WO2017183381A1 - Verre feuilleté pour véhicules - Google Patents

Verre feuilleté pour véhicules Download PDF

Info

Publication number
WO2017183381A1
WO2017183381A1 PCT/JP2017/011491 JP2017011491W WO2017183381A1 WO 2017183381 A1 WO2017183381 A1 WO 2017183381A1 JP 2017011491 W JP2017011491 W JP 2017011491W WO 2017183381 A1 WO2017183381 A1 WO 2017183381A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
glass plate
less
laminated glass
compressive stress
Prior art date
Application number
PCT/JP2017/011491
Other languages
English (en)
Japanese (ja)
Inventor
田中　敦
Original Assignee
日本電気硝子株式会社
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 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to CN201780023988.5A priority Critical patent/CN109071339A/zh
Priority to JP2018513073A priority patent/JPWO2017183381A1/ja
Publication of WO2017183381A1 publication Critical patent/WO2017183381A1/fr

Links

Images

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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
    • 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
    • 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

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.
  • Patent Document 1 discloses that the ratio of the thickness of the outer glass plate to the thickness of the inner glass plate is 0.6 or more and 0.9 or less in order to prevent breakage of the intermediate layer when the airbag is deployed.
  • Laminated glass is disclosed.
  • patent document 2 in order to improve crime prevention etc., the difference of the thickness of an inner side glass plate and an outer side glass plate shall be 1.0 mm or more, and the plate
  • the physical tempered glass when installed in a place close to the human body, the physical tempered glass is broken into particles due to physical impact, and the fine fragments may damage the eyeballs and the like.
  • 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 body damage at the time of breakage.
  • the idea is to create a laminated glass.
  • the laminated glass for vehicles according to the present invention is a laminated glass for vehicles in which an inner glass plate and an outer glass plate are integrated via an organic resin intermediate layer, and the inner glass plate has a compressive stress layer on its surface. It is glass, and an outer side glass plate is the physical strengthening glass which has a compressive-stress layer on the surface, It is characterized by the above-mentioned.
  • the “inner glass plate” refers to a glass plate disposed on the vehicle inner side
  • the “outer glass plate” refers to a glass plate disposed on the vehicle outer side.
  • a laminated glass has the curved-surface shape curved in three dimensions, a glass plate with a small curvature radius turns into an inner side glass plate, and a glass plate with a large curvature radius turns into an outer side glass plate.
  • the inner glass plate is chemically strengthened glass.
  • the strength can be maintained even when the plate thickness is small, and the risk of the granular glass piece damaging the human body inside the vehicle at the time of breakage can be reduced.
  • the laminated glass for vehicles of this invention uses the outer side glass plate as physically strengthened glass. Physically tempered glass tends to increase the stress depth. For this reason, an outer side glass plate becomes difficult to be damaged by the point impact of fine flying objects, such as gravel.
  • two glass plates are integrated with an organic resin intermediate layer. Thereby, 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.
  • a laminated glass 10 for a vehicle includes an inner glass plate 11 made of chemically strengthened glass, an outer glass plate 12 made of physically strengthened glass, an organic resin intermediate layer 13 sandwiched between the inner glass plate 11 and the outer glass plate 12, It has.
  • the laminated glass 10 for vehicles makes the outer side glass plate 12 side convex, 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 curved surface shape that is three-dimensionally curved.
  • the inner glass plate is alkali aluminosilicate glass and the thickness thereof is 1.5 mm or less.
  • the inner glass plate has a glass composition of 40% by weight, SiO 2 40-80%, Al 2 O 3 1-30%, B 2 O 3 0-10% as a glass composition. Na 2 O 5 to 20% and K 2 O 0 to 5% are preferably contained.
  • the laminated glass for vehicles of the present invention preferably has a compressive stress value of the compressive stress layer of the inner glass plate of 300 MPa or more and a stress depth of 5 ⁇ m or more.
  • 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 laminated glass for vehicles of the present invention preferably has a crack occurrence rate of 80% or less on the inner glass plate before chemical strengthening when a load of 800 gf is applied with a Vickers indenter.
  • 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 is grown at room temperature and humidity. It is desirable to cancel the difference in moisture state on the surface. Ps indicates a strain point.
  • the outer glass plate is preferably alkali aluminosilicate glass or soda lime glass, and the plate thickness is preferably 1.0 to 4.0 mm.
  • 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 is preferably used for a windshield of an automobile.
  • the inner glass plate and the outer glass plate have a compressive stress layer on the surface.
  • a method for forming a compressive stress layer on the surface there are a physical strengthening method and a chemical strengthening method.
