Explosion-proof impact-resistant toughened glass and preparation method thereof

Abstract

This invention discloses an explosion-proof and impact-resistant tempered glass and its preparation method, belonging to the field of tempered glass. The tempered glass comprises a glass base layer, a transition layer, and a functional layer. The glass base layer is ordinary tempered glass. The transition layer raw materials include 30-40 parts of titanate coupling agent-modified nano-silica and 20-30 parts of water-based epoxy resin. The functional layer raw materials include 40-50 parts of bio-based polylactic acid-modified epoxy resin, 10-15 parts of nano-calcium carbonate, 3-5 parts of ultrafine carbon fiber microfilaments, and 1-2 parts of environmentally friendly antioxidant. The preparation method includes glass base layer pretreatment, transition layer coating, functional layer coating, and curing. This invention enhances interfacial bonding through a gradient structure and uses bio-based raw materials to replace petrochemical-based resins, combining environmental friendliness, stability, and high performance.

Description

Technical Field

[0001] This invention relates to the field of glass, and in particular to an explosion-proof and impact-resistant tempered glass and its preparation method. Background Technology

[0002] Existing explosion-proof and impact-resistant tempered glass often employs coating spraying or laminated composite technologies to improve performance, but these generally suffer from insufficient interfacial bonding stability. For example, the sprayed coating disclosed in CN115851091A is prone to peeling off from the glass substrate after long-term use, affecting its service life; the interfacial film in CN119659114A is prone to bubble formation at the glass interface, reducing mechanical properties. Furthermore, existing technologies often use petrochemical-based resins as coating or film raw materials, resulting in poor environmental friendliness, and some solutions suffer from conflicts between light transmittance and strength; for instance, while metal wire interfacials increase strength, they block light. In addition, traditional composite structure designs are simplistic and do not consider the synergistic effects of each layer interface, leading to limited performance improvements. Therefore, developing a composite structure tempered glass with strong interfacial bonding, good environmental friendliness, and both high strength and high light transmittance has become a pressing technical problem for the industry. Summary of the Invention

[0003] The purpose of this invention is to provide an explosion-proof and impact-resistant tempered glass to solve the problems of easy explosion of tempered glass, weak bonding strength between coating and interface, and the impact on light transmittance while improving impact resistance in the prior art.

[0004] The present invention also aims to provide a preparation method for producing tempered glass with a composite structure that has strong interfacial bonding, good environmental performance, and high strength and high light transmittance.

[0005] In a first aspect, the present invention provides an explosion-proof and impact-resistant tempered glass, comprising a glass base layer, a transition layer, and a functional layer; The raw materials for the transition layer include, by weight, 30-40 parts of titanate coupling agent modified nano-silica and 20-30 parts of waterborne epoxy resin. The functional layer raw materials, by weight, include 40-50 parts of bio-based polylactic acid modified epoxy resin, 10-15 parts of nano-calcium carbonate, 3-5 parts of short-cut carbon fiber, and 1-2 parts of environmentally friendly antioxidant.

[0006] By adopting the above technical solutions, this invention achieves high strength, high interfacial bonding, high light transmittance, and long-term durability of tempered glass by constructing a composite structure through spraying a transition layer and a functional layer onto the glass substrate.

[0007] Specifically, the transition layer comprises titanate coupling agent-modified nano-silica and waterborne epoxy resin. The titanate coupling agent-modified nano-silica is the key interfacial bridging component. One end of the titanate coupling agent chemically reacts with the hydroxyl groups on the surface of the nano-silica, forming a strong chemical bond; the other end contains functional groups or long-chain alkyl groups that can react with organic resins, thus endowing the nanoparticles with excellent organic compatibility. The waterborne epoxy resin, as the continuous matrix of the transition layer, possesses good film-forming properties and wettability on glass surfaces. The modified nano-silica is uniformly dispersed in the waterborne epoxy resin, not only physically reinforcing the coating through the "pinning effect" of the nanoparticles, but more importantly, it constructs a gradient of chemical composition and modulus between the inorganic glass surface and the organic functional layer, achieving a synergistic effect of interfacial chemical bonding and physical interlocking, greatly improving interlayer adhesion and eliminating the risk of coating peeling.

