WO2019235470A1 - Verre chimiquement renforcé et procédé de fabrication d'un verre chimiquement renforcé - Google Patents

Verre chimiquement renforcé et procédé de fabrication d'un verre chimiquement renforcé Download PDF

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Publication number
WO2019235470A1
WO2019235470A1 PCT/JP2019/022140 JP2019022140W WO2019235470A1 WO 2019235470 A1 WO2019235470 A1 WO 2019235470A1 JP 2019022140 W JP2019022140 W JP 2019022140W WO 2019235470 A1 WO2019235470 A1 WO 2019235470A1
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stress layer
glass
chemically strengthened
less
strengthened glass
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PCT/JP2019/022140
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English (en)
Japanese (ja)
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清貴 木下
佐々木　博
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日本電気硝子株式会社
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Priority to JP2020523118A priority Critical patent/JP7332987B2/ja
Publication of WO2019235470A1 publication Critical patent/WO2019235470A1/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
    • 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
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Definitions

  • the present invention relates to tempered glass and a method for producing the same, and more particularly, to a tempered glass suitable for a cover glass of a mobile phone, a digital camera, a PDA (mobile terminal), and a touch panel display, and a method for producing the same.
  • Chemically strengthened glass has a compressive stress layer formed by ion exchange treatment on the surface, thereby suppressing the formation and progress of cracks on the surface and obtaining high strength. It is considered that the strength of tempered glass can be improved by adjusting the formation mode of such a compressive stress layer (for example, Patent Document 1).
  • This invention is made
  • the chemically tempered glass of the present invention is provided on the inner side in the plate thickness direction from the compression stress layer and has a compressive stress layer having a compressive stress of 20 MPa or more continuously from the main surface in the plate thickness direction, and continuous in the plate thickness direction.
  • a tensile stress layer having a tensile stress, and a plate-shaped chemically strengthened glass comprising a low stress layer between the compressive stress layer and the tensile stress layer, the low stress layer in the thickness direction Continuously having a compressive stress of less than 20 MPa and / or a tensile stress of less than 85% of the maximum tensile stress value of the tensile stress layer, and a thickness of 3.5% or more of the thickness of the chemically strengthened glass. It is characterized by.
  • the low stress layer preferably has a thickness of 8% or more of the thickness of the chemically strengthened glass.
  • the thickness of the chemically strengthened glass is T (mm) and the maximum tensile stress of the tensile stress layer is MaxCT (MPa)
  • the following formula (A) and the following formula (B) are It is preferable to satisfy.
  • the thickness of the low stress layer is preferably 25% or less of the thickness of the chemically strengthened glass.
  • the low-stress layer extends in the center direction of the plate thickness from a position shallower than 6% of the plate thickness of the chemically strengthened glass.
  • the plate thickness is 1.0 mm or less, each has a compressive stress layer and a low stress layer on both the front side and the back side, and the maximum compressive stress in the compressive stress layer is 750 MPa or more.
  • the maximum tensile stress in the tensile stress layer is preferably 5 to 32 MPa.
  • the stress change amount per unit thickness when the stress change in the depth direction from the surface toward the center in the compressive stress layer is linearly approximated using the least square method is A1 (MPa / ⁇ m).
  • the stress change amount per unit thickness when the stress change in the depth direction from the surface toward the center in the low stress layer is linearly approximated using the least square method is A2 (MPa / ⁇ m), A1 It is preferable to satisfy / A2> 30.
  • A1 is preferably ⁇ 80 to ⁇ 25 MPa / ⁇ m.
  • A2 is preferably ⁇ 1.5 to ⁇ 0.1 MPa / ⁇ m.
  • Chemically tempered glass of the present invention has a glass composition, in mass%, SiO 2 40 ⁇ 70% , Al 2 O 3 10 ⁇ 30%, B 2 O 3 0 ⁇ 3%, Na 2 O 5 ⁇ 25%, K It is preferable to contain 2 O 0 to 5.5%, Li 2 O 0 to 10%, MgO 0% to 5.5%, MgO 0% to 5.5%, and P 2 O 5 0 to 10%.
  • chemically strengthened glass of the present invention in chemically strengthened glass of the present invention, as a glass composition, in mass%, SiO 2 40 ⁇ 70% , Al 2 O 3 10 ⁇ 30%, B 2 O 3 0.1 ⁇ 3%, Na 2 O 5 ⁇ 25% , K 2 O 1 to 5.5%, Li 2 O 0.0001 to 10%, MgO 0.1 to 5.5%, P 2 O 5 2 to 10%, SnO 2 0.01 to 3% It is preferable to do.
