WO2017170053A1 - Verre chimiquement renforcé - Google Patents

Verre chimiquement renforcé Download PDF

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Publication number
WO2017170053A1
WO2017170053A1 PCT/JP2017/011493 JP2017011493W WO2017170053A1 WO 2017170053 A1 WO2017170053 A1 WO 2017170053A1 JP 2017011493 W JP2017011493 W JP 2017011493W WO 2017170053 A1 WO2017170053 A1 WO 2017170053A1
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Prior art keywords
compressive stress
depth
glass
ion exchange
mpa
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PCT/JP2017/011493
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English (en)
Japanese (ja)
Inventor
結城　健
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日本電気硝子株式会社
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Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to JP2018509133A priority Critical patent/JP6949313B2/ja
Priority to KR1020187018240A priority patent/KR102242188B1/ko
Priority to CN201780015401.6A priority patent/CN108779025B/zh
Publication of WO2017170053A1 publication Critical patent/WO2017170053A1/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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • 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
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

  • the present invention relates to a chemically tempered glass, and more particularly to a chemically tempered glass suitable for a cover glass of a mobile phone, a digital camera, a PDA (mobile terminal), or a touch panel display.
  • Devices such as mobile phones (especially smartphones), digital cameras, PDAs, touch panel displays, large TVs, etc. are becoming increasingly popular.
  • the breakage of the cover glass mainly occurs when an impact is applied to the end face.
  • it is effective to increase the stress depth of the end face so that cracks existing on the end face do not progress.
  • the stress depth of the end face is increased, the internal tensile stress value is increased, and the chemically strengthened glass is easily self-destructed.
  • the cover glass is thinned, the tendency becomes remarkable.
  • the present invention has been made in view of the above circumstances, and its technical problem is to create a chemically tempered glass that is not easily damaged even when an impact is applied to the end face.
  • the present inventor has found that there is a strong correlation between the compressive stress value at the specific depth from the surface of the chemically strengthened glass and the end face strength, and the specific depth from the surface of the chemically strengthened glass.
  • the present inventors have found that the above technical problem can be solved by restricting the compressive stress value to a predetermined value or more, and propose as the present invention. That is, the chemically tempered glass of the present invention is characterized in that it has a compressive stress layer on its surface and has an average compressive stress value of 350 MPa or more at a depth of 7 to 16 ⁇ m from the surface.
  • the last ion exchange treatment (for example, in the case of one ion exchange treatment, in the case of the first ion exchange treatment, in the case of two ion exchange treatments, In the second ion exchange treatment), when the temperature is 390 to 420 ° C., the time is 1.5 to 4 hours, and the ion exchange solution is 90% by mass or more of KNO 3 , the average compressive stress value at a depth of 7 to 16 ⁇ m is obtained. It can raise suitably.
  • the “compressive stress value” and “stress depth” are the number of interference fringes observed when the measurement sample is observed using the software FsmV of a surface stress meter (FSM-6000LE manufactured by Orihara Seisakusho Co., Ltd.).
  • the measurement setting (enhancement type) is set to the chemical strengthening II
  • the measurement mode is set to the exact solution mode
  • the inflection point position is used to calculate the boundary position of the depth measurement.
  • the value of DOL_zero calculated by FsmV is adopted as the “stress depth”.
  • the “internal tensile stress value” the value of CT_cv obtained by the above measurement is adopted.
  • the value of DOL_tail obtained by the above measurement is adopted as the “depth of the ion exchange layer”.
  • the chemically strengthened glass of the present invention preferably has a compressive stress value of 350 MPa or more at a depth of 12 ⁇ m from the surface.
  • the chemically tempered glass of the present invention preferably has a compressive stress value of 450 MPa or more at a depth of 7 ⁇ m from the surface and a compressive stress value of 250 MPa or more at a depth of 16 ⁇ m from the surface.
  • the chemically tempered glass of the present invention has a bent compressive stress curve in the depth direction from the surface.
