JP7011227B2 - Laminated glass for vehicles - Google Patents

Description

The present invention relates to a laminated glass for vehicles, and particularly to a laminated glass for vehicles suitable for a windshield of an automobile.

For the windshield of an automobile, laminated glass in which two glass plates are integrated via an organic resin intermediate layer is used. Laminated glass can ensure good visibility even if a part of the glass plate is damaged, and even if the glass plate breaks in the event of an accident, the elasticity of the organic resin intermediate layer allows passengers to go out of the vehicle. It has the advantage of being able to prevent it from popping out.

For example, in Patent Document 1, in order to prevent the organic resin intermediate layer from breaking when the airbag is unfolded, 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. Laminated glass is disclosed. Further, in Patent Document 2, in order to improve crime prevention and the like, the difference in thickness between the inner glass plate and the outer glass plate is set to 1.0 mm or more, and the thickness of the inner glass plate is larger than the plate thickness of the outer glass plate. Enlarged laminated glass is disclosed.

Japanese Patent Application Laid-Open No. 2003-55507 Japanese Unexamined Patent Publication No. 2001-39743

In recent years, in the automobile industry, there is a strong demand for improving fuel efficiency by reducing the weight of the vehicle body. As a result, weight reduction of automobile-related parts is required more than ever. The demand for laminated glass is no exception. In order to reduce the weight of laminated glass, it is effective to reduce the thickness of the glass plate, but it is not easy to realize it from the viewpoint of safety and the like. At present, in order to reduce the thickness of laminated glass, it is assumed that thin physically tempered glass is used as the glass plate. However, with thin physically tempered glass, it is difficult to form a temperature difference between the surface and the inside during heat treatment, so it is difficult to increase the stress depth of the compressive stress layer. As a result, it becomes difficult to maintain the strength of the laminated glass.

Further, as described above, the laminated glass has an organic resin intermediate layer in the plane, and this organic resin intermediate layer exhibits a shock absorbing effect. On the other hand, 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 of damage starting from the end face. In particular, if an impact is applied to the end face of a thin tempered glass plate, damage may occur starting from the end face and the glass piece may fall off, damaging the human body. Further, when laminated glass provided with a thin tempered glass plate is used for the door glass of an automobile, an impact is applied to the end face of the glass plate each time the door is closed, and there is a risk of damage starting from the end face.

As a measure to reduce such damage, it is effective to use a tempered glass plate and increase the stress depth of the end face so that cracks do not grow from the end face. However, when the stress depth of the end face is increased, the internal tensile stress value is increased, and the tempered glass plate is liable to self-destruct due to the point impact. In particular, the thinner the tempered glass plate, the more remarkable the tendency.

Therefore, the present invention has been made in view of the above circumstances, and its technical problem is to provide a laminated glass for vehicles that can achieve both high strength and thinness and is not easily damaged even when an impact is applied to the end face. It is to invent.

The present inventors have solved the above technical problems by laminating and integrating two tempered glass plates and further restricting the average compressive stress of the tempered glass plate having a depth of 7 to 16 μm, which should be inside the vehicle, within a predetermined range. We find that it can be solved and propose it as the present invention. That is, the laminated glass for vehicles of the present invention is a laminated glass for vehicles in which an inner tempered glass plate and an outer tempered glass plate are integrated by an organic resin intermediate layer, and has a depth of 7 to 16 μm away from the surface of the inner tempered glass plate. It is characterized in that the average value of compressive stress at the position is 350 MPa or more. By doing so, even if the thickness of the tempered glass plate is small, the end face strength can be maintained, and the granular glass pieces are less likely to fall off when broken. If the conditions of the ion exchange treatment are strictly regulated (preferably, the conditions of each ion exchange treatment are strictly regulated by performing the ion exchange treatment a plurality of times), 7 to 16 μm from the surface of the inner tempered glass plate. It becomes easy to regulate the average value of compressive stress at separated depth positions to 350 MPa or more.

Here, the "compressive stress value" and the "stress depth" are the number of interference fringes observed when the measurement sample is observed using the soft FsmV of a surface stress meter (FSM-6000LE manufactured by Orihara Seisakusho Co., Ltd.). In the measurement, the measurement setting (strengthening type) is set to chemical strengthening II, the measurement mode is set to the exact solution mode, and the bending point position is used to calculate the boundary position of the depth measurement. Then, the value of DOL_zero calculated by FsmV is adopted as the “stress depth”. Further, as 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 of the present invention. The laminated glass 10 for a vehicle 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 compressive stress at a depth position 7 to 16 μm away from the surface thereof is 350 MPa or more. The laminated glass 10 for vehicles is convex on the outer tempered glass plate 12 side, and the entire plate width direction is curved in an arc shape, and the entire length direction is curved in an arc shape.

Further, in the laminated glass for vehicles of the present invention, it is preferable that the inner tempered glass plate is alkaline aluminum nosilicate glass and the outer tempered glass plate is soda lime glass.

Further, in the laminated glass for vehicles of the present invention, the inner tempered glass plate has a glass composition of SiO ₂ 40 to 80%, Al ₂ O ₃ 3 to 30%, B ₂ O ₃₀ to 10%, by mass%. It preferably contains Na ₂ O 5 to 20% and K ₂ O 0 to 5%.

