧治具2(焼入れ鋼、直径10mm、鏡面仕上げ)を用いてガラス板を加圧し、ガラス板の面強度を測定した。
加圧治具の下降速度:1.0(mm/分)
ガラスの表面圧縮応力値(CS、単位はMPa)および圧縮応力層の深さ(DOL、単位はμm)は折原製作所社製表面応力計(FSM-6000)を用いて測定した。
ガラスの除去量厚みは、薬液処理前後の重量を分析用電子天秤(HR-202i;AND製)により測定し、次の式を用いて厚み換算することにより求めた。
(片面あたりの除去量厚み)=[(処理前重量)-(処理後重量)]/(ガラス比重)/処理面積/2
このとき、ガラス比重を2.48(g/cm3)として計算した。
ガラス表面におけるクラックや潜傷の有無は、照度1500Luxの光源下で目視検査を行い、視認できる欠点がなければ、クラックや潜傷が存在しないと判断した。
(イオン交換する工程)
ステンレススチール(SUS)製のポットに硝酸カリウム8454g、炭酸カリウム1324g、硝酸ナトリウム222gを加え、マントルヒーターで490℃まで加熱して炭酸カリウム10mol%、ナトリウム6000重量ppmの溶融塩を調製した。溶融塩の界面近傍の雰囲気中に55℃に加熱した水中に導入した空気を流すことにより、溶融塩中に水蒸気を含ませた。
ガラス板Aのガラス組成(酸化物基準のモル%表示):SiO2 64.2%、Al2O3 8.0%、Na2O 12.5%、K2O 4.0%、MgO 10.5%、CaO 0.1%、SrO 0.1%、BaO 0.1%、ZrO2 0.5%
6.0重量%の硝酸(硝酸1.38(関東化学社製)をイオン交換水で希釈)をビーカーに用意し、ウォーターバスを用いて40℃に温度調整を行った。前記化学強化工程で得られたガラスを、調製した硝酸中に120秒間浸漬させ、酸処理を行った。その後、該ガラスは水洗いし、次の工程に供した。
4.0重量%の水酸化ナトリウム水溶液(48%水酸化ナトリウム溶液(関東化学社製)をイオン交換水で希釈)をビーカーに用意し、ウォーターバスを用いて40℃に温度調整を行った。酸に接触させる工程の後に洗浄したガラスを、調製した水酸化ナトリウム水溶液中に120秒間浸漬させ、アルカリ処理を行った。その後、該ガラスは水洗いしてガラス表面のアルカリを洗浄した。その後、エアブローにより乾燥した。
以上により、実施例1の化学強化ガラスを得た。
得られた化学強化ガラスにはクラック及び潜傷の存在は確認されなかった。
イオン交換する工程における溶融塩の炭酸カリウム濃度を8mol%とし、溶融塩の界面近傍の露点を71℃、化学強化処理条件を450℃で2時間とした以外は実施例1と同様に化学強化ガラスを製造した。なお、露点制御のために水蒸気を含む気体を導入した際の、1cm3当たりの水蒸気供給量は0.08mg/分であった。得られた化学強化ガラスにはクラック及び潜傷の存在は確認されなかった。
<比較例1>
イオン交換する工程における溶融塩の界面近傍の露点を9℃、とした以外は実施例2と同様に化学強化ガラスを製造した。なお、露点制御のための水蒸気を含む気体の導入は行わなかった。
得られた化学強化ガラスにはクラック及び潜傷の存在は確認されなかった。
<比較例2>
イオン交換する工程における溶融塩に炭酸カリウムを加えず、ナトリウム2000重量ppmとし、酸処理とアルカリ処理を行わない以外は比較例1と同様に化学強化ガラスを製造した。得られたガラスにはクラック及び潜傷の存在は確認されなかった。
ガラス板Bを用いた以外は実施例1と同様の条件で化学強化ガラスを製造した。得られた化学強化ガラスにはクラック及び潜傷の存在は確認されなかった。
ガラス板Bのガラス組成(酸化物基準のモル%表示):SiO2 68.0%、Al2O3 12.0%、Na2O 18.6%、MgO 8.0%
<実施例4>
実施例3と同様のガラスを用いた以外は、実施例2と同様の条件で化学強化ガラスを製造した。得られた化学強化ガラスにはクラック及び潜傷の存在は確認されなかった。
<比較例3>
実施例3と同様のガラスを用いた以外は、比較例1と同様の条件で化学強化ガラスを製造した。得られた化学強化ガラスにはクラック及び潜傷の存在は確認されなかった。
<比較例4>
実施例3と同様のガラスを用いた以外は、比較例2と同様の条件で化学強化ガラスを製造した。得られたガラスにはクラック及び潜傷の存在は確認されなかった。
(イオン交換する工程)
厚さ0.55mmtのガラス板Cを用いて、溶融塩の界面近傍の露点を66℃とした以外は、実施例2と同様の条件で化学強化ガラスを製造した。得られた化学強化ガラスにはクラック及び潜傷の存在は確認されなかった。
