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WO2014115789A1 - Matériau à base de verre pour trempe chimique, verre chimiquement trempé et verre couvre-objet - Google Patents

Matériau à base de verre pour trempe chimique, verre chimiquement trempé et verre couvre-objet Download PDF

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Publication number
WO2014115789A1
WO2014115789A1 PCT/JP2014/051325 JP2014051325W WO2014115789A1 WO 2014115789 A1 WO2014115789 A1 WO 2014115789A1 JP 2014051325 W JP2014051325 W JP 2014051325W WO 2014115789 A1 WO2014115789 A1 WO 2014115789A1
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Prior art keywords
glass
temperature
chemical strengthening
range
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Japanese (ja)
Inventor
昭男 大垣
将也 木下
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Konica Minolta Inc
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

Definitions

  • the present invention relates to a chemically strengthened glass material, a chemically strengthened glass obtained by chemically strengthening the chemically strengthened glass material, and a cover glass made of the chemically strengthened glass.
  • the glass in order to start forming a glass, the glass needs to be moderately soft, and in order to form a particularly fine shape, the glass must be softer. Also, at the time of finishing the molding operation, the glass must not be too soft and at least hard enough to maintain the shape of the product.
  • the viscosity of the glass is ⁇ [dPa ⁇ s]
  • the viscosity of the glass at the start of molding is generally 3 to 4 in terms of log ⁇
  • the viscosity of log ⁇ is 7. About 65.
  • the viscosity of glass in an actual molding operation is slightly different depending on differences in molding method, product type, product size and color, and cannot be determined uniformly.
  • the shape of the cover glass for mobile terminals has a shape that matches the shape of the display screen of the device in addition to the conventional rectangular shape (for example, it has a negative curvature that is greatly recessed inward on one side of the cover glass) Complicated shapes, such as a shape in which holes are formed on the main surface of the cover glass.
  • a molding method by a press method is optimal.
  • the cover glass having these shapes is required to have a precise surface shape.
  • the viscosity of the glass at the start of molding is 3 to 7 in terms of log ⁇ , and the value of log ⁇ is 11 to 15 at the end of the molding operation, making use of a viscosity range where the glass is quite hard is doing.
  • the glass in order to form a precise surface over a wide range, the glass remains in the mold up to a viscosity range where the glass becomes hard.
  • the formed glass is subjected to chemical strengthening treatment by an ion exchange method. Therefore, it is desired to solve the above problems in the glass (chemical strengthening glass material) subjected to such chemical strengthening treatment.
  • the present invention has been made to solve the above-mentioned problems, and its purpose is to suppress the fusion of glass to a mold during molding and perform molding using a hard viscosity range. Even when the molding operation is completed, a glass material for chemical strengthening that can suppress the occurrence of cracks after the completion of the molding operation, a chemically strengthened glass obtained by chemically strengthening the glass material for chemical strengthening, and a cover glass made of the chemically strengthened glass And to provide.
  • the glass material for chemical strengthening is 1150 ° C. or lower, In the temperature range from the glass transition temperature (Tg) to the yield point (At), the maximum value of the average linear expansion coefficient ( ⁇ ) is less than 1000 ⁇ 10 ⁇ 7 / ° C., In mol% SiO 2 : 50 to 70% (excluding 70%), Al 2 O 3 : 4 to 8% (excluding 8%), B 2 O 3 : 0 to 4% Li 2 O not included, Na 2 O: 10-22% (excluding 10%), K 2 O: 0 to 2%, ZnO: 0 to 5%, MgO: 5 to 15% (excluding 5%), CaO: 0 to 3%, SrO: 0-5% BaO: 0-5%, TiO 2 : 0 to 10% ZrO 2 : 1.5-7%, Sb 2 O 3 : 0 to 0.5% CeO 2 : 0 to 0.5% It is the structure containing each glass component of.
  • the glass transition temperature (Tg) is desirably 650 ° C. or lower.
