Curved-surface composite glass plate and preparation method thereof

Abstract

The invention belongs to the field of composite glass plates, and discloses a curved-surface composite glass plate and a preparation method thereof. The curved-surface composite glass plate comprises a polycarbonate layer, a glass layer and an elastic bonding layer arranged between the outer side surface of the polycarbonate layer and the glass layer. Wherein the polycarbonate layer is a modified polycarbonate plate of which the inner side surface is provided with a hardened coating; the modified polycarbonate plate is prepared from modified polycarbonate and an ultraviolet light absorber. According to the curved-surface composite glass plate, due to the thickening design of the elastic bonding layer at curved-surface turning and edges and the introduction of modified polycarbonate prepared from bisphenol S and other raw materials and modified silicon dioxide in the hardened coating, the curved-surface composite glass plate has excellent stability, transparency, hardness, wear resistance, flame retardance, antifogging capacity, impact resistance and fragment scattering prevention capacity. Therefore, the method has a wider application prospect in the scenes of vehicle windows / skylights, rail transit, building curtain walls, curved surface electronic cover plates and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of composite glass panels, and particularly relates to a curved composite glass panel and a preparation method thereof. BACKGROUND

[0002] The curved composite glass panel is a composite panel formed by combining a glass in a curved form as a base material with a functional material such as a polymer material through a lamination process such as interlayer bonding and adhesion. The curved composite glass panel not only retains the light transmittance, aesthetic appearance and curved modeling adaptability of the glass, but also improves the impact resistance, heat insulation, anti-glare, explosion-proof and other properties through the composite layer, and is widely used in the fields of high-speed rail, bus, ship, aircraft, general passenger vehicle, building, consumer electronics and the like, and meets the requirements of form design and function.

[0003] However, in actual application, the curved composite glass panel still has the problems that the glass layer is easy to scatter when broken, the hardness of the commonly used polycarbonate polymer material layer is insufficient and is easy to wear, the polycarbonate polymer material layer is easy to burn and drop in the event of a fire, the polycarbonate polymer material layer is easy to fog due to changes in cold / humidity, the bonding layer is whitened / delaminated due to stress concentration at the curved turning and edge regions, and the adhesion of the high-performance hard coating layer on the surface of the polycarbonate base material is insufficient. Moreover, the existing technology mainly focuses on a single material formula or a single step optimization, and it is difficult to balance the anti-impact / anti-fragment, hardness / wear resistance, flame retardance, anti-fogging, hard coating adhesion and stability. SUMMARY

[0004] To solve the problems mentioned in the background, the present application aims to provide a curved composite glass panel and a preparation method thereof, and solve the following technical problems: The existing curved composite glass panel still has the problem that the anti-fragment scattering ability, hardness, wear resistance, flame retardance, anti-fogging ability, hard coating adhesion and stability cannot be balanced at the same time.

[0005] The purpose of the present application can be achieved by the following technical solutions: A curved composite glass panel, the curved composite glass panel comprising a polycarbonate layer, a glass layer and an elastic bonding layer arranged between the outer side of the polycarbonate layer and the glass layer. The polycarbonate layer is a bisphenol S structure unit modified polycarbonate plate with a hard coating on the inner side. The hard coating comprises an epoxy polysiloxane, modified silica, an epoxy resin and a curing agent. The modified silica is silica with a surface grafted sulfobetaine zwitterionic polymer. The thickness of the elastic bonding layer at the curved turning and edge regions is 115%-150% of that of other regions during the coating process.

[0006] A preparation method of a curved composite glass plate, comprising the following steps: Pre-bending the polycarbonate layer, so that the hardened coating is located on the inner side of the curved surface, then coating an elastic adhesive layer on the outer side of the polycarbonate layer, thickening the curved surface transition and edge area, then stacking a glass layer on the adhesive layer and performing laminating and curing treatment, finally performing gradient cooling treatment on the stack and rounding the edges to obtain the curved composite glass plate.

[0007] Preferably, the preparation method of the polycarbonate layer is as follows: B1: adding diphenyl chlorophosphate in dichloromethane and stirring to obtain a diphenyl chlorophosphate solution; B2: adding diethylenetriamine and triethylamine in dichloromethane and stirring, then adding the diphenyl chlorophosphate solution dropwise under nitrogen atmosphere at -1-1℃ and reacting for 10-11h, filtering and removing dichloromethane by rotary evaporation to obtain a curing agent; B3: adding deionized water in anhydrous ethanol and heating to 33-37℃, then adding ammonia water and tetraethyl orthosilicate and stirring for 6-7h, then adding γ-aminopropyl triethoxysilane and reacting at 33-37℃ for 12-13h, centrifuging and washing the precipitate, then dispersing the precipitate in deionized water to obtain a pretreated silica dispersion; B4: heating the pretreated silica dispersion to 68-72℃, then adding methacryloyl ethyl sulfobetaine under nitrogen atmosphere and stirring for 30-50min, then adding ammonium persulfate aqueous solution and reacting at 68-72℃ under nitrogen protection for 12-13h, cooling, dialysis treatment and freeze-drying to obtain modified silica; B5: adding triethylamine in deionized water and stirring for 10-30min, then adding tetrahydrofuran and stirring for 20-30min, then adding silane coupling agent KH-560 under nitrogen atmosphere and reacting for 36-37h, removing tetrahydrofuran by rotary evaporation, then adding dichloromethane and stirring for 20-30min, finally adding anhydrous magnesium sulfate and drying for 24-25h, removing the precipitate by filtration to obtain epoxy polysiloxane; B6: adding modified silica in epoxy polysiloxane and ultrasonic dispersing for 30-50min, then adding epoxy resin AG-80 and curing agent and stirring at 68-72℃ for 30-60min, then spin coating on the modified polycarbonate plate and curing at 89-92℃ for 8-9h to obtain a polycarbonate layer.

