A moisture and heat resistant anti-aging composite modified laminated glass interlayer and a preparation method thereof

Abstract

This invention relates to the field of laminated glass materials technology, specifically disclosing a moisture- and heat-resistant, anti-aging composite modified interlayer film for laminated glass and its preparation method. It aims to solve the problems of existing interlayer films in laminated glass, such as easy whitening in high humidity environments, insufficient anti-aging performance during long-term use, and a lack of adaptability to extreme environments and functional diversity. This interlayer film uses grafted modified plasticizable polyvinyl acetate resin as a matrix, and constructs a dual anti-aging system of "modified cyclosiloxane mixture (DMC) - nanocomposite powder" by precisely controlling the sodium and potassium content. It is compounded with multifunctional additives and prepared through a multi-stage interface modification treatment of "plasma pretreatment - composite coupling agent coating - anti-fogging coating modification". This invention achieves a synergistic improvement in moisture and heat resistance, long-lasting anti-aging performance, adaptability to extreme environments, and multifunctionality while maintaining basic properties such as transparency and weather resistance. Furthermore, the preparation process is highly compatible with existing production lines, possessing extremely high practical value and market competitiveness.

Description

Technical Field

[0001] This invention belongs to the field of laminated glass material technology, specifically relating to a moisture- and heat-resistant, anti-aging composite modified interlayer film for laminated glass and its preparation method. Background Technology

[0002] Laminated glass is widely used in the automotive and construction industries due to its excellent transparency, weather resistance, penetration resistance, and resistance to fragmentation. Most existing laminated glass uses plasticizable polyvinyl acetate resin as the interlayer, but traditional interlayers suffer from insufficient resistance to damp heat; in high-humidity environments, their edges are prone to whitening, affecting performance.

[0003] To address this issue, relevant patents propose controlling the sodium and potassium content in the interlayer to suppress whitening. While this has achieved some success, the interlayer is susceptible to aging and degradation under the influence of ultraviolet radiation and oxygen during long-term use, leading to decreased transparency and weakened adhesion. Furthermore, simply relying on elemental content control cannot simultaneously meet the dual requirements of resistance to damp heat and anti-aging. Existing products also suffer from limited anti-aging systems, exhibiting limited long-term effectiveness under strong ultraviolet radiation and high-temperature, high-humidity environments. The interfacial interaction mechanism is simple, and the interlayer bonding strength needs improvement. They also lack adaptability to extreme conditions such as low-temperature embrittlement below -40°C and high-temperature creep above 70°C. Moreover, their limited functionality makes it difficult to meet the diverse needs of high-end buildings, special vehicles, and medical facilities, thus restricting the service life and application scope of laminated glass in harsh environments and high-end fields.

[0004] Therefore, developing a modified intermediate membrane that integrates "dual anti-aging system - environmentally friendly multi-level interface modification - extreme environment adaptation" is of great practical significance. Summary of the Invention

[0005] The purpose of this invention is to address the problems existing in the prior art by providing a moisture- and heat-resistant, anti-aging composite modified interlayer for laminated glass and its preparation method. While maintaining the basic properties of existing laminated glass, it achieves a synergistic improvement in moisture and heat resistance, long-lasting anti-aging properties, extreme environment adaptability, and multifunctionality, thereby extending product lifespan, expanding application scenarios, and meeting the diversified needs of the high-end market.

[0006] This invention provides the following technical solution: a moisture- and heat-resistant, anti-aging composite modified interlayer glass membrane, using graft-modified plasticizable polyvinyl acetate resin as the matrix. The matrix contains 0.5 ppm to 12 ppm sodium and 0.5 ppm to 80 ppm potassium. The sodium and potassium content further tightens the control range of impurity elements, strengthening the moisture- and heat-resistant foundation. The matrix contains a dual anti-aging system and multifunctional additives. The dual anti-aging system consists of a modified cyclosiloxane mixture (DMC) and modified nanocomposite powder. The cyclosiloxane mixture (DMC) is composed of D3 (hexamethylcyclotrisiloxane), D4 (octamethylcyclotetrasiloxane), and D5 (decamethylcyclopentasiloxane) in a mass ratio of 1:2:1 to 1:3:2, and its addition amount is 0.1% to 0.5% of the weight of the polyvinyl acetate resin. The modified nanocomposite powder is a composite powder composed of nano-CeO2 and nano-ZnO modified with silane coupling agent in a mass ratio of 1:2 to 1:3, with an addition amount of 0.05% to 0.2% of the weight of polyvinyl acetate resin. The cyclosiloxane mixture and the modified nanocomposite powder form a synergistic anti-aging mechanism of "ultraviolet shielding-free radical scavenging-molecular chain protection". The surface of the intermediate film undergoes multi-level interface modification treatment to form an environmentally friendly surface treatment modification layer and a hydrophilic silica anti-fogging coating in sequence. The environmentally friendly surface treatment agent is a plant-based epoxy modified silane treatment agent, with a coating amount of 0.03 g / m² to 0.08 g / m² and an anti-fogging coating thickness of 1 to 2 μm. Combined with plasma pretreatment and resin grafting modification, the interfacial chemical bonding is strengthened, and the outer layer is coated with a hydrophilic silica anti-fogging coating to achieve anti-fogging function while taking into account environmental protection and practicality.

