JP2019172566A - Glass resin complex - Google Patents

Abstract

To create a glass resin complex that has excellent curved surface workability, and can effectively attenuate collision energy of scatter pieces even when the thickness and crystallinity are small.SOLUTION: A glass resin complex at least has a plurality of glass plates and a resin plate. At least one of the plurality of glass plates is a tempered glass plate having a surface compressive stress layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a glass resin composite, and more particularly to a glass resin composite suitable for an automobile windshield and door glass.

  In general, laminated glass in which a plurality of soda-lime glass plates are integrated with an organic resin intermediate layer is used for a windshield of an automobile or the like. For the purpose of weight reduction, a plurality of soda-lime glass plates are used. A glass resin composite in which a resin plate is integrated with an organic resin intermediate layer may be used (see Patent Documents 1 to 4).

  The soda-lime glass plate used for the windshield of automobiles, etc. has a function to attenuate the collision energy of the scattered pieces by deforming the tip shape of the flying pieces such as stepping stones while driving and increasing the impact resistance. Have.

  However, it cannot be said that the soda-lime glass plate has a sufficient effect of increasing the impact resistance of the scattered pieces. At present, the thickness of the soda-lime glass plate is increased or the number of laminated layers is increased to increase the impact resistance of the scattering pieces. However, this increases the thickness and mass of the windshield.

Then, in order to raise the impact resistance of a scattering piece, using a crystallized glass plate instead of a soda-lime glass plate is examined. For example, a crystal formed by precipitating Li ₂ O—Al ₂ O ₃ —SiO ₂ -based crystal such as β-quartz solid solution (Li ₂ O.Al ₂ O ₃ .nSiO ₂ [n ≧ 2]) as the main crystal Glass plate is being studied.

JP 2012-144217 A JP 2004-196184 A JP 2001-151539 A Japanese Utility Model Publication No. 1-8821

  By the way, if the crystallinity of the crystallized glass plate is increased, the hardness increases and the collision energy of the scattered pieces can be attenuated. However, since the precipitated crystals inhibit softening deformation, curved surface processing becomes difficult, automobiles, etc. It becomes impossible to apply to the windshield. In addition, the collision energy of the scattered pieces can be attenuated by increasing the thickness of the crystallized glass plate, but in this case, the mass of the windshield increases and the transparency may be impaired.

  Therefore, the present invention has been made in view of the above circumstances, and its technical problem is that it has excellent curved surface workability and can effectively attenuate the collision energy of the scattered pieces even if the thickness and crystallinity are small. The idea is to create a glass resin composite.

  The present inventors have found that the above technical problem can be solved by forming a surface compressive stress layer on a glass plate in a glass resin composite, and propose the present invention. That is, the glass resin composite of the present invention is a glass resin composite comprising at least a plurality of glass plates and a resin plate, and at least one of the plurality of glass plates has a surface compressive stress. It is a tempered glass plate having a layer. The “tempered glass plate” in the present invention refers to a glass plate having a surface compressive stress layer in a state of being integrated with another glass plate or the like. That is, it includes not only a glass plate that has been tempered in advance, but also a glass plate in which a surface compressive stress layer is generated after integration.

  In the glass resin composite of the present invention, the glass plate is a material having transparency and increasing impact resistance. The resin plate is a material that alleviates the impact caused by the collision of the scattered pieces and prevents the glass pieces from being scattered by the impact of the scattered pieces. By providing both, it becomes easy to ensure impact resistance.

  In the glass resin composite of the present invention, at least one glass plate has a surface compressive stress layer. Thereby, the impact resistance with respect to a scattering piece becomes high, and it becomes difficult to damage a glass resin composite.

Moreover, in the glass resin composite of this invention, it is preferable that the thermal expansion coefficient of a tempered glass board is ^3x10 < ^-7 > / degreeC or less lower than the thermal expansion coefficient of the glass board adjacent to a tempered glass board. If it does in this way, a surface compressive-stress layer can be formed efficiently by the thermal expansion coefficient difference of both glass plates. And since this surface compressive-stress layer has heat resistance, even after performing curved surface processing, it does not lose | disappear. Here, the “thermal expansion coefficient” of glass refers to a value measured using a dilatometer in a temperature range of 30 to 380 ° C.

Further, the glass resin composite of the present invention, it is preferred that SiO ₂ concentration on the surface of the tempered glass sheet is higher than the SiO ₂ concentration in the thickness direction central portion. If it does in this way, a surface compression stress layer can be formed efficiently. And since these surface compressive-stress layers have heat resistance, they do not disappear even after performing curved surface processing.

