WO2017038621A1 - Plaque de verre présentant une résistance aux uv - Google Patents

Plaque de verre présentant une résistance aux uv Download PDF

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Publication number
WO2017038621A1
WO2017038621A1 PCT/JP2016/074810 JP2016074810W WO2017038621A1 WO 2017038621 A1 WO2017038621 A1 WO 2017038621A1 JP 2016074810 W JP2016074810 W JP 2016074810W WO 2017038621 A1 WO2017038621 A1 WO 2017038621A1
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Prior art keywords
glass plate
irradiation
transmittance
glass
absorption coefficient
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PCT/JP2016/074810
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English (en)
Japanese (ja)
Inventor
聡司 大神
小池　章夫
林　英明
円佳 小野
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旭硝子株式会社
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Publication of WO2017038621A1 publication Critical patent/WO2017038621A1/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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass

Definitions

  • the present invention relates to a UV-irradiation glass plate and UV-irradiation glass plate having UV resistance, and more particularly to a high-intensity UV irradiation glass plate and UV-irradiation glass plate having UV resistance.
  • soda lime glass has been widely used for glass plates for display, but has poor chemical strengthening properties and poor strength properties.
  • aluminosilicate glass etc. are developed as glass for chemical strengthening which can implement
  • the chemically strengthened glass plate is useful for display applications because of its high strength, but it is required to have high transmittance in addition to high strength. Therefore, a highly permeable chemically strengthened glass plate with a reduced iron content that contributes to coloration has been studied.
  • Patent Document 1 As one of the factors that lower the transmittance of glass, so-called solarization is known in which the valence state of a transition metal changes due to the influence of ultraviolet rays or the like, and the color of the glass changes.
  • Patent Document 2 in order to increase the resistance to solarization of the glass, colored glass containing TiO 2 is disclosed.
  • Patent Document 2 discloses a highly transmissive soda lime glass in which a measure against solarization is achieved by reducing the iron content in the glass to 0.005 to 0.120% by weight.
  • a high-strength glass plate (chemically strengthened glass plate) subjected to chemical strengthening treatment is subjected to various pretreatments when used for a display or the like.
  • One of them is a cleaning treatment by UV irradiation on the short wavelength side using a low-pressure mercury lamp, and organic substances on the surface of the glass plate may be removed.
  • UV irradiation on the short wavelength side using a low-pressure mercury lamp
  • organic substances on the surface of the glass plate may be removed.
  • the transmittance in a specific wavelength region of the glass plate is reduced by UV irradiation on the short wavelength side.
  • UV on the short wavelength side is irradiated, the color of the glass plate is deteriorated according to the region where the transmittance is lowered.
  • the short wavelength side UV has a shorter wavelength than UV in solarization, which is cited as one of the problems in Patent Documents 1 and 2. It has been found that the chemically strengthened glass containing Ti described in Patent Document 1 does not exhibit the effect of suppressing the decrease in transmittance in the UV irradiation on the short wavelength side. Further, the glass described in Patent Document 2 is soda lime glass that has poor chemical strengthening properties and cannot achieve high strength, and further, there is no disclosure regarding resistance to UV on the short wavelength side. As a result of studies by the present inventors, it has been found that, in a high-strength glass plate, merely reducing the Fe content does not provide the effect of suppressing the decrease in transmittance in UV irradiation on the short wavelength side.
  • UV resistance refers to the change in transmittance of UV irradiation on the short wavelength side mainly using 185 nm and 254 nm using a low-pressure mercury lamp.
  • UV-C of 280 nm or less from sunlight is said to be completely absorbed by ozone and oxygen molecules in the stratosphere on the earth and hardly reaches the surface of the earth. It deals with a phenomenon different from “UV resistance” in the book.
  • the present invention relates to the following ⁇ 1> to ⁇ 8>.
  • ⁇ 1> By mass%, SiO 2 is 60 to 75%, Al 2 O 3 is 2 to 25%, Na 2 O is 10 to 20%, K 2 O is 0 to 7%, and MgO is 0.5 to 10 %, CaO 0-15% and Fe 2 O 3 0.035-0.12%,
  • a glass plate for UV irradiation having a redox ratio of less than 0.550 and a CaO / MgO (mass ratio) of 1.5 or less.
