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WO2017082311A1 - Verre pour trempe thermique par jets d'air, et verre trempé thermiquement par jets d'air - Google Patents

Verre pour trempe thermique par jets d'air, et verre trempé thermiquement par jets d'air Download PDF

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Publication number
WO2017082311A1
WO2017082311A1 PCT/JP2016/083273 JP2016083273W WO2017082311A1 WO 2017082311 A1 WO2017082311 A1 WO 2017082311A1 JP 2016083273 W JP2016083273 W JP 2016083273W WO 2017082311 A1 WO2017082311 A1 WO 2017082311A1
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Prior art keywords
glass
air
less
thermal expansion
content
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Ceased
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English (en)
Japanese (ja)
Inventor
博之 土屋
枝里子 前田
研輔 永井
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AGC Inc
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Asahi Glass Co Ltd
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Priority claimed from JP2016050648A external-priority patent/JP2019001662A/ja
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2017082311A1 publication Critical patent/WO2017082311A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • C03B27/04—Tempering or quenching glass products using gas
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/85—Protective back sheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a glass for air-cooling strengthening that can apply a sufficient residual stress by air-cooling strengthening even when it is a thin glass having a thickness of 2.5 mm or less.
  • the present invention also relates to an air-cooled tempered glass obtained by tempering the air-cooling tempered glass of the present invention.
  • Tempered glass has improved the disadvantage of being easily broken, which is a general glass problem, and is used in transportation equipment, construction, and the like.
  • transportation equipment include passenger cars, trucks, buses, railroads, ships, airplanes, and the like, which are used for windows, headlights, taillights, and the like.
  • a building, a building, a house, etc. are mentioned, It is used for a door, a partition, etc.
  • furniture such as bookshelves and showcases, electrical appliances such as cooking utensils, and office supplies.
  • Tempered glass is manufactured by a method called thermal strengthening, for example.
  • Thermal strengthening uses thermal contraction of glass during cooling, and cools the glass after heating it to a temperature near the softening point or yield point. At this time, since the temperature drop on the surface is faster than the temperature drop on the inside, a temperature difference occurs in the thickness direction, and tensile stress and compressive stress are generated on the surface. As a result, a compressive stress is generated on the surface and a tensile stress is generated inside and remains. Since the compressive stress remains on the surface, the strength is improved and the progress of the scratches is suppressed, and the scratch resistance is improved.
  • Heat strengthening is typically air-cooled strengthening, in which a plate-like glass is manufactured by the float method, etc., the cut glass plate is heated to a temperature near the softening point or the yield point, and then cooled rapidly by spraying a cooling medium on the surface. Is something.
  • the weight reduction of the tempered glass can be achieved by reducing the thickness of the tempered glass.
  • the thickness is required to be 2.5 mm or less.
  • heat strengthening utilizes the temperature difference between the surface and the interior during cooling, if the thickness is reduced, the temperature difference between the surface and the interior cannot be increased, making full-scale strengthening difficult.
  • the glass substrate occupies most of the module weight, so that the glass substrate is made thin and lightweight.
  • the merit to make is very big. Therefore, glass substrates made of chemically strengthened glass are used as the light receiving face plate and the back face plate. This is because, if the glass is chemically strengthened, sufficient residual stress can be applied even if the thickness is 2.5 mm or less.
  • chemically tempered glass is more expensive than air-cooled tempered glass, the solar cell module described in Patent Document 2 using chemically tempered glass as the light-receiving face plate and the back plate becomes expensive.
  • the present invention has been made in view of the above problems, and even when a thin glass having a thickness of 2.5 mm or less is used, sufficient residual stress can be applied by air cooling strengthening.
  • An object is to provide glass and air-cooled tempered glass obtained by tempering air-cooled tempered glass.
