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WO2018030095A1 - Verre feuilleté pour véhicules - Google Patents

Verre feuilleté pour véhicules Download PDF

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Publication number
WO2018030095A1
WO2018030095A1 PCT/JP2017/026154 JP2017026154W WO2018030095A1 WO 2018030095 A1 WO2018030095 A1 WO 2018030095A1 JP 2017026154 W JP2017026154 W JP 2017026154W WO 2018030095 A1 WO2018030095 A1 WO 2018030095A1
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WO
WIPO (PCT)
Prior art keywords
glass plate
tempered glass
less
glass
laminated glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/026154
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English (en)
Japanese (ja)
Inventor
結城　健
慎護 中根
浩佑 川本
田中　敦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to CN201780044378.3A priority Critical patent/CN109476538A/zh
Priority to JP2018532901A priority patent/JPWO2018030095A1/ja
Publication of WO2018030095A1 publication Critical patent/WO2018030095A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B61—RAILWAYS
    • B61D—BODY DETAILS OR KINDS OF RAILWAY VEHICLES
    • B61D25/00—Window arrangements peculiar to rail vehicles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

Definitions

  • the present invention relates to a laminated glass for a vehicle, and more particularly to a laminated glass for a vehicle suitable for a windshield of an automobile.
  • a laminated glass in which two glass plates are integrated through an organic resin intermediate layer is used for a windshield of an automobile.
  • Laminated glass can ensure good visibility even if part of the glass plate breaks, and even if the glass plate breaks in the event of an accident, the stretch of the organic resin intermediate layer allows the passenger to go outside the vehicle. There is an advantage that it can be prevented from jumping out.
  • the ratio of the thickness of the inner glass plate to the thickness of the outer glass plate is 0.6 or more and 0.9 or less in order to prevent the organic resin intermediate layer from being broken when the airbag is deployed.
  • a laminated glass is disclosed.
  • the difference of the thickness of an outer side glass plate and an inner side glass plate shall be 1.0 mm or more, and the plate
  • the physical tempered glass when used for the windshield of an automobile, the physical tempered glass may be broken into particles due to point impacts such as pebbles, and the human body may be damaged by the fine fragments.
  • the present invention has been made in view of the above circumstances, and its technical problem is that it is possible to achieve both high strength and thinning, and can effectively avoid the risk of human injury at the time of breakage.
  • the idea is to create a laminated glass.
  • the laminated glass for vehicles of the present invention is a laminated glass for vehicles in which an outer tempered glass plate and an inner tempered glass plate are integrated by an organic resin intermediate layer, and the thickness of the outer tempered glass plate is 2.0 mm or less.
  • the outer tempered glass plate has a surface compressive stress layer by ion exchange, the compressive stress value of the surface compressive stress layer of the outer tempered glass plate is 350 MPa or more, and the stress depth is 15 to 100 ⁇ m.
  • the “compressive stress value” and the “stress depth” are calculated by observing the number of interference fringes and their intervals using a surface stress meter (for example, FSM-6000 manufactured by Orihara Seisakusho Co., Ltd.). is there.
  • the thickness of the outer tempered glass is regulated to 2.0 mm or less, the compressive stress value of the compressive stress layer is 350 MPa or more, and the stress depth is regulated to 15 to 100 ⁇ m. If it does in this way, it will become difficult to damage an outer side tempered glass board by the point impact of fine flying objects, such as gravel.
  • two tempered glass plates are integrated by an organic resin intermediate layer. In this way, it is possible to prevent the passenger from jumping out of the vehicle when an accident occurs.
  • FIG. 1 is a schematic view for explaining a laminated glass for a vehicle according to the present invention.
  • the laminated glass 10 for a vehicle includes an inner tempered glass plate 11, an outer tempered glass plate 12 having a thickness of 2.0 mm or less, an organic resin intermediate layer 13 sandwiched between the inner tempered glass plate 11 and the outer tempered glass plate 12, and It is equipped with.
  • the outer tempered glass plate 12 has a surface compressive stress layer by ion exchange, the compressive stress value is 300 MPa or more, and the stress depth is 15 to 60 ⁇ m.
  • the laminated glass 10 for vehicles makes the outer side tempered glass board 12 side convex, and the whole board width direction curves in an arc shape, and the whole length direction curves in an arc shape.
  • the laminated glass for vehicles of the present invention preferably has a tensile stress value inside the outer tempered glass sheet of 70 MPa or less.
  • the vehicle for laminated glass of the present invention the outer tempered glass plate, as a glass composition, in mass%, SiO 2 40 ⁇ 80% , Al 2 O 3 3 ⁇ 30%, B 2 O 3 0 ⁇ 10%, It is preferable to contain 5 to 20% of Na 2 O and 0 to 5% of K 2 O.