  • the inner glass plate is a chemically strengthened glass
  • the outer glass plate is a physically strengthened glass.
  • the chemical strengthening method 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. If it is a chemical strengthening method, even when the plate
  • the physical strengthening method 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, and then rapidly cooling the glass with an air jet after processing a curved surface at a temperature particularly near the softening point of the glass. . If it is physically strengthened glass, a compressive stress layer having a large stress depth can be easily formed.
  • the thickness of the inner glass plate is preferably 1.5 mm or less, 1.2 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 thickness of the outer glass plate is preferably 4.0 mm or less, 3.5 mm or less, 3.0 mm or less, 2.5 mm or less, 2.0 mm or less, 1.8 mm or less, particularly 1.5 mm or less, preferably It 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, 0.8 mm or more, 0.9 mm or more, particularly 1.0 mm or more.
  • the plate thickness of the laminated glass is preferably 4.5 mm or less, 3.5 mm or less, 3.0 mm or less, 2.5 mm or less, 2.0 mm or less, particularly 1.5 mm or less. If each plate thickness is too large, it will be difficult to reduce the weight of the laminated glass. On the other hand, when each plate thickness is too small, it becomes difficult to obtain a desired strength.
  • the inner glass plate is regulated to 0.3 to 1.0 mm and the outer glass plate is regulated to 1.0 to 1.5 mm, mechanical impact force can be easily absorbed elastically. When applied to, it becomes difficult to be scratched.
  • the inner glass plate is preferably alkali aluminosilicate glass. Since alkali aluminosilicate glass has high ion exchange performance, it is possible to form a desired compressive stress layer in a short time of chemical strengthening treatment. Further, since the devitrification resistance is good, it can be easily formed into a glass plate.
  • the inner glass plate has a glass composition of 40 to 80% by mass, SiO 2 40 to 80%, Al 2 O 3 1 to 30%, B 2 O 3 0 to 10%, Na 2 O 5 to 20%, K 2 O 0. It preferably contains ⁇ 5%.
  • 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, if the content of SiO 2 is too large, the meltability and formability tend to be lowered, and the thermal expansion coefficient becomes too low, making it difficult to match the thermal expansion coefficient of the outer glass plate.
  • 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 1% or more, 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, particularly 18.5% or more.
  • the content of Al 2 O 3 is too large, devitrification crystal glass becomes easy to precipitate, and it becomes difficult to mold the glass sheet 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 crack generation rate, high-temperature viscosity, and density, stabilizes the glass, makes it difficult to precipitate crystals, and lowers the liquidus temperature.
  • 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 5%, 0 to 3.5%, 0 to 2%, 0 to 1.5%, 0 to 1%, 0.01 to less than 1.0% In particular, it is 0.1 to 0.5%.
  • Li ions act as an ion exchange component, so that the stress depth can be increased in a short time. As a result, when the chemical strengthening process is performed a plurality of times, the first ion exchange time can be shortened.
  • 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 there exists a tendency for glass to devitrify easily.
  • 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 is a component that lowers the high-temperature viscosity and increases meltability, moldability, strain point, and Young's modulus.
  • the SrO content is preferably 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to 0.5%, 0 to 0.1%, particularly 0 to less than 0.1%. is there.
  • BaO is a component that lowers the high-temperature viscosity and increases the meltability, moldability, strain point, and Young's modulus.
  • the content of BaO is preferably 0-2%, 0-1.5%, 0-1%, 0-0.5%, 0-0.1%, especially 0-0.1%. is there.
  • 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 enhances the ion exchange performance and is a component that lowers the high-temperature viscosity. However, if its content is too large, the glass tends to be colored or devitrified easily. Therefore, the content of TiO 2 is preferably 0 to 4.5%, 0 to 0.5%, particularly 0 to 0.3%.
  • ZrO 2 is a component that remarkably improves the ion exchange performance and a component that increases the viscosity and strain point in the vicinity of 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%.
  • 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, especially less than 300 ppm. Further, 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 set to 0.8 or more, 0.9 or more, particularly 0.95 or more. It is preferable to regulate. This makes it easy to improve the total light transmittance (400 to 770 nm) at a plate thickness of 1 mm (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. However, the cost of the raw material itself is high, and when it is added in a large amount, the devitrification resistance tends to be lowered. Therefore, the rare earth oxide content is preferably 3% or less, 2% or less, 1% or less, 0.5% or less, 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 inner glass plate has a compressive stress layer on the surface, and the compressive stress value of the compressive stress layer is preferably 300 MPa or more, 500 MPa or more, 600 MPa or more, 650 MPa or more, particularly 700 MPa or more. is there.