[0007] The cyclosiloxane mixture (DMC) is subjected to epoxy group modification treatment, with glycidyl etheroxypropyltrimethoxysilane as the modifier, the modification temperature being 80℃~100℃, and the modification time being 2~4 hours.

[0008] The plant-based epoxy-modified silane treatment agent uses cashew phenol epoxy propylene ether as a plant-based raw material and is compounded with γ-aminopropyltriethoxysilane in a mass ratio of 1:1 to 2:1, which has both environmental protection and interface adhesion enhancement functions.

[0009] The plasticizable polyvinyl acetate resin graft copolymer is modified by GMA grafting with a grafting rate of 1.5% to 3%, which gives the resin molecular chain epoxy groups, allowing it to form stable chemical bonds with environmentally friendly surface treatment agents and glass substrates. The composite plasticizer is composed of at least one of triethylene glycol di-2-ethylbutyrate and triethylene glycol di-2-ethylhexanoate and diisononyl adipate (DINP) in a mass ratio of 3:1 to 4:1, with a total addition amount of 25% to 65% of the weight of polyvinyl acetate resin. The composite plasticizer lowers the glass transition temperature of the resin to below -45°C, improving low-temperature flexibility.

[0010] The preparation method of the above-mentioned moisture- and heat-resistant anti-aging composite modified interlayer glass includes the following steps: (1) Resin pretreatment and grafting modification: Polyvinyl acetate resin, hydrochloric acid catalyst and aldehydes with 3 to 10 carbon atoms are acetylated. After the reaction is completed, 1% to 3% of GMA monomer and 0.05% to 0.1% of benzoyl peroxide (BPO) initiator are added to the polyvinyl acetate resin. The reaction is carried out at 80℃ to 90℃ for 2 to 3 hours. After washing with water at pH=5 or above for 3 to 4 hours and drying at 50℃ to 55℃, a polyvinyl acetate graft copolymer with sodium content of 0.5ppm to 12ppm, potassium content of 0.5ppm to 80ppm and grafting rate of 1.5% to 3% is obtained. This step strictly controls the sodium and potassium content and grafting rate in the resin through acetylation reaction, grafting reaction and precise water washing and drying process, which lays the foundation for moisture and heat resistance and interfacial bonding. (2) Modification of nano powder: Nano CeO2 and ZnO are mixed at a mass ratio of 1:2 to 1:3, and 0.5% to 1% of γ-glycidyl oxypropyltrimethoxysilane is added. The mixture is stirred at 60℃ to 70℃ for 1 to 2 hours and then vacuum dried for later use. This step modifies the nano CeO2 / ZnO composite powder with silane coupling agent to ensure that it is uniformly dispersed in the resin matrix and to avoid agglomeration that affects light transmittance. (3) Composite modification: The polyvinyl acetate graft copolymer obtained in step (1) is added to the internal mixer in sequence with the composite plasticizer, modified DMC and modified nanocomposite powder, and melt-mixed at 150℃~165℃ for 20~35 minutes to obtain a composite resin mixture. In this step, the graft copolymer, composite plasticizer, dual anti-aging components and multifunctional additives are melt-mixed to achieve uniform dispersion of each component and simultaneously impart anti-aging, antibacterial and extreme temperature resistance properties to the material. (4) Film forming: The composite resin mixture is calendered or extruded to form a base film with a thickness of 0.3mm to 1.6mm. This step adopts a mature calendering or extrusion process to ensure the thickness uniformity and flatness of the intermediate film. (5) Multi-level interface modification: ① Plasma pretreatment: The base film is treated with a plasma treatment machine with a power of 30~50W for 3~5 minutes; ② Environmentally friendly surface treatment agent coating: The plant-based epoxy modified silane treatment agent is prepared into an ethanol solution with a mass concentration of 1%~2.5%, and 0.5%~1% of environmentally friendly nonionic surfactant (fatty alcohol polyoxyethylene ether) is added. The solution is then coated onto the surface of the base film by spraying and dried at 90℃~105℃ for 8~12 minutes; ③ Anti-fog coating: The hydrophilic silica sol is uniformly coated onto the surface of the base film modified by the coupling agent and dried at 100℃~110℃ for 5~8 minutes to obtain a moisture-resistant and heat-resistant anti-aging composite modified interlayer glass intermediate film. This step improves the surface activity of the base film through plasma pretreatment, coating with composite coupling agent solution and drying, and then coating with hydrophilic silica sol to form an anti-fog coating, optimizing the interface bonding state between the intermediate film and the glass and giving it anti-fog function.

