WO2018163902A1 - Glass-resin composite - Google Patents

Glass-resin composite Download PDF

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Publication number
WO2018163902A1
WO2018163902A1 PCT/JP2018/007165 JP2018007165W WO2018163902A1 WO 2018163902 A1 WO2018163902 A1 WO 2018163902A1 JP 2018007165 W JP2018007165 W JP 2018007165W WO 2018163902 A1 WO2018163902 A1 WO 2018163902A1
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Prior art keywords
glass
plate
resin
resin composite
glass plate
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PCT/JP2018/007165
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French (fr)
Japanese (ja)
Inventor
洋平 細田
慎護 中根
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日本電気硝子株式会社
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Priority to JP2017-041662 priority Critical
Priority to JP2017041662A priority patent/JP2018145048A/en
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Publication of WO2018163902A1 publication Critical patent/WO2018163902A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60JWINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00Windows; Windscreens; Accessories therefor
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal

Abstract

A glass-resin laminate according to the present invention is a glass-resin composite which is used in window glass, and which is characterized by being provided with at least a resin sheet and a plurality of glass sheets, and in that at least one layer from among the outer layers of glass sheet has a glass transition temperature of 300–850°C, a Vickers hardness of 6 GPa or higher, and a degree of crystallinity of 30% or lower.

Description

Glass resin composite

The present invention relates to a glass resin composite used for a window glass, and particularly to a glass resin composite suitable for a window glass of a vehicle or the like.

In general, laminated glass made by combining and integrating multiple soda lime glass plates with an organic resin intermediate layer is used for window glass for vehicles, etc. For the purpose of weight reduction, multiple soda lime glass plates are used. In some cases, a glass resin composite is used in which a resin plate and a resin plate are combined and integrated with an organic resin intermediate layer.

The soda-lime glass plate used for the window glass of vehicles, etc., deforms the shape of the tip of the flying pieces such as stepping stones during running and increases the impact resistance, so that the kinetic energy of the scattered pieces at the time of collision (See Patent Documents 1 to 4).

However, it cannot be said that soda lime glass has sufficient ability to increase 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 weight of the window glass.

Therefore, it has been proposed to use a crystallized glass plate instead of a soda lime glass plate in order to increase the impact resistance of the scattering pieces. For example, Patent literature 2-4, as the predominant crystalline β- quartz solid solution (Li 2 O · Al 2 O 3 · nSiO 2 [ provided that, n ≧ 2]) Li 2, such O-Al 2 O 3 -SiO 2 A crystallized glass plate formed by precipitating a system crystal is disclosed.

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

However, since crystallized glass undergoes a crystallization process in which crystalline glass is baked and crystals are precipitated, the manufacturing cost is likely to increase, and furthermore, it is extremely difficult to thermally deform after crystal precipitation. It has the problem that it is difficult to apply to the window glass.

Therefore, the present invention has been made in view of the above circumstances, and its technical problem is that, even if the plate thickness is small, the impact resistance of the scattered pieces is high, stacking integration and bending are easy, and manufacturing is also possible. The idea is to create a window glass that can reduce the cost.

The inventors of the present invention, for a glass resin composite (glass resin laminate) comprising a plurality of glass plates and a resin plate, increase the hardness of the glass plate on the outside (outside air side) while increasing the glass transition temperature and crystallinity. It is found that the above-mentioned technical problem can be solved by lowering the value and is proposed as the present invention. That is, the glass resin composite of the present invention is a glass resin composite used for a window glass, comprising at least a plurality of glass plates and a resin plate, and at least one of the outer glass plates has a glass transition temperature of 300 to 850 ° C., Vickers hardness is 6 GPa or more, and crystallinity is 30% or less. Here, the “outer layer glass plate” refers to a glass plate other than the innermost layer glass plate. “Glass transition temperature” refers to a value measured using a dilatometer. “Vickers hardness” refers to a value calculated from the area of indentation generated by driving a Vickers indenter for 15 seconds at a temperature of 25 ° C. with a load of 0.98 N on the optically polished glass surface. “Crystallinity” is calculated by measuring the XRD by the powder method to calculate the halo area corresponding to the amorphous mass and the peak area corresponding to the crystal mass, respectively. ] × 100 / [peak area + halo area] (%).