  • the greater the compressive stress value the higher the strength of the inner glass plate.
  • the compressive stress value of the compressive stress layer is preferably 1200 MPa or less.
  • the stress depth of the compressive stress layer of the inner glass plate is preferably 5 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, particularly 50 ⁇ m or more.
  • the greater the stress depth the harder the inner glass plate breaks and the less the variation in strength, even if the inner glass plate is deeply scratched.
  • the stress depth is preferably 70 ⁇ m or less.
  • the tensile stress value inside the inner glass plate is preferably 200 MPa or less, 150 MPa or less, 90 MPa or less, 70 MPa or less, particularly 10 to 50 MPa. If the internal tensile stress value is too large, the glass plate may be destroyed by point collision.
  • the internal tensile stress value is a value calculated from the following mathematical formula.
  • the compressive stress curve in the depth direction from the surface of the inner glass plate is preferably bent. If it does in this way, it will become easy to prevent internal stress destruction, increasing the compressive stress value and stress depth of a compressive stress layer. In addition, when a chemical strengthening process is performed in multiple times, the compressive stress curve in the depth direction can be bent from the surface.
  • the temperature of the last chemical strengthening treatment is preferably 390 to 430 ° C., particularly 400 to 420 ° C.
  • the last chemical strengthening treatment time is preferably 1.5 to 5 hours, in particular 2 to 4.5 hours. If it does in this way, it will become easy to raise the compressive stress value of a compressive stress layer.
  • the ratio of small alkali ions (for example, Li ions, Na ions, particularly Na ions) in the ion exchange solution used for the second chemical strengthening treatment is the ion used for the first chemical strengthening treatment. Less than that in the exchange liquid is preferred. This makes it easier to increase the compressive stress value of the compressive stress layer.
  • the size of the alkali ions is Li ion ⁇ Na ion ⁇ K ion.
  • the content of KNO 3 in the ion exchange solution used for the first chemical strengthening treatment is preferably less than 75% by mass, 70% by mass or less, particularly 60% by mass or less.
  • the content of KNO 3 in the ion exchange solution used for the second chemical strengthening treatment is preferably 75% by mass or more, 85% by mass or more, 95% by mass or more, particularly 99.5% by mass or more.
  • the content of NaNO 3 in the ion exchange solution used for the second chemical strengthening treatment is smaller than the content of NaNO 3 in the ion exchange solution used for the first chemical strengthening treatment. It is preferably 5% by mass or less, more preferably 10% by mass or less, and particularly preferably 15% by mass or more. Further, the content of NaNO 3 in the ion exchange solution used for the second chemical strengthening treatment is preferably 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, and particularly 5% by mass or less. 0.5% by mass or less. If there is too much NaNO 3 in the ion exchange solution used for the second chemical strengthening treatment, it is difficult to increase the compressive stress value of the surface compressive stress layer.
  • the crack occurrence rate of the inner glass plate before chemical strengthening treatment when a load of 800 gf is applied with a Vickers indenter is preferably 80% or less. If this crack generation rate is too large, when a flying object collides with the outer glass plate and local stress is applied, cracks are likely to occur in the inner glass plate, which may lead to the destruction of the entire laminated glass. .
  • the outer glass plate is a physically tempered glass having a compressive stress layer on the surface.
  • the compressive stress value of the compressive stress layer of the outer glass plate is preferably 1 MPa or more, 5 MPa or more, 10 MPa or more, 20 MPa or more, 50 MPa or more, particularly 100 MPa or more. The greater the compressive stress value, the higher the strength of the outer glass plate.
  • the stress depth of the compressive stress layer of the outer glass plate is preferably 50 ⁇ m or more, 100 ⁇ m or more, or 150 ⁇ m or more. When the stress depth of the outer glass plate is too small, the point impact resistance against flying objects tends to be lowered.
  • the tensile stress value inside the outer glass plate is preferably 90 MPa or less, 70 MPa or less, particularly 10 to 50 MPa. If the tensile stress value inside the outer glass is too large, glass fragments may be shattered at the time of breakage, resulting in a temporary poor visibility and a very dangerous situation.
  • the alkali aluminosilicate glass is preferable, but from the viewpoint of production cost, soda lime glass is also preferable.
  • Soda lime glass generally has a glass composition of SiO 2 65-75%, Al 2 O 3 0-3%, CaO 5-15%, MgO 0-15%, Na 2 O 10-20%, K 2 O 0 to 3% and Fe 2 O 3 0 to 3% are contained.
  • the density of the glass sheet is 2.6 g / cm 3 or less, 2.55 g / cm 3 or less, 2.50 g / cm 3 or less, 2 .48g / 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 in the temperature range of 25 to 380 ° C. of the glass plate is preferably 100 ⁇ 10 ⁇ 7 / ° C. or lower, 95 ⁇ 10 ⁇ 7 / ° C. or lower, 90 ⁇ 10 It is ⁇ 7 / ° C. or lower, particularly 85 ⁇ 10 ⁇ 7 / ° C. or lower.
  • 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 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, particularly 1000 ° C. or lower. is there.