[0008] Preferably, the mass ratio of dichloromethane to diphenyl chlorophosphate in B1 is 70-80:26; The mass ratio of dichloromethane, diethylenetriamine, triethylamine and diphenyl chlorophosphate solution in B2 is 350-400:10:10:96-106; The mass ratio of the anhydrous ethanol, deionized water 1, ammonia water, tetraethyl orthosilicate, gamma-aminopropyl triethoxysilane, and deionized water 2 in B3 is 400-500:100-125:20-24:9.3-11.2:4.6-5.6:100; The mass fraction of the ammonia water in B3 is 25%-28%; The mass ratio of the pretreated silica dispersion solution, methacryloyl ethyl sulfobetaine, and ammonium persulfate aqueous solution in B4 is 105-106:20:20; The mass fraction of the ammonium persulfate aqueous solution in B4 is 2%; The dialysis treatment in B4 is: dialysis treatment with deionized water, water change every 8h, dialysis duration of 48h, and molecular weight cut-off of 8000-14000Da; The mass ratio of the deionized water, triethylamine, tetrahydrofuran, silane coupling agent KH-560, dichloromethane, and anhydrous magnesium sulfate in B5 is 27:0.1-0.2:220:118:70:5-7; The mass ratio of the epoxy polysiloxane, modified silica, epoxy resin AG-80, and curing agent in B6 is 50:1.5-2:40:36; The thickness of the hardened coating after curing in B6 is 3-10µm.

[0009] Preferably, the preparation method of the modified polycarbonate plate is as follows: The ultraviolet absorber is added to the modified polycarbonate and stirred for 5-10min, and then fed into a twin-screw extruder, sequentially mixed at 210-230℃, 245-255℃, and 265-270℃ for 10-15min each, and then the extrudate is water-cooled, pelletized, vacuum-dried at 75-80℃ for 2-2.5h, and then added to the hopper of an injection molding machine for preheating for 10-15min, and then melted at 260-280℃ and injected into a mold at 90-110℃, and then pressure-maintained at 50-60MPa for 10-20s, and then annealed at 115-120℃ for 2-2.5h, and then demolded after cooling, to obtain the modified polycarbonate plate.

[0010] Preferably, the mass ratio of the modified polycarbonate and the ultraviolet absorber is 50:0.05-0.25; The ultraviolet absorber is a benzotriazole ultraviolet absorber; Preferably, the benzotriazole ultraviolet absorber is any one of ultraviolet absorber UV-326, ultraviolet absorber UV-327, and ultraviolet absorber UV-328.

[0011] Preferably, the preparation method of the modified polycarbonate is as follows: A1: adding bisphenol A, bisphenol S into deionized water and stirring for 20-30 min at 0-5℃, then adjusting pH to 11.2-11.8 with 15% sodium hydroxide aqueous solution and stirring for 2-4 h at 0-5℃ to obtain an aqueous phase; A2: adding triphosgene into dichloromethane and stirring for 40-50 min to obtain an organic phase; A3: first adding the aqueous phase into a reaction kettle, then adding the organic phase at 5-10 g / min while stirring for 10-15 min, then adding triethylamine and stirring for 20-30 min, then adding phenol and stirring for 30-60 min at 25-45℃, standing for 20-30 min, then discharging the upper aqueous phase, washing the lower organic phase with deionized water until the pH of the washing liquid is 6.8-7.2, then adding to methanol at 50 mL / min and standing for 10-20 min, then filtering and washing the precipitate with a small amount of methanol 2-4 times, and drying at 75-80℃ under a vacuum of -0.095 MPa for 12-15 h to obtain a modified polycarbonate.

[0012] Preferably, the mass ratio of the deionized water, bisphenol A and bisphenol S in A1 is 600-700:43.4:2.5; The mass ratio of the dichloromethane and triphosgene in A2 is 315-760:42-45; The mass ratio of the aqueous phase, organic phase, triethylamine and phenol in A3 is 645.9-745.9:350-800:0.23:1.3-1.7.

[0013] Preferably, the glass layer is prepared as follows: The tempered glass is subjected to plasma treatment at a power of 600-800 W for 5-8 min, and then subjected to ion exchange treatment in a potassium nitrate molten salt at 390-410℃ for 2-8 h to obtain the glass layer.

[0014] Preferably, the thickness of the polycarbonate layer is 0.5-5 mm; The pre-bending treatment is as follows: the hard coating side is located on the inner side of the curved surface, and the polycarbonate layer is pre-bent to a radius of curvature of 50-300 mm at 110-130℃ under a pressure of 0.2-0.5 MPa; The thickness of the elastic bonding layer is 0.1-0.5 mm; The elastic bonding layer is prepared by any two of modified polyurethane, thermoplastic polyurethane, polyvinyl butyral, ethylene-vinyl acetate and silicone-based elastomer in a layered composite, compatible blending or reaction coupling manner and through compatible or interfacial treatment; The thickness of the glass layer is 0.5-4 mm; The laminating curing treatment is vacuum or pressurized laminating curing at 90-120 DEG C for 20-40 min. The gradient cooling is cooling at 5-10 DEG C / min to 40-50 DEG C, and then natural cooling. The edge treatment is rounding the edge with a radius R of 0.5 mm.

[0015] The present application has the following advantages: The present application provides a curved composite glass plate and a preparation method thereof.