The glass resin composite of the present invention includes at least a plurality of glass plates and resin plates. 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 scattered pieces and prevents the glass pieces from being scattered due to the impact of the scattered pieces. By providing both, it becomes easy to ensure impact resistance performance.

Further, in the glass resin composite of the present invention, at least one of the outer glass plates has a Vickers hardness of 6 GPa or more. Thereby, even if it does not crystallize a glass plate, impact resistance can be raised significantly.

Furthermore, in the glass resin composite of the present invention, the glass transition temperature of at least one of the outer glass plates is 300 to 850 ° C., and the crystallinity is 30% or less. Thereby, it becomes easy to bend a glass plate.

Second, in the glass resin composite of the present invention, at least one of the outer glass plates is an amorphous glass, and the glass composition is mol%, SiO 2 45-80%, Al It is preferable to contain 10-30% of 2 O 3 , 0-30% of Li 2 O + Na 2 O + K 2 O, and 3-35% of MgO + CaO + SrO + BaO. Here, “amorphous” refers to a case where the crystallinity is less than 1%. “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. “MgO + CaO + SrO + BaO” refers to the total amount of MgO, CaO, SrO and BaO.

Thirdly, in the glass resin composite of the present invention, it is preferable that the innermost (inner side) glass plate is soda lime glass.

Fourthly, in the glass resin composite of the present invention, the resin plate is preferably disposed on the inner side of the innermost glass plate.

Fifth, in the glass resin composite of the present invention, the resin plate is preferably a polycarbonate plate.

Sixth, the glass resin composite of the present invention preferably has a total plate thickness of 45 mm or less.

Seventh, the glass resin composite of the present invention preferably has a curved surface shape that is three-dimensionally curved. FIG. 1 is a schematic view for explaining an example of the window glass of the present invention. The glass resin composite 10 includes an outermost glass plate 11, an innermost glass plate 12, and a resin plate 13. The glass transition temperature of the outermost glass plate 11 is 300 to 850 ° C., the Vickers hardness is 6 GPa or more, and the crystallinity is 30% or less. The outermost glass plate 11, the innermost glass plate 12, and the resin plate 13 are laminated and integrated with an organic resin intermediate layer (not shown). The glass resin composite 10 has a curved shape that is curved three-dimensionally. Specifically, the glass plate 11 side of the outermost layer is convex, and the entire plate width direction is curved in an arc shape. And the whole of the length direction is curving in circular arc shape.

It is the schematic which shows an example of the glass resin composite of this invention. It is a schematic sectional drawing which shows an example of the glass resin composite of this invention.

The glass resin composite of the present invention includes a plurality of glass plates, preferably 2 to 7, more preferably 2 to 3, particularly 2 glass plates. When the number of glass plates is too small, that is, when the number of glass plates is one, the impact resistance performance tends to be lowered. When the number of glass plates is too large, the transparency of the glass resin composite is lowered, and the visibility of the window glass is likely to be lowered. Further, the weight increases, and the fuel efficiency and power consumption cost of the vehicle and the like are likely to decrease.

FIG. 2 is a schematic cross-sectional view showing an example of the glass resin composite of the present invention. The glass resin composite 20 is laminated and integrated in the order of the outermost glass plate 21, the glass plate 22, the glass plate 23, the glass plate 24, the innermost glass plate 25, and the resin plate 26 as viewed from the outside. The glass plates 22 to 24 have a Vickers hardness of 8 GPa, the outermost glass plate 21 has a Vickers hardness of 5.6 GPa, and the innermost glass plate 25 has a Vickers hardness of 5.6 GPa.