  • Fifth, chemically reinforced glass of the present invention has a glass composition, in mass%, SiO 2 40 ⁇ 80% , Al 2 O 3 5 ⁇ 30%, Li 2 O 0 ⁇ 5%, Na 2 O 5 ⁇ 25 % Is preferably contained.
  • the chemically strengthened glass of the present invention preferably has a liquidus viscosity of 10 4.0 dPa ⁇ s or more.
  • the “liquid phase temperature” refers to a temperature gradient after pulverizing glass, passing through a standard sieve 30 mesh (a sieve opening of 500 ⁇ m), and putting the glass powder remaining in 50 mesh (a sieve opening of 300 ⁇ m) into a platinum boat. It means a value obtained by measuring the temperature at which crystals are deposited while being kept in a furnace for 24 hours.
  • the “liquid phase viscosity” refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.
  • the temperature in the high temperature viscosity 10 4.0 dPa ⁇ s is 1300 ° C. or less.
  • the “temperature at a high temperature viscosity of 10 4.0 dPa ⁇ s” refers to a value measured by a platinum ball pulling method.
  • the chemically tempered glass of the present invention preferably has a thermal expansion coefficient of 95 ⁇ 10 ⁇ 7 / ° C. or less in a temperature range of 30 to 380 ° C.
  • thermal expansion coefficient in the temperature range of 30 to 380 ° C.” refers to a value measured with a dilatometer.
  • the chemically strengthened glass of the present invention has a flat plate shape. If it does in this way, it will become easy to apply to the cover glass etc. of a smart phone.
  • the chemically strengthened glass of the present invention preferably has a thickness of 0.1 to 2.0 mm and a stress depth of 10 ⁇ m or more.
  • the chemically strengthened glass of the present invention is preferably used for a cover glass of a touch panel display.
  • (A) is a conceptual perspective view which shows the shape of the test jig and test head which clamped the test piece.
  • (B) is a conceptual sectional view showing the collision state of the end face strength test.
  • 6 is a graph showing a relationship between an average compressive stress value at a depth of 7 to 16 ⁇ m from the surface and an average fracture height in an end face strength test.
  • the chemically tempered glass of the present invention has a compressive stress layer on the surface.
  • a method for forming a compressive stress layer on the surface there are a physical strengthening method and a chemical strengthening method.
  • a compressive stress layer is formed by a chemical strengthening method.
  • the chemical strengthening method is a method in which alkali ions having a large ion radius are introduced to the surface of the glass by ion exchange treatment at a temperature below the strain point of the glass. If the compressive stress layer is formed by the chemical strengthening method, the compressive stress layer can be appropriately formed even when the glass has a small thickness.
  • the composition of the ion exchange solution may be determined in consideration of the viscosity characteristics of the chemically strengthened glass.
  • Various ion exchange solutions can be used as the ion exchange solution, but a KNO 3 molten salt or a mixed molten salt of NaNO 3 and KNO 3 is preferable. In this way, the compressive stress layer can be efficiently formed on the surface.
  • the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface is 350 MPa or more, preferably 400 MPa or more, 450 MPa or more, 500 MPa or more, 520 MPa or more, 550 MPa or more, particularly preferably 570 MPa or more. is there. If the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface is too low, the end face strength tends to decrease. On the other hand, if the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface is too large, the internal tensile stress may become extremely high.
  • the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface is preferably 1000 MPa or less.
  • the last ion exchange treatment for example, in the case of one ion exchange treatment, in the case of the first ion exchange treatment, in the case of two ion exchange treatments, In the second ion exchange treatment
  • the temperature is 390 to 420 ° C.
  • the time is 1.5 to 4 hours
  • the ion exchange solution is 90% by mass or more of KNO 3
  • the average compressive stress value at a depth of 7 to 16 ⁇ m is obtained. It can raise suitably.