Further, in the laminated glass for vehicles of the present invention, it is preferable that the thickness of the inner tempered glass plate is smaller than the thickness of the outer tempered glass plate.

Further, in the laminated glass for vehicles of the present invention, it is preferable that 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 laminated and integrated after bending to form laminated glass, the dimensional difference between the outer tempered glass plate and the inner tempered glass plate becomes smaller, and the end faces of both are easily aligned. As a result, the end face strength of the laminated glass processed by the curved surface is improved.

Further, in the laminated glass for vehicles of the present invention, it is preferable that the end faces of the inner tempered glass plate and the outer tempered glass plate are chamfered.

Further, in the laminated glass for vehicles of the present invention, it is preferable that a part of the organic resin intermediate layer protrudes to the outside of the end surface of the outer tempered glass plate.

Further, in the laminated glass for vehicles of the present invention, it is preferable that the organic resin layer is composed of an ethylene-vinyl acetate copolymer or polyvinyl butyral.

Further, the laminated glass for vehicles of the present invention preferably has a three-dimensionally curved curved surface shape.

Further, the laminated glass for vehicles of the present invention is preferably used for the windshield of an automobile.

Further, the laminated glass for vehicles of the present invention is preferably used for the door glass of an automobile.

It is a schematic diagram which shows an example of the laminated glass for a vehicle of this invention. It is explanatory drawing for demonstrating the end face strength test in the column of Example 1, and (a) is a conceptual perspective view which shows the shape of the test jig and the test head which sandwiched the test piece. (B) is a conceptual cross-sectional view showing a collision state of an end face strength test. It is a graph which shows the relationship between the average value of compressive stress at a depth position 7 to 16 μm away from a surface, and the average fracture height in an end face strength test.

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. As a method for forming a compressive stress layer on the surface, there are physical strengthening treatment and chemical strengthening treatment (ion exchange treatment), and any strengthening treatment may be used.

The ion exchange treatment is a method of introducing alkaline ions having a large ionic radius into the glass surface by ion exchange at a temperature equal to or lower than the strain point of the glass plate. With the ion exchange treatment, the compressive stress layer can be appropriately formed even when the thickness of the glass plate is small. 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 quenching the glass after processing a curved surface particularly at a temperature near the softening point of the glass plate. If it is a physical strengthening process, the stress depth of the compressive stress layer can be increased.

In the inner tempered glass plate according to the present invention, the average value of compressive stress at a depth position 7 to 16 μm away from the surface, that is, at a depth of 7 to 16 μm from the surface is 350 MPa or more, preferably 400 MPa or more, 450 MPa or more. It is 500 MPa or more, 520 MPa or more, 550 MPa or more, and particularly preferably 570 MPa or more. If the average value of the compressive stress at a depth position 7 to 16 μm away from the surface is too low, the end face strength tends to decrease. On the other hand, if the average value of the compressive stress at a depth position 7 to 16 μm away from the surface is too large, the internal tensile stress may become extremely high. Therefore, the average value of compressive stress at a depth position 7 to 16 μm away from the surface is preferably 1000 MPa or less.

In the inner tempered glass plate according to the present invention, the compressive stress value at a depth position 7 μm away from the surface, that is, at a depth of 7 μm 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, in particular. It is preferably 700 MPa or more. If the compressive stress value at a depth position 7 μm 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 7 μm away from the surface is too large, the internal tensile stress may become extremely high. Therefore, the compressive stress value at a depth position 7 μm away from the surface is preferably 1000 MPa or less.

In the inner tempered glass plate according to the present invention, the compressive stress value at a depth position 12 μm away from the surface, that is, at a depth of 12 μm 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 mentioned above, it is particularly preferably 550 MPa or more. If the compressive stress value at a depth position 12 μm 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 12 μm away from the surface is too large, the internal tensile stress may become extremely high. Therefore, the compressive stress value at a depth position 12 μm away from the surface is preferably 1000 MPa or less. The compressive stress value at a depth position 12 μm away from the surface has a higher correlation with the end face strength than the compressive stress value at another depth position.

In the inner tempered glass plate according to the present invention, the compressive stress value at a depth position 16 μm away from the surface, that is, at a depth of 16 μm from the surface is preferably 250 MPa or more, 320 MPa or more, 360 MPa or more, 400 MPa or more, particularly. It is preferably 430 MPa or more. If the compressive stress value at a depth position 16 μm 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 μm away from the surface is too large, the internal tensile stress may become extremely high. Therefore, the compressive stress value at a depth position 16 μm away from the surface is preferably 800 MPa or less. The compressive stress value at a depth position 16 μm away from the surface has a stronger correlation with the end face strength than the compressive stress value 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. By doing so, it is possible to reduce the internal tensile stress while increasing the average value and stress depth of the compressive stress at the depth position 7 to 16 μm away from the surface. When the ion exchange treatment is performed a plurality of times, the compressive stress curve in the depth direction from the surface can be bent.

When performing a plurality of ion exchange treatments, the temperature of the final 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 of the final ion exchange treatment is preferably 1.5 to 5 hours, particularly 2 to 4.5 hours. By doing so, it becomes easy to increase the average value of the compressive stress at a depth position 7 to 16 μm away from the surface.

