JP6256763B2 - Laminated glass - Google Patents

Description

  The present invention relates to a laminated glass, and more particularly to a laminated glass suitable for a windshield of a vehicle.

  A laminated glass formed by bonding an organic resin film between two glass plates 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 passenger jumps out of the vehicle due to the stretchability of the organic resin film There is an advantage that it can be prevented.

  For example, Patent Document 1 discloses a laminated glass in which the ratio of the thickness of the second glass plate to the thickness of the first glass plate is 0.6 to 0.9 in order to achieve both strength and thinning. Is disclosed. Further, in Patent Document 2, in order to improve crime prevention, the difference in thickness between the first glass plate and the second glass plate is set to 1.0 mm or more, and the thicker glass plate is set to the indoor side. Glass is disclosed.

  In recent years, in the automobile industry, from the environmental point of view, it is strongly demanded to improve fuel consumption by reducing the weight of the vehicle body. For this reason, weight reduction of parts related to automobiles is required more than ever, and the demand for laminated glass is no exception. In order to reduce the weight of the laminated glass, it is effective to reduce the thickness of the glass plate, but its realization is not easy from the viewpoint of safety and the like. Therefore, in order to reduce the thickness of the laminated glass, it is assumed that a thin air-cooled tempered glass is used as the glass plate.

  However, in a thin air-cooled tempered glass, it is difficult to form a temperature difference between the surface and the interior during heating, and it is difficult to increase the stress depth of the compressive stress layer. As a result, when the air-cooled tempered glass is thinned, it becomes difficult to maintain the strength of the laminated glass.

JP 2003-55007 A JP 2001-39743 A JP-A-11-286784 JP 2000-144116 A Japanese Patent Laid-Open No. 2001-17907

  By the way, when the water repellency of the laminated glass is increased, rainwater hardly remains on the surface of the windshield or the like, and a clear view can be secured.

  It is known that the wettability of a glass plate is affected by the roughness of the surface. That is, when the surface is roughened, the water repellency of the glass plate is improved. Conversely, when the surface is smoothed, the water repellency of the glass plate is lowered.

  For example, Patent Document 3 discloses that a treatment liquid containing fine metal particles and a silane compound is applied to a glass surface and dried to form a fine concavo-convex structure on the surface and increase the water repellency of the glass plate. ing. However, with this method, the transmitted light is likely to be scattered, and the transparency of the laminated glass may be reduced.

  Patent Document 4 discloses that a treatment liquid containing a polycondensate of trialkoxysilane is applied to a glass surface and subjected to heat treatment, thereby forming an uneven film on the surface and increasing the water repellency of the glass plate. ing. However, this method requires high-temperature heat treatment, which increases the manufacturing cost of laminated glass.

  Furthermore, in Patent Document 5, a treatment liquid containing an aluminum compound is applied to the glass surface to form a film, and immersed in warm water to form a fine concavo-convex structure on the surface, thereby improving the water repellency of the glass plate. It is disclosed to enhance. However, since this method requires a hot water supply device, the manufacturing cost of laminated glass increases.

  Therefore, the present invention has been made in view of the above circumstances, and an object is to create a laminated glass that can maintain strength even when it is thinned, has high water repellency, and can be manufactured at low cost.

The present inventors have found that the above technical problem can be solved by using a specific chemically strengthened glass as the glass plate, and propose the present invention. That is, the laminated glass of the present invention is a laminated glass comprising a first glass plate, a second glass plate, and an organic resin film sandwiched between the first glass plate and the second glass plate. The thickness of the glass plate is 2.0 mm or less, the first glass plate is chemically strengthened glass made of alkali aluminosilicate glass, the first glass plate has a compressive stress layer on the surface, The molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Li ₂ O + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the glass composition (total glass composition) of one glass plate is 0.1-2. . Here, “Al ₂ O ₃ + B ₂ O ₃ ” is the total amount of Al ₂ O ₃ and B ₂ O ₃ . “Li ₂ O + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO” is the total amount of Li ₂ O, Na ₂ O, K ₂ O, MgO, CaO, SrO and BaO. “(Al ₂ O ₃ + B ₂ O ₃ ) / (Li ₂ O + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO)” means that the total amount of Al ₂ O ₃ and B ₂ O ₃ is Li ₂ O, Na ₂ O, K ₂ O, MgO , CaO, SrO and BaO divided by the total amount.

  In the laminated glass of the present invention, the thickness of the first glass plate is 2.0 mm or less. Thereby, weight reduction of a laminated glass can be achieved.

  In the laminated glass of the present invention, the first glass plate is chemically strengthened glass made of alkali aluminosilicate glass. Thereby, even if the plate | board thickness of a 1st glass plate is small, since the compressive-stress layer can be formed appropriately, the intensity | strength of a laminated glass can be maintained.

Furthermore, the laminated glass of the present invention, the molar ratio of the glass in the composition of the first glass plate _{(Al 2 O 3 + B 2} O 3) / (Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO + BaO) is from 0.1 to 2. Thereby, since non-crosslinked oxygen in the glass is reduced, the water repellency of the glass plate can be increased without forming an uneven shape on the surface.