  • the compressive stress value of the surface compressive stress layer of the inner tempered glass plate is preferably 350 MPa or more and the stress depth is preferably 15 to 100 ⁇ m. In this way, even when a point impact is applied to the inner tempered glass plate from the inside of the vehicle, the inner tempered glass plate is not easily damaged.
  • the tensile strength value of the inner tempered glass plate is 70 MPa or less.
  • the inner tempered glass plate has a glass composition of 40% by mass, SiO 2 40-80%, Al 2 O 3 3-30%, B 2 O 3 0-10%, It is preferable to contain 5 to 20% of Na 2 O and 0 to 5% of K 2 O.
  • the Young's modulus of the outer tempered glass plate and / or the inner tempered glass plate is 76 GPa or less. Therefore, since a tempered glass board becomes easy to bend, the impact absorption effect of laminated glass can be heightened.
  • the laminated glass for vehicles of the present invention preferably has a crack occurrence rate of 80% or less before the tempering treatment of the outer tempered glass plate and / or the inner tempered glass plate.
  • the “crack rate” is a value measured as follows. First, in a constant temperature and humidity chamber maintained at a humidity of 30% and a temperature of 25 ° C., a Vickers indenter set to a load of 800 gf is driven into the glass surface (optical polishing surface) for 15 seconds, and 15 seconds later, it is generated from the four corners of the indentation. Count the number of cracks (maximum 4 per indentation).
  • the driving of the Vickers indenter can be performed by a fully automatic Vickers hardness tester (for example, FLEC-50VX manufactured by Huatetec).
  • a fully automatic Vickers hardness tester for example, FLEC-50VX manufactured by Huatetec.
  • annealing is performed for 1 hour or more in the temperature range of (Ps-350 ° C) to (Ps-150 ° C) before measurement, and the glass at room temperature and humidity is used. It is desirable to cancel the difference in moisture state on the surface. Ps indicates a strain point.
  • the organic resin layer is preferably composed of an ethylene vinyl acetate copolymer or polyvinyl butyral.
  • the laminated glass for vehicles of the present invention preferably has a curved surface shape that is three-dimensionally curved.
  • the laminated glass for vehicles of the present invention is preferably used for a windshield of an automobile.
  • the laminated glass for vehicles of the present invention is preferably used for a window glass of a railway vehicle. Since railroad vehicles have a higher traveling speed than automobiles, the point impact on the window glass tends to increase. Therefore, the laminated glass for vehicles of the present invention is advantageous for this application.
  • the laminated glass for vehicles of the present invention has an outer tempered glass plate and an inner tempered glass plate. These tempered glass plates have a compressive stress layer on the surface. As a method for forming a compressive stress layer on the surface, there are a physical strengthening treatment and a chemical strengthening treatment (ion exchange treatment), but the outer strengthened glass plate is subjected to a chemical strengthening treatment. On the other hand, the inner tempered glass plate may be subjected to any tempering treatment.
  • the chemical strengthening treatment is a method of introducing alkali ions having a large ion radius to the glass surface by ion exchange at a temperature below the strain point of the glass plate. If it is a chemical strengthening process, even when the plate
  • the physical strengthening treatment is a method of forming a compressive stress layer on the surface by heat-treating at a temperature near the softening point of the glass plate, and then rapidly cooling the glass after processing a curved surface at a temperature near the softening point of the glass plate. If it is a physical reinforcement
  • the thickness of the outer tempered glass plate is preferably 2.0 mm or less, 1.5 mm or less, 1.3 mm or less, particularly 1.0 mm or less, particularly 0.8 mm or less, preferably Is 0.3 mm or more, 0.4 mm or more, 0.5 mm or more, 0.6 mm or more, 0.7 mm or more, particularly 1.0 mm or more.
  • the plate thickness of the inner tempered glass plate is preferably 1.5 mm or less, 1.2 mm or less, 1.1 mm or less, 1.0 mm or less, particularly 0.8 mm or less, preferably 0.3 mm or more, 0.4 mm or more. 0.5 mm or more, 0.6 mm or more, particularly 0.7 mm or more.
  • the outer tempered glass plate is regulated to 1.0 to 1.5 mm and the inner tempered glass plate to be regulated to 0.3 to 1.1 mm, mechanical impact force is easily absorbed elastically. When applied to the windshield, it is less likely to be scratched.
  • the outer tempered glass plate has a surface compressive stress layer by ion exchange, and the compressive stress value of the compressive stress layer is preferably 350 MPa or more, 400 MPa or more, 500 MPa or more, 550 MPa or more, In particular, it is 600 MPa or more.
  • the greater the compressive stress value the higher the strength of the outer tempered glass plate.