When performing the ion exchange treatment a plurality of times, it is preferable to perform the ion exchange treatment twice. By doing so, the compressive stress curve in the depth direction from the surface can be efficiently bent.

When the ion exchange treatment is performed twice, the proportion of small alkaline ions (for example, Li ion, Na ion, especially Na ion) in the ion exchange liquid used for the second ion exchange treatment is the ion used for the first ion exchange treatment. It is preferably less than that in the exchange. This makes it easy to increase the average value of compressive stress at a depth position 7 to 16 μm away from the surface. The magnitude of the alkali ion is Li ion <Na ion <K ion.

When the ion exchange treatment is performed twice, the content of KNO ₃ in the ion exchange liquid used for the first ion exchange treatment is preferably less than 75% by mass, 70% by mass or less, and particularly 60% by mass or less. The content of KNO ₃ in the ion exchange liquid 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. When the content of KNO ₃ in the ion exchange liquid is out of the above range, it becomes difficult to increase the average value of compressive stress at a depth position 7 to 16 μm away from the surface.

When the ion exchange treatment is performed twice, the content of NaNO ₃ in the ion exchange liquid used for the second ion exchange treatment is smaller than the content of NaNO ₃ in the ion exchange liquid used for the first ion exchange treatment. It is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. The content of NaNO ₃ in the ion exchange liquid 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, and particularly 0.5% by mass. It is as follows. If the content of NaNO ₃ in the ion exchange liquid used for the second ion exchange treatment is too large, it becomes difficult to increase the average value of the compressive stress at a depth position 7 to 16 μm away from the surface.

When the ion exchange treatment is performed twice, a heat treatment step may be provided between the ion exchange treatments. By doing so, the compressive stress curve in the depth direction from the surface can be efficiently bent by the same ion exchange liquid. Further, the time of the first ion exchange process can be shortened.

The surface compressive stress value of the compressive stress layer of the tempered glass plate (inner tempered glass plate and / or outer 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, and particularly preferably 900 MPa or more. be. The larger the surface compressive stress value, the higher the strength of the tempered glass plate. However, when an extremely large compressive stress is formed on the surface, microcracks are likely to occur on the surface, and conversely, the mechanical strength of the tempered glass plate may decrease. Further, the internal tensile stress may become extremely high. Therefore, the surface compressive stress value is preferably 1400 MPa or less. When the ion exchange time is shortened or the temperature of the ion exchange process is lowered, the compressive stress value tends to increase.

The stress depth of the tempered glass plate (inner tempered glass plate and / or outer tempered glass plate) is preferably 10 μm or more, 20 μm or more, 30 μm or more, 35 μm or more, 40 μm or more, 45 μm or more, and particularly preferably 50 μm or more and 90 μm or less. be. If the stress depth is too small, the end face strength tends to decrease. On the other hand, if the stress depth is too large, the internal tensile stress becomes excessive and the tempered glass plate tends to self-destruct. When the ion exchange time is lengthened or the temperature of the ion exchange process is raised, the stress depth tends to increase.

The internal tensile stress value of the tempered glass plate (inner tempered glass plate and / or outer tempered glass plate) is preferably 100 MPa or less, 80 MPa or less, 70 MPa or less, 60 MPa or less, and particularly 50 MPa or less. If the internal tensile stress value is too large, the tempered glass plate tends to self-destruct. 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.

In the laminated glass for vehicles of the present invention, the outer tempered glass plate is preferably an ion-exchanged tempered glass plate having the same stress profile as the inner tempered glass plate, but from the viewpoint of manufacturing cost, physically strengthened tempered glass. It may be a board. When the outer tempered glass plate is physically strengthened, its 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, and particularly 100 MPa or more. The larger the surface compressive stress value, the higher the strength of the outer tempered glass plate. When the outer tempered glass plate is physically strengthened, the stress depth is preferably 50 μm or more, 100 μm or more, and 150 μm or more. If the stress depth of the outer tempered glass plate is too small, the impact resistance to flying objects tends to decrease. The tensile stress value inside the outer tempered glass plate is preferably 90 MPa or less, 70 MPa or less, and particularly 10 to 50 MPa. If the tensile stress value inside the outer tempered glass plate is too large, the glass fragments may be scattered into pieces at the time of breakage, and the visibility may be temporarily impaired, resulting in a dangerous state.

In the laminated glass for vehicles of the present invention, the 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, and 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, and particularly preferably 1.5 mm or less. 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, and particularly 1.0 mm or more. 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, and particularly 1.5 mm or less. If each plate is too thick, it will be difficult to reduce the weight of the laminated glass. On the other hand, if the thickness of each plate is too small, it becomes difficult to obtain the desired strength.

In particular, if 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, it becomes easier to elastically absorb the mechanical impact force. When applied to, it is less likely to be scratched.

In the laminated glass for vehicles of the present invention, the long side dimension of the inner tempered glass plate is preferably smaller than the long side dimension of the outer tempered glass plate. The difference in long side dimensions between the two is preferably adjusted according to the difference in the coefficient of thermal expansion between the two. By doing so, when the two are laminated and integrated after bending to form a laminated glass, the dimensional difference between the two becomes small and the end faces of the two are easily aligned. As a result, the end face strength of the laminated glass processed by the curved surface is improved.

