WO2017209139A1 - 化学強化用ガラス及び化学強化ガラス - Google Patents

化学強化用ガラス及び化学強化ガラス Download PDF

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WO2017209139A1
WO2017209139A1 PCT/JP2017/020135 JP2017020135W WO2017209139A1 WO 2017209139 A1 WO2017209139 A1 WO 2017209139A1 JP 2017020135 W JP2017020135 W JP 2017020135W WO 2017209139 A1 WO2017209139 A1 WO 2017209139A1
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glass
less
chemical strengthening
tio
chemically strengthened
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PCT/JP2017/020135
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English (en)
French (fr)
Japanese (ja)
Inventor
公章 赤塚
盛輝 大原
林　英明
円佳 小野
雄一 山本
聡 沖
直樹 菅野
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旭硝子株式会社
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Priority to CN201780033344.4A priority Critical patent/CN109219583A/zh
Publication of WO2017209139A1 publication Critical patent/WO2017209139A1/ja

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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

Definitions

  • the present invention relates to a glass for chemical strengthening, and more particularly, to a glass for chemical strengthening excellent in chemical strengthening characteristics capable of further improving the surface compressive stress (CS) during chemical strengthening.
  • the present invention also relates to a chemically strengthened glass obtained by chemically strengthening the chemical strengthening glass.
  • Chemically tempered glass is useful for display applications because of its high strength, and various studies have been made. For example, there is known a glass used for chemically strengthened glass that does not easily decrease in strength even if an indentation is formed (Patent Document 1). Moreover, the chemically strengthened glass which has the characteristic that it is hard to break even if big load is applied, and also is hard to be damaged is known (patent document 2).
  • the present invention relates to the following ⁇ 1> to ⁇ 12>.
  • ⁇ 3> The glass for chemical strengthening according to ⁇ 1> or ⁇ 2>, wherein [(MgO / 2 + Na 2 O + K 2 O ⁇ 2) / (TiO 2 + ZrO 2 )] is 53 to 150.
  • ⁇ 4> The glass for chemical strengthening according to any one of ⁇ 1> to ⁇ 3>, wherein a temperature T2 at which the glass has a viscosity of 10 2 dPa ⁇ s is 1660 ° C. or lower.
  • ⁇ 5> The glass for chemical strengthening according to any one of ⁇ 1> to ⁇ 4>, wherein a temperature T4 at which the glass has a viscosity of 10 4 dPa ⁇ s is 1255 ° C. or lower.
  • ⁇ 6> The glass for chemical strengthening according to any one of ⁇ 1> to ⁇ 5>, containing ZrO 2 in a molar percentage display based on an oxide of more than 0.11% and 4.0% or less.
  • ⁇ 7> The glass for chemical strengthening according to any one of ⁇ 1> to ⁇ 6>, wherein the mirror constant is 1.96 MPa ⁇ m 1/2 or more.
  • ⁇ 8> The ratio of the internal friction value tan [delta 200 in internal friction value tan [delta 0 and 200 ° C. at 0 °C (tan ⁇ 0 / tan ⁇ 200 ) is less than 1 or 2.5 ⁇ 1> to any one of ⁇ 7>
  • ⁇ 9> Any one of ⁇ 1> to ⁇ 8>, wherein the average abundance of S atoms in a depth region from the glass surface to 3 ⁇ m as measured by secondary ion mass spectrometry is 1.0E + 19 atoms / cm 3 or less
  • ⁇ 10> A chemically strengthened glass obtained by chemically strengthening the glass for chemical strengthening according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> The chemically strengthened glass according to ⁇ 10>, wherein the surface compressive stress value (CS) is 900 MPa or more.
  • CS surface compressive stress value
  • DOL compressive stress layer depth
  • the chemically strengthened glass according to the present invention is a chemically strengthened glass having a higher CS as compared with a conventional glass when chemically strengthened under predetermined chemical strengthening conditions. Therefore, it is very useful as a chemical strengthening glass used for display applications.
  • FIG. 1 is a diagram schematically showing how cracking occurs around a fracture starting point when glass without residual stress inside is broken by uniform tensile stress.
  • FIG. 2 is a schematic diagram showing a test method for internal friction.
  • FIG. 3 is a graph showing measurement results of internal friction.
  • the glass for chemical strengthening according to the present invention (hereinafter sometimes simply referred to as “glass”) is expressed in terms of mole percentage on an oxide basis, SiO 2 : 60 to 67%, Al 2 O 3 : 9 to 13.5. %, Na 2 O: 13.5 to 18.5%, K 2 O: 0.1 to 3%, MgO: 6 to 10.5%, and TiO 2 : more than 0% and 5% or less, [ (Na 2 O + K 2 O ⁇ 5) / (Al 2 O 3 + ZrO 2 + TiO 2 ⁇ 10)] is 2.55 or less, and Al 2 O 3 / K 2 O is more than 10.
  • another aspect of the glass for chemical strengthening according to the present invention is expressed in terms of mole percentage on the basis of oxide, SiO 2 : 60 to 67%, Al 2 O 3 : 9 to 13.5%, Na 2 O: 13 0.5 to 18.5%, K 2 O: 0.1 to 3%, MgO: 6 to 10.5%, TiO 2 : 0 to 1%, and Fe 2 O 3 : 0.01 to 5% [(Na 2 O + K 2 O ⁇ 5) / (Al 2 O 3 + ZrO 2 + TiO 2 ⁇ 10)] is 2.55 or less, and Al 2 O 3 / K 2 O is more than 10. Below, each component in a glass composition is demonstrated.
