Interlayer composition for vehicle glazing manufacture

Abstract

This invention relates to the field of environmental functional glass and laminated glass manufacturing technology, and discloses a laminated composition for manufacturing automotive windshields, comprising: polyvinyl butyral resin, triethylene glycol diisooctanoate, cesium tungsten bronze nanoparticles, and a retarding component composed of 3-glycidyl etheroxypropyltrimethoxysilane and magnesium octanoate. This invention constructs a static buffer network structure in situ at the multiphase interface between the laminated composition and the glass through the retarding component, spontaneously eliminating the free acid-catalyzed chain hydrolysis reaction induced by localized radiative heat collection, improving the adhesion stability between the interlayer and the glass surface, effectively eliminating edge delamination, delamination, and bubble defects that occur during long-term service of automotive windshields as environmental functional glass, slowing down chromatic drift during aging, and maintaining high visible light transmittance and low haze rise rate of the laminated glass.

Description

Technical Field

[0001] This invention relates to the field of environmental functional glass and laminated glass manufacturing technology, specifically to a laminated composition for manufacturing automotive windshields. Background Technology

[0002] Currently, automotive windshields typically use polyvinyl butyral resin combined with high-boiling-point ester plasticizers as the polymer binder. To enable the laminated glass to block near-infrared radiation, cesium tungsten bronze nanofillers with specific surface modifications are isotropically dispersed in the resin phase during the manufacturing process. This constructs a multi-phase composite sheet with broad-spectrum thermal radiation shielding. Under normal service conditions, this type of polymer multiphase laminate can maintain the required visible light transparency and safety impact and splash resistance of the windshield. However, as the vehicle's service environment changes, the edges of the windshield sheet continuously... Exposed to thermal radiation, alternating temperature differences, and concentrated stress from moisture penetration, cesium tungsten bronze nanofillers form thermo-oxygen aggregation centers at the interface between particles and polymers when converting near-infrared light energy. Continuous thermal stress triggers thermo-oxygen decomposition of polyvinyl butyral resin, leading to ring-opening and chain breaking of the acetal structure and the generation of volatile organic acids. These released free acids accumulate at the lamination interface, catalyzing macromolecular hydrolysis reactions, resulting in a loose interlayer structure and the accumulation of gaseous products. Ultimately, this leads to delamination, bubble clustering, and perimeter white edge defects at the windshield edge where tangential shear forces are concentrated.

[0003] To delay multiphase interface hydrolysis, increasing the proportion of antioxidants or the dosage of coupling agents is often chosen. However, these exogenous small-molecule additives are prone to decomposition and inactivation under the localized heat accumulation on the surface of functional particles, failing to cut off the chain release of free acid molecules at the source of self-degradation. Simultaneously, excess low-molecular-weight additives lack chain segment anchoring and migrate towards the sheet edge under hygrothermal stress, disrupting the hydrogen bond network of silanol groups on the resin and glass surface, leading to a decrease in film adhesion strength. However, existing improvements are usually limited to mechanical modifications of processing equipment. Besides the structural limitations of hardware such as extrusion or casting roller forms, there are also shortcomings in software control methods such as adaptive formulation control. For example, [authorization announcement number] Chinese invention patent CN104231306B discloses a heat-insulating plasticizer composition, a transparent heat-insulating interlayer film, and a transparent heat-insulating sandwich panel. It introduces a dispersant to pre-disperse inorganic particles in the plasticizer to improve flowability. However, it implicitly relies on the static physical compatibility in the early stage of mixing, which is completely detached from the dynamic working conditions of automotive glass subjected to high-energy radiation and alternating temperature differences. Under the objective reality that the polymer skeleton breaks and releases free acids in the heat collection center of particles, the dispersant in this system lacks chemical counterbalancing and phase interface anchoring mechanisms against free acids. Free additives migrate to the boundary with temperature and humidity stress, which accelerates the destruction of hydrogen bond network and edge delamination, exposing the fundamental mismatch of the underlying control method.

[0004] Therefore, how to design a composite stable system with polymer chain segment coordination function to eliminate organic acid molecules generated in situ at the local radiation heat collection center, thereby eliminating cracking and delamination slippage at the edge of the laminated material, has become the technical problem to be solved by this invention. Summary of the Invention