  FIG. 1 is a conceptual cross-sectional view for explaining a laminated glass of the present invention. The laminated glass 1 includes a first glass plate 2, a second glass plate 3, and an organic resin film 4 sandwiched between the first glass plate 2 and the second glass plate 3.

  In the laminated glass of the present invention, the first glass plate is chemically strengthened glass, but the second glass plate may not be chemically strengthened glass from the viewpoint of cost reduction. For example, the second glass plate may be general-purpose soda lime glass. However, in that case, the first glass plate is arranged outside the vehicle and the second glass plate is arranged inside the vehicle from the viewpoint of accurately enjoying the effects of the present invention.

Secondly, in the laminated glass of the present invention, the thickness of the second glass plate is 2.0 mm or less, the second glass plate is a chemically tempered glass made of alkali aluminosilicate glass, and the second glass The plate has a compressive stress layer on the surface, and the molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Li ₂ O + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the glass composition of the second glass plate is 0.1 to 2 It is preferable that

Third, in the laminated glass of the present invention, the molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the surface layer of the first glass plate is 0.3 to 2.0. Is preferred. The “molar ratio in the surface layer (Al ₂ O ₃ + B ₂ O ₃ ) / (Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO)” refers to a value analyzed with a wavelength dispersive electron beam microanalyzer, acceleration voltage is 10 kV, irradiation current is Assume that analysis is performed with 20 nA and a beam diameter of 50 μm.

Fourthly, in the laminated glass of the present invention, the molar ratio Na ₂ O / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the surface layer of the first glass plate is 0.020 or less. Is preferred. “SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO” means SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , Na ₂ O, K ₂ O, MgO, CaO, SrO and BaO. Total amount. “Na ₂ O / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO)” indicates that the content of Na ₂ O is SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , Na ₂ O, K _It refers to the value divided by the total amount of ₂ O, MgO, CaO, SrO and BaO. “Molar ratio in the surface layer Na ₂ O / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + Na ₂ O + M ₂ O + MgO + CaO + SrO + BaO)” refers to a value analyzed with a wavelength dispersive electron microanalyzer, acceleration voltage is 10 kV, irradiation current Is 20 nA and the beam diameter is 50 μm.

Fifth, in the laminated glass of the present invention, the first glass plate has a glass composition (total glass composition) of 50% by mass, SiO ₂ 50-80%, Al ₂ O ₃ 3-30%, B _{2. O 3 0~10%, Na 2 O} 5~20%, preferably contains K less than 2 O 0 to 2%.

  Sixth, in the laminated glass of the present invention, the thickness of the first glass plate is 0.3 to 1.0 mm, and the thickness of the second glass plate is 0.3 to 1.0 mm. Is preferred.

  Seventh, in the laminated glass of the present invention, the surface roughness Ra of the first glass plate is preferably 0.2 nm or less. Here, the “surface roughness Ra” can be measured, for example, by a method based on SEMI D7-97 “Method for measuring surface roughness of FPD glass substrate”.

  Eighth, the laminated glass of the present invention preferably has a β-OH value of the first glass plate of 0.60 or less. The “β-OH value” refers to a value obtained by measuring the transmittance of glass using FT-IR and using Equation 1 below. Thereby, since the moisture in the glass is reduced, the number of OH groups in the glass is reduced, and as a result, the water repellency of the glass plate can be enhanced without forming an uneven shape on the surface.

  Ninthly, the laminated glass of the present invention preferably has a compressive stress value of 600 MPa or more on the surface of the first glass plate and a stress depth of 5 μm or more. Here, 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.

  Tenth, in the laminated glass of the present invention, the resin forming the organic resin film is preferably an ethylene vinyl acetate copolymer or polyvinyl butyral.

  Eleventh, the laminated glass of the present invention preferably has a curved surface shape that is three-dimensionally curved.

  12thly, it is preferable to use the laminated glass of this invention for the windshield of a vehicle.

Thirteenth, the laminated glass of the present invention is a laminated glass comprising a first glass plate, a second glass plate, and an organic resin film sandwiched between the first glass plate and the second glass plate. The thickness of the first glass plate is 2.0 mm or less, the first glass plate is chemically strengthened glass made of alkali aluminosilicate glass, and the first glass plate has a compressive stress layer on the surface. The molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the surface layer of the first glass plate is 0.3 to 2.0.

Fourteenth, the laminated glass of the present invention is a laminated glass comprising a first glass plate, a second glass plate, and an organic resin film sandwiched between the first glass plate and the second glass plate. The thickness of the first glass plate is 2.0 mm or less, the first glass plate is chemically strengthened glass made of alkali aluminosilicate glass, and the first glass plate has a compressive stress layer on the surface. The molar ratio Na ₂ O / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the surface layer of the first glass plate is 0.020 or less.

It is a cross-sectional conceptual diagram for demonstrating the laminated glass of this invention. It is a conceptual perspective view which shows an example of the laminated glass of this invention.