  • the compressive stress value at a depth of 7 ⁇ m from the surface is preferably 450 MPa or more, 550 MPa or more, 600 MPa or more, 650 MPa or more, 680 MPa or more, particularly preferably 700 MPa or more. If the compressive stress value at a depth of 7 ⁇ m from the surface is too low, the end face strength tends to decrease. On the other hand, if the compressive stress value at a depth of 7 ⁇ m from the surface is too large, the internal tensile stress may become extremely high. Therefore, the compressive stress value at a depth of 7 ⁇ m from the surface is preferably 1000 MPa or less.
  • the compressive stress value at a depth of 12 ⁇ m from the surface is preferably 350 MPa or more, 400 MPa or more, 450 MPa or more, 480 MPa or more, 500 MPa or more, 530 MPa or more, particularly preferably 550 MPa or more. If the compressive stress value at a depth of 12 ⁇ m from the surface is too low, the end face strength tends to decrease. On the other hand, if the compressive stress value at a depth of 12 ⁇ m from the surface is too large, the internal tensile stress may become extremely high. Therefore, the compressive stress value at a depth of 12 ⁇ m from the surface is preferably 1000 MPa or less. It should be noted that the compressive stress value at a depth of 12 ⁇ m from the surface has a higher correlation with the end face strength than the compressive stress values at other depths.
  • the compressive stress value at a depth of 16 ⁇ m from the surface is preferably 250 MPa or more, 280 MPa or more, 320 MPa or more, 360 MPa or more, 400 MPa or more, and particularly preferably 430 MPa or more. If the compressive stress value at a depth of 16 ⁇ m from the surface is too low, the end face strength tends to decrease. On the other hand, if the compressive stress value at a depth of 16 ⁇ m from the surface is too large, the internal tensile stress may become extremely high. Therefore, the compressive stress value at a depth of 16 ⁇ m from the surface is preferably 800 MPa or less. The compressive stress value at a depth of 16 ⁇ m from the surface has a stronger correlation with the end face strength than the compressive stress values at other depths.
  • the surface compressive stress value is preferably 600 MPa or more, 700 MPa or more, 750 MPa or more, 800 MPa or more, 850 MPa or more, and particularly preferably 900 MPa or more.
  • the surface compressive stress value increases, the mechanical strength of the chemically strengthened glass increases.
  • the mechanical strength of the chemically strengthened glass may be reduced.
  • the surface compressive stress value is preferably 1400 MPa or less. Note that when the ion exchange treatment time is shortened or the ion exchange treatment temperature is lowered, the surface compressive stress value tends to increase.
  • the stress depth is preferably 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 35 ⁇ m or more, 40 ⁇ m or more, 45 ⁇ m or more, particularly preferably 50 ⁇ m or more and 90 ⁇ m or less. If the stress depth is too small, the end face strength tends to decrease. On the other hand, if the stress depth is too large, the internal tensile stress becomes excessive, and the chemically strengthened glass tends to self-break. Note that the stress depth tends to increase if the time of the ion exchange treatment is increased or the temperature of the ion exchange solution is increased.
  • the compressive stress curve in the depth direction from the surface is preferably bent. In this way, it is possible to reduce the internal tensile stress while increasing the average compressive stress value and the stress depth at a depth of 7 to 16 ⁇ m from the surface.
  • the compressive stress curve in the depth direction from the surface can be bent.
  • the temperature of the last ion exchange treatment (for example, in the case of two ion exchange treatments, the second ion exchange treatment) is preferably 390 to 430 ° C., particularly 400 to 420 ° C.
  • the time for the final ion exchange treatment is preferably 1.5 to 5 hours, in particular 2 to 4.5 hours. This makes it easy to increase the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface.
  • the proportion of small alkali ions (for example, Li ions, Na ions, particularly Na ions) in the ion exchange solution used for the second ion exchange treatment is the ion used for the first ion exchange treatment. Less than that in the exchange liquid is preferred. This makes it easy to increase the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface.
  • the size of the alkali ions is Li ion ⁇ Na ion ⁇ K ion.
  • the content of KNO 3 in the ion exchange solution used for the first ion exchange treatment is preferably less than 75% by mass, 70% by mass or less, particularly 60% by mass or less.