[0005] To address the problems in the background art, the present invention provides a laminated composition for the manufacture of automotive windshields, comprising: Polyvinyl butyral resin, triethylene glycol diisooctanoate, cesium tungsten bronze nanoparticles, and a blocking component composed of 3-glycidyl etheroxypropyltrimethoxysilane and magnesium octanoate; Based on 100 parts by weight of polyvinyl butyral resin, the content of triethylene glycol diisooctanoate is 31.5 to 34.5 parts by weight, the content of cesium tungsten bronze nanoparticles is 0.07 to 0.14 parts by weight, the content of 3-glycidyl etheroxypropyltrimethoxysilane is 0.16 to 0.33 parts by weight, and the content of magnesium octanoate is 0.040 to 0.075 parts by weight; wherein, the mass ratio of 3-glycidyl etheroxypropyltrimethoxysilane to magnesium octanoate is 4.0:1 to 4.4:1. The cesium tungsten bronze nanoparticles have a coating layer on their surface, which is composed of the hydrolysis and condensation products of 3-glycidyl etheroxypropyltrimethoxysilane. At the multiphase interface between the sandwich composition and the glass, the ring-opening addition reaction product of glycidyl etheroxy group in 3-glycidyl etheroxypropyltrimethoxysilane and free butyric acid coexists with the coordination reaction product of magnesium ion and butyrate group in magnesium octoate. The ring-opening addition reaction product and the coordination reaction product form a static buffer network structure at the multiphase interface.

[0006] Preferably, the water content of the polyvinyl butyral resin is 0.30 wt% to 0.55 wt%; and the concentration of free butyric acid at the multiphase interface is 0 mol / L to 0.015 mol / L.

[0007] Preferably, the average particle size of the cesium tungsten bronze nanoparticles is 20 nm to 50 nm; the octanoate ions in magnesium octanoate and the molecular chains of polyvinyl butyral resin are physically entangled, and the total mass percentage content of the blocking component in the sandwich composition is 0.20 wt% to 0.40 wt%.

[0008] Preferably, the haze rise rate of the interlayer composition under light radiation conditions is 0.01% / 100d to 0.05% / 100d, and the total haze value of the interlayer composition after light radiation is not greater than 1%.

[0009] Preferably, the content of triethylene glycol diisooctanoate is 32.0 parts by weight to 33.5 parts by weight, the content of cesium tungsten bronze nanoparticles is 0.08 parts by weight to 0.12 parts by weight, the content of 3-glycidyl etheroxypropyltrimethoxysilane is 0.20 parts by weight to 0.28 parts by weight, and the content of magnesium octanoate is 0.045 parts by weight to 0.065 parts by weight, and the mass ratio of 3-glycidyl etheroxypropyltrimethoxysilane to magnesium octanoate is 4.1:1 to 4.3:1.

[0010] Preferably, the polyvinyl butyral resin has a butyraldehyde content of 68wt% to 72wt%, a free hydroxyl content of 18wt% to 22wt%, and an average molecular weight of 100,000 g / mol to 150,000 g / mol.

[0011] Preferably, the cesium tungsten bronze nanoparticles are dispersed in polyvinyl butyral resin, and the coating layer is limited to the surface of the cesium tungsten bronze nanoparticles, with a coating layer thickness of 1.5 nm to 3.5 nm.

[0012] Preferably, the interlayer composition further comprises antioxidant 1010 and ultraviolet absorber UV-326; based on 100 parts by weight of polyvinyl butyral resin, the content of antioxidant 1010 is 0.10 parts by weight to 0.25 parts by weight, and the content of ultraviolet absorber UV-326 is 0.15 parts by weight to 0.35 parts by weight.

[0013] Preferably, the intermediate layer sheet is in the form of a middle layer sheet with a thickness of 0.38 mm to 1.14 mm, and the intermediate layer sheet has a visible light transmittance of 85% to 92% in the wavelength range of 400 nm to 700 nm and a near-infrared light blocking rate of 80% to 95% in the wavelength range of 780 nm to 2500 nm.

[0014] The beneficial effects of this invention are: 1. In the interlayer composition of automotive windshield manufacturing, by synergistically combining surface-coupled modified near-infrared blocking particles with multivalent metal salt components, an in-situ thermo-oxidative passivation network is constructed at the resin matrix phase interface. When inorganic particles absorb radiation to generate microscopic local thermo-oxidative aggregation and induce polymer skeleton degradation to produce trace amounts of free butyric acid, the metal ions in the multivalent metal salt form spatial interlocked coordination with the adjacent epoxy ring, reducing the transition state activation energy of the carboxyl nucleophilic ring-opening, allowing the epoxy ring to undergo a ring-opening addition reaction at a higher kinetic rate, converting it into a chemically stable hydroxy ester covalently bonded entity at the source of free acid release, spontaneously eliminating the inducement of acid-catalyzed chain hydrolysis, and maintaining the chemical stability of the intermediate layer inside the multilayer composite glass.

[0015] 2. The specific residual hydroxyl content in the resin matrix interacts with the in-situ interfacial thermo-oxidative barrier components, promoting covalent block formation between the barrier components and the macromolecular matrix in the melt shear reaction zone. This prevents low molecular weight modified materials from isotropically migrating to the phase interface. This tight phase chemical cross-linking network not only increases the hydrogen bond association density between the intermediate film and the silanol groups on the glass surface, but also locks the mechanical bonding defense line of the multiphase interface when the edge area is subjected to high humidity water penetration and alternating environmental shear stress concentration. This effectively slows down the peeling tendency caused by interfacial stress concentration and limits water vapor erosion and delamination slippage in the edge area of ​​the windshield throughout its entire life cycle.

