Manufacturing method of hydrophobic special coated glass door with self-cleaning function

Abstract

The invention relates to the technical field of special coated glass treatment, and discloses a method for manufacturing a hydrophobic special coated glass door with a self-cleaning function, which comprises the following steps: adding perfluoroalkyl silane, a near-infrared absorption component and an interface adjusting monomer into a silica sol base material to prepare a hybrid coating solution; coating a solar control glass substrate with the hybrid coating liquid, constructing an anchoring site by utilizing chemical coordination of an interface adjusting monomer and a metal oxide, and driving a hydrophobic group to directionally migrate by utilizing surface tension gradient; adjusting solvent partial pressure to induce curing of the film layer to form a gradient structure; according to the method, the adhesion stability of a film layer is enhanced through the interface chemical bonding effect, light energy is converted into a local micro thermal field through a near-infrared absorption component, and active pumping of hydrophobic components to a damaged area is achieved in cooperation with siloxane network thermal shrinkage driving force; the long-acting self-cleaning performance of the film layer is maintained.

Description

Technical Field

[0001] This invention belongs to the field of special coated glass processing technology, and particularly relates to a method for manufacturing a hydrophobic special coated glass door with self-cleaning function. Background Technology

[0002] Currently, coated glass with sunlight control function adjusts energy transmittance by setting a metal oxide layer on the surface. The industry often prepares a hydrophobic layer with low surface energy on the outer surface of this type of special glass. It uses a silica network as a rigid framework and hybridizes fluorinated silane hydrophobic groups. The cross-linking strength of the siloxane network provides mechanical support, while the hydrophobic groups reduce the adhesion of pollutants. Since special glass doors are in high-frequency friction scenarios such as shopping malls or office building entrances, the surface film layer is subjected to continuous mechanical stress impact. When the hybrid liquid solidifies on the surface of the metal oxide layer with specific surface energy, the electrical distribution at the interface causes stress mismatch in the hybrid sol, resulting in a thermodynamic disorder in the arrangement of hydrophobic units at the interface. This not only weakens the bonding strength between the film layer and the underlying layer, but also obstructs the migration path of hydrophobic molecules after mechanical friction.

[0003] Existing solutions often focus on adjusting the static morphology of the inorganic framework to enhance physical resistance, neglecting the dynamic adaptive requirements under complex service environments. For example, Chinese invention patent CN101235480B discloses a method for preparing antimony-doped tin oxide thin film carrier materials. It constructs a functional layer on the substrate surface through magnetron sputtering combined with multi-step chemical grafting to improve the electrical properties and chemical stability of the thin film. However, the formed film layer is a static anchored structure, the process is lengthy and has poor compatibility with large-scale industrial production. When such static films face continuous mechanical friction and wear, they lack a material replenishment mechanism. Once the surface functional units are depleted, the hydrophobic self-cleaning performance of the film layer rapidly declines, making it difficult to achieve long-term service while ensuring optical fidelity. Existing technologies have a fundamental constraint between film strength and functional durability. Increasing the crosslinking density of the silica framework can enhance the film hardness, but excessively high network density will block the migration channels of hydrophobic units, resulting in the inability to replenish damaged surface groups. Increasing hydrophobic active components can improve self-repair capabilities, but it will lead to a decrease in the overall mechanical properties of the film layer and easily induce optical interference chromatic aberration in the metal oxide underlayer.

[0004] Therefore, the technical problem to be solved by this invention is how to construct a gradient hybrid structure that adapts to the interface stress of the sunlight control coating layer and actively replenishes the damaged sites while maintaining optical fidelity. Summary of the Invention

[0005] This invention provides a method for manufacturing a hydrophobic special coated glass door with self-cleaning function, comprising the following steps:

[0006] Step S1: Prepare a hybrid coating solution by adding perfluoroalkyl silane, nano-scale near-infrared absorbing components, and organosilicon regulating monomers with metal coordination functional groups to an acidic silica sol base. The mass percentage of organosilicon regulating monomers in the hybrid coating solution is controlled to be 2% to 5%, and the dynamic viscosity of the hybrid coating solution is adjusted to be maintained between 2.0 mPa·s and 5.0 mPa·s.

[0007] Step S2, Interface Anchoring and Deposition: The hybrid coating solution is applied to the surface of a glass substrate with a sunlight control coating layer. The organosilicon is used to adjust the chemical coordination between the monomer and the metal ions on the surface of the sunlight control coating layer, forming chemical anchoring points at the interface. The surface tension gradient between the perfluoroalkylsilane and the acidic silica sol matrix is ​​used to drive the hydrophobic groups to migrate directionally to the air interface.

[0008] Step S3, gradient structure construction: adjust the solvent partial pressure of the drying environment to 15 kPa to 25 kPa, induce the hybrid coating liquid to generate a component concentration gradient during the curing process, and form a bottom anchoring layer and a top energy storage layer on the surface of the glass substrate, wherein the nanoscale near-infrared absorbing components are distributed inside the bottom anchoring layer.