  • the compressive stress value of the compressive stress layer is preferably 1000 MPa or less, 800 MPa or less, and particularly preferably 650 MPa or less.
  • the stress depth of the compressive stress layer of the outer tempered glass plate is preferably 15 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, particularly 50 ⁇ m or more.
  • the stress depth is preferably 100 ⁇ m or less, 90 ⁇ m or less, 80 ⁇ m or less, 75 ⁇ m or less, 70 ⁇ m or less, 65 ⁇ m or less, and particularly preferably 60 ⁇ m or less.
  • the tensile stress value inside the outer tempered glass plate is preferably 70 MPa or less, particularly 10 to 60 MPa. If the internal tensile stress value is too large, the outer tempered glass sheet may be self-destructed by point collision.
  • the internal tensile stress value is a value calculated from the following mathematical formula.
  • the inner tempered glass plate has a surface compressive stress layer
  • the compressive stress value of the compressive stress layer is preferably 350 MPa or more, 400 MPa or more, 500 MPa or more, 550 MPa or more, particularly 600 MPa or more. It is.
  • the greater the compressive stress value the higher the strength of the inner tempered glass sheet.
  • the compressive stress value of the compressive stress layer is preferably 1000 MPa or less, 800 MPa or less, and particularly preferably 650 MPa or less.
  • the stress depth of the compressive stress layer of the inner tempered glass plate is preferably 15 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, particularly 50 ⁇ m or more.
  • the stress depth is larger, even if the inner tempered glass plate is deeply scratched by point impact, the inner tempered glass plate is less likely to break and the variation in strength tends to be smaller.
  • the stress depth is too large, the internal tensile stress becomes extremely high, and the inner tempered glass plate may be self-destructed by point collision. Therefore, the stress depth is preferably 100 ⁇ m or less, 90 ⁇ m or less, 80 ⁇ m or less, 75 ⁇ m or less, 70 ⁇ m or less, 65 ⁇ m or less, and particularly preferably 60 ⁇ m or less.
  • the tensile stress value inside the inner tempered glass plate is preferably 70 MPa or less, particularly 10 to 50 MPa. If the internal tensile stress value is too large, the inner tempered glass sheet may be self-destructed by point collision.
  • the tempered glass plate (outer tempered glass plate and / or inner tempered glass plate) is preferably alkali aluminosilicate glass, alkali borosilicate glass, or soda lime glass, and particularly preferably alkali aluminosilicate glass. . Since the alkali aluminosilicate glass has high ion exchange performance, a desired compressive stress layer can be formed by chemical strengthening treatment in a short time. Moreover, since devitrification resistance is good, it can be easily formed into a plate shape.
  • the tempered glass plate (outer tempered glass plate and / or inner tempered glass plate) has a glass composition of mass%, SiO 2 40-80%, Al 2 O 3 3-30%, B 2 O 3 0-10%. Na 2 O 5 to 20% and K 2 O 0 to 5% are preferably contained.
  • the reason why the content range of each component is regulated as described above is shown below.
  • % display shall show the mass%.
  • SiO 2 is a component that forms a network of glass.
  • the content of SiO 2 is preferably 40 to 80%, 45 to 75%, 52 to 73%, 55 to 71%, 57 to 68%, particularly 58 to 67%. If the content of SiO 2 is too small, vitrification becomes difficult, and the thermal expansion coefficient becomes too high, so that the thermal shock resistance tends to decrease. On the other hand, when the content of SiO 2 is too large, the meltability and moldability tend to be lowered, and the thermal expansion coefficient becomes too low, making it difficult to match the thermal expansion coefficient of the organic resin intermediate layer.
  • Al 2 O 3 is a component that improves ion exchange performance, and is a component that increases the strain point and Young's modulus.
  • the lower limit range of Al 2 O 3 is preferably 3% or more, 8% or more, 12% or more, 16% or more, 16.5% or more, 17.1% or more, 17.5% or more, 18% or more. In particular, it is 18.5% or more.
  • the content of Al 2 O 3 is too large, devitrification crystal glass becomes easy to precipitate, hardly molded into a plate by an overflow down draw method or the like.
  • the upper limit range of Al 2 O 3 is preferably 30% or less, 28% or less, 26% or less, 24% or less, 23.5% or less, 22% or less, 21% or less, particularly 20.5% or less. is there.
  • B 2 O 3 is a component that lowers the liquidus temperature, crack generation rate, high temperature viscosity and density, and stabilizes the glass to make it difficult to precipitate crystals.
  • the lower limit range of B 2 O 3 is preferably 0% or more, 0.1% or more, 1% or more, 2% or more, particularly 3% or more.
  • the upper limit range of B 2 O 3 is preferably 10% or less, 6% or less, 5% or less, and particularly less than 4%.