[0016] 3. Combined with a specific multi-stage gradient temperature control and strong shear reaction mixing process, the specific long-chain structure in the retardant component forms a stable molecular-level coordination anchor with the high-boiling-point organic carboxylate. This spatial structure exhibits low volatility in the high-temperature molten state and does not undergo molecular thermal decomposition during the multi-stage reaction extrusion and vacuum degassing stages. The high-temperature chemical stability of the above-mentioned material flow process spontaneously eliminates the potential risk of internal micropores caused by the vaporization of additives during the casting and shaping of intermediate film sheets, ensuring that the film sheet has high thickness uniformity and optical isotropy, which is conducive to achieving high-quality sheet assembly in large-scale continuous industrial production lines. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a diagram of the multiphase interface static buffer network structure of the sandwich composition of the present invention; Figure 2 This is a flow chart of the process for preparing the interlayer sheet of the sandwich composition of the present invention by casting. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0020] A laminated composition for use in the manufacture of automotive windshields, comprising: Polyvinyl butyral resin, triethylene glycol diisooctanoate, cesium tungsten bronze nanoparticles, and a blocking component composed of 3-glycidyl etheroxypropyltrimethoxysilane and magnesium octanoate; Based on 100 parts by weight of polyvinyl butyral resin, the content of triethylene glycol diisooctanoate is 31.5 to 34.5 parts by weight, the content of cesium tungsten bronze nanoparticles is 0.07 to 0.14 parts by weight, the content of 3-glycidyl etheroxypropyltrimethoxysilane is 0.16 to 0.33 parts by weight, and the content of magnesium octanoate is 0.040 to 0.075 parts by weight; wherein, the mass ratio of 3-glycidyl etheroxypropyltrimethoxysilane to magnesium octanoate is 4.0:1 to 4.4:1. The cesium tungsten bronze nanoparticles have a coating layer on their surface, which is composed of the hydrolysis and condensation products of 3-glycidyl etheroxypropyltrimethoxysilane. At the multiphase interface between the sandwich composition and the glass, the ring-opening addition reaction product of glycidyl etheroxy group in 3-glycidyl etheroxypropyltrimethoxysilane and free butyric acid coexists with the coordination reaction product of magnesium ion and butyrate group in magnesium octoate. The ring-opening addition reaction product and the coordination reaction product form a static buffer network structure at the multiphase interface.

[0021] Preferably, the water content of the polyvinyl butyral resin is 0.30 wt% to 0.55 wt%; and the concentration of free butyric acid at the multiphase interface is 0 mol / L to 0.015 mol / L.

[0022] Preferably, the average particle size of the cesium tungsten bronze nanoparticles is 20 nm to 50 nm; the octanoate ions in magnesium octanoate and the molecular chains of polyvinyl butyral resin are physically entangled, and the total mass percentage content of the blocking component in the sandwich composition is 0.20 wt% to 0.40 wt%.

[0023] Preferably, the haze rise rate of the interlayer composition under light radiation conditions is 0.01% / 100d to 0.05% / 100d, and the total haze value of the interlayer composition after light radiation is not greater than 1%.

[0024] Preferably, the content of triethylene glycol diisooctanoate is 32.0 parts by weight to 33.5 parts by weight, the content of cesium tungsten bronze nanoparticles is 0.08 parts by weight to 0.12 parts by weight, the content of 3-glycidyl etheroxypropyltrimethoxysilane is 0.20 parts by weight to 0.28 parts by weight, and the content of magnesium octanoate is 0.045 parts by weight to 0.065 parts by weight, and the mass ratio of 3-glycidyl etheroxypropyltrimethoxysilane to magnesium octanoate is 4.1:1 to 4.3:1.

[0025] Preferably, the polyvinyl butyral resin has a butyraldehyde content of 68wt% to 72wt%, a free hydroxyl content of 18wt% to 22wt%, and an average molecular weight of 100,000 g / mol to 150,000 g / mol.

[0026] Preferably, the cesium tungsten bronze nanoparticles are dispersed in polyvinyl butyral resin, and the coating layer is limited to the surface of the cesium tungsten bronze nanoparticles, with a coating layer thickness of 1.5 nm to 3.5 nm.

[0027] Preferably, the interlayer composition further comprises antioxidant 1010 and ultraviolet absorber UV-326; based on 100 parts by weight of polyvinyl butyral resin, the content of antioxidant 1010 is 0.10 parts by weight to 0.25 parts by weight, and the content of ultraviolet absorber UV-326 is 0.15 parts by weight to 0.35 parts by weight.

[0028] Preferably, the intermediate layer sheet is in the form of a middle layer sheet with a thickness of 0.38 mm to 1.14 mm, and the intermediate layer sheet has a visible light transmittance of 85% to 92% in the wavelength range of 400 nm to 700 nm and a near-infrared light blocking rate of 80% to 95% in the wavelength range of 780 nm to 2500 nm.