  • Method for producing a chemically tempered glass of the present invention has a glass composition, in mass%, SiO 2 40 ⁇ 70% , Al 2 O 3 10 ⁇ 30%, B 2 O 3 0 ⁇ 3%, Na 2 O 5 ⁇ 25 %, K 2 O 0 to 5.5%, Li 2 O 0 to 10%, MgO 0% to 5.5%, MgO 0% to 5.5%, P 2 O 5 0 to 10%
  • a glass for tempering is obtained by immersing the glass for use in the first molten salt and subjecting it to the first ion exchange treatment, and then immersing it in the second molten salt and subjecting it to the second ion exchange treatment.
  • the first molten salt is a molten salt containing 185000 ppm or more of detached ions that are separated from the glass by the first ion exchange treatment, and the concentration of the detached ions in the second molten salt is the number of the detached ions in the first molten salt. Less than the concentration, the first ion exchange treatment time is the second ion exchange It is characterized by being at least twice the processing time of the processing.
  • the leaving ions are sodium ions
  • the concentration of the leaving ions in the second molten salt is less than 5000 ppm
  • the treatment time of the second ion exchange treatment is less than 60 minutes. It is preferable that
  • the chemically strengthened glass 1 is a plate-like glass chemically strengthened by ion exchange.
  • the plate thickness T of the chemically strengthened glass 1 may be arbitrarily determined, but is, for example, 2.0 mm or less, preferably 1.0 mm or less, more preferably 0.1 to 0.9 mm, and further preferably 0.3 to 0.6 mm. It is.
  • the chemically strengthened glass 1 includes a compressive stress layer 2, a tensile stress layer 3, and a low stress layer 4 as shown in FIG.
  • FIG. 1 is a schematic cross-sectional view showing the arrangement of stress layers in a chemically strengthened glass 1 according to an embodiment of the present invention.
  • the compressive stress layer 2 is provided on each of the main surfaces on the front and back sides of the chemically strengthened glass 1. Further, the tensile stress layer 3 is formed at the center in the thickness direction, that is, at a position deeper than the compressive stress layer 2.
  • the low stress layer 4 is formed between the compressive stress layer 2 and each tensile stress layer 3.
  • each stress layer is shown in FIG. 2, for example.
  • the vertical axis represents stress
  • the horizontal axis represents the position (depth) in the plate thickness direction on the basis of one main surface.
  • a positive value stress indicates a compressive stress
  • a negative value stress indicates a tensile stress. That is, the stress in the graph of FIG. 2 is shown to be larger as the absolute value is larger.
  • FIG. 2 is a conceptual diagram exaggerated for understanding, and it goes without saying that the stress distribution of the chemically strengthened glass according to the present invention is not limited to this mode.
  • the compressive stress layer 2 is a layer formed along the main surface S and having a compressive stress of 20 MPa or more continuously from the main surface S in the thickness direction.
  • the maximum compressive stress MaxCS in the compressive stress layer 2 is preferably 650 MPa or more, more preferably 700 MPa or more, and further preferably 750 to 1700 MPa.
  • the compressive stress in the compressive stress layer 2 becomes maximum near the main surface S and gradually decreases in the depth direction from the surface toward the center.
  • the compressive stress layer 2 may have a plurality of compressive stress peaks in the thickness direction.
  • the tensile stress layer 3 is a layer having a tensile stress of 85% or more of the maximum tensile stress value MaxCT continuously in the thickness direction.
  • the maximum tensile stress value MaxCT (MPa) in the tensile stress layer 3 preferably satisfies the following expressions (1) and (2) when the thickness of the chemically strengthened glass 1 is T (mm).
  • the maximum tensile stress value MaxCT is more preferably 32 MPa or less, further preferably 25 MPa or less, 20 MPa or less, and most preferably 18 MPa or less.
  • the lower limit of the maximum tensile stress value MaxCT is, for example, 5 MPa or more.
  • the tensile stress layer 3 is formed in a region including the central portion C in the plate thickness direction. The tensile stress of the tensile stress layer 3 is maximized in the vicinity of the central portion C and gradually decreases toward the main surface S.
  • the low stress layer 4 is a layer that has a smaller stress than the compressive stress layer 2 and the tensile stress layer 3 and is formed over a predetermined thickness (depth). Specifically, the low stress layer 4 has a compressive stress of less than 20 MPa and / or a tensile stress of less than 85% of the maximum tensile stress value MaxCT continuously in the thickness direction, and a thickness T of 3.5. % Is a layer having a thickness of at least%. Therefore, when the thickness of the low stress layer 4 is ⁇ Dtw, the following expression (3) is satisfied.