  • SiO 2 is a main component constituting the glass. Further, it is a component that reduces the occurrence of cracks when scratches (indentations) are made on the glass surface, or reduces the fracture rate when indentations are made after chemical strengthening. SiO 2 is also a component that increases the acid resistance of the glass and reduces the amount of sludge during etching (hydrofluoric acid resistance).
  • the productivity such as solubility and moldability SiO 2 content is too large the viscosity becomes too high tends to be low. Therefore, the SiO 2 content is 60 to 67%, preferably 62% or more, more preferably 63% or more, and preferably 66% or less, more preferably 65% or less.
  • the Al 2 O 3 content is 9 to 13.5%, preferably 9.5% or more, more preferably 10% or more, more preferably 12% or less, and even more preferably 11.5% or less.
  • Na 2 O is an essential component for forming a surface compressive stress layer by ion exchange, and has the effect of deepening the DOL. Moreover, it is a component which lowers
  • the Na 2 O content is 13.5 to 18.5%, preferably 14.5% or more, more preferably 15% or more, more preferably 17.5% or less, and more preferably 16.5% or less. preferable.
  • K 2 O is a component that increases the ion exchange rate, deepens the DOL, lowers the melting temperature of the glass, and increases non-crosslinked oxygen. Further, it is possible to avoid an increase in variation of surface compressive stress due NaNO 3 concentration in the potassium nitrate molten salt used during the chemical strengthening treatment. Furthermore, since a small amount of K 2 O has an effect of suppressing the intrusion amount of tin from the bottom surface at the time of molding by the float process, it is preferably contained when molding by the float process. In order to achieve the above effect, the content of K 2 O in the glass of the present invention is 0.1% or more, preferably 0.3% or more, and more preferably 0.4% or more.
  • the K 2 O content is 3% or less, preferably 2% or less, more preferably 1.3% or less, still more preferably 1% or less, and even more preferably 0.95% or less.
  • MgO is a component that can stabilize the glass, improve the solubility, and reduce the alkali metal content by adding this to suppress the increase in the coefficient of thermal expansion (CTE).
  • the content of MgO in the glass of the present invention is 6% or more, preferably 7% or more, and more preferably 7.5% or more.
  • the content of MgO is 10.5% or less, preferably 9.5% or less, and more preferably 9% or less.
  • TiO 2 is a component that improves DUV resistance for preventing a decrease in transmittance in a specific wavelength region with respect to ultraviolet rays in a wavelength region called Deep UV (DUV).
  • DUV decreases when TiO 2 is too large.
  • the TiO 2 content is more than 0% and 5% or less, and when not containing other coloring components described later, 0.01% or more is preferable, 0.03% or more is more preferable, and 3% The following is preferable, 1% or less is more preferable, 0.5% or less is further preferable, 0.4% or less is further more preferable, and 0.3% or less is particularly preferable.
  • the TiO 2 content is 0 to 1%, and TiO 2 may not be contained.
  • the amount of TiO 2 added is preferably 0.002% or more, and more preferably 0.005% or more. Moreover, 0.5% or less is preferable, 0.4% or less is more preferable, and 0.3% or less is further more preferable.
  • ZrO 2 is a component that imparts excellent DUV resistance and at the same time improves chemical durability, increases CS during chemical strengthening, and improves Vickers hardness after chemical strengthening, and can be contained.
  • the glass according to the present invention does not contain Fe 2 O 3 , it preferably contains both TiO 2 and ZrO 2 , and the content in the case of containing ZrO 2 is preferably 0.1% or more, 0.11% More than 0.12% is more preferable, 0.12% or more is further preferable, and 0.13% or more is more preferable.
  • the content of ZrO 2 is preferably 4.0% or less, more preferably 3% or less, and more preferably 2% or less from the viewpoint of suppressing devitrification during the production of glass and preventing a decrease in DOL during chemical strengthening. More preferably, it is more preferably 1.5% or less, and particularly preferably 1% or less.
  • chemically tempered glass according to the present invention Na 2 O, K 2 O , the content expressed by Al 2 O 3, ZrO 2, TiO 2 based on oxides molar percentages display, [(Na 2 O + K 2 O ⁇ 5) / (Al 2 O 3 + ZrO 2 + TiO 2 ⁇ 10)] satisfies a relationship of 2.55 or less.
  • Na 2 O and K 2 O are components that can deepen DOL while reducing CS and DUV resistance.
  • the temperature T2 at which the viscosity of the glass becomes 10 2 dPa ⁇ s and the temperature T4 at which the viscosity of the glass becomes 10 4 dPa ⁇ s can be lowered, and this component contributes to good productivity.
  • Al 2 O 3, ZrO 2 , and TiO 2 are components that reduce the DOL while increasing the CS and DUV resistance. Further, Al 2 O 3 is a component to increase the temperature T2 and the temperature T4, the productivity such as solubility and moldability too is reduced.