[0016] (1) The sulfone group of the modified polycarbonate is a strong polar rigid group, which has large steric hindrance and significantly enhanced intermolecular force, thereby limiting the movement of the polycarbonate main chain and improving the rigidity of the molecular chain. After modification, the hardness is improved, the "anti-deformation ability" of the material surface to resist external friction and scratches is enhanced, and plastic deformation or surface peeling is not easy to occur due to friction. The sulfone group of bisphenol S can also make the molecular chains more closely combined, and the molecular chains are not easy to be "stripped" during the friction process. During the modification process, bisphenol A and bisphenol S are the same type of aromatic dihydric phenol, and the molecular structures are similar. When copolymerized, a homogeneous copolymer is formed without obvious phase separation. The interfacial condensation reaction of triphosgene is controllable, and the molecular weight distribution of the product is narrow, so that light scattering caused by impurities or phase separation is avoided. Pure polycarbonate is prone to dripping when burning, but the sulfone group in the modified polycarbonate can promote the polycarbonate main chain to form a dense aromatic carbon layer, which can isolate heat and oxygen and prevent the spread of flames and reduce dripping. The sulfone group can decompose to produce inert gases such as sulfur dioxide at high temperatures, which can dilute the oxygen and combustible gases in the combustion zone. The polarity of the pure polycarbonate main chain is weak, and the interaction between the epoxy group in the hard coating is mainly weak van der Waals force, so the adhesion is easily affected by environmental humidity and temperature. However, the introduction of the sulfone group in the modified polycarbonate can significantly enhance the polarity of the molecular chain, and the oxygen atoms in the sulfone group can also form hydrogen bonds or strong interactions with the hydroxyl groups after ring opening of the epoxy groups in the hard coating and the amino groups on the surface of the modified silicon dioxide. In addition, the epoxy groups of the epoxy polysiloxane in the hard coating may also have a weak crosslinking reaction with the hydroxyl groups remaining at the end of the modified polycarbonate main chain, further strengthening the interfacial bonding and improving the adhesion of the hard coating, and the coating is not easy to delaminate after cold and hot cycle and vibration fatigue.

[0017] (2) The modified silica in the present application will be uniformly embedded in the organic crosslinked network as "nano-enhanced points", enhancing the ability of the coating to resist external force deformation, reducing the plastic deformation of the coating under pressure and scratching, significantly improving the hardness, improving the "anti-scratching threshold" of the coating, and reducing the generation and deepening of scratches during abrasion; the surface grafted methacryloyl ethyl sulfobetaine can also improve the compatibility of the particles and the organic matrix, avoid the particles from falling off during abrasion, and the presence of nanoparticles can reduce the friction coefficient of the coating surface, thereby effectively improving the wear resistance. The uniformly dispersed nanoparticles after grafting reaction with methacryloyl ethyl sulfobetaine can fill the small gaps generated during the crosslinking process of the epoxy matrix, and improve the transparency of the composite glass. When heated, the inorganic siloxane structure of the modified silica will preferentially form a dense inorganic silica layer covering the surface of the hardened coating, blocking the contact of oxygen with the combustible matrix, and at the same time inhibiting the heat transfer to the inside; in cooperation with the crosslinked structure of the epoxy system, it can also reduce the molten dripping of the coating during combustion, and reduce the risk of flame spread. The modified silica can hydrolyze and condense with the hydroxyl groups on the surface of the polycarbonate layer to form chemical bonds; it can also undergo ring-opening reaction with the epoxy groups of epoxy polysiloxane and epoxy resin, "chemically linking" the inorganic particles with the organic matrix and the coating with the polycarbonate layer; it can also form hydrogen bonds, van der Waals forces and other physical interactions with the surface of the polycarbonate layer, improving the adhesion of the hardened coating. The grafted methacryloyl ethyl sulfobetaine has strong hydrophilicity and hydrophilicity durability, can quickly adsorb water vapor in the air through electrostatic interaction and hydrogen bonds, and form a uniform and continuous water film on the surface of the coating; the continuous water film does not scatter light, thereby achieving anti-fogging and long-acting anti-fogging effect.

[0018] (3) The reaction of the epoxy groups in the hardened coating with the curing agent will form a three-dimensional dense crosslinked network, and the rigidity of the Si-O-Si bond is much higher than that of the C-O-C bond of polycarbonate, which can significantly enhance the rigidity of the coating; combined with the modified silica, the hardness can be greatly improved. The high-hardness coating can reduce the direct damage of external force to the surface of polycarbonate, and reduce the probability of scratch generation; the dense epoxy-siloxane crosslinked network combined with the modified silica can "share the friction stress", effectively avoiding the brittle falling off of the coating during friction, and further improving the wear resistance. When burning, the phosphorus element in the hardened coating will form a phosphoric acid-based flame-retardant carbon layer, and the nitrogen element will release inert gas to achieve the synergistic flame retardation of condensed phase and gas phase; the silicon element will be converted into a silica glass protective layer during combustion, covering the surface of the carbon layer, and further enhancing the barrier effect; the silica as an inorganic filler can also inhibit the molten dripping during combustion.

[0019] Of course, any product implementing the present application does not necessarily need to achieve all the advantages described above. BRIEF DESCRIPTION OF DRAWINGS

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or prior art description will be briefly introduced. Obviously, for those skilled in the art, other drawings can also be obtained without creative labor on the basis of these drawings.

[0021] Figure 1 is a production process flow diagram of the curved composite glass plate of the present application; Figure 2 is a plate structure cross-sectional view of the curved composite glass plate of the present application. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0023] In the description of the present application, it should be understood that the terms "opening", "upper", "lower", "thickness", "top", "middle", "length", "inner", "periphery" and the like indicate the orientation or positional relationship, which are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the indicated components or elements must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation of the present application.

[0024] Unless otherwise specified, the following raw material information is used in the following examples and comparative examples of the present application: Polycarbonate was purchased from Zhengzhou Alpha Chemical Co., Ltd. (Alpha), with the product number A037450. Polyvinyl butyral was purchased from Shanghai Yuan Ye Biological Technology Co., Ltd., with the product number S30198-500g. Thermoplastic polyurethane was purchased from Meirui New Material Co., Ltd. Styrene-acrylonitrile-glycidyl methacrylate copolymer was purchased from Jia Yicong Polymer (Shanghai) Co., Ltd., with the model number HPC-20. Maleic anhydride grafted thermoplastic polyurethane was purchased from Wuxi Yiyuan New Material Technology Co., Ltd., with the CAS number 66070-58-4. Ethylene-vinyl acetate was purchased from Nantong Runfeng Petroleum Chemical Co., Ltd., with the CAS number 24937-78-8. Modified polyether polyurethane was purchased from Meirui New Material Co., Ltd.