  • Na 2 O is an ion exchange component, and is a component that lowers the high temperature viscosity and improves the meltability and moldability. Na 2 O is also a component that improves devitrification resistance. When Na 2 O content is too small, the melting property and ion exchange performance tends to decrease. Therefore, the content of Na 2 O is preferably 5% or more, more than 7.0%, 10% or more, 12% or more, 13% or more, particularly 14% or more. On the other hand, when the content of Na 2 O is too large, the thermal expansion coefficient becomes too high, and the thermal shock resistance is lowered or it is difficult to match the thermal expansion coefficient of the organic resin intermediate layer.
  • the strain point may be excessively lowered or the component balance of the glass composition may be lost, and the devitrification resistance may be deteriorated. Therefore, the content of Na 2 O is preferably 20% or less, 19% or less, 17% or less, 16.3% or less, 16% or less, and particularly 15% or less.
  • K 2 O is a component that promotes ion exchange, and is a component that easily increases the stress depth among alkali metal oxides. Moreover, it is a component which reduces high temperature viscosity and improves a meltability and a moldability. Furthermore, it is also a component that improves devitrification resistance. However, when the content of K 2 O is too large, the thermal expansion coefficient becomes too high, the thermal shock resistance is lowered, and it becomes difficult to match the thermal expansion coefficient of the organic resin intermediate layer. On the other hand, if the strain point is too low, the component balance of the glass composition is lost, and the devitrification resistance tends to be lowered.
  • the upper limit range of K 2 O is preferably 5% or less, 4% or less, less than 2%, particularly less than 1%.
  • the addition amount thereof is preferably 0.1% or more, 0.3% or more, particularly 0.5% or more.
  • Li 2 O is an ion exchange component, and is a component that lowers the high-temperature viscosity to increase the meltability and moldability, and also increases the Young's modulus. Furthermore, Li 2 O has a large effect of increasing the compressive stress value among alkali metal oxides. However, in a glass system containing 5% or more of Na 2 O, if the Li 2 O content is extremely increased, the compressive stress is rather increased. The value tends to decrease. Further, when the content of Li 2 O is too large, and decreases the liquidus viscosity, in addition to the glass tends to be devitrified, the thermal expansion coefficient becomes too high, the thermal shock resistance may decrease, It becomes difficult to match the thermal expansion coefficient of the organic resin intermediate layer.
  • the content of Li 2 O is preferably 0 to 4%, 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to less than 1.0%, 0 to 0.5%, 0 To 0.1%, especially 0.01 to 0.05%.
  • MgO is a component that lowers the high-temperature viscosity and increases the meltability, moldability, strain point, and Young's modulus, and is a component that has a large effect of enhancing ion exchange performance among alkaline earth metal oxides. Therefore, the lower limit range of MgO is preferably 0% or more, 0.5% or more, 1% or more, 1.2% or more, 1.3% or more, particularly 1.4% or more. However, when there is too much content of MgO, a density and a thermal expansion coefficient will become high easily, and it will become easy to devitrify glass.
  • the upper limit range of MgO is preferably 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2.3% or less, especially 2.2% or less.
  • CaO is a component that increases the meltability, moldability, strain point, and Young's modulus by lowering the high-temperature viscosity without lowering devitrification resistance compared to other components.
  • the content of CaO is too large, the density and thermal expansion coefficient become high, and the balance of the composition of the glass composition is lacking. On the contrary, the glass is liable to devitrify, the ion exchange performance is lowered, or the ion exchange. It becomes easy to degrade the solution. Therefore, the CaO content is preferably 0 to 6%, 0 to 5%, 0 to 4%, 0 to 3.5%, 0 to 3%, 0 to 2%, 0 to less than 1%, 0 to 0.5%, especially 0 to 0.1%.
  • SrO and BaO are components that lower the high-temperature viscosity and increase the meltability, moldability, strain point, and Young's modulus.
  • the contents of SrO and BaO are 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to 0.5%, 0 to 0.1%, especially 0 to less than 0.1%, respectively. Is preferred.
  • the total amount of MgO, CaO, SrO and BaO is preferably 0 to 9.9%, 0 to 8%, 0 to 6%, particularly 0 to 5%.
  • TiO 2 is a component that improves ion exchange performance and resistance to solarization, and is a component that lowers the high-temperature viscosity. However, if its content is too large, the glass tends to be colored or easily devitrified. Therefore, the content of TiO 2 is preferably 0 to 4.5%, 0.01 to 0.5%, particularly 0.05 to 0.3%.