  • the thickness ⁇ Dtw of the low stress layer 4 is preferably 8% or more of the plate thickness T, more preferably 10% or more of the plate thickness T, and further preferably 13 to 25% of the plate thickness T.
  • the thickness ⁇ Dtw of the low stress layer 4 is preferably 20% or more of the plate thickness T.
  • the low stress layer 4 includes a region where the stress value of the tensile stress and the compressive stress is zero.
  • the low stress layer 4 extends from the position 8% shallower than the plate thickness T (on the main surface S side) to the central portion C side to the tensile stress layer 3 with respect to the main surface S. That is, it is preferable that the depth DCtw from the main surface S to the end portion on the surface side of the low stress layer 4 (a position where the compressive stress is 20 MPa) satisfies the following formula (4).
  • DCtw is more preferably less than 4% of the plate thickness T, and more preferably less than 3% of the plate thickness T. In the present embodiment, DCtw is substantially equal to the depth of the compressive stress layer 2.
  • the amount of stress change in the depth direction (plate thickness direction from the surface to the center) per unit thickness (depth) in the compressive stress layer 2 is A1 (MPa / ⁇ m), and the unit thickness (depth in the low stress layer 4) ))
  • A1 / A2 is preferably 30 or more, more preferably 100 or more. , 200 or more.
  • the stress change amounts A1 and A2 in the depth direction per unit thickness are, for example, the portion of the corresponding layer using the least square method in the graph showing the stress and the stress change in the depth direction as shown in FIG. Can be obtained as a slope of the straight line.
  • the chemically strengthened glass 1 has a stress profile that is symmetrical about the center of the plate thickness.
  • A1 is preferably ⁇ 80 to ⁇ 24 MPa / ⁇ m, and A2 is preferably ⁇ 1.5 to ⁇ 0.1 MPa / ⁇ m.
  • the stress and distribution of the chemically strengthened glass 1 can be measured and synthesized using, for example, FSM-6000LE and SLP-1000 manufactured by Orihara Seisakusho Co., Ltd.
  • the chemically strengthened glass 1 of the present invention can be manufactured, for example, in the following manner. First, a glass containing an alkali metal oxide as a composition and subjected to a tempering treatment (hereinafter referred to as tempering glass) is prepared. Next, after the first molten salt is brought into contact with the surface of the glass for strengthening and ion exchange treatment (first strengthening step) is performed, the second molten salt having a higher KNO 3 concentration than the first molten salt is brought into contact with the surface of the glass. To perform ion exchange (second strengthening step). More specifically, after the glass for strengthening is immersed in the first molten salt, it is immersed in the second molten salt.
  • the tempered glass is, for example, in terms of glass composition in terms of mass%, SiO 2 40 to 70%, Al 2 O 3 10 to 30%, B 2 O 3 0 to 3%, Na 2 O 5 to 25%, K 2. It is preferable to contain O 0 to 5.5%, Li 2 O 0 to 10%, MgO 0% to 5.5%, and P 2 O 5 0 to 10%.
  • SiO 2 is a component that forms a network of glass.
  • the preferable lower limit range of SiO 2 is 40% or more, 40.5% or more, 41% or more, 41.5% or more, 42% or more, 42.5% or more, 43% or more, 44% or more, 45% or more. 46% or more, 47% or more, 48% or more, 49% or more, and particularly 50% or more.
  • the content of SiO 2 is too large, the meltability and moldability tend to be lowered, and the thermal expansion coefficient becomes too low to make it difficult to match the thermal expansion coefficient of the surrounding materials.
  • the preferable upper limit range of SiO 2 is 70% or less, 68% or less, 65% or less, 62% or less, 60% or less, 58% or less, 57% or less, 56% or less, 55% or less, particularly 54% or less. is there.
  • Al 2 O 3 is a component that increases the ion exchange rate, and is a component that increases the Young's modulus and increases the Vickers hardness. Furthermore, it is a component that increases the phase separation viscosity.
  • the content of Al 2 O 3 is 10 to 30%. When the content of Al 2 O 3 is too small, the ion exchange speed and the Young's modulus tends to decrease. Therefore, the preferred lower limit range of Al 2 O 3 is 10% or more, 11% or more, 12% or more, 13% or more, 14% or more, 14.5% or more, 15% or more, 15.5% or more, 16% These are 16.5% or more, 17% or more, 17.5% or more, 18% or more, 18.5% or more, 19% or more, particularly 19.5% or more.
  • the preferable upper limit range of Al 2 O 3 is 30% or less, 28% or less, 26% or less, 25% or less, 24% or less, 23.5% or less, 23% or less, 22.5% or less, 22% Below, it is 21.5% or less, especially 21% or less.