[0025] Example 1: A curved composite glass plate was prepared as follows: S1: 43.4 g of bisphenol A, 2.5 g of bisphenol S were added to 600 mL of deionized water at 0°C and stirred for 20 min, then the pH was adjusted to 11.2 with a 15% by mass sodium hydroxide aqueous solution and stirred at 0°C for 2 h to obtain an aqueous phase; S2: In a fume hood, 42 g of triphosgene was added to 315 g of dichloromethane and stirred for 40 min to obtain an organic phase; S3: 645.9 g of the aqueous phase was first added to a reaction kettle, then 350 g of the organic phase was added while stirring at 5 g / min and stirred for 10 min, then 0.23 g of triethylamine was added and stirred for 20 min, then 1.3 g of phenol was added and stirred at 25°C for 30 min, the upper aqueous phase was discharged after standing for 20 min, the lower organic phase was washed with deionized water until the pH of the washing liquid was 6.8, and finally it was added to 15 L of methanol at 50 mL / min and stood for 10 min, then filtered and the precipitate was washed twice with a small amount of methanol, and dried at 75°C under a vacuum of -0.095 MPa for 12 h to obtain a modified polycarbonate; S4: 0.05 g of ultraviolet absorber UV-328 was added to 50 g of the modified polycarbonate and stirred for 5 min, then it was fed into a twin-screw extruder and sequentially mixed at 210°C, 245°C, and 265°C for 10 min each, then the extrudate was water-cooled, pelletized, vacuum dried at 75°C for 2 h, then added to the hopper of an injection molding machine and preheated for 10 min, then melted at 260°C and injected into a 90°C mold, and pressure maintained at 50 MPa for 10 s, then annealed at 115°C for 2 h, then cooled and demolded to obtain a modified polycarbonate plate; S5: 26 g of diphenyl chlorophosphate was added to 70 g of dichloromethane and stirred for 30 min to obtain a diphenyl chlorophosphate solution; S6: 10 g of diethylenetriamine, 10 g of triethylamine were added to 350 g of dichloromethane and stirred for 20 min, then 96 g of the diphenyl chlorophosphate solution was added dropwise at 1 mL / min under a nitrogen atmosphere at -1°C and reacted for 10 h, then filtered and the dichloromethane was removed by rotary evaporation to obtain a curing agent; S7: 100 mL of deionized water was added to 400 g of anhydrous ethanol and heated to 33°C, then 20 g of 25% by mass ammonia water, 9.3 g of tetraethyl orthosilicate were added in sequence and stirred for 6 h, then 4.6 g of γ-aminopropyl triethoxysilane was added dropwise and reacted at 33°C for 12 h, then centrifuged and the precipitate was washed with a mixture of anhydrous ethanol and deionized water at a volume ratio of 1:1 for 3 times, then the precipitate was dispersed in 100 mL of deionized water to obtain a pretreated silica dispersion; S8: 105 g of the pretreated silica dispersion liquid was warmed to 68℃, then 20 g of methacryloyl ethyl sulfobetaine was added under nitrogen atmosphere and stirred for 30 min, after which 20 g of 2% mass fraction ammonium persulfate aqueous solution was added and reacted at 68℃ under nitrogen protection for 12 h, after cooling to room temperature, it was dialyzed with deionized water for 48 h, the molecular weight cut-off was 8000-14000 Da, and the water was changed every 8 h, finally it was freeze-dried to obtain modified silica; S9: 0.1 g of triethylamine was added to 27 g of deionized water and stirred for 10 min, then 220 g of tetrahydrofuran was added and stirred for 20 min, then 118 g of silane coupling agent KH-560 was added under nitrogen atmosphere and reacted for 36 h, after removing tetrahydrofuran by rotary evaporation, 70 g of dichloromethane was added and stirred for 20 min, and finally 5 g of anhydrous magnesium sulfate was added and dried for 24 h, after removing the precipitate by filtration, an epoxy polysiloxane was obtained; S10: 1.5 g of modified silica was added to 50 g of epoxy polysiloxane and ultrasonically dispersed for 30 min, then 40 g of epoxy resin AG-80 and 36 g of curing agent were added and stirred at 68℃ for 30 min, then it was spin-coated on a modified polycarbonate plate, and after curing at 89℃ for 8 h, a 3µm thick hardened coating was formed, obtaining a 0.5mm thick polycarbonate layer; S11: The tempered glass was treated with plasma at a power of 600W for 5min, then ion exchanged in a 390℃ potassium nitrate molten salt for 2h, obtaining a 0.5mm thick glass layer; S12: The polycarbonate layer was bent (hardened coating side inside the curve) into a curve with a radius of 50mm at 110℃ and a pressure of 0.2MPa, then an elastic adhesive layer was coated on the outer side of the curved surface of the polycarbonate layer, then a 60℃ glass layer was stacked on the coated surface, and after vacuum and pressure laminating curing at 90℃ for 20min, it was cooled to 40℃ at a rate of 5℃ / min, then naturally cooled to room temperature, finally edge rounding was performed, obtaining a curved composite glass sheet with a rounding radius R of 0.5mm.

[0026] The elastic adhesive layer includes a 0.03mm thick thermoplastic polyurethane layer on the polycarbonate layer side, a 0.05mm thick polyvinyl butyral layer on the glass layer side, and a 0.02mm thick styrene-acrylonitrile-glycidyl methacrylate copolymer compatible layer in the middle; the thickness of the polyvinyl butyral layer at the curved transition and edge region is 0.065mm.