  • the value represented by [(Na 2 O + K 2 O ⁇ 5) / (Al 2 O 3 + ZrO 2 + TiO 2 ⁇ 10)] is 2.55 or less. Yes, preferably 2.0 or less, more preferably 1.9 or less, still more preferably 1.8 or less, still more preferably 1.75 or less, and particularly preferably 1.71 or less. Moreover, 0.1 or more are preferable, 0.5 or more are more preferable, and 1.0 or more are further more preferable.
  • the content of Al 2 O 3 and K 2 O expressed in terms of mole percentages based on oxides may be expressed as Al 2 O 3.
  • / K 2 O satisfies the relationship of more than 10.
  • Al 2 O 3 / K 2 O is preferably 10.3 or more, more preferably 10.5 or more, further preferably 11.5 or more, still more preferably 12.5 or more, and particularly preferably 14.0 or more, Most preferred is 15.0 or more.
  • the content expressed in terms of mole percentages based on oxides of MgO, Na 2 O, K 2 O, ZrO 2 and TiO 2 [(MgO / 2 + Na 2 O + K 2 O ⁇ 2) / (TiO 2 It is preferable that + ZrO 2 )] satisfy the relationship of 53 to 150 because the amount of sludge during etching described later can be reduced (hydrofluoric acid resistance improved).
  • the value represented by [(MgO / 2 + Na 2 O + K 2 O ⁇ 2) / (TiO 2 + ZrO 2 )] is preferably 140 or less, more preferably 130 or less, and further 125 or less. 120 or less is more preferable.
  • 55 or more are more preferable and 60 or more are further more preferable.
  • the composition of the glass can be measured by a fluorescent X-ray method.
  • B 2 O 3 is a component that promotes melting of the glass raw material and improves the brittleness and weather resistance of the glass.
  • B 2 O 3 does not have to be contained, and when it is contained, the content is 1% or more, so that the fracture rate when Vickers indentation is made after chemical strengthening can be reduced, or at a high temperature This improves the meltability.
  • the content of B 2 O 3 is preferably 15% or less, more preferably 10% or less, and more preferably 7.5%, in order not to cause inconvenience such as generation of striae due to volatilization and furnace wall erosion. % Or less is further preferable, 5% or less is more preferable, and 3% or less is particularly preferable.
  • P 2 O 5 is a component that improves damage resistance without hindering ion exchange performance.
  • P 2 O 5 does not have to be contained, and when it is contained, its content is preferably 1% or more, more preferably 2% or more, and even more preferably 2.5% or more.
  • a glass having a high (CIL) can be obtained. Further, by making the content of P 2 O 5 preferably 10% or less, more preferably 5% or less, and still more preferably 3% or less, a glass having particularly excellent acid resistance can be obtained.
  • CaO is a component that stabilizes glass, and can be contained because it has an effect of improving the solubility while preventing devitrification due to the presence of MgO and suppressing an increase in CTE.
  • the content of CaO is preferably 0 to 5%, more preferably 0 to 3%, still more preferably 0 to 1%.
  • the content of CaO is 5% or less, a sufficient ion exchange rate is obtained, and a desired DOL is obtained.
  • the content of CaO is more preferably less than 1%, and particularly preferably 0.5% or less.
  • CaO / MgO is preferably 0.5 or less from the viewpoint of improving ion exchange performance in chemical strengthening and increasing the transmittance of the glass plate.
  • SrO may be contained as necessary, but since the effect of lowering the ion exchange rate is greater than that of MgO and CaO, SrO is not substantially contained or even if contained.
  • the content is preferably 3% or less.
  • it does not contain substantially means that it does not contain except an unavoidable impurity, for example, Preferably it is less than 0.05%, More preferably, it is less than 0.01%.
  • BaO has the greatest effect of reducing the ion exchange rate among alkaline earth metal oxides. Therefore, BaO is not substantially contained or even if contained, its content is 3% or less. Preferably, it is preferably 1% or less, and more preferably 0.5% or less.
  • the total content thereof is preferably 3% or less, more preferably 1% or less, still more preferably 0.5% or less, and still more preferably 0.3%. Is less than.
  • the total content of these three components is preferably 3% or less, and more preferably less than 3%.
  • the total is 3% or less, a decrease in ion exchange rate can be avoided. More preferably, it is 1% or less, More preferably, it is 0.5% or less, Most preferably, it is less than 0.3%.
  • Li 2 O is a component that excessively lowers the strain point and the low-temperature viscosity to facilitate stress relaxation, and as a result the stress value of the compressive stress layer decreases.
  • Li 2 O may be eluted in a molten salt such as KNO 3 during chemical strengthening treatment, but when the chemical strengthening treatment is performed using a molten salt containing Li, the surface compressive stress is remarkably reduced. Therefore, Li 2 O is preferably substantially free from this point of view.
  • Li 2 O is preferably 100 ppm or less in terms of oxide-based weight percentage in order to improve chemical strengthening characteristics.
  • SnO 2 is a component that makes DUV resistance better.
  • SnO 2 may not be contained, and when it is contained, its content is preferably 0.001% or more, more preferably 0.005% or more, still more preferably 0.01% or more, and 0.02% The above is particularly preferable.