  • B 2 O 3 is a component that reduces high temperature viscosity and density and increases devitrification resistance.
  • the ion exchange rate (particularly the stress depth) tends to decrease.
  • ion exchange causes coloration of the glass surface called burn, and acid resistance and water resistance are liable to decrease. Therefore, the preferable range of B 2 O 3 is 0 to 3%, 0 to 2.5%, 0 to 2%, 0 to 1.9%, 0 to 1.8%, 0 to 1.7%, 0 To 1.6%, 0 to 1.5%, 0 to 1.3%, especially 0 to less than 1%.
  • Na 2 O is an 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 the devitrification resistance, the molded product refractory, particularly the reaction devitrification with the alumina refractory.
  • the preferable lower limit range of Na 2 O is 5% or more, 7% or more, 8% or more, 8.5% or more, 9% or more, 9.5% or more, 10% or more, 11% or more, 12% or more. In particular, it is 12.5% or more.
  • the preferable upper limit range of Na 2 O is 25% or less, 22% or less, 20% or less, 19.5% or less, 19% or less, 18% or less, 17% or less, 16.5% or less, 16% or less. 15.5% or less, particularly 15% or less.
  • K 2 O is a component that lowers the high temperature viscosity and improves the meltability and moldability. Further, it is a component that improves devitrification resistance and increases Vickers hardness. However, when the content of K 2 O is too large, the phase separation generated viscosity tends to decrease. Moreover, there exists a tendency for acid resistance to fall or to lack the component balance of a glass composition, and to reduce devitrification resistance on the contrary.
  • the preferable lower limit range of K 2 O is 0% or more, 0.01% or more, 0.02% or more, 0.1% or more, 0.5% or more, 1% or more, 1.5% or more, 2 % Or more, 2.5% or more, 3% or more, particularly 3.5% or more, and a preferable upper limit range is 5.5% or less, 5% or less, and particularly less than 4.5%.
  • Li 2 O is an ion exchange component, and is a component that lowers the high temperature viscosity and improves the meltability and moldability. Furthermore, it is a component that increases the Young's modulus. Li 2 O is a component that is eluted during the ion exchange treatment and degrades the ion exchange solution. Therefore, the preferred content of Li 2 O is 0 to 10%, 0 to 5%, 0 to 2%, 0 to 1%, 0 to less than 1%, 0 to 0.5%, 0 to 0.3%. 0 to 0.1%, particularly 0.0001 to 0.05%.
  • MgO is a component that lowers the high-temperature viscosity and improves the meltability and moldability. It is also a component that increases Young's modulus to increase Vickers hardness and acid resistance. Therefore, the preferable lower limit range of MgO is 0% or more, 0.1% or more, 0.5% or more, 1% or more, 1.5% or more, and particularly 2% or more. However, if the content of MgO is too large, the ion exchange rate tends to decrease, and the glass tends to be devitrified.
  • a preferable upper limit range of MgO is 5.5% or less, 4.5% or less, 4% or less, 3.5% or less, 3% or less, particularly 2.5% or less.
  • P 2 O 5 is a component that increases the ion exchange rate while maintaining the compressive stress value. Therefore, the preferable lower limit range of P 2 O 5 is 0% or more, 2% or more, 2.5% or more, 3% or more, 4% or more, particularly 4.5% or more. However, when the content of P 2 O 5 is too large, or cause cloudiness by phase separation in the glass, the water resistance tends to decrease. Therefore, the preferable upper limit range of P 2 O 5 is 10% or less, 8.5% or less, 8% or less, 7.5% or less, 7% or less, 6.5% or less, 6.3% or less, 6% Below, 5.9% or less, 5.7% or less, 5.5% or less, 5.3% or less, 5.1% or less, especially 5% or less.
  • one or two or more selected from the group of Cl, SO 3 and CeO 2 may be added in an amount of 0 to 3%.
  • the SnO 2 has an effect of improving ion exchange performance. Accordingly, the SnO 2 content is preferably 0 to 3%, 0.01 to 3%, 0.05 to 3%, particularly 0.1 to 3%, and particularly preferably 0.2 to 3%.
  • the Fe 2 O 3 content is preferably less than 1000 ppm (less than 0.1%), less than 800 ppm, less than 600 ppm, less than 400 ppm, and particularly preferably less than 300 ppm. In this way, the transmittance (400 to 770 nm) at a plate thickness of 1 mm can be easily improved.
