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WO2018062141A1 - 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 PDF

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Publication number
WO2018062141A1
WO2018062141A1 PCT/JP2017/034671 JP2017034671W WO2018062141A1 WO 2018062141 A1 WO2018062141 A1 WO 2018062141A1 JP 2017034671 W JP2017034671 W JP 2017034671W WO 2018062141 A1 WO2018062141 A1 WO 2018062141A1
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WIPO (PCT)
Prior art keywords
glass
chemical strengthening
inorganic salt
strength
acid treatment
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
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PCT/JP2017/034671
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English (en)
French (fr)
Japanese (ja)
Inventor
出 鹿島
祐輔 藤原
洋一 世良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
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Asahi Glass Co Ltd
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Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2018542579A priority Critical patent/JP6919658B2/ja
Priority to KR1020197008010A priority patent/KR102436191B1/ko
Priority to CN201780060568.4A priority patent/CN109803938B/zh
Publication of WO2018062141A1 publication Critical patent/WO2018062141A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface

Definitions

  • the present invention relates to a method for producing chemically strengthened glass.
  • a thin plate-like cover glass is formed so as to have a wider area than the image display portion in order to enhance display protection and beauty. Is placed in front of the display. Although glass has a high theoretical strength, the strength is greatly reduced due to scratches. Therefore, a chemically strengthened glass with a compressive stress layer formed on the glass surface by ion exchange or the like is used for the cover glass that requires strength. Yes.
  • the cover glass With the demand for weight reduction and thinning of flat panel display devices, it is also required to make the cover glass itself thinner. Accordingly, the cover glass is required to have further strength on the surface in order to satisfy its purpose.
  • Patent Document 1 discloses a method of performing acid treatment and alkali treatment after chemical strengthening with an inorganic salt containing a specific salt.
  • the depth of the compressive stress layer (defined as a depth at which the compressive stress value becomes zero, hereinafter referred to as DOC; Depth of Compression) is increased in order to obtain high strength.
  • DOC Depth of Compression
  • the surface strength is improved by polishing after the chemical strengthening treatment, but the glass surface may be damaged by the polishing, and the surface strength may be lowered. Furthermore, there is a possibility that the warping of the glass increases due to polishing.
  • the present invention does not limit the temperature condition and time for chemical strengthening, and does not weaken the strength of the glass even when chemical strengthening treatment is performed for a long time at a high temperature.
  • a method for producing tempered glass is provided.
  • the present inventors conducted a chemical strengthening step in which the pH of the salt used for chemical strengthening is in a predetermined range and an acid treatment step of acid-treating the glass after the chemical strengthening step.
  • the present invention is completed by finding that a chemically strengthened glass showing a deep DOC and a high surface strength can be obtained even if a chemical strengthening treatment is performed at a high temperature for a long time without limiting the temperature conditions and time for chemical strengthening. It came to.
  • the present invention is as follows. 1. Chemistry in which glass is brought into contact with an inorganic salt having a hydrogen ion index (pH) of 7.5 or more and 10.5 or less and containing at least one of sodium nitrate and potassium nitrate when ionized into a 10% by mass aqueous solution, and ion exchange is performed. Strengthening process, A method for producing chemically tempered glass, comprising: an acid treatment step in which the glass after the chemical tempering step is contacted with an acidic solution having a hydrogen ion index (pH) of less than 7.0. 2. 2. 2.
  • the method for producing chemically strengthened glass according to 1 or 2 wherein the chemical strengthening step is a step of bringing the glass into contact with the inorganic salt at 400 ° C. or higher for 2 hours or more for ion exchange. 4).
  • the surface strength F (N) measured by the ball-on-ring test under the following conditions is F ⁇ 1000 ⁇ t 2 with respect to the thickness t (mm) of the glass plate. 5.
  • the sphere is lowered at a descending speed of 1 mm / min and loaded onto the center of the ring, and the breaking load (unit N) when the glass plate is broken is defined as BOR strength.
  • the value is the surface strength F (N).
  • the fracture start point of the glass plate is 2 mm or more away from the load point of the sphere, it is excluded from the data for calculating the average value.
  • the glass is chemically strengthened using an inorganic salt having a pH within a predetermined range, so that the Si—O—Si bond of the glass is appropriately adjusted by OH ⁇ in the inorganic salt.
