WO2020080162A1

WO2020080162A1 - Glass plate

Info

Publication number: WO2020080162A1
Application number: PCT/JP2019/039489
Authority: WO
Inventors: 田中　歩; 洋平細田
Original assignee: 日本電気硝子株式会社
Priority date: 2018-10-15
Filing date: 2019-10-07
Publication date: 2020-04-23
Also published as: JPWO2020080162A1

Abstract

This glass plate is integrated with a resin plate to produce a glass-resin composite, and is characterized in that the glass composition contains, on a molar basis: 45-80% of SiO₂; 5-30% of Al₂O₃; 0-20% of Li₂O + Na₂O + K₂O; 3-35% of MgO; 1-35% of CaO; and 0-15% of SrO + BaO.

Description

Glass plate

The present invention relates to a glass plate for composite-integrating with a resin plate to produce a glass-resin composite, and particularly to a glass plate used for a glass-resin composite suitable for an automobile windshield or door glass.

Laminated glass, which is a composite of multiple soda lime glass plates combined with an organic resin intermediate layer, is generally used for window glass of vehicles and the like. A glass-resin composite in which a resin plate and a resin plate are integrally integrated with an organic resin intermediate layer may be used (see Patent Documents 1 to 4).

The soda lime glass plate used for window glass of vehicles etc. has the function of attenuating the collision energy of the flying pieces by deforming the tip shape of the flying pieces of flying stones and increasing their impact resistance. Have

However, soda lime glass plate is not enough to increase the impact resistance of the scattering pieces. At present, the soda-lime glass plate is made thicker or the number of laminated sheets is increased to increase the impact resistance of the scattered pieces, but this causes an increase in the thickness and mass of the window glass.

Therefore, using a crystallized glass plate instead of the soda-lime glass plate has been studied in order to increase the impact resistance of the scattered pieces. For example, a crystal formed by precipitating a 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 [where n ≧ 2]) as the main crystal. Glass plates are under consideration.

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

By the way, when the crystallinity of the crystallized glass is increased, the hardness of the crystallized glass is increased, and the collision energy of the scattered pieces may be attenuated, but since the precipitated crystals inhibit softening deformation, bending becomes difficult, It cannot be applied to windshields of automobiles. Further, by increasing the thickness of the crystallized glass, the collision energy of the scattered pieces can be attenuated, but in this case, the mass of the window glass is increased and the transparency may be impaired.

Therefore, the present invention has been made in view of the above circumstances, the technical problem is excellent bending workability, even if the thickness and crystallinity is small, it is possible to effectively attenuate the collision energy of the flying pieces. The idea is to create a glass plate.

The present inventors have found that the above technical problems can be solved by strictly controlling the glass composition range of the glass plate, and propose as the present invention. That is, the glass plate of the present invention is a glass plate for composite-integrating with a resin plate to produce a glass-resin composite, and has a glass composition of mol% of SiO ₂ 45 to 80% and Al ₂ O. _{_{_{_{3 5 ~ 30%, Li 2}}}} O + Na 2 O + K 2 O 0 ~ 20%, MgO 3 ~ 35%, CaO 0.1 ~ 35%, characterized in that it contains SrO + BaO 0 ~ 15%. Here, _{_{"Li 2 O + Na 2 O +}} K 2 O " _means, Li 2 O, refers to the total amount of Na ₂ O and _{K 2} O. “SrO + BaO” refers to the total amount of SrO and BaO.

The glass plate of the present invention is a glass plate for composite-integrating with a resin plate to produce a glass-resin composite. In the glass resin composite, the glass plate is a material that has transparency and enhances 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 scattering due to the impact of the scattered pieces. By providing both, it becomes easy to ensure impact resistance.