  • ZrO 2 is a component that enhances the ion exchange performance and a component that increases the viscosity and strain point near the liquid phase viscosity. However, if the content of ZrO 2 is too large, the devitrification resistance may be remarkably reduced, and the density may be too high. Therefore, the content of ZrO 2 is preferably 0 to 5%, 0 to 3%, 0 to less than 1%, particularly 0.001 to 0.5%.
  • ZnO is a component that enhances ion exchange performance, and is a component that is particularly effective in increasing the compressive stress value. Moreover, it is a component which reduces high temperature viscosity, without reducing low temperature viscosity. However, when the content of ZnO is too large, the glass tends to undergo phase separation, the devitrification resistance decreases, the density increases, or the stress depth decreases. Therefore, the content of ZnO is preferably 0 to 6%, 0 to 3%, 0 to 1%, particularly 0 to 0.1%.
  • P 2 O 5 is a component that enhances ion exchange performance, and in particular, a component that increases the stress depth.
  • a suitable lower limit range of P 2 O 5 is 0% or more, 1% or more, 3% or more, 5% or more, particularly more than 7%.
  • the preferable upper limit range of the content of P 2 O 5 is 20% or less, 18% or less, 15% or less, 13% or less, 10% or less, particularly 7% or less.
  • the SnO 2 content is preferably 0 to 3%, 0.01 to 3%, 0.05 to 3%, 0.1 to 3%, particularly 0.2 to 3%.
  • one or two or more selected from the group of Cl, SO 3 and CeO 2 may be added in an amount of 0 to 3%.
  • Fe 2 O 3 is a component that enhances the ultraviolet absorption characteristics when coexisting with TiO 2 , but if its content is too large, the visible light transmittance tends to be lowered. Therefore, the content of Fe 2 O 3 is preferably 10 ppm or more (0.001% or more), 30 ppm or more, 50 ppm or more, 100 ppm or more, particularly 200 ppm or more. Further, the content of Fe 2 O 3 is preferably less than 1000 ppm (less than 0.1%), less than 800 ppm, less than 600 ppm, less than 400 ppm, particularly less than 300 ppm.
  • the Fe 2 O 3 content is regulated within the above range, and the molar ratio Fe 2 O 3 / (Fe 2 O 3 + SnO 2 ) is regulated to 0.8 or more, 0.9 or more, particularly 0.95 or more. It is preferable to do. In this way, the total light transmittance at a wavelength of 400 to 770 nm and a plate thickness of 1 mm can be increased (for example, 90% or more).
  • Rare earth oxides such as Nd 2 O 3 and La 2 O 3 are components that increase the Young's modulus.
  • the cost of the raw material itself is high, and when it is added in a large amount, the devitrification resistance tends to be lowered. Therefore, the total amount of the rare earth oxide is preferably 3% or less, 2% or less, 1% or less, 0.5% or less, particularly 0.1% or less.
  • the glass composition does not substantially contain As 2 O 3 , Sb 2 O 3 , PbO, Bi 2 O 3 and F.
  • substantially does not contain means that the glass component does not positively add an explicit component but allows it to be mixed as an impurity. Specifically, It indicates that the content is less than 0.05%.
  • the alkali aluminosilicate glass is suitable as the tempered glass plate, but soda lime glass may be used from the viewpoint of manufacturing cost.
  • Soda lime glass generally has a glass composition of SiO 2 65 to 75%, Al 2 O 3 0 to 3%, CaO 5 to 15%, MgO 0 to 15%, Na 2 O 10 to 10% by mass. 20%, K 2 O 0-3%, Fe 2 O 3 0-3%.
  • the crack occurrence rate of a tempered glass plate (outer tempered glass plate and / or inner tempered glass plate) before tempering treatment, that is, an untempered glass plate is 90% or less, preferably 80% or less.
  • the load at which the crack occurrence rate is 80% or less is preferably 500 gf or more, particularly 800 gf or more. If the crack generation rate is too large, when a flying object collides with the tempered glass plate and local stress is applied, cracks are likely to occur in the tempered glass plate, which may lead to the destruction of the entire laminated glass. Also, if the load at which the crack generation rate is 80% or less is too small, when a flying object collides with the tempered glass plate and local stress is applied, cracks are likely to occur in the tempered glass plate, There is a risk of destruction.
  • Density of tempered glass is 2.60 g / cm 3 or less, 2.55 g / cm 3 or less, 2.50 g / cm 3 or less, 2.48 g / cm 3 or less , 2.46 g / cm 3 or less, particularly preferably 2.45 g / cm 3 or less.
  • the “density” can be measured by the Archimedes method.
  • the thermal expansion coefficient of the tempered glass plate (outer tempered glass plate and / or inner tempered glass plate) in the temperature range of 25 to 380 ° C. is preferably 100 ⁇ 10 ⁇ 7 / ° C. or lower, 95 ⁇ 10 ⁇ 7 / ° C. or lower, It is 90 ⁇ 10 ⁇ 7 / ° C. or less, particularly 85 ⁇ 10 ⁇ 7 / ° C. or less.