  • the content of KNO 3 in the ion exchange solution used for the second ion exchange treatment is preferably 75% by mass or more, 85% by mass or more, 95% by mass or more, and particularly 99.5% by mass or more.
  • the content of NaNO 3 in the ion exchange solution used for the second ion exchange treatment is smaller than the content of NaNO 3 in the ion exchange solution used for the first ion exchange treatment. It is preferably 5% by mass or less, more preferably 10% by mass or less, and particularly preferably 15% by mass or more. Further, the content of NaNO 3 in the ion exchange solution used for the second ion exchange treatment is preferably 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, particularly 5% by mass or less, 0.5% by mass or less. If there is too much NaNO 3 in the ion exchange solution used for the second ion exchange treatment, it is difficult to increase the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface.
  • Chemically tempered glass of the present invention has a glass composition, in mass%, containing SiO 2 40 ⁇ 80%, Al 2 O 3 5 ⁇ 30%, Li 2 O 0 ⁇ 5%, the Na 2 O 5 ⁇ 25% It is preferable.
  • the reason for limiting the content range of each component as described above will be described below.
  • SiO 2 is a component that forms a network of glass.
  • the content of SiO 2 is preferably 40 to 80%, 50 to 75%, 56 to 70%, 58 to 68%, particularly preferably 59 to 65%.
  • the content of SiO 2 is preferably 40 to 65%, 45 to 60%, 50 to 60%, particularly preferably 53 to 58%. If the content of SiO 2 is too small, vitrification becomes difficult, and the thermal expansion coefficient becomes too high, so that the thermal shock resistance tends to decrease. On the other hand, if the content of SiO 2 is too large, the meltability and the formability tends to decrease.
  • Al 2 O 3 is a component that improves ion exchange performance, and is a component that increases the strain point and Young's modulus.
  • the content of Al 2 O 3 is preferably 5 to 30%. If the content of Al 2 O 3 is too small, the thermal expansion coefficient becomes too high and the thermal shock resistance tends to be lowered, and there is a possibility that the ion exchange performance cannot be sufficiently exhibited. Therefore, the preferable lower limit range of Al 2 O 3 is 7% or more, 8% or more, 10% or more, 12% or more, 14% or more, 15% or more, particularly 16% or more.
  • the preferable lower limit range of Al 2 O 3 is 16% or more, 18% or more, 20% or more, 22% or more, 24% or more, particularly 26% or more.
  • the preferable upper limit range of Al 2 O 3 is 28% or less, 25% or less, 21.5% or less, particularly 19.5% or less.
  • Li 2 O is an ion exchange component and a component that lowers the high-temperature viscosity and improves the meltability and moldability. It is also a component that increases Young's modulus. Furthermore, the effect of increasing the compressive stress value is large among alkali metal oxides. However, when the content of Li 2 O is too large, and decreases the liquidus viscosity, it tends glass devitrified. In addition, the thermal expansion coefficient becomes too high, so that the thermal shock resistance is lowered or it is difficult to match the thermal expansion coefficient of the surrounding material. Furthermore, if the low-temperature viscosity is too low and stress relaxation is likely to occur, the compressive stress value may be reduced.
  • the content of Li 2 O is preferably 0 to 5%, 0.01 to 3%, 0.01 to 2%, 0.01 to 1%, 0.01 to 0.5%, particularly preferably 1 to 0.2%.
  • Li ions act as an ion exchange component, so that the stress depth can be increased in a short time. As a result, the first ion exchange time can be shortened.
  • Na 2 O is a main ion exchange component, and is a component that lowers the high temperature viscosity and improves the meltability and moldability. Na 2 O is also a component that improves devitrification resistance.
  • the content of Na 2 O is preferably 5 to 25%. When Na 2 O content is too small, or reduced meltability, lowered coefficient of thermal expansion tends to decrease the ion exchange performance. Therefore, a preferable lower limit range of Na 2 O is 8% or more, 10% or more, 11% or more, and particularly 12% or more. On the other hand, when the content of Na 2 O is too large, the thermal expansion coefficient becomes too high, the thermal shock resistance is lowered, and it becomes difficult to match the thermal expansion coefficient of the surrounding materials.
