[go: up one dir, main page]

WO2018030094A1 - Verre feuilleté pour véhicules - Google Patents

Verre feuilleté pour véhicules Download PDF

Info

Publication number
WO2018030094A1
WO2018030094A1 PCT/JP2017/026153 JP2017026153W WO2018030094A1 WO 2018030094 A1 WO2018030094 A1 WO 2018030094A1 JP 2017026153 W JP2017026153 W JP 2017026153W WO 2018030094 A1 WO2018030094 A1 WO 2018030094A1
Authority
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/JP2017/026153
Other languages
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 JP2018532900A priority Critical patent/JP7011227B2/ja
Publication of WO2018030094A1 publication Critical patent/WO2018030094A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • 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
    • C03C3/089—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 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 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 inner side glass plate and an outer side glass plate shall be 1.0 mm or more, and the plate
  • the laminated glass has an organic resin intermediate layer in the plane as described above, and this organic resin intermediate layer has an impact absorbing effect.
  • the end face of the laminated glass cannot fully enjoy the impact absorbing effect of the organic resin intermediate layer, and when an impact is applied to the end face of the laminated glass, there is a risk that breakage will occur starting from the end face.
  • an impact is applied to the end face of a thin tempered glass plate, there is a risk that breakage will occur from the end face and the glass piece will fall off, damaging the human body.
  • laminated glass having a thin tempered glass plate is used for a door glass of an automobile, an impact is applied to the end surface of the glass plate every time the door is closed, and there is a risk that breakage occurs starting from the end surface.
  • the present invention has been made in view of the above circumstances, and its technical problem is to provide a laminated glass for a vehicle that is capable of achieving both high strength and thinning and is not easily damaged even when an impact is applied to the end face. It is to create.
  • the laminated glass for a vehicle according to the present invention is a laminated glass for a vehicle in which an inner tempered glass plate and an outer tempered glass plate are integrated by an organic resin intermediate layer, and the depth is 7 to 16 ⁇ m apart from the surface of the inner tempered glass plate.
  • the average value of the compressive stress at the position is 350 MPa or more.
  • the conditions for ion exchange treatment are strictly regulated (preferably, ion exchange treatment is performed a plurality of times, and the conditions for each ion exchange treatment are strictly regulated), 7 to 16 ⁇ m from the surface of the inner tempered glass plate. It becomes easy to regulate the average value of the compressive stress at the separated depth positions to 350 MPa or more.
  • the “compressive stress value” and “stress depth” are the number of interference fringes observed when the measurement sample is observed using the software FsmV of a surface stress meter (FSM-6000LE manufactured by Orihara Seisakusho Co., Ltd.).
  • the measurement setting (enhancement type) is set as the chemical strengthening II
  • the measurement mode is set as the exact solution mode
  • the use of the bending point position is used for the calculation of the boundary position of the depth measurement.
  • the value of DOL_zero calculated by FsmV is adopted as the “stress depth”.
  • the “internal tensile stress value” the value of CT_cv obtained by the above measurement is adopted.
  • FIG. 1 is a schematic view for explaining a laminated glass for a vehicle according to the present invention.
  • the laminated glass 10 for vehicles includes an inner tempered glass plate 11, an outer tempered glass plate 12, and an organic resin intermediate layer 13 sandwiched between the inner tempered glass plate 11 and the outer tempered glass plate 12.
  • the inner glass plate 11 has a compressive stress layer, and the average value of the compressive stress at a depth position 7 to 16 ⁇ m apart from the surface thereof is 350 MPa or more.
  • 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 inner tempered glass plate is preferably alkali aluminosilicate glass
  • the outer tempered glass plate is preferably soda lime glass
  • 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 thickness of the inner tempered glass plate is smaller than the thickness of the outer tempered glass plate.
  • the long side dimension of the inner tempered glass plate is smaller than the long side dimension of the outer tempered glass plate. In this way, when the laminated glass is integrated after bending, and the laminated glass is used, the dimensional difference between the outer tempered glass plate and the inner tempered glass plate is reduced, and the end surfaces of both are easily aligned. As a result, the end face strength of the laminated glass that has been curved is improved.
