WO2013035840A1 - Procédé de production d'un verre protecteur pour appareil portatif - Google Patents

Procédé de production d'un verre protecteur pour appareil portatif Download PDF

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Publication number
WO2013035840A1
WO2013035840A1 PCT/JP2012/072885 JP2012072885W WO2013035840A1 WO 2013035840 A1 WO2013035840 A1 WO 2013035840A1 JP 2012072885 W JP2012072885 W JP 2012072885W WO 2013035840 A1 WO2013035840 A1 WO 2013035840A1
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glass
molten salt
salt melt
ion exchange
cover glass
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PCT/JP2012/072885
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English (en)
Japanese (ja)
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貢 今井
橋本　和明
杉原　理
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Hoya株式会社
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Priority to CN201280043503.6A priority Critical patent/CN103781739A/zh
Publication of WO2013035840A1 publication Critical patent/WO2013035840A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • 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

Definitions

  • the present invention relates to a method for manufacturing a cover glass for a portable device used in a portable device such as a mobile phone, a PDA (Personal Digital Assistant), or a portable game machine.
  • a portable device such as a mobile phone, a PDA (Personal Digital Assistant), or a portable game machine.
  • chemical strengthening treatment is usually performed.
  • This chemical strengthening treatment is performed by bringing a molten chemical strengthening salt into contact with a glass article, so that an alkali metal element having a relatively large ionic radius in the chemical strengthening salt and a relatively small ionic radius in the glass are obtained.
  • This is a treatment in which an alkali metal element is ion-exchanged and the surface of the glass article is infiltrated with the alkali metal element having a large ionic radius to generate a compressive stress on the surface of the glass article.
  • an alkali metal such as Li, Na, or K
  • an alkali metal having a larger ionic radius for Li in the glass, Na, K having a larger ionic radius and in the glass
  • K By substituting K with a larger ionic radius for Na, the compressive stress of the glass surface layer can be increased, the strength of the glass article can be improved, and the impact resistance can be increased.
  • Patent Document 1 when soda lime glass is chemically strengthened with a mixed molten salt of KNO 3 , K 2 SO 4 and KCl, this mixed molten salt is a special clay known as a hectorite rich in K + ions. It is disclosed that the concentration in the mixed molten salt of Na + ions emitted from soda lime glass can be kept low by adding particles.
  • Patent Document 1 discloses clays such as bentonite and montmorillonite, silicates, borates, glassy and non-glassy aluminosilicates as substances for regenerating the strengthening treatment liquid. Examples include solid gels that can fix salts, protons, and alkali metal ions.
  • Patent Document 1 does not disclose a mechanism for regenerating the tempered treatment liquid, and depending on the type of glass used or the type of molten salt, regeneration is insufficient, water or washing Some of them were not usable, such as acids that are insoluble in acids, alkalis, and those that react with the water of washing to attack the glass surface.
  • examples of glass articles that are subjected to chemical strengthening treatment include cover glasses for portable devices.
  • cover glasses Conventionally, in mobile devices such as mobile phones, PDAs, and portable game machines, acrylic resin plates having excellent transparency and light weight have been generally used for their display screens.
  • acrylic resin plates having excellent transparency and light weight have been generally used for their display screens.
  • it has replaced conventional acrylic resin plates.
  • It is a cover glass made of a glass material that is thin but has high strength and is superior to conventional acrylic resin plates in terms of surface smoothness, protection (weather resistance, antifouling properties), appearance and luxury. Are increasingly being used.
  • touch-panel portable devices have become mainstream.
  • the mobile device is operated mainly by pressing a predetermined part (for example, an icon displayed on the screen) of the display screen. Therefore, there is a demand for an improvement in the strength of the display screen.
  • a cover glass having a sufficient strength even for a thin, lightweight, large screen (large area) is desired.
  • the present invention has been made to solve such a conventional problem, and its purpose is to carry a molten glass having a long life in a chemical strengthening treatment and to obtain a tempered glass product having stable characteristics. It is providing the manufacturing method of the cover glass for apparatuses. In particular, it is to provide a method for producing a cover glass for a portable device suitable for a cover glass used for a touch panel type portable device or the like.
  • the present invention has the following configuration.