[0029] Example 1: This experiment constructed multiple simulated irradiation platforms with parameter gradient variations to verify the in-situ thermal-oxidative passivation efficiency of the composition under different local heat collection intensities. The experimental platform used a full-spectrum xenon lamp aging chamber, with the radiation intensity set at 1120 W / m². 2 This simulates the steady-state heat accumulation state of a windshield under high exposure conditions. An infrared thermal imager is used to monitor the highest apparent temperature in the localized area at the edge of the interlayer film in real time. The system temperature measurement accuracy is set to ±0.5℃. The experimental group design is as follows: Sample A of this invention: The formulation contains 100 parts by weight of polyvinyl butyral resin, 33.0 parts by weight of triethylene glycol diisooctanoate, 0.07 parts by weight of cesium tungsten bronze nanoparticles, 0.16 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane, and 0.04 parts by weight of magnesium octanoate. 0 parts by weight, silane coupling agent to metal salt mass ratio of 4.0:1, partial deficiency control group; Sample group B: based on the formula of sample group A, magnesium octanoate is removed; out-of-range control group; Sample group C: the formula contains 100 parts by weight of polyvinyl butyral resin, 32.5 parts by weight of triethylene glycol diisooctanoate, 0.11 parts by weight of cesium tungsten bronze nanoparticles, 0.38 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane, and 0.015 parts by weight of magnesium octanoate, silane coupling agent to metal salt mass ratio of 25.3:1.

[0030] To ensure that the experimental data reflects the interfacial behavior under real-world operating conditions, the moisture content of each sample group was pre-set at 0.5 g / kg to simulate a high-humidity service environment at the edges. Ion chromatography was used to extract interfacial substances from the edges of the laminated glass components at the 500th, 1000th, and 2000th hours of the aging cycle, and the concentration of residual free butyric acid was measured. Calculate the in-situ hedging efficiency The formula is: ,in, This represents the baseline molar concentration of butyric acid produced by the system at a specific irradiation node without the addition of any blocking component. The residual butyric acid molar concentration measured at the corresponding nodes for each experimental group, where the baseline molar concentration is... The determination process was as follows: Under the exact same blending, extrusion, and casting film-forming processes, a blank control laminated glass assembly containing only 100 parts by weight of polyvinyl butyral resin, 33.0 parts by weight of triethylene glycol diisooctanoate, and 0.07 parts by weight of cesium tungsten bronze nanoparticles, without introducing any hindering components, was prepared. This assembly was also pre-treated with 0.5 g / kg of moisture and subjected to a radiation intensity of 1120 W / m². 2 Synchronous radiation aging was performed in a full-spectrum xenon lamp aging chamber. At specific aging time points, edge substances were extracted using the same interfacial extraction procedure and detected by ion chromatography. The baseline concentration of free butyric acid released by the system at this point due to pure heat oxygen and localized heat collection and natural degradation was measured and used as the unhindered background parameter for calculating the hedging efficiency. The experimental data are recorded as follows: At 1000 hours, the residual butyric acid concentration of sample A was 0.0042 mol / L, and the in-situ hedging efficiency was... The concentration of butyric acid in sample group B was 0.88; the residual butyric acid concentration in sample group B was 0.028 mol / L. The concentration of butyric acid in sample group C was 0.21; the residual butyric acid concentration in sample group C was 0.019 mol / L. The value is 0.46. It should be noted that the baseline concentration obtained by back-calculating the above measured data is... The existence of extremely minor technical deviations is not a contradiction in mechanism, but rather a slight difference in the local polarity and swelling properties of the intermediate membrane matrix caused by the different amounts of the retardant components added in different groups. This results in a normal engineering fluctuation of approximately ±1.2% in the interfacial recovery rate during edge butyric acid solvent extraction using ion chromatography with external standard method. This is compounded by the standard error of signal detection in the ion chromatograph under a high concentration of inorganic ions. The data fluctuations are completely within the statistically permissible experimental error range, and the basic degradation kinetic equilibrium and physical closed loop at the bottom of the system still hold.

[0031] Data evolution trends show that sample A effectively reduces the activation energy of the addition reaction through the chelation transition state formed by metal cations and epoxy groups. Comparative data between sample B and sample C confirm that when the ratio deviates from the preset range of 4.0:1 to 4.4:1, the chemical kinetic path of the interface passivation network is blocked, resulting in a nonlinear decay of acid capture efficiency. This experimental result confirms that the component ratio range is a necessary technical window for achieving multiphase interface thermo-oxidative passivation. After 2400 hours of strong ultraviolet irradiation aging, the haze drift of sample A is 0.11%, the maximum debonding slip distance of edge water vapor penetration is 0.10 mm, and the tapping bond strength Pummel value remains at level 6, indicating that the interlayer composition has long-term service stability under the local thermal environment of the edge of the vehicle glass.

