JP2019131431A - Glass resin composite - Google Patents

Abstract

To propose a glass resin composite excellent in curved surface workability, and hardly connecting cracks each other when a scattering piece crashes at a plurality of times even when thickness is small.SOLUTION: The glass resin composite is a glass resin composite having at least a plurality of glass sheets and resin sheets, in which crystallization degree of at least one glass sheet in the plurality of glass sheets is 30% or less, and crack resistance of the glass sheet inside neighboring the glass sheet of an outermost layer is 300 gf or more lower than crack resistance of the glass sheet of the outermost 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 with multiple soda lime glass plates combined with an organic resin intermediate layer is used for windshields of vehicles, etc. For the purpose of weight reduction, multiple soda lime glass plates are used. A glass resin composite in which a resin plate and a resin plate are combined and 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 vehicles, etc., attenuates the kinetic energy of the scattered pieces at the time of collision by deforming the tip shape of the flying pieces such as stepping stones while driving and increasing the impact resistance. It has a function to make it.

  However, it cannot be said that soda lime glass has sufficient ability to increase the impact resistance of the scattered pieces.

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

  According to the inventors' investigation, when the scattering pieces collide with the windshield several times, the cracks generated from one impact point are connected with the cracks generated from the other impact points, resulting in a large crack, and the entire windshield Was revealed to be damaged.

  However, in the conventional windshield, when the scattering pieces collide a plurality of times, the cracks are easily connected to each other, and it is difficult to prevent the entire windshield from being damaged. On the other hand, if the thickness of the glass plate is increased or the number of composites (the number of laminated layers) is increased, damage to the entire windshield can be suppressed, but in this case, the weight of the windshield increases and transparency is also impaired. There is a fear.

Therefore, it has been studied to use a crystallized glass plate for a windshield of a vehicle or the like. 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. However, since crystallized glass undergoes a crystallization process in which crystalline glass is baked and crystals are precipitated, manufacturing costs are likely to increase, and it is difficult to process curved surfaces after crystal precipitation. It has the problem that it is difficult to apply.

  The present invention has been made in view of the above circumstances, and the technical problem thereof is a glass resin composite that is excellent in curved surface processability, and even if the thickness is small, the cracks are difficult to connect when the scattered pieces collide multiple times. Is to invent.

  The present inventors make the crack resistance of the outermost glass plate higher than the crack resistance of the glass plate adjacent to the glass resin composite (glass resin laminate) having a plurality of glass plates and resin plates. Thus, the present inventors have found that the above technical problem can be solved, 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 the crystallinity of at least one glass plate among the plurality of glass plates is 30% or less, and the crack resistance of the inner glass plate adjacent to the outermost glass plate is 300 gf or more lower than the crack resistance of the outermost glass plate.

  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 and the area of the peak corresponding to the mass of the crystal, respectively. Peak area] × 100 / [peak area + halo area] (%) is a value determined by the formula. “Amorphous” refers to a crystallinity of less than 1%. “Crack resistance” refers to a load at which the crack occurrence rate is 50%. “Crack occurrence rate” refers to a value measured as follows. First, in a constant temperature and humidity chamber maintained at a humidity of 30% and a temperature of 25 ° C., a Vickers indenter set to a predetermined load is driven into the glass surface (optical polishing surface) for 15 seconds, and 15 seconds later, it is generated from the four corners of the indentation. Count the number of cracks (maximum 4 per indentation). Thus, after indenting the indenter 20 times and determining the total number of cracks generated, the total number of cracks generated is calculated by the formula of (total cracks generated / 80) × 100. The “inner glass plate adjacent to the outermost glass plate” usually refers to a glass plate adjacent to the outermost glass plate via an organic resin intermediate layer, and the organic resin intermediate layer is applied to the outermost glass plate. When the resin plate is interposed, the inner glass plate closest to the outermost glass plate is indicated.

  The glass resin composite of the present invention is a glass resin composite including at least a plurality of glass plates and resin plates. The glass plate is a material having transparency and increasing the impact resistance of the scattered pieces. 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, the crystallinity of at least one glass plate (preferably all glass plates) of the plurality of glass plates is 30% or less. Thereby, the curved surface workability of a glass plate can be improved.

  Furthermore, in the glass resin composite of the present invention, the crack resistance of the inner glass plate adjacent to the outermost glass plate is preferably 300 gf or more lower than the crack resistance of the outermost glass plate. The outermost glass plate is easily affected directly by the scattering pieces, and cracks are likely to occur from the impact point. Therefore, when a glass plate having a relatively high resistance is disposed as the outermost glass plate and the crack resistance of the inner glass plate is relatively reduced, the outermost layer glass is produced when the scattered pieces collide a plurality of times. It becomes easy to reduce the power of the scattered pieces with the board. As a result, breakage of the glass resin composite can be prevented appropriately. Furthermore, although the details of the mechanism are unknown, if the crack resistance of the inner glass plate adjacent to the outermost glass plate is lower by 300 gf or more than the crack resistance of the outermost glass plate, it is adjacent to the outermost glass plate. The number of cracks generated in the inner glass plate can be greatly reduced.