[0011] The modified cyclosiloxane mixture (DMC) in step (3) is prepared by mixing D3, D4 and D5 according to a preset mass ratio, adding 1%-3% of glycidyl etheroxypropyltrimethoxysilane according to the total mass of the mixture, reacting at 80℃~100℃ for 2~4 hours under nitrogen protection, and then purifying by vacuum distillation.

[0012] The above-mentioned moisture- and heat-resistant, anti-aging composite modified interlayer film for laminated glass is used in the preparation of laminated glass.

[0013] The preparation of laminated glass includes the following steps: an interlayer film is sandwiched between glass substrates to form a laminate, which is then placed in a vacuum bag and degassed under reduced pressure of -80kPa to -95kPa for 20 to 30 minutes. Subsequently, it is heated and pressed at 90℃ to 110℃ and a pressure of 3kg / cm² to 12kg / cm² of approximately 0.3MPa to 1.2MPa for 25 to 35 minutes to complete the composite molding.

[0014] Compared with the prior art, the significant advantages of the present invention are: 1. Extremely optimized resistance to damp heat: By precisely controlling the sodium and potassium content, the sodium and potassium content is tightened to 0.5ppm~12ppm and 0.5ppm~80ppm respectively. Combined with the interface modification of the composite coupling agent and the auxiliary protection of fluorocarbon surfactant, the whitening and corrosion of the intermediate film under high humidity and salt spray environment are effectively suppressed. After being placed at 50℃ and 95%RH for 6 weeks, the whitening distance is ≤0.8mm, and there is no corrosion in the 500-hour salt spray test. 2. Significantly improved anti-aging and long-lasting performance: The "modified DMC-nanocomposite powder" dual anti-aging system is constructed. After 1500 hours of UV aging test, the light transmittance of the intermediate film decreases by ≤1.5%, the bonding strength retention rate is ≥95%, and the service life is extended by more than 30% compared with traditional products. 3. Enhanced adaptability to extreme environments: The compound plasticizer ensures that the drop ball test at -45℃ (2kg steel ball) has a non-penetration height of ≥5.5m and creep deformation at 70℃ is ≤0.3%, making it adaptable to complex working conditions such as severe cold, extreme heat, and marine climates. 4. Significantly improved environmental performance: Plant-based epoxy-modified silane treatment agents are used to replace traditional chemically synthesized surface treatment agents, combined with environmentally friendly nonionic surfactants. There are no harmful volatile substances, and the biodegradability is excellent, which is in line with the green and low-carbon development trend and reduces the impact on the environment. 5. Stable and reliable basic performance: It maintains the original high transparency of polyvinyl acetate resin interlayer, with light transmittance ≥93%, weather resistance and penetration resistance, meeting the stringent requirements for laminated glass. 6. Strong process feasibility: The core preparation process is compatible with existing interlayer glass production lines. Only small-scale equipment such as nanopowder pretreatment and plasma treatment are needed. No large-scale modification is required. The preparation process of modified DMC and nanopowder is simple and controllable, which facilitates industrial promotion.

[0015] The D3, D4, and D5 components of the cyclosiloxane mixture (DMC) exhibit excellent weather resistance, UV resistance, and chemical stability, and show good compatibility potential with polyvinyl acetate resin. After modification, their dispersibility in the resin matrix can be further improved, effectively blocking UV damage to the resin molecular chains and delaying the aging process. Nano-CeO2 can capture free radicals and inhibit oxidation chain reactions, while nano-ZnO also has UV shielding function. Together with the modified DMC, they form a synergistic anti-aging effect. The combination of environmentally friendly plant-based surface treatment agents and resin grafting modification can enhance interfacial adhesion while improving the product's environmental performance. Composite plasticizers can expand the adaptability to extreme environments. Detailed Implementation

[0016] The present invention will be further described below with reference to specific embodiments, and the advantages and features of the present invention will become clearer with the description. However, the embodiments are merely exemplary and do not constitute any limitation on the scope of the present invention. Those skilled in the art should understand that modifications or substitutions can be made to the details and form of the technical solutions of the present invention without departing from the spirit and scope of the present invention, but all such modifications and substitutions fall within the protection scope of the present invention.