[0032] Example 2: This example focuses on the interfacial adhesion stability of automotive windshields under extreme temperature and humidity cycling conditions. It involves the calibration and quantitative analysis of the thermo-oxidative evolution process. In a typical automotive windshield application scenario, the glass assembly must withstand rapid temperature cycling from -40°C to 120°C. During this process, the polyvinyl butyral resin matrix softens at high temperatures, increasing the free volume of its molecular chain segments. This leads to a decrease in the wettability of the resin interface with cesium tungsten bronze nanoparticles. Trace amounts of free butyric acid generated from resin matrix degradation migrate to the glass surface, thereby causing a decrease in interfacial adhesion strength. To quantify the thermo-oxidative defense capability of this composition, a standardized thermal cycling aging procedure was used to assess the continuous degradation of its properties. Based on 100 parts by weight of polyvinyl butyral resin, a composition containing 33.0 parts by weight of triethylene glycol diisooctanoate, 0.10 parts by weight of cesium tungsten bronze nanoparticles, 0.24 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane, and 0.055 parts by weight of magnesium octanoate was formulated. The mass ratio of silane coupling agent to metal salt was set at 4.36:1. During the actual melt blending reaction, the octanoate ions in the magnesium octanoate reacted with the polyvinyl butyral resin... The molecular chains of aldehyde resins exhibit a physically entangled structure. The microscopic realization path and chain segment dynamics constraint mechanism are as follows: Long-chain, low-polarity aliphatic octanoic acid segments in magnesium octanoate spontaneously diffuse into the non-polar butyraldehyde-rich region of the polyvinyl butyral resin macromolecule due to structural compatibility, achieving localized dynamic entanglement and compatibility. Meanwhile, the polar magnesium ion ends, through multi-point dipole-dipole interactions and coordination bonding tendencies, construct a transient non-covalent polar network within the bulk phase with the free hydroxyl groups on the resin macromolecule chain. This network then interacts with the polar ends through end-topological permeation of the low-molecular-weight long-chain ends. The multi-point complexation and locking cause a nonlinear increase in the resistance to the slippage of resin polymer chain segments. Macroscopically, this manifests as a macroscopic condensed-state physical behavior equivalent to a decrease in the critical molecular weight of physical entanglement between resin macromolecular chains and an increase in entanglement density. This locks in the internal structural stability of the blended sheet. The material is melt-mixed in a twin-screw extruder. The temperature of the extruder reaction zone is set at 190℃ and the screw speed is 200rpm to ensure that the microscopic distribution of each component is uniform. The extruded melt is rapidly shaped at a constant temperature of 20℃ in the cooling roller group to prepare an intermediate film with a thickness of 0.76mm.

[0033] The experimental setup was as follows: Sample Group D: A sandwich glass assembly prepared using the above composition, with a median particle size of 35 nm for the D50 of cesium tungsten bronze nanoparticles in the interlayer. Comparative Sample Group E: The formulation did not contain 3-glycidyl etheroxypropyltrimethoxysilane or magnesium octanoate as a blocking component; the remaining components were the same as Sample Group D. Out-of-range control group F: The content of 3-glycidyl etheroxypropyltrimethoxysilane was increased to 0.80 parts by mass, achieving a silane coupling agent to metal salt mass ratio of 14.5:1. The assembly was placed in an aging chamber, and an extreme thermal cycle was performed every 12 hours, from -40°C for 2 hours to 120°C for 2 hours. After the 50th, 100th, and 150th cycles, the interfacial shear modulus of the glass assembly was tested. , ,in, The measured interfacial shear force, The thickness of the intermediate film. To effectively test the area, It represents the instantaneous displacement of the interface under stress.

[0034] The experimental data are recorded as follows: After the 150th cycle, the shear modulus of sample group D is... The haze level remained at 93.5% of the initial value, with a haze growth rate of 0.12%. Sample group E, lacking an interface passivation mechanism, experienced continuous accumulation of free butyric acid, resulting in a decrease in shear modulus. The haze decreased to 78.2% of the initial value, with a haze growth rate of 1.15%. In sample group F, excessive silane coupling agent led to nanoparticle aggregation, causing fluctuations in interfacial bonding strength and shear modulus. The haze decreased to 85.1% of the initial value, with a haze growth rate of 0.82%. Data analysis shows that when the mass ratio of silane coupling agent to magnesium octanoate is maintained in the range of 4.0:1 to 4.4:1, the chelated transition state can effectively reduce the interfacial hydrolysis rate initiated by free butyric acid. Specifically, the chemical cross-linking network construction path of the static buffer network structure is as follows: 3-glycidyl etheroxypropyltrimethoxysilane contains three methoxy groups at one end, which undergo hydrolysis under the action of trace amounts of water in the system, dehydrating and condensing to form an inorganic oligomeric siloxane network framework with a high degree of cross-linking. After the monofunctional glycidyl etheroxy groups suspended on its flanks capture free butyric acid and undergo ring-opening addition reactions, the oxygen atoms in the hydroxyl ester structure generated in situ react with the adjacent magnesium octanoate to transform... Magnesium butyrate complexes undergo polydentate coordination, utilizing the multi-coordination number of magnesium ions to construct spatial chemical bridges between different oligomeric siloxane segments. This allows the one-dimensional ring-opening addition product and the low-molecular-weight complex product to be networked within the micro-regions of the phase interface, intertwining to form a three-dimensional network static hybrid entity structure with inorganic silicon-oxygen bonds as the network skeleton and organic polydentate complexes as the cross-linking links. When this ratio deviates from the above range, the acid capture kinetic rate decreases, leading to an irreversible physical phase transition in the interfacial adhesive layer. The experimental data confirm that by constructing a static buffer network in situ at the multiphase interface, the interfacial slip distance of environmental functional glass can be controlled within 0.15 mm during complex service cycles, demonstrating the structural reliability of the composition of the present invention under thermo-oxidative cycling conditions.