  In the glass resin composite of the present invention, the Young's modulus of the inner glass plate adjacent to the outermost glass plate is preferably 5 GPa or more higher than the Young's modulus of the outermost glass plate. In this way, the number of cracks generated in the inner glass plate adjacent to the outermost glass plate can be further reduced. Here, “Young's modulus” refers to a value measured by a known resonance method.

In the glass resin composite of the present invention, the outermost glass plate is preferably any of borosilicate glass, aluminosilicate glass, and alkali-free glass. These glasses tend to have high crack resistance. Here, “borosilicate glass” refers to a glass containing SiO ₂ and B ₂ O ₃ in the glass composition and the total amount of which is more than 50 mol%. “Aluminosilicate glass” refers to a glass containing SiO ₂ and Al ₂ O ₃ in the glass composition, and the total amount thereof is more than 50 mol%. “Non-alkali glass” refers to a glass in which the total amount of alkali metal oxides (Li ₂ O, Na ₂ O, K ₂ O) in the glass composition is 0.5 mol% or less.

Further, the glass resin composite of the present invention, the inside of the glass plate adjacent to the glass plate of the outermost layer is, 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 0~20%, MgO 2~25%, preferably contains 0~15% CaO + SrO + BaO. In this way, the crack resistance can be increased. Here, “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.

  Moreover, in the glass resin composite of this invention, it is preferable that a resin plate is arrange | positioned inside the glass plate of the innermost layer.

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

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

  The glass resin composite of the present invention preferably has a curved shape that is three-dimensionally curved. FIG. 1 is a schematic perspective view for explaining an example of the glass resin composite of the present invention. The glass resin composite 10 includes an outermost glass plate 11, an inner glass plate (an innermost glass plate) 12 adjacent to the outermost glass plate, and a resin plate 13. The outermost glass plate 11, the inner glass plate (the innermost glass plate) 12 adjacent to the outermost glass plate, and the resin plate 13 are combined and integrated with an organic resin intermediate layer (not shown). The crystallinity of the outermost glass plate 11 is 30% or less, and the crystallinity of the inner glass plate (the innermost glass plate) 12 adjacent to the outermost glass plate is 30% or less. 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. Furthermore, the crack resistance of the inner glass plate (the innermost glass plate) 12 adjacent to the outermost glass plate is 300 gf or more lower than the crack resistance of the outermost glass plate 11.

It is a schematic perspective view 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. If the number of glass plates is too small, that is, if the number of glass plates is one, it becomes difficult to ensure impact resistance. When there are too many glass plates, transparency will fall and visibility will fall easily. In addition, the weight increases, and the fuel consumption and the like of the automobile tend to decrease.

  FIG. 2 is a schematic cross-sectional view showing an example of the glass resin composite of the present invention. When viewed from the outside, the glass resin composite 20 includes an outermost glass plate 21, an inner glass plate 22 adjacent to the outermost glass plate, a glass plate 23, a glass plate 24, an innermost glass plate 25, and a resin plate. The composites are combined in the order of 26.

  In the glass resin composite of the present invention, the crystallinity of at least one glass plate (desirably, all glass plates) of the plurality of glass plates is 30% or less, preferably 10% or less, more preferably Amorphous (less than 1%). When the crystallinity of the glass plate is too high, curved surface processing becomes difficult.

Among the plurality of glass plates, the viscosity at 800 ° C. of at least one glass plate (desirably all glass plates) is preferably 10 ¹² dPa · s or less, 10 ^11.5 dPa · s or less, 10 ¹¹ dPa · s. 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.

  Of the plurality of glass plates, at least one glass plate (preferably all glass plates) preferably does not have a compressive stress layer by ion exchange. Thereby, the increase in the manufacturing cost of the glass plate by an ion exchange process can be avoided.

  The crack resistance of the inner glass plate adjacent to the outermost glass plate is 300 gf or more, preferably 500 gf or more, preferably 700 gf or more, particularly 800 gf or more lower than the crack resistance of the outermost glass plate. When the crack resistance of the inner glass plate adjacent to the outermost glass plate is higher than or equal to the crack resistance of the outermost glass plate, the cracks are easily connected when a plurality of scattered pieces collide. The glass resin composite is easily damaged.

  The Young's modulus of the inner glass plate adjacent to the outermost glass plate is preferably 5 GPa or more, preferably 10 GPa or more, more preferably 15 GPa or more, particularly 20 GPa than the Young's modulus of the outermost glass plate. It is preferable that the height is higher. If the Young's modulus of the inner glass plate adjacent to the outermost glass plate is lower than or comparable to the Young's modulus of the outermost glass plate, cracks are likely to be connected when a plurality of scattered pieces collide. The glass resin composite is easily damaged.