  • the end surfaces of the inner tempered glass plate and the outer tempered glass plate are chamfered.
  • the organic resin intermediate layer protrudes outside the end face of the outer tempered glass plate.
  • 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 an automobile door glass.
  • the laminated glass for vehicles of the present invention has an inner tempered glass plate and an outer tempered glass plate. These tempered glass plates have a compressive stress layer on the surface.
  • 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), and any strengthening treatment may be used.
  • the ion exchange 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 an ion exchange 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 average value of the compressive stress at a depth position separated from the surface by 7 to 16 ⁇ m is 350 MPa or more, preferably 400 MPa or more, preferably 450 MPa or more, 500 MPa or more, 520 MPa or more, 550 MPa or more, particularly preferably 570 MPa or more. If the average value of the compressive stress at the depth position 7 to 16 ⁇ m away from the surface is too low, the end face strength tends to be lowered. On the other hand, if the average value of the compressive stress at the depth position 7 to 16 ⁇ m away from the surface is too large, the internal tensile stress may become extremely high. Therefore, the average value of the compressive stress at a depth position separated from the surface by 7 to 16 ⁇ m is preferably 1000 MPa or less.
  • the compressive stress value at a depth of 7 ⁇ m away from the surface is preferably 450 MPa or more, 550 MPa or more, 600 MPa or more, 650 MPa or more, 680 MPa or more, particularly Preferably it is 700 MPa or more. If the compressive stress value at a depth position separated by 7 ⁇ m from the surface is too low, the end face strength tends to decrease. On the other hand, if the compressive stress value at a depth position spaced 7 ⁇ m away from the surface is too large, the internal tensile stress may become extremely high. Therefore, the compressive stress value at a depth position separated by 7 ⁇ m from the surface is preferably 1000 MPa or less.
  • the compressive stress value at a depth position 12 ⁇ m away from the surface is preferably 350 MPa or more, 400 MPa or more, 450 MPa or more, 480 MPa or more, 500 MPa or more, 530 MPa. As described above, it is particularly preferably 550 MPa or more. If the compressive stress value at a depth position separated by 12 ⁇ m from the surface is too low, the end face strength tends to decrease. On the other hand, if the compressive stress value at a depth position 12 ⁇ m away from the surface is too large, the internal tensile stress may become extremely high.
  • the compressive stress value at a depth position 12 ⁇ m away from the surface is preferably 1000 MPa or less. Note that the compressive stress value at a depth position 12 ⁇ m away from the surface has a higher correlation with the end face strength than the compressive stress values at other depth positions.
  • the compressive stress value at a depth position 16 ⁇ m away from the surface is preferably 250 MPa or more, 280 MPa or more, 320 MPa or more, 360 MPa or more, 400 MPa or more, particularly Preferably it is 430 MPa or more. If the compressive stress value at a depth position spaced 16 ⁇ m away from the surface is too low, the end face strength tends to decrease. On the other hand, if the compressive stress value at a depth position 16 ⁇ m away from the surface is too large, the internal tensile stress may become extremely high.
  • the compressive stress value at a depth position spaced 16 ⁇ m from the surface is preferably 800 MPa or less. It should be noted that the compressive stress value at a depth position 16 ⁇ m away from the surface has a stronger correlation with the end face strength than the compressive stress values at other depth positions.
  • the inner tempered glass plate according to the present invention preferably has a bent compressive stress curve in the depth direction from the surface. In this way, it is possible to reduce the internal tensile stress while increasing the average value and the stress depth of the compressive stress at the depth position 7 to 16 ⁇ m away from the surface.
  • the compressive stress curve in the depth direction from the surface can be bent.
  • the temperature of the last ion exchange treatment (for example, in the case of two ion exchange treatments, the second ion exchange treatment) is preferably 390 to 430 ° C., particularly 400 to 420 ° C.