The tempered glass plate (inner tempered glass plate and / or outer tempered glass plate) is preferably alkaline aluminosilicate glass. Since the alkaline aluminosilicate glass has high ion exchange performance, it is possible to form a desired compressive stress layer by a short-time ion exchange treatment. Moreover, since it has good devitrification resistance, it can be easily molded into a plate shape.

The tempered glass plate (inner tempered glass plate and / or outer tempered glass plate) has a glass composition of SiO ₂ 40 to 80%, Al ₂ O ₃ 3 to 30%, and B ₂ O ₃₀ to 10% by mass. , Na ₂ O 5 to 20% and K ₂ O 0 to 5% are preferable. The reasons for restricting the content range of each component as described above are shown below. In addition, in the description of the content range of each component,% indication shall indicate 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%, and particularly 58 to 67%. If the content of SiO ₂ is too small, it becomes difficult to vitrify, and the coefficient of thermal expansion becomes too high, so that the thermal impact resistance tends to decrease. On the other hand, if the content of SiO ₂ is too large, the meltability and moldability tend to decrease, and the coefficient of thermal expansion becomes too low, making it difficult to match the coefficient of thermal expansion of the organic resin intermediate layer.

Al ₂ O ₃ is a component that enhances the ion exchange performance, and is a component that enhances the strain point and Young's modulus. If the content of Al ₂ O ₃ is too small, there is a risk that the ion exchange performance cannot be fully exhibited. 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. Especially, it is 18.5% or more. On the other hand, if the content of Al ₂ O ₃ is too large, devitrified crystals are likely to precipitate on the glass, and it becomes difficult to form a plate by an overflow down draw method or the like. In addition, the acid resistance is lowered, which makes it difficult to apply to the acid treatment process. Further, the high-temperature viscosity becomes high, and the meltability tends to decrease. 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, especially 20.5% or less. be.

B ₂ O ₃ is a component that lowers the liquid phase temperature, crack generation rate, high temperature viscosity and density, and stabilizes the glass to make it difficult for crystals to precipitate. The lower limit range of B ₂ O ₃ is preferably 0% or more, 0.1% or more, 1% or more, 2% or more, and particularly 3% or more. However, if the content of B ₂ O ₃ is too large, ion exchange tends to cause coloring of the glass surface, which is called discoloration, deterioration of water resistance, and reduction of stress depth. 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%.

Na ₂ O is an ion exchange component, and is a component that lowers high-temperature viscosity and enhances meltability and moldability. Na ₂ O is also a component that improves devitrification resistance. If the Na ₂ O content is too low, the meltability and ion exchange performance tend to deteriorate. 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, and particularly 14% or more. On the other hand, if the content of Na ₂ O is too large, the coefficient of thermal expansion becomes too high, the thermal impact resistance is lowered, and it becomes difficult to match the coefficient of thermal expansion of the organic resin intermediate layer. In addition, the strain point may be lowered too much, or the component balance of the glass composition may be lost, and the devitrification resistance may be lowered. 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. It is also a component that lowers high-temperature viscosity and enhances meltability and moldability. Furthermore, it is also a component that improves devitrification resistance. However, if the content of K ₂ O is too large, the coefficient of thermal expansion becomes too high, the thermal impact resistance deteriorates, and it becomes difficult to match the coefficient of thermal expansion of the organic resin intermediate layer. Further, if the strain point is lowered too much, the component balance of the glass composition is lost, and the devitrification resistance tends to be lowered. Therefore, the upper limit range of K2O is preferably 5% or less, 4% or less, less than ₂ %, and particularly less than 1%. When K ₂ O is added, the amount of K 2 O added is preferably 0.1% or more, 0.3% or more, and particularly 0.5% or more.

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

Li ₂ O is an ion exchange component, a component that lowers high-temperature viscosity, enhances meltability and moldability, and a component that enhances Young's modulus. Furthermore, Li ₂ O has a large effect of increasing the compressive stress value among alkali metal oxides, but in a glass system containing 5% or more of Na ₂ O, when the Li ₂ O content becomes extremely large, the compressive stress is rather high. The value tends to decrease. Further, if the content of Li ₂ O is too large, the liquidus viscosity is lowered and the glass is easily devitrified. In addition, the coefficient of thermal expansion is too high and the thermal shock resistance is lowered. It becomes difficult to match with the coefficient of thermal expansion of the organic resin intermediate layer. Further, the low-temperature viscosity is lowered too much, stress relaxation is likely to occur, and the compressive stress value may be lowered. Therefore, 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. It is ~ 0.1%, especially 0.01 ~ 0.05%.

MgO is a component that lowers high-temperature viscosity and enhances meltability, formability, 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, and particularly 1.4% or more. However, if the content of MgO is too large, the density and the coefficient of thermal expansion tend to be high, and the glass tends to be devitrified. 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, It is 2.3% or less, especially 2.2% or less.

CaO is a component that lowers high-temperature viscosity and enhances meltability, moldability, strain point, and Young's modulus without lowering devitrification resistance as compared with other components. However, if the CaO content is too high, the density and coefficient of thermal expansion become high, and the component balance of the glass composition is lost, so that the glass tends to be devitrified, the ion exchange performance deteriorates, and ion exchange occurs. It tends to 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%, less than 0-1%, 0 to. It is 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. However, if the content of SrO or BaO is too large, the ion exchange reaction is likely to be inhibited, the density and the coefficient of thermal expansion are increased, and the glass is likely to be devitrified. Therefore, 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%, and particularly less than 0 to 0.1%, respectively. Is preferable.