[0035] Example 3: This example focuses on the long-term dynamic stability of the composition in the service environment of automotive windshields. The optical and physicochemical properties of the interlayer film are verified in a closed-loop manner throughout the entire cycle through an offline calibration procedure. In the manufacturing process of automotive windshields, the interfacial bonding strength of the interlayer composition is affected by the interplay of ambient temperature fluctuations and ultraviolet radiation intensity. Moreover, the hydrolysis resistance of the resin matrix is ​​the core technology that determines the edge sealing stability. In order to avoid performance deviations of the interlayer film caused by batch fluctuations of raw materials during production and actual automotive applications, the system has set up a standardized engineering calibration process that includes dynamic threshold calibration.

[0036] The experimental sample group used the following formulation: 100 parts by weight of polyvinyl butyral resin, 32.5 parts by weight of triethylene glycol diisooctanoate, 0.12 parts by weight of cesium tungsten bronze nanoparticles, 0.25 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane, and 0.05 parts by weight of magnesium octanoate. The components were premixed for 8 minutes at room temperature using a high-speed mixer, then fed into a co-rotating twin-screw extruder and melt-blended under a temperature gradient of 180°C to 205°C. Finally, the mixture was formed using a 1.6-meter wide casting die. To quantitatively characterize the heat and oxygen degradation resistance of the sandwich composition during service, the calibration procedure followed these steps: the glass transition temperature of the matrix resin under different heat treatment cycles was measured using a differential scanning calorimeter. And build based on measurement data Time decay function: ,in, The initial glass transition temperature of the intermediate film. The material degradation constant, The activation energy for thermal degradation, Let be the ideal gas constant. The ambient thermodynamic temperature, For service life, the thermo-oxidative degradation of polymer materials causes molecular chain breakage and free volume changes, which are reflected in the time decay function. As service time increases The glass transition temperature of the evolved intermediate layer sheet The initial glass transition temperature is between 15°C and 25°C. The thermal degradation constant ranges from 0.05 to 0.25. The activation energy for thermal degradation is between 65 kJ / mol and 85 kJ / mol. The gas constant is 8.314. The ambient thermodynamic temperature was determined by testing the glass transition temperature of interlayer sheet samples under different aging cycles and then using the least squares exponential fitting method. and In the specific lamination process and service life, the spatial dynamic synergy mechanism between the covalent block of the retarding component and the macromolecular matrix, and the in-situ construction of a static buffer network at the multiphase interface, is as follows: In the high-shear section of twin-screw reactive extrusion, the silanol groups generated by the partial hydrolysis of 3-glycidyl etheroxypropyltrimethoxysilane in the retarding component undergo local dehydration condensation with the free hydroxyl groups in the macromolecular matrix polyvinyl butyral resin, achieving covalent anchoring within the bulk phase to suppress the disordered isotropic loss of the modified component during subsequent service; while in the laminated lamination... During the high-temperature hot-pressing stage, due to the close adhesion between the surface of the intermediate layer sheet and the glass surface, the remaining free silane coupling agent and some free metal salts that are not completely fixed by the bulk phase in the micro-region of the sheet's extreme surface undergo short-range anisotropic diffusion along the direction perpendicular to the interface under the strong polar affinity of the high-density silanol groups on the glass surface, and are directionally enriched at the multiphase interface. In this multiphase interface region, the free butyrate ions generated by aging are captured in situ and coordination and ring-opening addition reactions are completed, ultimately constructing a multi-level physicochemical defense line across scales between the bulk covalent constraint and the interface directional response.

[0037] Experimental monitoring shows that, with The increase caused slight chain segment breakage in the sample components, resulting in The experiment produced a downward trend that conformed to the above exponential function law. By adjusting the cooling roller speed of the extruder online, the calender thickness deviation was controlled within ±0.01mm, ensuring the uniformity of the spatial distribution of the blocking components. At the end of the test, the edge moisture penetration degumming slip distance of the composition remained below 0.12mm. This verified that the calibration procedure can effectively correct the nonlinear fluctuations caused by raw material batches through offline calibration of key thermo-oxidative kinetic parameters, ensuring that the service reliability of the interlayer membrane in the vehicle environment meets industry technical standards.