  • an inorganic salt having a pH within a predetermined range so that the Si—O—Si bond of the glass is appropriately adjusted by OH ⁇ in the inorganic salt.
  • the temperature condition and time for chemical strengthening are not limited, and even if chemical strengthening treatment is performed at a high temperature for a long time, deep DOC is exhibited and the surface strength is high. Chemically tempered glass can be easily obtained.
  • FIG. 1 (a) to 1 (d) are schematic views showing a process for producing chemically strengthened glass according to the present invention.
  • FIG. 2 is a schematic diagram for explaining a ball-on-ring test method.
  • FIG. 3A is an AFM image of a glass surface having surface polishing flaws
  • FIG. 3B is an AFM image of a glass surface having no surface polishing flaws.
  • FIG. 4A is a diagram illustrating a state where white clouding is not generated in the glass surface
  • FIG. 4B is a diagram illustrating a state where white clouding is generated in the glass surface.
  • 5A is the stress profile of the chemically strengthened glass obtained in Examples 1 and 3 and Comparative Example 1, FIG.
  • FIG. 5B is the stress profile of the chemically strengthened glass obtained in Examples 7 and 8 and Comparative Example 6, and FIG. The stress profile of the chemically strengthened glass obtained in Examples 10 and 11 and Comparative Example 11 is shown.
  • 6A and 6B show the results of evaluating the surface strength of the chemically strengthened glass obtained in Examples 1 and 5 and Comparative Examples 1, 4 and 5.
  • FIG. 7A and 7B show the results of evaluating the surface strength of the chemically strengthened glass obtained in Examples 7 and 8 and Comparative Example 6.
  • FIG. 8A and 8B show the results of evaluating the surface strength of the chemically strengthened glass obtained in Examples 10 and 11 and Comparative Example 11.
  • mass% and “wt%”, “mass ppm” and “weight ppm” have the same meaning.
  • ppm when “ppm” is simply described, it indicates “weight ppm”.
  • the hydrogen ion index (pH) when the aqueous solution is 10% by mass is 7.5 or more and 10.5 or less, and an inorganic salt containing at least one of sodium nitrate and potassium nitrate is glass.
  • Na in the glass and K in the inorganic salt are ion-exchanged to form a compressive stress layer on the glass surface, and the surface layer of the compressive stress layer is modified to lower the density. This is a step of forming a low density layer.
  • the inorganic salt has a hydrogen ion index (pH) of 7.5 or more, preferably 8.0 or more, and more preferably 8.5 or more when a 10% by mass aqueous solution is used. Further, the hydrogen ion index (pH) when the aqueous solution is 10% by mass is 10.5 or less, preferably 10.0 or less, and more preferably 9.5 or less.
  • the Si—O—Si bond of the glass is appropriately cut by OH ⁇ in the inorganic salt, and a low-density layer in which the surface layer of the compressive stress layer is modified on the glass surface is formed. can do.
  • the pH of the inorganic salt can be measured at 25 ° C. using a pH meter such as a handy type pH meter D-71S manufactured by Horiba.
  • the inorganic salt preferably contains at least one salt selected from the group consisting of KNO 2 , NaNO 2 , K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO 3 , KOH or NaOH.
  • the pH of the inorganic salt can be appropriately adjusted depending on the amount.
  • the inorganic salt contains at least one of sodium nitrate and potassium nitrate.
  • the inorganic salt By containing at least one of sodium nitrate and potassium nitrate in the inorganic salt, it becomes a molten state below the strain point of the glass, and handling becomes easy in a general temperature range when chemical strengthening treatment is performed.
  • sodium nitrate in the inorganic salt chemically strengthened glass having a large DOC can be obtained at a CTlimit value or less.
  • the CTlimit value is empirically known to be ⁇ 38.7 ⁇ ln (t) +48.2 [MPa].
  • t represents the plate thickness of the glass, and the unit is mm.
  • the content of sodium nitrate in the inorganic salt is preferably 1% by mass or more, more preferably 5% by mass or more.
  • the content of sodium nitrate in the inorganic salt refers to the sodium concentration of the liquid phase salt in which the inorganic salt is in a liquid state.
  • the content of sodium nitrate in the inorganic salt When the content of sodium nitrate in the inorganic salt is 1% by mass or more, it becomes a molten state below the strain point of the glass, and handling becomes easy in a general temperature range when chemical strengthening treatment is performed.