[0009] Step S4, instantaneous heat treatment, subjecting the coated glass substrate to 250°C. Up to 300 The heat treatment lasts for 30 to 90 seconds, with a heating rate of not less than 10%. / s, to construct continuous micropores containing hydrophobic molecular fluids inside the bottom anchoring layer and the top energy storage layer, ultimately forming a self-cleaning membrane layer.

[0010] Preferably, in step S1, the organosilicon regulating monomer is selected from one or more of carboxyl-containing organosilicon alkane, phosphonic acid-containing organosilicon alkane, and amino-containing silane coupling agent, and the number average molecular weight of the organosilicon regulating monomer is 800 g / mol to 1200 g / mol, and is used to form an interface transition layer with a thickness of 2 nm to 5 nm on the surface of the sunlight control coating layer in step S2.

[0011] Preferably, the nanoscale near-infrared absorbing component is selected from one or more of antimony-doped tin oxide nanoparticles, cesium tungsten bronze nanoparticles, and indium tin oxide nanoparticles, and the average particle size of the nanoscale near-infrared absorbing component is 20 nm to 50 nm.

[0012] Preferably, the total thickness of the self-cleaning membrane layer is 100 nm to 300 nm, wherein the porosity of the top energy storage layer is 10% to 25%, and the hydrophobic molecular fluid inside the top energy storage layer is at 25 nm. The diffusion coefficient under the given conditions is not less than .

[0013] Preferably, in step S4, the cooling rate of the instantaneous heat treatment is controlled to be 5. / s to 15 / s, to lock the chemical bonding state between the bottom anchor layer and the glass substrate.

[0014] Preferably, after the self-cleaning membrane is damaged, the local heat energy generated by the nano-scale near-infrared absorbing components is used to reduce the dynamic viscosity of the hydrophobic molecular fluid, and the structural shrinkage pressure of the siloxane network formed by the curing of the acidic silica sol matrix under the temperature rise state is used to drive the hydrophobic molecular fluid to migrate along the continuous micropores to the damaged area on the surface of the self-cleaning membrane.

[0015] Preferably, the pumping efficiency of the hydrophobic molecular fluid is evaluated using a self-healing evaluation index. Characterization: ,in, This is a self-repair evaluation index; The permeability constant of the top energy storage layer is determined based on its porosity; This represents the temperature rise per unit time of the self-cleaning film layer under solar radiation. This represents the dynamic viscosity of the hydrophobic molecular fluid at the current temperature.

[0016] Preferably, in step S1, the solid content of the acidic silica sol base is 8% to 12%, and the surface tension of the hybrid coating solution during coating is adjusted to 22mN / m to 28mN / m.

[0017] Preferably, in step S2, the coating is performed using an dip-coating method with a coating speed of 100 mm / min to 200 mm / min, so that the final surface energy of the self-cleaning film is less than 15 mN / m.

[0018] Preferably, in step S2, the relative humidity of the coating environment is 40% to 60% to coordinate with the solvent partial pressure adjustment in step S3 to regulate the volatilization gradient of the components in the hybrid coating solution.

[0019] Compared with existing technologies, the method for manufacturing hydrophobic special coated glass doors with self-cleaning function of the present invention has the following advantages:

[0020] 1. In the manufacturing of hydrophobic special coated glass doors, chemical anchoring points are constructed at the glass interface through the chelation effect of interface adjustment factors and metal ions on the surface of the special coating layer. The synergistic phase separation induction mechanism drives the hydrophobic active units to directionally aggregate towards the air interface. The intrinsic electrotropy of the substrate surface generates polarization repulsion force, which enables the hybrid liquid to spontaneously form a gradient structure of a bottom high-adhesion pinning layer and a top high-capacity energy storage layer during the drying process. While eliminating the concentration of interfacial shear stress between the film layer and the metal oxide layer, it ensures that the hydrophobic components are distributed to the service wear area to the maximum extent, and avoids the risk of edge peeling of the film layer during high-frequency opening process from a physical perspective.

[0021] 2. By capturing ambient light energy and converting it into a local micro-thermal field using a near-infrared absorption unit, and coordinating with the volume contraction of the organosilicon comonomer under the action of the thermal field to generate a physical extrusion vector, hydrophobic molecules deep in the pores are actively pumped to the damaged sites on the surface. The near-infrared energy, which was originally an interfering factor, is converted into a driving force for the migration of active molecules, so that the self-repair response rate is adjusted in sync with the ambient sunlight intensity. This solves the contradiction between the repair rate and the high-frequency wear intensity under the room temperature random diffusion mode, and inhibits the ineffective dissipation of components under low-energy resting state, thereby improving the effective service limit of the sustained-release system.