[0027] Example 2: A method for preparing a curved composite glass sheet is as follows: S1: 43.4 g of bisphenol A, 2.5 g of bisphenol S were added to 650 mL of deionized water at 3°C and stirred for 20-30 min, then the pH was adjusted to 11.5 with a 15% by mass sodium hydroxide aqueous solution and stirred at 3°C for 3 h to obtain an aqueous phase; S2: 43.5 g of triphosgene was added to 537.5 g of dichloromethane in a fume hood and stirred for 45 min to obtain an organic phase; S3: 695.9 g of the aqueous phase was first added to a reaction kettle, then 575 g of the organic phase was added while stirring at 8 g / min and stirred for 13 min, then 0.23 g of triethylamine was added and stirred for 25 min, then 1.5 g of phenol was added and stirred at 35°C for 45 min, the upper aqueous phase was discharged after standing for 25 min, the lower organic phase was washed with deionized water until the pH of the washing liquid was 7, and finally it was added to 15 L of methanol at 50 mL / min and stood for 15 min, then it was filtered and the precipitate was washed with a small amount of methanol for 3 times, and then it was dried at 78°C under a vacuum of -0.095 MPa for 14 h to obtain a modified polycarbonate; S4: 0.15 g of ultraviolet absorber UV-327 was added to 50 g of the modified polycarbonate and stirred for 8 min, then it was fed into a twin-screw extruder and sequentially mixed at 220°C, 250°C and 268°C for 13 min each, then the extrudate was water-cooled, pelletized, vacuum dried at 78°C for 2.2 h, then added to the hopper of an injection molding machine and preheated for 13 min, then melted at 270°C and injected into a 100°C mold, and then pressure-maintained at 55 MPa for 15 s, then annealed at 118°C for 2.2 h, then demolded after cooling to obtain a modified polycarbonate plate; S5: 26 g of diphenyl chlorophosphate was added to 75 g of dichloromethane and stirred for 45 min to obtain a diphenyl chlorophosphate solution; S6: 10 g of diethylenetriamine, 10 g of triethylamine were added to 375 g of dichloromethane and stirred for 40 min, then 101 g of the diphenyl chlorophosphate solution was added dropwise at 1.5 mL / min under a nitrogen atmosphere at 0°C and reacted for 10.5 h, then filtered and rotary evaporated to remove dichloromethane to obtain a curing agent; S7: 112.5 mL of deionized water was added to 450 g of anhydrous ethanol and heated to 35°C, then 22 g of 27% by mass ammonia water, 10.2 g of tetraethyl orthosilicate were added in sequence and stirred for 6.5 h, then 5.1 g of γ-aminopropyl triethoxysilane was added dropwise and reacted at 35°C for 12.5 h, then the precipitate was separated by centrifugation and washed with a mixture of anhydrous ethanol and deionized water at a volume ratio of 1:1 for 4 times, then the precipitate was dispersed in 100 mL of deionized water to obtain a pretreated silica dispersion; S8: After the 105.5 g pretreated silica dispersion liquid was warmed to 70 °C, 20 g of methacryloyl ethyl sulfobetaine was added under a nitrogen atmosphere and stirred for 40 min, then 20 g of a 2% by mass ammonium persulfate aqueous solution was added and reacted at 70 °C under nitrogen protection for 12.5 h, after cooling to room temperature, it was subjected to dialysis treatment with deionized water for 48 h, with a molecular weight cut-off of 8000-14000 Da, and the water was changed every 8 h, and finally freeze-dried to obtain modified silica; S9: 0.15 g of triethylamine was added to 27 g of deionized water and stirred for 20 min, then 220 g of tetrahydrofuran was added and stirred for 25 min, then 118 g of silane coupling agent KH-560 was added under a nitrogen atmosphere and reacted for 36.5 h, after removing the tetrahydrofuran by rotary evaporation, 70 g of dichloromethane was added and stirred for 25 min, and finally 6 g of anhydrous magnesium sulfate was added and dried for 24.5 h, after removing the precipitate by filtration, an epoxy polysiloxane was obtained; S10: 1.8 g of modified silica was added to 50 g of epoxy polysiloxane and ultrasonically dispersed for 40 min, then 40 g of epoxy resin AG-80, 36 g of curing agent were added and stirred at 70 °C for 45 min, then spin-coated on a modified polycarbonate plate, and after curing at 90 °C for 8.5 h, a 6 µm thick hardened coating was formed to obtain a 3 mm thick polycarbonate layer; S11: The tempered glass was subjected to plasma treatment at a power of 700 W for 6 min, and then ion exchange treatment in a 400 °C potassium nitrate molten salt for 5 h to obtain a 2 mm thick glass layer; S12: The polycarbonate layer was bent (the hardened coating side was inside the curve) into a curve with a radius of 150 mm at 120 °C and a pressure of 0.4 MPa, then an elastic adhesive layer was coated on the outside of the curved surface of the polycarbonate layer, then a 70 °C glass layer was stacked on the coated surface, and after vacuum and pressure laminating curing at 115 °C for 30 min, it was cooled to 45 °C at a rate of 8 °C / min, then naturally cooled to room temperature, and finally edge rounding was performed to obtain a curved composite glass sheet with a rounding radius R of 0.5 mm.

[0028] The elastic adhesive layer was obtained by blending thermoplastic polyurethane, polyvinyl butyral, and maleic anhydride grafted thermoplastic polyurethane at a mass ratio of 70:30:4; the thickness of the elastic adhesive layer at the curved transition and edge regions was 0.4 mm, and the thickness of the elastic adhesive layer in other regions was 0.3 mm.