In the glass resin composite of the present invention, the Vickers hardness of at least one of the outer glass plates (preferably the outermost glass plate) is 6 GPa or more, preferably 6.5 GPa or more, particularly preferably 7 to 15 GPa. If the Vickers hardness is too low, the impact resistance tends to decrease.

Among the outer glass plates, the glass transition temperature of at least one layer (preferably the outermost glass plate) is 300 to 850 ° C., preferably 320 to 820 ° C., and particularly preferably 350 to 800 ° C. If the glass transition temperature is too low, when the plurality of glass plates and the resin plate are laminated and integrated, the shape of the glass plate changes, and the dimensional accuracy of the glass resin composite tends to be lowered. On the other hand, if the glass transition temperature is too high, it becomes difficult to bend the glass plate. The glass transition temperature of the glass plate other than the innermost glass plate is preferably 300 to 850 ° C., more preferably 320 to 820 ° C., and particularly preferably 350 to 800 ° C.

Of the outer glass plates, the crystallinity of at least one layer (preferably the outermost glass plate) is 30% or less, preferably 10% or less, particularly preferably less than 1%, that is, an amorphous glass. is there. If the crystallinity is too high, it becomes difficult to bend the glass plate. The crystallinity of the innermost glass plate is preferably 30% or less, more preferably 10% or less, and particularly preferably less than 1%, that is, an amorphous glass.

It is preferable that the glass plate does not have a compressive stress layer by ion exchange. Thereby, an ion exchange process becomes unnecessary and the manufacturing cost of a glass plate can be reduced.

In the glass resin composite of the present invention, the thickness of the glass plate other than the innermost layer, preferably the glass plate of the outermost layer, is preferably 15 mm or less, 12 mm or less, 10 mm or less, particularly 8 mm or less, preferably 3 mm or more, It is 4 mm or more, 5 mm or more, 6 mm or more, particularly 7 mm or more. The thickness of the innermost 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. When the plate thickness of the glass plate is too small, the impact resistance is lowered and it is difficult to ensure the impact resistance performance. On the other hand, if the plate thickness of the glass plate is too large, it is difficult to make the window glass thinner, and the visibility tends to be lowered. In addition, the weight of the glass resin composite increases, and the fuel efficiency and power consumption cost of the vehicle and the like increase.

In the glass resin composite of the present invention, the long side dimension of the innermost layer glass plate is preferably smaller than the long side dimension of the outermost layer glass plate. And it is preferable that the long side dimension difference of both is adjusted according to both thermal expansion coefficient difference. In this way, when both are laminated and integrated after bending, the dimensional difference between the two becomes small and the end faces of both become easy to align. As a result, the end surface strength of the glass resin composite is improved.

The glass plate (preferably a glass plate other than the innermost layer, particularly preferably the outermost layer glass plate) is preferably an aluminosilicate glass. Aluminosilicate glass has high impact resistance due to its high Vickers hardness. Moreover, since devitrification resistance is good, it can be easily formed into a plate shape.

The glass plate (preferably a glass plate other than the innermost layer, particularly preferably the outermost layer glass plate) has a glass composition of mol%, SiO 2 45 to 80%, Al 2 O 3 10 to 30%, Li 2 O + Na. It is preferable to contain 0-30% of 2 O + K 2 O and 3-35% of MgO + CaO + SrO + BaO. 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 and is a component that increases Vickers hardness. The content of SiO 2 is preferably 45 to 80%, 50 to 75%, in particular 55 to 70%. When the content of SiO 2 is too small, it becomes difficult to vitrify, Vickers hardness is liable to lower. 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, making it difficult to match the thermal expansion coefficient of the resin plate or organic resin intermediate layer.

Al 2 O 3 is a component that increases weather resistance and Vickers hardness. The content of Al 2 O 3 is preferably 10 to 30%, 15 to 25%, particularly 17 to 23%. When the content of Al 2 O 3 is too small, weather resistance and the Vickers hardness is liable to lower. On the other hand, when the content of Al 2 O 3 is too large, the melting properties, formability, and resistance to devitrification tends to drop.