If the total amount of MgO, CaO, SrO and BaO is too large, the density and the coefficient of thermal expansion tend to be high, the glass tends to be devitrified, and the ion exchange performance tends to be deteriorated. Therefore, the total amount of MgO, CaO, SrO and BaO is preferably 0 to 9.9%, 0 to 8%, 0 to 6%, and particularly 0 to 5%.

TiO ₂ is a component that enhances ion exchange performance and solarization resistance, and is a component that lowers high-temperature viscosity. However, if the content thereof is too large, the glass tends to be colored or devitrified. Therefore, the content of TiO ₂ is preferably 0 to 4.5%, 0.05 to 0.5%, and particularly 0.1 to 0.3%.

ZrO ₂ is a component that enhances ion exchange performance and a component that enhances viscosity and strain points near the liquid phase viscosity. However, if the content of ZrO ₂ is too large, the devitrification resistance may be significantly lowered, and the density may be too high. Therefore, the content of ZrO ₂ is preferably 0 to 5%, 0 to 3%, less than 0-1%, and particularly 0.001 to 0.5%.

ZnO is a component that enhances the ion exchange performance, and is a component that has a particularly large effect of increasing the compressive stress value. It is also a component that lowers the high temperature viscosity without lowering the low temperature viscosity. However, if the ZnO content is too high, the glass tends to be phase-separated, the devitrification resistance is lowered, the density is high, and the stress depth is low. Therefore, the ZnO content is preferably 0 to 6%, 0 to 3%, 0-1%, and particularly 0 to 0.1%.

P ₂ O ₅ is a component that enhances the ion exchange performance, and is a component that particularly 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, and particularly more than 7%. However, if the content of P ₂ O ₅ is too large, the glass tends to be phase-separated and the water resistance tends to decrease. Therefore, the preferred upper limit of the content of P ₂ O ₅ is 20% or less, 18% or less, 15% or less, 13% or less, 10% or less, and particularly 7% or less.

SnO ₂ has the effect of enhancing the 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%, and particularly 0.2 to 3%.

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

Fe ₂ O ₃ is a component that enhances the ultraviolet absorption characteristics by coexisting with TiO ₂ , but if the content is too large, the visible light transmittance tends to decrease. 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, and particularly 200 ppm or more. 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, and particularly less than 300 ppm. Further, after restricting the content of Fe ₂ O ₃ to the above range, the molar ratio Fe ₂ O ₃ / (Fe ₂ O ₃ + SnO ₂ ) is regulated to 0.8 or more, 0.9 or more, especially 0.95 or more. It is preferable to do so. By doing so, 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 Young's modulus. However, the cost of the raw material itself is high, and if a large amount is added, the devitrification resistance tends to decrease. Therefore, the total amount of rare earth oxides is preferably 3% or less, 2% or less, 1% or less, 0.5% or less, and 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 , Pb O, Bi ₂ O ₃ and F. Here, "substantially free of ..." means that although the explicit component is not positively added as a glass component, it is allowed to be mixed as an impurity. It means that the content is less than 0.05%.

The alkaline aluminosilicate glass is suitable as the outer tempered glass plate, but soda lime glass may be used from the viewpoint of manufacturing cost. Soda lime glass generally has a glass composition of SiO ₂ 65 to 75%, Al ₂ O ₃₀ to 3%, CaO 5 to 15%, MgO 0 to 15%, Na ₂ O 10 to 10 by mass. It contains 20%, K ₂ O 0 to 3%, and Fe ₂ O ₃₀ to 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 unreinforced glass plate, is 90% or less, preferably 80% or less. Alternatively, the load at which the crack generation rate is 80% or less is preferably 500 gf or more, particularly 800 gf or more. If the crack generation rate is too high, cracks are likely to occur in the tempered glass plate when a flying object collides with the tempered glass plate and local stress is applied, which may lead to destruction of the entire laminated glass. If the load at which the crack generation rate is 80% or less is too small, cracks are likely to occur in the tempered glass plate when a flying object collides with the tempered glass plate and local stress is applied, and the entire laminated glass is liable to crack. It may lead to destruction.

The density of the tempered glass plate (inner tempered glass plate and / or outer tempered glass plate) 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. If the density is too high, it becomes difficult to reduce the weight of the tempered glass plate, and it becomes difficult to reduce the weight of the laminated glass. The "density" can be measured by the Archimedes method.

The coefficient of thermal expansion 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 less, 95 × ^10-7 / ° C. or less, It is 90 × 10 ^-7 / ° C or less, especially 85 × 10 ^-7 / ° C or less. If the coefficient of thermal expansion of the tempered glass plate is too high, it becomes difficult to match the coefficient of thermal expansion of the organic resin intermediate layer, and the tempered glass plate and the organic resin intermediate layer are likely to be peeled off. The "coefficient of thermal expansion in the temperature range of 25 to 380 ° C." is an average value measured by a dilatometer.