  • the content of sodium nitrate in the inorganic salt is determined by appropriately adjusting so as to obtain a desired surface compressive stress value (CS, unit is MPa).
  • 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 and potassium borate
  • examples include chlorides and alkali borates. These may be added alone or in combination of two or more.
  • the content of KNO 2 in the inorganic salt is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, and further preferably 0.6% by mass. % Or more. Moreover, 10.0 mass% or less is preferable, More preferably, it is 8.0 mass% or less, More preferably, it is 6.0 mass% or less.
  • the pH of the inorganic salt when the aqueous solution is 10% by mass can be 7.5 or more and 10.5 or less.
  • 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, and a method of immersing the glass in a salt bath of a molten salt heated to a melting point or higher. Although possible, in these, the method of immersing in molten salt is preferable.
  • the glass used in the method of the present invention may contain sodium as long as it contains sodium and has a composition that can be strengthened by molding and chemical strengthening treatment.
  • Specific examples include aluminosilicate glass, soda lime glass, borosilicate glass, lead glass, alkali barium glass, and aluminoborosilicate glass.
  • 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 produced by forming into a plate shape and slowly cooling it.
  • various methods can be adopted for forming the glass.
  • various forming methods such as a down draw method (for example, an overflow down draw method, a slot down method, a redraw method, etc.), a float method, a roll out method, and a press method can be adopted.
  • the thickness of the glass is not particularly limited, but is preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 1 mm or less in order to effectively perform the chemical strengthening treatment.
  • the shape of the glass used in the method of 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 glass composition used in the method of the present invention include the following glass compositions.
  • (Viii) expressed in mole percentages on the oxide basis, SiO 2 67-75%, Al 2 O 3 0-4%, Na 2 O 7-15%, K 2 O 1-9%, MgO 6 to 14% and 0 to 1.5% of ZrO 2 , the total content of SiO 2 and Al 2 O 3 is 71 to 75%, the total content of Na 2 O and K 2 O is 12 to Glass which is 20% and contains CaO when its content is less than 1%.
  • the glass is immersed in a molten salt of an inorganic salt in a molten salt bath, and metal ions (Na ions) in the glass are replaced with metal ions (K ions) having a large ionic radius in the molten salt. Done in By this ion exchange, the composition of the glass surface can be changed to form the compressive stress layer 20 having a high density on the glass surface [FIGS. 1 (a) to 1 (b)]. Since compressive stress is generated by increasing the density of the glass surface, the glass can be strengthened.
  • the hydrogen ion index (pH) when the aqueous solution is 10% by mass is 7.5 or more and 10.5 or less, and at least one of sodium nitrate and potassium nitrate is used.
  • the Si—O—Si bond of the glass is appropriately cut by OH ⁇ in the inorganic salt, and the surface layer of the compressive stress layer is modified to reduce the density.
  • the density layer 10 is formed [FIGS. 1B to 1C].
  • 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 step can be performed as follows.
  • the glass is preheated and the molten salt is adjusted to the processing temperature for chemical strengthening.
  • the preheated glass is immersed in the molten salt for a predetermined time, and then the glass is pulled up from 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 the glass depends on the temperature at which the molten salt is immersed, but is generally preferably 100 ° C. or higher.
  • the temperature at which chemical strengthening is performed is preferably 400 ° C. or higher, more preferably 450 ° C. or higher, and further preferably 470 ° C. or higher from the viewpoint of obtaining chemically strengthened glass having a deep DOC.
  • the upper limit of the temperature at which chemical strengthening is performed is not particularly limited, but typically, the strain point of the glass to be tempered (usually 500 to 600 ° C.) or less is preferable.
  • the immersion time of the glass in the molten salt depends on the chemical strengthening temperature, but is preferably 2 hours or longer, more preferably 4 hours or longer, and even more preferably 8 hours or longer from the viewpoint of obtaining chemically strengthened glass having a deep DOC. It is.
  • the upper limit is not particularly limited, but is usually 48 hours or shorter, and preferably 24 hours or shorter from the viewpoint of productivity.
  • the depth (DOC) of the compressive stress layer formed on the surface layer of the glass after the chemical strengthening step is preferably 35 ⁇ m or more, more preferably 45 ⁇ m or more, and still more preferably. It is 55 ⁇ m or more.