  • the time for the final ion exchange treatment is preferably 1.5 to 5 hours, in particular 2 to 4.5 hours. In this way, it becomes easy to increase the average value of the compressive stress at the depth position that is 7 to 16 ⁇ m away from the surface.
  • the proportion of small alkali ions (for example, Li ions, Na ions, particularly Na ions) in the ion exchange solution used for the second ion exchange treatment is the ion used for the first ion exchange treatment. Less than that in the exchange liquid is preferred. This makes it easy to increase the average value of compressive stress at a depth position that is 7 to 16 ⁇ m away from the surface.
  • 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 ion exchange 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 ion exchange treatment is preferably 75% by mass or more, 85% by mass or more, 95% by mass or more, and particularly 99.5% by mass or more. If the content of KNO 3 in the ion exchange solution is out of the above range, it is difficult to increase the average value of compressive stress at a depth position 7 to 16 ⁇ m away from the surface.
  • the content of NaNO 3 in the ion exchange solution used for the second ion exchange treatment is smaller than the content of NaNO 3 in the ion exchange solution used for the first ion exchange 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 ion exchange treatment is preferably 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, particularly 0.5% by mass. It is as follows. When the content of NaNO 3 in the ion exchange solution used for the second ion exchange treatment is too large, it is difficult to increase the average value of the compressive stress at a depth position 7 to 16 ⁇ m away from the surface.
  • a heat treatment step may be provided between the ion exchange treatments. In this way, the compressive stress curve in the depth direction from the surface can be bent efficiently with the same ion exchange solution. Furthermore, the time for the first ion exchange treatment can be shortened.
  • the surface compressive stress value of the compressive stress layer of the tempered glass plate is preferably 600 MPa or more, 700 MPa or more, 750 MPa or more, 800 MPa or more, 850 MPa or more, particularly preferably 900 MPa or more. is there.
  • the larger the surface compressive stress value the higher the strength of the tempered glass sheet.
  • the surface compressive stress value is preferably 1400 MPa or less. Note that when the ion exchange time is shortened or the temperature of the ion exchange treatment is lowered, the compressive stress value tends to increase.
  • the stress depth of the tempered glass plate is preferably 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 35 ⁇ m or more, 40 ⁇ m or more, 45 ⁇ m or more, particularly preferably 50 ⁇ m or more and 90 ⁇ m or less. is there. If the stress depth is too small, the end face strength tends to decrease. On the other hand, when the stress depth is too large, the internal tensile stress becomes excessive, and the tempered glass sheet is easily self-destructed. Note that when the ion exchange time is lengthened or the temperature of the ion exchange treatment is increased, the stress depth tends to increase.
  • the tensile stress value inside the tempered glass plate is preferably 100 MPa or less, 80 MPa or less, 70 MPa or less, 60 MPa or less, particularly 50 MPa or less. If the internal tensile stress value is too large, the tempered glass sheet is likely to self-break. On the other hand, if the internal tensile stress value is too small, the end face strength tends to decrease. Therefore, the internal tensile stress value is preferably 10 MPa or more, 20 MPa or more, 30 MPa or more, 40 MPa or more, and particularly preferably 45 MPa or more.
  • the outer tempered glass plate is preferably an ion exchange-treated tempered glass plate having a stress profile similar to that of the inner tempered glass plate. It may be a plate.
  • the surface compressive stress value 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 surface compressive stress value, the higher the strength of the outer tempered glass plate.
  • the stress depth is preferably 50 ⁇ m or more, 100 ⁇ m or more, or 150 ⁇ m or more.
  • the tensile stress value inside the outer tempered glass sheet is preferably 90 MPa or less, 70 MPa or less, particularly 10 to 50 MPa. If the tensile stress value inside the outer tempered glass plate is too large, glass fragments may be shattered at the time of breakage, resulting in a temporary loss of visibility and a danger.