  • 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 glass plate is preferably 65 GPa or more, 69 GPa or more, 71 GPa or more, 75 GPa or more, particularly 77 GPa or more.
  • 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 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 resin intermediate layer Various materials can be used as the organic resin intermediate layer, for example, polyethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polystyrene (PS), methacrylic resin (PMA), polychlorinated.
  • PE polyethylene
  • EVA ethylene vinyl acetate copolymer
  • PP polypropylene
  • PS polystyrene
  • PMA methacrylic resin
  • PE polychlorinated.
  • PVB Polyvinyl butyral
  • PVF polyvinyl formal
  • PVD polyvinyl alcohol
  • PVDF vinyl acetate resin
  • IO ionomer
  • TPX polymethylpentene
  • PVDC vinylidene chloride
  • PSF polyph Vinylidene chloride
  • MS methacryl-styrene copolymer resin
  • MS polyarate
  • PAR polyallyl sulfone
  • PASF polybutadiene
  • PESF polyether sulfone
  • PEEK polyether ether ketone
  • 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 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, then supplied to a molding apparatus and formed into a flat plate shape, A glass plate can be produced by slow 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 more 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 chemically strengthened to obtain an inner glass plate, and is physically strengthened to obtain an outer glass plate.
  • 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 KNO 3 molten salt at 390 to 480 ° C. for 1 to 8 hours.
  • K ions in the KNO 3 molten salt are ion-exchanged with Na components in the glass, a compressive stress layer can be efficiently formed on the glass surface.
  • strengthening process After heating to the temperature of the softening point vicinity of a glass plate, it is preferable to quench rapidly with an air jet.
  • the physical strengthening treatment may be performed in a separate heat treatment step, but from the viewpoint of production efficiency, it is preferably performed by rapidly cooling the glass after the curved surface processing.
  • the two glass plates after the tempering treatment are laminated and integrated with an organic resin intermediate layer to obtain a laminated glass.
  • a method of stacking and integrating a method of curing an organic resin after injecting an organic resin between two glass plates, a method of placing an organic resin sheet between two glass plates, and a method of performing pressure heat treatment (thermocompression bonding), etc.
  • the latter method is preferable because stacking and integration are easier.
  • a hard coat film or an infrared reflective film may be formed on the surface of the inner glass plate or the outer glass plate.
  • Table 1 shows the glass composition and glass characteristics of the inner glass plates (Sample Nos. 1 to 5).
  • each sample was prepared as follows. First, to prepare the glass composition in the table, each glass raw material was prepared, melted, clarified and stirred to obtain a homogeneous glass, then formed into a plate shape by the overflow down draw method, A glass plate was obtained. Various characteristics were evaluated for each obtained sample.
  • the density ⁇ is a value measured by the well-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 E is a value measured by a well-known resonance method.
  • the liquid phase temperature TL passes through a standard sieve 30 mesh (a sieve opening of 500 ⁇ m), and glass powder remaining in a 50 mesh (a sieve opening of 300 ⁇ m) is put in a platinum boat, and then held in a temperature gradient furnace for 24 hours. This is a value obtained by measuring the temperature at which crystals are deposited.
  • the liquidus viscosity log 10 ⁇ TL is a value obtained by measuring the viscosity of the glass at the liquidus temperature by a platinum ball pulling method.
  • the crack occurrence rate was measured as follows. First, it was kept in an electric furnace kept at a temperature of 200 ° C. for 1 hour to make the surface moisture state constant. Then, in a constant temperature and humidity chamber maintained at a humidity of 30% and a temperature of 25 ° C., a Vickers indenter set at a load of 800 gf was driven into the glass surface for 15 seconds, and the number of cracks generated from four corners of the indentation after 15 seconds. Counted (maximum 4 per indentation). Thus, after indenting the indenter 50 times and determining the total number of cracks generated, the total number of cracks generated was calculated by the formula (total number of cracks generated / 200) ⁇ 100.
  • each sample 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 an arc shape. Curved to a curved shape.
  • the glass plate (plate thickness 1.5mm) which consists of soda-lime glass which has the same size as the said inner side glass plate, it curved-surface-processed by the method similar to the case of the said inner side glass plate about this glass plate. Thereafter, the outer glass plate was obtained by quenching and physical strengthening treatment.
  • CS was calculated by the above method for the obtained outer glass plate, CS was 50 MPa.
  • the inner glass plate (Sample Nos. 1 to 4) and the outer glass plate are laminated and integrated by pressure heat treatment to obtain a curved surface shape.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Glass Compositions (AREA)
  • Laminated Bodies (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Surface Treatment Of Glass (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