  • the compressive stress value of the chemically strengthened glass produced by the method of the present invention is preferably 100 MPa or more, more preferably 200 MPa or more, and further preferably 300 MPa or more.
  • the upper limit is not particularly limited, but is typically 1200 MPa or less.
  • the depth of the compressive stress layer 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
  • FSM-6000 manufactured by Orihara Seisakusho
  • the thickness of the low density layer is preferably 10 nm or more, and more preferably 20 nm or more from the viewpoint of the glass surface removal amount.
  • the thickness of the low density layer can be controlled by the sodium concentration, temperature or time in the molten salt in the chemical strengthening step.
  • the low-density layer After removing the low-density layer in the acid treatment step, the low-density layer can be further removed by performing an alkali treatment.
  • 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 is determined from the period ( ⁇ ) measured by the X-ray reflectivity method (X-ray-Reflectometry: XRR).
  • the density of the low density layer is determined by the critical angle ( ⁇ c) measured by XRR.
  • SEM scanning electron microscope
  • the above-described chemical strengthening treatment with an inorganic salt having a hydrogen ion index (pH) of 7.5 to 10.5 and containing at least one of sodium nitrate and potassium nitrate in a 10% by mass aqueous solution.
  • the chemical strengthening treatment described above is a chemical strengthening treatment step in which at least one of the conditions of the inorganic salt composition, hydrogen ion index, chemical strengthening temperature and chemical strengthening time is changed. You may perform several times before and after a process.
  • the glass is cleaned using industrial water, ion exchange water, or the like. Of these, ion-exchanged water is preferred.
  • the washing conditions vary depending on the washing solution used, but when ion-exchanged water is used, washing at 0 to 100 ° C. is preferable because the attached salt is completely removed.
  • the glass cleaned after the chemical strengthening step is further subjected to acid treatment.
  • the acid treatment of glass is performed by bringing the glass into contact with an acidic solution having a hydrogen ion index (pH) of less than 7.0.
  • the solution used for the acid treatment is not particularly limited as long as it is acidic, and may have a pH of less than 7.0.
  • the acid used may be a weak acid or a strong acid. Specifically, acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid or 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 lower. Moreover, 20 degreeC or more is preferable from a viewpoint of making it easy to remove a low density layer.
  • the time for the acid treatment 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 with less concern about container corrosion, and specifically 0.1% by mass to 20% by mass.
  • Specific conditions for the acid treatment include, for example, a condition in which the glass after the chemical strengthening step is preferably contacted with a 0.1% by mass to 10% by mass nitric acid aqueous solution at 35 to 75 ° C. for 1 to 15 minutes. Can be mentioned.
  • the acid treatment accelerates the reduction of the density of the glass surface and exposes the surface layer from which part or all of the low density layer has been removed [FIGS. 1 (c) and (d)]. Thereby, a chemically strengthened glass having a significantly improved surface strength is obtained. Further, since the scratches existing on the glass surface are also removed at the same time by removing the low density layer, this point is also considered to contribute to the strength improvement.
  • an alkali treatment may be performed after the acid treatment.
  • the surface strength can be further increased by increasing the removal amount of the low-density layer as compared with the case of only the acid treatment.
  • the solution used for the alkali treatment is not particularly limited as long as it is basic, and may have a pH exceeding 7.0, and a weak base or a strong base may be used. Specifically, a base such as sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate is 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 mass to 20% by mass from the viewpoint of glass surface removability.
  • the glass after the acid treatment step is preferably contacted with a 0.1% to 10% by weight sodium hydroxide aqueous solution at 35 to 75 ° C. for 1 to 15 minutes.
  • the condition to make is mentioned.
  • the surface treatment from which the low-density layer is further removed is exposed by the alkali treatment as compared with the glass after the acid treatment step. Thereby, the chemically strengthened glass whose surface strength is further improved is obtained. Moreover, since the flaw which existed on the glass surface is further removed, it is thought that this point contributes to further improvement of surface strength.
  • cleaning process it is preferable to have the same washing
  • the amount of the low density layer to be removed depends on the acid treatment step and at least one of the conditions of the acid treatment step and the alkali treatment step.