  • SnO 2 reduces solarization resistance, so 1% or less is preferable, 0.7% or less is more preferable, 0.5% or less is more preferable, 0.3% or less is further more preferable, and 0. 1% or less is particularly preferable.
  • coloring and using glass you may add a coloring component in the range which does not inhibit achievement of a desired chemical strengthening characteristic.
  • the coloring component include Co 3 O 4 , MnO 2 , Fe 2 O 3 , NiO, CuO, Cr 2 O 3 , V 2 O 5 , Bi 2 O 3 , SeO 2 , TiO 2 , CeO 2 , and Er 2.
  • O 3 and Nd 2 O 3 are preferable.
  • CeO 2 is also a component that makes DUV resistance more excellent, but on the other hand it greatly reduces the resistance to solarization. CeO 2 is preferably less than 0.1%, more preferably less than 0.05%, further preferably less than 0.01%, and most preferably not substantially contained.
  • Fe 2 O 3 is a component that is inevitably contained because it is widely distributed in nature. Therefore, Fe 2 O 3 is usually 0.0005% or more, and 0.001% or more is more common. However, when it is desired to increase the transmittance, it is preferably less than 0.01%, more preferably 0.007% or less, and further preferably 0.004% or less. When added as a coloring component or the like, Fe 2 O 3 is preferably 0.01% or more, and more preferably 0.05% or more. In particular, when it is desired to be colored black, Fe 2 O 3 is preferably 0.1% or more, and more preferably 0.3% or more. Fe 2 O 3 is preferably in the range of 7% or less even when it is desired to be colored black. It can suppress that a glass devitrifies by setting it as 7% or less. Preferably it is 5% or less, More preferably, it is 3% or less, More preferably, it is 1% or less.
  • Co 3 O 4 and Fe 2 O 3 When it is desired to make the glass black, it is preferable to add Co 3 O 4 and Fe 2 O 3 .
  • the Co 3 O 4 and Fe 2 O 3 molar ratio Co 3 O 4 / Fe 2 O 3 is 0.01 or more, so is easily obtained effect of fining agent preferred.
  • Co 3 O 4 / Fe 2 O 3 is more preferably 0.05 or more, and further preferably 0.08 or more. If Co 3 O 4 / Fe 2 O 3 is too large, the number of bubbles may be increased. Therefore, 0.6 or less is preferable, and 0.3 or less is more preferable.
  • the content of the coloring component is preferably in the range of 7% or less in total in terms of oxide-based mole percentage even if it is desired to be colored.
  • This content is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less. In order to increase the visible light transmittance of the glass, it is preferable that these components are not substantially contained.
  • SO 3 , chloride, fluoride, etc. may be appropriately contained in the range of 0 to 1%.
  • Sb 2 O 3 content preferably 0.3% or less, more preferably 0.1% or less, and most preferably not contained.
  • As 2 O 3 is a component that makes DUV resistance more excellent and promotes clarification of the glass batch, but has a high environmental load. Therefore, it is most preferable that As 2 O 3 is not substantially contained.
  • the average abundance of S atoms in the depth region of from the surface to 3 ⁇ m is preferably 1.0E + 19atoms / cm 3 or less, 8.0E + 18atoms / cm 3 or less is more preferable. By doing so, coloring can be suppressed.
  • the amount of the component in the vicinity of the surface is determined by SIMS (secondary ion mass spectrometry), and the quantitative standard is obtained by ion-implanting a certain amount of S element into SiO 2 .
  • the average abundance of Sn atoms in the depth region from the surface to 3 ⁇ m is preferably 1.0E + 19 atoms / cm 3 or less, more preferably 9.5E + 18 atoms / cm 3 or less. Warpage can be suppressed by reducing the difference in compressive stress during strengthening.
  • the analysis in the vicinity of the surface is performed by SIMS (secondary ion mass spectrometry), and the quantitative standard is obtained by ion-implanting a certain amount of Sn element into SiO 2 .
  • Float-formed glass has a Sn contact surface and a Sn non-contact surface, so that a lot of Sn exists near the surface of the Sn contact surface.
  • Sn concentration near the surface of the Sn contact surface is high, a difference occurs in the ion exchange behavior during chemical strengthening between the Sn contact surface and the Sn non-contact surface, and warpage due to a compressive stress difference occurs.
  • FIG. 1 schematically shows how a glass having no residual stress inside, that is, a glass not subjected to chemical strengthening, breaks around a fracture starting point when it is broken by a uniform tensile stress.
  • a smooth surface called a mirror surface 2 is generated around the fracture starting point 1 indicated by a black circle.
  • a slightly rough boundary surface called a mist surface 3 is generated around the surface, and a rough surface called a hackle surface 4 is formed beyond the boundary surface.
  • ⁇ A / R 1/2
  • the mirror constant A is obtained experimentally by measuring the stress ⁇ at the time of fracture and the distance R from the fracture starting point 1 to the boundary surface between the mirror surface 2 and the mist surface 3.
  • a glass having a large mirror constant A has a small number of pieces when broken.
  • the mirror constant A is a parameter relating to glass that has not been chemically strengthened, but how to break the chemically strengthened glass depends on the properties of the glass before chemical strengthening (chemical strengthening glass). Therefore, glass (chemically tempered glass) obtained by subjecting glass having a large mirror constant A before chemical strengthening to chemical strengthening treatment has a small number of fragments even when it is broken, so that the fragments are not easily scattered and safety is high.