L'invention concerne un verre feuilleté pour véhicules, obtenu en intégrant une feuille de verre interne et un verre externe avec une couche intermédiaire de résine organique interposée entre ceux-ci, la feuille de verre interne étant un verre trempé chimiquement ayant une couche de contrainte de compression sur sa surface, et la feuille de verre externe étant un verre trempé physiquement ayant une couche de contrainte de compression sur sa surface.
PCT/JP2017/011491 2016-04-18 2017-03-22 Verre feuilleté pour véhicules WO2017183381A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201780023988.5A CN109071339A (zh) 2016-04-18 2017-03-22 车辆用夹层玻璃
JP2018513073A JPWO2017183381A1 (ja) 2016-04-18 2017-03-22 車両用合わせガラス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-082645 2016-04-18
JP2016082645 2016-04-18

Publications (1)

Publication Number Publication Date
WO2017183381A1 true WO2017183381A1 (fr) 2017-10-26

Family

ID=60116698

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/011491 WO2017183381A1 (fr) 2016-04-18 2017-03-22 Verre feuilleté pour véhicules

Country Status (3)

Country Link
JP (1) JPWO2017183381A1 (fr)
CN (1) CN109071339A (fr)
WO (1) WO2017183381A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019151000A1 (fr) * 2018-01-31 2019-08-08 日本電気硝子株式会社 Composite verre/résine
WO2019186114A1 (fr) * 2018-03-27 2019-10-03 Pilkington Group Limited Vitrage feuilleté
JP2019210208A (ja) * 2018-05-31 2019-12-12 エージーシー オートモーティヴ アメリカズ カンパニー 直交ドローラインを有するガラス製品
JP2021519258A (ja) * 2018-03-27 2021-08-10 ピルキントン グループ リミテッド 積層グレイジング
WO2021187051A1 (fr) * 2020-03-19 2021-09-23 セントラル硝子株式会社 Verre pour vitre de véhicule
US11745459B2 (en) 2016-12-22 2023-09-05 Schott Ag Thin glass substrate, in particular a borosilicate glass thin glass substrate, method and apparatus for its production

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114905810A (zh) * 2022-05-17 2022-08-16 上海耀皮康桥汽车玻璃有限公司 一种钢化夹层车门玻璃
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015006201A1 (fr) * 2013-07-09 2015-01-15 Corning Incorporated Stratifiés-verres hybrides légers
WO2015125584A1 (fr) * 2014-02-19 2015-08-27 日本電気硝子株式会社 Procédé de fabrication du verre trempé et verre trempé
JP2015525193A (ja) * 2012-06-01 2015-09-03 コーニング インコーポレイテッド 最適化された破損性能のためのガラス積層体構築
JP2015533113A (ja) * 2012-08-21 2015-11-19 エージーシー グラス ユーロップ 自動車のガラス