Further, the glass resin composite of the present invention, tempered glass plate, as a glass composition, in _{mol%, SiO 2 40~80%, Al} 2 O 3 5~30%, B 2 O 3 + P 2 O 5 0 than _{~25%, B 2 O 3 0~15} %, P 2 O 5 0~15%, Li 2 O + Na 2 O + K 2 O 0 super to 20%, MgO 0 super 35%, containing 0~15% CaO + SrO + BaO It is preferable. Here, “B ₂ O ₃ + P ₂ O ₅ ” refers to the total amount of B ₂ O ₃ and P ₂ O ₅ . “Li ₂ O + Na ₂ O + K ₂ O” refers to the total amount of Li ₂ O, Na ₂ O and K ₂ O. “CaO + SrO + BaO” refers to the total amount of CaO, SrO and BaO.

  The glass resin composite of the present invention preferably has a curved shape that is three-dimensionally curved. If it does in this way, it will become easy to apply to the windshield etc. of a car.

  Moreover, in the glass resin composite of this invention, it is preferable that the resin plate is arrange | positioned inside the glass plate of the innermost layer. Here, the “innermost layer glass plate” refers to the innermost (indoor side) glass plate.

FIG. 1 is a schematic view for explaining an example of a glass resin composite. The glass resin composite 10 has a glass plate (tempered glass plate) 11, a glass plate (innermost layer glass plate) 12, and a resin plate 13 in order from the outside (outside air side). It has a curved surface shape that is three-dimensionally curved. The glass plate 11 and the glass plate 12 are fused, and the thermal expansion coefficient of the glass plate 11 is 10 × 10 ⁻⁷ / ° C. lower than the thermal expansion coefficient of the glass plate 12. Then, the glass plate 11 has a surface compressive stress layer, as a glass composition, in _{mol%, SiO 2 40~80%, Al} 2 O 3 5~30%, B 2 O 3 0~15%, _{P 2 O 5 0~15%, Li} 2 O + Na 2 O + K 2 O 0 super to 20%, MgO 0 super 35%, contains a 0~15% CaO + SrO + BaO. The resin plate 13 is polycarbonate. The resin plate 13 is integrated with the glass plate 12 by an organic resin intermediate layer (not shown).

The glass plate of the present invention is a glass plate used for a glass resin composite including at least a plurality of glass plates and a resin plate, and the SiO ₂ concentration on the surface of the glass plate is more than the SiO ₂ concentration in the center portion in the plate thickness direction. It is also characterized by high.

It is the schematic for demonstrating an example of a glass resin composite.

  The glass resin composite of the present invention is a glass resin composite comprising at least a plurality of glass plates and a resin plate, and at least one glass plate is a tempered glass plate having a surface compressive stress layer. The total number of glass plates is preferably 2 to 8, and the number of tempered glass plates is not particularly limited, but is preferably one. Moreover, it is preferable that a tempered glass board is arrange | positioned in an outermost layer among several glass plates from a viewpoint which enjoys the effect of this invention exactly. That is, the outermost glass plate is preferably a tempered glass plate. Here, the “outermost layer glass plate” refers to the outermost (atmosphere side) glass plate.

  The surface compressive stress layer may be formed on both surfaces of the glass plate, but is preferably formed on one surface from the viewpoint of manufacturing efficiency.

Surface compressive stress layer may be formed by ion exchange treatment, from SiO ₂ concentration in the thickness direction central portion of the SiO ₂ concentration on the surface of a method or a glass plate using a thermal expansion coefficient difference between the glass plates It is preferable to form by the method of making it high. If it does in this way, a surface compression stress layer can be efficiently formed in a glass plate. And since these surface compressive-stress layers have heat resistance, they do not disappear even after performing curved surface processing.

  As a method of utilizing the difference in coefficient of thermal expansion between glass plates, high expansion glass is obtained by laminating a high expansion glass plate (tempered glass plate) and a low expansion glass plate (glass plate adjacent to the tempered glass plate). A method of forming a surface compressive stress layer on a plate is preferable, and a method of forming a surface compressive stress layer on a high expansion glass plate by fusing a high expansion glass plate and a low expansion glass plate is preferable. A method of forming a surface compressive stress layer on a high expansion glass plate by fusing a high expansion glass plate and a low expansion glass plate is particularly preferable. In the present invention, when a high-expansion glass plate and a low-expansion glass plate are fused, the two glass plates are not handled as one sheet, but are handled as a plurality of sheets.