  • a preferable upper limit range of Na 2 O is 20% or less, 17% or less, and particularly 16% or less.
  • Li 2 O content is 0.1% or more, it is preferred to reduce the content of Na 2 O, the content of 15% or less, 13% or less, or less, especially 11%.
  • B 2 O 3 is a component that lowers the high temperature viscosity and density, stabilizes the glass, makes it difficult to precipitate crystals, and lowers the liquidus temperature. It is also a component that increases crack resistance. However, if the content of B 2 O 3 is too large, the ion exchange treatment may cause coloring of the surface called burnt, decrease in water resistance, decrease in the compressive stress value of the compressive stress layer, The stress depth of the stress layer tends to decrease. Therefore, the content of B 2 O 3 is preferably 0 to 15%, 0 to 10%, 0.1 to 8%, 0.5 to 6%, 1 to 4%, particularly more than 1 to 3%. .
  • K 2 O is a component that promotes ion exchange, and is a component that has a large effect of increasing the stress depth of the compressive stress layer among alkali metal oxides. Moreover, it is a component which reduces high temperature viscosity and improves a meltability and a moldability. Furthermore, it is also a component that improves devitrification resistance.
  • the content of K 2 O is 0 to 10%. When the content of K 2 O is too large, the thermal expansion coefficient becomes too high, the thermal shock resistance becomes difficult to match or decreased, the thermal expansion coefficient with those of peripheral materials. Moreover, there is a tendency that the strain point is excessively lowered, the component balance of the glass composition is lacking, and the devitrification resistance is lowered. Therefore, the preferable upper limit range of K 2 O is 6% or less, 4% or less, less than 2%, particularly less than 1%.
  • MgO is a component that lowers the viscosity at high temperature, increases meltability and moldability, and increases the strain point and Young's modulus.
  • MgO is a component that has a large effect of improving ion exchange performance. is there.
  • the preferable upper limit range of MgO is 12% or less, 10% or less, 8% or less, 5% or less, and particularly 4% or less.
  • the suitable minimum range of MgO is 0.1% or more, 0.5% or more, 1% or more, especially 2% or more.
  • CaO compared with other components, has a great effect of lowering the high-temperature viscosity without increasing devitrification resistance, improving meltability and moldability, and increasing the strain point and Young's modulus.
  • the CaO content is preferably 0 to 10%.
  • the preferable content of CaO is 0 to 5%, particularly 0 to less than 1%.
  • ZrO 2 is a component that enhances the ion exchange performance and is a component that increases the viscosity and strain point near the liquid phase viscosity, but if its content is too large, the devitrification resistance may be significantly reduced, Also, the density may become too high. Therefore, a suitable upper limit range of ZrO 2 is 10% or less, 8% or less, or 6% or less, particularly 5% or less. In addition, when it is desired to improve the ion exchange performance, it is preferable to introduce ZrO 2 into the glass composition. In this case, a suitable lower limit range of ZrO 2 is 0.01% or more, 0.5%, particularly 1% or more. is there.
  • P 2 O 5 is a component that increases the stress depth, and is a component that shortens the first ion exchange time particularly when performing ion exchange treatment a plurality of times.
  • the content of P 2 O 5 is preferably 0 to 10%, 0 to 8%, 0.1 to 6%, particularly 3 to 6%.
  • ZnO is a component that increases the compressive stress value, and is a component that shortens the second ion exchange time, particularly when performing multiple ion exchange treatments.
  • the content of ZnO is preferably 0 to 10%, 0 to 5%, 0 to 3%, particularly 0.1 to 2%.
  • SnO 2 is a component that increases the compressive stress value while acting as a refining agent, and a suitable content range thereof is preferably 0 to 10,000 ppm (1%), 500 to 7000 ppm, particularly 1000 to 5000 ppm. Incidentally, when the content of SnO 2 is too large, the visible light transmittance tends to decrease.