[0017] Example 1 1. Resin pretreatment and graft modification: 275 parts of polyvinyl acetate resin with an average degree of polymerization of 1700 and a saponification degree of 98.9 mol% were added to 2890 parts of pure water and heated to dissolve. The reaction temperature was adjusted to 12℃, and 201 parts of 35% hydrochloric acid catalyst and 148 parts of n-butyraldehyde were added. The temperature was maintained to precipitate the reactants. Then, the temperature was raised to 45℃ and reacted for 3 hours. 3.5 parts of GMA monomer and 0.14 parts of BPO initiator were added, and the temperature was raised to 85℃ and reacted for 2.5 hours. The mixture was washed with excess water until pH≥5 (washing time 3.5 hours), and then vacuum dried at 52℃ to obtain a polyvinyl acetate graft copolymer with a sodium content of 10 ppm, a potassium content of 0.5 ppm, and a grafting rate of 2.2%. 2. Nanopowder modification: Nano CeO2 and ZnO were mixed at a mass ratio of 1:2.5, and 0.8% γ-glycidoxypropyltrimethoxysilane was added. The mixture was stirred at 65°C for 1.5 hours and then vacuum dried for later use. 3. Preparation of modified DMC: D3, D4, and D5 were mixed in a mass ratio of 1:2:1, and 2% of glycidyl etheroxypropyltrimethoxysilane was added. The mixture was reacted at 90°C for 3 hours under nitrogen protection, and purified by vacuum distillation to obtain epoxy-modified DMC. 4. Composite modification: Take 100 parts by weight of the polyvinyl acetate graft copolymer obtained in step 1, add 32 parts by weight of triethylene glycol di-2-ethylbutyrate, 8 parts by weight of DINP, 0.12 parts by weight of modified nanocomposite powder, and 0.3 parts by weight of modified DMC, and melt-mix at 155℃ for 25 minutes to obtain a composite resin mixture. 5. Film forming: The composite resin mixture is formed by calendering at 150°C for 30 minutes to obtain a base film with a thickness of 0.76 mm; 6. Multi-level interface modification: ① Plasma pretreatment: The base film is treated with a 40W plasma treatment machine for 4 minutes; ② Environmentally friendly surface treatment agent coating: Cashew phenol epoxy propylene ether and γ-aminopropyltriethoxysilane are mixed at a mass ratio of 1.5:1 to prepare a 2% mass concentration ethanol solution, and 0.8% fatty alcohol polyoxyethylene ether is added. The solution is sprayed onto the base film surface at a coating amount of 0.05g / m² and dried at 100℃ for 10 minutes; ③ Anti-fog coating: Hydrophilic silica sol is uniformly coated onto the base film surface with a coating thickness of 1μm and dried at 105℃ for 6 minutes to obtain a moisture-resistant and heat-resistant anti-aging composite modified intermediate film; 7. Preparation of laminated glass: The interlayer film is sandwiched between two pieces of 30cm×30cm×2.5mm float glass, placed in a vacuum bag, degassed under -85KPa pressure for 25 minutes, and then heated and pressed at 100℃ and 8kg / cm² pressure for 30 minutes to produce laminated glass.

[0018] Example 2 1. Resin pretreatment and graft modification: Using the same process parameters as in Example 1, the following parameters were adjusted: 8.25 parts of GMA monomer and 2.75 parts of BPO initiator were added, and the water washing time was 3 hours to obtain a polyvinyl acetate graft copolymer with a sodium content of 8 ppm, a potassium content of 0.5 ppm, and a grafting rate of 2.5%. 2. Nanopowder modification: Nano CeO2 and ZnO are mixed at a mass ratio of 1:3, and 0.6% of γ-glycidoxypropyltrimethoxysilane is added. The mixture is stirred at 60°C for 2 hours and then vacuum dried for later use. 3. Preparation of modified DMC: D3, D4, and D5 were mixed in a mass ratio of 1:3:2, and 1.5% of glycidyl etheroxypropyltrimethoxysilane was added. The mixture was reacted at 85°C for 3.5 hours under nitrogen protection and purified by vacuum distillation to obtain epoxy-modified DMC. 4. Composite modification: Take 100 parts by weight of the polyvinyl acetate graft copolymer obtained in step 1, add 36 parts by weight of triethylene glycol di-2-ethylhexanoate, 9 parts by weight of DINP, 0.15 parts by weight of modified nanocomposite powder, and 0.4 parts by weight of modified DMC, and melt-mix at 160℃ for 20 minutes to obtain a composite resin mixture. 5. Film forming: The composite resin mixture is formed into a base film with a thickness of 0.76 mm using an extrusion molding process; 6. Multi-level interface modification: ① Plasma pretreatment: The base film was treated with a 35W plasma treatment machine for 3.5 minutes; ② Environmentally friendly surface treatment agent coating: Cashew phenol epoxy propylene ether and γ-aminopropyltriethoxysilane were mixed at a mass ratio of 2:1 to prepare an ethanol solution with a mass concentration of 1.8%, and 0.6% fatty alcohol polyoxyethylene ether was added. The solution was sprayed onto the base film surface at a coating amount of 0.04 g / m² and dried at 95°C for 11 minutes; ③ Anti-fog coating: The same hydrophilic silica sol as in Example 1 was used to coat the film with a thickness of 2 μm and dried at 100°C for 7 minutes to obtain a moisture-resistant and heat-resistant anti-aging composite modified intermediate film; 7. Laminated glass preparation: Laminated glass was prepared using the same process parameters as in Example 1.