[0008] The functional layer is made from bio-based polylactic acid (PLA) modified epoxy resin, nano-calcium carbonate, chopped carbon fibers, and environmentally friendly antioxidants. The functional layer is the main component responsible for impact resistance. As the matrix material, the bio-based PLA modified epoxy resin, through chemical hybridization of PLA segments with the epoxy resin, retains the high strength of the epoxy resin while introducing the toughness of the PLA segments. This results in higher elongation at break and energy dissipation capacity, which is fundamental to achieving impact toughening. Nano-calcium carbonate, as a dispersed reinforcing phase, has nanoscale particles that are uniformly dispersed in the resin matrix. It effectively hinders the movement of polymer molecular chains and can induce crazes and absorb energy under stress, thereby refining the material structure and significantly improving the stiffness, hardness, and toughness of the matrix. Short-cut carbon fibers, as the primary load-bearing and toughening reinforcing phase, possess high modulus and high strength, enabling them to bear most of the stress in composite materials. Uniformly dispersed short-cut fibers form a three-dimensional network within the matrix. When the material is subjected to impact, the fibers effectively bridge cracks, prevent crack propagation, and dissipate a significant amount of impact energy through processes such as fiber pull-out and debonding. Nano-calcium carbonate and short-cut carbon fibers form a synergistic reinforcing and toughening system at the microscopic level, achieving an optimal balance between rigidity and toughness. Environmentally friendly antioxidants inhibit thermo-oxidative aging of the resin matrix during processing and use, extending the service life of the functional layers.

[0009] Furthermore, in terms of interface bonding, the titanate coupling agent modified nano-silica in the transition layer forms a chemical bond with the glass substrate and achieves molecular-level compatibility with the bio-based modified epoxy resin in the functional layer, constructing an integrated structure of glass, transition layer and functional layer, which greatly improves the interlayer peel strength and solves the problem of easy peeling of traditional coatings; secondly, in terms of performance balance, the density of the transition layer and the rigidity and toughness of the functional layer work together, which not only improves the impact resistance and explosion-proof performance through nano-calcium carbonate and short-cut carbon fiber, but also avoids the scattering and absorption of light by controlling the size of nanofillers and the content and size of carbon fibers, thus achieving a unity of high strength and high light transmittance.

[0010] Preferably, the titanate coupling agent modified nano-silica is prepared by the following method: Nano-silica is added to toluene, and 2%–5% of titanate coupling agent by mass of nano-silica is added. The mixture is stirred at 250–300 r / min and 70–110 °C for 0.5–3 h. The mixture is then filtered, washed, and dried to obtain the final product.

[0011] Preferably, the titanate coupling agent includes titanate coupling agent NDZ-201 and titanate coupling agent NDZ-311.

[0012] Preferably, the bio-based polylactic acid modified epoxy resin is obtained by the following preparation method: Polylactic acid and epoxy resin are dispersed in a solvent, and isocyanate crosslinking agent is added. The mixture is stirred at 80-90°C for 2-3 hours, cooled, and dried to obtain the final product.

[0013] Preferably, the solvent includes ethyl acetate or acetone.

[0014] Preferably, the mass ratio of polylactic acid to epoxy resin is 1:(3-4).

[0015] Preferably, the amount of isocyanate crosslinking agent added is 2% to 3% of the mass of polylactic acid; Preferably, the isocyanate crosslinking agent includes hexamethylene diisocyanate, triallyl isocyanurate, and 4,4-diphenylmethane diisocyanate.

[0016] Preferably, the diameter of the chopped carbon fiber monofilament is 5-15 μm and the length is 50-200 μm.

[0017] Preferred environmentally friendly antioxidants include tea polyphenols and vitamin E in a mass ratio of 1:(0.5-1).

[0018] Preferably, the thickness of the transition layer is 0.01–1 μm, and the thickness of the functional layer is 0.1–1 μm.

[0019] Secondly, the present invention also provides a preparation method, comprising the following steps: S1. Pre-treatment of tempered glass by cutting, grinding, cleaning and drying to obtain the glass base layer; S2. Mix the titanate coupling agent modified nano-silica with water-based epoxy resin in a certain proportion and stir evenly to obtain a transition layer spraying liquid. Apply the liquid to the surface of the glass substrate using an ultrasonic spraying process and then cure the glass substrate coated with the transition layer. S3. Mix bio-based polylactic acid modified epoxy resin, nano-calcium carbonate short carbon fiber and environmentally friendly antioxidant in proportion, stir evenly to obtain functional layer spray liquid, apply it to the surface of the transition layer using ultrasonic spraying process, place the glass coated with functional layer in a curing mold, and allow it to cool naturally to room temperature.

[0020] Preferably, the solvents for the transition layer spray liquid and the functional layer spray liquid are ethyl acetate and n-hexane in a mass ratio of 1:(0.1-0.5), and the amount used is 3 to 5 times the mass of the raw materials of the transition layer or functional layer.