ガラス板Cのガラス組成(酸化物基準のモル%表示):SiO2 67%、B2O3 4%、Al2O3 13%、Na2O 14%、K2O <1%、MgO 2%、CaO<1%
実施例5と同様のガラスを用いた以外は、比較例2と同様の条件で化学強化ガラスを製造した。得られた化学強化ガラスにはクラック及び潜傷の存在は確認されなかった。
2 加圧治具
3 受け治具
10 低密度層
20 圧縮応力層
30 中間層
21 レギュレータ
22 フローメータ
23 逆止弁
24 水
25 水槽
26 溶融塩
27 溶融塩槽
Claims (19)
- アルカリイオンを含むガラス板を準備する工程と、
前記アルカリイオンのイオン半径よりも大きい他のアルカリイオンを含む無機塩を準備する工程と、
露点温度が20℃以上の雰囲気で、前記ガラス板の前記アルカリイオンと前記無機塩の前記他のアルカリイオンとのイオン交換をする工程と、
前記イオン交換された前記ガラス板の表面の一部を除去する工程と、
を含むことを特徴とする化学強化ガラスの製造方法。 - 前記イオン交換をする工程は、前記露点温度が30℃以上の雰囲気で行われることを特徴とする請求項1に記載の化学強化ガラスの製造方法。
- 前記イオン交換をする工程は、前記露点温度が40℃以上の雰囲気で行われることを特徴とする請求項1または2に記載の化学強化ガラスの製造方法。
- 前記イオン交換をする工程は、前記露点温度が50℃以上の雰囲気で行われることを特徴とする請求項1~3のいずれか1項に記載の化学強化ガラスの製造方法。
- 前記イオン交換をする工程は、前記露点温度が前記無機塩の温度以下の雰囲気で行われることを特徴とする請求項1~4のいずれか1項に記載の化学強化ガラスの製造方法。
- 前記イオン交換する工程における雰囲気は、水蒸気供給部から前記無機塩の上部の空間に水蒸気を含む気体が導入されることで形成され、前記水蒸気を含む気体の導入量は、1cm3あたりの水蒸気供給量が0.01mg/分以上であることを特徴とする請求項1~5のいずれか1項に記載の化学強化ガラスの製造方法。
- 前記イオン交換する工程における雰囲気は、バブリング部から前記無機塩の中に水蒸気を含む気体が導入されることで形成され、前記水蒸気を含む気体の導入量は、1cm3あたりの水蒸気供給量が0.01mg/分以上であることを特徴とする請求項1~5のいずれか1項に記載の化学強化ガラスの製造方法。
- 前記無機塩を準備する工程は、K2CO3、Na2CO3、KHCO3、NaHCO3、Li2CO3、Rb2CO3、Cs2CO3、MgCO3、CaCO3及びBaCO3からなる群より選ばれる少なくとも一種の塩と硝酸カリウムとを含む無機塩を準備することを特徴する請求項1~7のいずれか1項に記載の化学強化ガラスの製造方法。
- 前記ガラス板の表面の一部を除去する工程は、前記イオン交換された前記ガラス板を酸に接触させる工程を含むことを特徴とする請求項1~8のいずれか1項に記載の化学強化ガラスの製造方法。
- 前記ガラス板の表面の一部を除去する工程は、前記酸に接触させる工程の後に前記ガラス板をアルカリに接触させる工程をさらに含むことを特徴とする請求項9に記載の化学強化ガラスの製造方法。
- 前記酸に接触させる工程と前記アルカリに接触させる工程との間に、前記ガラス板を洗浄する工程、をさらに含むことを特徴とする請求項10に記載の化学強化ガラスの製造方法。
- 前記イオン交換する工程と前記ガラス板の表面の一部を除去する工程との間に、前記ガラス板を洗浄する工程、をさらに含むことを特徴とする請求項1~11のいずれか1項に記載の化学強化ガラスの製造方法。
- 前記アルカリに接触させる工程の後に、前記ガラス板を洗浄する工程、を更に含むことを特徴とする請求項10~12のいずれか1項に記載の化学強化ガラスの製造方法。
- 前記酸に接触させる工程は、pH7未満である溶液を用いることを特徴とする請求項9~13のいずれか1項に記載の化学強化ガラスの製造方法。
- 前記pH7未満である溶液は、弱酸であることを特徴とする請求項14に記載の化学強化ガラスの製造方法。
- 前記pH7未満である溶液は、強酸であることを特徴とする請求項14に記載の化学強化ガラスの製造方法。
- 前記アルカリに接触させる工程は、pH7超である溶液を用いることを特徴とする請求項10~16いずれか1項に記載の化学強化ガラスの製造方法。
- 前記pH7超である溶液は、弱塩基であることを特徴とする請求項17に記載の化学強化ガラスの製造方法。
- 前記pH7超である溶液は、強塩基であることを特徴とする請求項17に記載の化学強化ガラスの製造方法。
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