The difference in thermal expansion coefficient between the glass plates is preferably 3 × 10 ⁻⁷ / ° C. or higher, 5 × 10 ⁻⁷ / ° C., 10 × 10 ⁻⁷ / ° C. or higher, from the viewpoint of properly forming the surface compressive stress layer. It is 15 × 10 ⁻⁷ / ° C. or more, particularly 20 × 10 ⁻⁷ / ° C. or more. The larger the difference in thermal expansion coefficient, the larger the compressive stress value of the surface compressive stress layer. On the other hand, if the difference in thermal expansion coefficient is too large, the glass plate is likely to be self-destructed by internal tensile stress. Therefore, the difference in thermal expansion coefficient between the glass plates is preferably 30 × 10 ⁻⁷ / ° C. or less.

Further, as a method of increasing than SiO ₂ concentration in the thickness direction central portion of the SiO ₂ concentration on the surface of the glass plate, a method of heat-treating the surface of the glass plate in a flame such as a gas burner is preferred. According to this method, Na, P, B, etc., which are easily evaporated components in the glass, are evaporated, and a SiO ₂ rich layer can be efficiently formed on the surface. Then, the SiO ₂ rich layer has a lower thermal expansion coefficient than the plate thickness direction center portion of the glass plate. As a result, the surface compressive stress layer can be efficiently formed on the glass plate.

The thickness of the SiO ₂ rich layer is preferably 100 nm to 1 mm from the viewpoint of properly forming the surface compressive stress layer. The SiO ₂ concentration on the surface should be 0.5 mol% or more, 1.0 mol% or more, 2 mol% or more, 3 mol% or more, particularly 5 mol% or more higher than the SiO ₂ concentration in the center in the thickness direction. preferable. If the surface SiO ₂ concentration is equal to or lower than the SiO ₂ concentration in the central portion in the plate thickness direction, it is difficult to form a surface compressive stress layer. On the other hand, if the SiO ₂ concentration on the surface is too higher than the SiO ₂ concentration in the central portion in the plate thickness direction, the glass may be phase-divided or crystallized to lose transparency. Therefore, the difference between the SiO ₂ concentration and SiO ₂ concentration in the thickness direction central portion of the surface is preferably 10 mol% or less.

  In the tempered glass plate, the compressive stress value of the surface compressive stress layer is preferably 50 MPa or more, 100 MPa or more, particularly 200 MPa or more. The greater the compressive stress value, the higher the resistance to impact. On the other hand, if an extremely large compressive stress is formed on the surface, the inherent tensile stress may be extremely high. For this reason, the compressive stress value of the compressive stress layer is preferably 1800 MPa or less, 1650 MPa or less, and particularly preferably 1500 MPa or less. Here, the “compressive stress value” refers to a value calculated by a surface stress meter (FSM-6000 manufactured by Orihara Seisakusho).

  The glass system of the tempered glass plate is not particularly limited, but is preferably aluminosilicate glass, borosilicate glass, alkali-free glass, or soda lime silicate glass from the viewpoint of curved surface workability and weather resistance.

In particular, tempered glass plate, a glass composition, in _{mol%, SiO 2 40~80%, Al} 2 O 3 5~30%, B 2 O 3 0~15%, P 2 O 5 0~15%, Li ₂ O + Na ₂ O + K ₂ O more than 0 to 20%, MgO more than 0 to 35%, CaO + SrO + BaO 0 to 15% are preferably contained. The reason why the content range of each component is regulated as described above is shown below. In addition, in description of the containing range of each component,% display shall show mol%.

SiO ₂ is a component that forms a network of glass. The content of SiO ₂ is preferably 40 to 80%, 42 to 75%, particularly 45 to 70%. When the content of SiO ₂ is too small, it becomes difficult to vitrify and weather 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, and the resin plate is likely to be deformed due to the expansion mismatch between the glass plate and the resin plate. .

Al ₂ O ₃ is a component that increases Young's modulus and weather resistance. The content of Al ₂ O ₃ is preferably 5 to 30%, 9 to 25%, 15 to 24%, particularly 18 to 23%. When the content of Al ₂ O ₃ is too small, it becomes difficult to enjoy the above-mentioned effects. On the other hand, when the content of Al ₂ O ₃ is too large, meltability, moldability, resistance to devitrification is liable to decrease.

The content of B ₂ O ₃ + P ₂ O ₅ is preferably 0 to 25%, more than 0 to 15%, 1 to 10%, particularly 2 to 8%. When B ₂ O ₃ + _{P 2} content of _{O 5} is too small, meltability, moldability, curved workability tends to decrease. When the content of _{B 2 O 3 + P 2 O} 5 is too large, the weather resistance tends to decrease. “B ₂ O ₃ + P ₂ O ₅ ” is the total amount of B ₂ O ₃ and P ₂ O ₅ .