  • the glass for chemical strengthening of the present invention has a mirror constant A of preferably 1.96 MPa ⁇ m 1/2 or more, so that the number of fragments when broken after chemical strengthening is reduced. Therefore, even if it is destroyed, the fragments are not easily scattered and safety is high.
  • Chemically strengthened glass of the present invention are preferably mirror constant A is 2.0 MPa ⁇ m 1/2 or more, more preferably 2.07 MPa ⁇ m 1/2 or more, more preferably 2.1 MPa ⁇ m 1/2 or more 2.3 MPa ⁇ m 1/2 or more is particularly preferable.
  • the mirror constant can be measured, for example, by performing glass processing, scratching, heat treatment, bending test, and fracture surface observation according to the following procedure.
  • a sample having a fictive temperature near the glass transition temperature Tg and a sample having a Tg + 60 ° C. are prepared, and a mirror constant is measured for each sample, whereby a glass mirror having an arbitrary fictive temperature is obtained.
  • a constant can be estimated.
  • Glass processing The glass is processed into a size of 40 ⁇ 6 ⁇ 3 mm, and the front and back surfaces and the end surfaces in the longitudinal direction (four surfaces in total) are mirror-polished.
  • the indentation load is, for example, 0.05 kgf, 0.1 kgf, 0.3 kgf, 0.5 kgf, 0.75 kgf, 1.0 kgf, 2.0 kgf, and 3.0 kgf.
  • Heat treatment is performed to remove the influence of distortion due to the scratch. This heat treatment is performed according to the following procedure also for adjusting the fictive temperature. Sample with fictive temperature near Tg: Hold for 1 hour at a temperature 30 ° C. higher than Tg, and gradually cool by lowering to room temperature at 1 ° C./min. Sample with a fictive temperature of Tg + 60 ° C .: Hold at a temperature 60 ° C. higher than Tg for 1 hour and rapidly cool.
  • the fracture surface is observed using a microscope (for example, KEYENCE digital microscope VHX-5000), and the distance R from the fracture starting point to the boundary surface between the mirror surface and the mist surface is measured.
  • a microscope for example, KEYENCE digital microscope VHX-5000
  • the distance R from the fracture starting point to the boundary surface between the mirror surface and the mist surface is measured.
  • the sample and the lens of the microscope are made parallel, and observation is performed at a magnification of 20 ⁇ 150 times.
  • the glass according to the present invention has an appropriate chemical ratio because the ratio of the internal friction value at 0 ° C., which is an index of relaxation caused by sodium, and the internal friction value at 200 ° C., which is an index of relaxation caused by potassium, is in an appropriate range.
  • the ratio of the internal friction value tan ⁇ 200 is less than 1 to 2.5 in the internal friction value tan [delta 0 and 200 ° C. at 0 ° C., 1.5 or 2. Less than 0 is more preferable.
  • the internal friction tan ⁇ indicates the tangent of the phase shift of the stress response when strain is applied to the specimen of the glass material that is the measurement sample.
  • the change of the internal friction tan ⁇ with respect to the temperature is, for example, dynamic viscoelasticity measurement It can be measured by a device (DMA: Dynamic Mechanical Analysis).
  • a resonance method or a forced vibration method is known.
  • the resonance method an attenuation method, a half-width method, or the like is used, and measurement can be performed with a simple mechanism, which is widely used.
  • a phase difference method is used for the forced vibration method, and a slight displacement can be detected by measuring at a frequency of approximately 10 Hz or less.
  • the change of the internal friction tan ⁇ with respect to the temperature can be carried out, for example, by setting the plate-like test body 11 on a three-point bending measurement jig provided with support members 12A and 12B and a pressing member 13.
  • the plate-like test body 11 has a length l of 60 mm, a width (perpendicular to the paper surface of FIG. 2) of 5 mm, and a plate thickness d of 0.5 mm, for example.
  • the support members 12A and 12B have a mutual distance, that is, a support interval L of 50 mm along the length direction of the test body. To place.
  • both ends of the test body 11 set on the jig are supported from the lower surface side by the support members 12A and 12B. And the center part of the upper surface of the test body 11 can be applied by the pressing member 13 in the downward direction with a static load of 1N. At this time, it is preferable that the pressing member 13 is configured to simultaneously press the central portion between the support member 12A and the support member 12B.
  • the center portion of the upper surface of the test body 11 is periodically pressed so that the amplitude is 120 ⁇ m and the frequency is 1 Hz. 13, repeatedly pressing down and releasing the pressing.
  • the test body 11 can be strained, the stress when the strain is applied can be measured, and the internal friction tan ⁇ can be calculated from the measurement result.
  • the temperature serving as an example of the standard at the time of glass melting that is, the temperature T2 at which the viscosity of the glass is 10 2 dPa ⁇ s is preferably 1660 ° C. or less, more preferably 1650 ° C. or less, and more preferably 1645 ° C. or less. Even more preferred.
  • the temperature serving as an example of the standard at the time of glass forming that is, the temperature T4 at which the viscosity of the glass becomes 10 4 dPa ⁇ s is preferably 1255 ° C. or less, more preferably 1240 ° C. or less, and more preferably 1230 ° C. or less. More preferably, 1225 degrees C or less is still more preferable.