  In the laminated glass of the present invention, the plate thickness of the glass plate (first glass plate and / or second glass plate) is preferably 2.0 mm or less, 1.5 mm or less, 1.2 mm or less, 1.0 mm or less. 0.7 mm or less, particularly 0.5 mm or less. Further, the 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 the plate thickness is too thick, it is difficult to reduce the weight of the laminated glass. On the other hand, if the plate thickness is too thin, it is difficult to obtain a desired mechanical strength. Therefore, the plate thickness of the glass plate is preferably 0.1 mm or more, 0.2 mm or more, 0.3 mm or more, and particularly preferably 0.4 mm or more. Moreover, the plate | board thickness of a laminated glass becomes like this. Preferably it is 0.5 mm or more, 0.8 mm or more, 1.0 mm or more, Most preferably, it is 1.2 mm or more.

  In particular, if both the first glass plate and the second glass plate are 1 mm or less, it becomes easy to elastically absorb the mechanical impact force. As a result, when applied to the windshield of a vehicle, the laminated glass is less likely to be damaged.

  In the laminated glass of the present invention, the first glass plate preferably has a compressive stress layer on the surface, and the second glass plate preferably has a compressive stress layer on the surface. As a method for forming a compressive stress layer on the surface, there are a physical strengthening method and a chemical strengthening method. In the present invention, the compressive stress layer is formed by the chemical strengthening method.

  The chemical strengthening method is a method in which alkali ions having a large ion radius are introduced to the surface of the glass by ion exchange treatment at a temperature below the strain point of the glass. If the compressive stress layer is formed by the chemical strengthening method, the compressive stress layer can be properly formed even when the thickness of the glass plate is small. A glass plate does not break easily like a physical strengthening method such as a cold strengthening method.

  In the laminated glass of the present invention, it is preferable that the first glass plate is alkali aluminosilicate glass and the second glass plate is 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. Further, since the devitrification resistance is good, it can be easily formed into a glass plate.

In the laminated glass of the present invention, the molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Li ₂ O + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the glass composition of the glass plate (first glass plate and / or second glass plate). ) Is preferably 0.1 to 2, 0.3 to 1.5, 0.5 to 1.3, 0.6 to 1.2, 0.7 to 1.1, particularly 0.8 to 1. is there. When the molar ratio is out of the predetermined range, non-crosslinked oxygen in the glass becomes excessive, and OH groups in the glass increase. As a result, the water repellency of the glass plate tends to decrease.

In the laminated glass of the present invention, the glass plate (first glass plate and / or second glass plate) is, as a glass composition, mass%, SiO ₂ 50 to 80%, Al ₂ O ₃ 3 to 30% ( preferably _{16-30% is), B 2 O 3 0~10%} ( preferably _{0.1~10%), Na 2 O 5~20} %, K 2 O 0~10% ( preferably less than 0-2% ) Is preferably contained. The reason for limiting the content range of each component as described above will be described below. In addition, in description of the containing range of each component,% display points out the mass% unless there is particular notice.

SiO ₂ is a component that forms a network of glass. The content of SiO ₂ is preferably 50 to 80%, 55 to 75%, 56 to 73%, 56 to 71%, 57 to 69%, 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 moldability tend to be lowered, and the thermal expansion coefficient becomes too low to make it difficult to match the thermal expansion coefficient of the surrounding materials.

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. When the content of Al ₂ O ₃ is too small, resulting is a possibility which can not be sufficiently exhibited ion exchange performance. Therefore, 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. On the other hand, when 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. Moreover, acid resistance also falls and it becomes difficult to apply to an acid treatment process. Furthermore, the high-temperature viscosity becomes high and the meltability tends to be lowered. Therefore, 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 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. However, when the content of B ₂ O ₃ is too large, coloring of the glass surface called burnt occurs due to ion exchange, water resistance is lowered, and the stress depth tends to be small. Therefore, 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%.

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 surrounding material. Furthermore, the low-temperature viscosity decreases too much, and stress relaxation is likely to occur, and the compressive stress value may decrease instead. Therefore, the content of Li ₂ O is preferably 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to less than 1.0%, 0 to 0.5%, 0 to 0.1%. In particular, 0 to 0.05%.

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, or reduced meltability, lowered coefficient of thermal expansion tends to decrease the ion exchange performance. 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, the thermal shock resistance is lowered, and it becomes difficult to match the thermal expansion coefficient of the surrounding materials. In addition, 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, if the content of K 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 surrounding materials. Moreover, there is a tendency that the strain point is excessively lowered, the component balance of the glass composition is lacking, and the devitrification resistance is lowered. Therefore, the upper limit range of K ₂ O is preferably 10% or less, 6% or less, 4% or less, less than 2%, particularly less than 1%. Incidentally, when adding _{K 2} O, the addition amount thereof is preferably 0.1% or more, 0.3% or more, particularly 0.5% or more.

  MgO is a component that lowers the viscosity at high temperature, increases meltability and moldability, and increases the strain point and Young's modulus. Among alkaline earth metal oxides, MgO is a component that has a large effect of improving ion exchange performance. is there. 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. Therefore, 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, 2.4% or less, 2.3% or less, particularly 2.2% or less.

  Compared with other components, CaO has a large effect of lowering the high temperature viscosity and improving the meltability and moldability, and increasing the strain point and Young's modulus without deteriorating devitrification resistance. However, if 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 easily devitrified, the ion exchange performance is lowered, There is a tendency to easily deteriorate 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%, in particular 0-0.1%.