[0021] Preferably, the ultrasonic spraying process has a frequency of 2-5MHz, a power of 10-30W, a spray gun flow rate of 3-4mL / min, a spraying distance of 10-20mm, and a spraying speed of 200-300mm / s.

[0022] Preferably, the curing process includes curing at 120–130°C for 0.5–1 h, followed by curing at 150–180°C for 1–3 h.

[0023] The beneficial effects of this invention are: 1. This invention achieves the goals of high strength, high interfacial adhesion, high light transmittance, and long-term durability of tempered glass by constructing a composite structure through spraying a transition layer and a functional layer onto a glass substrate. The transition layer is constructed from nano-silica modified with a titanate coupling agent and waterborne epoxy resin. The modified nanoparticles act as a key bridge, forming a strong bond with the glass surface and tightly interlocking with the functional layer, thereby improving the interlayer peel strength to an excellent level and fundamentally overcoming the problem of easy peeling off of the protective coating. The functional layer uses bio-based polylactic acid modified epoxy resin as the matrix. While introducing bio-based components to improve environmental friendliness, it effectively toughens the glass by utilizing polylactic acid segments. Nano-calcium carbonate acts as a dispersed reinforcing phase, significantly refining and strengthening the resin structure. Uniformly dispersed short-cut carbon fibers form a three-dimensional network that effectively passivates cracks and disperses stress. The size effect and synergistic effect of the nanofillers and microfibers enable this layer to achieve a balance of rigidity and toughness at the microscopic level, and macroscopically endow the glass with excellent impact resistance and anti-shatter properties.

[0024] 2. This invention selects a resin matrix that matches the refractive index of glass, strictly controls the size of the core reinforcing phases, silica and calcium carbonate, to the nanoscale, which is much smaller than the wavelength of visible light, and meticulously manages the diameter, length, and content of short-cut carbon fibers. This ensures that all functional components exert their reinforcing effect while minimizing light scattering and absorption. Combined with optimized spraying and stepped curing processes, the final composite coating is uniform, dense, and has a clear interface, enabling the finished product to have the mechanical protective properties of tempered glass while maintaining extremely high optical transparency.

[0025] 3. This invention effectively inhibits the thermo-oxidative aging of the resin matrix during processing and use by adding environmentally friendly antioxidants, further ensuring the performance stability and lifespan of the product under long-term use. Detailed Implementation

[0026] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below.

[0027] An explosion-proof and impact-resistant tempered glass includes a glass base layer, a transition layer, and a functional layer; The raw materials for the transition layer include, by weight, 30-40 parts of titanate coupling agent modified nano-silica and 20-30 parts of waterborne epoxy resin. The functional layer raw materials, by weight, include 40-50 parts of bio-based polylactic acid modified epoxy resin, 10-15 parts of nano-calcium carbonate, 3-5 parts of short-cut carbon fiber, and 1-2 parts of environmentally friendly antioxidant.

[0028] By adopting the above technical solutions, this invention achieves high strength, high interfacial bonding, high light transmittance, and long-term durability of tempered glass by constructing a composite structure through spraying a transition layer and a functional layer onto the glass substrate.

[0029] Specifically, the transition layer comprises titanate coupling agent-modified nano-silica and waterborne epoxy resin. The titanate coupling agent-modified nano-silica is the key interfacial bridging component. One end of the titanate coupling agent chemically reacts with the hydroxyl groups on the surface of the nano-silica, forming a strong chemical bond; the other end contains functional groups or long-chain alkyl groups that can react with organic resins, thus endowing the nanoparticles with excellent organic compatibility. The waterborne epoxy resin, as the continuous matrix of the transition layer, possesses good film-forming properties and wettability on glass surfaces. The modified nano-silica is uniformly dispersed in the waterborne epoxy resin, not only physically reinforcing the coating through the "pinning effect" of the nanoparticles, but more importantly, it constructs a gradient of chemical composition and modulus between the inorganic glass surface and the organic functional layer, achieving a synergistic effect of interfacial chemical bonding and physical interlocking, greatly improving interlayer adhesion and eliminating the risk of coating peeling.