[0022] 3. Based on the kinetic spacetime difference generated by solvent evaporation, a non-uniform densification response is induced in the silica framework during gradient heat treatment. An optical matching layer with a continuous transition of refractive index from the substrate to the air interface is constructed within a single film layer, eliminating interference rainbow patterns caused by refractive index jumps and ensuring the optical color fidelity of the sunlight control glass. Combined with the elastic damping structure constructed at the interface by hydroxyl-terminated polydimethylsiloxane, residual stress generated by temperature difference expansion and contraction cycles is dissipated, maintaining the geometric topological stability of the mesoporous slow-release channels during substrate deformation and ensuring the functional integrity of the film layer under complex stress conditions. Attached Figure Description

[0023] Fig. 1 This is a flowchart of the manufacturing process of hydrophobic special coated glass door based on the interface coordination anchoring and gradient structure construction of the present invention.

[0024] Fig. 2 This is a schematic diagram of the component feeding sequence and dynamic viscosity closed-loop feedback control of the hybrid coating solution of the present invention. Detailed Implementation

[0025] The technical solutions of the embodiments of this application will be clearly described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this application are within the scope of protection of this application.

[0026] It should be noted that all directional and positional terms used in this invention, such as: up, down, left, right, front, back, vertical, horizontal, inner, outer, top, bottom, transverse, longitudinal, center, etc., are only used to explain the relative positional relationship and connection between components in a specific state (as shown in the accompanying drawings). They are only for the convenience of describing this invention and do not require that this invention be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting this invention. In addition, the descriptions of "first," "second," etc., in this invention are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated.

[0027] In the description of this invention, unless otherwise explicitly specified and limited, the terms installation, connection, and linking should be interpreted broadly. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to mechanical connections; they can refer to direct connections or indirect connections through an intermediate medium; they can refer to the internal communication between two components. For those skilled in the art, the specific meaning of the above terms in this invention can be understood according to the specific circumstances.

[0028] In the description of this specification, references to the terms "an embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example, and the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0029] This invention provides a method for manufacturing a hydrophobic special coated glass door with self-cleaning function, comprising the following stages: preparing a hybrid coating solution containing an acidic silica sol base, perfluoroalkyl silane, nano-scale near-infrared absorbing components, and organosilicon regulating monomers; coating the solution onto the surface of a solar control glass substrate, utilizing the interface regulating monomers to generate chemical coordination with the metal oxide layer to construct anchoring points, and using the surface tension gradient to drive the directional migration of hydrophobic groups; then inducing the formation of a concentration gradient structure in the film layer during curing by adjusting the partial pressure of the environmental solvent; finally, constructing micropores containing hydrophobic fluid through an instantaneous heat treatment process, thereby achieving active replenishment of damaged sites while ensuring the optical color fidelity of the special glass; addressing the bottleneck of interfacial stress mismatch and bonding strength caused by the metal oxide layer on the surface of the solar control glass, this method prepares a hybrid coating solution with specific rheological characteristics in step S1; using a solid content of... to Acidic silica sol was used as the film-forming matrix, and perfluoroalkyl silanes were introduced into it as hydrophobic components, while a mass percentage of [missing information] was added. to Organosilicon modulating monomers with metal coordination functional groups; and those with a number average molecular weight of to Carboxyl-containing organosiloxanes are used to establish the directional response state of the hybrid liquid at the instant of interfacial contact; by adjusting the stirring speed to... and maintain This stabilizes the dynamic viscosity of the hybrid coating solution at a certain level. to Within the range; in step S1, the dynamic viscosity of the hybrid coating solution In 25 As measured by a rotational viscometer, to ensure the hydrophobic molecular fluid maintains its molecular migration activity after the instantaneous heat treatment in step S4, a non-reactive perfluoropolyether component with a mass fraction of 25% in the perfluoroalkylsilane, which does not participate in the siloxane network polycondensation reaction, is required. The initial boiling point of the perfluoropolyether component must be higher than 320°C. Using acidic silica sol as a base at 250 Up to 300 The steric hindrance confines the perfluoropolyether component within the micropores of the top energy storage layer in a physically encapsulated form. After the siloxane network completes cross-linking, it maintains liquid flow characteristics. When the film is damaged and the nanoscale near-infrared absorbing component converts light energy into a localized microthermal field, the synergistic effect of the siloxane network under temperature rise causes structural contraction pressure, driving hydrophobic molecular fluids to actively migrate along the continuous micropores towards the damaged surface area. The organosilicon regulates the quantitative matching relationship between the distribution density of metal coordination functional groups in the monomer and the electrotropic characteristics of the substrate surface; the organosilicon also regulates the molar density of carboxyl functional groups in the monomer. Set at to This value is obtained by measuring the total acid value of the monomers and is used to adjust the amount of monomers added to the organosilicon. The calculation benchmark enables the chemical anchoring layer formed by the organosilicon regulating monomer in step S2 to achieve saturated adsorption at the atomic scale, solving the problem of binding energy fluctuation at the metal oxide interface of conventional physical hybrid films.