  SrO is a component that lowers the viscosity at high temperature to increase meltability and moldability, and increases the strain point and Young's modulus. However, if its content is too large, the ion exchange reaction tends to be inhibited. As a result, the density and the coefficient of thermal expansion increase, and the glass tends to devitrify. Therefore, the content of SrO is preferably 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to 0.5%, 0 to 0.1%, particularly less than 0 to 0.1%. is there.

  BaO is a component that lowers the high-temperature viscosity to increase the meltability and moldability, and increases the strain point and Young's modulus. However, when there is too much content of BaO, an ion exchange reaction will become easy to be inhibited, and also a density and a thermal expansion coefficient will become high, or glass will become devitrified easily. Therefore, the content of BaO 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.

  When there is too much content of MgO + CaO + SrO + BaO, there exists a tendency for a density and a thermal expansion coefficient to become high, for glass to devitrify, or for ion exchange performance to fall. Therefore, the content of MgO + CaO + SrO + BaO is preferably 0 to 9.9%, 0 to 8%, 0 to 6%, particularly 0 to 5%.

The molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Li ₂ O + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) is preferably regulated as described above.

  In addition to the above components, for example, the following components may be added.

TiO ₂ is a component that enhances ion exchange performance and a component that lowers the high-temperature viscosity. However, if its content is too large, the glass tends to be colored or devitrified. 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 is a component that increases the viscosity and strain point near the liquid phase viscosity. However, if its content is too large, the devitrification resistance may be significantly reduced. There is also a possibility that the density becomes too high. Therefore, the content of ZrO ₂ is preferably 0 to 5% 0 to 4%, 0 to 3%, particularly 0.001 to 2%.

  ZnO is a component that enhances the 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. However, when the content of P ₂ O ₅ is too large, or glass phase separation, the water resistance tends to decrease. Therefore, the content of P ₂ O ₅ is preferably 0 to 3%, 0 to 1%, particularly 0 to 0.5%.

SnO ₂ has an effect of improving ion exchange performance. Therefore, the content of SnO ₂ is preferably 0 to 3%, 0.01 to 3%, 0.05 to 3%, 0.1 to 3%, particularly 0.2 to 3%.

As a clarifier, one or more selected from the group of Cl, SO ₃ and CeO ₂ (preferably a group of Cl and SO ₃ ) may be added in an amount of 0 to 3%.

From the viewpoint of simultaneously enjoying the clarification effect and the effect of improving the ion exchange performance, the content of SnO ₂ + SO ₃ + Cl is preferably 0.01 to 3%, 0.05 to 3%, particularly 0.1 to 3%. 0.2 to 3%. “SnO ₂ + SO ₃ + Cl” is the total amount of SnO ₂ , Cl and SO 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. If it does in this way, the transmittance | permeability (400-770 nm) in board thickness 1mm will become easy to improve (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.

From the environmental consideration, it is preferable that the glass composition does not substantially contain As ₂ O ₃ , Sb ₂ O ₃ , PbO, and F. Moreover, environmental considerations, it is also preferable to contain substantially no Bi ₂ O _3. “Substantially free of” means that, although no explicit component is positively added as a glass component, it is allowed to be mixed as an impurity. Specifically, the content of the explicit component is It indicates less than 0.05%.

  The surface layer of the glass plate is in direct contact with water or the like. Therefore, in order to increase the water repellency of the glass plate, it is preferable to regulate the glass composition of the surface layer. In addition, since the glass composition of the surface layer of a glass plate receives influence of an ion exchange process etc., it will differ from the glass composition inside said glass plate. Hereinafter, the glass composition of the surface layer will be described.

The molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) of the surface layer is preferably 0.3 to 2.0, 0.4 to 1.8, 0.5 to 1.6, 0.6 to 1.4, 0.7 to 1.2, 0.8 to 1.0, particularly 0.85 to 0.95. When the molar ratio is out of the predetermined range, the non-crosslinked oxygen in the surface glass becomes excessive, and the OH groups in the surface layer increase. As a result, the water repellency of the glass plate tends to decrease. The molar ratio of the surface layer (Al ₂ O ₃ + B ₂ O ₃ ) / (Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) can be adjusted by the overall glass composition and ion exchange conditions.

The molar ratio of the surface layer Na ₂ O / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) is preferably 0.020 or less, 0.018 or less, 0.016 or less, 0.014 or less, 0 0.013 or less, 0.012 or less, particularly 0.011 or less. When the Na concentration in the surface layer is too high, sodium ions in the glass are likely to react with water in the air, so that the hydrophilicity of the surface is easily improved, and as a result, the water repellency of the glass plate is likely to be reduced.

  Various methods can be used as a method for reducing the Na concentration in the surface layer. In addition to controlling the ion exchange conditions, for example, a method of deionizing by corona discharge, a method of deionizing by plasma, high-temperature steam And the like. Note that the K concentration of the surface layer can be adjusted by adjusting the ion exchange conditions.