FIG. 1 is a schematic diagram for explaining an example of a glass resin composite. The glass resin composite 10 has a glass plate 11, a glass plate 12, and a resin plate 13 in this order from the outside, and these have a three-dimensionally curved curved surface shape and are not shown. It is compositely integrated by the organic resin intermediate layer. The glass plate 11 has a glass composition of mol% of SiO ₂ 45 to 80%, Al ₂ O ₃ 5 to 30%, Li ₂ O + Na ₂ O + K ₂ O 0 to 20%, MgO 3 to 35%, CaO 0. It contains 1 to 35% and 0 to 15% of SrO + BaO. The resin plate 13 is polycarbonate.

When the present inventors analyzed the collision of the scattered pieces in detail, it was found that the glass plate was first damaged by the shock wave due to the collision of the scattered pieces, and then the scattered pieces penetrated through the glass plate. Then, it was found that when the shock waves generated by the collision of the flying pieces are dispersed, the collision energy of the flying pieces can be attenuated and the penetration of the flying pieces can be prevented. Furthermore, when the shock wave is analyzed in detail, when the shock wave disperses and attenuates in the traveling direction of the flying pieces and in the direction perpendicular thereto, the speed of the shock wave increases in proportion to the Young's modulus of the glass plate. Therefore, since the glass plate of the present invention has the above glass composition, the Young's modulus can be increased. As a result, when the scattering pieces collide with each other, the dispersion area of the shock waves becomes wider, the energy absorption of the shock waves increases, and the speed of the scattering pieces themselves can be effectively reduced. As a result, it becomes difficult for the scattered pieces to penetrate through the glass plate.

Also, the glass sheet of the present invention preferably has a Young's modulus of 80 GPa or more. By doing so, since the velocity of the shock wave is increased in the glass plate, the dispersion region of the shock wave is expanded, and the collision energy of the flying object can be greatly attenuated. Here, "Young's modulus" refers to a value measured by a well-known resonance method.

Further, the glass plate of the present invention preferably has a liquidus viscosity of 10 ^2.0 d · Pa or more. By doing so, it is difficult for the particles and devitrification to occur, and continuous melting is possible. Here, "liquidus viscosity" refers to a value obtained by measuring the viscosity of glass at a liquidus temperature by a platinum ball pulling method. “Liquid phase temperature” refers to a temperature at which crystals precipitate after glass powder passing through a standard sieve of 30 mesh (500 μm) and remaining at 50 mesh (300 μm) is put into a platinum boat and kept in a temperature gradient furnace for 24 hours.

Further, the glass plate of the present invention preferably has a crystallinity of 30% or less. By doing so, the bending workability of the glass plate can be improved. Here, 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 material and the area of the peak corresponding to the mass of the crystal. Area of peak] × 100 / [area of peak + area of halo] (%).

Also, the glass plate of the present invention preferably has a plate thickness of 3 to 15 mm.

Moreover, it is preferable that the glass plate of the present invention has a curved surface shape that is three-dimensionally curved. This makes it easy to apply it to the windshield of an automobile or the like.

It is a schematic diagram for explaining an example of a glass resin composite.

The glass plate of the present invention has a glass composition of, in mol%, SiO ₂ 45 to 80%, Al ₂ O ₃ 5 to 30%, Li ₂ O + Na ₂ O + K ₂ O 0 to 20%, MgO 3 to 35%, CaO. It contains 0.1 to 35% and 0 to 15% of SrO + BaO. The reasons for limiting the content range of each component as described above are shown below. In the description of the content range of each component, the% indication means mol%.

SiO ₂ is a component that forms a glass network. The content of SiO ₂ is preferably 45 to 80%, 52 to 75%, and particularly 58 to 72%. If the content of SiO ₂ is too small, it becomes difficult to vitrify, and the weather resistance tends to decrease. On the other hand, if the content of SiO ₂ is too large, the meltability and moldability are likely to be lowered, and the thermal expansion coefficient is too low, making it difficult to match the thermal expansion coefficient of the resin plate or the organic resin intermediate layer.