B ₂ O ₃ is a component that enhances meltability, moldability, and curved surface processability, and is a component that facilitates the formation of a SiO ₂ rich layer on the surface. The content of B ₂ O ₃ is preferably 0 to 15%, 1 to 12%, particularly 2 to 10%. When the content of B ₂ O ₃ is too large, the Young's modulus, weather resistance tends to decrease.

P ₂ O ₅ is a component that enhances meltability, moldability, and curved surface processability, and is a component that facilitates the formation of a SiO ₂ rich layer on the surface. The content of P ₂ O ₅ is preferably 0 to 15%, 1 to 12%, particularly 2 to 10%. When the content of P ₂ O ₅ is too large, the weather resistance tends to decrease.

Li ₂ O, Na ₂ O, and K ₂ O are components that lower the high-temperature viscosity and increase the meltability, moldability, and curved surface processability, and are components that facilitate the formation of a SiO ₂ rich layer on the surface. . The total amount of Li ₂ O, Na ₂ O and K ₂ O is preferably more than 0 to 20%, 1 to 15%, particularly 5 to 12%. The respective contents of Li ₂ O and K ₂ O are preferably 0-15%, 0-3%, in particular 0-1%. The content of Na ₂ O is preferably more than 0 to 15%, 1 to 12%, particularly 3 to 10%. Li ₂ O, when the content of Na ₂ O and _{K 2} O is too large, the Young's modulus, weather resistance tends to decrease. The content of Li 2 _O is too large, the glass tends to be devitrified when curved machining.

The molar ratio (Li ₂ O + Na ₂ O + K ₂ O) / (B ₂ O ₃ + P ₂ O ₅ ) is preferably 0 to 1.5, more than 0 to 1.5, 0.1 to 1.2, 0.5 To 1.1, especially 0.9 to 1.0. When the molar ratio (Li ₂ O + Na ₂ O + K ₂ O) / (B ₂ O ₃ + P ₂ O ₅ ) is too small, curved surface processability tends to be lowered. On the other hand, if the molar ratio (Li ₂ O + Na ₂ O + K ₂ O) / (B ₂ O ₃ + P ₂ O ₅ ) is too large, the Young's modulus tends to decrease. In addition, “(Li ₂ O + Na ₂ O + K ₂ O) / (B ₂ O ₃ + P ₂ O ₅ )” indicates that the total amount of Li ₂ O, Na ₂ O and K ₂ O is B ₂ O ₃ and P ₂ O _5. The value divided by the total amount.

  MgO is a component that significantly increases the Young's modulus, is a flux that lowers the high-temperature viscosity and increases the meltability, and further increases the moldability and curved surface processability. The content of MgO is preferably more than 0 to 35%, 1 to 33%, 3 to 33%, 5 to 32%, 8 to 32%, 12 to 31%, particularly 15 to 30%. When there is too little content of MgO, it will become difficult to receive the said effect. On the other hand, when there is too much content of MgO, devitrification resistance will fall easily.

  CaO, SrO, and BaO are components that lower the high-temperature viscosity and improve the meltability, moldability, and curved surface workability. The total amount of CaO, SrO and BaO is preferably 0-15%, 0-5%, especially 0-1%. The respective contents of CaO, SrO and BaO are preferably 0 to 12%, 0 to 5%, 0 to 2%, especially 0 to less than 1%. When there is too much content of CaO, SrO, and BaO, devitrification resistance, a Young's modulus, etc. will fall easily.

  From the viewpoint of increasing the Young's modulus, the molar ratio MgO / (MgO + CaO + SrO + BaO) is preferably more than 0, 0.5 or more, 0.7 or more, 0.8 or more, particularly 0.9 or more. “MgO / (MgO + CaO + SrO + BaO)” is a value obtained by dividing the content of MgO by the total amount of MgO, CaO, SrO and BaO.

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

TiO ₂ is a component that improves weather resistance, but is also a component that colors glass. Therefore, the content of TiO ₂ is preferably 0 to 0.5%, particularly 0 to less than 0.1%.

ZrO ₂ is a component that increases Young's modulus and weather resistance, but is also a component that decreases devitrification resistance. Therefore, the content of ZrO ₂ is preferably 0 to 0.5%, particularly 0 to less than 0.1%.

As a fining agent, 0.05 to 0.5% of one or more selected from the group of SnO ₂ , Cl, SO ₃ and CeO ₂ (preferably a group of SnO ₂ and SO ₃ ) may be added. .