  • FIG. 1D shows a mode in which the low density layer 10 is completely removed, a part of the low density layer 10 may be removed and a part may remain. From the viewpoint of improving the strength, the effect can be obtained even if the entire low-density layer is not removed.
  • ⁇ Chemical tempered glass> The surface strength of the chemically strengthened glass produced by the method of the present invention can be evaluated by a ball-on-ring test shown below.
  • the chemically strengthened glass produced according to the present invention preferably satisfies F ⁇ 1000 ⁇ t 2, and more preferably F ⁇ 1200 ⁇ t 2 [wherein F is the BOR strength (N) measured by a ball-on-ring test. And t is the thickness (mm) of the glass plate. ].
  • F is the BOR strength (N) measured by a ball-on-ring test.
  • t is the thickness (mm) of the glass plate. ].
  • FIG. 2 shows a schematic diagram for explaining the ball-on-ring test.
  • a glass plate 1 is used with a pressure jig 2 (hardened steel, diameter 10 mm, mirror finish) made of SUS304 with the glass plate 1 placed horizontally. And the strength of the glass plate 1 is measured.
  • a pressure jig 2 hardened steel, diameter 10 mm, mirror finish
  • a glass plate 1 serving 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).
  • a pressurizing jig 2 for pressurizing the glass plate 1 is installed above the glass plate 1.
  • the central region of the glass plate 1 is pressurized from above the glass plate 1.
  • the test conditions are as follows. Lowering speed of the pressure jig 2: 1.0 (mm / min) At this time, the breaking load (unit N) when the glass plate is broken is defined as BOR strength, and the average value of 20 measurements of the BOR strength is defined as surface strength F (N). However, in the case where the fracture start point of the glass plate is 2 mm or more away from the load point of the sphere, it is excluded from the data for calculating the average value.
  • the depth (DOC) of the compressive stress layer of the chemically strengthened glass produced by the method of the present invention is preferably 35 ⁇ m or more, more preferably 45 ⁇ m or more, and further preferably 55 ⁇ m or more.
  • the thickness of the low-density layer removed by the acid treatment step or the alkali treatment step is about 1000 nm as in the example even if it is large from about 10 nm, so the depth (DOC) of the compressive stress layer is The depth (DOC) formed in the chemical strengthening step and the depth (DOC) after the acid treatment step or the alkali treatment step are substantially the same.
  • the surface compressive stress value (CS) of the chemically strengthened glass produced by the method of the present invention is preferably 100 MPa or more, more preferably 200 MPa or more, and further preferably 300 MPa or more.
  • the upper limit is not particularly limited, but is typically 1200 MPa or less.
  • the compressive stress value can be measured using an EPMA (Electron Probe Micro Analyzer) or a surface stress meter (for example, FSM-6000 manufactured by Orihara Seisakusho).
  • the compressive stress value can be calculated using a stress profile calculation method disclosed in Japanese Unexamined Patent Publication No. 2016-142600.
  • the chemically strengthened glass produced by the method of the present invention has an internal tensile stress (CT) of preferably 72 MPa or less, more preferably 62 MPa or less, and further preferably 52 MPa or less.
  • CT internal tensile stress
  • the lower limit is not particularly limited, but is typically 20 MPa or more.
  • the stress distribution was measured, and the stress distribution was integrated with the thickness to obtain the CT value.
  • the CTlimit value is empirically known to be -38.7 ⁇ ln (t) +48.2 [MPa].
  • t represents the plate thickness of the glass, and the unit is mm.
  • the chemically strengthened glass manufactured by the method of the present invention may be manufactured by performing a polishing step of polishing the glass surface before the chemical strengthening step.
  • polishing in the present invention refers to smoothing by polishing the glass surface using abrasive grains.
  • the presence or absence of polishing flaws that may occur in the polishing process can be determined by surface observation with an AFM (Atomic Force Microscope), and a scratch having a length of 5 ⁇ m or more and a width of 0.1 ⁇ m or more is present in a 10 ⁇ m ⁇ 5 ⁇ m region. When two or more are not present, it can be said that there is no polishing scratch on the surface.
  • FIG. 3A shows a state having surface polishing flaws
  • FIG. 3B shows a state having no surface polishing flaws.