[0030] Given the risk of film peeling at the edges of glass doors in high-frequency opening scenarios such as shopping malls, an interface anchoring procedure is performed in step S2. A hybrid coating solution is applied to the surface of a glass substrate with a sunlight control coating using an immersion-lift method, with the lift speed set to [specified value]. to In this process, the organosilicon regulating monomer utilizes its polar groups to chemically coordinate with metal ions in the sunlight control layer, forming a layer at the interface with a thickness of [missing information]. to The chemical anchoring layer; simultaneously utilizing the surface tension gradient between perfluoroalkyl silane and acidic silica sol matrix, hydrophobic groups are driven to migrate directionally towards the air interface, ultimately reducing the surface energy of the film to below... This chemically bonded layer replaces traditional physical adsorption, eliminating shear stress concentration at the interface. To address the problem of rigid cross-linked networks blocking the migration pathways of hydrophobic molecules, gradient structure generation is induced in step S3 by adjusting environmental parameters. (The last sentence appears to be incomplete and possibly refers to a specific process involving relative humidity.) to In an environment where the solvent partial pressure is controlled at to Between; in step S3, the solvent partial pressure The pressure is adjusted by real-time acquisition of the actual solvent partial pressure in the environment through a pressure sensor array within a sealed drying chamber. The signal will determine the actual solvent partial pressure. The deviation from the reference pressure of 20 kPa is used as feedback input to the frequency converter of the exhaust system to determine the frequency adjustment increment of the exhaust system. Adjust the exhaust volume to create localized solvent partial pressure above the coating area. Maintaining a pressure range of 15 kPa to 25 kPa, a component concentration gradient is generated by utilizing the difference in evaporation rates between the main solvent and perfluoroalkylsilanes, inducing the directional enrichment of perfluoroalkylsilanes towards the air interface. A relative humidity of 40% to 60% in the environment slows down the crosslinking rate of siloxanes on the liquid film surface. Within a film layer with a total thickness of 100 nm to 300 nm, a continuously transitioning optical matching layer with a gradient distribution structure capable of material replenishment is constructed. Utilizing the kinetic differences generated by solvent evaporation, component concentration segregation is induced in the hybrid liquid during the curing stage, forming a bottom anchoring layer and a top energy storage layer on the glass substrate surface. The nanoscale near-infrared absorbing component, antimony-doped tin oxide nanoparticles, is mainly distributed within the bottom anchoring layer; while the perfluoroalkylsilanes accumulate on the liquid film surface, thus achieving a total thickness of [missing information - likely related to a specific thickness range]. to The film layer exhibits spatial distribution differences; the solvent system in the hybrid coating solution employs a gradient boiling point design, with the main solvent's boiling point... Initial boiling point of perfluoroalkylsilanes The temperature difference between them is set to to Between; this boiling point gradient is adjusted when the partial pressure of the solvent in the environment is... to In the process, the solute entrainment effect generated by the rapid vaporization of low-boiling-point components is used to drive the perfluoroalkyl segments to aggregate towards the air interface before the complete cross-linking of the siloxane network, thereby transforming the originally disordered blend state into a gradient distribution structure with high adhesion at the bottom layer and high repair activity at the top layer.

[0031] To address the drawback of conventional thermosetting, which easily leads to excessive cross-linking of active components and loss of fluidity, a transient heat treatment procedure is performed in step S4; the coated glass substrate is then subjected to... to The heat treatment, the treatment time is to And the heating rate is set to be no less than This rapid heating process causes the siloxane framework to undergo condensation and solidification, and the shrinkage pressure of the framework extrudes continuous micropores. During the instantaneous heat treatment in step S4, the physical mismatch between the 20% to 15% volume shrinkage rate of the siloxane network during the condensation stage and the thermal expansion coefficient of the hydrophobic molecular fluid embedded within it generates localized microscopic tensile stress within the framework. Since the heating rate is set to be no less than 10 [units per second], [further details are needed]. This instantaneous thermal stress causes directional phase separation microcracks to form incompletely cross-linked siloxane frameworks, resulting in interconnected continuous microchannels. The physical connectivity of these channels is controlled by setting the heating rate; for every 5 seconds the heating rate increases... The average path tortuosity of the micropores will be reduced by 8%, ensuring that the migration channels of hydrophobic components will not close due to excessive densification of the skeleton before thermosetting is complete, while preserving the migration activity of the internal hydrophobic molecular fluid; the cooling rate is controlled at... to To lock in the chemical bonding state; the final top layer of the energy storage layer has a porosity of to And hydrophobic molecular fluid at 25 The diffusion coefficient under the given conditions is not less than .