  • the glass transition temperature (Tg) is less than 600 ° C., Mol%, SiO 2 : 60 to 67%, Al 2 O 3 : 4.5 to 6% (excluding 6%), B 2 O 3 : 0 to 2.5%, Li 2 O not included, Na 2 O: 15-18%, K 2 O: 0 to 2%, ZnO: 0 to 5%, MgO: 6-9%, CaO: 0-2%, SrO: 0 to 1%, BaO: 0 to 1%, TiO 2 : 0 to 3%, ZrO 2 : 1.5 to 4%, Sb 2 O 3 : 0 to 0.5% CeO 2 : 0 to 0.5% It is desirable to contain each glass component.
  • the glass transition temperature (Tg) is desirably 500 ° C. or higher.
  • a chemically strengthened glass according to another aspect of the present invention includes any of the above-described chemically strengthened glass materials and a compressive stress layer formed on the surface of the chemically strengthened glass material by a chemical strengthening treatment. It is a configuration.
  • the thickness of the compressive stress layer is 5 to 50 ⁇ m and the surface compressive stress is 800 MPa or more.
  • the cover glass according to still another aspect of the present invention is composed of the above-described chemically strengthened glass and is formed by press molding.
  • the glass material for chemical strengthening it is possible to suppress the fusion of glass to the mold, and even when molding is performed using a hard viscosity range, cracks, chips, etc. are generated after the molding operation is completed. Occurrence can be suppressed, and stable press molding and precise surface formation are possible. Further, by performing the chemical strengthening treatment, a glass having a sufficient strength (chemically strengthened glass) can be realized, which is suitable for a cover glass of a portable terminal.
  • it is sectional drawing which shows the generation
  • the numerical value range includes the lower limit A and the upper limit B unless otherwise specified.
  • the viscosity log ⁇ represents the logarithm of the viscosity ⁇ , and the unit of the viscosity ⁇ is [dPa ⁇ s].
  • FIG. 1 shows an occurrence pattern of glass cracking in press molding. This will be specifically described below.
  • glass 1 is first charged into lower mold 2 (the viscosity of glass 1 at this time is 3 to 5 in terms of log ⁇ ). Subsequently, the glass 1 is pressurized by the upper mold 3 (the viscosity of the glass 1 at this time is 5 to 7 in terms of log ⁇ ). Next, the glass 1 is gradually cooled while being pressed and held by the upper mold 3, and the glass 1 contracts with the slow cooling at this time. Then, as the glass 1 contracts, pressure is applied to the mold (for example, the upper mold 3) to deform the mold, and the glass 1 is broken by this deformation (the viscosity of the glass 1 at this time is 9 in terms of log ⁇ ). To 13).
  • Tg glass transition point
  • the use of the glass component having a large influence on the expansion in the temperature range is limited to a specific range, and the average linear expansion coefficient ( ⁇ ) in the temperature range is 1000 ⁇ 10 ⁇ 7 /
  • ⁇ average linear expansion coefficient
  • the glass material for chemical strengthening is a glass material capable of chemical strengthening used for precision press molding, such as a cover glass of a mobile terminal
  • the maximum value of the average linear expansion coefficient ( ⁇ ) is less than 1000 ⁇ 10 ⁇ 7 / ° C.
  • the above-mentioned average linear expansion coefficient ( ⁇ ) is determined when a plurality of temperature sections are considered in the temperature range (temperature range higher than the glass transition temperature) from the glass transition temperature (Tg) to the yield point (At). (Some of the different temperature sections may overlap each other), which is a value representative of the linear expansion coefficient (linear expansion coefficient) in each temperature section, and indicates the average value here.
  • the maximum value of the average linear expansion coefficient ( ⁇ ) refers to the maximum value among the average linear expansion coefficients ( ⁇ ) of the respective temperature sections.