[0030] The functional layer is made from bio-based polylactic acid (PLA) modified epoxy resin, nano-calcium carbonate, chopped carbon fibers, and environmentally friendly antioxidants. The functional layer is the main component responsible for impact resistance. As the matrix material, the bio-based PLA modified epoxy resin, through chemical hybridization of PLA segments with the epoxy resin, retains the high strength of the epoxy resin while introducing the toughness of the PLA segments. This results in higher elongation at break and energy dissipation capacity, which is fundamental to achieving impact toughening. Nano-calcium carbonate, as a dispersed reinforcing phase, has nanoscale particles that are uniformly dispersed in the resin matrix. It effectively hinders the movement of polymer molecular chains and can induce crazes and absorb energy under stress, thereby refining the material structure and significantly improving the stiffness, hardness, and toughness of the matrix. Short-cut carbon fibers, as the primary load-bearing and toughening reinforcing phase, possess high modulus and high strength, enabling them to bear most of the stress in composite materials. Uniformly dispersed short-cut fibers form a three-dimensional network within the matrix. When the material is subjected to impact, the fibers effectively bridge cracks, prevent crack propagation, and dissipate a significant amount of impact energy through processes such as fiber pull-out and debonding. Nano-calcium carbonate and short-cut carbon fibers form a synergistic reinforcing and toughening system at the microscopic level, achieving an optimal balance between rigidity and toughness. Environmentally friendly antioxidants inhibit thermo-oxidative aging of the resin matrix during processing and use, extending the service life of the functional layers.

[0031] Furthermore, in terms of interface bonding, the titanate coupling agent modified nano-silica in the transition layer forms a chemical bond with the glass substrate and achieves molecular-level compatibility with the bio-based modified epoxy resin in the functional layer, constructing an integrated structure of glass, transition layer and functional layer, which greatly improves the interlayer peel strength and solves the problem of easy peeling of traditional coatings; secondly, in terms of performance balance, the density of the transition layer and the rigidity and toughness of the functional layer work together, which not only improves the impact resistance and explosion-proof performance through nano-calcium carbonate and short-cut carbon fiber, but also avoids the scattering and absorption of light by controlling the size of nanofillers and the content and size of carbon fibers, thus achieving a unity of high strength and high light transmittance.

[0032] In some embodiments, titanate coupling agent modified nano-silica is prepared by the following method: Nano-silica is added to toluene, and 2%–5% of titanate coupling agent by mass of nano-silica is added. The mixture is stirred at 250–300 r / min and 70–110 °C for 0.5–3 h. The mixture is then filtered, washed, and dried to obtain the final product.

[0033] By adopting the above technical solutions, nanoparticles with uniform surface modification and excellent dispersibility are obtained. The alkoxy groups of the titanate coupling agent modified nano silica can undergo a condensation reaction with the hydroxyl groups on the glass substrate surface to form a strong chemical bond. At the same time, the functional groups at the other end of the coupling agent achieve a compatible combination with the epoxy groups of the waterborne epoxy resin.

[0034] In some embodiments, the titanate coupling agent includes titanate coupling agent NDZ-201 and titanate coupling agent NDZ-311; both coupling agents have a bifunctional structure and high reactivity with nano-silica. After modification, they can significantly improve the compatibility between nanoparticles and waterborne epoxy resin. Moreover, their molecular chain length is adapted to the modulus gradient design of the transition layer, which can better connect the inorganic glass and the organic functional layer and further optimize the interlayer bonding force.

[0035] In some embodiments, the bio-based polylactic acid modified epoxy resin is obtained by the following preparation method: Polylactic acid and epoxy resin are dispersed in a solvent, and isocyanate crosslinking agent is added. The mixture is stirred at 80-90°C for 2-3 hours, cooled, and dried to obtain the final product.

[0036] By employing the above technical solutions, the isocyanate crosslinking agent fully reacts with the hydroxyl groups of polylactic acid and the active groups of epoxy resin, ultimately forming a hybrid matrix that combines the high strength of epoxy resin with the high toughness of polylactic acid, providing structural support for the impact resistance of the functional layer. The isocyanate in the isocyanate crosslinking agent reacts with the terminal hydroxyl or carboxyl groups of polylactic acid, generating urethane or amide bonds that graft PLA segments onto the epoxy resin system. Simultaneously, some NCO groups can also react with a small amount of hydroxyl groups on the epoxy resin chain, thereby constructing a three-dimensional crosslinked network. This enhances the mechanical strength and solvent resistance of the matrix while retaining the flexibility of the PLA segments, achieving a balance between rigidity and toughness.

[0037] In some embodiments, the solvent includes ethyl acetate and acetone, which ensures that the bio-based polylactic acid and epoxy resin form a uniform dispersion system.

[0038] In some embodiments, the mass ratio of polylactic acid to epoxy resin is 1:(3-4). This ratio can precisely control the performance balance of the modified resin. If the proportion of polylactic acid is too high, the matrix strength will decrease and it will not meet the impact resistance requirements. If the proportion is too low, the toughening effect will not be significant. The ratio of 1:(3-4) can enable the hybrid matrix to retain the high strength of epoxy resin while effectively relieving impact stress and improving the elongation at break by means of PLA segments.