[0032] After the membrane is damaged, active repair is achieved through an environmental energy conversion mechanism. Nanoscale near-infrared absorbing components distributed within the membrane capture near-infrared energy from sunlight and convert it into a localized microthermal field. This microthermal field reduces the dynamic viscosity of the hydrophobic molecular fluid and, in conjunction with the structural contraction pressure of the siloxane network under temperature rise, drives the hydrophobic components to migrate along continuous micropores towards the damaged area. The self-repair evaluation index during this process... Determined based on the following formula: ,in, This is a self-repair evaluation index; The permeability constant of the top energy storage layer; This represents the temperature rise per unit time of the self-cleaning film layer under solar radiation. The dynamic viscosity of the hydrophobic molecular fluid at the current temperature is given. Through this physical pumping mechanism, the membrane can automatically adjust the replenishment rate according to the ambient light intensity to maintain the stability of its self-cleaning performance. The self-repair evaluation index, a dimensionless value characterizing the material transport efficiency, has a logical trigger threshold of 0.5 for effective response. In the actual control logic, when the product of the temperature rise measured by the temperature sensor and the preset permeability constant is divided by the dynamic viscosity corresponding to the current temperature, and the calculated result is greater than 0.5, it is determined to enter the active repair state. At this time, the dynamic pressure generated by the hydrophobic molecular fluid can overcome the capillary resistance of the micropore inner wall, driving the hydrophobic molecules to migrate directionally to the damaged area of ​​the surface at a rate of not less than five nanometers per second. If the index is less than 0.5, it is determined to be in a resting state, using the spatial steric hindrance effect of the micropores to suppress the ineffective dissipation of components. The permeability constant is obtained by measuring the gas flow rate per unit area of ​​the membrane at a standard pressure difference of 0.1 MPa and performing linear mapping calibration, and its magnitude is fixed at 1.0 × 10⁻⁶. -18 m 2 level.

[0033] Example 1: In the high-frequency access control system of large commercial complexes, the surface of special coated glass doors faces technical pressure due to the high-frequency contact with hand oils and the mechanical friction of cleaning tools, causing the hydrophobic active units on the surface to wear out at a rate exceeding the natural repair rate. By adopting the aforementioned method for manufacturing hydrophobic special coated glass doors with self-cleaning function, a solid content of [missing information] is prepared. An acidic silica sol-based material, to which perfluoroalkyl silanes and a mass percentage of [missing information] are added. The organosilicon-modifying monomers were selected, with a number average molecular weight of [missing information]. Carboxyl-containing organosiloxanes; an average particle size of [missing information] is introduced into this formulation system. Antimony-doped tin oxide particles were used as nanoscale near-infrared absorbing components, and the stirring speed was adjusted to... and maintain This stabilizes the dynamic viscosity of the hybrid coating solution at a certain level. The hybrid coating solution is used to The coating is applied at a high pull-out speed to the surface of a glass substrate with a sunlight control coating layer. Organosilicon is used to regulate the chemical coordination between the polar groups in the monomer and the substrate surface, forming a layer at the interface with a thickness of [missing information]. The bottom anchoring layer; at relative humidity partial pressure with solvent In this environment, perfluoroalkylsilanes are induced to migrate directionally to the air interface, and antimony-doped tin oxide particles are enriched near the substrate due to kinetic differences, forming a total thickness of The gradient distribution structure; then through a heating rate of The heat treatment process raises the substrate temperature to and maintain During this process, the siloxane framework undergoes condensation and solidification, and the pressure generated by the framework shrinkage creates a porosity of [missing information - likely a percentage] within the film layer. The top layer of energy storage is used to lock in hydrophobic molecular fluids and provide a continuous physical supply channel.

[0034] When scratches appear on the surface of the glass door, causing a decrease in hydrophobicity, antimony-doped tin oxide particles distributed in the bottom anchoring layer capture near-infrared radiation from ambient light, converting light energy into localized heat energy, causing a localized temperature rise in the film layer. achieve The thermal field acts on the hydrophobic molecular fluid within the top energy storage layer, causing its dynamic viscosity to... As the temperature rises, the hydrophobic molecular fluid actively migrates along continuous micropores to the damaged area of ​​the surface, driven by the physical extrusion vector of the siloxane network under thermal stress. The response intensity of the self-healing process is evaluated by the self-healing evaluation index. Confirmed, the formula is as follows: ,in, It is a self-healing evaluation index used to characterize the self-healing response performance of self-cleaning films; The permeability constant of the top energy storage layer, in units of ; The temperature rise per unit time, in units of . ; The dynamic viscosity of the hydrophobic molecular fluid at the current temperature, in units of... ,exist Excited by solar radiation energy, the water contact angle in the damaged area is Internally Restore to This indicates that the structural support provided by the bottom anchoring layer and the material compensation provided by the top energy storage layer work synergistically to convert near-infrared energy from the environment into a repair driving force to maintain the low surface energy of the interface. This gradient hybrid structure undergoes... After standard mechanical wiping, the hydrophobic properties of its surface and the optical properties of the sunlight control coating are maintained within the preset tolerance range, achieving performance fidelity under high-frequency operating conditions.

[0035] Example 2: In a test environment equipped with a simulated solar radiation source and a precision contact angle measuring instrument, a verification system consisting of an experimental group, a control group, and an out-of-range control group was set up for a glass substrate with a sunlight control coating. The data in this experiment came from measured values ​​collected by the physical experiment platform, where the measurement resolution of the contact angle measuring instrument was better than... The environmental temperature control accuracy is maintained at Radiation intensity was monitored using an online power meter; the key parameter, antimony-doped tin oxide concentration, was set based on the balance between near-infrared capture efficiency and visible light transmittance; as the concentration of antimony-doped tin oxide increased, the near-infrared energy capture efficiency improved, but scattering in the visible light region also increased; to balance photothermal conversion dynamics and optical transparency, the concentration of antimony-doped tin oxide was set at... to Within the specified range; for comparison, control group A (without antimony-doped tin oxide), control group B (without carboxyl organosiloxanes), and antimony-doped tin oxide with a concentration of [missing information] were set. The out-of-range control group C; in the experiment, the following was used. A substandard mechanical grinding head was used to linearly wear the surfaces of each group of samples to simulate frictional loss during high-frequency operation. At this time, the initial water contact angle of each sample group decreased to [value missing]. to Between; turn on the radiation source and monitor the performance recovery status under different radiation intensity gradients, as shown in Table 1.