Al ₂ O ₃ is a component that enhances Young's modulus and weather resistance. The content of Al ₂ O ₃ is preferably 5 to 30%, 9 to 25%, 10 to 20%, and particularly 12 to 18%. When the content of Al ₂ O ₃ is too small, Young's modulus and weather resistance are likely to decrease. On the other hand, if the content of Al ₂ O ₃ is too large, the meltability, moldability, and devitrification resistance tend to decrease.

Li ₂ O, Na ₂ O and K ₂ O are components that lower the high temperature viscosity and enhance the meltability, moldability and bendability. The total amount of Li ₂ O, Na ₂ O and K ₂ O is preferably 0 to 20%, 1 to 15%, especially 2 to 10%. The content of Li ₂ O is preferably 0 to 15%, 1 to 12%, and particularly 2 to 10%. The respective contents of Na ₂ O and K ₂ O are preferably 0 to 15%, 0 to 3%, in particular 0 to less than 1%. If the total amount of Li ₂ O, Na ₂ O and K ₂ O is too large, the weather resistance tends to decrease. If the content of Li ₂ O is too large, the devitrification resistance tends to decrease. If the contents of Na ₂ O and K ₂ O are too large, the Young's modulus tends to decrease.

MgO is a component that significantly increases the Young's modulus, and also lowers the high temperature viscosity to enhance the meltability, moldability, and bendability. The content of MgO is preferably 3 to 35%, 8 to 30%, 12 to 25%, and particularly 14 to 20%. If the content of MgO is too small, it becomes difficult to enjoy the above effects. On the other hand, if the content of MgO is too large, the devitrification resistance tends to decrease.

CaO is a component that increases the Young's modulus and also a component that lowers the high temperature viscosity and enhances the meltability, moldability, and bending workability. In addition, when CaO is introduced in the composition region where the content of MgO is high, the liquidus temperature is lowered and the reduction of devitrification resistance is alleviated. The content of CaO is preferably 0.1 to 35%, 1 to 25%, 2 to 20%, particularly 4 to 15%. If the content of CaO is too small, it becomes difficult to enjoy the above effects. On the other hand, when the content of CaO is too large, the balance of the glass composition is lost and the devitrification resistance is rather lowered.

SrO and BaO are components that lower the high temperature viscosity and improve the meltability, moldability and bending workability. The total amount of SrO and BaO is preferably 0 to 15%, 0 to 5%, particularly 0 to less than 1%. The respective contents of SrO and BaO are preferably 0 to 12%, 0 to 5%, 0 to 2%, and particularly 0 to less than 1%. If the contents of SrO and BaO are too large, the devitrification resistance, Young's modulus, etc. tend to decrease, and the density increases, so the mass of the glass resin composite may increase too much.

From the viewpoint of lowering the liquidus temperature, the molar ratio MgO / (MgO + CaO + SrO + BaO) is preferably 0.95 or less, 0.9 or less, and particularly 0.85 or less. Note that “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.

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

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

B ₂ O ₃ is a component that forms a glass network and lowers the high temperature viscosity to enhance the meltability, moldability and bending workability. Therefore, the content of B ₂ O ₃ is preferably 0 to 15%, 0 to 10%, and particularly 0 to 5%. On the other hand, when the content of B ₂ O ₃ is too large, Young's modulus and weather resistance are likely to be lowered.

P ₂ O ₅ is a component that forms a glass network and enhances meltability, moldability, and bending workability, and is a component that enhances viscosity particularly near the liquidus temperature. The content of P ₂ O ₅ is preferably 0 to 15%, 0 to 10%, and particularly 0 to 5%. On the other hand, when the content of P ₂ O ₅ is too large, Young's modulus and weather resistance are likely to be lowered, and phase separation is likely to occur.

Y ₂ O ₃ and La ₂ O ₃ are components that significantly increase the Young's modulus and also components that enhance the meltability. The total and individual contents of Y ₂ O ₃ and La ₂ O ₃ are preferably 0 to 15%, 0 to 10%, and particularly 0 to 5%. On the other hand, if the contents of Y ₂ O ₃ and La ₂ O ₃ are too large, the devitrification resistance tends to decrease, and the density increases, so the mass of the glass resin composite may increase too much.