[0039] In some embodiments, the amount of isocyanate crosslinking agent added is 2% to 3% of the mass of polylactic acid; this range is the optimal range for the crosslinking reaction to reach its limit. If the amount added is insufficient, the degree of crosslinking between polylactic acid and epoxy resin is insufficient, the matrix structure is loose, and the mechanical properties are poor; if the amount added is too high, it will lead to over-crosslinking, the matrix becomes brittle, and the impact resistance decreases.

[0040] In some embodiments, the isocyanate crosslinking agent includes hexamethylene diisocyanate, triallyl isocyanurate, and 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate is an aliphatic crosslinking agent that can impart good flexibility to the matrix; triallyl isocyanurate has high crosslinking efficiency and can improve the strength of the matrix; 4,4-diphenylmethane diisocyanate has good compatibility with the resin and the crosslinked product has a stable structure.

[0041] In some embodiments, the diameter of the chopped carbon fiber monofilament is 5-15 μm and the length is 50-200 μm. The diameter of the chopped carbon fiber is small enough to reduce light shading. The length is moderate, which can not only ensure effective stress transfer and reinforcement in the matrix, but also facilitate uniform dispersion in the spraying process, avoiding agglomeration and rough coating surface caused by excessive fiber length.

[0042] In some embodiments, the environmentally friendly antioxidant includes tea polyphenols and vitamin E in a mass ratio of 1:(0.5-1); tea polyphenols are rich in phenolic hydroxyl groups and are highly efficient natural free radical scavengers; vitamin E is a classic fat-soluble antioxidant. The synergistic effect of both can more effectively inhibit the aging and degradation of the resin matrix caused by heat and oxygen during processing and long-term use, thereby extending product lifespan.

[0043] In some embodiments, the thickness of the transition layer is 0.01–1 μm, and the thickness of the functional layer is 0.1–1 μm. This thickness design ensures that the transition layer can fully exert its interfacial bridging effect without introducing excessive internal stress, while the functional layer has sufficient thickness to accommodate the reinforcing phase and dissipate impact energy, ultimately achieving optimal overall performance.

[0044] A preparation method comprising the following steps: S1. Pre-treatment of tempered glass by cutting, grinding, cleaning and drying to obtain the glass base layer; S2. Mix the titanate coupling agent modified nano-silica with water-based epoxy resin in a certain proportion and stir evenly to obtain a transition layer spraying liquid. Apply the liquid to the surface of the glass substrate using an ultrasonic spraying process and then cure the glass substrate coated with the transition layer. S3. Mix bio-based polylactic acid modified epoxy resin, nano-calcium carbonate short carbon fiber and environmentally friendly antioxidant in proportion, stir evenly to obtain functional layer spray liquid, apply it to the surface of the transition layer using ultrasonic spraying process, place the glass coated with functional layer in a curing mold, and allow it to cool naturally to room temperature.

[0045] By adopting the above technical solutions, in S1, the cutting and edge grinding processes can precisely control the size and edge flatness of the glass substrate, avoiding edge defects from affecting coating adhesion. The cleaning step removes oil, dust, and other impurities from the glass surface, while the drying step removes surface moisture, creating clean surface conditions for the chemical bonding between the transition layer and the glass substrate. In S2, the ultrasonic spraying process allows the transition layer material to uniformly cover the glass surface, forming a dense film. The curing process allows the water-based epoxy resin to fully cross-link, while the modified nano-silica forms a pre-bonded bond with the hydroxyl groups on the glass surface and the functional layer material, improving interlayer adhesion. In S3, the ultrasonic spraying process is suitable for the uniform coating of multi-component systems of functional layers. Targeted curing conditions ensure complete cross-linking of the bio-based polylactic acid modified epoxy resin, allowing nano-calcium carbonate, chopped carbon fibers, and the resin matrix to bond tightly. The stepped curing process avoids damage to the formed transition layer caused by high temperatures, ultimately forming a structurally integrated and performance-stable composite tempered glass.

[0046] In some embodiments, the solvents for the transition layer spray liquid and the functional layer spray liquid are ethyl acetate and n-hexane in a mass ratio of 1:(0.1 to 0.5), and the amount used is 3 to 5 times the mass of the transition layer or functional layer raw materials.

[0047] In some embodiments, the ultrasonic spraying process has a frequency of 2-5 MHz, a power of 10-30 W, a spray gun flow rate of 3-4 mL / min, a spraying distance of 10-20 mm, and a spraying speed of 200-300 mm / s.