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10035331B2 (en) * 2011-06-24 2018-07-31 Corning Incorporated Light-weight hybrid glass laminates
GB201322240D0 (en) * 2013-12-16 2014-01-29 Pilkington Group Ltd Laminated glazing
US10144198B2 (en) * 2014-05-02 2018-12-04 Corning Incorporated Strengthened glass and compositions therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015525193A (ja) * 2012-06-01 2015-09-03 コーニング インコーポレイテッド 最適化された破損性能のためのガラス積層体構築
JP2015533113A (ja) * 2012-08-21 2015-11-19 エージーシー グラス ユーロップ 自動車のガラス
WO2015006201A1 (fr) * 2013-07-09 2015-01-15 Corning Incorporated Stratifiés-verres hybrides légers
WO2015125584A1 (fr) * 2014-02-19 2015-08-27 日本電気硝子株式会社 Procédé de fabrication du verre trempé et verre trempé

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11745459B2 (en) 2016-12-22 2023-09-05 Schott Ag Thin glass substrate, in particular a borosilicate glass thin glass substrate, method and apparatus for its production
US11890844B2 (en) 2016-12-22 2024-02-06 Schott Ag Thin glass substrate, method and apparatus for its production
US11993062B2 (en) 2016-12-22 2024-05-28 Schott Ag Composite glass pane
US12005687B2 (en) 2016-12-22 2024-06-11 Schott Ag Thin glass substrate, method and apparatus for its production
WO2019151000A1 (fr) * 2018-01-31 2019-08-08 日本電気硝子株式会社 Composite verre/résine
WO2019186114A1 (fr) * 2018-03-27 2019-10-03 Pilkington Group Limited Vitrage feuilleté
JP2021519258A (ja) * 2018-03-27 2021-08-10 ピルキントン グループ リミテッド 積層グレイジング
JP2021519257A (ja) * 2018-03-27 2021-08-10 ピルキントン グループ リミテッド 積層グレイジング
JP2019210208A (ja) * 2018-05-31 2019-12-12 エージーシー オートモーティヴ アメリカズ カンパニー 直交ドローラインを有するガラス製品
JP7345280B2 (ja) 2018-05-31 2023-09-15 エージーシー オートモーティヴ アメリカズ カンパニー 直交ドローラインを有するガラス製品
WO2021187051A1 (fr) * 2020-03-19 2021-09-23 セントラル硝子株式会社 Verre pour vitre de véhicule

Also Published As

Publication number Publication date
JPWO2017183381A1 (ja) 2019-02-28
CN109071339A (zh) 2018-12-21

Similar Documents

Publication Publication Date Title
WO2017183381A1 (fr) Verre feuilleté pour véhicules
JP6256763B2 (ja) 合わせガラス
JP6080279B2 (ja) イオン交換ガラスを製造する方法および結果として得られた装置
JP2022120162A (ja) 軽量複合合わせガラス
JP6538662B2 (ja) イオン交換ガラスを製造する方法および結果として得られた装置
WO2018030093A1 (fr) Verre feuilleté pour véhicules
EA031978B1 (ru) Тонкое многослойное стекло
WO2018030095A1 (fr) Verre feuilleté pour véhicules
WO2017183382A1 (fr) Verre feuilleté pour véhicules
JP2019182692A (ja) ガラス板及びそれを用いたガラス樹脂複合体
JP7011227B2 (ja) 車両用合わせガラス
US20200023617A1 (en) Glass-resin composite
US11401199B2 (en) Glass plate
WO2019151000A1 (fr) Composite verre/résine
WO2018163903A1 (fr) Composite verre-résine
WO2018193788A1 (fr) Composite verre-résine
JP2019131430A (ja) ガラス板
JP2019182706A (ja) ガラス板及びそれを用いたガラス樹脂複合体
JP6959566B2 (ja) ガラス板
WO2018163904A1 (fr) Composite de verre et de résine
JP2019172566A (ja) ガラス樹脂複合体
JP2019151516A (ja) ガラス板及びそれを用いたガラス樹脂複合体
WO2023074638A1 (fr) Verre borosilicaté
WO2018163902A1 (fr) Composite verre-résine
WO2020080162A1 (fr) Plaque de verre

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2018513073

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17785723

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17785723

Country of ref document: EP

Kind code of ref document: A1