  • the average linear expansion coefficient ( ⁇ ) is 1000 ⁇ 10 ⁇ 7 / ° C. or more, the glass shrinks greatly during the cooling process. There is a risk of occurrence of cracks (hereinafter referred to as cracks).
  • the maximum value of the average linear expansion coefficient ( ⁇ ) is less than 1000 ⁇ 10 ⁇ 7 / ° C.
  • the degree of shrinkage can be reduced and the occurrence of cracks and the like can be suppressed.
  • a preferable range of the average linear expansion coefficient ( ⁇ ) is 900 ⁇ 10 ⁇ 7 / ° C. or less, a more preferable range is 800 ⁇ 10 ⁇ 7 / ° C. or less, and a more preferable range is 700 ⁇ 10 ⁇ 7. / ° C or less.
  • the glass transition temperature (Tg) and yield point (At) can be measured, for example, with a thermomechanical analyzer manufactured by Seiko Instruments Inc. with a weight of 10 g and a temperature increase rate of 10 ° C./min.
  • the linear expansion coefficient ( ⁇ ) can be calculated from the result of thermomechanical analysis using the above-described apparatus (details will be described in Examples described later).
  • typical components that increase the average linear expansion coefficient ( ⁇ ) are B 2 O 3 and CaO, and typical components that decrease the average linear expansion coefficient ( ⁇ ) are SiO 2 . is there.
  • ZnO, ZrO 2 , MgO, TiO 2 , SrO, and BaO function as an intermediate between B 2 O 3 , CaO, and SiO 2 .
  • the average linear expansion coefficient ( ⁇ ) can be decreased by substituting B 2 O 3 or CaO with SiO 2
  • the average linear expansion coefficient ( ⁇ ) can be increased by performing reverse substitution. Can do.
  • the amount of change in the average linear expansion coefficient ( ⁇ ) can be controlled by the replacement amount of the glass component to be replaced.
  • SiO 2 50 to 70% (excluding 70%), Al 2 O 3 : 4 to 8% (excluding 8%), B 2 O 3 : 0 to 4%, Li 2 O not included, Na 2 O: 10 to 22% (excluding 10%), K 2 O: 0 to 2%, ZnO: 0 to 5%, MgO: 5 to 15% (provided 5%) CaO: 0 to 3%, SrO: 0 to 5%, BaO: 0 to 5%, TiO 2 : 0 to 10%, ZrO 2 : 1.5 to 7%, Sb 2 O 3 : 0
  • the average linear expansion coefficient ( ⁇ in the temperature range higher than the glass transition temperature (Tg) ) Can be controlled to be less than 1000 ⁇ 10 ⁇ 7 / ° C.
  • the glass transition temperature (Tg) is preferably 650 ° C. or lower, more preferably 630 ° C. or lower, and 620 ° C. or lower. It is even more desirable that the temperature is less than 600 ° C.
  • the temperature of the mold at the time of press molding is set near the glass transition temperature (Tg)
  • the temperature of the mold can be lowered when the glass transition temperature (Tg) is low. As a result, the life of the press mold can be extended.
  • It can be controlled to be less than ⁇ 10 -7 / ° C. Thereby, it is possible to reduce the degree of shrinkage of the glass during the cooling process and suppress the occurrence of cracks and the like while reliably obtaining the effect of extending the life of the press mold.
  • the glass transition temperature (Tg) is 500 ° C. or higher.
  • the glass transition temperature (Tg) is as high as 500 ° C. or higher, stress relaxation hardly occurs during ion exchange by chemical strengthening treatment. Thereby, it becomes easy to obtain a high surface compressive stress by the chemical strengthening treatment.
  • the maximum value of the average linear expansion coefficient ( ⁇ ) is 900 ⁇ in the temperature range higher than the glass transition temperature (Tg) while suppressing the glass transition temperature (Tg) to 500 ° C.