[0038] Example 4: In the production of interlayer compositions for automotive environmental functional glass, the microscopic dispersion state of each component determines the hydrolysis resistance performance of the interfacial acid-base trapping network. To eliminate the dispersion of interfacial bonding strength caused by batch raw material fluctuations, a standardized engineering procedure covering offline parameter pre-calibration and online dynamic compensation during the production process was established. Using 100 parts by weight of polyvinyl butyral resin as a baseline, a composition containing 32.5 parts by weight of triethylene glycol diisooctanoate, 0.10 parts by weight of cesium tungsten bronze nanoparticles, 0.24 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane, and 0.055 parts by weight of magnesium octanoate was prepared. The mass ratio of 3-glycidyl etheroxypropyltrimethoxysilane to magnesium octanoate was set at 4.36:1. The offline calibration process adopted a 5×5 grid gradient sampling method. Samples were prepared under blending shear conditions at 190℃, and the bonding strength was determined by an interfacial peel test. Based on the experimental data, an interface passivation response surface model was fitted, and the model formula is as follows: ,in, To measure the interfacial bond strength, The amount of 3-glycidyl etheroxypropyltrimethoxysilane added. This refers to the amount of magnesium octanoate added. The interfacial reactivity coefficient, This represents the weighting coefficient for metal salt catalysis. As the sensitivity attenuation factor, the multiphase interfacial bonding strength depends on the covalent bond density of the silane coupling agent on the glass surface and the coordination equilibrium of the metal salt hydrolysis retardation groups. In the model formula, For multiphase interfacial bond strength, The amount of 3-glycidyl etheroxypropyltrimethoxysilane added. This refers to the area where magnesium octanoate is added. The interfacial reactivity coefficient ranges from 1.2 to 1.8. The metal salt catalytic weighting coefficients range from 0.5 to 0.9. A sensitivity attenuation factor of 1.5 to 2.5 is used to eliminate noise interference caused by mechanism friction, fixture slippage, and sheet creep during peel testing, and to improve bond strength. The test was conducted using a 180° peel tester at 23°C and 50% relative humidity at a speed of 100 mm / min. High-frequency vibration signals were filtered out by a low-pass filter, and the average force of the steady-state peel segment was extracted as the output value.

[0039] Based on the optimal feed ratio determined by the response surface model, the system integrates real-time environmental data into the dynamic feedback loop, including ambient humidity. With ambient temperature The fluctuations are adjusted by a real-time correction function to regulate the feeding rate. , The calculation relationship is as follows: ,in, The adjusted instantaneous feed rate of the retarding component. As the baseline feeding rate, This is the humidity correction factor. Given the current ambient humidity, To calibrate the reference humidity, This is the temperature correction factor. The current ambient temperature. To calibrate the reference temperature, in the feeding rate formula, The adjusted instantaneous feed rate of the retarding component. For the baseline feeding rate range, The external control range is for an environmental humidity correction factor of 0.003 to 0.006. The ambient humidity is collected by a humidity sensor. The baseline humidity is 50%. An ambient temperature correction factor ranging from 0.002 to 0.005. The ambient temperature range collected by the temperature sensor. With a reference temperature of 23℃, humidity and temperature sensors are installed inside the sealed housing of the feed inlet, with a sampling frequency of no less than 10Hz and a temperature measurement accuracy of no less than 0.1℃. These sensors output electrical signals to the controller, which calculates the instantaneous feed rate and drives the proportional metering pump to adjust the valve opening. During actual control execution, the controller uses the calculated instantaneous target mass flow rate. Dividing the volumetric flow rate by the liquid density of the premixed retarder component stored in the system, the target volumetric flow rate is converted. Based on a preset linear calibration curve of the variable frequency metering pump, this volumetric flow rate is mapped to a proportionally proportional pump drive motor inverter output frequency control signal or proportional control valve voltage drive signal. This achieves the conversion of digital control commands into physical quantities such as the piston stroke frequency of the proportional metering pump and the valve core opening displacement, ensuring that the actual material mass injection rate of the retarder component tracks the target flow rate within microseconds. .

[0040] When the ambient humidity deviates from the baseline 5%RH or more, the system automatically activates the metering pump for flow smoothing compensation. For the specific production line conditions in this embodiment, the interfacial reactivity coefficient is calculated by performing a quadratic multivariate nonlinear regression analysis on the 5×5 gridded gradient sampling sample data. The catalytic weighting coefficient for metal salts was determined to be 1.45 N / cm·part. The sensitivity attenuation factor was determined to be 0.72. The value was determined to be 1.98; simultaneously, based on feedback data from on-site environmental monitoring, an environmental humidity correction factor was determined through dynamic fitting calibration. The independently determined value is 0.00451 / %RH, which is the ambient temperature correction factor. The independently determined value is 0.00321 / ℃, thus forming a set of digital control quantification constants that perfectly matches the environmental disturbances in this preparation workshop. After the above calibration and closed-loop control, the fluctuation range of the haze measurement value of the laminated intermediate film converges to within 0.02%. After 150 extreme thermal cycle tests, the interfacial water vapor permeation degumming slip distance is controlled below 0.10 mm. This calibration process eliminates the performance dispersion caused by environmental disturbances by quantifying the mapping relationship between process parameters and interfacial passivation performance, ensuring the service reliability of the composition in different production batches.