  • the absorption coefficient of Fe 2+ after polishing the UV-irradiated glass plate in the depth direction from the surface by 150 ⁇ m is 0.001 cm ⁇ 1 or more larger than the absorption coefficient of Fe 2+ before the polishing, and then UV having a wavelength of 254 nm ⁇ 2>
  • the absorption coefficient of Fe 2+ after the UV-irradiated glass plate is held at a temperature of (Tg + 40) ° C. for 1 hour and slowly cooled to room temperature at a cooling rate of 1 ° C./min is the pre-treatment absorption coefficient.
  • the absorption coefficient of Fe 2+ is 0.001 cm ⁇ 1 or more larger than the absorption coefficient of Fe 2+
  • the absorption coefficient of Fe 2+ after irradiation with UV having a wavelength of 254 nm is smaller than the absorption coefficient of Fe 2+ before the irradiation by 0.017 cm ⁇ 1 or more.
  • the transmittance T1 ′′ satisfies the relationship ⁇ ln (T1 ′′ / T0 ′′) ⁇ 0.001, and then the transmittance T1 after irradiation with UV having a wavelength of 254 nm, the transmittance T0 before the irradiation,
  • ⁇ 8> The glass plate for UV irradiation according to ⁇ 1> or ⁇ 2>, wherein an average transmittance at a wavelength of 380 to 780 nm is 91% or more.
  • the present invention it is possible to obtain a UV irradiation glass plate and a UV irradiation glass plate that maintain high strength without lowering the transmittance in a specific wavelength region even when UV on the short wavelength side is irradiated. Therefore, a glass plate with high transmission and high strength can be obtained without deteriorating the color of the glass plate, and it is very useful as a chemically strengthened glass plate for which high transmission is required for display applications and the like.
  • UV irradiation glass plate means a glass plate before irradiation with short wavelength UV
  • UV irradiation glass plate means a glass plate after irradiation with short wavelength UV.
  • glass plates are sometimes collectively referred to simply as “glass plates”.
  • % when “%” is simply described, it means “% by mass”, and “ ⁇ ” means that the value is not less than the lower limit and not more than the upper limit.
  • the glass plate according to the present invention is expressed in terms of an oxide-based mass percentage (hereinafter sometimes simply referred to as “mass%”), and SiO 2 is 60 to 75%, Al 2 O 3 is 2 to 25%, 10-20% Na 2 O, 0-7% K 2 O, 0.5-10% MgO, 0-15% CaO and 0.035-0.12% Fe 2 O 3
  • the redox ratio is less than 0.550, and CaO / MgO (mass ratio) is 1.5 or less.
  • the composition of the glass plate can be measured simply by the fluorescent X-ray method, and more precisely by the wet analysis method.
  • the surface compressive stress (CS) is preferably 600 to 1000 MPa, and more preferably 650 to 950 MPa. If it is less than 600 MPa, scratches are likely to occur on the surface of the glass, and there is a possibility that a practically sufficient strength cannot be obtained.
  • the compressive stress layer depth (DOL; Depth of Layer) is preferably 5 to 50 ⁇ m, and more preferably 7 to 40 ⁇ m. If the surface is less than 5 ⁇ m, if the surface of the glass is scratched, the depth of the scratch may exceed the DOL and the glass may be easily broken.
  • CS tensile stress value
  • C Center Tension
  • the UV resistance means that a decrease in transmittance at a wavelength of 300 to 800 nm is suppressed when short-wavelength UV light such as a low-pressure mercury lamp is irradiated.
  • the UV irradiation on the short wavelength side is carried out at a wavelength of 100 to 280 nm in a range of 0.1 to 1000 mW / cm 2 and an irradiation time of 1 to 20000 seconds. From the aspect of reducing the processing cost, it is preferable that the irradiation time is 1 to 100 mW / cm 2 and the irradiation time is 1200 seconds or less.
  • the exposure preferably be carried out at the 10 ⁇ 10000mJ / cm 2 condition, more preferably of 50 ⁇ 5000mJ / cm 2 conditions.