  • the present invention has an Fe 3+ content of 0.8 mass% or more and less than 2.2 mass% in terms of Fe 2 O 3 , and an Fe 2+ content in terms of Fe 2 O 3. 0.45% by mass or less, the value of Fe-Redox is 20% or less, and the average thermal expansion coefficient ⁇ 50 to 350 at 50 to 350 ° C. is 75 ⁇ 10 ⁇ 7 / ° C. or more and 90 ⁇ 10 ⁇ 7. / ° C. or less, the glass transition point is 500 ° C. or more and 600 ° C. or less, and the maximum value ⁇ max of the thermal expansion coefficient between the glass transition point and the yield point is 410 ⁇ 10 ⁇ 7 / ° C. or more.
  • a glass for air-cooling strengthening is provided.
  • the present invention also provides an air-cooled tempered glass obtained by tempering the air-cooling tempered glass of the present invention.
  • the glass for air cooling strengthening of the present invention is a thin glass having a thickness of 2.5 mm or less, sufficient residual stress can be applied by air cooling strengthening.
  • FIG. 1 is a schematic plan view of a portion provided with a cooling nozzle of the air-cooling strengthening equipment used in the examples.
  • the glass for air-cooling strengthening of the present invention has a glass transition point of 500 ° C. or higher.
  • a plate-like glass is manufactured by a float method or the like, and after the cut glass plate is heated to a temperature near the softening point or the yield point, the surface is rapidly cooled by spraying a cooling medium. By doing so, residual stress is imparted to the glass.
  • the glass transition point is preferably 530 ° C. or higher, and more preferably 540 ° C. or higher.
  • the upper limit of the temperature at the time of a heating process is glass transition point +200 degreeC. If the upper limit of the temperature during the heating step is higher than the glass transition point + 200 ° C., the glass tends to undergo viscous flow deformation at a high temperature, and the optical quality of the final tempered glass may be deteriorated.
  • the glass transition point is 600 ° C. or lower, preferably 590 ° C. or lower, more preferably 580 ° C. or lower.
  • the maximum value ⁇ max of the thermal expansion coefficient between the glass transition point and the yield point (hereinafter referred to as “high temperature thermal expansion coefficient ⁇ max ” in the present specification) is 410. ⁇ 10 -7 / ° C or more.
  • the high-temperature thermal expansion coefficient ⁇ max is less than 410 ⁇ 10 ⁇ 7 / ° C.
  • air cooling strengthening is performed by quenching from a temperature about 100 ° C. higher than the glass transition point.
  • ⁇ max By setting the high-temperature thermal expansion coefficient ⁇ max to 410 ⁇ 10 ⁇ 7 / ° C. or more, even when a thin glass having a thickness of 2.5 mm or less is used, a general wind-cooling strengthening device is used from such a temperature. It can be used to effectively apply residual stress.
  • the high temperature thermal expansion coefficient ⁇ max is a maximum value between the glass transition point and the yield point in the thermal expansion coefficient curve of the glass to be processed measured by a thermal dilatometer as described later.
  • the high temperature coefficient of thermal expansion ⁇ max is preferably as large as possible from the viewpoint of imparting residual stress, but normally 600 ⁇ 10 ⁇ 7 / ° C. is sufficient. Further, when the high temperature thermal expansion coefficient ⁇ max is increased, the glass is cracked due to temporary strain generated in the initial stage of cooling, which may deteriorate the yield.
  • the high temperature thermal expansion coefficient ⁇ max is 410 ⁇ 10 ⁇ 7 / It is preferably at least 600 ⁇ 10 ⁇ 7 / ° C., more preferably at least 412 ⁇ 10 ⁇ 7 / ° C. and at most 450 ⁇ 10 ⁇ 7 / ° C., and at least 415 ⁇ 10 ⁇ 7 / ° C. and at most 430 ⁇ 10 ⁇ 7 / ° C. Further preferred.
  • the yield point of the air-cooling strengthening glass of the present invention is not necessarily limited, it is preferable to exceed 600 ° C.