[0048] In some embodiments, curing includes curing at 120–130°C for 0.5–1 h, followed by curing at 150–180°C for 1–3 h.

[0049] The specific embodiments of the present invention will be described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0050] Preparation Example

[0051] Preparation Example 1: A titanate coupling agent modified nano-silica was prepared by the following method: 1 g of nano-silica was added to 50 mL of toluene and stirred to disperse. Then, 3% (by mass) of titanate coupling agent NDZ-201 was added, and the mixture was stirred at 280 r / min and 90 °C for 2 h. After the reaction was complete, the mixture was filtered, washed three times with anhydrous ethanol, and dried under vacuum at 60 °C to obtain titanate coupling agent modified nano-silica powder.

[0052] Preparation Example 2: A bio-based polylactic acid modified epoxy resin was obtained by the following preparation method: 10g of bio-based polylactic acid and 30g of bisphenol A epoxy resin were added to a 200mL three-necked flask containing ethyl acetate and stirred. Under nitrogen protection, hexamethylene diisocyanate (2.5% by mass of polylactic acid) was added, and the mixture was stirred at 80℃ for 3 hours. After the reaction was complete, the solution was poured into a polytetrafluoroethylene mold, and the solvent was removed by vacuum distillation at 60℃. The solution was then dried in a vacuum drying oven at 60℃ to obtain bio-based polylactic acid-modified epoxy resin.

[0053] Example

[0054] Example 1: An explosion-proof and impact-resistant tempered glass is obtained by the following preparation method: S1. Glass substrate pretreatment: Cut and grind the edges of ordinary tempered glass, clean it, and dry it at 120℃ for later use.

[0055] S2. Transition Layer Coating and Curing: Take 35 parts of the titanate coupling agent modified nano-silica prepared in Example 1 and 25 parts of waterborne epoxy resin 128, add ethyl acetate and n-hexane in a mass ratio of 1:0.2, the amount of which is 3 times the mass of the transition layer raw materials, and stir at high speed to prepare a transition layer spraying liquid. Use an ultrasonic spraying process with a frequency of 3MHz, an ultrasonic power of 20W, a spray gun flow rate of 3mL / min, a spraying distance of 20mm, and a spraying speed of 250mm / s. Spray the transition layer spraying liquid onto the glass substrate surface and cure at 125℃ for 45min to form a dense transition layer with a thickness of approximately 0.05μm.

[0056] S3. Functional Layer Coating and Curing: Take 45 parts of the bio-based polylactic acid modified epoxy resin prepared in Example 2, 13 parts of nano-calcium carbonate, 4 parts of short-cut carbon fibers (7 μm in diameter and 200 μm in length), and 2 parts of tea polyphenols and vitamin E in a mass ratio of 1:0.5. Add ethyl acetate and n-hexane in a mass ratio of 1:0.3 and stir at high speed to prepare a functional layer spraying liquid. Use an ultrasonic spraying process with a frequency of 3 MHz, an ultrasonic power of 25 W, a spray gun flow rate of 3 mL / min, a spraying distance of 20 mm, and a spraying speed of 265 mm / s. Spray the transition layer spraying liquid onto the surface of the glass transition layer and cure at 180°C for 2 h. After naturally cooling to room temperature, a functional layer with a thickness of about 0.1 μm is formed, resulting in an explosion-proof and impact-resistant tempered glass.

[0057] Example 2: An explosion-proof and impact-resistant tempered glass is obtained by the following preparation method: S1. Glass substrate pretreatment: Cut and grind the edges of ordinary tempered glass, clean it, and dry it at 120℃ for later use.

[0058] S2. Transition Layer Coating and Curing: Take 30 parts of the titanate coupling agent modified nano-silica prepared in Example 1 and 20 parts of waterborne epoxy resin 128, add ethyl acetate and n-hexane in a mass ratio of 1:0.2, the amount of which is 3 times the mass of the transition layer raw materials, and stir at high speed to prepare a transition layer spraying liquid. Use an ultrasonic spraying process with a frequency of 3MHz, an ultrasonic power of 20W, a spray gun flow rate of 3mL / min, a spraying distance of 20mm, and a spraying speed of 250mm / s. Spray the transition layer spraying liquid onto the glass substrate surface and cure at 125℃ for 45min to form a dense transition layer with a thickness of approximately 0.05μm.