The molar ratio of the surface layer (Na ₂ O + K ₂ O) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) is preferably 0.30 or less, 0.25 or less, 0.23 or less, 0. 20 or less, 0.17 or less, 0.16 or less, particularly 0.15 or less. When the alkali concentration of the surface layer is too large, alkali ions in the glass easily react with water in the air, so that the hydrophilicity of the surface is easily improved, and as a result, the water repellency of the glass plate is easily lowered. “Na ₂ O + K ₂ O” is the total amount of Na ₂ O and K ₂ O. “(Na ₂ O + K ₂ O) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO)” represents the total amount of Na ₂ O and K ₂ O as SiO ₂ , Al ₂ O ₃ , B _2. It is the value divided by the total amount of O ₃ , Na ₂ O, K ₂ O, MgO, CaO, SrO and BaO.

  In the laminated glass of the present invention, the glass plate (first glass plate and / or second glass plate) preferably has, for example, the following characteristics.

  The β-OH value is preferably 0.60 / mm or less, 0.50 / mm or less, 0.45 / mm or less, 0.4 / mm or less, 0.35 / mm or less, 0.3 / mm or less, They are 0.25 / mm or less, 0.2 / mm or less, and 0.18 / mm or less. The smaller the β-OH value, the higher the water repellency of the glass plate. On the other hand, when the β-OH value is too small, the meltability is lowered and the productivity of the glass plate is easily lowered. Therefore, the β-OH value is preferably 0.01 / mm or more, 0.02 / mm or more, 0.03 / mm or more, particularly 0.05 / mm or more.

The β-OH value is determined by (1) selecting a raw material having a high water content (for example, a hydroxide raw material), (2) adding water to the raw material, and (3) a component for reducing the water content in the glass (Cl , SO ₃ etc.) to reduce or avoid the use of (4) oxyfuel combustion at the time of melting, or direct introduction of steam into the melting furnace, furnace atmosphere It can be increased by increasing the amount of moisture in the glass, (5) performing steam bubbling in the molten glass, (6) employing a large melting furnace, or slowing the flow rate of the molten glass. Therefore, if the operation opposite to the above operations (1) to (6) is performed, the β-OH value can be lowered. That is, the β-OH value is selected from (7) a raw material having a low water content, (8) no moisture added to the raw material, and (9) a component that reduces the moisture content in the glass (Cl, SO ₃ etc.) (10) Decrease the amount of water in the furnace atmosphere, (11) Perform N ₂ bubbling in the molten glass, (12) Adopt a small melting furnace or change the flow rate of the molten glass It can be reduced by increasing the speed.

  The surface roughness Ra of the surface is preferably 0.5 nm or less, 0.3 nm or less, particularly 0.2 nm or less. If it does in this way, it will become difficult to break a glass plate. If the surface roughness Ra is small, the water repellency may be lowered. However, in the present invention, the OH group in the surface layer is reduced, so that the water repellency is maintained even if the surface is smooth. can do.

  After the surface cleaning, the contact angle with water after standing for 1 month at a temperature of 23 ° C. and a humidity of 50% is preferably 35 ° or more, 37 ° or more, 40 ° or more, 45 ° or more, 50 ° or more, 53 ° In particular, the angle is preferably 55 ° or more. If this contact angle is too small, the water repellency tends to decrease. In addition, the measurement of a contact angle shall be performed by dripping 3 microliters of pure waters on the surface of a glass plate using Kyowa Interface Science Co., Ltd. automatic contact angle meter DMe-200.

  From the viewpoint of accurately enjoying the effects of the present invention, it is preferable that a functional film such as a water-repellent film is not formed on the surface of the glass plate opposite to the organic resin film. For example, when used for a windshield of a vehicle, it is preferable that a functional film such as a water-repellent film is not formed on the surface of the vehicle exterior and / or the interior.

The compressive stress value of the compressive stress layer is preferably 300 MPa or more, 600 MPa or more, 700 MPa or more, 800 MPa or more, particularly 900 MPa or more. The larger the compressive stress value, the higher the mechanical strength of the glass plate. On the other hand, when an extremely large compressive stress is formed on the surface, the tensile stress inherent in the glass plate becomes extremely high, and the glass plate may be self-destructed. Therefore, the compressive stress value of the compressive stress layer is preferably 1200 MPa or less. If the content of Al ₂ O ₃ , TiO ₂ , ZrO ₂ , MgO, ZnO in the glass composition is increased or the content of SrO, BaO is decreased, the compressive stress value tends to increase. Further, if the ion exchange time is shortened or the temperature of the ion exchange solution is lowered, the compressive stress value tends to increase.

The stress depth is preferably 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, particularly 30 μm or more. As the stress depth increases, even if the glass plate is deeply scratched, the glass plate becomes difficult to break and the variation in mechanical strength is reduced. On the other hand, as the stress depth increases, the tensile stress inherent in the glass plate becomes extremely high, and the glass plate may be self-destructed. Therefore, the stress depth is preferably 60 μm or less. In addition, if the content of K ₂ O or P ₂ O _{5 in} the glass composition is increased or the content of SrO or BaO is decreased, the stress depth tends to increase. Moreover, if the ion exchange time is lengthened or the temperature of the ion exchange solution is increased, the stress depth tends to increase.