  • the yield point is 600 ° C. or lower, when the cut glass sheet is heated to a softening point or a temperature near the yield point, the heating temperature, that is, the strengthening start temperature is lowered, and there is a possibility that the residual stress cannot be effectively applied.
  • the yield point is preferably 750 ° C. or lower.
  • the yield point exceeds 750 ° C. it is necessary to heat to a high temperature, and the peripheral members for holding the glass are exposed to a high temperature. It is necessary to use an expensive member having excellent heat resistance.
  • the yield point of the glass for air-cooling strengthening of this invention 700 degrees C or less is more preferable.
  • the average thermal expansion coefficient ⁇ 50 to 350 at 50 to 350 ° C. is large. If it is too large, expansion mismatch with other current members may become a problem, or it may become weak against thermal shock. Therefore, the average coefficient of thermal expansion ⁇ 50 to 350 is 75 ⁇ 10 ⁇ 7 / ° C. or higher, more preferably 77 ⁇ 10 ⁇ 7 / ° C. or higher, and further preferably 79 ⁇ 10 ⁇ 7 / ° C. or higher. On the other hand, the average thermal expansion coefficient ⁇ 50 to 350 is 110 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 100 ⁇ 10 ⁇ 7 / ° C. or less, and further preferably 95 ⁇ 10 ⁇ 7 / ° C. or less.
  • the difference in thermal expansion coefficient ( ⁇ ) is more preferably 360 ⁇ 10 ⁇ 7 / ° C. or more, and further preferably 370 ⁇ 10 ⁇ 7 / ° C. or more.
  • the difference in thermal expansion coefficient ( ⁇ ) is preferably as large as possible, but is usually preferably 500 ⁇ 10 ⁇ 7 / ° C. or less, and more preferably 350 ⁇ 10 ⁇ 7 / ° C. or less.
  • the glass transition point, the yield point, and the thermal expansion coefficient ( ⁇ max , ⁇ 50 to 350 ) are measured by the following methods. That is, a cylindrical sample having a diameter of 5 mm and a length of 20 mm was prepared, and the thermal expansion was measured using a thermal dilatometer at a heating rate of 5 ° C./min under a load condition of 10 g, and the glass transition point, yield point, The coefficient of thermal expansion ( ⁇ max , ⁇ 50-350 ) is obtained.
  • the air-cooled tempered glass uses the temperature difference between the surface and the inside caused by carrying out the heating step and the cooling step described above, if the thickness is reduced, the temperature difference between the surface and the inside cannot be increased. It was difficult to apply sufficient residual stress.
  • the present inventors have found that the content of trivalent iron (Fe 3+ ), the content of divalent iron (Fe 2+ ), and Fe-Redox It has been found that ⁇ max can be increased when the value of satisfies the specific condition, and as a result, the residual stress of the air-cooled tempered glass is improved.
  • the glass for air cooling strengthening of the present invention is a thin glass having a thickness of 2.5 mm or less because the Fe 3+ content is 0.8% by mass or more and less than 2.2% by mass in terms of Fe 2 O 3. Even in this case, the residual stress can be effectively applied using a general air cooling strengthening device.
  • the Fe 3+ content is less than 0.8% by mass in terms of Fe 2 O 3
  • the residual stress is reduced using a general air cooling strengthening device. There is a possibility that it cannot be granted effectively.
  • the Fe 3+ content is 2.2% by mass or more in terms of Fe 2 O 3 , the yellowish color becomes strong and the appearance deteriorates, which is not preferable.
  • the Fe 3+ content is preferably 0.9% by mass to 2.1% by mass in terms of Fe 2 O 3 , more preferably 1.0% by mass to 2%. 0.0 mass% or less.
  • the glass for air-cooling strengthening of the present invention has an Fe 2+ content of 0.45% by mass or less in terms of Fe 2 O 3 .