[0059] S3. Functional Layer Coating and Curing: Take 40 parts of the bio-based polylactic acid modified epoxy resin prepared in Example 2, 10 parts of nano-calcium carbonate, 3 parts of short-cut carbon fibers (7 μm in diameter and 200 μm in length), and 1 part of tea polyphenols and vitamin E in a mass ratio of 1:0.5. Add ethyl acetate and n-hexane in a mass ratio of 1:0.3 and stir at high speed to prepare a functional layer spraying liquid. Use an ultrasonic spraying process with a frequency of 3 MHz, an ultrasonic power of 25 W, a spray gun flow rate of 3 mL / min, a spraying distance of 20 mm, and a spraying speed of 265 mm / s. Spray the transition layer spraying liquid onto the surface of the glass transition layer and cure at 180°C for 2 h. After naturally cooling to room temperature, a functional layer with a thickness of about 0.09 μm is formed, resulting in an explosion-proof and impact-resistant tempered glass.

[0060] Example 3: An explosion-proof and impact-resistant tempered glass is obtained by the following preparation method: S1. Glass substrate pretreatment: Cut and grind the edges of ordinary tempered glass, clean it, and dry it at 120℃ for later use.

[0061] S2. Transition Layer Coating and Curing: Take 40 parts of the titanate coupling agent modified nano-silica prepared in Example 1 and 30 parts of waterborne epoxy resin 128, add ethyl acetate and n-hexane in a mass ratio of 1:0.2, the amount of which is 3 times the mass of the transition layer raw materials, and stir at high speed to prepare a transition layer spraying liquid. Use an ultrasonic spraying process with a frequency of 3MHz, an ultrasonic power of 20W, a spray gun flow rate of 3mL / min, a spraying distance of 20mm, and a spraying speed of 250mm / s. Spray the transition layer spraying liquid onto the glass substrate surface and cure at 125℃ for 45min to form a dense transition layer with a thickness of approximately 0.06μm.

[0062] S3. Functional Layer Coating and Curing: Take 50 parts of the bio-based polylactic acid modified epoxy resin prepared in Example 2, 15 parts of nano-calcium carbonate, 5 parts of short-cut carbon fibers (7 μm in diameter and 200 μm in length), and 2 parts of tea polyphenols and vitamin E in a mass ratio of 1:0.5. Add ethyl acetate and n-hexane in a mass ratio of 1:0.3 and stir at high speed to prepare a functional layer spraying liquid. Use an ultrasonic spraying process with a frequency of 3 MHz, an ultrasonic power of 25 W, a spray gun flow rate of 3 mL / min, a spraying distance of 20 mm, and a spraying speed of 265 mm / s. Spray the transition layer spraying liquid onto the surface of the glass transition layer and cure at 180°C for 2 h. After naturally cooling to room temperature, a functional layer with a thickness of about 0.11 μm is formed, resulting in an explosion-proof and impact-resistant tempered glass.

[0063] Comparative Example

[0064] Comparative Example 1, an explosion-proof and impact-resistant tempered glass, differs from Example 1 only in that the amount of titanate coupling agent modified nano-silica added is 20 parts.

[0065] Comparative Example 2, an explosion-proof and impact-resistant tempered glass, differs from Example 1 only in that it does not contain titanate coupling agent modified nano-silica.

[0066] Comparative Example 3, an explosion-proof and impact-resistant tempered glass, differs from Example 1 only in that the amount of bio-based polylactic acid modified epoxy resin added is 30 parts.

[0067] Comparative Example 4 is an explosion-proof and impact-resistant tempered glass, which differs from Example 1 only in that it does not contain bio-based polylactic acid modified epoxy resin.

[0068] Comparative Example 5 is an explosion-proof and impact-resistant tempered glass, which differs from Example 1 only in that it does not contain nano-calcium carbonate.

[0069] Comparative Example 6 is an explosion-proof and impact-resistant tempered glass, which differs from Example 1 only in that it does not contain chopped carbon fibers.

[0070] Comparative Example 7 is an explosion-proof and impact-resistant tempered glass, which differs from Example 1 only in that it does not contain water-based epoxy resin.