  The internal tensile stress value 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, glass fragments are shattered at the time of breakage, and when used for a vehicle, the field of view may be temporarily deteriorated, resulting in a very dangerous state. The internal tensile stress value is a value calculated from the following formula 2.

Density 2.6 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, in particular 2.45 g / cm ³ or less Is preferred. A glass plate can be reduced in weight, so that a density is small. In addition, the content of SiO ₂ , B ₂ O ₃ , P ₂ O _{5 in} the glass composition is increased, or the content of alkali metal oxide, alkaline earth metal oxide, ZnO, ZrO ₂ , TiO ₂ is decreased. As a result, the density tends to decrease.

The thermal expansion coefficient in the temperature range of 25 to 380 ° C. is preferably 100 × 10 ⁻⁷ / ° C. or lower, 95 × 10 ⁻⁷ / ° C. or lower, 90 × 10 ⁻⁷ / ° C. or lower, particularly 85 × 10 ⁻⁷ / ° C. It is as follows. If the thermal expansion coefficient is regulated within the above range, it becomes easy to match the thermal expansion coefficient of the organic resin film, and it becomes easy to prevent the glass plate and the organic resin film from peeling off. If the content of alkali metal oxides and alkaline earth metal oxides in the glass composition is increased, the coefficient of thermal expansion tends to increase, and conversely the content of alkali metal oxides and alkaline earth metal oxides is reduced. If it decreases, the thermal expansion coefficient tends to decrease. The “thermal expansion coefficient in the temperature range of 25 to 380 ° C.” can be measured with a dilatometer or the like.

The liquidus temperature 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. In addition, devitrification resistance and a moldability improve, so that liquidus temperature is low. Also, increase the content of Na ₂ O, K ₂ O, B ₂ O _{3 in} the glass composition or reduce the content of Al ₂ O ₃ , Li ₂ O, MgO, ZnO, TiO ₂ , ZrO _2. In this case, the liquidus temperature tends to decrease. 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. In addition, devitrification resistance and a moldability improve, so that liquid phase viscosity is high. Also, if the content of Na ₂ O, K ₂ O in the glass composition is increased or the content of Al ₂ O ₃ , Li ₂ O, MgO, ZnO, TiO ₂ , ZrO ₂ is reduced, the liquidus viscosity Tends to be high. “Liquid phase temperature” passes through a standard sieve 30 mesh (500 μm sieve opening), puts the glass powder remaining in 50 mesh (300 μm sieve sieve) into a platinum boat, and holds it in a temperature gradient furnace for 24 hours. The value at which the temperature at which crystals precipitate is measured. “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 is preferably 65 GPa or more, 69 GPa or more, 71 GPa or more, 75 GPa or more, particularly 77 GPa or more. As the Young's modulus is higher, the glass plate is more difficult to bend and the glass plate is less likely to be deformed by its own weight. The “Young's modulus” can be measured by a resonance method or the like.

  In the laminated glass of the present invention, the thickness of the organic resin film is preferably 0.1 to 2 mm, 0.3 to 1.5 mm, 0.5 to 1.2 mm, and 0.6 to 0.9 mm. If the thickness of the organic resin film is too small, the impact absorbability tends to be lowered, and the stickiness tends to vary, so that the glass plate and the organic resin film are easily peeled off. On the other hand, when the thickness of the organic resin film is too large, the visibility of the laminated glass tends to be lowered.

  Various materials can be used as the organic resin film, for example, polyethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polystyrene (PS), methacrylic resin (PMA), polyvinyl chloride. (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), cellulose acetate (CA), diallyl phthalate resin (DAP), urea resin (UP), melamine resin (MF), 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), polyfluoride Bi Used for redene (PVDF), methacryl-styrene copolymer resin (MS), polyarate (PAR), polyallylsulfone (PASF), polybutadiene (BR), polyethersulfone (PESF), or polyetheretherketone (PEEK) Is possible. Among these, EVA and PVB are preferable from the viewpoint of transparency and adhesiveness, and PVB is particularly preferable because it can provide sound insulation.

  A colorant may be added to the organic resin film, or an absorber that absorbs light of a specific wavelength such as infrared rays or ultraviolet rays may be added.

  The laminated glass of the present invention can be produced as follows.

  First, the glass raw material prepared so as to become alkali aluminosilicate glass is put into a continuous melting furnace, heated and melted at 1500 to 1700 ° C., clarified and stirred, and then supplied to a molding apparatus to be formed into a flat plate shape or the like. By slowly cooling, an unchemically strengthened glass plate can be produced.

  As a method of forming into a flat plate shape, it is preferable to employ an overflow down draw method. 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.

  In addition to the overflow downdraw method, various molding methods can be employed. For example, a forming method such as a float method, a downdraw method (slot down method, redraw method, etc.), a rollout method, a press method, or the like can be employed.

Next, chemically tempered glass can be produced by subjecting the obtained unchemically tempered glass plate to ion exchange treatment. The conditions for the ion exchange treatment are not particularly limited, and an optimum condition may be selected in consideration of the viscosity characteristics, application, thickness, internal tensile stress, dimensional change, and the like of the glass. For example, the ion exchange treatment can be performed by immersing in KNO ₃ molten salt at 390 to 500 ° C. for 1 to 8 hours. In particular, when 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.