  • Fe 2+ content is higher than 0.45% by mass in terms of Fe 2 O 3 , the temperature of the melting kiln becomes low and the solubility of the glass decreases.
  • it is preferable that Fe 2+ content is not more than 0.43 mass% in terms of Fe 2 O 3, more preferably not more than 0.41 mass%.
  • the glass for air-cooling strengthening of the present invention preferably has an Fe 2+ content of 0.1% by mass or more in terms of Fe 2 O 3 .
  • Fe 2+ content is 0.1% by mass or more in terms of Fe 2 O 3 , the melting furnace temperature does not rise too much and the solubility can be maintained. Among them, it is preferable that Fe 2+ content is not less than 0.2 mass% in terms of Fe 2 O 3, more preferably not less than 0.3 mass%.
  • the air-cooled tempered glass of the present invention has an Fe-Redox value of 20% or less.
  • the Fe-Redox a ratio of Fe 2+ content in terms of Fe 2 O 3 to the total iron content in terms of Fe 2 O 3.
  • the Fe-Redox value is preferably 16% or less, more preferably 13% or less, and even more preferably 10% or less.
  • the value of Fe-Redox is preferably 5% or more. If the value of Fe-redox is 5% or more, defoaming is easy and high-quality glass without bubbles can be produced.
  • the Fe-Redox value is more preferably 7% or more, further preferably 10% or more, and particularly preferably 13% or more.
  • the glass for air-cooling strengthening of the present invention preferably contains the following components in terms of mass% based on oxide.
  • the mass% based on oxide is simply expressed as%. SiO 2 66-75%, Al 2 O 3 0-15%, B 2 O 3 0-20%, MgO + CaO + SrO + BaO 1-30%, Li 2 O + Na 2 O + K 2 O 1-25%
  • the basic component is the same as the component of soda-lime glass generally used for manufacture of tempered glass, productivity becomes favorable. Further, according to such a composition, a glass transition point of 500 ° C. or higher and 600 ° C. or lower and a high temperature thermal expansion coefficient ⁇ max of 410 ⁇ 10 ⁇ 7 / ° C. or higher can be obtained.
  • ⁇ max the range of the composition of each component will be described.
  • the content of SiO 2 is preferably 66% or more and 75% or less. If it is less than 66%, the glass density increases, the thermal expansion coefficient increases, and the scratch resistance deteriorates.
  • the content of SiO 2 is preferably 67% or more, more preferably 68% or more. On the other hand, when the content of SiO 2 exceeds 75%, the viscosity becomes high and the glass is hardly dissolved.
  • the content of SiO 2 is preferably 73% or less.
  • Al 2 O 3 can be contained as required, and its content is preferably 15% or less. If the Al 2 O 3 content exceeds 15%, the coefficient of thermal expansion above the glass transition point is difficult to increase, and it may be difficult to increase the residual stress.
  • the content of Al 2 O 3 is preferably 10% or less, more preferably 5% or less.
  • B 2 O 3 can be contained as necessary, and its content is preferably 20% or less. If the content of B 2 O 3 exceeds 20%, the coefficient of thermal expansion above the glass transition point is difficult to increase, and it may be difficult to increase the residual stress.
  • the content of B 2 O 3 is preferably 15% or less, more preferably 10% or less.
  • the total content of alkaline earth metal oxides is preferably 1% or more.
  • MgO + CaO + SrO + BaO is less than 1%, a large amount of alkali metal oxides, that is, Li 2 O, Na 2 O and K 2 O are added in order to maintain the glass at a high temperature and an appropriate coefficient of thermal expansion. As a result, the temperature difference between the strain point and the yield point is reduced, and the residual stress may be reduced.
  • MgO + CaO + SrO + BaO is preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more.
  • MgO + CaO + SrO + BaO is preferably 30% or less. When it exceeds 30%, the devitrification tendency of the glass becomes strong, and the productivity deteriorates. MgO + CaO + SrO + BaO is preferably 25% or less.