  • the temperature T2 and the temperature T4 can be measured using a rotary viscometer.
  • the glass may be etched for the purpose of adjusting the surface characteristics of the glass, but sludge (residue) is generated when the glass is etched.
  • sludge can affect the life of the etching solution, it is preferable from the viewpoint of productivity and the like that the sludge is small when the glass is etched.
  • the analysis method of sludge is shown below.
  • Etching solution is added to a glass plate as a sample and stirred.
  • the produced sludge is filtered with a filter paper and washed with water. After drying the sludge, weigh it and calculate the sludge weight.
  • the component analysis of sludge can be performed by XRD or SEM-EDX.
  • the amount of sludge varies depending on the etching conditions.
  • a glass plate as a sample is a glass plate of 2.5 cm ⁇ 2.5 cm ⁇ 0.55 mm, and 50 mL of an etching solution containing 7% by weight of HF and 20% by weight of HCl is used.
  • the amount of sludge when etched at 25 ° C. for 3 minutes is preferably 0.66 g or less, more preferably 0.65 g or less, and even more preferably 0.64 g or less per 1 g of glass.
  • the components of the sludge although different depending on the glass composition, for example, Na 2 SiF 6, NaMgAlF 6 , Na 2 MgAlF 7, KNaSiF 6 and KMgAlF 6, and the like.
  • the DUV resistance means that UV (DUV) with a wavelength of 100 to 280 nm is irradiated, that is, a low-pressure mercury lamp with main wavelengths of 185 nm and 254 nm, an Xe gas excimer lamp with a main wavelength of 172 nm, and an ArF excimer lamp with a main wavelength of 193 nm.
  • UV (DUV) with a wavelength of 100 to 280 nm is irradiated, that is, a low-pressure mercury lamp with main wavelengths of 185 nm and 254 nm, an Xe gas excimer lamp with a main wavelength of 172 nm, and an ArF excimer lamp with a main wavelength of 193 nm.
  • the transmittance in the wavelength region of 380 to 780 nm before UV irradiation on the short wavelength side is T0
  • the transmittance in the wavelength region of 380 to 780 nm after irradiation is T1.
  • the DUV-induced absorption ⁇ at each wavelength represented by the following formula is preferably 0.095 or less, more preferably 0.085 or less, and even more preferably 0.08 or less.
  • ⁇ -ln (T1 / T0)
  • the glass according to the present invention is preferably a glass plate, and the thickness (plate thickness) of the glass plate is preferably 0.1 to 2 mm, more preferably 0.1 to 1.5 mm, and more preferably 0.1 to 1.5 mm. 1 mm is more preferable, 0.1 to 0.7 mm is still more preferable, and 0.1 to 0.5 mm is particularly preferable.
  • the glass transition temperature (Tg) of the glass according to the present invention is preferably 550 ° C. or higher, more preferably 580 ° C. or higher, further preferably 600 ° C. or higher, more preferably 620 ° C. or higher, and 700 ° C. or lower. preferable.
  • Tg is 550 ° C. or higher, it is advantageous in terms of suppression of stress relaxation and thermal warpage during chemical strengthening treatment.
  • Tg can be adjusted by adjusting the total amount of SiO 2 and Al 2 O 3 and the amount of alkali metal oxide and alkaline earth oxide.
  • the average thermal expansion coefficient ⁇ of the glass according to the present invention is preferably 65 ⁇ 10 ⁇ 7 to 110 ⁇ 10 ⁇ 7 / K, more preferably 70 ⁇ 10 ⁇ 7 / K in the temperature range of 50 to 350 ° C. Or more, more preferably 80 ⁇ 10 ⁇ 7 / K or more, still more preferably 85 ⁇ 10 ⁇ 7 / K or more, still more preferably 100 ⁇ 10 ⁇ 7 / K or less, still more preferably 97 ⁇ 10 ⁇ 7 / K. It is as follows.
  • the average coefficient of thermal expansion ⁇ is 65 ⁇ 10 ⁇ 7 / K or more, it is advantageous in terms of matching the coefficient of thermal expansion with metals and other substances.
  • the average coefficient of thermal expansion can be adjusted by adjusting the amount of alkali metal oxide and alkaline earth oxide.
  • the specific gravity at room temperature of the glass according to the present invention is preferably 2.35 to 2.6 g / cm 3 , more preferably 2.38 g / cm 3 or more, and further preferably 2.40 g / cm 3 or more. , and more preferably 2.55 g / cm 3 or less, further preferably 2.50 g / cm 3 or less.
  • the Young's modulus E of the glass according to the present invention is preferably 60 GPa or more.
  • the glass has sufficient crack resistance and breaking strength. More preferably, it is 68 GPa or more, More preferably, it is 70 GPa or more.
  • the Poisson's ratio ⁇ of the glass of the present invention is preferably 0.28 or less.
  • the crack resistance of the glass is sufficient. More preferably, it is 0.25 or less.
  • the chemically strengthened glass of the present invention is a chemically strengthened glass obtained by chemically strengthening the above-described chemically strengthened glass.
  • it is a chemically strengthened glass having the composition of the glass for chemical strengthening of the present invention as a mother composition and having a compressive stress layer on the surface.