  • 0 to 30000 ppm (3%) of one or more selected from the group of As 2 O 3 , Sb 2 O 3 , F, Cl, and SO 3 may be introduced.
  • the chemically tempered glass of the present invention preferably has the following glass characteristics.
  • the liquidus temperature is preferably 1200 ° C. or lower, 1100 ° C. or lower, 1050 ° C. or lower, 1000 ° C. or lower, 930 ° C. or lower, 900 ° C. or lower, particularly 880 ° C. or lower.
  • Liquidus viscosity preferably of 10 4.0 dPa ⁇ s or more, 10 4.3 dPa ⁇ s or more, 10 4.5 dPa ⁇ s or more, 10 5.0 dPa ⁇ s or more, 10 5.5 dPa ⁇ s
  • the above is 10 5.7 dPa ⁇ s or more, 10 5.9 dPa ⁇ s or more, particularly 10 6.0 dPa ⁇ s or more.
  • the higher the liquidus viscosity the more difficult it is to devitrify the glass when it is formed into a flat plate shape by the overflow downdraw method or the like.
  • the temperature at a high temperature viscosity of 10 4.0 dPa ⁇ s is preferably 1400 ° C. or lower, 1350 ° C. or lower, 1300 ° C. or lower, 1260 ° C. or lower, 1230 ° C. or lower, particularly 1200 ° C. or lower.
  • Lower the temperature in the high temperature viscosity 10 4.0 dPa ⁇ s is alleviated the burden on the molded body refractory molded body refractory and long life, as a result, it tends to reduce the manufacturing cost of the chemically strengthened glass .
  • the thermal expansion coefficient in the temperature range of 30 to 380 ° C. is preferably 95 ⁇ 10 ⁇ 7 / ° C. or less, particularly 92 ⁇ 10 ⁇ 7 / ° C. or less. If the thermal expansion coefficient in the temperature range of 30 to 380 ° C. is too high, the thermal shock resistance tends to decrease. Therefore, the preheating time before being immersed in the ion exchange solution and the slow cooling time after being immersed in the ion exchange solution are reduced. It needs to be long. Moreover, the glass for chemical strengthening tends to be broken during bending.
  • the thickness in the case of a flat plate shape
  • the thickness is preferably 0.1 to 2.0 mm, 0.2 to 1.0 mm, 0.3 to 0.8 mm, particularly 0.4. ⁇ 0.7 mm. In this way, it becomes easy to reduce the weight of the display device while maintaining the mechanical strength.
  • the glass for chemical strengthening according to the present invention can be produced as follows.
  • a glass raw material prepared to have a desired glass composition is put into a continuous melting furnace, heated and melted at 1500 to 1600 ° C., clarified, fed into a molding apparatus, shaped into a flat plate shape, etc.
  • the glass for chemical strengthening can be produced by cooling.
  • the overflow downdraw method is a method with high surface smoothness and capable of forming a large glass for chemical strengthening, and a method for reducing surface scratches on the glass for chemical strengthening as much as possible.
  • a forming method such as a float method, a downdraw method (slot down method, redraw method, etc.), a rollout method, a press method, or the like can be employed.
  • the glass for chemical strengthening After forming the glass for chemical strengthening, it may be bent as necessary. Moreover, you may perform chamfering as needed.
  • the time for cutting to a desired dimension is preferably before the ion exchange treatment. Thereby, a compressive stress layer can also be formed on the end face.
  • Each chemically strengthened glass (sample Nos. 1 to 10) was produced as follows. First, glass raw materials were prepared to produce a glass batch. Next, this glass batch was put into a continuous melting furnace, and the obtained molten glass was clarified and stirred, and then supplied to a molding apparatus. Subsequently, an alumina-based molded body was used as a molded body and formed into a 0.7 mm-thick flat plate shape by the overflow down draw method, and then cut into a predetermined size to obtain each glass for chemical strengthening. Thereafter, the end face of each chemically strengthened glass was chamfered and polished with a # 800 metal bond grindstone.