  • the content of MgO is preferably 0.1% or more. MgO is necessary for maintaining the thermal expansion coefficient of the glass moderately and can improve the scratch resistance.
  • the content of MgO is preferably 2% or more, more preferably 3% or more.
  • the content of MgO is preferably 25% or less. When the content of MgO exceeds 25%, the tendency to devitrify the glass becomes strong and the productivity deteriorates.
  • the content of MgO is preferably 23% or less, more preferably 21% or less, and still more preferably 20% or less.
  • the content of CaO is preferably 0.1% or more. CaO is necessary to maintain the thermal expansion coefficient of the glass moderately.
  • the content of CaO is preferably 2% or more, more preferably 3% or more.
  • the CaO content is preferably 15% or less. When the content of CaO exceeds 15%, the tendency to devitrify the glass becomes strong and the productivity deteriorates.
  • the content of CaO is preferably 14% or less, more preferably 13% or less.
  • SrO can be contained as required, and its content is preferably 10% or less. By containing SrO, the solubility at high temperatures and the thermal expansion coefficient of the glass can be adjusted. If the SrO content exceeds 10%, the density of the glass increases and the weight of the glass increases. When SrO is contained, it is preferably 1% or more, more preferably 1.5% or more. The SrO content is more preferably 7% or less, still more preferably 5% or less.
  • BaO can be contained as required, and the content is preferably 10% or less.
  • the solubility at high temperatures and the thermal expansion coefficient of the glass can be adjusted.
  • the BaO content is preferably 7% or less, more preferably 5% or less, and still more preferably 3% or less.
  • the total content of alkali metal oxides is preferably 1% or more. If Li 2 O + Na 2 O + K 2 O is less than 1%, the alkaline earth metal oxides, ie MgO, CaO, SrO, and It is necessary to add a large amount of BaO. As a result, the tendency to devitrify the glass is increased and the productivity is deteriorated.
  • Li 2 O + Na 2 O + K 2 O is preferably 3% or more, more preferably 5% or more, still more preferably 8% or more, and particularly preferably 10% or more.
  • Li 2 O + Na 2 O + K 2 O is preferably 25% or less. If it exceeds 25%, the temperature difference between the strain point and the yield point becomes small, and the residual stress may be reduced.
  • Li 2 O + Na 2 O + K 2 O is preferably 25% or less, and more preferably 20% or less.
  • the Na 2 O content is preferably 8% or more.
  • Na 2 O is a component that increases the thermal expansion coefficient even when the density of the glass is low, so it is included in the glass composition for the purpose of adjusting the thermal expansion coefficient.
  • the content of Na 2 O is preferably 9% or more, and more preferably 10% or more.
  • the content of Na 2 O is preferably 20% or less. When the content of Na 2 O exceeds 20%, the temperature difference between the strain point and the yield point becomes small, so that the strengthening stress becomes small and the thermal expansion coefficient becomes too large.
  • the content of Na 2 O is preferably 17% or less, more preferably 15% or less.
  • K 2 O is, can be contained if necessary, its content is preferably 0.1% or more. When the content of K 2 O is 0.1% or more, it is possible to maintain the solubility of glass at a high temperature and an appropriate thermal expansion coefficient.
  • the content of K 2 O is more preferably 0.5% or more, particularly preferably 1% or more.
  • the content of K 2 O is preferably 4% or less. When the content of K 2 O exceeds 4%, the density of the glass increases and the weight of the glass increases.
  • the content of K 2 O is preferably 3.5% or less, more preferably 3% or less.
  • the air-cooling tempered glass of the present invention is preferably substantially composed of the above components, but contains other components up to 10% in total as necessary and within the limits not departing from the spirit of the present invention. Also good. Examples of other components include ZrO 2 , Y 2 O 3 , CeO 2 , MnO, and CoO. Moreover, although PbO etc. can also be contained, it is preferable not to contain these substantially. Note that “substantially not contained” indicates less than 0.01%.