[0019] Example 3 1. Resin pretreatment and graft modification: Using the same process parameters as in Example 1, only the neutralizing agent was adjusted to an aqueous solution of potassium hydroxide, and the water washing time was 3.2 hours, to obtain a polyvinyl acetate graft copolymer with a sodium content of 5 ppm, a potassium content of 20 ppm, and a grafting rate of 1.8%. 2. Nanopowder modification: Nano CeO2 and ZnO are mixed at a mass ratio of 1:2, and 0.9% γ-glycidoxypropyltrimethoxysilane is added. The mixture is stirred at 70°C for 1 hour and then vacuum dried for later use. 3. Preparation of modified DMC: D3, D4, and D5 were mixed in a mass ratio of 1:2.5:1.5, and 2.5% of glycidyl etheroxypropyltrimethoxysilane was added. The mixture was reacted at 95°C for 2.5 hours under nitrogen protection, and purified by vacuum distillation to obtain epoxy-modified DMC. 4. Composite modification: Take 100 parts by weight of the polyvinyl acetate graft copolymer obtained in step 1, add 30 parts by weight of a mixed plasticizer of triethylene glycol di-2-ethylbutyrate and triethylene glycol di-2-ethylhexanoate (weight ratio 1:1), 10 parts by weight of DINP, 0.1 parts by weight of modified nanocomposite powder, and 0.2 parts by weight of modified DMC, and melt-mix at 150℃ for 30 minutes to obtain a composite resin mixture; 5. Film forming: A base film with a thickness of 0.76 mm is produced using a calendering process; 6. Multi-level interface modification: ① Plasma pretreatment: The base film was treated with a 45W plasma treatment machine for 3 minutes; ② Environmentally friendly surface treatment agent coating: Cashew phenol epoxy propylene ether and γ-aminopropyltriethoxysilane were mixed at a mass ratio of 1:1 to prepare a 2.2% mass concentration ethanol solution, and 0.9% fatty alcohol polyoxyethylene ether was added. The solution was sprayed onto the base film surface at a coating amount of 0.06 g / m² and dried at 102℃ for 9 minutes; ③ Anti-fog coating: The same hydrophilic silica sol as in Example 1 was used to coat the film with a thickness of 1.5 μm and dried at 110℃ for 5 minutes to obtain a moisture-resistant and heat-resistant anti-aging composite modified intermediate film; 7. Laminated glass preparation: Laminated glass was prepared using the same process parameters as in Example 1.

[0020] Example 4 1. Resin pretreatment and graft modification: Using the same process parameters as in Example 3, the water washing time was adjusted to 4 hours to obtain a polyvinyl acetate graft copolymer with a sodium content of 7 ppm, a potassium content of 15 ppm, and a grafting rate of 2.7%. 2. Nanopowder modification: Modified nanocomposite powders were prepared using the same process parameters as in Example 2; 3. Preparation of modified DMC: Modified DMC was prepared using the same process parameters as in Example 1; 4. Composite modification: Take 100 parts by weight of the polyvinyl acetate graft copolymer obtained in step 1, add 28 parts by weight of triethylene glycol di-2-ethylbutyrate, 7 parts by weight of DINP, 0.18 parts by weight of modified nanocomposite powder, and 0.5 parts by weight of modified DMC, and melt-mix at 165℃ for 18 minutes to obtain a composite resin mixture. 5. Membrane forming: A base film with a thickness of 0.76 mm is produced using an extrusion molding process; 6. Multi-level interface modification: Plasma pretreatment, composite coupling agent coating and anti-fogging coating were performed using the same process parameters as in Example 2, with the composite coupling agent coating amount adjusted to 0.07 g / m². 7. Laminated glass preparation: The pressing temperature was adjusted to 95°C, and other process parameters were the same as in Example 1, to prepare laminated glass.