The liquidus temperature of the tempered glass plate (inner tempered glass plate and / or outer 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, particularly 1000. It is below ° C. The liquidus viscosity is preferably 10 ^4.0 dPa · s or higher, 10 ^4.4 dPa · s or higher, 10 ^4.8 dPa · s or higher, 10 ^5.0 dPa · s or higher, and 10 ^5.3 dPa · s. ^105.5 dPa · s or more, 10 ^5.7 dPa · s or more, 10 ^5.8 dPa · s or more, especially 10 ^6.0 dPa · s or more. When the liquid phase temperature and the liquid phase viscosity are out of the above ranges, the glass tends to be devitrified during molding. The "liquid phase temperature" is set in a temperature gradient furnace for 24 hours after the glass powder that has passed through a standard sieve of 30 mesh (screen opening of 500 μm) and remains in 50 mesh (screen opening of 300 μm) is placed in a platinum boat. Refers to the measured value of the temperature at which the crystals precipitate while being held. "Liquid phase viscosity" refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by the platinum ball pulling method.

The Young's modulus of the tempered glass plate (inner tempered glass plate and / or outer tempered glass plate) is preferably 76 GPa or less, 74 GPa or less, 72 GPa or less, and particularly 70 GPa or less. If the Young's modulus is too high, the tempered glass plate is less likely to bend, and the impact absorption of the laminated glass tends to decrease. The "Young's modulus" can be measured by a resonance method or the like.

In the laminated glass for vehicles of the present invention, it is preferable that a part of the organic resin intermediate layer protrudes to the outside of 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 preferable. In this way, when an impact is applied to the end face of the tempered glass plate from an oblique direction, the organic resin intermediate layer bends to cover the end face of the tempered glass plate, and the impact on the end face of the tempered glass plate is applied. Can be relaxed.

In the laminated glass for vehicles of the present invention, 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, and particularly 0.6 to 0.9 mm. be. If the thickness of the organic resin intermediate layer is too small, the impact absorption tends to decrease, the adhesiveness tends to vary, and the tempered glass plate and the organic resin intermediate layer tend to peel off. On the other hand, if the thickness of the organic resin intermediate layer is too large, the visibility of the laminated glass tends to decrease.

Various organic resins can be used as the organic resin intermediate layer, for example, polyethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polystyrene (PS), methacrylic resin (PMA), and poly. Vinyl chloride (PVC), polyethylene terephthalate (PET), polyvinylidene 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), Polysulphon (PSF), Polyvinylidene chloride (PVDF), methacrylic-styrene copolymer resin (MS), polyarate (PAR), polyallyl sulfone (PASF), polybutadiene (BR), polyether sulfone (PESF), polyether ether ketone (PEEK), etc. Can be used. Among them, EVA and PVB are preferable from the viewpoint of transparency and adhesiveness, and PVB is particularly preferable because it can impart sound insulation.

A colorant may be added to the organic resin intermediate layer, or an absorbent that absorbs a specific wavelength ray such as infrared rays or ultraviolet rays may be added.

As the organic resin intermediate layer, a combination of a plurality of types of the above organic resins may be used. For example, when two layers of organic resin intermediate layers are used, the outer tempered glass plate and the inner tempered glass plate are fixed by different organic resins, so that it is easy to reduce the warp of the laminated glass at the time of laminating and integrating.

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

First, a glass raw material prepared 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 supplied to a molding apparatus to be molded into a plate shape. By cooling, a glass plate can be produced.

It is preferable to adopt the overflow down draw method as a method for forming into a flat plate shape. The overflow down draw method is a method in which a large number of high-quality glass plates can be produced 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 down draw method, it is also preferable to form a glass plate by a float method. The float method is a method that can inexpensively produce a large glass plate.

The glass plate is preferably chamfered, if necessary. In that case, it is preferable to perform C chamfering with a # 800 metal bond grindstone or the like. By doing so, the end face strength can be increased. If necessary, it is also preferable to etch the end face of the glass plate to reduce the crack source existing on the end face.

Next, the obtained glass plate is subjected to curved surface processing as necessary. Various methods can be adopted as the method for processing the curved surface. In particular, a method of press-molding a glass plate with a mold is preferable, and it is preferable to pass the glass plate through a heat treatment furnace with the glass plate sandwiched between molds having a predetermined shape. By doing so, the dimensional accuracy of the curved surface shape can be improved. Further, a method in which a glass plate is placed on a mold having a predetermined shape and then a part or the whole of the glass plate is heat-treated to soften and deform the glass plate by its own weight along the shape of the mold is also preferable. By doing so, the efficiency of curved surface processing can be improved.

Subsequently, the glass plate after the curved surface processing is subjected to tempering treatment to obtain two tempered glasses. The strengthening treatment is not particularly limited, and either an ion exchange treatment or a physical strengthening treatment may be used, 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, applications, thickness, internal tensile stress, dimensional change, etc. of the glass. However, as described above, the ion exchange treatment It is preferable to carry out this multiple times. In particular, when K ions in the ion exchange liquid are ion-exchanged with the Na component in the glass, a compressive stress layer can be efficiently formed on the glass surface. As the ion exchange liquid, various ion exchange liquids can be used, and for example, a molten salt of KNO ₃ , a mixed molten salt of KNO ₃ and NaNO ₃ and the like can be used.