  • SO 3 , chloride, fluoride, halogen, SnO 2 , Sb 2 O 3 , As 2 O 3 and the like may be appropriately contained as a fining agent when the glass is melted.
  • Ni, Cr, V, Se, Au, Ag, Cd and the like may be contained for adjusting the color. It is preferable that the glass to be treated contains substantially no As, Sb, or Pb. Since these are toxic, it is preferable that they are not contained in the glass in order to prevent environmental impact. Note that “substantially not contained” indicates less than 0.01%.
  • the glass for air cooling strengthening of the present invention is a thin glass having a thickness of 2.5 mm or less, residual stress can be effectively applied using a general known air cooling strengthening apparatus or method. Can be reduced in weight.
  • a known air-cooling strengthening apparatus and method used in the present invention for example, a glass plate is arranged so as to be sandwiched between upper and lower air-cooling-strengthening blower members at a predetermined interval, and rapidly cooled by cooling air. An air cooling strengthening apparatus is mentioned.
  • the air-cooling strengthened glass of the present invention preferably has a thickness of 2.4 mm or less, more preferably 2.3 mm or less, and a thickness of 2.0 mm or less, 1.5 mm or less, 1 More preferably, it is 3 mm or less.
  • the plate thickness is preferably 0.5 mm or more, and more preferably 0.7 mm or more.
  • the glass for air cooling strengthening according to the present invention is manufactured by any one of glass plate forming methods such as a float method, a fusion method, a download method, and a roll-out method.
  • the float method is preferable because it is easy to produce a large-area glass plate and the thickness deviation can be easily reduced.
  • the glass for air-cooling strengthening of the present invention is a thin glass having a thickness of 2.5 mm or less, it can effectively impart residual stress.
  • the surface compressive stress value of the glass after air cooling strengthening is preferably 110 MPa or more, more preferably 122 MPa or more, and further preferably 130 MPa or more.
  • the surface compressive stress value of the glass after air cooling strengthening is preferably 70 MPa or more, more preferably 78 MPa or more, and further preferably 85 MPa or more.
  • the surface compressive stress value of the glass after air cooling strengthening is preferably 60 MPa or more, more preferably 65 MPa or more, and further preferably 70 MPa or more. .
  • the air-cooled tempered glass of the present invention is obtained by tempering the air-cooled tempered glass of the present invention.
  • the thickness of the air-cooled tempered glass of the present invention varies depending on the application, it preferably has a thickness of 2.5 mm or less due to the characteristics of the air-cooled tempered glass of the present invention described above.
  • the surface compressive stress value of the air-cooled tempered glass of the present invention varies depending on the thickness of the air-cooled tempered glass, but when the thickness is 2.5 mm or less, the surface compressive stress value is preferably 110 MPa or more, more preferably. Is 122 MPa or more, more preferably 130 MPa or more.
  • the surface compressive stress value is preferably 70 MPa or more, more preferably 78 MPa or more, and further preferably 85 MPa or more.
  • the surface compressive stress value is preferably 60 MPa or more, more preferably 65 MPa or more, and further preferably 70 MPa or more.
  • the air-cooled tempered glass When used as a back plate of a solar cell module, if the air-cooled tempered glass is highly transparent, the wiring and the like are visually observed and the design is deteriorated.
  • the air-cooled tempered glass preferably has a visible light transmittance (D65 light source) Tv_D65 defined by ISO-9050 (2003) of 82% or less, more preferably 80% or less. Preferably, it is 77% or less.
  • the surface of the obtained glass sample was polished into a mirror surface, and Fe-Redox was calculated from the spectrum curve measured with a spectrophotometer using the following equation (1).
  • Fe-Redox (%) ( ⁇ log e (T 1000 nm /91.4)/(Fe 2 O 3 amount ⁇ t ⁇ 20.79)) ⁇ 100 (1).