  • the “thermal expansion coefficient in the temperature range of 25 to 380 ° C.” is an average value measured with a dilatometer.
  • the liquidus temperature of the tempered glass plate is preferably 1200 ° C. or lower, 1150 ° C. or lower, 1100 ° C. or lower, 1080 ° C. or lower, 1050 ° C. or lower, 1020 ° C. or lower, especially 1000 It is below °C.
  • Liquidus viscosity preferably of 10 4.0 dPa ⁇ s or more, 10 4.4 dPa ⁇ s or more, 10 4.8 dPa ⁇ s or more, 10 5.0 dPa ⁇ s or more, 10 5.3 dPa ⁇ s Above, 10 5.5 dPa ⁇ s or more, 10 5.7 dPa ⁇ s or more, 10 5.8 dPa ⁇ s or more, particularly 10 6.0 dPa ⁇ s or more. If the liquidus temperature and the liquidus viscosity are out of the above ranges, the glass tends to devitrify during molding.
  • liquid phase temperature is obtained by passing the glass powder that passes through a standard mesh of 30 mesh (a sieve opening of 500 ⁇ m) and remains in a mesh of 50 mesh (a sieve opening of 300 ⁇ m) into a platinum boat, and then in a temperature gradient furnace for 24 hours. This is a value obtained by measuring the temperature at which crystals are deposited.
  • Liquid phase viscosity refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.
  • the Young's modulus of the tempered glass plate is preferably 76 GPa or less, 74 GPa or less, 72 GPa or less, particularly 70 GPa or less.
  • the Young's modulus can be measured by a resonance method or the like.
  • the thickness of the organic resin intermediate layer is preferably 0.1 to 2 mm, 0.3 to 1.5 mm, 0.5 to 1.2 mm, particularly 0.6 to 0.9 mm. is there. If the thickness of the organic resin intermediate layer is too small, the impact absorbability tends to be lowered, and the sticking property tends to vary, so that the tempered glass plate and the organic resin intermediate layer are easily peeled off. On the other hand, when the thickness of the organic resin intermediate layer is too large, the visibility of the laminated glass tends to be lowered.
  • organic resins can be used as the organic resin intermediate layer.
  • PE polyethylene
  • EVA ethylene vinyl acetate copolymer
  • PP polypropylene
  • PS polystyrene
  • PMA methacrylic resin
  • PVC poly Vinyl chloride
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • CA diallyl phthalate resin
  • UP urea resin
  • MF melamine resin
  • unsaturated polyester UP
  • Polyvinyl butyral (PVB) polyvinyl formal (PVF), polyvinyl alcohol (PVAL), vinyl acetate resin (PVAc), ionomer (IO), polymethylpentene (TPX), vinylidene chloride (PVDC), polysulfone (PSF), Po Vinylidene fluoride (PVDF), methacryl-styrene copolymer resin (MS), polyarate (PAR), polyallyl sulfonomer
  • IO polymethyl
  • a colorant may be added to the organic resin intermediate layer, or an absorber that absorbs light of a specific wavelength such as infrared rays or ultraviolet rays may be added.
  • the organic resin intermediate layer a combination of a plurality of the above organic resins may be used.
  • the outer tempered glass plate and the inner tempered glass plate are fixed with different organic resins, so that it becomes easy to reduce the warp of the laminated glass during the lamination integration.
  • the laminated glass for vehicles of the present invention can be produced as follows.
  • a glass raw material prepared so as to have a predetermined glass composition is put into a continuous melting furnace, heated and melted at 1500 to 1700 ° C., clarified and stirred, and then fed to a molding apparatus to be formed into a plate shape.
  • a glass plate can be produced by cooling.
  • the overflow downdraw method is a method in which a high-quality glass plate can be produced in a large amount and a large glass plate can be easily produced while the surface is unpolished. If the surface is unpolished, the manufacturing cost of the glass plate can be reduced.
  • the float method is a method capable of producing a large glass plate at low cost.
  • the obtained glass plate is subjected to curved surface processing as necessary.
  • Various methods can be employed as a method of processing the curved surface.
  • a method of press-molding a glass plate with a mold is preferable, and it is preferable to pass through a heat treatment furnace with the glass plate sandwiched between molds having a predetermined shape. In this way, the dimensional accuracy of the curved surface shape can be increased.
  • the glass plate after the curved surface processing is tempered to obtain two tempered glasses.
  • the outer tempered glass plate is subjected to a chemical strengthening treatment from the viewpoint of increasing the point impact strength.