  • (Configuration 1) By contacting a glass article having a Li-containing composition with a molten salt melt containing an alkali metal element having an ionic radius larger than that of Li contained in the glass, Li in the glass article and an alkali in the molten salt melt a metal a method of manufacturing a cover glass for portable devices including an ion exchange step of ion exchange, NaF, KF, K 3 AlF 6, Na 2 CO 3, NaHCO 3, K 2 CO 3, KHCO 3, Na 2 At least one additive selected from the group consisting of SO 4 , K 2 SO 4 , KAl (SO 4 ) 2 , Na 3 PO 4 , K 3 PO 4 is added to the molten salt melt, and the additive Is a method for producing a cover glass for portable equipment, wherein the ion exchange step is performed in a solid state.
  • a method for manufacturing a cover glass for a portable device including an ion exchange step for ion exchange with a metal, wherein KCl, KBr, KF, K 3 AlF 6 , K 2 CO 3 , KHCO 3 , K 2 SO 4 , KAl (SO 4 ) At least one additive selected from the group consisting of 2 and K 3 PO 4 is added to the molten salt melt, and the additive performs the ion exchange step in a solid state. It is a manufacturing method of the cover glass for apparatuses.
  • An additive that reacts with Li eluted in the liquid and precipitates the Li compound as a solid in the molten salt melt is added to the molten salt melt, and the ion exchange is performed when the additive is in a solid state. It is a manufacturing method of the cover glass for portable devices characterized by performing a process.
  • the said ion exchange is a low temperature type ion exchange, It is a manufacturing method of the cover glass for portable devices in any one of the structures 1 thru
  • the lifetime of the molten salt can be kept long in the chemical strengthening treatment, and a cover glass for a portable device having stable characteristics with small variations in strength and the like can be obtained.
  • a cover glass for a portable device having stable characteristics with small variations in strength and the like can be obtained.
  • a tempered glass having stable characteristics suitable for a cover glass used for a touch panel type portable device which is required to have sufficient strength even if it is thin, lightweight, and has a large screen (large area). Can do.
  • the glass article having a Li-containing composition is brought into contact with a molten salt melt containing an alkali metal element having an ionic radius larger than that of Li contained in the glass.
  • the Li glass articles in the alkali metal of the molten salt melt liquid method of manufacturing a cover glass for portable devices including an ion exchange step of ion exchange, NaF, KF, K 3 AlF 6 , Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , KHCO 3 , Na 2 SO 4 , K 2 SO 4 , KAl (SO 4 ) 2 , Na 3 PO 4 , K 3 PO 4
  • One type of additive is added to the molten salt melt, and the additive performs the ion exchange step in a solid state.
  • the second embodiment of the present invention is a molten salt melt containing an alkali metal element having an ionic radius larger than that of Na contained in the glass, as in composition 2 above.
  • a method for producing a cover glass for a portable device comprising an ion exchange step of ion exchange of Na in the glass article and an alkali metal in the molten salt melt by contacting with the solution, comprising KCl, KBr, KF
  • At least one additive selected from the group consisting of K 3 AlF 6 , K 2 CO 3 , KHCO 3 , K 2 SO 4 , KAl (SO 4 ) 2 , K 3 PO 4 is added to the molten salt melt.
  • the said ion exchange process is performed by the said additive in a solid state, It is characterized by the above-mentioned.
  • the molten salt can have a long lifetime in the chemical strengthening treatment, and a tempered glass product (cover glass for portable devices) having stable characteristics can be obtained. That is, the life of the molten salt is prolonged and the characteristics of the tempered glass product are stabilized.
  • this chemical strengthening treatment is performed by bringing the molten chemically strengthened salt and the glass article into contact with each other so that the alkali metal element having a relatively large ionic radius in the chemically strengthened salt and the relative strength in the glass. And ion exchange with an alkali metal element having a small ionic radius, the alkali metal element having a large ionic radius is permeated into the surface layer of the glass article, and a compressive stress is generated on the surface of the glass article.
  • a part of alkali ions having a small ionic radius can be obtained by immersing it in, for example, a mixed molten salt melt of KNO 3 and NaNO 3.
  • Chemical strengthening is performed by substituting alkali metals with larger ionic radii. Note that the order of the ionic radii is Li + ⁇ Na + ⁇ K + .