The conditions of the physical strengthening treatment are not particularly limited, but it is preferable to heat the glass plate to a temperature near the softening point and then quench it with an air jet or the like. Although the physical strengthening treatment may be performed in a separate heat treatment step, it is preferable to perform the physical strengthening treatment by quenching the glass plate after the curved surface processing from the viewpoint of manufacturing efficiency.

Further, two tempered glass plates are laminated and integrated by an organic resin intermediate layer to form a laminated glass. As a method of laminating and integrating, a method of injecting an organic resin between two glass plates and then curing the organic resin, a method of placing an organic resin sheet between the two tempered glass plates, and then performing a pressure heat treatment (thermocompression bonding). However, the latter method is preferable because it is easy to stack and integrate.

In the pressure heat treatment (thermocompression bonding), the heating temperature of the heaters arranged on the outside and the inside may be different depending on the coefficient of thermal expansion of the tempered glass plate. In this case, it is preferable to raise the heating temperature of the heater on the tempered glass plate side with low expansion and lower the heating temperature of the heater on the tempered glass plate side with high expansion. As a result, the amount of expansion and contraction between the tempered glass plates can be easily matched, and the warp of the laminated glass can be reduced.

Further, after obtaining the laminated glass, 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.

Hereinafter, the present invention will be described in detail based on examples. The following examples are merely examples. The present invention is not limited to the following examples.

First, the inner tempered glass plate was prepared as follows. As the glass composition, in terms of 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 The glass raw material was prepared so as to obtain a glass containing 3.0% and SnO ₂ 0.5%. Next, 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 supplied into the molded body and overflows so as to have a plate thickness of 0.7 mm. It was formed into a plate by the downdraw method.

When various characteristics of the obtained glass plate were evaluated, the density was 2.45 g / cm ³ , the coefficient of thermal expansion was 91 × 10 ^-7 / ° C, the Young's ratio was 71 GPa, the liquid phase temperature was 970 ° C, and the liquid phase viscosity. Was 10 ^6.3 dPa · s, and the crack occurrence rate was 65%. Here, the density is a value measured by the well-known Archimedes method. The coefficient of thermal expansion is a value obtained by measuring the average coefficient of thermal expansion in the temperature range of 25 to 380 ° C. using a dilatometer. Young's modulus is a value measured by a well-known resonance method. The liquidus temperature was measured by passing through a standard sieve of 30 mesh (seam opening of 500 μm), putting the glass powder remaining in 50 mesh (screen opening of 300 μm) into a platinum boat, and then holding the glass powder in a temperature gradient furnace for 24 hours. It is a value measured by the temperature at which crystals precipitate. The liquidus viscosity is a value obtained by measuring the viscosity of glass at the liquidus temperature by the platinum ball pulling method. The crack generation rate was first held in an electric furnace kept at a temperature of 200 ° C. for 1 hour to keep the surface moisture state constant, and then in a constant temperature and humidity chamber kept at a humidity of 30% and a temperature of 25 ° C. A Vickers indenter set to a load of 800 gf is driven into the glass surface for 15 seconds, and after 15 seconds, the number of cracks generated from the four corners of the indentation is counted (the maximum is 4 per indentation), and the indenter is further formed in this way. It is a value obtained by the formula of total number of cracks generated / 200 × 100 after driving 50 times to obtain the total number of cracks generated.

Further, by passing each sample through the heat treatment furnace with the glass plate sandwiched between the molds having a predetermined shape, 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. Then, the end face of the glass plate after the curved surface was chamfered and polished with a # 800 metal bond grindstone.

Subsequently, the curved glass plate was subjected to ion exchange treatment using the ion exchange liquid shown in Table 1 under the conditions shown in Table 1 to obtain each inner tempered glass plate. In Table 1, DOL_zero represents the stress depth, DOL_tile represents the depth of the ion exchange layer, and CT_cv represents the internal tensile stress value. The "CS" and "DOL" in the table are the number of interference fringes observed when observing the measurement sample using the soft FsmV of a surface stress meter (FSM-6000LE manufactured by Orihara Seisakusho Co., Ltd.) and the number thereof. It is a value calculated from the interval. In the measurement, the measurement setting (strengthening type) was set to chemical strengthening II, the measurement mode was set to the exact solution mode, and the bending point position was used to calculate the boundary position of the depth measurement. In the measurement, the refractive index of each sample was 1.50 and the optical elastic constant was 29.5 [(nm / cm) / MPa].

Each tempered glass plate was subjected to an end face strength test using the pendulum end face tester shown in FIG. However, in the end face strength test, a test piece subjected to ion exchange treatment was used without processing a curved surface. FIG. 2A is a conceptual perspective view showing the shapes of a metal jig and a test head holding a test piece. The test piece 21 is fixed to the metal jig 23 in a state of being sandwiched between a pair of Bakelite resin plates 22. The dimensions of the test piece 21 are 22 mm × 30 mm × 0.7 mm thick, and the 2 mm × 30 mm portion of the test piece 21 is in a state of protruding from the metal jig 23. The end face of this protruding portion will collide with the test head 24. The test head 24 is made of SUS and has a radius of curvature R = 2.5 mm. FIG. 2B is a conceptual cross-sectional view showing a collision method for an end face strength test. As shown in FIG. 2B, first, 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 collides with the end face of the test piece 21 sandwiched between the metal jigs 23. rice field. After that, 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 defined as the damage height. This end face strength test was performed 10 times for each chemically strengthened glass, and the arithmetic mean value of the fracture height was calculated as the average fracture height.