TiO ₂ is a component that enhances weather resistance, but is 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 improves Young's modulus and weather resistance, but is a component that reduces 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 the group of SnO ₂ and SO ₃ ) may be added. .

Fe ₂ O ₃ is a component that is inevitably mixed in the glass raw material as an impurity, 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 content of each of V ₂ O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO is preferably 0.1% or less, and particularly less than 0.01%.

From an 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 case where the explicit component is not positively added as a glass component, but the case where the glass component is mixed as an impurity is allowed. It means that the content is less than 0.05%.

The glass plate of the present invention preferably has the following characteristics.

The Young's modulus is preferably 80 GPa or more, 85 GPa or more, 90 GPa or more, and particularly 95 to 150 GPa. If the Young's modulus is too low, the velocity of the shock wave due to the collision of the flying 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 flying pieces.

The liquidus viscosity is preferably 10 ^2.0 dPa · s or more, 10 ^2.5 dPa · s or more, 10 ^3.0 dPa · s or more, 10 ^3.5 dPa · s or more, and particularly 10 ^4.0 dPa · s. s or more. In this way, devitrification crystals are less likely to occur, making it easier to mold by the float method or roll-out method. As a result, the manufacturing cost of the glass plate can be reduced and the quality of the glass plate can be improved. The upper limit of the liquidus viscosity is not particularly limited, but considering the balance for satisfying various properties required for the glass plate, it is a standard to design it to be 10 ^6.5 dPa · s or less.

The strain point is preferably 600 ° C. or higher, 650 ° C. or higher, 700 ° C. or higher, particularly 720 to 850 ° C. If the strain point is too low, the heat resistance tends to decrease.

The softening point is preferably 1100 ° C or lower, 1020 ° C or lower, 980 ° C or lower, and particularly 950 ° C or lower. If the softening point is too high, bending workability tends to decrease.

The glass temperature at a high temperature viscosity of 10 ^2.0 dPa · s is preferably 1600 ° C. or lower, 1580 ° C. or lower, 1560 ° C. or lower, and particularly 1550 ° C. or lower. If the temperature of the glass at a high temperature viscosity of 10 ^2.0 dPa · s is too high, the meltability and moldability are likely to deteriorate.

The crystallinity is preferably 30% or less, 10% or less, 5% or less, 1% or less, particularly 0%, that is, amorphous. If the crystallinity is too high, bending workability tends to decrease.

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 3 mm or more, 4 mm or more, 5 mm or more, 6 mm or more, particularly 7 mm or more. If the glass plate is too thin, it becomes difficult to ensure impact resistance. On the other hand, if the thickness of the glass plate is too large, it is difficult to make the window glass thinner, and the visibility is likely to decrease. In addition, the mass of the window glass increases, and the fuel efficiency of automobiles and the like increases.

The glass plate of the present invention is a glass plate for composite-integrating with a resin plate to produce a glass-resin composite. In the glass resin composite, it is preferable that the number of glass plates is plural. When the glass resin composite has a plurality of glass plates, it may include a glass plate other than the glass plate of the present invention (for example, a soda glass plate), but from the viewpoint of properly enjoying the effect of the present invention. Therefore, it is preferable that all the glass plates are the glass plates of the present invention.

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

The plate 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, and preferably 0.5 mm or more, 0.7 mm or more, 1 mm or more, 2 mm or more, especially 3 mm or more. . If the thickness of the resin plate is too small, it becomes difficult to absorb the impact when the flying pieces collide. On the other hand, if the thickness of the resin plate is too large, it becomes difficult to make the window glass thinner, and the visibility of the window glass is likely to deteriorate.

In the glass-resin composite, it is preferable that the glass plates, or the glass plate and the resin plate are combined and 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, and 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 inside of the room when the flying pieces collide. On the other hand, if the thickness of the organic resin intermediate layer is too large, the visibility of the window glass tends to deteriorate.