[0021] Performance testing The laminated glass prepared in the above embodiments was subjected to performance tests. The test standards and results are as follows:

[0022] Comparative Example Comparative Example 1 (Modified DMC missing in dual anti-aging system) 1. Resin pretreatment and grafting modification, nanopowder modification: Using the same process as in Example 1, a polyvinyl acetate graft copolymer with a sodium content of 10 ppm, a potassium content of 0.5 ppm, and a grafting rate of 2.2% was prepared, as well as silane coupling agent modified nano CeO2 / ZnO composite powder. 2. Composite modification: Take 100 parts by weight of the polyvinyl acetate graft copolymer obtained in step 1, add 32 parts by weight of triethylene glycol di-2-ethylbutyrate, 8 parts by weight of DINP, and 0.12 parts by weight of modified nanocomposite powder, without adding modified DMC, and melt-mix at 155°C for 25 minutes to obtain a composite resin mixture; 3. Film forming, multi-level interface modification and laminated glass preparation: The same process parameters as in Example 1 were used to complete the preparation (including plasma pretreatment, coating with environmentally friendly surface treatment agent, coating with anti-fog coating, and laminated glass forming processes such as depressurization and heating pressing).

[0023] Comparative Example 2 (Nanocomposite powder missing in dual anti-aging system) 1. Resin pretreatment and grafting modification, preparation of modified DMC: The process was exactly the same as in Example 1; 2. Composite modification: Take 100 parts by weight of the polyvinyl acetate graft copolymer obtained in step 1, add 32 parts by weight of triethylene glycol di-2-ethylbutyrate, 8 parts by weight of DINP, and 0.3 parts by weight of modified DMC, without adding nanocomposite powder, and melt-mix at 155℃ for 25 minutes. 3. Film forming, multi-level interface modification and laminated glass preparation: The preparation was completed using the same process parameters as in Example 1.

[0024] Comparative Example 3 (Lacking Plasma Pretreatment and Graft Modification in Multi-Level Interface Modification) 1. Resin pretreatment: Only acetylation reaction, water washing, and drying were performed without grafting modification to obtain ordinary polyvinyl acetate resin with a sodium content of 10 ppm and a potassium content of 0.5 ppm. 2. Nanopowder modification, DMC modification preparation, composite modification, and film forming: The same process parameters as in Example 1 were used; 3. Multi-level interface modification: The plasma pretreatment step is omitted, and environmentally friendly surface treatment agent coating and anti-fog coating are applied directly; 4. Laminated glass preparation: The preparation was completed following the pressing process parameters of Example 1.

[0025] Comparative Example 4 (Sodium content exceeds the standard) 1. Resin pretreatment and graft modification: Using the same process as in Example 1, the washing time was shortened to 0.8 hours. ICP analysis revealed a polyvinyl acetate graft copolymer with a sodium content of 22 ppm, a potassium content of 0.5 ppm, and a grafting rate of 2.2%. 2. Other steps: The process parameters of Example 1 are used exactly as described above; 3. Laminated glass preparation: The preparation was completed following the pressing process parameters of Example 1.

[0026] Comparative Example 5 (Modified DMC and modified nanocomposite powder in a dual anti-aging system) 1. Resin pretreatment and graft modification: Using the same process as in Example 1, a polyvinyl acetate graft copolymer with a sodium content of 10 ppm, a potassium content of 0.5 ppm, and a grafting rate of 2.2% was prepared. 2. Composite modification: Take 100 parts by weight of the polyvinyl acetate graft copolymer obtained in step 1, add only 32 parts by weight of triethylene glycol di-2-ethylbutyrate and 8 parts by weight of DINP, without adding modified DMC and modified nanocomposite powder, and melt-mix at 155°C for 25 minutes to obtain a composite resin mixture; 3. Film forming, multi-level interface modification and laminated glass preparation: The preparation was completed using the same process parameters as in Example 1.