  • the plate thickness of the inner tempered 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, It is 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 tempered 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 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 long side dimension of the inner tempered glass plate is preferably smaller than the long side dimension of the outer tempered glass plate. And it is preferable that the long side dimension difference of both is adjusted according to both thermal expansion coefficient difference. If it does in this way, when both are laminated and integrated after bending and it is set as a laminated glass, both dimensional difference will become small and both end surfaces will become easy to align. As a result, the end face strength of the laminated glass that has been curved is improved.
  • the tempered 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 ion exchange treatment. Moreover, since devitrification resistance is good, it can be easily formed into a plate shape.
  • the tempered glass plate (inner tempered glass plate and / or outer tempered glass plate) is, as a glass composition, 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%, 0.05 to 0.5%, particularly 0.1 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%.
  • 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 the tempered glass plate (inner tempered glass plate and / or outer tempered glass plate) before the tempering treatment, that is, the 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.
  • 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 (inner tempered glass plate and / or outer 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 organic resin intermediate layer protrudes outside the end face of the outer tempered glass plate, and the protrusion width is larger than the plate thickness of the outer glass plate. Larger is preferred. In this way, when an impact is applied from an oblique direction to the end surface of the tempered glass plate, the organic resin intermediate layer is curved to cover the end surface of the tempered glass plate, and the impact to the end surface of the tempered glass plate is prevented. Can be relaxed.
  • 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 glass plate is preferably chamfered as necessary. In that case, it is preferable to perform C chamfering with a # 800 metal bond grindstone or the like. If it does in this way, end face strength can be raised. It is also preferable to reduce the crack source existing on the end face by etching the end face of the glass plate as necessary.
  • 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 strengthening treatment is not particularly limited and may be either an ion exchange treatment or a physical strengthening treatment, but the ion exchange treatment is preferable from the viewpoint of increasing the end face strength.
  • the conditions for the ion exchange 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, etc. of the glass. Is preferably performed a plurality of times.
  • K ions in the ion exchange solution are ion exchanged with Na components in the glass, a compressive stress layer can be efficiently formed on the glass surface.
  • the ion-exchange solution a variety of ion-exchange liquid can be used, for example, can be used molten salt of KNO 3, mixed molten salt of KNO 3 and NaNO 3, and the like.
  • the conditions of 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 laminating and integrating, a method of curing an organic resin after injecting an organic resin between two glass plates, and a method of applying pressure and heat treatment (thermocompression bonding) after placing an organic resin sheet between two tempered glass plates is preferable because stacking and integration are easier.
  • the heating temperatures of the heaters arranged on the outside and inside 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 inner tempered glass plate or the outer tempered glass plate.
  • an inner tempered glass plate was produced as follows.
  • a glass composition in mass%, SiO 2 61.5%, Al 2 O 3 18.0%, B 2 O 3 0.5%, Na 2 O 14.5%, K 2 O 2.0%, MgO Glass raw materials were prepared so that a glass containing 3.0% and SnO 2 0.5% was obtained.
  • the prepared glass raw material is put into a continuous melting furnace, melted, clarified and stirred to obtain a homogeneous molten glass, which is then fed into the molded body and overflowed to a thickness of 0.7 mm. It was formed into a plate shape by the downdraw 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 entire plate width direction is curved in an arc shape, and the entire length direction is curved in an arc shape.
  • the curved surface was processed into a curved surface shape. Thereafter, the end face of the glass plate after the curved surface processing was C-chamfered and polished with a # 800 metal bond grindstone.
  • the glass plate after the curved surface processing was subjected to ion exchange treatment using the ion exchange solution shown in Table 1 under the conditions shown in Table 1 to obtain respective inner tempered glass plates.
  • DOL_zero represents the stress depth
  • DOL_tail represents the depth of the ion exchange layer