The thermal expansion coefficient of the organic resin intermediate layer is preferably not less than the coefficient of thermal expansion of the glass plate and not more than the coefficient of thermal expansion of the resin plate. With this configuration, when the window glass is heated by direct sunlight, the glass plate and the resin plate are difficult to separate and deform. The "coefficient of thermal expansion" refers to the average coefficient of linear thermal expansion in the temperature range of 0 to 300 ° C.

As the organic resin intermediate layer, various organic resins can be used, and 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), Po Vinylidene fluoride (PVDF), methacryl-styrene copolymer resin (MS), polyalate (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, PVB, and PU are preferable from the viewpoint of transparency and adhesion, 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 and 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, when two organic resin intermediate layers are used for composite integration of a glass plate and a resin plate, the glass plate and the resin plate are fixed by different organic resins, so that the warp of the window glass can be easily reduced.

The total plate thickness of the glass resin composite is preferably 65 mm or less, 60 mm or less, 55 mm or less, preferably 4 mm or more, 5 mm or more, 7 mm or more, and particularly 10 mm or more. If the total thickness of the glass-resin composite is too small, the impact resistance of the window glass tends to deteriorate. On the other hand, when the total plate thickness of the glass resin composite is too large, the weight of the window glass becomes heavy, and the visibility of the window glass is likely to decrease.

The glass plate can be manufactured as follows.

First, a glass raw material prepared to have a predetermined glass composition is charged into a continuous melting furnace, heated and melted at 1500 to 1700 ° C., clarified and stirred, and then supplied to a molding device to be molded into a plate shape, and then gradually cooled. A glass plate can be produced by cooling.

It is preferable to adopt the float method as a method for forming a glass plate. The float method is a method capable of inexpensively producing a glass plate.

Besides the float method, the rollout method or the overflow downdraw method may be adopted. The overflow downdraw method is a method capable of producing a large number of thin glass plates with the surface not polished. If the surface is not polished, the manufacturing cost of the glass plate can be reduced.

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 if necessary. Various methods can be adopted as the curved surface processing method. In particular, a method of press-molding glass plates one by one or by stacking them with a mold is preferable, and it is preferable to pass through a heat treatment furnace with the glass plates sandwiched by molds of a predetermined shape. By doing so, it is possible to improve the dimensional accuracy of the curved surface shape. In addition, after arranging the glass plates one by one or stacking them on the mold of a predetermined shape, heat-treating a part or the whole of the glass plates to soften the glass plates by their own weight along the shape of the mold. A method of deforming is also preferable. By doing so, the efficiency of curved surface processing can be improved.

Next, a glass plate (preferably a plurality of glass plates) and a resin plate can be compositely integrated with an organic resin intermediate layer to produce a glass resin composite. As a method of composite integration, a method of injecting an organic resin between glass plates or between a glass plate and a resin plate and then curing the organic resin, pressurizing and heating after placing an organic resin sheet between the glass plates or between the glass plate and the resin plate Examples include a method of treatment (thermocompression bonding). The former method can suppress the deformation of the resin plate due to the expansion mismatch between the glass plate and the resin plate. The latter method is easier for complex integration.

After the composite integration, a functional film such as a hard coat film or an infrared reflection film may be formed on the outer surface of the outermost glass plate. A functional film may be formed on the inner surface of the outermost glass plate before the composite integration.

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

Table 1 shows examples (Sample Nos. 1 to 12) of the present invention and comparative examples (Sample Nos. 13 to 16).

A glass plate was produced as follows. The glass raw materials were prepared so that the glass plate described in Table 1 was obtained. Next, the prepared glass batch was put into a continuous melting furnace, melted at 1600 ° C. for 20 hours, clarified and stirred to obtain a homogeneous molten glass, and then a plate having a thickness of 8.0 mm was formed. Molded. The density, Young's modulus, liquidus temperature, liquidus viscosity, strain point, softening point, glass temperature and crystallinity at a high temperature viscosity of 10 ^2.0 dPa · s were evaluated for the obtained glass plate. Sample No. In the glass plates according to Nos. 1 to 12, the amount of Fe ₂ O ₃ mixed impurities was 0.05 mol%, and the amount of V ₂ O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO mixed impurities was 0.01 mol each. Was less than%.