[0029] Example 3: A method for preparing a curved composite glass sheet is as follows: S1: At 5 °C, 43.4 g of bisphenol A and 2.5 g of bisphenol S were added to 700 mL of deionized water and stirred for 30 min, then the pH was adjusted to 11.8 with a 15% by mass sodium hydroxide aqueous solution and stirred at 5 °C for 4 h to obtain an aqueous phase; S2: In a fume hood, 45 g of triphosgene was added to 760 g of dichloromethane and stirred for 50 min to obtain an organic phase; S3: First, 745.9 g of an aqueous phase was added to a reaction kettle, then 800 g of the organic phase was added while stirring at 10 g / min and stirred for 15 min, then 0.23 g of triethylamine was added and stirred for 30 min, then 1.7 g of phenol was added and stirred at 45°C for 60 min, after standing for 30 min, the upper aqueous phase was discharged, the lower organic phase was washed with deionized water until the pH of the washing liquid was 7.2, and finally it was added to 15 L of methanol at 50 mL / min and stood for 20 min, after suction filtration, the precipitate was washed with a small amount of methanol for 4 times, and dried at 80°C under a vacuum degree of -0.095 MPa for 15 h to obtain a modified polycarbonate; S4: 0.25 g of ultraviolet absorber UV-326 was added to 50 g of the modified polycarbonate and stirred for 10 min, then it was fed into a twin-screw extruder, and after being mixed at 230°C, 255°C and 270°C for 15 min respectively, the extrudate was water-cooled, pelletized, vacuum dried at 80°C for 2.5 h, then added to the hopper of an injection molding machine and preheated for 15 min, then melted at 280°C and injected into a 110°C mold, and after being pressure-maintained at 60 MPa for 20 s, it was annealed at 120°C for 2.5 h, then demolded after cooling to obtain a modified polycarbonate plate; S5: 26 g of diphenyl chlorophosphate was added to 80 g of dichloromethane and stirred for 60 min to obtain a diphenyl chlorophosphate solution; S6: 10 g of diethylenetriamine, 10 g of triethylamine were added to 400 g of dichloromethane and stirred for 60 min, then 106 g of the diphenyl chlorophosphate solution was added dropwise at 2 mL / min under a nitrogen atmosphere at 1°C and reacted for 11 h, after filtration, dichloromethane was removed by rotary evaporation to obtain a curing agent; S7: 125 mL of deionized water was added to 500 g of anhydrous ethanol and warmed to 37°C, then 24 g of 28% mass fraction ammonia water, 11.2 g of tetraethyl orthosilicate were added in sequence and stirred for 7 h, then 5.6 g of γ-aminopropyl triethoxysilane was added dropwise and reacted at 37°C for 13 h, after centrifugal separation, the precipitate was washed with a mixture of anhydrous ethanol and deionized water at a volume ratio of 1:1 for 5 times, then the precipitate was dispersed in 100 mL of deionized water to obtain a pretreated silica dispersion; S8: 106 g of the pretreated silica dispersion was warmed to 72°C, then 20 g of methacryloyl ethyl sulfobetaine was added under a nitrogen atmosphere and stirred for 50 min, then 20 g of 2% mass fraction ammonium persulfate aqueous solution was added and reacted at 72°C under nitrogen protection for 13 h, after cooling to room temperature, it was subjected to dialysis treatment with deionized water for 48 h, with a molecular weight cutoff of 8000-14000 Da, and the water was changed every 8 h, and finally it was freeze-dried to obtain modified silica. S9: 0.2 g of triethylamine was added to 27 g of deionized water and stirred for 30 min, then 220 g of tetrahydrofuran was added and stirred for 30 min, then 118 g of silane coupling agent KH-560 was added under a nitrogen atmosphere and reacted for 37 h, after removing the tetrahydrofuran by rotary evaporation, 70 g of dichloromethane was added and stirred for 30 min, and finally 7 g of anhydrous magnesium sulfate was added and dried for 25 h, after removing the precipitate by filtration, an epoxy polysiloxane was obtained; S10: 2 g of modified silica was added to 50 g of epoxy polysiloxane and ultrasonically dispersed for 50 min, then 40 g of epoxy resin AG-80, 36 g of curing agent were added and stirred at 72°C for 60 min, then spin-coated on a modified polycarbonate plate, and after curing at 92°C for 9 h, a 10 µm thick hardened coating was formed to obtain a 5.0 mm thick polycarbonate layer; S11: The tempered glass was treated with plasma at a power of 800 W for 8 min, and then ion exchanged in a potassium nitrate molten salt at 410°C for 8 h to obtain a 4 mm thick glass layer; S12: The polycarbonate layer was bent (the hardened coating side was inside the curve) into a curve with a radius of 300 mm at 130°C and a pressure of 0.5 MPa, then an elastic adhesive layer was coated on the outside of the curved surface of the polycarbonate layer, then a layer of 80°C glass was superimposed on the coated surface, and after vacuum and pressure laminating curing at 120°C for 40 min, it was cooled to 50°C at a rate of 10°C / min, then naturally cooled to room temperature, and finally edge rounding was performed to obtain a curved composite glass sheet with a rounding radius R of 0.5 mm.

[0030] The elastic adhesive layer was obtained by blending ethylene-vinyl acetate, modified polyether polyurethane, and epoxy-modified ethylene-vinyl acetate at a mass ratio of 60:40:5; the thickness of the elastic adhesive layer at the curved transition and edge region was 0.75 mm, and the thickness of the elastic adhesive layer in other regions was 0.5 mm.

[0031] Comparative Example 1: This comparative example is compared with Example 1 only by replacing the "modified polycarbonate" added in the preparation process of S4 with "polycarbonate", and the rest of the steps and parameters are the same. This comparative example will not be repeated here. Finally, a curved composite glass sheet was obtained.

[0032] Comparative Example 2: This comparative example is compared with Example 1 only by not adding "ultraviolet absorber UV-328" in the preparation process of S3, and the rest of the steps and parameters are the same. This comparative example will not be repeated here. Finally, a curved composite glass sheet was obtained.

[0033] Comparative Example 3: The comparative example is compared with example 1 only without adding "modified silica" in the preparation process of S10, and the rest of the steps and parameters are the same. The comparative example will not be repeated. Finally, the curved composite glass plate is obtained.