  Subsequently, two chemically strengthened glass plates are laminated and integrated with an organic resin film to obtain a laminated glass. Examples of the lamination integration method include a method in which an organic resin is injected between two glass plates and then the organic resin is cured, a method in which an organic resin sheet is disposed between the two glass plates, and a pressure heat treatment method. The latter method is preferable because stacking and integration are easier.

  The windshield of a vehicle often has a curved shape that is curved three-dimensionally. The curved surface processing is performed, for example, by giving a curved surface shape to an unchemically strengthened glass plate and performing ion exchange treatment to obtain a chemically strengthened glass plate having a curved surface shape, and then, two glass plates and an organic resin film. And a method of obtaining laminated glass by laminating and integrating a non-chemically strengthened glass plate by ion exchange treatment to obtain a chemically strengthened glass plate, and then adding a curved shape to the glass plate. Although the method of laminating and integrating two glass plates and an organic resin film to obtain laminated glass is mentioned, the former method is preferable because the compressive stress layer does not disappear during curved surface processing.

  Various methods can be employed as a method of processing the curved surface. In particular, 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. Also preferred is a method of softening and deforming the glass plate by its own weight along the shape of the mold by heat-treating a part or the whole of the glass plate after arranging the glass plate on the mold having a predetermined shape. If it does in this way, the efficiency of curved surface processing can be raised.

  FIG. 2 is a conceptual perspective view showing an example of the laminated glass of the present invention. The laminated glass 10 includes a first glass plate 11, a second glass plate 12, and an organic resin film 13 sandwiched between the first glass plate 11 and the second glass plate 12, It has a shape suitable for an automobile windshield. And as for the laminated glass 10, the whole board width direction curves in the circular arc shape, and the whole length direction curves in the circular arc shape.

  Hereinafter, based on an Example, this invention is demonstrated in detail. The following examples are merely illustrative. The present invention is not limited to the following examples.

  Table 1 shows the glass composition and glass characteristics of the glass plates (Sample Nos. A to D).

  Each sample was produced as follows. First, glass raw materials are prepared so that the entire glass composition in the table is obtained, and after each glass raw material is prepared, melted, clarified, stirred, supplied, the resulting molten glass is formed into a plate shape by the overflow down draw method. Thus, glass plates having various thicknesses were obtained. Various characteristics were evaluated about the obtained glass plate.

  The density ρ is a value measured by the well-known Archimedes method.

  The thermal expansion coefficient α 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 known resonance method.

  The liquid phase temperature TL passes through a standard sieve 30 mesh (a sieve opening of 500 μm), and glass powder remaining in a 50 mesh (a sieve opening of 300 μm) 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 η _TL is a value obtained by measuring the viscosity of the glass at the liquidus temperature by a platinum ball pulling method.

  The β-OH value is a value obtained by measuring the transmittance of glass using FT-IR and using Equation 1 above. Note that the β-OH value is adjusted by the glass material (ratio of hydroxide and hydrate material).

Subsequently, after both surfaces of each sample were subjected to optical polishing, ion exchange treatment was performed by immersing in KNO ₃ molten salt (new KNO ₃ molten salt) at 430 ° C. for 4 hours. The surface of each sample was washed after the ion exchange treatment. Subsequently, the compressive stress value CS and the stress depth DOL of the compressive stress layer on the surface were calculated from the number of interference fringes observed using a surface stress meter (FSM-6000 manufactured by Orihara Seisakusho Co., Ltd.). In the calculation, the refractive index of each sample was 1.5, and the optical elastic constant was 30 [(nm / cm) / MPa]. Furthermore, about the sample B, the Na density | concentration of surface layer was reduced by making it contact with high temperature water vapor | steam after an ion exchange process.

  For the samples A to C after the ion exchange treatment, the glass composition of the surface layer was measured. The measured value indicates the value analyzed with a wavelength dispersion electron beam microanalyzer, and the analysis was performed with an acceleration voltage of 10 kV, an irradiation current of 20 nA, and a beam diameter of 50 μm. For reference, the Si-Kα detection depth of samples A to C calculated by simulation (electron range method: electron microanalyzer manufactured by Shimadzu Corporation) is 2.2 μm, detection of Al-Kα. Depth is 2.2 μm, B-Kα detection depth is 2.3 μm, Na-Kα detection depth is 2.3 μm, K-Kα detection depth is 1.9 μm, Mg-Kα detection depth Was 2.3 μm, the detection depth of Ca-Kα was 1.8 μm, the detection depth of Sr-Lα was 2.2 μm, and the detection depth of Ba-Lα was 1.6 μm.

  The glass after the ion exchange treatment has a microscopically different glass composition in the surface layer portion, but the influence is slight when viewed as a whole.

  Using the samples A to D after chemical strengthening and the organic resin film shown in Table 2, laminated glasses (Sample Nos. 1 to 9) shown in Table 2 were produced. The two glass plates and the organic resin film were laminated and integrated by pressure and heat treatment.