Fe ₂ O ₃ is a component that is inevitably mixed as an impurity in the glass raw material, and is a coloring component. Therefore, the content of Fe ₂ O ₃ is preferably 0.5% or less, particularly 0.01 to 0.07%.

V ₂ O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO are coloring components. Therefore, the respective contents of V ₂ O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO are preferably 0.1% or less, particularly less than 0.01%.

Rare earth oxides such as Y ₂ O ₃ , 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 total amount of the rare earth oxide is preferably 3% 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, Bi ₂ O ₃ and F. Here, “substantially does not contain” means that the glass component does not actively add an explicit component, but allows it to be mixed as an impurity. It indicates that the content is less than 0.05%.

  The Young's modulus of the tempered glass plate is preferably 80 GPa or more, 85 GPa or more, 90 GPa or more, particularly 95 to 150 GPa. If the Young's modulus is too low, the speed of the shock wave due to the collision of the scattering pieces becomes slow, so that the shock wave spreads only in a narrow region, and it becomes difficult to attenuate the collision energy of the scattering pieces. Here, “Young's modulus” refers to a value measured by a known resonance method.

  In a glass plate (preferably a tempered glass plate), the glass transition point is preferably less than 820 ° C., 800 ° C. or less, 790 ° C. or less, and particularly 780 ° C. or less. When the glass transition point is too high, curved surface processability tends to be lowered. The “glass transition point” refers to a value measured with a dilatometer.

In a glass plate (preferably a tempered glass plate), the viscosity at 800 ° C. is preferably 10 ^12.0 dPa · s or less, 10 ^11.5 dPa · s or less, 10 ^11.0 dPa · s or less, particularly 10 ^{10. 5} dPa · s or less. When the viscosity at 800 ° C. is too high, curved surface processability tends to be lowered. “Viscosity log η at 800 ° C.” refers to a value obtained from an interpolated value of a temperature-viscosity curve obtained from the temperature of the strain point, annealing point, and softening point. “Strain point” and “annealing point” refer to values measured based on the method of ASTM C336. “Softening point” refers to a value measured according to the method of ASTM C338.

  In a glass plate (preferably a tempered glass plate), the crystallinity is preferably 30% or less, 10% or less, 5% or less, 1% or less, particularly 0%, that is, amorphous. When the degree of crystallinity is too high, curved surface processability tends to be lowered. The “crystallinity” is calculated by measuring the XRD by a powder method to calculate the area of the halo corresponding to the mass of the amorphous and the area of the peak corresponding to the mass of the crystal. Area] × 100 / [peak area + halo area] (%).

  The plate thickness of the glass plate is preferably 15 mm or less, 12 mm or less, 10 mm or less, particularly 8 mm or less, preferably 1.5 mm or more, 3 mm or more, 4 mm or more, 5 mm or more, 6 mm or more, particularly 7 mm or more. If the thickness of the glass plate is too small, it will be difficult to ensure impact resistance. On the other hand, if the plate thickness of the glass plate is too large, it is difficult to make the windshield thin, and the visibility is likely to deteriorate. In addition, the mass of the windshield increases and the fuel efficiency of automobiles and the like increases.

  In the glass resin composite of the present invention, a plurality of resin plates may be used, but one is preferable from the viewpoint of improving visibility. Various resins such as acrylic and polycarbonate can be used for the resin plate, but polycarbonate is particularly preferable from the viewpoint of transparency, impact relaxation, and weight reduction.

  The thickness of the resin plate is preferably 10 mm or less, 8 mm or less, 7 mm or less, 6 mm or less, particularly 5 mm or less, preferably 0.5 mm or more, 0.7 mm or more, 1 mm or more, 2 mm or more, particularly 3 mm or more. . If the thickness of the resin plate is too small, it will be difficult to mitigate the impact when the scattered pieces collide. On the other hand, if the thickness of the resin plate is too large, it is difficult to make the windshield thinner, and the visibility of the windshield is liable to be reduced.

In the glass resin composite of the present invention, the glass plate and the resin plate are preferably integrated by an organic resin intermediate layer. The thickness of the organic resin intermediate layer is preferably 0.1 to 2 mm, 0.3 to 1.5 mm, 0.5 to 1.2 mm, particularly 0.6 to 0.9 mm. If the thickness of the organic resin intermediate layer is too small, the energy of the shock wave easily propagates to the indoor side when the scattered pieces collide. On the other hand, when the thickness of the organic resin intermediate layer is too large, the visibility of the windshield tends to be lowered. In the method of the SiO ₂ concentration on the surface of the glass plate above the SiO ₂ concentration in the thickness direction central portion, it is preferable to perform the same organic resin intermediate layer integration of glass plates together.