  • T 1000nm is spectrophotometer (Perkin Elmer Corp., Lambda950) is the transmissivity of the wavelength 1000nm as measured by (%), t is an glass sample thickness (cm)
  • the Fe-Redox is a method of finding the spectral curve of the glass sample was measured by spectrophotometer, the value, Fe of terms of Fe 2 O 3 to the total iron content calculated as Fe 2 O 3 in the same glass It can be regarded as being equal to the proportion of 2+ content.
  • a cylindrical sample having a diameter of 5 mm and a length of 20 mm was prepared from a glass sample, and 5 using a thermal dilatometer (manufactured by Bruker AXS, TMA4000SA). The thermal expansion was measured at a heating rate of 10 ° C./min and a load of 10 g to determine the glass transition point (Tg).
  • a glass sample was heated at a rate of 5 ° C./minute using a thermal dilatometer (manufactured by Bruker AXS, TMA4000SA) in the same manner as the measurement of the glass transition point.
  • the thermal expansion was measured, and the average thermal expansion coefficient ⁇ 50 to 350 at 50 to 350 ° C. and the high temperature thermal expansion coefficient ⁇ max were determined.
  • the visible light transmittance (Tv_D65) was measured using a spectrophotometer (Perkin Elmer, Lambda 950).
  • FIG. 1 is a schematic plan view of a portion provided with a cooling nozzle of this air cooling strengthening facility.
  • the diagram on the left side shows the shape of the end face of the portion where the cooling nozzle is provided.
  • the plurality of cooling nozzles 20, 30, and 40 are arranged in steps.
  • the nozzle 20 is provided in a direction perpendicular to the surface to be processed of the glass plate to be processed to be air-cooled.
  • the nozzles 20 have a diameter of 3.1 mm, and the pitch between the nozzles 20 is 24 mm.
  • the nozzles 30 and 40 are provided in an oblique direction with respect to the surface to be processed of the glass plate to be processed.
  • the nozzles 30 and 40 each have a diameter of 3.9 mm, and the pitch between the nozzles 30 and the pitch between the nozzles 40 are both 24 mm. With respect to the nozzle 30, the pitch of the nearest nozzle 20 and the pitch of the nearest nozzle 40 are both 8 mm.
  • the distance between the nozzle 20 and the treated surface of the treated glass plate is 10 mm.
  • the temperature of the air supplied as a cooling medium from the nozzles 20, 30, 40 is 60 ° C.
  • the wind pressure (blown air pressure) is 18-19 kPa
  • the glass plate to be processed is heated from 630 ° C. to 635 ° C.
  • the treatment surface was cooled by blowing air as a cooling medium.
  • the surface compressive stress value of the air-cooled tempered glass thus prepared was measured with a glass surface stress meter (FSM-7000H, manufactured by Orihara Seisakusho). A value obtained by dividing the surface compressive stress value of each sample by the surface compressive stress value of Comparative Example 5 was defined as a relative surface compressive stress value.
  • Fe 3+ content is 0.8 mass% or more and less than 2.2 mass% in terms of Fe 2 O 3
  • Fe 2+ content is 0.45 mass% or less in terms of Fe 2 O 3
  • Fe-Redox The glass of Examples 1 to 5 having a value of 20% or less has a high-temperature thermal expansion coefficient ⁇ max of 410 ⁇ 10 ⁇ 7 / ° C. or higher, and the relative surface compressive stress value of the glass after air cooling strengthening is 1.1 or higher. Met.