  • the chemically strengthened glass produced by the production method of the present invention has a surface roughness Ra in a measurement range of 10 ⁇ m ⁇ 5 ⁇ m measured by AFM surface observation, preferably 0.2 nm or more, more preferably 0.25 nm or more. is there. Moreover, it is preferably 1.5 nm or less, more preferably 1.2 nm or less.
  • the surface roughness of the chemically tempered glass plate which has not been polished is usually 0.15 nm or more and less than 0.2 nm.
  • the total amount was 100% by mass as KNO 3 .
  • the pH of the inorganic salt is a value measured with a handy type pH meter D-71S manufactured by Horiba, Ltd. at 25 ° C. when the aqueous solution is 10% by mass.
  • a 6 mass% nitric acid aqueous solution was prepared in a beaker, and the temperature was adjusted to 40 ° C. using a water bath.
  • the glass obtained in the chemical strengthening step was immersed in the adjusted aqueous nitric acid solution for 120 seconds, acid-treated, then washed several times with pure water, and then dried by air blowing. The glass thus obtained was subjected to the next step.
  • Alkali treatment process A 4.0 wt% aqueous sodium hydroxide solution was prepared in a beaker, and the temperature was adjusted to 40 ° C. using a water bath. The glass obtained in the acid treatment step was immersed in the prepared sodium hydroxide aqueous solution for 120 seconds, subjected to alkali treatment, then washed several times with pure water, and then dried by air blowing.
  • polishing process cerium oxide having an average particle diameter (d50) of 1 ⁇ m was dispersed in water to prepare a slurry, and the resulting slurry was used to apply a pressure of 0. Under the condition of 1 kPa, both surfaces of the flat glass were polished for a total of about 6 ⁇ m.
  • FIG. 2 is a schematic diagram for explaining the ball-on-ring test used in the present invention.
  • the glass plate 1 aluminosilicate glass A in the following examples
  • the glass plate 1 is pressed using a pressure jig 2 made of SUS304 (hardened steel, diameter 10 mm, mirror finish). The strength of the glass plate 1 was measured.
  • a glass plate 1 serving 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).
  • a pressurizing jig 2 for pressurizing the glass plate 1 is installed above the glass plate 1.
  • the central region of the glass plate 1 was pressurized from above the glass plate 1 obtained in the examples and comparative examples.
  • the test conditions are as follows. Lowering speed of the pressure jig 2: 1.0 (mm / min)
  • the breaking load (unit N) when the glass was broken was defined as the BOR strength
  • the average value of 20 measurements of the BOR strength was defined as the surface strength F (N).
  • the surface strength F (N) depends on the thickness t (mm) of the glass plate.
  • the comparison is made by normalizing (normalizing) the thickness t (mm) of the glass plate.
  • the value normalized (normalized) by the thickness t (mm) of the glass plate was defined as a (unit: N / mm 2 ).
  • the surface compressive stress value (CS) and the depth (DOC, unit: ⁇ m) of the compressive stress layer were measured using a surface stress meter (FSM-6000) manufactured by Orihara Seisakusho.
  • the compressive stress value (CS) and the compressive stress layer depth (DOC) were calculated using the stress profile calculation method disclosed in Japanese Patent Application Laid-Open No. 2016-142600.
  • the tensile stress value (CT, unit MPa) was calculated by measuring the stress distribution using the stress profile calculation method disclosed in Japanese Patent Application Laid-Open No. 2016-142600 and integrating the stress distribution with the thickness.
  • polishing scratches The presence or absence of polishing flaws was determined by surface observation with AFM. When there were no two or more scratches having a length of 5 ⁇ m or more and a width of 0.1 ⁇ m or more in a 10 ⁇ m ⁇ 5 ⁇ m region, the surface was made free of polishing scratches.
  • FIG. 4A is a diagram illustrating a state where white clouding is not generated in the glass surface
  • FIG. 4B is a diagram illustrating a state where white clouding is generated in the glass surface.
  • ⁇ No white clouding occurred in the glass surface.
  • X White cloudiness is generated in the glass surface.
  • a chemical strengthening step in which the glass is brought into contact with an inorganic salt having a pH of 7.5 or more and 10.5 or less and containing at least one of sodium nitrate and potassium nitrate, and the chemical strengthening step.
  • the chemically tempered glasses of Examples 1 to 12 obtained by the production method of the present invention including the acid treatment step of bringing the latter glass into contact with an acidic solution having a pH of less than 7 and acid-treating were obtained.