[0027] Performance testing The laminated glass prepared in the above comparative example was subjected to performance tests. The test standards (same as in the example) and the results are as follows:

[0028] Results analysis: 1. Examples 1-4, after 1500 hours of UV aging, showed a transmittance decrease of only 1.2% and a bond strength retention rate of 96.5%. In contrast, Comparative Example 2, lacking only the nanocomposite powder, showed a transmittance decrease of 4.8% and a bond strength retention rate of 82%; Comparative Example 1, lacking only the modified DMC, showed a transmittance decrease of 5.1% and a bond strength retention rate of 80%, indicating a significant performance decline. Comparative Example 5, completely lacking the system, showed a performance collapse, with a transmittance decrease of 8.5% and a bond strength retention rate of 65%. The average whitening distance of each example was only 0.65 mm, and no corrosion was observed in the 500-hour salt spray test. Comparative Examples 1-2 showed a whitening distance of 2.1-2.3 mm, indicating slight corrosion; Comparative Example 5 showed a whitening distance as high as 6.8 mm, indicating severe corrosion and complete whitening. This demonstrates that the dual anti-aging system not only performs anti-aging functions but also inhibits ion migration and material degradation under high humidity conditions through molecular chain stabilization, providing crucial support for its resistance to damp heat.

[0029] 2. In the example, after thorough water washing for 3-4 hours and strict control of element content, the whitening distance was ≤0.8mm, and no corrosion was observed in the salt spray test; Comparative Example 4 showed that insufficient rinsing resulted in sodium levels exceeding the standard by 22 ppm, with a whitening distance of 5.2 mm, and severe corrosion and whitening in the salt spray test. This indicates that the excessive presence of impurity elements sodium and potassium accelerates ion migration and chemical reactions under high humidity conditions, leading to whitening and corrosion of the intermediate film. Precise control can suppress this problem at its source, providing a fundamental guarantee for the resistance to damp heat.

[0030] 3. In this embodiment, the bonding strength retention rate reaches 96.5% and the surface contact angle is only 26°, exhibiting excellent anti-fogging properties. Comparative Example 3, lacking plasma pretreatment and resin grafting modification, showed a decrease in bond strength retention to 75%, an increase in surface contact angle to 82°, and failure of anti-fogging function. The reason is that plasma pretreatment enhances the surface activity of the base film, and the epoxy groups introduced by resin grafting modification form stable chemical bonds with the plant-based treatment agent. This strengthens the interfacial bonding between the intermediate film and the glass, and provides a good adhesion foundation for the hydrophilic silica coating, achieving a dual effect of "bond enhancement and functional imparting."

[0031] in conclusion Test results show that, compared with traditional interlayer films in laminated glass, this invention, through the synergy of multiple technologies, achieves significantly improved resistance to damp heat, long-lasting anti-aging properties, and adaptability to extreme environments, with a whitening distance ≤0.8mm, light transmittance reduction ≤1.5%, drop height at -45℃ ≥5.5m, and creep at 70℃ ≤0.3%. This extends the product's service life by more than 30%. While maintaining basic performance, it adds anti-fogging functionality, a surface contact angle ≤28°, and achieves environmental upgrades through plant-based treatment agents, resulting in no harmful volatiles and biodegradability, meeting the diverse needs of high-end buildings, special vehicles, medical facilities, and other scenarios.

Claims

1. A moisture- and heat-resistant, anti-aging composite modified interlayer glass film, characterized in that, The matrix is ​​made of graft-modified plasticized polyvinyl acetate resin, wherein the sodium content in the matrix is ​​0.5ppm~12ppm and the potassium content is 0.5ppm~80ppm; the matrix contains a dual anti-aging system, which is composed of a modified cyclosiloxane mixture and a modified nanocomposite powder. The cyclosiloxane mixture is composed of D3, D4 and D5, and the modified nanocomposite powder is a composite powder of nano CeO2 and nano ZnO modified by silane coupling agent.

2. The moisture- and heat-resistant, anti-aging composite modified interlayer glass membrane according to claim 1, characterized in that, The cyclosiloxane mixture is composed of D3, D4, and D5 in a mass ratio of 1:2:1 to 1:3:2, and its addition amount is 0.1% to 0.5% of the weight of polyvinyl acetate resin.

3. The moisture- and heat-resistant, anti-aging composite modified interlayer glass membrane according to claim 1, characterized in that, The modified nanocomposite powder is a composite powder composed of nano CeO2 modified with silane coupling agent and nano ZnO in a mass ratio of 1:2 to 1:3, and the amount added is 0.05% to 0.2% of the weight of polyvinyl acetate resin.

4. The moisture- and heat-resistant, anti-aging composite modified interlayer glass membrane according to claim 2, characterized in that, The cyclosiloxane mixture is subjected to epoxy group modification treatment, with glycidyl etheroxypropyltrimethoxysilane as the modifier, the modification temperature being 80℃~100℃, and the modification time being 2~4 hours.