Li 2 O, Na 2 O, and K 2 O are components that lower the high-temperature viscosity and improve the meltability, moldability, and thermal processability. The total amount of Li 2 O, Na 2 O and K 2 O is preferably 0-30%, 5-25%, in particular 10-20%. The respective contents of Li 2 O, Na 2 O and K 2 O are preferably 0 to 20%, 3 to 15%, in particular 8 to 16%. When Li 2 O, the content of Na 2 O and K 2 O is too large, devitrification resistance and weather resistance tends to decrease.

MgO, CaO, SrO, and BaO are components that lower the high-temperature viscosity and increase the meltability, moldability, and thermal processability. In particular, MgO is a component that significantly increases the Vickers hardness. The total amount of MgO, CaO, SrO and BaO is preferably 3 to 35%, 10 to 30%, in particular 20 to 25%. The content of MgO is preferably 0-20%, 2-15%, in particular 5-16%. The respective contents of CaO, SrO and BaO are preferably 0 to 20%, 0 to 15%, in particular 1 to 16%. When there is too much content of MgO, CaO, SrO, and BaO, devitrification resistance will fall easily. From the viewpoint of simultaneously improving Vickers hardness and thermal workability, the molar ratio MgO / (MgO + CaO + SrO + BaO) is preferably 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.

B 2 O 3 is a component that forms a glass network, and is a component that lowers the crack generation rate, but is a component that lowers weather resistance. Therefore, the content of B 2 O 3 is preferably 0 to 20%, 0 to 10%, particularly 0 to 5%.

TiO 2 is a component that enhances the weather resistance, but is a component that colors the 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 weather resistance, but is 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 the 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 Nd 2 O 3 and La 2 O 3 are components that increase Vickers hardness. 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 positively add an explicit component but allows it to be mixed as an impurity. Specifically, It indicates that the content is less than 0.05%.

Although the aluminosilicate glass may be used as the innermost glass plate, it is preferable to use soda lime glass from the viewpoint of manufacturing cost. Soda lime glass generally has a glass composition of mol%, SiO 2 68-78%, Al 2 O 3 0-2%, CaO 6-15%, MgO 0-10%, Na 2 O 10- 20%, K 2 O 0 to 3%, Fe 2 O 3 0 to 1%.

The glass resin composite of the present invention includes a resin plate in order to relieve the impact force when scattered pieces such as stepping stones collide. The number of resin plates is not particularly limited, but is preferably one from the viewpoint of improving visibility. When the number of resin plates is too large, the transparency of the glass resin composite is lowered, and the visibility of the window glass is easily lowered.

It is preferable that the resin plate is disposed inside the innermost glass plate. If it does in this way, it will become easy to relieve the impact by a scattering piece, and when a glass plate is damaged by a scattering piece, the situation where a glass piece will scatter toward the inner side can be prevented.

Various resin plates such as an acrylic plate and a polycarbonate plate can be used as the resin plate. Among these, a polycarbonate plate is particularly preferable from the viewpoints 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 reduce the thickness of the glass resin composite, and the visibility is likely to decrease.

The plate thickness of the glass resin composite is preferably 45 mm or less, 35 mm or less, 30 mm or less, 25 mm or less, particularly 22 mm or less, preferably 7 mm or more, 11 mm or more, 12 mm or more, particularly 15 mm or more. If the plate thickness of the glass resin composite is too small, the impact resistance performance tends to decrease. On the other hand, if the plate thickness of the glass resin composite is too large, the weight of the glass resin composite becomes heavy and the visibility tends to decrease.

In the glass resin composite of the present invention, it is preferable to use an organic resin (organic resin intermediate layer) in order to laminate and integrate a plurality of glass plates and resin plates. 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, impact absorbability tends to be lowered, and stickiness tends to vary, and the glass plate and the resin plate are easily peeled off. On the other hand, when the thickness of the organic resin intermediate layer is too large, the transparency of the glass resin composite is lowered, and the visibility of the window glass is easily lowered.