  • CT_cv represents the internal tensile stress value.
  • CS and “DOL” in the table indicate the number of interference fringes observed when the measurement sample is observed using the software FsmV of a surface stress meter (FSM-6000LE manufactured by Orihara Seisakusho). This value was calculated from the interval.
  • the measurement setting (enhancement type) was set to chemical strengthening II, the measurement mode was set to the exact solution mode, and the use of the inflection point position was adopted to calculate the boundary position for depth measurement.
  • the refractive index of each sample was 1.50, and the optical elastic constant was 29.5 [(nm / cm) / MPa].
  • Fig.2 (a) is a conceptual perspective view which shows the shape of the metal jig
  • the test piece 21 is fixed to a metal jig 23 in a state of being sandwiched between a pair of resin plates 22 made of bakelite.
  • the dimension of the test piece 21 is 22 mm ⁇ 30 mm ⁇ 0.7 mm thick, and a 2 mm ⁇ 30 mm portion of the test piece 21 is in a state of protruding from the metal jig 23.
  • the end surface of the protruding portion collides with the test head 24.
  • FIG. 2B is a conceptual cross-sectional view showing a collision method of the end face strength test. As shown in FIG.
  • the pendulum 25 (arm length 500 mm) to which the test head 24 is attached is swung down from a height of 10 mm and made to collide with the end face of the test piece 21 held between the metal jigs 23. It was. Thereafter, while increasing the height of the pendulum 25 by 10 mm, this operation was continued until the test piece 21 was damaged, and the height when the test piece 21 was damaged was taken as the damaged height. For each chemically strengthened glass, this end face strength test was performed 10 times, and the arithmetic average value of the breakage height was calculated as the average breakage height.
  • FIG. 3 is a graph showing the relationship between the average value of the compressive stress at the depth position 7 to 16 ⁇ m away from the surface of the tempered glass plate and the average fracture height in the end face strength test.
  • the average value of the compressive stress at the depth position 7 to 16 ⁇ m away from the surface of the tempered glass plate and the average fracture height in the end face strength test are because the correlation coefficient R 2 is 0.8926. A strong correlation is observed.
  • sample no. The inner tempered glass sheets according to Nos. 1 and 2 had a good average value of the compressive stress at a depth position 7 to 16 ⁇ m away from the surface, and therefore the evaluation of the end face strength test was good.
  • sample No. The inner tempered glass sheets according to 3 and 4 had poor evaluation of the end face strength test because the average value of the compressive stress at a depth position 7 to 16 ⁇ m away from the surface was small.
  • an outer tempered glass plate was produced.
  • a glass plate (thickness of 1.5 mm) made of soda lime glass having the same dimensions as the inner tempered glass plate was prepared.
  • the outer side tempered glass plate was obtained by quenching and performing a physical strengthening process.
  • CS was computed by the said method about the obtained outside tempered glass board, CS was 50 MPa.
  • the inner tempered glass plate and the outer tempered glass plate are laminated and integrated by pressure heat treatment using polyvinyl butyral (PVB) having a thickness of 0.7 mm to obtain a laminated glass having a curved shape (sample No. 1). 1-4) were obtained.
  • Sample No. 1 and 2 have both high strength and thinning, and are considered to be difficult to break even when an impact is applied to the end face.
  • the sample No. Ion exchange treatment was performed under the same conditions as the inner tempered glass plate according to No. 2 to obtain an inner tempered glass plate.
  • the average value of the compressive stress at a depth position 7 to 16 ⁇ m away from the surface of the inner tempered glass plate was 400 MPa or more.
  • the inner tempered glass plate and a glass plate (thickness 1.5 mm) made of soda lime glass having a slightly longer side dimension than the inner tempered glass plate were used as sample Nos.
  • the laminated glass was laminated and integrated in the same manner as the laminated glass No. 2 to produce laminated glasses. Note that the soda lime glass plate was sample No. Ion exchange treatment similar to 2 is performed.
  • 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.
  • the laminated glass for vehicles of the present invention is used for applications that require high impact strength, such as exhibition glass for aquariums, solar cell substrates, digital signage substrates, aircraft window glass, Applications to railcar window glass, rocket window glass, etc. can be expected.