5. The moisture- and heat-resistant, anti-aging composite modified interlayer glass membrane according to claim 1, characterized in that, The surface of the intermediate membrane also includes an environmentally friendly surface treatment modified layer and a hydrophilic silica anti-fog coating formed sequentially through multi-level interface modification treatment. The environmentally friendly surface treatment agent is a plant-based epoxy modified silane treatment agent, with a coating amount of 0.03 g / m² to 0.08 g / m² and an anti-fog coating thickness of 1 to 2 μm.

6. The moisture- and heat-resistant, anti-aging composite modified interlayer glass membrane according to claim 5, characterized in that, The plant-based epoxy-modified silane treatment agent is formulated with cashew phenol epoxy propylene ether as a plant-based raw material and γ-aminopropyltriethoxysilane in a mass ratio of 1:1 to 2:

1.

7. The moisture- and heat-resistant, anti-aging composite modified interlayer glass membrane according to claim 1, characterized in that, The plasticizable polyvinyl acetate resin is composed of a polyvinyl acetate graft copolymer and a composite plasticizer. The grafting monomer of the polyvinyl acetate graft copolymer is glycidyl methacrylate, and the grafting rate is 1.5% to 3%. The composite plasticizer is composed of at least one of triethylene glycol di-2-ethylbutyrate and triethylene glycol di-2-ethylhexanoate and diisononyl adipate in a mass ratio of 3:1 to 4:1, and the total addition amount is 25% to 65% of the weight of the polyvinyl acetate resin.

8. The method for preparing a moisture- and heat-resistant, anti-aging composite modified interlayer glass membrane as described in claims 1-7, characterized in that, It includes the following steps: (1) Resin pretreatment and graft modification: Polyvinyl acetate resin, hydrochloric acid catalyst and aldehydes with 3 to 10 carbon atoms are acetylated. After the reaction is completed, GMA monomer and benzoyl peroxide initiator are added. The reaction is carried out at 80℃ to 90℃ for 2 to 3 hours. After washing with water for 3 to 4 hours to make the pH reach above 5, the product is dried at 50℃ to 55℃ to obtain a polyvinyl acetate graft copolymer with sodium content of 0.5ppm to 12ppm, potassium content of 0.5ppm to 80ppm and grafting rate of 1.5% to 3%. (2) Modification of nanopowder: Mix nano CeO2 with ZnO, add 0.5%~1% γ-glycidyl oxypropyltrimethoxysilane, stir at 60℃~70℃ for 1~2 hours, and vacuum dry for later use; (3) Preparation of modified DMC: D3, D4 and D5 were mixed and 2% of glycidyl etheroxypropyltrimethoxysilane was added. The mixture was reacted at 90°C for 3 hours under nitrogen protection and purified by vacuum distillation to obtain epoxy-modified DMC. (4) Composite modification: The polyvinyl acetate graft copolymer obtained in step (1) is added to the internal mixer in sequence with the composite plasticizer, modified DMC and modified nanocomposite powder, and melt-mixed at 150℃~165℃ for 20~35 minutes to obtain a composite resin mixture. (5) Film forming: The composite resin mixture is calendered or extruded to form a base film with a thickness of 0.3 mm to 1.6 mm; (6) Multi-level interface modification: ① Plasma pretreatment: The base film is treated with a plasma treatment machine with a power of 30~50W for 3~5 minutes; ② Environmentally friendly surface treatment agent coating: The plant-based epoxy modified silane treatment agent is prepared into an ethanol solution with a mass concentration of 1%~2.5%, and 0.5%~1% of environmentally friendly nonionic surfactant fatty alcohol polyoxyethylene ether is added. The solution is coated on the surface of the base film by spraying and dried at 90℃~105℃ for 8~12 minutes; ③ Anti-fog coating: The hydrophilic silica sol is uniformly coated on the surface of the base film modified by the coupling agent and dried at 100℃~110℃ for 5~8 minutes to obtain a moisture-resistant and heat-resistant anti-aging composite modified interlayer glass membrane.

9. The application of the moisture-resistant, heat-resistant, and anti-aging composite modified interlayer film of laminated glass as described in any one of claims 1 to 7 in the preparation of laminated glass.

10. The application according to claim 9, characterized in that, The preparation of laminated glass includes the following steps: an interlayer film is sandwiched between glass substrates to form a laminate, which is then placed in a vacuum bag and degassed under reduced pressure of -80kPa to -95kPa for 20 to 30 minutes. Subsequently, it is heated and pressed at 90℃ to 110℃ and a pressure of 3kg / cm² to 12kg / cm² of approximately 0.3MPa to 1.2MPa for 25 to 35 minutes to complete the composite molding.

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