The thermal expansion coefficient of the organic resin intermediate layer is preferably not less than the thermal expansion coefficient of the glass plate and not more than the thermal expansion coefficient of the resin plate. If it does in this way, when a glass resin composite is heated by direct sunlight, a glass plate and a resin plate will become difficult to isolate | separate and deform | transform. The “thermal expansion coefficient” refers to an average linear thermal expansion coefficient in a temperature range of 0 to 300 ° C.

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), Po Vinylidene fluoride (PVDF), methacryl-styrene copolymer resin (MS), polyarate (PAR), polyallyl sulfone (PASF), polybutadiene (BR), polyether sulfone (PESF), polyether ether ketone (PEEK), etc. Can be used. Among these, EVA and PVB are preferable from the viewpoint of transparency and adhesiveness, and PVB is particularly preferable because it can provide sound insulation.

A colorant may be added to the organic resin 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 a two-layer organic resin intermediate layer is used when stacking and integrating a glass plate and a resin plate, the glass plate and the resin plate are fixed with different organic resins, so it is easy to reduce the warpage of the glass resin composite. Become.

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, heated and melted at 1500 to 1700 ° C., clarified and stirred, and then fed to a molding apparatus to be formed into a plate shape. A glass plate can be produced by cooling.

It is preferable to adopt an overflow down draw method as a method of forming into a flat plate shape. The overflow downdraw method is a method in which a high-quality glass plate can be produced in a large amount and a large glass plate can be easily produced while the surface is unpolished. If the surface is unpolished, the manufacturing cost of the glass plate can be reduced.

In addition to the overflow downdraw method, it is also preferable to form a glass plate by the float method. The float method is a method capable of producing a large glass plate at low cost.

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

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 a glass plate with a mold is preferable, and it is preferable to pass through a heat treatment furnace with the glass plate sandwiched between molds having a predetermined shape. In this way, the dimensional accuracy of the curved surface shape can be increased. Also preferred is a method of softening and deforming the glass plate by its own weight along the shape of the mold by heat-treating a part or the whole of the glass plate after arranging the glass plate on the mold having a predetermined shape. If it does in this way, the efficiency of curved surface processing can be raised.

Further, a plurality of glass plates and resin plates are laminated and integrated to obtain a glass resin composite. As a method of stacking 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, pressurizing and heating after placing an organic resin sheet between glass plates or between a glass plate and a resin plate The method of processing (thermocompression bonding) etc. are mentioned. 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 easier to stack and integrate.

Further, after the lamination and integration, a functional film such as a hard coat film, an infrared reflection film, or a heat ray reflection film may be formed on the outer surface of the outermost glass plate. In addition, before lamination and integration, a functional film such as a hard coat film, an infrared reflection film, or a heat ray reflection film may be formed on the inner surface of the outermost glass plate.

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

A glass plate was produced as follows. The glass raw material was prepared so that the glass plate of Table 1 was obtained. 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. About the obtained glass plate, glass transition temperature, Vickers hardness, and crystallinity were evaluated. Sample No. The glass plates according to Nos. 1 to 7 have an Fe 2 O 3 mixing impurity amount of 0.05 mol%, and V 2 O 5 , Cr 2 O 3 , CoO 3 and NiO contamination amounts of 0.01 mol, respectively. %.

Figure JPOXMLDOC01-appb-T000001

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

The Vickers hardness is a value calculated from the area of the indentation generated by driving the Vickers indenter for 15 seconds with a load of 0.98 N on the optically polished glass surface at a temperature of 25 ° C.

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 / [Area of peak + Area of halo] (%) indicates a value obtained by the formula.

Also, by passing a glass plate through a heat treatment furnace with each sample 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 into a curved surface shape. Thereafter, the end face of the glass plate after the curved surface processing was C-chamfered and polished with a # 800 metal bond grindstone.

Next, a polycarbonate plate (plate thickness: 4.0 mm) and a soda glass plate (plate thickness: 8.0 mm) having the same curved shape as the glass plate were prepared. The glass composition, glass transition temperature, Vickers hardness and crystallinity of the soda glass plate are as shown in Table 1.