  • the light source include a low-pressure mercury lamp having main wavelengths of 185 nm and 254 nm, an excimer lamp having a main wavelength of 172 nm, and the like.
  • This UV irradiation on the short wavelength side is generally used for UV cleaning treatment or UV sterilization treatment of a substrate.
  • solarization resistance due to sunlight is an evaluation for UV irradiation in a long wavelength region that is not absorbed by the stratosphere, and thus is an evaluation different from the evaluation for wavelengths of 300 nm or less in the present invention.
  • the transmittance at a wavelength of 300 to 800 nm before UV irradiation on the short wavelength side is T0 a
  • the transmittance at a wavelength of 300 to 800 nm after irradiation based on the irradiation condition A is preferably when formed into a T1 a
  • the UV induced absorption ⁇ at each wavelength represented by the following formula is 0.07 or less, and more preferably 0.05 or less.
  • the irradiation condition A means that a PLW 21-200 made by Sen Special Light Source is used for 600 seconds from a position 5 cm away from the surface of the glass plate using a 200 W low-pressure mercury lamp (EUV200GS-14: main wavelengths 185 nm and 254 nm). Irradiation.
  • EUV200GS-14 main wavelengths 185 nm and 254 nm.
  • the transmittance of a glass plate at a wavelength of 300 to 800 nm hardly changes before and after UV irradiation on the long wavelength side with a main wavelength of 365 nm using, for example, a high-pressure mercury lamp.
  • the transmittance decreases due to UV irradiation on the short wavelength side.
  • the degree of transmittance decrease is not uniform depending on the wavelength, and the rate of decrease varies depending on the wavelength, the color is complementary to the color of the wavelength region in which the transmittance is lower due to UV irradiation on the short wavelength side. As a result, the color becomes worse.
  • the glass composition in the present invention it is possible to suppress a decrease in transmittance at a wavelength of 300 to 800 nm before and after UV irradiation on the short wavelength side and to prevent the color of the glass plate from being deteriorated.
  • the UV resistance can be further improved by making Fe 2 O 3 0.035 to 0.12% and the redox ratio less than 0.550.
  • Fe 2 O 3 is preferably 0.05% or more, and more preferably 0.1% or more.
  • the redox ratio is preferably 0.500 or less, and more preferably 0.450 or less.
  • the redox ratio refers to the ratio (atomic ratio) of divalent iron Fe 2+ to the total iron Fe amount contained in the glass.
  • the redox ratio may be expressed in%.
  • the value of the redox ratio can be appropriately adjusted by introducing oxygen into the molten glass and oxidizing the divalent iron Fe 2+ to the trivalent iron Fe 3+ .
  • the redox ratio can be determined by a method such as quantifying Fe 2+ in glass by bipyridyl absorptiometry and quantifying the value of total iron Fe by ICP emission analysis. Note that the total iron amount can also be obtained simply by fluorescent X-rays.
  • the glass plate according to the present invention is preferably colorless glass when used for a display.
  • Colorless glass means glass having a coloring component of 2% or less, and glass having an average transmittance of 91% or more at a wavelength of 380 to 780 nm.
  • the coloring component is preferably 1% or less, more preferably 0.5% or less, further preferably 0.2% or less, and still more preferably substantially not contained. “Substantially not contained” means not containing any inevitable impurities.
  • the average transmittance at a wavelength of 380 to 780 nm is preferably 91% or more, more preferably 91.2% or more, and further preferably 91.4% or more.
  • the coloring component examples include a component represented by M p O q , where M is Co, Cu, V, Cr, Pr, Ce, Bi, Eu, Mn, Er, Ni, Nd, W, Rb, Sn, and It is at least one selected from the group consisting of Ag, and p and q represent the atomic ratio of M and O (oxygen atom).
  • the glass plate according to the present invention may contain other components as long as the effects are not impaired.
  • the component that may be included include SO 3 , ZnO 2 , ZrO 2 , TiO 2 , SrO, BaO, Li 2 O, Cs 2 O, Fr 2 O, AsO, SbO, and SeO 2 . These can be included in a total of 0 to 2%.