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

Young's modulus is a value measured by the well-known resonance method.

Each sample was crushed, passed through a standard sieve of 30 mesh (500 μm), and the glass powder remaining on 50 mesh (300 μm) was put into a platinum boat and kept in a temperature gradient furnace for 24 hours, and then the platinum boat was taken out and the glass was removed. The temperature at which devitrification (crystalline foreign matter) was recognized was defined as the liquidus temperature. Further, the viscosity at the liquidus temperature was measured by the platinum ball pull-up method, and this was defined as the liquidus viscosity.

The strain point and softening point are values measured based on the method of ASTM C336.

It is a value obtained by measuring the temperature of the glass at a high temperature viscosity of 10 ^2.0 dPa · s by a platinum ball pulling method.

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 material and the area of the peak corresponding to the mass of the crystal. The value obtained by the formula of 100 / [area of peak + area of halo] (%).

As can be seen from Table 1, Sample Nos. 1 to 12 have high Young's modulus, high impact resistance, and low crystallinity, so bending is easy. Further, since the liquidus viscosity is high, it is considered that continuous melting is possible. Therefore, the sample No. It is considered that 1 to 12 are suitable as a glass plate for composite-integrating with a resin plate to produce a glass-resin composite. On the other hand, sample No. Since Nos. 13 to 15 have a low Young's modulus, they have low impact resistance. Sample No. Since No. 16 has a low liquidus viscosity, it is considered that continuous melting is difficult.

Next, sample No. By passing through the heat treatment furnace with the glass plate according to No. 1 sandwiched between molds of 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. After that, the C-chamfering process and the polishing process were performed on the end surface of the glass plate after the curved surface processing with a # 800 metal bond grindstone.

Next, a polycarbonate plate (4.0 mm thick) having the same curved surface shape as the glass plate was prepared.

Finally, using polyvinyl butyral (PVB) with a thickness of 0.8 mm, from the outside (atmosphere side), sample No. No. 1 glass plate (glass plate of the outer layer), Sample No. Sample No. 1 was composited and integrated by autoclave treatment so that the glass plate (inner layer glass plate) according to No. 1 and the polycarbonate plate were laminated in this order. A glass resin composite according to No. 1 was obtained. Further, the sample No. The same experiment was performed for Sample Nos. 2 to 12, and Sample No. Glass resin composites according to 2 to 12 were obtained.

The glass plate of the present invention is suitable as a glass plate for composite-integrating with a resin plate to produce a glass-resin composite, and the glass-resin composite is suitable for window glass of automobiles, railways, aircrafts, etc. Besides, it is also suitable for window glass of buildings such as high-rise buildings.

10 glass-resin composite 11 glass plate 12 glass plate 13 resin plate

Claims

A glass plate for composite-integrating with a resin plate to produce a glass-resin composite,
As a glass composition, in mol%, SiO 2 45 to 80%, Al 2 O 3 5 to 30%, Li 2 O + Na 2 O + K 2 O 0 to 20%, MgO 3 to 35%, CaO 0.1 to 35%, A glass plate containing 0 to 15% of SrO + BaO.
The glass plate according to claim 1, which has a Young's modulus of 80 GPa or more.
Liquid glass viscosity is 10 2.0 dPa or more, The glass plate of Claim 1 or 2 characterized by the above-mentioned.
The glass plate according to any one of claims 1 to 3, which has a crystallinity of 30% or less.
The glass plate according to any one of claims 1 to 4, wherein the glass plate has a thickness of 3 to 15 mm.
The glass plate according to any one of claims 1 to 5, which has a curved surface shape curved three-dimensionally.