  • the thickness of the glass material for chemical strengthening of the present embodiment is preferably 1.2 mm or less, and the thinner the thickness, the lighter the weight can be reduced. Therefore, the thickness is more preferably 1.0 mm or less, and 0.8 mm or less. Is more preferable, and it is still more preferable that it is 0.5 mm or less.
  • FIG. 3 is a cross-sectional view schematically showing the configuration of the chemically strengthened glass 10 of the present embodiment.
  • the chemically strengthened glass 10 has the glass material 11 for chemical strengthening having the above-described configuration and a compressive stress layer 12 formed on the surface thereof.
  • the compressive stress layer 12 is formed by immersing the chemical strengthening glass material 11 in a molten salt having a temperature of 380 ° C. to 450 ° C. for 1 to 12 hours and performing chemical strengthening treatment by an ion exchange method. . That is, the compressive stress layer 12 can be formed on the surface of the glass material 11 for chemical strengthening by converting the alkali ions inside the glass into other alkali ions by an ion exchange method.
  • the thickness of the compressive stress layer 12 after the chemical strengthening treatment exceeds 50 ⁇ m, a part of the chemically strengthened glass (chemically strengthened glass 10) is cut or a process such as drilling is performed on the glass. In addition, cracks are likely to occur from the surface. Therefore, the thickness of the compressive stress layer 12 is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, still more preferably 20 ⁇ m or less, and even more preferably 15 ⁇ m or less. In addition, when the thickness of the compressive stress layer 12 is less than 5 ⁇ m, it is difficult to obtain sufficient surface compressive stress. Therefore, the thickness of the compressive stress layer 12 is preferably 5 ⁇ m or more, and more preferably 8 ⁇ m or more.
  • the surface compressive stress is preferably 800 MPa or more, more preferably 900 MPa or more, and 1000 MPa or more. Is more preferable, and more preferably 1100 MPa or more.
  • the cover glass of the portable terminal is composed of the above chemically strengthened glass 10 and is formed by press molding. Thereby, various shapes of cover glass having sufficient strength can be easily realized.
  • the content of SiO 2 is preferably in the range of 50 to 70% (but not including 70%), more preferably in the range of 55 to 67%, still more preferably in the range of 60 to 67%, and 61 to A range of 67% is more preferred.
  • Al 2 O 3 is a component that greatly affects chemical strengthening.
  • Al 2 O 3 works as a network-forming oxide and has the effect of promoting ion exchange.
  • the content of Al 2 O 3 is preferably in the range of 4 to 8% (excluding 8%), more preferably in the range of 4.5 to 7%, and 4.5 to 6% (however, 6%) Is more preferable, and the range of 4.5 to 5.5% is even more preferable.
  • B 2 O 3 is a component that has a very strong effect of increasing ⁇ , and is preferably avoided. However, it also has the effect of lowering the liquidus temperature and high temperature viscosity of the glass and improving the meltability.
  • the content of B 2 O 3 is preferably in the range of 0 to 4%, more preferably in the range of 0 to 3%, and in the range of 0 to 2.5%. Is even more preferable, and the range of 0 to 2% is still more preferable.
  • Li 2 O was not included. This means that when Li 2 O is contained, lithium ions that dissolve into the molten salt during chemical strengthening inhibit the necessary ion exchange reaction between sodium ions and potassium ions, and continuously perform stable chemical strengthening. This is because the effect of increasing the thickness of the surface compressive stress layer is larger than necessary.
  • Na 2 O is an essential component because the strength of the glass can be improved by replacing sodium ions with other cations such as potassium ions in the molten salt. Moreover, since Na 2 O is a component that has a very strong effect of increasing ⁇ , ⁇ can be reduced by reducing the amount of use. However, if the amount of Na 2 O used is reduced, the chances of ion exchange are reduced, and chemical strengthening becomes difficult and sufficient strength cannot be obtained. That is, when the content of Na 2 O is less than 10%, ion exchange is insufficient and a sufficient effect cannot be obtained. On the other hand, when the content of Na 2 O exceeds 22%, the weather resistance deteriorates.