  • the total thickness of the glass plate may be 0.1 to 2 mm, and 0.2 to 1 mm is preferable from the viewpoint of achieving both rigidity and light weight.
  • SiO 2 is known as a component that forms a network structure in the glass microstructure, and is a main component constituting the glass.
  • the content of SiO 2 is 60% or more, preferably 63% or more, more preferably 65% or more, particularly preferably at least 67%.
  • the content of SiO 2 is 75% or less, preferably 73% or less, more preferably 71% or less, and particularly preferably 70% or less.
  • the content of SiO 2 is 60% or more, it is advantageous in terms of stability and weather resistance as glass. Moreover, an increase in thermal expansion can be suppressed by forming a network structure.
  • the content of SiO 2 is 75% or less, it is advantageous in terms of solubility and moldability.
  • Al 2 O 3 has an effect of improving the ion exchange performance in chemical strengthening, and in particular, an effect of improving CS. It is also known as a component that improves the weather resistance of glass. Moreover, there exists an effect
  • the content of Al 2 O 3 is 2% or more, preferably 3% or more, more preferably 4% or more.
  • the content of Al 2 O 3 is 25% or less, preferably 20% or less, more preferably 15% or less, still more preferably 9.5% or less, and particularly preferably 8.6% or less.
  • a desired CS value is obtained by ion exchange, and in addition to the float method, tin from the surface (bottom surface) in contact with the tin melting bath is obtained.
  • the effect of suppressing intrusion and making the glass difficult to warp during chemical strengthening, the effect of stability against moisture content change, and the effect of promoting dealkalization are obtained.
  • the content of Al 2 O 3 is 25% or less, the devitrification temperature does not increase greatly even when the viscosity of the glass is high, which is advantageous in terms of melting and forming in a float facility.
  • B 2 O 3 is a component that promotes melting of the glass raw material and improves mechanical properties and weather resistance, but it does not cause inconveniences such as generation of striae due to volatilization and furnace wall erosion. You may contain in 6% or less of range. When it contains B 2 O 3 , it is preferably 5% or less, more preferably 4% or less, and particularly preferably not substantially contained.
  • 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
  • Na 2 O is a component that generates non-crosslinked oxygen, and the variation in chemical strengthening characteristics when the amount of moisture in the glass varies is reduced.
  • the content of Na 2 O is 10% or more, preferably 11% or more, more preferably 13% or more. Further, the content of Na 2 O is 20% or less, preferably 18% or less, more preferably 16% or less.
  • a desired surface compressive stress layer can be formed by ion exchange, and fluctuations due to changes in moisture content can be suppressed.
  • the content of Na 2 O is 20% or less, sufficient weather resistance can be obtained, the amount of intrusion of tin from the bottom surface during molding by the float method can be suppressed, and the glass is hardly warped after chemical strengthening treatment. be able to.
  • K 2 O is an ingredient that increases the ion exchange rate, deepens the DOL, lowers the melting temperature of the glass, and increases non-crosslinked oxygen, so it may be contained in a range of 7% or less. If it is 7% or less, the DOL does not become too deep, sufficient CS is obtained, and the melting temperature of the glass can be lowered. Preferably 5% or less when they contain K 2 O, more preferably 4% or less, more preferably 2% or less. On the other hand, since a small amount of K 2 O has an effect of suppressing the amount of intrusion 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 this case, the content of K 2 O is preferably 0.01% or more, more preferably 0.1% or more.
  • MgO is a component that can stabilize the glass, improve the solubility, and reduce the alkali metal content by adding this to suppress an increase in the coefficient of thermal expansion (CTE).
  • the content of MgO is 0.5% or more, preferably 3% or more, more preferably 5% or more. Further, the content of MgO is 10% or less, preferably 9% or less, more preferably 8% or less. When the content of MgO is 0.5% or more, the CTE increase suppressing effect is exhibited. On the other hand, when the content of MgO is 10% or less, the difficulty of devitrification is maintained, or a sufficient ion exchange rate is obtained.
  • CaO is a component that stabilizes the glass, and has the 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 0 to 15%, preferably 0.5 to 12%, more preferably 2 to 10%. When the content of CaO is 15% or less, a sufficient ion exchange rate is obtained, and a desired DOL is obtained.