  • Li ions are eluted from the glass.
  • Li ions in the molten salt melt increase, Na and K in the glass introduced into the glass by ion exchange and the Li ions in the molten salt melt are in an equilibrium state. Over time, the molten salt Na and K ions will not enter the glass.
  • the molten salt melt is solid at the heating temperature (temperature at which the molten salt is melted), that is, the temperature at which ion exchange is performed.
  • An additive for reacting with Li ions (or Na ions) eluted in the interior and discharging the Li ions (or Na ions) as precipitates to the outside of the system, that is, out of the molten salt melt (outside the liquid state) Is used.
  • a mixed salt melt of KNO 3 and NaNO 3 or a salt of Na or K that is solid at the heating temperature (ion exchange temperature) of a molten salt melt of KNO 3 or NaNO 3 alone (ion exchange temperature) for example, when carbonates are used, these Na and K carbonates remain solid in the molten salt melt, but are replaced with Li ions and carbonate Na and K present in the molten salt melt. The reaction can occur to produce Li 2 CO 3 which can be precipitated out as a solid.
  • glass does not contain Li and contains Na and K or Na.
  • KNO 3 may be used as the composition (main agent) of the molten salt, and K 2 CO 3 that is a carbonate of K may be added as an additive.
  • the interfering ions for chemical strengthening are Na ions
  • Na ions are selectively precipitated as carbonates and removed from the reaction system.
  • the melting point of Na 2 CO 3 is 851 ° C. and the melting point of K 2 CO 3 is 891 ° C.
  • by performing ion exchange below this temperature Na 2 CO 3 or K 2 CO 3 is used as a precipitate, It can be precipitated as a solid from the molten salt melt.
  • chemical strengthening treatment is performed without adding such an additive in the molten salt melt (conventional method)
  • Na ions are gradually accumulated in the molten salt melt and returned to the glass, causing the strengthening reaction. It becomes difficult to proceed.
  • the present invention can be applied to a glass article having a composition containing at least one of Li and Na as an alkali metal capable of chemical strengthening.
  • a glass article having a composition containing at least one of Li and Na as an alkali metal capable of chemical strengthening In addition to the glass containing Li, Na, and K described above, the glass containing Na and K, the glass containing Li, the glass containing Li and Na, the glass containing Li and K, and Na. It can be applied to chemical strengthening of glass.
  • the molten salt composition for chemically strengthening various glasses differs depending on the composition of each glass.
  • the molten salt composition is added to keep the molten salt life long and make the chemical strengthening stability constant.
  • the melting point is higher than the heating temperature (ion exchange temperature) of the molten salt melt, and the molten salt is melted from the glass by the ion exchange step.
  • An additive that reacts with Li eluted in the molten liquid and precipitates the Li compound as a solid in the molten salt molten liquid is added to the molten salt molten liquid, and the ion exchange step in which the additive is in a solid state Is to do.
  • the product or additive can be removed by washing, for example, by dissolving in water, and the molten salt base is regenerated from the reaction between the additive and interfering ions eluted from the glass. Is particularly desirable.
  • additives to be added to the molten salt melt include Na, K carbonates, phosphates, sulfates and fluorides.
  • the main specific example of the preferable combination of the glass reinforced salt composition and additive in this invention is given to the following, this invention is not limited to these.
  • the composition of the main component of the molten salt is, for example, Any of NaNO 3 , KNO 3 , and a mixed salt of NaNO 3 and KNO 3 can be preferably used.
  • additives can be preferably used.
  • the composition of the main component of the molten salt is preferably KNO 3 , for example.
  • additives include, for example, KCl, KBr, KF, K 3 AlF 6 , K 2 CO 3 , KHCO 3 , K 2 SO 4 , KAl (SO 4 ) 2 , K At least one additive selected from the group consisting of 3 PO 4 can be preferably used.
  • the alkali metal carbonates are most preferable, sulfates are particularly preferable, phosphates are more preferable, and fluorides are then preferable.
  • sulfates, carbonates, phosphoruss are not used in order not to damage the chemical strengthening tank that performs ion exchange or to damage the surface of the glass article by washing the strengthened glass article after ion exchange. Acid salts are preferred.