[0036] Table 1: Comparison of performance data of self-cleaning membranes under different component configurations and radiation intensities

[0037]

[0038] Based on the data recorded in Table 1, compare the temperature rise of sample group A (lacking antimony-doped tin oxide) under radiation excitation. Only This leads to the dynamic viscosity of hydrophobic molecular fluids. Maintaining at room temperature, self-repair evaluation index The response angle was below the effective response threshold. While control group B exhibited a temperature rise effect, the lack of carboxyl organosiloxane prevented the formation of continuous micropores with coordination anchoring at the membrane interface. This hindered the physical pathway for hydrophobic components to migrate to the surface, resulting in a reduced water contact angle after recovery. Experimental groups 1 to 3 exhibited a gradient recovery pattern, with the antimony-doped tin oxide content decreasing from... Increase to Improved photothermal conversion efficiency and reduced temperature rise With self-repair evaluation index Synchronous growth confirmed the synergistic effect between the energy conversion mechanism and the physical supply channel; the out-of-range control group C at an antimony-doped tin oxide concentration of At that time, its visible light transmittance decreased to This does not comply with the application specifications for solar control glass, indicating to To achieve the optimal operating window for performance synergy; experimental results confirm that the self-healing response rate of the self-cleaning film increases with increasing radiation intensity, and its stability depends on the gradient structural integrity between the bottom anchoring layer and the top energy storage layer; by introducing nanoscale near-infrared absorbing components such as antimony-doped tin oxide, the near-infrared energy in the environment that would originally cause thermal stress is converted into the physical driving force for material replenishment; after experiencing After one standard mechanical wiping cycle, the water contact angle of the special coated glass door surface manufactured using the method of this invention is maintained at [value missing]. Furthermore, the optical properties of the sunlight-controlled coating are maintained within the design tolerance range. This gradient hybrid structure solves the problem of short service life of conventional hydrophobic films under high-frequency friction conditions by establishing an energy-driven material compensation mechanism.

[0039] Example 3: This example combines Figs. 1-2 This describes a manufacturing method for a hydrophobic special coated glass door with self-cleaning function, such as... Fig. 1 As shown, the manufacturing process involves parallel input of the substrate and raw materials. The substrate input stage provides a sunlight-controlled coated glass substrate as the deposition surface. The raw material input stage introduces a mixed component comprising acidic silica sol, perfluoroalkyl silane, near-infrared absorbing components, and organosilicon regulating monomers. This mixture is then introduced in step S1 to prepare the hybrid coating solution. During this process, the monomer mass ratio is controlled to be 2% to 5%, and the dynamic viscosity is adjusted to 2.0. Up to 5.0 After the prepared coating solution is applied, it enters step S2 for interface anchoring and deposition. Anchor points are formed by the chemical coordination of monomers and metal ions, and the surface tension gradient drives the migration of hydrophobic groups. Next, in step S3, the gradient structure construction stage, the solvent partial pressure is adjusted to induce a component concentration gradient to form the bottom anchoring layer and the top energy storage layer. Then, step S4, instantaneous heat treatment, is performed at 250°C. Up to 300 Processing temperature and heating rate ≥10 Curing under conditions of / s, a continuous micropore channel containing hydrophobic molecular fluid is constructed, ultimately outputting a self-cleaning hydrophobic special coated glass.

[0040] like Fig. 2 As shown, in the specific preparation process of the hybrid coating solution, the batching operator takes an acidic silica sol base with a solid content of 8% to 12% from the silica sol container and pours it into the mixing tank. Then, perfluoroalkyl silane providing hydrophobic properties, a near-infrared absorbing component selected from antimony-doped tin oxide nanoparticles, and an organosilicon adjusting monomer with a mass percentage of 2% to 5% are added sequentially. After the addition is complete, the stirring program is started, the speed is set to 300 rpm and maintained for 120 minutes to ensure uniform dispersion of the components. After stirring, sampling and testing are performed. A viscometer is used to measure the dynamic viscosity and the data is fed back to the quality control unit. If the measured value falls below 2.0... Up to 5.0 If the viscosity is deemed acceptable within the specified range, the preparation is complete and can be transferred. If the viscosity is unacceptable, the formula needs to be adjusted, and the batching operator must adjust the component ratios before the mixture is re-entered into the mixing process.