  • the chemically tempered glasses of Examples 1 to 12 have higher surface strength even when subjected to chemical tempering treatment at a higher temperature for a longer time than the chemically tempered glasses obtained in Comparative Examples 1 to 11, and the depth of the compressive stress layer ( DOC) is deep and shows a high surface compressive stress value (CS), and there is no occurrence of white haze in the glass surface, which is excellent in appearance quality.
  • Comparative Examples 1 and 2 in which the pH was 7.5 or more and 10.5 or less, and the acid treatment was not performed after the chemical strengthening step in which the glass was brought into contact with an inorganic salt containing at least one of sodium nitrate and potassium nitrate to perform ion exchange.
  • the chemically tempered glasses of 4, 6, 7, 10 and 11 had lower surface strength than the chemically tempered glasses obtained in the examples.
  • white cloudiness occurred in the glass surface.
  • polishing treatment is performed without acid treatment after the chemical strengthening step in which the glass is brought into contact with an inorganic salt containing at least one of sodium nitrate and potassium nitrate having a pH of 7.5 or more and 10.5 or less and subjected to ion exchange.
  • the chemically strengthened glass of Comparative Example 5 had a slightly higher surface strength than the other comparative examples. However, polishing scratches were observed on the glass surface, and the surface strength was low compared to the chemically strengthened glass obtained in the examples.
  • the chemically strengthened glass of Comparative Example 3 which was subjected to acid treatment and alkali treatment after the chemical strengthening step using an inorganic salt having a pH of less than 7.5, and an inorganic salt having a pH of more than 10.5
  • Comparative Example 8 in which acid treatment was performed after using the chemical strengthening step
  • Comparative Example 9 in which acid treatment and alkali treatment were performed after performing the chemical strengthening step using an inorganic salt having a pH of more than 10.5
  • the chemically strengthened glass had lower surface strength than the chemically strengthened glass obtained in the examples, and white cloudiness was generated in the glass surface.
  • FIG. 5A is the stress profile of the chemically strengthened glass obtained in Examples 1 and 3 and Comparative Example 1
  • FIG. 5B is the stress profile of the chemically strengthened glass obtained in Examples 7 and 8 and Comparative Example 6
  • FIG. The stress profile of the chemically strengthened glass obtained in Examples 10 and 11 and Comparative Example 11 is shown.
  • Example 5A the stress profiles of the chemically tempered glass obtained in Example 1 and Comparative Example 1 were almost the same. Moreover, as shown to FIG. 5B, the stress profile of the chemically strengthened glass obtained in Example 7 and 8 and the comparative example 6 substantially corresponded. Furthermore, as shown in FIG. 5C, the stress profiles of the chemically tempered glasses obtained in Examples 10 and 11 and Comparative Example 11 almost coincided.
  • FIG. 6A and FIG. 6B show the results of evaluating the surface strength of the chemically strengthened glass obtained in Examples 1 and 5 and Comparative Examples 1, 4 and 5. As shown in FIGS. 6A and 6B, the chemically strengthened glasses obtained in Examples 1 and 5 were not subjected to acid treatment after the chemical strengthening step, and Comparative Examples 1 and 4 were not subjected to acid treatment after the chemical strengthening step. The surface strength was remarkably improved as compared with Comparative Example 5 in which the polishing treatment was performed.
  • FIGS. 7A and 7B show the results of evaluating the surface strength of the chemically strengthened glass obtained in Examples 7 and 8 and Comparative Example 6.
  • FIG. 7A and 7B the chemically strengthened glass obtained in Examples 7 and 8 has a significantly improved surface strength as compared with Comparative Example 6 in which acid treatment was not performed after the chemical strengthening step. It was.
  • FIGS. 8A and 8B show the results of evaluating the surface strength of the chemically strengthened glass obtained in Examples 10 and 11 and Comparative Example 11.
  • FIG. 8A and 8B the chemically strengthened glass obtained in Examples 10 and 11 has a significantly improved surface strength compared to Comparative Example 11 in which acid treatment was not performed after the chemical strengthening step. It was.

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CN111807718A (zh) * 2020-07-24 2020-10-23 江苏铁锚玻璃股份有限公司 高透光、高强度抗菌玻璃的制备方法

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