  • the above additive when selecting the above additive, it is precipitated as a solid in the molten salt melt by the reaction of an alkali metal having a small ionic radius eluted from the glass into the molten salt melt by the ion exchange step, for example, Li and the above additive.
  • the reaction product to be removed removes the chemically strengthened molten salt adhering to the cover glass surface after the chemical strengthening treatment (for example, a cooling step (also called a heat shock step) for lowering the temperature of the glass substrate after the chemical strengthening treatment)
  • a cooling step also called a heat shock step
  • Li ions present as LiNO 3
  • Na, K of the above sulfate and substitution reaction To produce Li 2 SO 4 .
  • Li ions present as LiNO 3
  • a substitution reaction occurs with Na and K of the above carbonate to produce Li 2 CO 3 .
  • the chemical strengthening of the glass containing Li as an alkali metal it is preferable to use a sulfate of Na or K as the additive from the viewpoint of the surface roughness of the cover glass after the chemical strengthening treatment.
  • K sulfate is more preferable because KNO 3 is produced as shown in the above chemical reaction formula, and K ions in the molten salt melt that decreases with the progress of chemical strengthening can be supplied.
  • the PH of the aqueous solution is less than 10 on the surface of the cover glass when the cover glass comes into contact with the aqueous solution in the cooling step or cleaning step of the cover glass after the chemical strengthening treatment.
  • the solution on the glass surface is brought into a neutral region by contacting with a weak acid or a buffer solution before contacting with water in a cooling step or a washing step. Then, since the deterioration of the local surface roughness accompanying an etching can be suppressed, it is desirable.
  • the amount of the additive added is not limited as long as the ions eluted from the glass into the molten salt melt can be precipitated as solid precipitates, and do not interfere with strengthening by precipitation or floating in large quantities. It may be a moderate amount.
  • the additive for example, it may be added before ion exchange. Also, for example, when many glass articles are ion-exchanged by batch processing, every batch processing or every several batches You may add an additive to.
  • a structure of the chemical tempering tank for performing ion exchange for example, it is possible to use a batch-type tempering tank in which a plurality of glasses are ion-exchanged at a time and then the glass is replaced. It is good also as a continuous strengthening tank which performs.
  • the additive to be added to the molten salt melt has a melting point higher than the heating temperature of the molten salt melt, the additive performs the ion exchange step in a solid state, and By adding the additive to the molten salt melt, it reacts with an alkali metal having a small ionic radius eluted from the glass into the molten salt melt by the ion exchange step, for example, Li, and the Li compound is melted. It is an important point to make it precipitate as a solid.
  • the present invention by adding the above additives to the molten salt melt, it is possible to prevent alkali metal ions having a small ion radius that interfere with chemical strengthening, which are eluted from the glass, from being present as ions in the molten salt melt. Therefore, the compound of the ion can be deposited as a solid, and accumulation of these interfering ions can be suppressed.
  • Li ions are more easily eluted in the molten salt melt as compared with Na ions, etc. Is particularly effective.
  • the surface of the glass article is washed by washing the glass article after the ion exchange step. It is particularly preferable to select an additive such that precipitates attached to the surface can be removed. For that purpose, it is preferable that the precipitate is dissolved in water, acid, weak alkali or the like.
  • the additive it is particularly preferable to select the additive so that the precipitate precipitated in the molten salt melt by the ion exchange step has a specific gravity different from that of the molten salt melt. This is because it is easy to remove precipitates from the molten salt melt by filtering with a filter or the like.
  • the composition of the molten salt and the precipitate are not suspended in the molten salt melt, but accumulated at the bottom of the chemical strengthening tank for ion exchange or floated in the molten salt melt. It is preferred to determine the composition of the additive.
  • the composition of the molten salt and the additive When determining the composition of the molten salt and the additive so that the deposit accumulates in the chemical strengthening tank, it is possible to prevent the deposit from adhering to the surface of the article to be ion-exchanged.
  • the composition and additive of the molten salt are determined so that the precipitate floats in the molten salt melt, it is easy to remove the precipitate.
  • the additive for example, it may be added to the molten salt melt in the form of a powder, or may be added in the form of, for example, a pellet.