Landscapes

  • 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)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un verre feuilleté pour véhicules qui a une feuille de verre trempé interne et une feuille de verre trempé externe qui sont intégrées au moyen d'une couche intermédiaire de résine organique, et qui est caractérisé en ce que la valeur moyenne de la contrainte de compression à une position de profondeur séparée de 7 à 16 µm de la surface de la feuille de verre trempé interne est d'au moins 350 MPa.
PCT/JP2017/026153 2016-08-10 2017-07-19 Verre feuilleté pour véhicules Ceased WO2018030094A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018532900A JP7011227B2 (ja) 2016-08-10 2017-07-19 車両用合わせガラス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016157509 2016-08-10
JP2016-157509 2016-08-10

Publications (1)

Publication Number Publication Date
WO2018030094A1 true WO2018030094A1 (fr) 2018-02-15

Family

ID=61163287

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/026153 Ceased WO2018030094A1 (fr) 2016-08-10 2017-07-19 Verre feuilleté pour véhicules

Country Status (2)

Country Link
JP (1) JP7011227B2 (fr)
WO (1) WO2018030094A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074638A1 (fr) * 2021-10-27 2023-05-04 Ａｇｃ株式会社 Verre borosilicaté
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH092846A (ja) * 1995-05-15 1997-01-07 Saint Gobain Vitrage 窓ガラス及びその製造方法
WO2012157610A1 (fr) * 2011-05-13 2012-11-22 日本電気硝子株式会社 Stratifié, procédé pour découper un stratifié, procédé pour traiter un stratifié, et dispositif et procédé pour découper un objet cassant de type plaque
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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5483262B2 (ja) 2009-12-04 2014-05-07 日本電気硝子株式会社 合わせガラス
US9387651B2 (en) 2012-09-26 2016-07-12 Corning Incorporated Methods for producing ion exchanged glass and resulting apparatus
CN106495507B (zh) 2015-09-07 2020-11-13 Ａｇｃ株式会社 夹层玻璃

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH092846A (ja) * 1995-05-15 1997-01-07 Saint Gobain Vitrage 窓ガラス及びその製造方法
WO2012157610A1 (fr) * 2011-05-13 2012-11-22 日本電気硝子株式会社 Stratifié, procédé pour découper un stratifié, procédé pour traiter un stratifié, et dispositif et procédé pour découper un objet cassant de type plaque
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074638A1 (fr) * 2021-10-27 2023-05-04 Ａｇｃ株式会社 Verre borosilicaté
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

Also Published As

Publication number Publication date
JP7011227B2 (ja) 2022-01-26
JPWO2018030094A1 (ja) 2019-06-06

Similar Documents

Publication Publication Date Title
JP6256763B2 (ja) 合わせガラス
CN105492205B (zh) 离子交换玻璃以及所得的制品
WO2017183381A1 (fr) Verre feuilleté pour véhicules
WO2018030093A1 (fr) Verre feuilleté pour véhicules
CN109250904A (zh) 制备经过离子交换的玻璃的方法以及所得装置
JPWO2017183382A1 (ja) 車両用合わせガラス
WO2018030095A1 (fr) Verre feuilleté pour véhicules
JP7011227B2 (ja) 車両用合わせガラス
JP2018145082A (ja) ガラス樹脂複合体
JP2019182692A (ja) ガラス板及びそれを用いたガラス樹脂複合体
WO2018193788A1 (fr) Composite verre-résine
JP7439054B2 (ja) 積層体用の軟質で化学強化可能なガラス
WO2024225086A1 (fr) Verre, verre de fenêtre pour véhicules, verre pour capteurs et verre feuilleté
JP2019151516A (ja) ガラス板及びそれを用いたガラス樹脂複合体
WO2019151000A1 (fr) Composite verre/résine
WO2018193721A1 (fr) Plaque de verre
WO2018163903A1 (fr) Composite verre-résine
JP6959566B2 (ja) ガラス板
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
WO2025142914A1 (fr) Verre feuilleté
WO2025142918A1 (fr) Verre pour construction, pour véhicule ou pour capteur, verre bombé, verre trempé par ventilation d'air froid, et verre feuilleté
JP2019172566A (ja) ガラス樹脂複合体
WO2025142920A1 (fr) Verre pour construction, pour véhicule ou pour capteur, et verre feuilleté
JP2024069067A (ja) ガラス板、曲げガラス、合わせガラス、車両用窓ガラス及び建築用窓ガラス

Legal Events

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

Ref document number: 2018532900

Country of ref document: JP

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

Ref document number: 17839167

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17839167

Country of ref document: EP

Kind code of ref document: A1