The inner glass plate adjacent to the outermost glass plate has a glass composition of 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 0~20%, MgO 2~25%, preferably contains 0~15% 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. 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, 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 enhances weather resistance and Young's modulus. The content of Al ₂ O ₃ is preferably 5 to 30%, 10 to 28%, 15 to 25%, 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, the melting properties, formability, and resistance to devitrification tends to drop.

B ₂ O ₃ is a component that enhances crack resistance while improving meltability, moldability, and curved surface processability. 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, it tends Young's modulus decreases, the crack resistance tends to be excessive.

P ₂ O ₅ is a component that improves meltability, moldability, and curved surface processability. The content of P ₂ O ₅ is preferably 0 to 15%, 1 to 12%, particularly 2 to 10%. If the content of P ₂ O ₅ is too large, the crack resistance tends to be too small.

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. The total amount of Li ₂ O, Na ₂ O and K ₂ O is preferably 0-20%, 1-15%, in particular 5-12%. The respective contents of Li ₂ O, Na ₂ O and K ₂ O are preferably 0-15%, 1-12%, in particular 3-10%. Li ₂ O, when the content of Na ₂ O and _{K 2} O is too large, the Young's modulus and the weather resistance tends to decrease.

  MgO is a component that increases the Young's modulus, and is a component that increases the meltability, moldability, and curved surface processability by reducing the high temperature viscosity. The content of MgO is preferably 2 to 25%, 3 to 15%, particularly 5 to 16%. 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 to 15%, 0 to 10%, particularly 0 to 5%. The respective contents of CaO, SrO and BaO are preferably 0 to 12%, 0 to 5%, particularly 0 to 2%. When there is too much content of CaO, SrO, and BaO, devitrification resistance and Young's modulus will fall easily.

  From the viewpoint of increasing the Young's modulus, 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.

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 Young's modulus and weather resistance, but it 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 SnO ₂ and / or SO ₃ ) may be added. .

Fe ₂ O ₃ is a component 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 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 outermost glass plate is preferably any one of borosilicate glass, aluminosilicate glass, and alkali-free glass. These glass plates have higher crack resistance and so-called Young's modulus than soda lime glass. Moreover, since these glass plates have good devitrification resistance, plate-shaped molding is easy. Borosilicate glass tends to have particularly high crack resistance.

  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 combined and integrated after the curved surface processing to form a glass resin composite, 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.

  In the glass resin composite of the present invention, the plate thickness of at least one glass plate (preferably all glass plates) 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. If the thickness of the glass plate is too small, it is 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 glass resin composite thin, and the visibility tends to be lowered. In addition, the weight of the glass resin composite increases, and the fuel efficiency of automobiles and the like increases.

  The glass resin composite of the present invention includes a resin plate in order to reduce the impact force when the scattering pieces 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 is lowered and the visibility of the glass resin composite is easily lowered.

  The resin plate is preferably arranged on the inner side of the innermost glass plate. If it does in this way, while becoming easy to relieve the impact by the collision of a scattering piece, when the glass plate is damaged by a scattering piece, the situation where a glass piece is scattered 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 total 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 total thickness of the glass resin composite is too small, the impact resistance tends to decrease. On the other hand, when the total plate thickness of the glass resin composite is too large, the weight of the glass resin composite becomes heavy and the visibility tends to be lowered.

  In the glass resin composite of the present invention, it is preferable to use an organic resin in order to combine 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 visibility of the glass resin composite tends to be 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. “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), Poly 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, when a two-layer organic resin intermediate layer is used for composite integration of a glass plate and a resin plate, the glass plate and the resin plate are fixed with different organic resins, so that the warpage of the glass resin composite can be easily reduced.

  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, then supplied to a forming apparatus and formed into a plate shape, and gradually A glass plate can be produced by cooling.

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

  In addition to the overflow downdraw method, it is also preferable to form the glass plate by a float method or a rollout method. In particular, 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 a resin plate are combined and integrated to obtain a glass resin composite. As a method of composite 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 combine and integrate.

  Further, after the composite integration, a functional film such as a hard coat film or a heat ray reflective film may be formed on the outer surface of the outermost glass plate. Further, before the composite integration, a functional film such as a hard coat film or a heat ray reflective 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.

Sample No. in the table is as follows. 1-8 were produced. 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. The glass plate obtained was evaluated for glass transition temperature, Young's modulus, crack resistance, and crystallinity. Sample No. In the glass plates according to Nos. 1 to 8, the impurity content of Fe ₂ O ₃ is 0.05 mol%, and the amounts of impurities contained in V ₂ O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO are each 0.01 mol. %. In addition, “NA” in the table means that it has not been measured.