  • the additive used in the present invention is preferably a compound containing an alkali metal component, and particularly preferably the alkali metal component contained in the additive contains the same alkali metal contained in the molten salt melt.
  • the alkali metal component contained in the additive is not necessarily the same as the alkali metal contained in the molten salt melt, but if it is the same, the alkali metal ion in the glass and the molten salt melt This is more preferable because the reduced alkali metal ions in the molten salt melt can be supplemented with the alkali metal ions contained in the additive by ion exchange with the alkali metal ions. This will be described in detail.
  • Alkali metal ions eluted from the glass into the molten salt molten solution cause a solid-phase reaction with the additive and become precipitates. At this time, alkali metal ions are released from the additive.
  • the alkali metal ions released from this additive By keeping the alkali metal ions released from this additive the same as the alkali metal ions in the molten salt melt for ion exchange with the glass, the alkali metal ions in the molten salt melt reduced by the ion exchange are reduced. Can be replenished. That is, it is more desirable that the above is the same from the viewpoint of regenerating the molten salt main agent and keeping the alkali metal ion concentration in the molten salt constant.
  • the molten salt can be used semipermanently in principle, and it is not necessary to replace the molten salt, and it is only necessary to remove additional and sometimes unnecessary reaction products as necessary.
  • the present invention it is possible to suppress the accumulation of alkali metal ions having a small ion radius that are eluted from the glass by the ion exchange process, thereby preventing the chemical strengthening by ion exchange from being disturbed.
  • the life of the salt can be kept long, and the number of exchanges of the molten salt can be significantly reduced.
  • a tempered glass product having a small intensity variation and uniform characteristics can be manufactured stably.
  • the present invention is particularly suitable for manufacturing a cover glass for portable devices.
  • the cover glass for portable devices is required to have higher strength than other glass articles, and chemical strengthening treatment is indispensable for improving the strength.
  • the thickness (plate thickness) of such a cover glass for portable devices is preferably in the range of, for example, about 0.3 mm to 1.5 mm from the viewpoint of meeting the market needs for the recent thinning and weight reduction of portable devices. More preferably, it is in the range of about 0.5 mm to 0.7 mm.
  • the glass constituting the cover glass for portable devices is preferably amorphous aluminosilicate glass.
  • a glass substrate made of such an aluminosilicate glass is excellent in strength after chemical strengthening.
  • As such an aluminosilicate glass in terms of oxides, SiO 2 is 58 to 75% by weight, Al 2 O 3 is 0 to 20% by weight, Li 2 O is 0 to 10% by weight, and Na 2 O is 4 to 4%.
  • An aluminosilicate glass containing 20% by weight and ZrO 2 as a main component of 5.5% to 15% by weight can be used.
  • a chemical strengthening treatment for example, a low temperature ion exchange method in which ion exchange is performed in a temperature range that does not exceed the temperature of the glass transition point, for example, a temperature of 300 ° C. to 500 ° C. is preferable.
  • the details of the chemical strengthening treatment (ion exchange step) in the present invention are as described above.
  • This chemical strengthening treatment is performed by mounting a large number of cover glasses on a substrate holder, which is generally called a rack, and immersing the chemical strengthening salt in a molten salt melt (chemical strengthening treatment solution) obtained by heating and melting. Is called.
  • a cooling step may be included in which the cover glass is taken out from the molten salt melt while being mounted on the substrate holder and immersed in an aqueous solution bath as it is to lower the temperature of the cover glass.
  • the chemically strengthened cover glass has improved strength and excellent impact resistance, it is suitable for a cover glass used for a portable device that requires impact and pressure and requires high strength.
  • variation in strength due to chemical strengthening is small, and a cover glass with uniform characteristics can be manufactured stably.
  • Example 1 The cover glass for portable devices of the present Example was manufactured through the following (1) plate glass cutting process and (2) chemical strengthening process.
  • the cover glass was chemically strengthened.
  • Chemical strengthening uses potassium nitrate (KNO 3 ) as a molten salt and a molten salt melt prepared by adding sodium carbonate (Na 2 CO 3 ) as an additive at a ratio of 70 g / 4.5 kg of molten salt main component weight.
  • the molten salt melt was heated to 360 to 380 ° C., and the cover glass was immersed for about 2 to 4 hours for chemical strengthening treatment.