  • the air-cooled tempered glass of the present invention can be preferably used for various applications in which tempered glass is used. Specifically, it can be preferably used for automobile use and construction use. Moreover, it can use preferably as a light-receiving surface plate or back plate of a solar cell module.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention fournit un verre pour trempe thermique par jets d'air qui permet d'appliquer une tension résiduelle suffisante au moyen d'une trempe thermique par jets d'air, dans le cas d'un verre fin dont l'épaisseur est inférieure ou égale à 2,5mm. Plus précisément, l'invention concerne un verre pour trempe thermique par jets d'air dans lequel la teneur en Ｆｅ3+ est supérieure ou égale à 0,8% en masse et inférieure à 2,2% en masse en termes de Ｆｅ2Ｏ3, la teneur en Ｆｅ2+ est inférieure ou égale à 0,45% en masse en termes de Ｆｅ2Ｏ3, la valeur Fe-Redox est inférieure ou égale à 20%, le coefficient de dilatation thermique moyen α50～350 entre 50 et 350°C est supérieur ou égal à ７５×１０-7／℃ et inférieur ou égal à ９０×１０-7／℃, le point de transition vitreuse est supérieur ou égal à 500°C et inférieur ou égal à 600°C, et la valeur maximale αmax du coefficient de dilatation thermique entre le point de transition vitreuse et la limite de résistance, est supérieure ou égale à ４１０×１０-7／℃.
PCT/JP2016/083273 2015-11-10 2016-11-09 Verre pour trempe thermique par jets d'air, et verre trempé thermiquement par jets d'air Ceased WO2017082311A1 (fr)

Applications Claiming Priority (4)

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JP2015-220528 2015-11-10
JP2015220528 2015-11-10
JP2016-050648 2016-03-15
JP2016050648A JP2019001662A (ja) 2015-11-10 2016-03-15 風冷強化用ガラス、および、風冷強化ガラス

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019172568A (ja) * 2018-03-27 2019-10-10 株式会社カネカ 熱強化ガラス基板の製造方法および太陽電池モジュール
WO2021064927A1 (fr) * 2019-10-02 2021-04-08 株式会社カネカ Procédé de production de substrat de verre thermiquement trempé et module de cellule solaire

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000203877A (ja) * 1999-01-12 2000-07-25 Nippon Sheet Glass Co Ltd 紫外線赤外線吸収低透過ガラス
JP2004091308A (ja) * 2002-07-11 2004-03-25 Nippon Electric Glass Co Ltd 照明用ガラス
WO2013042739A1 (fr) * 2011-09-22 2013-03-28 旭硝子株式会社 Plaque de verre pour trempe
JP2013089938A (ja) * 2011-10-24 2013-05-13 Central Glass Co Ltd 太陽電池用カバーガラス及びその製造方法
WO2014030682A1 (fr) * 2012-08-24 2014-02-27 旭硝子株式会社 Verre trempé
WO2015122342A1 (fr) * 2014-02-14 2015-08-20 旭硝子株式会社 Verre armé et verre à traiter pour verre armé

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000203877A (ja) * 1999-01-12 2000-07-25 Nippon Sheet Glass Co Ltd 紫外線赤外線吸収低透過ガラス
JP2004091308A (ja) * 2002-07-11 2004-03-25 Nippon Electric Glass Co Ltd 照明用ガラス
WO2013042739A1 (fr) * 2011-09-22 2013-03-28 旭硝子株式会社 Plaque de verre pour trempe
JP2013089938A (ja) * 2011-10-24 2013-05-13 Central Glass Co Ltd 太陽電池用カバーガラス及びその製造方法
WO2014030682A1 (fr) * 2012-08-24 2014-02-27 旭硝子株式会社 Verre trempé
WO2015122342A1 (fr) * 2014-02-14 2015-08-20 旭硝子株式会社 Verre armé et verre à traiter pour verre armé

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019172568A (ja) * 2018-03-27 2019-10-10 株式会社カネカ 熱強化ガラス基板の製造方法および太陽電池モジュール
JP7288780B2 (ja) 2018-03-27 2023-06-08 株式会社カネカ 熱強化ガラス基板の製造方法
WO2021064927A1 (fr) * 2019-10-02 2021-04-08 株式会社カネカ Procédé de production de substrat de verre thermiquement trempé et module de cellule solaire

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