  • CaO is preferably less than 5%, more preferably 4% or less.
  • CaO / MgO (mass ratio) is preferably 1.5 or less from the viewpoint of improving ion exchange performance in chemical strengthening and increasing the transmittance of the glass plate. More preferably, it is 0.1 to 1.2, and still more preferably 0.2 to 1.0.
  • SO 3 , chlorides, fluorides and the like may be appropriately contained in the range of 0 to 1% as glass refining agents.
  • Absorption coefficient alpha Fe @ 2 + and is of Fe 2+ of the glass plate in the present specification the absorption at a wavelength of 780nm regarded as zero, may be determined according to the following equation.
  • the reason why the absorption at the wavelength of 780 nm is regarded as zero and used as a reference is to subtract the influence of the reflection of the glass plate.
  • ⁇ Fe2 + 2.303 ⁇ log ( T 780 / Ti) / d Ti: Transmittance of measurement wavelength (%)
  • T780 Transmittance (%) at a wavelength of 780 nm
  • d Glass thickness (cm)
  • the measurement wavelength for Ti is 380 to 780 nm.
  • the absorption coefficient and transmittance of Fe 2+ of the UV-irradiated glass plate vary depending on the irradiation time and irradiation intensity of the irradiated UV. Therefore, in order to uniformly evaluate the characteristics of the glass plate, after polishing the UV-irradiated glass plate in the depth direction from the surface by 150 ⁇ m, UV irradiation is again performed under the irradiation condition A to measure the absorption coefficient and transmittance of Fe 2+. I do. Since the absorption coefficient of Fe 2+ of the glass plate after polishing 150 ⁇ m in the depth direction from the surface is the same value as the absorption coefficient of Fe 2+ of the glass plate not irradiated with UV, the glass plate after polishing is UV-treated. It can be regarded as an unirradiated glass plate.
  • the absorption coefficient of Fe 2+ after polishing (corresponding to UV non-irradiation) is the same as that before polishing (UV irradiation in the actual process).
  • the absorption coefficient of Fe 2+ after) is 0.001 cm ⁇ 1 or more.
  • the absorption coefficient of Fe 2+ after irradiation with UV under irradiation condition A following the polishing is 0.017 cm ⁇ 1 or more smaller than the absorption coefficient of Fe 2+ before irradiation. Is preferable, and it is more preferably 0.019 cm ⁇ 1 or less.
  • the absorption coefficient of the Fe 2+ after UV irradiation of the short wavelength side is smaller than the absorption coefficient of the Fe 2+ before UV irradiation
  • the surface layer portion of the glass plate of the Fe 2+ ⁇ Fe 3+ Indicates that a reaction is taking place.
  • the absorption coefficient of Fe 2+ after UV irradiation is preferably 0.017 cm ⁇ 1 or more smaller than the absorption coefficient of Fe 2+ before UV irradiation.
  • a slow cooling process may be performed instead of the above polishing. That is, since the absorption coefficient of Fe 2+ of the glass plate after performing the slow cooling treatment under a certain condition is the same value as the absorption coefficient of Fe 2+ of the glass plate not irradiated with UV, the slow cooling treatment The latter glass plate can be regarded as a glass plate not irradiated with UV.
  • the absorption coefficient of Fe 2+ after the slow cooling process (corresponding to UV non-irradiation) is the same as that before the slow cooling process (actual process). larger 0.001 cm -1 or more than the absorption coefficient of the Fe 2+ after UV irradiation) in.
  • the UV-irradiated glass plate is held at a temperature of (Tg + 40) ° C. for 1 hour and slowly cooled to room temperature at a cooling rate of 1 ° C./min.
  • the absorption coefficient of Fe 2+ after irradiation with UV under irradiation condition A following the slow cooling treatment is 0.017 cm ⁇ 1 or more than the absorption coefficient of Fe 2+ before irradiation. It is preferably small, more preferably 0.019 cm ⁇ 1 or more.
  • the transmittance can be regarded as a glass plate not irradiated with UV by performing the above polishing or slow cooling treatment on the UV irradiated glass plate.