  • Rare earth oxides such as Nb 2 O 5 and La 2 O 3 are components that increase the Young's modulus. However, the cost of the raw material itself is high, and when it is added in a large amount, the devitrification resistance tends to be lowered. Therefore, the rare earth oxide content is preferably 3% or less, 2% or less, 1% or less, 0.5% or less, and particularly preferably 0.1% or less.
  • the reinforced glass from environmental considerations it is preferable to contain substantially no As 2 O 3, Sb 2 O 3, PbO.
  • environmental considerations it is also preferable to contain substantially no Bi 2 O 3, F.
  • Reinforced glass is more preferably as a glass composition, in mass%, SiO 2 40 ⁇ 70% , Al 2 O 3 10 ⁇ 30%, B 2 O 3 0.1 ⁇ 3%, Na 2 O 5 ⁇ 25% , K 2 O 1 to 5.5%, Li 2 O 0.01 to 10%, MgO 0.1 to 5.5%, P 2 O 5 2 to 10%, SnO 2 0.01 to 3% To do.
  • composition of the tempering glass is an example, and a tempering glass having a known composition may be used as long as chemical strengthening by ion exchange is possible.
  • composition of the chemically strengthened glass obtained by performing the ion exchange treatment on the glass for strengthening is the same as the composition of the glass for strengthening before the ion exchange treatment.
  • the glass for strengthening can be produced as follows.
  • a glass raw material prepared so as to have the above glass composition is put into a continuous melting furnace, heated and melted at 1500 to 1600 ° C., clarified, fed into a molding apparatus, formed into a plate shape, etc.
  • strengthening can be produced by cooling.
  • the overflow downdraw method is a method that can produce a high-quality glass plate in a large amount and can easily produce a large glass plate, and can reduce the scratches on the surface of the glass plate as much as possible.
  • alumina or dense zircon is used as a molded body.
  • the tempered glass according to the present invention has good compatibility with alumina and dense zircon, particularly alumina (it is difficult to react with the molded body to generate bubbles and blisters).
  • 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.
  • bending may be performed as necessary. Moreover, you may perform processes, such as a cutting process, a drilling process, surface polishing process, a chamfering process, an end surface polishing process, an etching process, as needed.
  • the dimensions of the tempering glass may be arbitrarily determined, but the thickness is 2.0 mm or less, 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 1.0 mm or less, 0.8 mm or less, 0.7 mm or less, 0.55 mm or less, 0.5 mm or less, 0.45 mm or less, 0.4 mm or less, 0.35 mm or less, and particularly 0.30 mm or less are preferable.
  • the plate thickness is preferably 0.05 mm or more, 0.10 mm or more, 0.15 mm or more, particularly 0.20 mm or more.
  • the ion exchange treatment is performed a plurality of times on the reinforcing glass obtained as described above.
  • a case where ion exchange processing is performed twice will be described as an example.
  • the second strengthening step is performed after the first strengthening step.
  • the tempered glass is immersed in a tank filled with the first molten salt and held at a predetermined temperature for a predetermined time to perform ion exchange treatment on the surface of the tempered glass.
  • the first molten salt includes nitrates of alkali metal ions (leaving ions) that are preliminarily included in the composition of the strengthening glass and are released in ion exchange, and nitrates of alkali metal ions (introduced ions) that are introduced into the strengthening glass by ion exchange. And mixed salt as a main component.
  • the leaving ions are sodium ions and the introduced ions are potassium ions. That is, in the present embodiment, the first molten salt is a mixed salt containing NaNO 3 and KNO 3 as main components.
  • the concentration of detached ions in the first molten salt is 185000 ppm (18.5%) or more.
  • the concentration of leaving ions in the first molten salt is preferably 190000 ppm (19.0%) or more, more preferably 195000-205000 ppm (19.5-20.5%).
  • the temperature of the first molten salt (first strengthening temperature) in the ion exchange treatment of the first strengthening step is higher than the temperature of the second molten salt (second strengthening temperature) in the ion exchange treatment of the second strengthening step.
  • first strengthening temperature is higher than the temperature of the second molten salt (second strengthening temperature) in the ion exchange treatment of the second strengthening step.
  • second strengthening temperature is higher than the temperature of the molten salt (second strengthening temperature) in the ion exchange treatment of the second strengthening step.
  • the ion exchange treatment temperature in the first strengthening step is preferably 420 ° C. or higher, more preferably 430 ° C. or higher, and further preferably 440 to 500 ° C.
  • the ion exchange treatment time (first strengthening time) in the first strengthening step is at least 3 times longer than the ion exchange treatment time (second strengthening time) in the second strengthening step, preferably 5 times or more, more preferably 10 to 200. Is double.