  • the mother composition of chemically strengthened glass is the composition of the glass (chemical strengthening glass) before chemical strengthening.
  • the part (henceforth a tensile-stress part) which has the tensile stress of chemically strengthened glass is a part which is not ion-exchanged. Since the tensile stress portion of the chemically strengthened glass has the same composition as the chemically strengthened glass, the composition of the tensile stress portion can be regarded as the mother composition.
  • the surface of the chemically strengthened glass is less likely to be scratched and a practically sufficient strength can be obtained.
  • the surface compressive stress value (CS) is preferably 900 MPa or more, more preferably 920 MPa or more, further preferably 950 MPa or more, and 1000 MPa or more. Even more preferable is 1100 MPa or more.
  • CS is preferably 1400 MPa or less, and more preferably 1300 MPa or less. More preferably, it is 1280 MPa or less.
  • the chemically strengthened glass may be easily broken, so the DOL is 30 ⁇ m or more. Is preferable, 31 ⁇ m or more is more preferable, 32 ⁇ m or more is further preferable, and 34 ⁇ m or more is more preferable.
  • the DOL is preferably 60 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the values of CS and DOL can be measured by a surface stress meter.
  • the CS and DOL of the chemically strengthened glass can be appropriately adjusted by adjusting the processing conditions of the chemical strengthening treatment, the composition of the glass for chemical strengthening, and the like.
  • the manufacturing method of the glass for chemical strengthening which concerns on this invention is not specifically limited,
  • molding molten glass is also not specifically limited.
  • a glass raw material is appropriately prepared, heated to about 1500-1700 ° C. and melted, and then homogenized by defoaming, stirring, etc., and plate-shaped by a well-known float method, downdraw method (fusion method, etc.), press method, etc. Or cast into a block shape, and after slow cooling, cut into a desired size to produce a glass plate.
  • polishing is performed as necessary, but it is also possible to treat the glass plate surface with a fluorine agent in addition to or instead of polishing.
  • the float method or downdraw method is preferred, and in particular, the float method is preferred in consideration of producing large glass plates.
  • the glass plate of the present invention is the size of a display such as a tablet PC or a smartphone or the size of a window glass of a building or a house.
  • the glass of the present invention is generally cut into a rectangle, but other shapes such as a circle or a polygon may be used without any problem, and a glass subjected to drilling is also included.
  • the glass of the present invention is preferably chemically strengthened. Prior to the chemical strengthening treatment, it is preferable to perform shape processing according to the application, for example, mechanical processing such as cutting, end surface processing and drilling processing.
  • the chemical strengthening treatment is performed by cutting the manufactured glass to a desired size to obtain a glass plate, and then preheating the glass plate to about 400 ° C., and in the molten salt, Na on the surface of the glass plate and K in the molten salt. Can be processed by ion exchange.
  • an acid treatment and an alkali treatment may be performed to obtain a chemically strengthened glass plate with higher strength.
  • molten salt for performing the ion exchange treatment examples include alkali nitrates such as potassium nitrate, potassium sulfate and potassium chloride, alkali sulfates and alkali chloride salts. These molten salts may be used alone or in combination of two or more. Further, a salt containing sodium may be mixed in order to adjust the chemical strengthening characteristics.
  • the CS of the chemically strengthened glass can be adjusted by adjusting the Na concentration, the strengthening time, and the molten salt temperature in the molten potassium nitrate salt used for ion exchange. In order to obtain higher CS, the Na concentration in the molten potassium nitrate is reduced.
  • DOL can be adjusted by adjusting Na concentration, strengthening time and molten salt temperature in the molten potassium nitrate salt used for ion exchange. In order to obtain a higher DOL, the temperature of the molten salt is increased.
  • Chemically tempered glass can be cut after chemical tempering treatment.
  • a cutting method scribing and breaking with a normal wheel tip cutter can be applied, and laser cutting is also possible.
  • the cutting edge may be chamfered after cutting.
  • the chamfering may be a mechanical grinding process or a method of treating with a chemical solution such as hydrofluoric acid.
  • the use of the glass of the present invention is not particularly limited. Since chemically strengthened glass has high mechanical strength, it is suitable for use in places where impact due to dropping or contact with other substances is expected.
  • mobile phones including multifunctional information terminals such as smartphones
  • PHS, PDA, tablet terminals notebook personal computers, game machines, portable music / video players, electronic books, electronic terminals
  • Cover glass for display parts such as watches, cameras or GPS, and cover glass for touch panel operation monitors of these devices
  • cover glass for cookers such as microwave ovens and oven toasters
  • top plates such as electromagnetic cookers, meters
  • machines or devices such as cover glass for instruments such as gauges and glass plates for reading parts such as copying machines or scanners.
  • window glass for vehicles, ships, airplanes, etc. household or industrial lighting equipment, signals, guide lights, cover boards for electric bulletin boards, showcases, bulletproof glass, etc.
  • Examples include a cover glass for protecting a solar cell and a glass material for condensing for increasing the power generation efficiency of the solar cell.
  • glass for mirror surfaces there are various glass for mirror surfaces, and further, as a substrate for information storage media such as HDDs, and as a substrate for information recording media such as CDs, DVDs, and Blu-ray discs.