  • a shorter irradiation time or a lower irradiation intensity is often used compared to the irradiation condition A, and the transmittance T0 ′ or T0 ′′ after polishing or annealing (corresponding to UV non-irradiation) and polishing or
  • the transmittance T1 ′ or T1 ′′ before annealing is ⁇ ln (T1 ′ / T0 ′) ⁇ 0.001 or ⁇ ln (T1 ′′ / T0 ′′) ⁇ The relationship of 0.001 is satisfied.
  • the UV-irradiated glass plate according to the present invention has a transmittance T1 b after irradiation with UV under irradiation condition A following the polishing or annealing process and a transmittance T0 b before UV irradiation of ⁇ ln (T1 b / It is preferable to satisfy the relationship of T0 b ) ⁇ 0.07, and more preferably 0.05 or less.
  • the transmittances Tn b , Tn ′ and Tn ′′ and the above-described Tn a are all transmittances at wavelengths of 300 to 800 nm, and the transmittances T1 a and T1 b are the irradiation conditions described above.
  • a transmittance after UV irradiation with A is the same as a transmittance for UV irradiation with A.
  • the glass transition temperature (Tg) of the glass plate according to the present invention is, for example, 530 ° C. or more, preferably 540 ° C. or more, more preferably 550 ° C. or more, and further preferably 550 to 600 ° C. preferable.
  • Tg is 530 ° 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 thermal expansion coefficient CTE of the glass plate according to the present invention is, for example, 80 ⁇ 10 ⁇ 7 to 100 ⁇ 10 ⁇ 7 / K, preferably 80 ⁇ 10 ⁇ 7 to 95 ⁇ 10 in the temperature range of 50 to 350 ° C. -7 / K.
  • CTE can be adjusted by adjusting the amount of alkali metal oxide and alkaline earth oxide.
  • the density at room temperature of the glass plate according to the present invention is 2.38 from the viewpoint of reducing the difference in density from soda lime glass, considering that it is alternately produced in the same float equipment as normal soda lime glass.
  • To 2.54 g / cm 3 preferably 2.40 to 2.52 g / cm 3 .
  • the manufacturing method of the glass plate for UV irradiation which concerns on this invention is not specifically limited,
  • molding molten glass into a plate-shaped glass plate is not specifically limited.
  • appropriate amounts of various raw materials are prepared, heated to about 1500-1600 ° C and melted, and then homogenized by defoaming, stirring, etc., and the plate is obtained 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.
  • a polishing process 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 the polishing process.
  • the glass plate after production is SiO 2 60-75%, Al 2 O 3 2-25%, Na 2 O 10-20%, K 2 O 0-7%, MgO 0.5-10%
  • the raw materials are selected so that 0-15% of CaO and 0.035-0.12% of Fe 2 O 3 are contained, and CaO / MgO (mass ratio) is 1.5 or less.
  • the UV irradiation glass plate concerning this invention is obtained by irradiating UV of the short wavelength side to the obtained glass plate for UV irradiation.
  • the glass plate is preheated to about 400 ° C., and ion exchange is performed between Na on the surface of the glass plate and K in the molten salt in the molten salt. It is preferable to perform a chemical strengthening treatment. Further, after ion exchange in a molten salt containing a specific salt, an acid treatment and an alkali treatment may be performed to obtain a chemically strengthened glass plate having higher strength.
  • the obtained glass plate preferably has a CS of 600 to 1000 MPa, more preferably 650 to 950 MPa.
  • CS can be adjusted by adjusting Na concentration, strengthening time and molten salt temperature in the molten potassium nitrate salt used for ion exchange.
  • the Na concentration in the molten potassium nitrate is reduced.
  • the Na concentration is preferably 3% by mass or less, more preferably 2.5% by mass or less, and further preferably 1% by mass or less.
  • the DOL is preferably 5 to 50 ⁇ m, more preferably 7 to 40 ⁇ m. DOL can be adjusted by adjusting Na concentration, strengthening time and molten salt temperature in the molten potassium nitrate salt used for ion exchange.
  • the temperature of the molten salt is increased.
  • the temperature of the molten salt is preferably 400 ° C or higher, more preferably 420 ° C or higher, and further preferably 430 ° C or higher.