  The thermal expansion coefficient of the organic resin intermediate layer is preferably not less than the thermal expansion coefficient of all glass plates and not more than the thermal expansion coefficient of the resin plates. If it does in this way, when a windshield will be heated by direct sunlight, a glass plate and a resin board will become difficult to isolate | separate and deform | transform.

  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), poly Vinyl 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), Poly Vinylidene fluoride (PVDF), methacryl-styrene copolymer resin (MS), polyarate (PAR), polyallyl sulfone (PASF), polybutadiene (BR), polyether sulfone (PESF), or polyether ether ketone (PEEK), Polyurethane (PU) or the like 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 absorber that absorbs light of a specific wavelength such as infrared rays or ultraviolet rays may be added.

  For the organic resin intermediate layer, a combination of a plurality of the above organic resins may be used. For example, if two organic resin intermediate layers are used to integrate the glass plate and the resin plate, an organic resin that matches the thermal expansion coefficient of the glass plate and the resin plate can be selected. It becomes easy to alleviate the difference. As a result, it becomes easy to reduce the curvature of the windshield.

  The total plate thickness of the glass resin composite is preferably 55 mm or less, 45 mm or less, or 40 mm or less, preferably 4 mm or more, 5 mm or more, 7 mm or more, particularly 10 mm or more. If the total plate thickness of the glass resin composite is too small, the impact resistance of the windshield tends to decrease. On the other hand, when the total plate thickness of the glass resin composite is too large, the mass of the windshield becomes large, and the visibility of the windshield tends to be lowered.

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

  First, a glass raw material prepared so as to have a predetermined glass composition is put into a continuous melting furnace, melted at 1500 to 1700 ° C., clarified and stirred, then supplied to a molding apparatus to be formed into a plate shape, and slowly cooled. By doing so, a glass plate can be produced.

  As a method for forming the glass plate, it is preferable to employ a float method. The float method is a method by which a glass plate can be produced at low cost.

  In addition to the float method, an overflow downdraw method may be employed. The overflow downdraw method is a method capable of producing a large amount of thin glass plates with the surface being unpolished. If the surface is unpolished, the manufacturing cost of the glass plate can be reduced.

  The glass plate is preferably chamfered as necessary. In that case, it is preferable to perform C chamfering with a # 800 metal bond grindstone or the like. If it does in this way, end face strength can be raised. It is also preferable to reduce the crack source existing on the end face by etching the end face of the glass plate as necessary.

Next, a surface compressive stress layer is formed on the obtained glass plate. As described above, the surface compressive stress layer may be formed by a method using a difference in thermal expansion coefficient between glass plates or a method in which the SiO ₂ concentration on the surface of the glass plate is made higher than the SiO ₂ concentration in the central portion in the plate thickness direction. it can. As the former method, for example, two glass plates having different thermal expansion coefficients are prepared so that the glass plate on which the surface compressive stress layer is to be formed has high expansion, and after laminating them, the softening point of the glass plate (A temperature corresponding to a viscosity of 10 ^7.6 dPa · s) A method of bonding the two together in an electric furnace maintained at a temperature in the vicinity. In this case, in order to promote bonding, it is preferable to heat-treat in a state where a load is applied to the glass plate, and it is also preferable to bond the two together during curved surface processing described later. Examples of the latter method include a method of heat-treating the surface of the glass plate with a gas burner flame.

  Next, the obtained glass plate is subjected to curved surface processing as necessary. Various methods can be employed as a method of processing the curved surface. In particular, a method of press-molding glass plates one by one or by laminating them with a mold is preferable, and it is preferable to pass through a heat treatment furnace with a glass plate sandwiched between molds having a predetermined shape. In this way, the dimensional accuracy of the curved surface shape can be increased. In addition, after placing glass plates one by one or in layers on a mold with a predetermined shape, the glass plate is softened by its own weight along the shape of the mold by heat-treating part or all of the glass plate. A method of deforming is also preferable. If it does in this way, the efficiency of curved surface processing can be raised.

  Next, a glass plate (preferably a plurality of glass plates) and a resin plate can be integrated with an organic resin intermediate layer to produce a glass resin composite. As a method of integration, a method of curing an organic resin after injecting an organic resin between glass plates or between a glass plate and a resin plate, a pressure heating treatment after placing an organic resin sheet between glass plates or between a glass plate and a resin plate (Thermocompression bonding) and the like. The former method can suppress deformation of the resin plate due to expansion mismatch between the glass plate and the resin plate. The latter method is easy to integrate.