  • the obtained glass for chemical strengthening is a glass composition by mass%, SiO 2 61.4%, Al 2 O 3 18%, B 2 O 3 0.5%, Li 2 O 0.1%, Containing Na 2 O 14.5%, K 2 O 2%, MgO 3%, BaO 0.1%, SnO 2 0.4%, liquid phase viscosity 10 6.3 dPa ⁇ s, high temperature viscosity 10 4
  • the temperature at 0.0 dPa ⁇ s was 1255 ° C., and the thermal expansion coefficient was 91 ⁇ 10 ⁇ 7 / ° C. in the temperature range of 30 to 380 ° C.
  • each chemical strengthening glass was subjected to the ion exchange treatment shown in Table 1 using the ion exchange solution shown in Table 1.
  • DOL_zero represents the stress depth
  • DOL_tail represents the depth of the ion exchange layer
  • CT_cv represents the internal tensile stress value.
  • “CS” and “DOL” in the table indicate the number of interference fringes observed when the measurement sample is observed using the software FsmV of a surface stress meter (FSM-6000LE manufactured by Orihara Seisakusho). This value is calculated from the interval.
  • the measurement setting (enhancement type) was set to chemical strengthening II
  • the measurement mode was set to the exact solution mode
  • the inflection point position was used to calculate the boundary position for depth measurement.
  • the refractive index of each sample was 1.50
  • the optical elastic constant was 29.5 [(nm / cm) / MPa].
  • FIG. Fig.1 (a) is a conceptual perspective view which shows the metal jig
  • the test piece 11 is fixed to a metal jig 13 while being sandwiched between a pair of resin plates 12 made of bakelite.
  • the dimension of the test piece 11 is 22 mm ⁇ 30 mm ⁇ 0.7 mm thick, and a 2 mm ⁇ 30 mm portion of the test piece 11 is in a state of protruding from the metal jig 23.
  • the end surface of the protruding portion collides with the test head 14.
  • FIG.1 (b) is a conceptual sectional drawing which shows the collision method of an end surface strength test.
  • the pendulum 15 arm length 500 mm
  • the pendulum 15 is swung down from a height of 10 mm, and is made to collide with the end face of the test piece 11 held between the metal jigs 13. It was. Thereafter, while increasing the height of the pendulum 15 by 10 mm, this operation was continued until the test piece 11 was broken, and the height when the test piece 11 was broken was taken as the breakage height.
  • this end face strength test was performed 10 times, and the arithmetic average value of the breakage height was calculated as the average breakage height.
  • FIG. 2 is a graph showing the relationship between the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface and the average fracture height in the end face strength test. As can be seen from FIG. 2, there is a strong correlation between the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface and the average fracture height in the end face strength test because the correlation coefficient R 2 is 0.8847. .
  • sample no. For 1-4 the average compressive stress value at a depth of 7-16 ⁇ m from the surface was large, so the evaluation of the end face strength test was good.
  • sample No. Nos. 5 to 10 had poor evaluation of the end face strength test because the average compressive stress value at a depth of 7 to 16 ⁇ m from the surface was small.
  • the chemically tempered glass of the present invention is suitable for a cover glass of a mobile phone, a digital camera, a PDA, or a touch panel display.
  • the chemically tempered glass of the present invention is used for applications requiring high mechanical strength, such as window glass, magnetic disk substrates, solar cells, flat panel display substrates, and solid-state image sensor covers. Application to glass, tableware, etc. can be expected.
  • test piece 11 test piece, 12 resin plate, 13 metal jig, 14 test head, 15 pendulum

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Human Computer Interaction (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

La présente invention décrit un verre chimiquement renforcé caractérisé en ce qu'une couche de contrainte de compression est prévue au niveau de sa surface, et la valeur de contrainte de compression moyenne à une profondeur de 7 à 16 µm depuis la surface est de 350 MPa ou plus.