  • the content of Na 2 O is preferably in the range of 10 to 22% (but not including 10%), more preferably in the range of 12 to 20%, and in the range of 14 to 19%. More preferably, it is more preferably in the range of 15 to 18%.
  • K 2 O is a component that has a very strong effect of increasing ⁇ , it is preferable to avoid use.
  • K 2 O is a component that easily volatilizes during melting. In particular, this volatile component tends to adhere to the press mold, but it is also a component that improves the meltability of the glass.
  • K 2 O has an effect of promoting ion exchange if used in a small amount. Therefore, K 2 O is preferably used in a small range of 0 to 2%.
  • ZnO is a component having a large effect of reducing ⁇ according to SiO 2 , but also has an effect of suppressing ion exchange. If ZnO is used in excess of 5%, the effect of suppressing ion exchange becomes large, and the compressive stress layer on the surface becomes thin. Further, when ZnO is introduced into a glass containing a relatively large amount of ZrO 2 or MgO described later, the glass is easily devitrified. For this reason, the content of ZnO is preferably in the range of 0 to 5%, more preferably in the range of 0 to 3%, even more preferably in the range of 0 to 1%, and not contained More preferably.
  • MgO is a component that lowers the high temperature viscosity of the glass and improves the meltability.
  • MgO is a component that has a large effect of reducing ⁇ according to ZnO, but does not have a large effect of suppressing ion exchange like ZnO.
  • MgO in excess of 5%, it becomes easy to make ⁇ less than 1000 ⁇ 10 ⁇ 7 / ° C. However, devitrification tends to occur when MgO exceeds 15%. If MgO is used in excess of 9%, it becomes difficult to make the glass transition temperature (Tg) less than 600 ° C.
  • the content of MgO is preferably in the range of 5 to 15% (but not including 5%), more preferably in the range of 5.5 to 10%, and 5.5 to 9%.
  • the range is even more preferable, and the range of 6 to 9% is still more preferable.
  • CaO is a component that has a very strong effect of increasing ⁇ , so it is preferable to avoid using it.
  • CaO also has the effect of greatly reducing the liquidus temperature and high-temperature viscosity of the glass and improving the meltability.
  • the CaO content is preferably in the range of 0 to 3%, more preferably in the range of 0 to 2.5%, and in the range of 0 to 2%. Is more preferable, and the range of 0 to 1.5% is still more preferable.
  • SrO and BaO have the effect of making glass difficult to devitrify, but BaO is a deleterious substance, and SrO has properties similar to BaO. Accordingly, the SrO and BaO contents are each preferably limited to a range of 0 to 5%, more preferably a range of 0 to 3%, and still more preferably a range of 0 to 1%.
  • TiO 2 is a component that increases the glass transition temperature (Tg) and lowers the high-temperature viscosity to improve the meltability.
  • TiO 2 acts as an intermediate between B 2 O 3 , CaO and SiO 2 from the viewpoint of influence on ⁇ , but has an action somewhat close to CaO, and increases ⁇ when used in large quantities. There is danger.
  • the content of TiO 2 exceeds 10%, ion exchange is suppressed.
  • the content of TiO 2 is preferably in the range of 0 to 10%, more preferably in the range of 0 to 7%, even more preferably in the range of 0 to 5%. More preferably, it is in the range of ⁇ 3%.
  • ZrO 2 works in the middle of B 2 O 3 , CaO and SiO 2 from the viewpoint of the influence on ⁇ , but has an action close to SiO 2 , and uses ZrO 2 in an amount of 1.5% or more. Thus, it becomes easy to make ⁇ less than 1000 ⁇ 10 ⁇ 7 / ° C. ZrO 2 also has the effect of increasing the glass transition temperature (Tg) and improving the weather resistance. However, when ZrO 2 is used in excess of 7%, it becomes extremely easy to devitrify. Therefore, the content of ZrO 2 is preferably in the range of 1.5 to 7%, more preferably in the range of 1.5 to 5%, and in the range of 1.5 to 4%. Even more preferred.