[0041] Example 4: In simulated service conditions of special glass located on a tropical coast, the glass substrate with a sunlight control coating faces the dual corrosion pressure of high-intensity near-infrared radiation and high salt spray concentration. The hydrophobic active units on the coating surface are prone to nonlinear dissipation under cyclic thermal stress. To calibrate the stability of the self-healing mechanism under this condition, the initial state of the sunlight control coating on the glass substrate surface is defined, requiring the surface roughness of the metal oxide layer to be... Maintain at to Between, and the surface oxygen vacancy concentration was measured to be per square centimeter. One to Each site provides an initial electrical distribution that anchors the chemical coordination of the hybrid liquid; using the formulation described in the aforementioned specific embodiment, the hybrid coating solution is applied to the substrate surface and then subjected to a rapid heat treatment stage; in order to... To preserve the migration activity of perfluoroalkylsilanes during the instantaneous heat treatment process, the heating rate was set to... Utilizing the physical characteristic that the kinetic rate of thermally induced polycondensation of siloxane backbones is higher than that of pyrolysis of long-chain fluorosiloxanes, the backbone is cross-linked before the organic long chains undergo thermal oxidation. During this process, the shrinkage rate of the film thickness is monitored using an in-situ ellipsometry. When the shrinkage rate reaches a certain percentage of the initial liquid film thickness... At that time, the air-cooling process is activated, and the cooling rate is set to [value missing]. ; By utilizing volume shrinkage to generate interconnected free volume spaces within the siloxane network, continuous micropores are formed; by characterizing the cured top energy storage layer, the average pore size distribution is measured. to Between, the porosity is .

[0042] Regarding the self-repair evaluation index Permeability constant in Calibration was performed, and the parameter was determined based on a kinetic model of fluid flowing through a porous medium. The specific calibration steps were as follows: A standard membrane sample with a thickness of 200 nanometers was prepared and placed in a closed test fixture equipped with a precision flow meter. Next, a constant pressure difference of 0.1 MPa was applied across the membrane, dry nitrogen was introduced, and the steady-state flow rate per unit time was recorded. Finally, according to the discretized expression of Darcy's law, the measured flow rate, sample area, membrane thickness, and nitrogen viscosity were substituted into the comparison logic to calculate the permeability constant of the top layer of the energy storage layer in this embodiment as 2.45 × 10⁻¹⁸ square meters. This calibration process was performed once before the start of each production batch, serving as a fixed constant input for subsequent calculations of the self-healing evaluation index, ensuring the accuracy of self-healing performance prediction under different production environments. The permeability constant of the top layer of the energy storage layer in this embodiment was calculated by measuring the flow velocity of the hydrophobic molecular fluid through the energy storage layer under a unit pressure gradient. for By increasing the intensity of environmental radiation to By simulating extreme operating conditions, the temperature rise caused by the conversion of nanoscale near-infrared absorbing components inside the film was monitored. It is 28.5 The self-repair evaluation index at this time is determined according to the calculation formula. Improved compared to normal times; among which, It is a self-healing evaluation index used to characterize the material transport efficiency of self-cleaning membranes; Permeability constant, in units of ; The temperature rise per unit time, in units of . ; The dynamic viscosity of the hydrophobic molecular fluid at the current temperature, in units of... Experimental observations showed that the water contact angle at the damaged site recovered to [value missing]. The above times are This method, by controlling the heating rate and the shrinkage stress of the skeleton, constructs a gradient hybrid structure with transport capabilities, ensuring the performance stability of special glass doors under high irradiation environments.

[0043] Example 5: In the production process of alternating batches of acidic silica sol raw materials, the initial solid content and functional group density of the acidic silica sol vary with each batch. The reproducibility of the gradient hybrid structure is maintained through a pre-calibration process. The online monitoring unit collects the initial viscosity of the current batch of acidic silica sol. Intrinsic surface energy of sunlight-controlling glass substrate surface The controller is based on the initial viscosity. With intrinsic surface energy Calculate the amount of organosilicon-modifying monomer added. At initial viscosity for And intrinsic surface energy for At that time, the controller adjusts the stirring speed to Set the material mixing time for Dynamic viscosity of hybrid coating solution Maintain at .

[0044] Ambient humidity from Change to At that time, the method utilizes solvent partial pressure. Dynamic regulation maintains the migration rate of perfluoroalkyl silanes during curing; sensor array monitors the actual solvent partial pressure in the environment. The controller is based on the actual solvent partial pressure. voltage divider with reference The deviation between them determines the frequency adjustment increment of the exhaust system. The exhaust system adjusts the exhaust volume to adjust the local solvent partial pressure in the coating area. Maintain within the target range; at local solvent partial pressure Below, the migration flux of hydrophobic components to the air interface Maintaining a constant temperature, with a heating rate of Heat treatment, porosity of the top energy storage layer Maintain at The resulting continuous micropores improve the self-healing response stability of the membrane under different humidity conditions.