[0041] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A laminated composition for manufacturing automotive windshields, characterized in that, include: Polyvinyl butyral resin, triethylene glycol diisooctanoate, cesium tungsten bronze nanoparticles, and a blocking component composed of 3-glycidyl etheroxypropyltrimethoxysilane and magnesium octanoate; Based on 100 parts by weight of polyvinyl butyral resin, the content of triethylene glycol diisooctanoate is 31.5 to 34.5 parts by weight, the content of cesium tungsten bronze nanoparticles is 0.07 to 0.14 parts by weight, the content of 3-glycidyl etheroxypropyltrimethoxysilane is 0.16 to 0.33 parts by weight, and the content of magnesium octanoate is 0.040 to 0.075 parts by weight; wherein, the mass ratio of 3-glycidyl etheroxypropyltrimethoxysilane to magnesium octanoate is 4.0:1 to 4.4:

1. The cesium tungsten bronze nanoparticles have a coating layer on their surface, which is composed of the hydrolysis and condensation products of 3-glycidyl etheroxypropyltrimethoxysilane. At the multiphase interface between the sandwich composition and the glass, the ring-opening addition reaction product of glycidyl etheroxy group in 3-glycidyl etheroxypropyltrimethoxysilane and free butyric acid coexists with the coordination reaction product of magnesium ion and butyrate group in magnesium octoate. The ring-opening addition reaction product and the coordination reaction product form a static buffer network structure at the multiphase interface.

2. The laminated composition for manufacturing automotive windshields according to claim 1, characterized in that, The water content of the polyvinyl butyral resin is 0.30 wt% to 0.55 wt%; and the concentration of free butyric acid at the multiphase interface is 0 mol / L to 0.015 mol / L.

3. The laminated composition for manufacturing automotive windshields according to claim 1, characterized in that, The average particle size of the cesium tungsten bronze nanoparticles is 20 nm to 50 nm; the octanoate ions in magnesium octanoate and the molecular chains of polyvinyl butyral resin are physically entangled, and the total mass percentage content of the retarding component in the sandwich composition is 0.20 wt% to 0.40 wt%.

4. The laminated composition for manufacturing automotive windshields according to claim 1, characterized in that, The haze rise rate of the interlayer composition under light radiation conditions is 0.01% / 100d to 0.05% / 100d, and the total haze value of the interlayer composition after light radiation is not greater than 1%.

5. The laminated composition for manufacturing automotive windshields according to claim 1, characterized in that, The content of triethylene glycol diisooctanoate is 32.0 to 33.5 parts by weight, the content of cesium tungsten bronze nanoparticles is 0.08 to 0.12 parts by weight, the content of 3-glycidyl etheroxypropyltrimethoxysilane is 0.20 to 0.28 parts by weight, and the content of magnesium octanoate is 0.045 to 0.065 parts by weight, and the mass ratio of 3-glycidyl etheroxypropyltrimethoxysilane to magnesium octanoate is 4.1:1 to 4.3:

1.

6. The laminated composition for manufacturing automotive windshields according to claim 1, characterized in that, The polyvinyl butyral resin has a butyraldehyde content of 68wt% to 72wt%, a free hydroxyl content of 18wt% to 22wt%, and an average molecular weight of 100,000 g / mol to 150,000 g / mol.

7. The laminated composition for manufacturing automotive windshields according to claim 1, characterized in that, Cesium tungsten bronze nanoparticles are dispersed in polyvinyl butyral resin, and the coating layer is limited to the surface of the cesium tungsten bronze nanoparticles, with a thickness of 1.5 nm to 3.5 nm.

8. The laminated composition for manufacturing automotive windshields according to claim 1, characterized in that, The sandwich composition also includes antioxidant 1010 and ultraviolet absorber UV-326; based on 100 parts by weight of polyvinyl butyral resin, the content of antioxidant 1010 is 0.10 to 0.25 parts by weight, and the content of ultraviolet absorber UV-326 is 0.15 to 0.35 parts by weight.

9. The laminated composition for manufacturing automotive windshields according to claim 1, characterized in that, Its form is an intermediate layer sheet with a thickness of 0.38 mm to 1.14 mm. The intermediate layer sheet has a visible light transmittance of 85% to 92% in the wavelength range of 400 nm to 700 nm and a near-infrared light blocking rate of 80% to 95% in the wavelength range of 780 nm to 2500 nm.

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