  • the first strengthening time is preferably 2 hours or more, and more preferably 10 to 200 hours. Since the low stress layer 4 can be formed deeply by lengthening the ion exchange treatment time in the first strengthening step, it is preferable to lengthen the treatment time as long as productivity does not decrease.
  • the glass for strengthening immersed in the first molten salt in the first strengthening step may be preheated to the first strengthening temperature in advance, or may be immersed in the first molten salt while maintaining a normal temperature state.
  • normal temperature refers to 1 to 40 ° C.
  • the glass for strengthening (hereinafter referred to as primary tempered glass) that has completed the processing in the first tempering step is drawn out from the first molten salt and used in the processing in the second tempering step. At this time, it is preferable that the primary tempered glass is washed in advance in the washing step before the treatment of the second tempering step. By performing the cleaning, it becomes easy to remove the deposits adhered to the primary tempered glass, and the ion exchange treatment can be performed more uniformly in the second tempering step.
  • the primary tempered glass surface is further ion-exchanged by immersing the primary tempered glass in a tank filled with the second molten salt.
  • the concentration of leaving ions in the second molten salt is less than the concentration of leaving ions in the first molten salt. That is, in this embodiment, the sodium ion concentration of the second molten salt is adjusted to be smaller than the sodium ion concentration of the first molten salt. Specifically, the concentration of leaving ions of the second molten salt is preferably less than 5000 ppm, more preferably less than 3000 ppm, and still more preferably 1000 to 1 ppm.
  • the second molten salt for example, can be used molten salt consisting only of KNO 3.
  • the concentration of introduced ions in the second molten salt is adjusted to be larger than the concentration of introduced ions in the first molten salt. That is, in this embodiment, it is preferable that the potassium ion concentration in the second molten salt is set higher than the potassium ion concentration in the first molten salt.
  • the content ratio of alkali metal ions (for example, Li ions, Na ions, particularly Na ions) having a small ionic radius in the second molten salt is preferably smaller than that in the first molten salt. This makes it easy to increase the concentration of large alkali metal ions on the outermost surface while forming a deep stress depth.
  • size of an alkali metal ion has the relationship of Li ion ⁇ Na ion ⁇ K ion (potassium ion) ⁇ Ce ion ⁇ Rb ion.
  • the high compressive stress layer 2 can be formed in the vicinity of the surface.
  • the ion exchange temperature in the second strengthening step is preferably lower than the ion exchange temperature in the first strengthening step by 10 ° C., 20 ° C., 30 ° C., particularly 50 ° C. or more. Specifically, the ion exchange temperature in the second strengthening step is preferably 350 to 410 ° C., particularly 360 to 400 ° C.
  • the ion exchange treatment time in the second strengthening process is relatively shorter than the ion exchange treatment time in the first strengthening process.
  • the ion exchange treatment time in the second strengthening step is preferably set to be within 20 hours, more preferably 0.5 to 15 hours.
  • the chemical tempered glass 1 of the present invention having the above-mentioned characteristics can be obtained by appropriately adjusting the treatment time and treatment temperature within the condition ranges of the first and second strengthening steps described above.
  • the sodium ion in glass was ion-exchanged as a leaving ion was illustrated in the said embodiment, this invention is applicable also about the ion exchange of another ion.
  • the leaving ions may be lithium ions and the introduced ions may be sodium ions and / or potassium ions.
  • a mixed salt of NaNO 3 and KNO 3 can be used as the first molten salt in the same manner as in the above embodiment, and LiNO 3 It may be added. That is, a mixed salt of LiNO 3 and NaNO 3 and / or KNO 3 can also be used as the first molten salt.
  • the chemically strengthened glass 1 showed the example provided with the compressive-stress layer 2 and the low-stress layer 4 in the both sides of the front and back main surfaces, the compressive-stress layer 2 and A low stress layer 4 may be provided.
  • the chemically strengthened glass 1 has a flat plate shape, but the concept of the plate shape in the present invention includes a bent plate shape having a curved surface.
  • a sample was prepared as follows. First, two types of tempering glasses having compositions A and B as glass compositions were prepared.
  • Glass composition A is a mass%, SiO 2 53.59%, Al 2 O 3 20.0%, B 2 O 3 0.5%, K 2 O 4.4%, Na 2 O 13.7% , including Li 2 O 0.01%, MgO 2.1 %, P 2 O 5 5.4%, a SnO 2 0.3%.
  • the glass of composition B is, by mass%, SiO 2 61.69%, Al 2 O 3 18%, B 2 O 3 0.5%, K 2 O 2.0%, Na 2 O 14.5%, Li 2 O 0.01%, MgO 3%, SnO 2 0.3%.