  • the glass plate of this embodiment can be cut after chemical strengthening.
  • 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.
  • ⁇ Glass composition The composition of the obtained glass plate was identified by the fluorescent X-ray method.
  • the redox ratio was determined by quantifying Fe 2+ in the glass by bipyridyl absorptiometry and quantifying the value of total Fe by ICP emission spectrometry. These results are shown in Table 1.
  • UV irradiation glass plate is irradiated with UV under irradiation condition A, that is, the light of a low-pressure mercury lamp (main wavelengths 185 nm and 254 nm) is irradiated for 600 seconds from a position 5 cm away, and then transmitted through the UV irradiation glass plate at a wavelength of 200 to 2500 nm. The rate was measured. The transmittance was measured in steps of 1 nm with a spectrophotometer trade name U-4100 manufactured by Hitachi High-Technologies Corporation.
  • Table 1 shows the results of the UV resistance test.
  • ⁇ (UV resistance) indicates the value of UV-induced absorption ⁇ at a wavelength where the difference in UV-induced absorption was the largest before and after light irradiation.
  • ⁇ indicates that the UV-induced absorption ⁇ was 0.07 or less at the wavelength where the difference in UV-induced absorption was the largest before and after light irradiation.
  • X means that the UV-induced absorption ⁇ was larger than 0.07.
  • ⁇ Redox ratio> The obtained glass was pulverized and dissolved in an HF aqueous solution to prepare a test liquid.
  • the test liquid, a 2,2′-dipyridyl solution, and an ammonium acetate solution were mixed to develop color, the absorption peak intensity was measured, and the Fe 2+ amount was calculated based on a calibration curve prepared in advance.
  • the above test liquid, hydroxylamine hydrochloric acid solution, 2,2'-dipyridyl solution, and ammonium acetate solution were mixed to reduce the color of all iron to divalent iron, and the absorbance peak intensity. To calculate the total iron content.
  • the ratio (redox ratio) between the amount of Fe 2+ and the total iron Fe was determined and indicated in% in the “Redox” column of Table 1.
  • the Fe 2+ absorption coefficient (cm ⁇ 1 ) of the polished glass plate after polishing the surface of the UV irradiated glass plate in the depth direction by 150 ⁇ m is the glass plate not irradiated with UV (glass plate for UV irradiation).
  • the Fe 2+ absorption coefficient (cm ⁇ 1 ) after polishing the UV-irradiated glass plate becomes the same value as “Fe 2+ absorption coefficient (cm ⁇ 1 ) before light irradiation” in Table 1, and the UV-irradiated glass plate
  • the Fe 2+ absorption coefficient (cm ⁇ 1 ) after polishing is 0.001 cm ⁇ 1 or more larger than the Fe 2+ absorption coefficient (cm ⁇ 1 ) before polishing.
  • Fe 2+ absorption coefficient (cm ⁇ 1 ) after the UV irradiation glass plate was polished and irradiated with UV under the irradiation condition A was almost the same as “Fe 2+ absorption coefficient (cm ⁇ 1 ) after light irradiation” in Table 1. Value.
  • Table 1 shows the value of ⁇ ln (T1 a / T0 a ) derived by using the transmittances T0 a and T1 a at wavelengths of 300 to 800 nm before and after the UV irradiation glass plate was irradiated with UV under the irradiation condition A.
  • the transmittance T1 b after the UV irradiation glass plate is irradiated with UV under the irradiation condition A after polishing the UV irradiation glass plate is similar to the transmittance T1 a after the UV irradiation glass plate is irradiated with the UV under the irradiation condition A.
  • the value of ⁇ ln (T1 b / T0 b ) calculated from the transmittance before and after UV irradiation under irradiation condition A after polishing the UV-irradiated glass plate is represented by “ ⁇ (UV resistance)” in Table 1. This is approximately the same as the value of ⁇ ln (T1 a / T0 a ).