  • the number of processed sheets was 100 sheets.
  • the cover glass that had been chemically strengthened was sequentially immersed in each of cleaning baths of pure water, IPA, and IPA (steam drying), ultrasonically cleaned, and dried.
  • the cover glass (100 sheets) for portable devices of this example was manufactured.
  • the precipitate deposited in the molten salt melt after completion of the chemical strengthening step was analyzed by XRD (X-ray refraction). As a result, it was confirmed that a large amount of lithium carbonate was present.
  • the strength variation of the manufactured 100 cover glasses was evaluated. Specifically, the four-point bending strength (unit: MPa) of the main surface of the cover glass measured using the four-point bending method was measured, and the ratio of the cover glass that was 500 MPa or more was determined.
  • the 4-point bending test was conducted based on JIS standard R1602.
  • a test piece here, a cover glass
  • the maximum bending stress is measured as a 4-point bending strength.
  • a rotating four-point bending test jig as shown in FIGS. 1A and 1B was used.
  • a cross head 4 is arranged above the support members 3, and a fixed part is provided below the cross head 4.
  • Two roller-shaped supports 5 and 5 arranged on the left and right are provided at a distance.
  • the crosshead is located at an equal distance from the center between the fulcrums of the supports 3 and 3.
  • a load is applied to the test piece 1 by dividing it into two points 4 and 5.
  • the material of the jig was SUS material. Further, the speed at the time of loading of the crosshead 4 was fixed at 5 to 10 mm / min.
  • P maximum load when the test piece breaks [N]
  • L 1 distance between external fulcrums (between fulcrums of the support tools 3 and 3) [mm]
  • L 2 between internal fulcrums (support tools 5, 5) 5) distance [mm]
  • w width of the short side of the test piece [mm]
  • t thickness of the test piece [mm].
  • the width L 3 long sides of the test piece, a longer distance than the L 1.
  • Example 2 In the chemical strengthening step in Example 1, sodium phosphate (Na 3 PO 4 ) was added as an additive to be added to the molten salt melt at a ratio of (addition amount 70 g / 4.5 kg molten salt main agent weight). The chemical strengthening step was performed in the same manner as in Example 1 to produce a cover glass (100 sheets) for portable devices.
  • sodium phosphate Na 3 PO 4
  • Example 3 In the chemical strengthening step in Example 1, potassium sulfate (K 2 SO 4 ) was added as an additive to be added to the molten salt melt at a ratio of (addition amount 70 g / 4.5 kg molten salt main component weight), A chemical strengthening step was performed in the same manner as in Example 1 to produce a cover glass (100 sheets) for portable devices.
  • K 2 SO 4 potassium sulfate
  • Example 4 Example 1 except that potassium fluoride (KF) was added at a ratio of (addition amount 70 g / 4.5 kg molten salt main agent weight) as an additive to be added to the molten salt melt in the chemical strengthening step in Example 1.
  • the chemical strengthening step was performed in the same manner as in Example 1 to produce a cover glass (100 sheets) for portable devices.
  • the cover glasses obtained in Examples 2 to 5 were also evaluated for strength variation and presence / absence of surface deposits in the same manner as in Example 1. The results are summarized in Table 1 below.
  • Example 1 In the chemical strengthening step in Example 1, the chemical strengthening step was performed in the same manner as in Example 1 except that no additive was used in the molten salt melt, and a cover glass (100 sheets) for portable devices was manufactured. did.
  • Comparative Example 2 In the chemical strengthening step in Example 1, the same procedure as in Example 1 was carried out except that hectorite was added as an additive to be added to the molten salt melt at a ratio of (addition amount 70 g / 4.5 kg molten salt main agent weight). Then, a chemical strengthening process was performed to produce a cover glass (100 sheets) for portable devices. The cover glasses obtained in Comparative Examples 1 and 2 were also evaluated for strength variations and presence / absence of surface deposits in the same manner as in Example 1. The results are summarized in Table 1 below.