  In addition, after integration, a functional film such as a hard coat film, an infrared reflection film, or an ultraviolet shielding film may be formed on the outer surface of the outermost glass plate. Prior to integration, a functional film such as a hard coat film, an infrared reflection film, or an ultraviolet shielding film may be formed on the inner surface of the outermost glass plate.

  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.

The glass plate for outermost layers was produced as follows. First, in order to obtain a glass composition containing, as a glass composition, 45% SiO ₂ , 23% Al ₂ O ₃ , 7% P ₂ O ₅ , 2% Li ₂ O, and 23% MgO, Prepared. Next, the prepared glass batch is put into a continuous melting furnace, melted at 1600 ° C. for 20 hours, clarified and stirred to obtain a homogeneous molten glass, and then formed into a plate having a plate thickness of 8.0 mm. Molded (Glass 1). Further, as a glass composition, in _{mol%, SiO 2 72%, Al} 2 O 3 14%, P 2 O 5 1%, Li 2 O 8%, MgO 1%, TiO 2 2%, ZrO 2 1%, SnO ₂ Glass raw materials were prepared so as to be 1%. Next, the glass batch was put into a continuous melting furnace, melted in the same process at 1650 ° C., and formed into a plate shape having a plate thickness of 8.0 mm (Glass 2). The obtained outermost layer glass plate was evaluated for thermal expansion coefficient, glass transition temperature, Young's modulus, viscosity log η at 800 ° C. and crystallinity, and the results are shown in Table 1. Each of these outermost glass plates has an impurity content of Fe ₂ O ₃ of less than 0.05 mol%, and the impurity content of V ₂ O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO is 0. It was less than 0.01 mol%.

  The thermal expansion coefficient is a value measured in a temperature range of 30 to 380 ° C., and is a value measured using a dilatometer.

  The glass transition temperature is a value measured using a dilatometer.

  The Young's modulus is a value measured by a known resonance method.

  The viscosity log η at 800 ° C. is obtained from the interpolated value of the temperature-viscosity curve obtained from the temperatures of the strain point, annealing point, and softening point. In addition, a strain point and a slow cooling point are the values measured based on the method of ASTM C336. The softening point is a value measured based on the method of ASTM C338.

  The degree of crystallinity was calculated by measuring the XRD by a powder method to calculate the area of the halo corresponding to the amorphous mass and the area of the peak corresponding to the mass of the crystal, respectively, 100 / [peak area + halo area] (%).

  Table 2 shows examples (samples No. 1 to 4) and comparative examples (samples No. 5 and 6) of the present invention.

  Sample no. 1-4 were produced. First, while preparing the above-mentioned outermost layer glass plate, various glass plates having the same dimensions as the outermost layer glass plate and having a lower expansion than the outermost layer glass plate were prepared. Next, the outermost layer glass plate and the low expansion glass plate were fused at the temperature of the softening point of the outermost layer glass plate to obtain a glass plate laminate in which the outermost layer side was convex. Thereafter, the glass plate laminate was processed into a curved surface at a temperature of (softening point + 50) ° C. Sample No. The low expansion glass plates according to 1 to 4 have different glass compositions and thermal expansion coefficients.

  Sample no. 5 and 6 were produced. First, while preparing the said outermost layer glass plate, the innermost layer glass plate which has the same dimension and the same glass composition as the outermost layer glass plate was prepared. Next, the glass plate for outermost layers and the glass plate for innermost layers were melt | fused at the temperature of the softening point of the glass plate for outermost layers, and the glass plate laminated body from which the outermost layer side becomes convex was obtained. Thereafter, the glass plate laminate was processed into a curved surface at a temperature of (softening point + 50) ° C.

  Next, regarding the outermost glass plate in the obtained glass plate laminate, the compression stress value of the surface compressive stress layer after fusion and before the curved surface processing and the compressive stress value of the surface compressive stress layer after the curved surface processing are expressed on the surface. It measured with the stress meter (FSM-6000 by Orihara Seisakusho). In calculating the compressive stress value, the refractive index of the measurement sample was 1.50, and the optical elastic constant was 30 [(nm / cm) / MPa].

  As can be seen from Table 2, sample no. 1-4 have the tempered glass board in which the surface compressive-stress layer was formed, and since the compressive-stress value is high, it is thought that the collision energy of a scattering piece can be attenuate | damped effectively. On the other hand, sample No. Since 5 and 6 do not have a tempered glass plate on which a surface compressive stress layer is formed, it is considered difficult to attenuate the collision energy of the scattering pieces.

  Thereafter, a polycarbonate plate (plate thickness: 4.0 mm) having a curved shape similar to that of the outermost glass plate was prepared.