  • it can be used as a building material such as an aquarium, dishes such as dishes and cups, various cooking utensils such as bottles or chopping boards, cupboards, shelf boards and walls of refrigerators, roofs or partitions.
  • a building material such as an aquarium, dishes such as dishes and cups, various cooking utensils such as bottles or chopping boards, cupboards, shelf boards and walls of refrigerators, roofs or partitions.
  • chemically strengthened glass produced after the chemical strengthening treatment is optimal as a glass material for display incorporated in various image display devices such as liquid crystal, plasma, and organic EL.
  • Examples 1 to 5 and 7 to 9 are examples, and example 6 is a comparative example.
  • Table 1 values shown in parentheses are calculated values, and blanks indicate that they are not contained or not evaluated.
  • Fe 2 O 3 is not added in the compositions of Examples 1 to 6, it is blank, but since Fe 2 O 3 is an unavoidable component, it is estimated that it is contained at about 0.0018 mol%.
  • the raw materials are prepared so as to have the composition shown in Table 1 in terms of oxide-based mole percentage, put into a platinum crucible, put into a 1650 ° C. resistance heating electric furnace, melted for 3 hours, defoamed, Homogenized.
  • the obtained glass was poured into a mold material, held at a temperature of 680 ° C. for 1 hour, and then cooled to room temperature at a rate of 1 ° C./min to obtain a glass block. Next, the glass block was cut and polished, and both surfaces were mirror-finished to obtain a glass having a predetermined size.
  • T4 > The temperature T2 at which the viscosity of the glass becomes 10 2 dPa ⁇ s and the temperature T4 at which the viscosity becomes 10 4 dPa ⁇ s were measured using a rotary viscometer.
  • ⁇ Sludge amount, sludge component> The amount of sludge was measured by etching the glass.
  • the glass used as a sample was a glass plate of 2.5 cm ⁇ 2.5 cm ⁇ 0.55 mm, and was etched by being immersed in 50 mL of an etching solution containing 7% by weight of HF and 20% by weight of HCl at 25 ° C. for 3 minutes.
  • the produced sludge was filtered with 5A filter paper, washed with water, dried, and the weight of the sludge was measured. The amount of sludge was converted per 1 g of glass.
  • Sludge components were identified by XRD measurement. Detailed measurement conditions are as follows. Device: Rigaku SmartLab, X-ray source: CuK ⁇ ray, X-ray output: 45 kV, 200 mA, optical system: BB, incident parallel slit: Soller slit 5 °, incident slit: 1/3 °, receiving parallel slit: Soller slit 5 °, Scan speed: 10 ° / min, sampling width: 0.02 °, measurement range: 20-60 °, analysis: PDXL (ver. 2.0.3.0)
  • Table 1 shows T2, T4, the amount of sludge, and the main components of the sludge of the obtained glass.
  • the glass according to the present invention was a glass having a smaller amount of sludge during etching than the glass of Example 6.
  • the values of CS (MPa) and DOL ( ⁇ m) of the obtained chemically strengthened glass plate were measured by a surface stress meter (manufactured by Orihara Seisakusho). The results are shown in Table 1.
  • the chemically strengthened glass according to the present invention had a higher CS than the chemically strengthened glass according to Example 6. .
  • each glass was heat-treated at (Tg + 50) ° C. for 1 hour, slowly cooled to room temperature at 1 ° C./minute, and then the glass polished to have the same plate thickness was left on the table horizontally.
  • a low-pressure mercury lamp PL21-200 manufactured by Sen Special Light Source, main wavelengths 185 nm and 254 nm
  • the transmittance at a wavelength of 380 nm was measured.
  • the illuminance at 254 nm at the place where the glass plate was installed was 8 mW / cm 2 (measured with an illuminance meter UV-M03A and a photoreceiver UV-SD25-M10 manufactured by Oak Manufacturing Co., Ltd.).
  • the transmittance was measured with a spectrophotometer (trade name U-4100) manufactured by Hitachi High-Technologies Corporation.
  • Example 1 was 2.18
  • Example 2 was 2.35
  • Example 3 was 2.08.
  • 4 is 2.09
  • Example 5 is 2.10
  • Example 6 is 2.06.
  • the mirror constants of Examples 7 to 9 are similar to those of Example 3.
  • the glass of the example has a large CS
  • the mirror constant is large, so it can be said that the risk of severe breakage is small.
  • FIG. 3A shows the value of tan ⁇ with respect to temperature for the glass of the example (Example 3) and B for the glass of the comparative example (Example 6).
  • the glass of Comparative Example 6 has a ratio of tan ⁇ 0 at 0 ° C. to tan ⁇ 200 at 200 ° C. (tan ⁇ 0 / tan ⁇ 200 ) of 0.4, and ion exchange of Na ions hardly occurs, and K ions It shows that the structural relaxation caused by is likely to occur. Such glass is difficult to obtain appropriate chemical strengthening properties.
  • the glass of Example 3 as an example has a ratio of tan ⁇ 0 at 0 ° C. to tan ⁇ 200 at 200 ° C. of 1.81, and appropriate chemical strengthening characteristics can be obtained.

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PCT/JP2017/020135 2016-06-03 2017-05-30 化学強化用ガラス及び化学強化ガラス WO2017209139A1 (ja)

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