  • the chemical strengthening treatment of 100 cover glasses was continuously performed, and the molten salt was not exchanged on the way. Glass was obtained. Moreover, the surface deposit
  • Comparative Example 1 in which no additive was added to the molten salt melt, the strength variation of the obtained cover glass was large. Particularly in the 50th and subsequent products, the strength variation is large, and the high strength required for the cover glass for portable devices is not obtained. The reason is considered to be that the chemical strengthening treatment of 100 cover glasses was continuously performed, but the molten salt deteriorated during the process, and the ion exchange process for chemical strengthening did not proceed. Further, in Comparative Example 2 in which hectorite (clay) was added as an additive, the molten salt melt was in a suspended state, and the cover glass after washing had a lot of surface deposits, so that it could not be used as it is. It was. Further, the strength variation is larger than that of the embodiment of the present invention, and a tempered glass having uniform characteristics cannot be obtained.
  • Example 7 In the chemical strengthening step in Example 1, the cover glass that had been subjected to the chemical strengthening was taken out from the molten salt melt, and a cooling step was performed to lower the temperature of the cover glass. Cooling was first performed in the air, and then the cover glass was immersed in water and quenched. After cooling, cleaning was performed to remove deposits on the cover glass. The chemical strengthening step was performed in the same manner as in Example 1 except that the above cooling step was performed. As the additive to be added to the molten salt melt, the same sodium carbonate as in Example 1 was used in the same amount. Thus, the cover glass (100 sheets) for portable devices was manufactured.
  • Example 8 A chemical strengthening process was performed in the same manner as in Example 7 except that potassium carbonate (addition amount was the same as in Example 7) was used as an additive to be added to the molten salt melt, and a cover glass for portable devices (100 sheets) ) was manufactured.
  • Example 9 The chemical strengthening process was performed in the same manner as in Example 7 except that sodium sulfate (addition amount was the same as in Example 7) was used as an additive to be added to the molten salt melt, and a cover glass for portable devices (100 sheets) ) was manufactured.
  • Example 10 A chemical strengthening process was performed in the same manner as in Example 7 except that potassium sulfate (addition amount was the same as in Example 7) was used as an additive to be added to the molten salt melt, and a cover glass for portable devices (100 sheets) ) was manufactured.
  • Example 2 About the cover glass for portable devices obtained in Examples 7 to 10 described above, the four-point bending strength and the presence or absence of surface deposits were evaluated in the same manner as in Example 1.
  • the main surface is divided into 10 sections by dividing the main surface into 5 equal parts in the long side direction and into 2 parts in the short side direction, and the surface roughness of the central part of each section is measured, The uniformity of the 10 surface roughness variations was evaluated.
  • ⁇ indicates that the variation width of the surface roughness Ra is within 0.30 nm ⁇ 0.05 nm
  • ⁇ indicates that the variation width of the surface roughness Ra is within Ra 0.30 nm ⁇ 0.10 nm.
  • the surface roughness Ra is represented by an arithmetic average roughness Ra defined by JIS B0601: 2001, and is measured with, for example, a scanning probe microscope (atomic force microscope; AFM) nanoscope manufactured by Veeco, Japan. R1683: It can be calculated by a method defined in 2007. In Examples 7 to 10, measurement was performed using the arithmetic average roughness Ra when measured at a resolution of 512 ⁇ 128 pixels in a measurement area of 1 ⁇ m ⁇ 1 ⁇ m square.

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Abstract

La présente invention concerne un procédé de production d'un verre protecteur pour appareils portatifs qui fait appel à une étape d'échange d'ions dans laquelle un article en verre ayant une composition contenant du lithium est mis en contact avec un sel en fusion qui contient un élément de métal alcalin ayant un rayon ionique plus grand que celui du lithium, qui est contenu dans le verre, pour provoquer ainsi un échange d'ions entre certains des ions lithium contenus dans l'article en verre et le métal alcalin contenu dans le sel en fusion. Au moins un additif choisi dans le groupe comprenant NaF, KF, K3AlF6, Na2CO3, NaHCO3, K2CO3, KHCO3, Na2SO4, K2SO4, KAl(SO4)2, Na3PO4 et K3PO4 est ajouté au sel en fusion et l'étape d'échange d'ions est effectuée de sorte que l'additif se trouve à l'état solide.
PCT/JP2012/072885 2011-09-09 2012-09-07 Procédé de production d'un verre protecteur pour appareil portatif WO2013035840A1 (fr)

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