FIG. 3 is a graph showing the relationship between the average value of compressive stress at a depth position 7 to 16 μm away from the surface of the tempered glass plate and the average fracture height in the end face strength test. As can be seen from FIG. 3, the average value of the compressive stress and the average fracture height in the end face strength test at a depth position 7 to 16 μm away from the surface of the tempered glass plate have a correlation coefficient ^R2 of 0.8926. , Strong correlation is observed.

As can be seen from Table 1, the sample No. The inner tempered glass plates according to 1 and 2 had a large average value of compressive stress at a depth position 7 to 16 μm away from the surface, so that the end face strength test was evaluated well. On the other hand, sample No. The inner tempered glass plates according to 3 and 4 had a small average value of compressive stress at a depth position 7 to 16 μm away from the surface, so that the evaluation of the end face strength test was poor.

Next, an outer tempered glass plate was produced. A glass plate (plate thickness 1.5 mm) made of soda lime glass having the same dimensions as the inner tempered glass plate was prepared. The outer glass plate was obtained by subjecting the glass plate to a curved surface in the same manner as in the case of the inner glass plate, and then quenching and physically strengthening the glass plate. When CS was calculated for the obtained outer tempered glass plate by the above method, CS was 50 MPa.

Finally, using polyvinyl butyral (PVB) having a thickness of 0.7 mm, the inner tempered glass plate and the outer tempered glass plate are laminated and integrated by pressure heat treatment to form a laminated glass having a curved surface shape (Sample No. 1 to 4) were obtained. Sample No. The laminated glass of 1 and 2 has both high strength and thinness, and it is considered that the laminated glass is not easily damaged even when an impact is applied to the end face.

The glass plates (a to h) shown in Table 2 are curved by the method described in the column of Example 1, and then 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 μm away from the surface of these inner tempered glass plates was 400 MPa or more. After that, a glass plate (plate thickness 1.5 mm) made of soda lime glass having a slightly larger long side dimension than the inner tempered glass plate was used as a sample No. Laminated glass was produced by laminating and integrating in the same manner as in No. 2 laminated glass. The soda lime glass plate is the sample No. The same ion exchange treatment as in 2 is performed.

The laminated glass for vehicles of the present invention is suitable for the windshield of an automobile, but is also suitable for the rear glass, door glass, and roof glass of an automobile. In addition to these applications, the laminated glass for vehicles of the present invention includes applications that require high impact strength, such as exhibition glass for aquariums, solar cell substrates, digital signage substrates, and aircraft windowpanes. It can be expected to be applied to windowpanes of railway vehicles, windowpanes of rockets, etc.

10 Laminated glass for vehicles 11 Inner tempered glass plate 12 Outer tempered glass plate 13 Organic resin intermediate layer 21 Test piece 22 Resin plate 23 Metal jig 24 Test head 25 Pendulum

Claims (11)

In laminated glass for vehicles, in which the inner tempered glass plate and the outer tempered glass plate are integrated by an organic resin intermediate layer.
The inner tempered glass plate contains 0 to 7% MgO in% by mass as a glass composition.
The surface compressive stress value of the compressive stress layer of the inner tempered glass plate is 932 MPa or more.
A laminated glass for vehicles characterized in that the average value of compressive stress at a depth position 7 to 16 μm away from the surface of the inner tempered glass plate is 350 MPa or more. The laminated glass for vehicles according to claim 1, wherein the inner tempered glass plate is alkaline aluminosilicate glass and the outer tempered glass plate is soda lime glass. The inner tempered glass plate has a glass composition of SiO ₂ 40 to 80%, Al ₂ O ₃ 3 to 30%, B ₂ O ₃₀ to 10%, Na ₂ O 5 to 20%, K ₂ O in terms of glass composition. The laminated glass for vehicles according to claim 1 or 2, which contains 0 to 5%. The laminated glass for a vehicle according to any one of claims 1 to 3, wherein the plate thickness of the inner tempered glass plate is smaller than the plate thickness of the outer tempered glass plate. The laminated glass for a vehicle according to any one of claims 1 to 4, wherein the long side dimension of the inner tempered glass plate is smaller than the long side dimension of the outer tempered glass plate. The laminated glass for a vehicle according to any one of claims 1 to 5, wherein the end faces of the inner tempered glass plate and the outer tempered glass plate are chamfered. The laminated glass for a vehicle according to any one of claims 1 to 6, wherein a part of the organic resin intermediate layer protrudes to the outside of the end face of the outer tempered glass plate. The laminated glass for vehicles according to any one of claims 1 to 7, wherein the organic resin layer is composed of an ethylene-vinyl acetate copolymer or polyvinyl butyral. The laminated glass for a vehicle according to any one of claims 1 to 8, wherein the laminated glass has a three-dimensionally curved curved surface shape. The laminated glass for a vehicle according to any one of claims 1 to 9, wherein the laminated glass is used for a windshield of an automobile. The laminated glass for a vehicle according to any one of claims 1 to 9, wherein the laminated glass is used for a door glass of an automobile.

Images