[0071] Performance testing: 1. Impact strength, flexural strength, and spontaneous breakage rate were tested according to GB 15763.2-2005; 2. Light transmittance test, conducted according to GB / T 40415-2021 "Test Method for Light Transmittance of Photovoltaic Glass Modules for Building Use"; Table 1 Performance test results

[0072] The data above demonstrates the superior performance of the embodiments, showcasing a complete gradient structural design. The sufficient amount of titanate coupling agent-modified nano-silica in the transition layer acts as a crucial bridge, achieving strong chemical bonding and physical interlocking between the glass substrate and the functional layer. This results in high impact and flexural strength, and a low spontaneous breakage rate. In the functional layer, bio-based polylactic acid-modified epoxy resin provides a matrix with a balanced rigidity and toughness, while nano-calcium carbonate and chopped carbon fibers synergistically enhance each other, further dissipating impact energy. Each comparative example, lacking a key component, disrupted this synergistic system. For instance, Comparative Example 2, completely lacking modified nano-silica, experienced a sharp drop in interfacial bonding force, resulting in the worst mechanical properties and explosion-proof performance. Comparative Example 6, lacking chopped carbon fibers, caused the stress-bearing network to fail, significantly reducing impact strength.

[0073] The above-disclosed embodiments are merely a few specific examples of the present invention. However, the embodiments of the present invention are not limited thereto, and any variations that can be conceived by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. An explosion-proof and impact-resistant tempered glass, characterized in that, It includes a glass base layer, a transition layer, and a functional layer; The raw materials of the transition layer include, by weight, 30-40 parts of titanate coupling agent modified nano-silica and 20-30 parts of waterborne epoxy resin. The functional layer raw materials, by weight, include 40-50 parts of bio-based polylactic acid modified epoxy resin, 10-15 parts of nano-calcium carbonate, 3-5 parts of short-cut carbon fiber, and 1-2 parts of environmentally friendly antioxidant.

2. The explosion-proof and impact-resistant tempered glass according to claim 1, characterized in that, The titanate coupling agent modified nano-silica was prepared by the following method: Nano-silica is added to toluene, and 2%–5% of titanate coupling agent by mass of nano-silica is added. The mixture is stirred at 250–300 r / min and 70–110 °C for 0.5–3 h. The mixture is then filtered, washed, and dried to obtain the final product.

3. The explosion-proof and impact-resistant tempered glass according to claim 1, characterized in that, The bio-based polylactic acid modified epoxy resin is obtained by the following preparation method: Polylactic acid and epoxy resin are dispersed in a solvent, and isocyanate crosslinking agent is added. The mixture is stirred at 80-90°C for 2-3 hours, cooled, and dried to obtain the final product.

4. The explosion-proof and impact-resistant tempered glass according to claim 3, characterized in that, The mass ratio of polylactic acid to epoxy resin is 1:(3-4); the amount of isocyanate crosslinking agent added is 2%-3% of the mass of polylactic acid; the isocyanate crosslinking agent includes hexamethylene diisocyanate, triallyl isocyanurate, and 4,4-diphenylmethane diisocyanate.

5. The explosion-proof and impact-resistant tempered glass according to claim 1, characterized in that, The chopped carbon fibers have a single filament diameter of 5–15 μm and a length of 50–200 μm.

6. The explosion-proof and impact-resistant tempered glass according to claim 1, characterized in that, The environmentally friendly antioxidant includes tea polyphenols and vitamin E in a mass ratio of 1:(0.5-1).

7. The explosion-proof and impact-resistant tempered glass according to claim 1, characterized in that, The thickness of the transition layer is 0.01–1 μm, and the thickness of the functional layer is 0.1–1 μm.

8. A preparation method for preparing the explosion-proof and impact-resistant tempered glass according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Pre-treatment of tempered glass by cutting, grinding, cleaning and drying to obtain the glass base layer; S2. Mix the titanate coupling agent modified nano-silica with water-based epoxy resin in a certain proportion and stir evenly to obtain a transition layer spraying liquid. Apply the liquid to the surface of the glass substrate using an ultrasonic spraying process and then cure the glass substrate coated with the transition layer. S3. Mix bio-based polylactic acid modified epoxy resin, nano-calcium carbonate short carbon fiber and environmentally friendly antioxidant in proportion, stir evenly to obtain functional layer spray liquid, apply it to the surface of the transition layer using ultrasonic spraying process, place the glass coated with functional layer in a curing mold, and allow it to cool naturally to room temperature.

9. The preparation method according to claim 8, characterized in that, The solvents for the transition layer spraying liquid and the functional layer spraying liquid are ethyl acetate and n-hexane in a mass ratio of 1:(0.1-0.5), and the amount used is 3-5 times the mass of the raw materials for the transition layer or functional layer.

10. The preparation method according to claim 8, characterized in that, The ultrasonic spraying process has a frequency of 2-5MHz, a power of 10-30W, a spray gun flow rate of 3-4mL / min, a spraying distance of 10-20mm, and a spraying speed of 200-300mm / s. The curing process in S2 includes curing at 120–130°C for 0.5–1 hour, and the curing process in S3 includes curing at 150–180°C for 1–3 hours.

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