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

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

  The crack resistance is a load at which the crack occurrence rate is 50%. “Crack occurrence rate” is a value measured as follows. First, in a constant temperature and humidity chamber maintained at a humidity of 30% and a temperature of 25 ° C., a Vickers indenter set to a predetermined load is driven into the glass surface (optical polishing surface) for 15 seconds, and 15 seconds later, it is generated from the four corners of the indentation. Count the number of cracks (maximum 4 per indentation). Thus, after indenting the indenter 20 times and determining the total number of cracks generated, the total number of cracks generated is calculated by the formula of (total cracks generated / 80) × 100.

  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.

  In addition, by passing each sample through a heat treatment furnace in a state of being sandwiched between molds of a predetermined shape, a curved surface shape in which the entire plate width direction is curved in an arc shape and the entire length direction is curved in an arc shape Curved surface. 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), a borosilicate glass plate (plate thickness 8.0 mm, Young's modulus 70 GPa, crack resistance 1500 gf), and a soda glass plate (plate thickness 8. 0 mm, Young's modulus 70 GPa, crack resistance 200 gf).

  Finally, in order from the outermost layer, a borosilicate glass plate, a 0.8 mm thick polyvinyl butyral (PVB), sample No. No. 1 glass plate, polyvinyl butyral (PVB) having a thickness of 0.8 mm, and a polycarbonate plate were laminated so as to be combined and integrated by autoclave treatment to obtain a glass resin composite. Sample No. in Table 1 About the glass plates of 2-8, the glass resin composite was produced by the same method, respectively. As an application example, in order from the outermost layer, a borosilicate glass plate, a 0.8 mm thick polyvinyl butyral (PVB), a soda glass plate, a 0.8 mm thick polyvinyl butyral (PVB), and a polycarbonate plate are arranged. Laminated and integrated by autoclave treatment to obtain a glass resin composite.

  As can be seen from Table 1, sample no. The crack resistance of the glass plates 1 to 8 is 300 gf or more lower than the crack resistance of the outermost glass plate (borosilicate glass plate). Since the Young's modulus of the glass plates 1 to 8 is higher than the Young's modulus of the outermost glass plate (borosilicate glass plate) by 5 GPa or more, it is considered that the cracks are not easily connected when the scattered pieces collide a plurality of times. Furthermore, sample no. The glass resin composites according to 1 to 8 have a total plate thickness of 21.6 mm and are light in weight because they include a 4.0 mm thick polycarbonate plate. Sample No. Since the glass plates 1 to 8 are amorphous, curved surface processing is easy.

  In the glass resin composite according to the application example, the crack resistance of the soda glass plate is 300 gf or more lower than the crack resistance of the outermost layer glass plate (borosilicate glass plate). It is thought that it is difficult to connect each other. On the other hand, in the glass resin composite according to the application example, the Young's modulus of the soda glass plate is equivalent to the Young's modulus of the outermost layer glass plate (borosilicate glass plate). No. It is estimated that the cracks are somewhat easily connected to each other than the glass resin laminates according to 1 to 8.

  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, 20 Glass resin composite 11, 21 Outermost layer glass plate 12 Inside glass plate adjacent to outermost layer glass plate (innermost layer glass plate)
13, 26 Resin plate 22 Inner glass plates 23 and 24 adjacent to the outermost glass plate 25 Glass plate 25 Innermost glass plate

Claims (8)

A glass resin composite comprising at least a plurality of glass plates and a resin plate,
Of the plurality of glass plates, the crystallinity of at least one glass plate is 30% or less,
A glass resin composite, wherein the inner glass plate adjacent to the outermost glass plate has a crack resistance of 300 gf or more lower than the crack resistance of the outermost glass plate.   2. The glass resin composite according to claim 1, wherein the Young's modulus of the inner glass plate adjacent to the outermost glass plate is 5 GPa or more higher than the Young's modulus of the outermost glass plate.   The glass resin composite according to claim 1 or 2, wherein the outermost glass plate is any one of borosilicate glass, aluminosilicate glass, and non-alkali glass. The inner glass plate adjacent to the outermost glass plate has a glass composition of 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 0~20%, MgO 2~25%, glass resin according to any one of claims 1 to 3, characterized in that it contains 0~15% CaO + SrO + BaO Complex.   The glass resin composite according to any one of claims 1 to 4, wherein the resin plate is disposed on the inner side of the innermost glass plate.   The glass resin composite according to any one of claims 1 to 5, wherein the resin plate is a polycarbonate plate.   Total glass thickness is 45 mm or less, The glass resin composite in any one of Claims 1-6 characterized by the above-mentioned.   The glass resin composite according to claim 1, wherein the glass resin composite has a curved shape that is three-dimensionally curved.