  Sample No. About 1-9, water repellency was evaluated. Specifically, 3 μl of pure water was dropped on the surface of the first glass plate and left for one month at a temperature of 23 ° C. and a humidity of 50%, and then the contact angle of the water droplet with the glass plate was determined as Kyowa Interface Science Co., Ltd. It was measured with a company-made automatic contact angle meter DMe-200, and 37 ° or more was evaluated as “◯”, and less than 37 ° was evaluated as “×”.

  As apparent from Table 2, the sample No. Although 1-8 did not have uneven | corrugated shape on the surface, it showed water repellency. On the other hand, sample No. No. 9 had poor water repellency evaluation.

  The laminated glass of the present invention is suitable for a windshield of a vehicle (particularly an automobile), but is also suitable for a rear glass and a door glass of a vehicle. Furthermore, the laminated glass of the present invention can be applied to architectural window glass and cover glass for touch panel displays.

1, 10 Laminated glass 2, 11 First glass plate 3, 12 Second glass plate 4, 13 Organic resin film

Claims (14)

In a laminated glass comprising a first glass plate, a second glass plate, and an organic resin film sandwiched between the first glass plate and the second glass plate,
The thickness of the first glass plate is 2.0 mm or less,
The first glass plate is a chemically strengthened glass made of alkali aluminosilicate glass,
The first glass plate has a compressive stress layer on the surface,
First molar ratio in the glass composition of the glass plate _{(Al 2 O 3 + B 2} O 3) / (Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO + BaO) Ri is 0.3-1.2 der,
The β-OH value of the first glass plate is 0.60 / mm or less,
A laminated glass, wherein the second glass plate is a chemically strengthened glass made of alkali aluminosilicate glass. Plate thickness der less 2.0mm the second glass plate is,
The second glass plate has a compressive stress layer on its surface;
The molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / ( Li ₂ O + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the glass composition of the second glass plate is from 0.1 to 2, Laminated glass as described. _3. The molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the surface layer of the first glass plate is 0.3 to 2.0. 3. Laminated glass. The molar ratio Na ₂ O / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the surface layer of the first glass plate is 0.020 or less. Laminated glass according to crab. The first glass plate, as a glass composition, in _{mass%, SiO 2 50~80%, Al} 2 O 3 3~30%, B 2 O 3 0~10%, Na 2 O 5~20%, K 2 The laminated glass according to any one of claims 1 to 4, comprising O 0 to less than 2%.   The thickness of the first glass plate is 0.3 to 1.0 mm, and the thickness of the second glass plate is 0.3 to 1.0 mm. Laminated glass according to crab.   The laminated glass according to any one of claims 1 to 6, wherein the surface roughness Ra of the first glass plate is 0.2 nm or less. The laminated glass according to any one of claims 1 to 7, wherein the? -OH value of the first glass plate is 0.50 / mm or less.   The laminated glass according to claim 1, wherein the first glass plate has a compressive stress value of 600 MPa or more and a stress depth of 5 μm or more.   The laminated glass according to any one of claims 1 to 9, wherein the resin forming the organic resin film is an ethylene vinyl acetate copolymer or polyvinyl butyral.   The laminated glass according to claim 1, which has a curved surface shape that is three-dimensionally curved.   It uses for the windshield of a vehicle, The laminated glass in any one of Claims 1-11 characterized by the above-mentioned. In a laminated glass comprising a first glass plate, a second glass plate, and an organic resin film sandwiched between the first glass plate and the second glass plate,
The thickness of the first glass plate is 2.0 mm or less,
The first glass plate is a chemically strengthened glass made of alkali aluminosilicate glass,
The first glass plate has a compressive stress layer on the surface,
Molar ratio _{(Al 2 O 3 + B 2} O 3) / (Na 2 O + K 2 O + MgO + CaO + SrO + BaO) is from 0.3 to 2.0 der in the surface layer of the first glass plate is,
The molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Li ₂ O + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the glass composition of the first glass plate is 0.3 to 1.2,
The β-OH value of the first glass plate is 0.60 / mm or less,
A laminated glass, wherein the second glass plate is a chemically strengthened glass made of alkali aluminosilicate glass. In a laminated glass comprising a first glass plate, a second glass plate, and an organic resin film sandwiched between the first glass plate and the second glass plate,
The thickness of the first glass plate is 2.0 mm or less,
The first glass plate is a chemically strengthened glass made of alkali aluminosilicate glass,
The first glass plate has a compressive stress layer on the surface,
The molar ratio _{Na 2 O / (SiO 2 +} Al 2 O 3 + B 2 O 3 + Na 2 O + K 2 O + MgO + CaO + SrO + BaO) 0.020 der less in the surface layer of the first glass plate is,
The molar ratio (Al ₂ O ₃ + B ₂ O ₃ ) / (Li ₂ O + Na ₂ O + K ₂ O + MgO + CaO + SrO + BaO) in the glass composition of the first glass plate is 0.3 to 1.2,
The β-OH value of the first glass plate is 0.60 / mm or less,
A laminated glass, wherein the second glass plate is a chemically strengthened glass made of alkali aluminosilicate glass.