[0034] Performance detection: Determination of elastic modulus: The elastic modulus (MPa) of the elastic bonding layer of the curved composite glass plate prepared in examples 1-3 of the present application was determined at DMA 1Hz, temperatures of 25℃, 80℃ and 4℃ respectively. The determination results are shown in Table 1. Determination of stability: The curved composite glass plate prepared in examples 1-3 of the present application was determined whether the elastic bonding layer appeared delamination or whitening after being subjected to 100 cycles of treatment at -40℃ for 2h and then at 85℃ for 2h, then subjected to 96h salt spray corrosion with 5% sodium chloride solution, and finally subjected to 12h vibration fatigue treatment in X-axis direction under the condition of 20Hz and acceleration of 5g. The determination results are shown in Table 1. Determination of impact resistance: The adhesion rate (%) of glass fragments and whether the polycarbonate layer was penetrated by the steel ball after the curved composite glass plate prepared in examples 1-3 of the present application was hit by a steel ball with a speed of 50m / s and a diameter of 8mm were determined. The determination results are shown in Table 1.

[0035] Table 1: Basic performance detection results of examples 1-3

[0036] Determination of hardness: According to the standard GB / T 6739-2022, the pencil hardness grade of the polycarbonate layer hard coating surface of the curved composite glass plate prepared in examples 1-3 and comparative examples 1-3 of the present application was determined under a load of 750g. The determination results are shown in Table 2. Determination of wear resistance: According to the standard GB / T 1768-2021, the wear amount (mg) of the polycarbonate layer hard coating surface of the curved composite glass plate prepared in examples 1-3 and comparative examples 1-3 of the present application after 1000 revolutions of abrasion was determined. The determination results are shown in Table 2. Determination of light transmittance: According to the standard GB / T 2680-2021, the light transmittance (%) of the curved composite glass plate prepared in examples 1-3 and comparative examples 1-3 of the present application at 550nm was determined. The determination results are shown in Table 2. Determination of flame retardancy: The flame-retardant grade of the polycarbonate layer of the curved composite glass plate prepared from the application examples 1-3 and the comparative examples 1-3 was determined according to the vertical burning method in GB / T 2408-2021 standard, and the determination results are shown in Table 2. Measurement of adhesion: The adhesion grade of the surface hardening coating of the polycarbonate layer of the curved composite glass plate prepared from the application examples 1-3 and the comparative examples 1-2 was determined according to GB / T 9286-1998 standard, and the determination results are shown in Table 2. Measurement of anti-fogging property: The haze (%) of the hardening coating surface of the polycarbonate layer of the curved composite glass plate prepared from the application examples 1-3 and the comparative examples 1-3 was determined according to GB / T 29600-2013 standard, and the determination results are shown in Table 2.

[0037] Table 2: Performance detection results of the application examples 1-3 and the comparative examples 1-3

[0038] Data analysis: As can be seen from Table 1, the curved composite glass plate prepared by the application has excellent stability, impact resistance, anti-fragment scattering ability, hardness, wear resistance, transparency, flame retardancy, hardening coating adhesion, and anti-fogging ability.

[0039] Among them, the modified polycarbonate used in the preparation process of the polycarbonate layer in the comparative example 1 was replaced by polycarbonate, and its hardness, wear resistance, transparency, flame retardancy, and hardening coating adhesion were all significantly lower than those of the examples, which shows that the modification of the polycarbonate in the application can effectively improve the hardness, wear resistance, transparency, flame retardancy, and hardening coating adhesion of the curved composite glass plate. The comparative example 2 did not add modified silica in the preparation process of the hardening coating, and its hardness, wear resistance, transparency, flame retardancy, hardening coating adhesion, and anti-fogging ability were all significantly lower than those of the examples, which shows that the addition of modified silica in the application can also effectively improve the hardness, wear resistance, transparency, flame retardancy, hardening coating adhesion, and anti-fogging ability of the curved composite glass plate. The comparative example 3 did not set the hardening coating on the modified polycarbonate plate, and its hardness, wear resistance, transparency, flame retardancy, and anti-fogging ability were all significantly lower than those of the examples, which shows that the hardening coating in the application can improve the hardness, wear resistance, transparency, flame retardancy, and anti-fogging ability of the curved composite glass plate.

[0040] In the description of the specification, the description of the terms "one embodiment", "an example", "a specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Also, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0041] The basic principles, main features and advantages of the present application are shown and described above. Those skilled in the art should understand that the present application is not limited by the above embodiments, and the above embodiments and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A curved composite glass panel, characterized by, The curved composite glass plate comprises a polycarbonate layer, a glass layer and an elastic bonding layer arranged between the outer side of the polycarbonate layer and the glass layer; The polycarbonate layer is a bisphenol S structure unit modified polycarbonate plate with a hard coating on the inner side; The hard coating comprises epoxy polysiloxane, modified silica, epoxy resin and curing agent; The modified silica is silica with a surface grafted sulfobetaine zwitterionic polymer; The thickness of the elastic bonding layer at the curved turning part and the edge area is 115%-150% of that of other areas during the coating process.

2. A method of manufacturing a curved composite glass panel, characterized by, The method comprises the following steps: Pre-bending treatment is performed on the polycarbonate layer, so that the hard coating is located on the inner side of the curve, then the elastic bonding layer is coated on the outer side of the polycarbonate layer, the thickness of the elastic bonding layer at the curved turning part and the edge area is increased, then the glass layer is stacked on the bonding layer and subjected to lamination and curing treatment, finally, gradient cooling treatment is performed on the stack, and the edge is subjected to round corner treatment, thereby obtaining the curved composite glass plate.