  • the UV irradiating glass plate was held at (Tg + 40) ° C. for 1 hour, and the glass plate treated with gradual cooling to room temperature at a cooling rate of 1 ° C./min was subjected to the absorption coefficient and transmittance of Fe 2+. It can be considered that it is the same as the said grinding
  • the coefficient of thermal expansion is based on JIS R 1618: 2002, measured at a rate of temperature increase of 5 ° C./minute using a thermal dilatometer (Bruker Ax, TD5000SA), and an average linear expansion of 50 to 350 ° C. The rate was determined. Moreover, the glass transition temperature (Tg) was calculated
  • the glass plate was chemically strengthened by immersion in molten potassium nitrate having a concentration of 98% and a temperature of 425 ° C. for 3 hours.
  • the values of CS (MPa) and DOL ( ⁇ m) of the obtained chemically strengthened glass plate were measured with a surface stress meter FSM-6000 manufactured by Orihara Seisakusho and calculated as a calculated value.
  • the results are shown in “CS (MPa)” and “DOL ( ⁇ m)” in Table 1, respectively.
  • “DOL determination” of “ ⁇ ” indicates that the DOL is 8 ⁇ m or more, and “X” indicates that the DOL is less than 8 ⁇ m.
  • the present invention it is possible to obtain a glass plate excellent in UV resistance that maintains high strength without lowering the transmittance in a specific wavelength region even when UV on the short wavelength side is irradiated. Therefore, a glass plate with high transmission and high strength can be obtained without deteriorating the color of the glass plate, and it is very useful as a chemically strengthened glass plate for which high transmission is required for display applications 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)
  • Glass Compositions (AREA)

Abstract

La présente invention a pour but de fournir une plaque de verre à haute résistance, présentant une résistance aux UV, qui maintient la résistance élevée sans que le facteur de transmission soit diminué dans une plage de longueur d'onde particulière, même si elle est irradiée avec des UV de courte longueur d'onde. La présente invention concerne une plaque de verre pour irradiation par des UV, qui contient, en % en masse, 60 à 75 % de SiO2, 2 à 25 % d'Al2O3, 10 à 20 % de Na2O, 0 à 7 % de K2O, 0,5 à 10 % de MgO, 0 à 15 % de CaO et 0,035 à 0,12 % de Fe2O3, et qui présente un rapport redox inférieur à 0,550 et un rapport CaO/MgO (rapport en masse) de 1,5 ou moins.
PCT/JP2016/074810 2015-08-31 2016-08-25 Plaque de verre présentant une résistance aux uv WO2017038621A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11407675B2 (en) 2016-07-28 2022-08-09 Corning Incorporated Glasses having resistance to photo-darkening

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000290038A (ja) * 1999-02-01 2000-10-17 Nippon Electric Glass Co Ltd 蛍光ランプ用ガラス、蛍光ランプ用ガラス管、及び蛍光ランプ
WO2008099687A1 (fr) * 2007-02-16 2008-08-21 Nippon Electric Glass Co., Ltd. Substrat de verre pour batterie solaire
JP2010208906A (ja) * 2009-03-11 2010-09-24 Asahi Glass Co Ltd 光デバイス用基板ガラス
WO2012057232A1 (fr) * 2010-10-27 2012-05-03 旭硝子株式会社 Plaque de verre, et procédé de fabrication de celle-ci
WO2012128180A1 (fr) * 2011-03-18 2012-09-27 旭硝子株式会社 Verre chimiquement renforcé pour dispositif d'affichage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000290038A (ja) * 1999-02-01 2000-10-17 Nippon Electric Glass Co Ltd 蛍光ランプ用ガラス、蛍光ランプ用ガラス管、及び蛍光ランプ
WO2008099687A1 (fr) * 2007-02-16 2008-08-21 Nippon Electric Glass Co., Ltd. Substrat de verre pour batterie solaire
JP2010208906A (ja) * 2009-03-11 2010-09-24 Asahi Glass Co Ltd 光デバイス用基板ガラス
WO2012057232A1 (fr) * 2010-10-27 2012-05-03 旭硝子株式会社 Plaque de verre, et procédé de fabrication de celle-ci
WO2012128180A1 (fr) * 2011-03-18 2012-09-27 旭硝子株式会社 Verre chimiquement renforcé pour dispositif d'affichage

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11407675B2 (en) 2016-07-28 2022-08-09 Corning Incorporated Glasses having resistance to photo-darkening

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