  • Sb 2 O 3 and CeO 2 can be used as a defoaming agent, but the effect is sufficient when 0.5% or less is used. That is, the contents of Sb 2 O 3 and CeO 2 are each preferably in the range of 0 to 0.5%. It should be noted that one or more selected from the group of SO 3 , chloride and SnO 2 known as other defoaming agents may be selected and used within a range of 0.001 to 3%.
  • Example Hereinafter, specific examples of the chemically strengthened glass material and the chemically strengthened glass of the present embodiment will be described as examples. Moreover, a comparative example is also demonstrated for the comparison with an Example. Tables 1 to 6 show the glass compositions and physical properties of the examples and comparative examples. In these tables, the amount of the component in the column where no numerical value is described is 0 mol%.
  • the glass material for chemical strengthening and the chemically strengthened glass of each Example and each Comparative Example were produced as follows. First, commonly used glass materials such as oxides, hydroxides, carbonates and nitrates are selected so as to have the glass compositions shown in Tables 1 to 6, weighed to 1 kg as glass, and then mixed. did. Next, these glass raw materials are put into a platinum crucible, put into an electric furnace at 1400 to 1600 ° C., melted for 3 to 8 hours, homogenized by defoaming and stirring, poured into a mold, and near the glass transition temperature. The glass block was obtained by gradually cooling at a temperature of. This glass block was cut and ground, and then both surfaces were polished to a mirror surface to obtain a glass plate (a glass material for chemical strengthening) having a thickness of 0.70 mm, a width of 40 mm, and a length of 40 mm.
  • a glass plate a glass material for chemical strengthening
  • this glass plate was immersed in KNO 3 salt at 380 to 450 ° C. for 2 to 8 hours, washed and dried to obtain a chemically strengthened glass having a compression stress layer formed on the surface of the glass plate. Then, the surface compressive stress (unit: MPa) of the chemically strengthened glass and the thickness (unit: ⁇ m) of the compressive stress layer were measured with a glass surface stress meter (FSM-6000LE manufactured by Orihara Seisakusho).
  • a glass surface stress meter FSM-6000LE manufactured by Orihara Seisakusho
  • thermomechanical analyzer (TMA / SS6000" by Seiko Instruments Inc., it is 10 degreeC / min. It measured on temperature rising conditions.
  • Tg glass transition temperature
  • At glass yield point
  • ⁇ average linear expansion coefficient
  • thermomechanical analyzer 10 g / min while applying a constant load of 10 g in the direction of the upper and lower surfaces of the cylinder to a sufficiently annealed cylindrical glass sample having a length of 20 mm and a diameter of 5 mm. Heated at a constant rate of ° C. And the elongation amount of the sample at this time was repeatedly measured at intervals of 2 seconds.
  • TMA ThermomechanicalTMAnalysis
  • FIG. 4 shows the relationship (TMA curve) between the elongation amount TMA and the temperature of the obtained sample for Example 9.
  • Tg glass transition temperature defined in the Optical Glass Industry Association standard was determined, and the temperature at which the TMA reached a maximum was determined as the yield point (At).
  • Table 7 shows the average linear expansion coefficient ( ⁇ ) in each temperature section from the glass transition temperature (Tg) to the yield point (At) in Example 9. From Table 7, it can be seen that in Example 9, the maximum value of the average linear expansion coefficient ( ⁇ ) is 955 ⁇ 10 ⁇ 7 / ° C.
  • the maximum value of the expansion coefficient ( ⁇ ) is less than 1000 ⁇ 10 ⁇ 7 / ° C. Thereby, the fusion of the glass to the mold at the start of molding can be suppressed, and the degree of shrinkage of the glass during the cooling process can be reduced, and the generation of cracks, chips and cans can be suppressed.