Finally, using polyvinyl butyral (PVB) with a thickness of 0.8 mm, the glass plate (outermost layer glass plate), soda glass plate (innermost layer glass plate) and polycarbonate plate described in the table are arranged. In addition, sample No. 1 was laminated and integrated by autoclave treatment. Glass resin composites according to 1 to 7 were obtained.

Sample No. Nos. 1 to 5 have high Vickers hardness and a glass transition temperature of 400 to 820 ° C. Moreover, since the degree of crystallinity is low, impact resistance is high, and it is considered that lamination integration and curved surface processing are easy. On the other hand, sample No. Nos. 6 and 7 are considered to have low impact resistance because of low Vickers hardness. Sample No. Nos. 1 to 7 are lightweight because the total thickness of the glass resin composite is 21.6 mm and a polycarbonate plate having a thickness of 4.0 mm is provided.

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

10, 20 Glass resin composite 11, 21 Glass plate (outermost layer glass plate)
12, 25 Glass plate (the innermost glass plate)
13, 26 Resin plate 22-24 Glass plate

Claims (7)

  1. In the glass resin composite used for the window glass,
    Comprising at least a plurality of glass plates and resin plates,
    A glass resin composite having a glass transition temperature of 300 to 850 ° C., a Vickers hardness of 6 GPa or more, and a crystallinity of 30% or less of an outer layer glass plate.
  2. At least one of the outer glass plates is amorphous glass, and the glass composition is SiO 2 45-80%, Al 2 O 3 10-30%, Li 2 O + Na 2 O + K 2 O 0- The glass resin composite according to claim 1, comprising 30%, MgO + CaO + SrO + BaO 3 to 35%.
  3. The glass resin composite according to claim 1 or 2, wherein the innermost glass plate is soda lime glass.
  4. The glass resin composite according to any one of claims 1 to 3, wherein the resin plate is disposed on the inner side of the innermost glass plate.
  5. The glass resin composite according to any one of claims 1 to 4, wherein the resin plate is a polycarbonate plate.
  6. The glass resin composite according to any one of claims 1 to 5, wherein the total plate thickness is 45 mm or less.
  7. The glass resin composite according to any one of claims 1 to 6, which has a curved shape that is three-dimensionally curved.
PCT/JP2018/007165 2017-03-06 2018-02-27 Glass-resin composite WO2018163902A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009215166A (en) * 2001-09-14 2009-09-24 Saint-Gobain Glass France Functionally safety grazing unit
JP4590487B2 (en) * 2008-12-22 2010-12-01 日本化薬株式会社 Laminated body for laminated glass
JP2015143182A (en) * 2013-12-25 2015-08-06 旭硝子株式会社 Glass substrate for movable home fence and glass laminate
US20150314571A1 (en) * 2014-05-02 2015-11-05 Corning Incorporated Strengthened glass and compositions therefor
JP2016008161A (en) * 2014-06-26 2016-01-18 日本電気硝子株式会社 Glass laminate
JP2016052990A (en) * 2012-05-11 2016-04-14 旭硝子株式会社 Front glass plate for laminate, and laminate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009215166A (en) * 2001-09-14 2009-09-24 Saint-Gobain Glass France Functionally safety grazing unit
JP4590487B2 (en) * 2008-12-22 2010-12-01 日本化薬株式会社 Laminated body for laminated glass
JP2016052990A (en) * 2012-05-11 2016-04-14 旭硝子株式会社 Front glass plate for laminate, and laminate
JP2015143182A (en) * 2013-12-25 2015-08-06 旭硝子株式会社 Glass substrate for movable home fence and glass laminate
US20150314571A1 (en) * 2014-05-02 2015-11-05 Corning Incorporated Strengthened glass and compositions therefor
JP2016008161A (en) * 2014-06-26 2016-01-18 日本電気硝子株式会社 Glass laminate

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