  • the conditions for the chemical strengthening treatment are not particularly limited, and the optimum conditions may be selected in consideration of the viscosity characteristics, application, thickness, internal tensile stress, dimensional change, and the like of the glass. For example, it can be carried out by immersing in a molten salt at 390 to 490 ° C. for 1 to 8 hours.
  • K ions in the molten salt are ion exchanged with Na components in the glass, a compressive stress layer can be efficiently formed on the glass surface.
  • Various molten salts can be used as the molten salt.
  • a mixed molten salt of KNO 3 and NaNO 3 can be used. In this case, the concentration of NaNO 3 is preferably 5 to 20% by mass.
  • the chemical strengthening treatment may be performed a plurality of times (preferably twice) on one glass plate.
  • the chemical strengthening treatment is performed a plurality of times, the distribution curve of the K ion concentration in the depth direction can be bent, and the tensile stress accumulated inside can be increased while increasing the compressive stress value and the stress depth of the compressive stress layer. The total amount can be reduced.
  • a heat treatment step may be provided between the chemical strengthening processes. In this way, the compressive stress curve in the depth direction from the surface can be efficiently bent by the molten salt. Furthermore, the time for the first ion exchange treatment can be shortened.
  • the inner tempered glass plate may be subjected to physical tempering treatment.
  • the conditions for the physical strengthening treatment are not particularly limited, but it is preferable that the glass plate is rapidly cooled by an air jet or the like after being heated to a temperature near the softening point of the glass plate.
  • the physical strengthening treatment may be performed in a separate heat treatment step, but from the viewpoint of manufacturing efficiency, it is preferable to perform the quenching by rapidly cooling the glass plate after the curved surface processing.
  • two tempered glass plates are laminated and integrated with an organic resin intermediate layer to obtain a laminated glass.
  • a method of lamination and integration a method of curing an organic resin after injecting an organic resin between two tempered glass plates, an organic resin sheet is disposed between the two tempered glass plates, and then pressure heat treatment (thermocompression bonding)
  • the method etc. are mentioned, since the latter method is easy because lamination
  • the heating temperatures of the heaters arranged inside and outside may be differentiated according to the thermal expansion coefficient of the tempered glass plate.
  • a hard coat film or an infrared reflective film may be formed on the surface of the outer tempered glass plate or the inner tempered glass plate.
  • Glass raw materials were prepared so that a glass containing MgO 3.0% and SnO 2 0.5% was obtained.
  • the prepared glass raw material is put into a continuous melting furnace, it is melted, clarified and stirred to obtain a homogeneous molten glass, which is then fed into the molded body and formed into a plate shape by the overflow down draw method. .
  • the various characteristics of the obtained glass plate were evaluated.
  • the density was 2.45 g / cm 3
  • the thermal expansion coefficient was 91 ⁇ 10 ⁇ 7 / ° C.
  • the Young's modulus was 71 GPa
  • the liquidus temperature was 970 ° C.
  • the liquidus viscosity. was 10 6.3 dPa ⁇ s
  • the crack generation rate was 65%.
  • the density is a value measured by a known Archimedes method.
  • the thermal expansion coefficient is a value obtained by measuring an average thermal expansion coefficient in a temperature range of 25 to 380 ° C. using a dilatometer.
  • the Young's modulus is a value measured by a known resonance method.
  • the liquidus temperature passes through a standard sieve 30 mesh (a sieve opening of 500 ⁇ m), puts the glass powder remaining in 50 mesh (a sieve opening of 300 ⁇ m) in a platinum boat, and holds it in a temperature gradient furnace for 24 hours. This is a value obtained by measuring the temperature at which crystals precipitate.
  • the liquid phase viscosity is a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.
  • the crack generation rate is first maintained in an electric furnace maintained at a temperature of 200 ° C.
  • the point impact strength of the obtained tempered glass plate was evaluated.
  • the point impact strength is determined by placing a tempered glass plate on a granite precision surface plate and placing the abrasive surface of sandpaper (number P100, abrasive SiC) on the tempered glass plate side. Then, a 66.8 g stainless steel ball was naturally dropped from above toward the sandpaper, and the height at which the tempered glass plate was damaged was determined. The number of measurements was 15, and the average strength was calculated from steel ball weight ⁇ gravity acceleration ⁇ breakage height, and the Weibull coefficient was also calculated. The results are shown in Table 1.
  • sample no. Nos. 1 and 2 had high point impact strength because the plate thickness, compressive stress value CS, stress depth DOL, and internal tensile stress value CT were appropriate.
  • sample No. No. 3 had a low point impact strength because the stress depth DOL was too large.
  • Sample No. No. 4 had a low point impact strength because the stress depth DOL was too small.