  • the tempered glass was immersed in a KNO 3 molten salt bath under the conditions shown in Table 1, and subjected to ion exchange treatment to obtain plate-like chemically tempered glass (samples Nos. 1 to 8).
  • ion exchange treatment was performed using a molten salt of 100% KNO 3 .
  • Sample Nos. 1 to 5 were subjected to two strengthening processes of the first strengthening process and the second strengthening process, and sample Nos. 6 to 8 were subjected to only one strengthening process of the first strengthening process.
  • Sample No. 1 to 5 are examples of the present invention. 6 to 8 are comparative examples.
  • the stress distribution of each sample was measured.
  • the stress distribution is measured using surface stress meters FSM-6000LE and SLP-1000 manufactured by Orihara Seisakusho Co., Ltd., and the measurement results are synthesized using a data synthesis function provided in advance in these apparatuses.
  • the sample was measured with a refractive index of 1.50 and an optical elastic constant of 28.9 [(nm / cm) / MPa].
  • FIG. FIG. 3 It is a graph which shows the stress distribution of the plate
  • the horizontal axis indicates the depth ( ⁇ m) from one main surface, and the vertical axis indicates the magnitude of stress (MPa).
  • the compressive stress is indicated by a positive value and the tensile stress is indicated by a negative value.
  • FIG. 3 shows a distribution from one main surface to a depth of ⁇ m in the thickness direction of the glass.
  • MaxCS indicates the maximum compressive stress value in the compressive stress layer 2.
  • MaxCT indicates the maximum tensile stress value of the tensile stress layer 3.
  • DCtw indicates the depth from the main surface to the position where the compressive stress is 20 MPa. That is, DCtw indicates the end position of the compressive stress layer 2 in the present invention.
  • DTtw indicates the depth from the main surface to a position where the tensile stress is 85% of MaxCT. That is, DTtw indicates the starting position of the tensile stress layer 3 in the present invention.
  • ⁇ Dtw is the thickness of the low stress layer 4.
  • ⁇ Dtw is obtained from the difference between DTtw and DCtw. As shown in FIGS. 1 and 2, the low stress layer 4 exists for each main surface, and ⁇ Dtw is the thickness of one of the low stress layers 4.
  • A1 is the amount of stress change in the depth direction (the thickness direction from the surface to the center) per unit thickness in the compressive stress layer 2.
  • A2 is the amount of stress change in the depth direction (surface thickness direction from the surface to the center) per unit thickness in the low stress layer 4.
  • the stress change amounts A1 and A2 in the depth direction per unit thickness are, for example, the portion of the corresponding layer using the least square method in the graph showing the stress and the stress change in the depth direction as shown in FIG. Can be obtained as a slope of the straight line.
  • the drop breaking height is obtained when the pseudo casing 20, the glass sample (chemically tempered glass 1), and the sandpaper 40 are laminated in this order and dropped onto the iron surface plate 90.
  • the height at which the glass sample (chemically tempered glass 1) breaks is shown.
  • the pseudo housing 20 is attached to one main surface of a glass sample (chemically tempered glass 1) processed to have a width of 65 mm, a length of 130 m, and a thickness described in Table 1.
  • the pseudo housing 20 is a polycarbonate thick plate member having a mass of 110 g and a width of 70 mm, a length of 140 mm, and a thickness of 8 mm, imitating a portable terminal.
  • the glass sample (chemically tempered glass 1) and the pseudo casing 20 are bonded by sandwiching an optical adhesive film 30 having a thickness of 150 ⁇ m therebetween.
  • the surface of the sandpaper 40 (the surface provided with the abrasive) is applied to the other main surface of the glass sample (chemically tempered glass 1) (the main surface opposite to the main surface bonded to the pseudo housing).
  • the sandpaper 40 is pasted so that it may touch.
  • the sandpaper 40 has a width of 60 mm and a length of 120 mm, and is disposed at the center of the other main surface of the glass sample (chemically tempered glass 1). At this time, it arrange
  • Paper 40 is affixed to a glass sample (chemically tempered glass 1).
  • the vinyl tape piece 50 has a width of 19 mm, a length of 10 mm, and a thickness of 0.1 mm, and the pasting location is the center of each short side of the sandpaper 40.
  • the Riken Corundum SiC sandpaper P180 and the SiC sandpaper P100 manufactured by the company were used, and the drop breaking height at each count was measured.