PCT/JP2017/011493 2016-04-01 2017-03-22 Verre chimiquement renforcé WO2017170053A1 (fr)

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JP2018509133A JP6949313B2 (ja) 2016-04-01 2017-03-22 化学強化ガラス
KR1020187018240A KR102242188B1 (ko) 2016-04-01 2017-03-22 화학 강화 유리
CN201780015401.6A CN108779025B (zh) 2016-04-01 2017-03-22 化学强化玻璃

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WO2019235470A1 (fr) * 2018-06-07 2019-12-12 日本電気硝子株式会社 Verre chimiquement renforcé et procédé de fabrication d'un verre chimiquement renforcé
JP2020015654A (ja) * 2018-07-27 2020-01-30 日本電気硝子株式会社 強化ガラス及び強化用ガラス

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WO2020023234A1 (fr) 2018-07-23 2020-01-30 Corning Incorporated Articles en verre de couvercle et d'intérieur d'automobile ayant une performance d'impact de forme de tête et une visibilité de post-rupture améliorées
CN115784634A (zh) 2018-10-18 2023-03-14 康宁公司 展现改善头型冲击性能的强化玻璃制品和结合有该强化玻璃制品的车辆内部系统
WO2020123367A1 (fr) 2018-12-10 2020-06-18 Corning Incorporated Systèmes d'affichage intérieur d'automobile pouvant être courbés dynamiquement
KR102666860B1 (ko) 2018-12-28 2024-05-21 삼성디스플레이 주식회사 윈도우 패널, 이를 포함하는 전자 장치, 및 윈도우 패널의 제조 방법

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WO2015077179A1 (fr) * 2013-11-25 2015-05-28 Corning Incorporated Procédé pour générer un profil de contrainte dans le verre
WO2015127483A2 (fr) * 2014-02-24 2015-08-27 Corning Incorporated Articles en verre renforcé présentant une capacité de survie améliorée
WO2016033038A1 (fr) * 2014-08-28 2016-03-03 Corning Incorporated Article en verre feuilleté avec couches de cœur et de revêtement échangeuses d'ions ayant un contraste de diffusivité et son procédé de fabrication

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JP2006083045A (ja) 2004-09-17 2006-03-30 Hitachi Ltd ガラス部材
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US3433611A (en) * 1965-09-09 1969-03-18 Ppg Industries Inc Strengthening glass by multiple alkali ion exchange
JP2008115072A (ja) * 2006-10-10 2008-05-22 Nippon Electric Glass Co Ltd 強化ガラス基板
WO2015077179A1 (fr) * 2013-11-25 2015-05-28 Corning Incorporated Procédé pour générer un profil de contrainte dans le verre
WO2015127483A2 (fr) * 2014-02-24 2015-08-27 Corning Incorporated Articles en verre renforcé présentant une capacité de survie améliorée
WO2016033038A1 (fr) * 2014-08-28 2016-03-03 Corning Incorporated Article en verre feuilleté avec couches de cœur et de revêtement échangeuses d'ions ayant un contraste de diffusivité et son procédé de fabrication

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019235470A1 (fr) * 2018-06-07 2019-12-12 日本電気硝子株式会社 Verre chimiquement renforcé et procédé de fabrication d'un verre chimiquement renforcé
JPWO2019235470A1 (ja) * 2018-06-07 2021-06-17 日本電気硝子株式会社 化学強化ガラスおよび化学強化ガラスの製造方法
JP7332987B2 (ja) 2018-06-07 2023-08-24 日本電気硝子株式会社 化学強化ガラスおよび化学強化ガラスの製造方法
JP2020015654A (ja) * 2018-07-27 2020-01-30 日本電気硝子株式会社 強化ガラス及び強化用ガラス
JP7335541B2 (ja) 2018-07-27 2023-08-30 日本電気硝子株式会社 強化ガラス及び強化用ガラス

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CN108779025B (zh) 2021-08-10
KR20180128893A (ko) 2018-12-04
TWI791431B (zh) 2023-02-11
JP6949313B2 (ja) 2021-10-13
TW201806901A (zh) 2018-03-01
JPWO2017170053A1 (ja) 2019-02-14
CN108779025A (zh) 2018-11-09

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