3. The method of claim 2, wherein the method further comprises: The preparation method of the polycarbonate layer is as follows: B1: chlorophosphonate diphenyl ester is added to dichloromethane and stirred to obtain a chlorophosphonate diphenyl ester solution; B2: diethylene triamine, triethylamine and chlorophosphonate diphenyl ester solution are added to dichloromethane and stirred, then the chlorophosphonate diphenyl ester solution is added dropwise under nitrogen atmosphere at-1-1℃ and reacted for 10-11h, after filtration, dichloromethane is removed by rotary evaporation to obtain a curing agent; B3: deionized water 1 is added to anhydrous ethanol and heated to 33-37℃, then ammonia water and tetraethyl orthosilicate are added and stirred for 6-7h, then γ-aminopropyl triethoxysilane is added and reacted at 33-37℃ for 12-13h, after centrifugal separation and washing of the precipitate, the precipitate is dispersed in deionized water 2 to obtain a pretreated silica dispersion; B4: the pretreated silica dispersion is heated to 68-72℃, then methylacryloyl ethyl sulfobetaine is added under nitrogen atmosphere and stirred for 30-50min, then ammonium persulfate aqueous solution is added and reacted at 68-72℃ under nitrogen protection for 12-13h, after cooling, dialysis treatment and freeze-drying, modified silica is obtained; B5: triethylamine is added to deionized water and stirred, then tetrahydrofuran is added and stirred, then silane coupling agent KH-560 is added under nitrogen atmosphere and reacted for 36-37h, after removal of tetrahydrofuran by rotary evaporation, dichloromethane is added and stirred for 20-30min, finally, anhydrous magnesium sulfate is added and dried for 24-25h, after removal of the precipitate by filtration, epoxy polysiloxane is obtained; B6: epoxy polysiloxane is added to the modified silica and ultrasonically dispersed for 30-50min, then epoxy resin and curing agent are added and stirred at 68-72℃ for 30-60min, then it is spin-coated on the modified polycarbonate plate and cured at 89-92℃ for 8-9h to obtain a polycarbonate layer.

4. The method of making a curved composite glass panel according to claim 3, wherein, The mass ratio of dichloromethane to chlorophosphonate diphenyl ester in B1 is 70-80:26; The mass ratio of dichloromethane, diethylene triamine, triethylamine and chlorophosphonate diphenyl ester solution in B2 is 350-400:10:10:96-106; The mass ratio of the anhydrous ethanol, deionized water 1, ammonia water, tetraethyl orthosilicate, gamma-aminopropyl triethoxysilane, deionized water 2 in B3 is 400-500:100-125:20-24:9.3-11.2:4.6-5.6:100; The mass fraction of the ammonia water in B3 is 25%-28%; The mass ratio of the pretreated silica dispersion solution, methacryloyl ethyl sulfobetaine, and ammonium persulfate aqueous solution in B4 is 105-106:20:20; The mass fraction of the ammonium persulfate aqueous solution in B4 is 2%; The mass ratio of the deionized water, triethylamine, tetrahydrofuran, silane coupling agent KH-560, dichloromethane, and anhydrous magnesium sulfate in B5 is 27:0.1-0.2:220:118:70:5-7; The mass ratio of the epoxy polysiloxane, modified silica, epoxy resin, and curing agent in B6 is 50:1.5-2:40:

36.

5. The method of making a curved composite glass panel according to claim 3, wherein, The preparation method of the modified polycarbonate plate in B6 is as follows: The ultraviolet absorber is added to the modified polycarbonate and stirred for 5-10 min, then the mixture is fed into a twin-screw extruder for mixing, and the extrudate is then water-cooled, pelletized, and vacuum-dried. After that, the mixture is melted and injected into a mold at 90-110℃, and is pressed at 50-60MPa for 10-20s, and then annealed at 115-120℃ for 2-2.5h. After cooling, the modified polycarbonate plate is demolded.

6. The method of making a curved composite glass panel according to claim 5, wherein, The mass ratio of the modified polycarbonate and the ultraviolet absorber is 50:0.05-0.25; The ultraviolet absorber is a benzotriazole ultraviolet absorber.

7. The method of making a curved composite glass panel according to claim 5, wherein, The preparation method of the modified polycarbonate is as follows: A1: At 0-5℃, the bisphenol A and bisphenol S are added to deionized water and stirred until uniform, and then the pH is adjusted to 11.2-11.8 and stirred for 2-4h to obtain an aqueous phase; A2: The triphosgene is added to dichloromethane and stirred for 40-50 min to obtain an organic phase; A3: The aqueous phase and the organic phase are first added to a reaction kettle and stirred until uniform, then triethylamine is added and stirred for 20-30 min, then phenol is added and stirred for 30-60 min. After standing, the upper aqueous phase is discharged, and the lower organic phase is washed and then added to methanol and allowed to stand for 10-20 min. After filtration and washing of the precipitate, the modified polycarbonate is obtained by vacuum drying.

8. The method of making a curved composite glass panel according to claim 7, wherein, The mass ratio of the deionized water, bisphenol A, and bisphenol S in A1 is 600-700:43.4:2.5; The mass ratio of the dichloromethane and triphosgene in A2 is 315-760:42-45; The mass ratio of the aqueous phase, organic phase, triethylamine, and phenol in A3 is 645.9-745.9:350-800:0.23:1.3-1.

7.

9. The method of making a curved composite glass panel according to claim 2, wherein, The preparation method of the glass layer is as follows: The tempered glass is subjected to plasma treatment at a power of 600-800W for 5-8 min, and then subjected to ion exchange treatment in a potassium nitrate molten salt at 390-410℃ for 2-8h to obtain the glass layer.

10. The method of making a curved composite glass panel according to claim 2, wherein, The thickness of the polycarbonate layer is 0.5-5mm; The pre-bending treatment is that the polycarbonate layer is pre-bent to a curvature radius of 50-300 mm with the hardened coating layer surface located at the inner side of the curved surface at 110-130 DEG C and under a pressure of 0.2-0.5 MPa; The thickness of the elastic adhesive layer is 0.1-0.5 mm; The elastic adhesive layer is prepared by using any two of modified polyurethane, thermoplastic polyurethane, polyvinyl butyral, ethylene-vinyl acetate and silicon-based elastomer in a layered composite, compatible blending or reaction coupling manner and through compatibilization or interface treatment; The thickness of the glass layer is 0.5-4 mm; The gradient cooling is that the temperature is decreased to 40-50 DEG C at a rate of 5-10 DEG C / min and then naturally cooled.

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