  • the test specimen thus obtained is held in a horizontal posture so that the sandpaper faces downward, and is repeated toward the surface plate 90 while increasing the drop height until the glass sample (chemically strengthened glass 1) is broken. I dropped it. More specifically, in this application, the test body is clamped by the clamping means composed of an air cylinder, starts dropping together with the clamping means, and is released from clamping by the air cylinder at a position 20 cm before the surface of the surface plate 90. The test was conducted so that the liquid drops to the surface plate 90 while maintaining the horizontal posture. The sandpaper was replaced with a new one each time a drop test was performed. The drop height was set so that the height was 20 cm from the drop surface, and when the glass sample (chemically strengthened glass 1) was not broken, the height was increased by 10 cm for P180 and by 5 cm for P100.
  • the chemically tempered glass of the present invention can be used as a part of, for example, a mobile phone (particularly a smart phone), a tablet computer, a digital camera, a touch panel display, a large TV, and the like.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne un verre chimiquement renforcé, en forme de plaque, comprenant : une couche de contrainte de compression présentant une contrainte de compression continue de 20 MPa ou plus à partir de la surface principale dans la direction de l'épaisseur de la plaque ; et une couche de contrainte de traction qui est disposée plus vers le côté intérieur dans la direction de l'épaisseur de la plaque que la couche de contrainte de compression, et qui présente une contrainte de traction continue dans la direction de l'épaisseur de la plaque. Le verre chimiquement renforcé est caractérisé en ce qu'il comprend une couche de faible contrainte entre la couche de contrainte de compression et la couche de contrainte de traction ; et en ce que la couche de faible contrainte présente, dans la direction de l'épaisseur de la plaque, une contrainte de compression continue inférieure à 20 MPa et/ou une contrainte de traction inférieure à 85 % de la contrainte de traction maximale de la couche de contrainte de traction, et présente de même une épaisseur d'au moins 3,5 % de l'épaisseur de la plaque.
PCT/JP2019/022140 2018-06-07 2019-06-04 Verre chimiquement renforcé et procédé de fabrication d'un verre chimiquement renforcé WO2019235470A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130224492A1 (en) * 2012-02-29 2013-08-29 Corning Incorporated Ion exchanged glasses via non-error function compressive stress profiles
JP2016044119A (ja) * 2014-08-19 2016-04-04 日本電気硝子株式会社 強化ガラス及びその製造方法
JP2017506207A (ja) * 2014-02-24 2017-03-02 コーニング インコーポレイテッド 改善された残存性を有する強化ガラス物品
JP2017100929A (ja) * 2015-12-04 2017-06-08 日本電気硝子株式会社 強化ガラス
WO2017123596A1 (fr) * 2016-01-13 2017-07-20 Corning Incorporated Verre ultrafin, non frangible et procédés de fabrication
WO2017170053A1 (fr) * 2016-04-01 2017-10-05 日本電気硝子株式会社 Verre chimiquement renforcé
JP2017535498A (ja) * 2014-10-31 2017-11-30 コーニング インコーポレイテッド 圧縮深さが非常に深い強化ガラス
JP2017214282A (ja) * 2014-10-08 2017-12-07 コーニング インコーポレイテッド 金属酸化物濃度勾配を有するガラスおよびガラスセラミック
WO2019021930A1 (fr) * 2017-07-24 2019-01-31 日本電気硝子株式会社 Verre renforcé chimiquement et procédé de fabrication de verre renforcé chimiquement

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130224492A1 (en) * 2012-02-29 2013-08-29 Corning Incorporated Ion exchanged glasses via non-error function compressive stress profiles
JP2017506207A (ja) * 2014-02-24 2017-03-02 コーニング インコーポレイテッド 改善された残存性を有する強化ガラス物品
JP2016044119A (ja) * 2014-08-19 2016-04-04 日本電気硝子株式会社 強化ガラス及びその製造方法
JP2017214282A (ja) * 2014-10-08 2017-12-07 コーニング インコーポレイテッド 金属酸化物濃度勾配を有するガラスおよびガラスセラミック
JP2017535498A (ja) * 2014-10-31 2017-11-30 コーニング インコーポレイテッド 圧縮深さが非常に深い強化ガラス
JP2017100929A (ja) * 2015-12-04 2017-06-08 日本電気硝子株式会社 強化ガラス
WO2017123596A1 (fr) * 2016-01-13 2017-07-20 Corning Incorporated Verre ultrafin, non frangible et procédés de fabrication
WO2017170053A1 (fr) * 2016-04-01 2017-10-05 日本電気硝子株式会社 Verre chimiquement renforcé
WO2019021930A1 (fr) * 2017-07-24 2019-01-31 日本電気硝子株式会社 Verre renforcé chimiquement et procédé de fabrication de verre renforcé chimiquement

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