  Finally, from the outside (atmosphere side), the glass plate laminate, 0.8 mm-thick polyvinyl butyral (PVB), and polycarbonate plate were integrated in this order by autoclave treatment. Glass resin composites according to 1-4 were obtained.

  Table 3 shows examples of the present invention (sample Nos. 7 to 10) and comparative examples (samples No. 11 and 12).

Sample no. 7-12 were produced. First, one surface of the glass plate for outermost layer described in Table 3 is heat-treated with a gas burner, so that the SiO ₂ concentration on one surface is made higher than the SiO ₂ concentration in the central portion in the plate thickness direction, and surface compression is performed. A stress layer was formed. In addition, No. About the glass plate for outermost layers concerning 7-9, the compressive stress value of the surface compressive stress layer after heat processing was adjusted by changing the heating conditions of a gas burner. Sample No. The glass plates for outermost layers according to 11 and 12 were not subjected to heat treatment with a gas burner.

For each sample, the presence or absence of a concentration gradient of SiO ₂ in the thickness direction was confirmed by composition analysis in the depth direction of the EPMA.

  Next, by passing through the heat treatment furnace with the outermost layer glass plate sandwiched between molds of a predetermined shape, the entire plate width direction is curved in an arc shape and the entire length direction is an arc shape. The curved surface was processed into a curved shape. Thereafter, C end chamfering and polishing were performed on the end face of the outermost glass plate after the curved surface processing using a # 800 metal bond grindstone.

  Moreover, the compressive stress value after heat processing and before curved surface processing, and the compressive stress value after curved surface processing were measured with the surface stress meter (FSM-6000 by Orihara Manufacturing Co., Ltd.). In calculating the compressive stress value, the refractive index of the measurement sample was 1.50, and the optical elastic constant was 30 [(nm / cm) / MPa].

  As can be seen from Table 3, sample no. 7 to 10 are tempered glass plates having a surface compressive stress layer. Since the compressive stress value is high, it is considered that the collision energy of the scattered pieces can be effectively attenuated. On the other hand, sample No. Since 11 and 12 do not have a surface compressive stress layer, it is considered difficult to attenuate the collision energy of the scattering pieces.

  Then, while preparing the glass plate (the innermost layer glass plate) having the same dimensions, the same glass composition and the same curved surface shape as the outermost layer glass plate, and having no compressive stress layer, the outermost layer glass plate and A polycarbonate plate (plate thickness: 4.0 mm) having the same curved surface shape was prepared.

  Finally, from the outside (atmosphere side), the outermost layer glass plate, 0.8 mm thick polyvinyl butyral (PVB), glass plate (innermost layer glass plate), 0.8 mm thick polyvinyl butyral (PVB), polycarbonate plate The sample No. 1 was integrated by autoclaving so that the sample no. A glass resin composite according to 7 to 10 was obtained.

  The glass resin composite of the present invention is suitable for windshields and door glass of automobiles, railways, aircrafts, and the like, and is also suitable for window glass of buildings such as high-rise buildings.

10 Glass resin composite 11 Glass plate (tempered glass plate)
12 Glass plate (the innermost glass plate)
13 Resin plate

Claims (7)

A glass resin composite comprising at least a plurality of glass plates and a resin plate,
A glass resin composite, wherein at least one of the plurality of glass plates is a tempered glass plate having a surface compressive stress layer. 2. The glass resin composite according to claim 1, wherein the tempered glass plate has a thermal expansion coefficient of 3 × 10 ⁻⁷ / ° C. or more lower than that of a glass plate adjacent to the tempered glass plate. The glass resin composite according to claim 1, wherein the SiO ₂ concentration on the surface of the tempered glass plate is higher than the SiO ₂ concentration in the central portion in the plate thickness direction. Tempered glass plate, as a glass composition, in _{mol%, SiO 2 40~80%, Al} 2 O 3 5~30%, B 2 O 3 + P 2 O 5 0 super _~25%, B 2 O 3 _0~15 %, P ₂ O ₅ 0-15%, Li ₂ O + Na ₂ O + K ₂ O 0 more than 20%, MgO more than 0-35%, CaO + SrO + BaO 0-15% The glass resin composite according to any one of the above.   The glass resin composite according to claim 1, wherein the glass resin composite has a curved shape that is three-dimensionally curved.   The glass resin composite according to claim 1, wherein the resin plate is disposed on the inner side of the innermost glass plate. A glass plate for use in a glass resin composite comprising at least a plurality of glass plates and a resin plate, wherein the surface SiO ₂ concentration is higher than the SiO ₂ concentration in the central portion in the plate thickness direction.