  • the obtained glass plate is passed through a heat treatment furnace in a state where each sample is sandwiched between molds of a predetermined shape, so that the entire plate width direction is curved in an arc shape, and the entire length direction is Were curved into a curved shape curved in an arc shape.
  • the glass plate after the curved surface machining, mixed molten salt (KNO 3 87.43 wt%, NaNO 3 12.57 wt%) was used to perform ion-exchanged for 2 hours at 480 ° C., to obtain a tempered glass plate. Furthermore, after preparing two tempered glass plates after curved surface processing, using a 0.7 mm thick organic resin intermediate layer (PVB), these are laminated and integrated by pressure heat treatment, and laminated glass having a curved surface shape Got. It is considered that this laminated glass can achieve both high strength and thinning, and can effectively avoid the risk of human injury at the time of breakage.
  • PVB organic resin intermediate layer
  • Example Nos. 5 to 11 were processed into a curved surface by the method described in the column of Example 2 and then tempered to obtain tempered glass plates.
  • the density, thermal expansion coefficient, Young's modulus, liquid phase temperature, liquid phase viscosity, and crack generation rate of each sample were measured by the measurement methods described in the column of Example 1.
  • the laminated glass for vehicles of the present invention is suitable for an automobile windshield, but is also suitable for an automobile rear glass, door glass, and roof glass. Moreover, it is suitable also for the window glass of a railway vehicle.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un verre feuilleté pour véhicules qui présente une feuille de verre trempé externe et une feuille de verre trempé interne qui sont intégrées au moyen d'une couche intermédiaire de résine organique, et qui est caractérisé en ce que l'épaisseur de la feuille de verre trempé externe n'est pas supérieure à 2,0 mm, la feuille de verre trempé externe est pourvue d'une couche de contrainte de compression sur la surface par échange d'ions, et dans la couche de contrainte de compression de surface de la feuille de verre trempé externe, la valeur de contrainte de compression est d'au moins 350 MPa et la profondeur de contrainte résiduelle est de 15 à 100 µm.
PCT/JP2017/026154 2016-08-10 2017-07-19 Verre feuilleté pour véhicules Ceased WO2018030095A1 (fr)

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JPWO2021153654A1 (fr) * 2020-01-31 2021-08-05
WO2021187051A1 (fr) * 2020-03-19 2021-09-23 セントラル硝子株式会社 Verre pour vitre de véhicule
JP2025503713A (ja) * 2022-01-29 2025-02-04 フーイャォ グラス インダストリー グループ カンパニー リミテッド 車窓ガラス及び車両

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CN116161865A (zh) * 2023-02-15 2023-05-26 清远南玻节能新材料有限公司 轻量化复合玻璃及其制备方法、应用和汽车车窗
CN116409929A (zh) * 2023-02-15 2023-07-11 清远南玻节能新材料有限公司 复合玻璃及其制备方法、应用和汽车车窗

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JPH1160294A (ja) * 1997-06-10 1999-03-02 Nippon Sheet Glass Co Ltd 車両用合わせガラス
WO2015092385A1 (fr) * 2013-12-16 2015-06-25 Pilkington Group Limited Vitrage feuilleté
WO2015158464A1 (fr) * 2014-04-15 2015-10-22 Saint-Gobain Glass France Verre feuilleté à vitre intérieure mince
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JPH1160294A (ja) * 1997-06-10 1999-03-02 Nippon Sheet Glass Co Ltd 車両用合わせガラス
WO2015092385A1 (fr) * 2013-12-16 2015-06-25 Pilkington Group Limited Vitrage feuilleté
WO2015158464A1 (fr) * 2014-04-15 2015-10-22 Saint-Gobain Glass France Verre feuilleté à vitre intérieure mince
JP2016008161A (ja) * 2014-06-26 2016-01-18 日本電気硝子株式会社 合わせガラス

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JPWO2021153654A1 (fr) * 2020-01-31 2021-08-05
WO2021153654A1 (fr) * 2020-01-31 2021-08-05 Ａｇｃ株式会社 Verre feuilleté pour véhicules, automobile et procédé de production de verre feuilleté pour véhicules
US20220355653A1 (en) * 2020-01-31 2022-11-10 AGC Inc. Laminated glass for vehicle, automobile, and method for producing laminated glass for vehicle
EP4098439A4 (fr) * 2020-01-31 2024-02-21 Agc Inc. Verre feuilleté pour véhicules, automobile et procédé de production de verre feuilleté pour véhicules
WO2021187051A1 (fr) * 2020-03-19 2021-09-23 セントラル硝子株式会社 Verre pour vitre de véhicule
JP2025503713A (ja) * 2022-01-29 2025-02-04 フーイャォ グラス インダストリー グループ カンパニー リミテッド 車窓ガラス及び車両

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