  • the thickness of the compressive stress layer is in the range of 5 to 50 ⁇ m, and the surface compressive stress exceeds 800 MPa. Thereby, it is possible to realize a chemically strengthened glass having a sufficiently large strength and difficult to break during processing. Therefore, such a chemically strengthened glass is suitable for a cover glass for a portable terminal that requires high strength.
  • the maximum value of the average linear expansion coefficient ( ⁇ ) in the above temperature range exceeds 1000 ⁇ 10 ⁇ 7 / ° C. This is because, in Comparative Example 1, a large amount of CaO, which is a component that increases the average linear expansion coefficient ( ⁇ ), is used. In Comparative Examples 2 and 3, the component that increases the average linear expansion coefficient ( ⁇ ). This is presumed to be because a large amount of B 2 O 3 is used. As a result, in the glasses of Comparative Examples 1 to 3, it is considered that the degree of shrinkage of the glass during the cooling process cannot be reduced, and the occurrence of cracks and the like cannot be suppressed.
  • the time for immersing the chemically strengthening glass material in the molten salt is 2 to 8 hours, but the immersion time can be appropriately adjusted. For example, even if the immersion time is adjusted in the range of 1 to 12 hours, the chemically strengthened glass having the characteristics described in the present embodiment can be obtained.
  • the temperature of the molten salt is not limited to 380 ° C. to 450 ° C., and may be appropriately adjusted as necessary. Further, it may be subjected to chemical strengthening process using a molten salt other than KNO 3 salt.
  • the chemically tempered glass material and the chemically tempered glass of the present invention can be used for, for example, a cover glass of a portable terminal or a display.

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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne un matériau à base de verre pour trempe chimique (11) présentant une température de 1150 °C ou moins à une viscosité de logη=4 et une valeur maximum de coefficient moyen d'expansion linéaire (α) inférieure à 1000×10-7/°C dans la gamme de températures allant de la température de transition vitreuse (Tg) au seuil d'écoulement (At), et comprend des composants de verre, en % en mole, de 50 à 70 % (à l'exclusion de 70 %) de SiO2, 4 à 8 % (à l'exclusion de 8 %) de Al2O3, 0 à 4 % de B2O3, pas de Li2O, 10 à 22 % (à l'exclusion de 10 %) de Na2O, 0 à 2 % de K2O, 0 à 5 % de ZnO, 5 à 15 % (à l'exclusion de 5 %) de MgO, 0 à 3 % de CaO, 0 à 5 % de SrO, 0 à 5 % de BaO, 0 à 10 % de TiO2, 1,5 à 7 % de ZrO2, 0 à 0,5 % de Sb2O3 et 0 à 0,5 % de CeO2.
PCT/JP2014/051325 2013-01-23 2014-01-23 Matériau à base de verre pour trempe chimique, verre chimiquement trempé et verre couvre-objet Ceased WO2014115789A1 (fr)

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CN105399449A (zh) * 2015-11-26 2016-03-16 陕西科技大学 一种复合微晶石的制备方法
CN107673602A (zh) * 2017-10-25 2018-02-09 北京工业大学 一种可高效化学强化的无碱土金属氧化物的高碱铝硅酸盐玻璃
CN113277730A (zh) * 2021-06-21 2021-08-20 成都光明光电有限责任公司 低介电常数玻璃组合物
CN114560631A (zh) * 2021-11-09 2022-05-31 河北视窗玻璃有限公司 一种防蓝光盖板玻璃及其制备方法和应用

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CN105399449A (zh) * 2015-11-26 2016-03-16 陕西科技大学 一种复合微晶石的制备方法
CN107673602A (zh) * 2017-10-25 2018-02-09 北京工业大学 一种可高效化学强化的无碱土金属氧化物的高碱铝硅酸盐玻璃
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