[0045] Example 6: In the adaptation scenarios of solar control glass production lines designed for different film systems, due to the types of metal oxides on the surface of the glass substrate and the intrinsic surface energy... The differences cause fluctuations in the wettability and migration driving force of the hybrid liquid, which can be addressed by measuring the intrinsic surface energy of the substrate. The obtained values ​​are then fed into the viscosity adjustment logic to determine the target dynamic viscosity. This allows the capillary osmotic pressure of the liquid film to match the interfacial diffusion rate during the coating stage, when the intrinsic surface energy of the solar control layer is detected. for to When the viscosity is within a specific range, the system calculates the target dynamic viscosity according to a preset mapping function, and adjusts the mass percentage of the monomer by adjusting the organosilicon. Furthermore, adjusting the stirring shear rate reduces the dynamic viscosity of the hybrid coating solution. Anchored at .

[0046] In the execution of instantaneous heat treatment procedures, the heating duration is determined through an online feedback mechanism based on the influence of the ambient reference temperature and the thermal inertia of the equipment. To maintain the stability of the gradient structure, this process uses an infrared monitoring unit to acquire the thermal response curve of the film surface and calculates the real-time thickness shrinkage acceleration of the siloxane skeleton based on the curve. When the thickness shrinkage acceleration The instant the value changes from positive to zero, it is determined that the skeleton network has reached the critical point of the permeation threshold. At this point, a cooling command is triggered to lock the pore structure, with a heating rate of... And the initial ambient temperature is Under these conditions, the heating duration determined by this procedure for The porosity of the constructed top-layer energy storage layer The deviation at each measurement point shall not exceed .

[0047] The embodiments of this application have been described above with reference to the accompanying drawings. Unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other. This application is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of this application without departing from the spirit of this application and the scope of protection of this invention, and all of these forms are within the protection scope of this application.

Claims

1. A method for manufacturing a hydrophobic special coated glass door with self-cleaning function, characterized in that, Includes the following steps: Step S1: Prepare a hybrid coating solution by adding perfluoroalkyl silane, nano-scale near-infrared absorbing components, and organosilicon regulating monomers with metal coordination functional groups to an acidic silica sol base. The mass percentage of organosilicon regulating monomers in the hybrid coating solution is controlled to be 2% to 5%, and the dynamic viscosity of the hybrid coating solution is adjusted to be maintained between 2.0 mPa·s and 5.0 mPa·s. Step S2, Interface Anchoring and Deposition: The hybrid coating solution is applied to the surface of a glass substrate with a sunlight control coating layer. The organosilicon is used to adjust the chemical coordination between the monomer and the metal ions on the surface of the sunlight control coating layer, forming chemical anchoring points at the interface. The surface tension gradient between the perfluoroalkylsilane and the acidic silica sol matrix is ​​used to drive the hydrophobic groups to migrate directionally to the air interface. Step S3, gradient structure construction: adjust the solvent partial pressure of the drying environment to 15 kPa to 25 kPa, induce the hybrid coating liquid to generate a component concentration gradient during the curing process, and form a bottom anchoring layer and a top energy storage layer on the surface of the glass substrate, wherein the nanoscale near-infrared absorbing components are distributed inside the bottom anchoring layer. Step S4, instantaneous heat treatment, subjecting the coated glass substrate to 250°C. Up to 300 The heat treatment lasts for 30 to 90 seconds, with a heating rate of not less than 10%. / s, to construct continuous micropores containing hydrophobic molecular fluids inside the bottom anchoring layer and the top energy storage layer, ultimately forming a self-cleaning membrane layer.

2. The method for manufacturing a hydrophobic special coated glass door with self-cleaning function according to claim 1, characterized in that, In step S1, the organosilicon regulating monomer is selected from one or more of carboxyl-containing organosilicon alkane, phosphonic acid-containing organosilicon alkane, and amino-containing silane coupling agent. The number average molecular weight of the organosilicon regulating monomer is 800 g / mol to 1200 g / mol, and it is used to form an interface transition layer with a thickness of 2 nm to 5 nm on the surface of the sunlight control coating layer in step S2.

3. The method for manufacturing a hydrophobic special coated glass door with self-cleaning function according to claim 1, characterized in that, The nanoscale near-infrared absorbing component is selected from one or more of antimony-doped tin oxide nanoparticles, cesium tungsten bronze nanoparticles, and indium tin oxide nanoparticles, and the average particle size of the nanoscale near-infrared absorbing component is 20 nm to 50 nm.

4. The method for manufacturing a hydrophobic special coated glass door with self-cleaning function according to claim 1, characterized in that, The total thickness of the self-cleaning membrane layer ranges from 100 nm to 300 nm, with the porosity of the top energy storage layer ranging from 10% to 25%. The hydrophobic molecular fluid within the top energy storage layer is at a porosity of 25%. The diffusion coefficient under the given conditions is not less than .

5. The method for manufacturing a hydrophobic special coated glass door with self-cleaning function according to claim 1, characterized in that, In step S4, the cooling rate of the instantaneous heat treatment is controlled to be 5. / s to 15 / s, to lock the chemical bonding state between the bottom anchor layer and the glass substrate.

6. The method for manufacturing a hydrophobic special coated glass door with self-cleaning function according to claim 1, characterized in that, After the self-cleaning membrane is damaged, the local heat energy generated by the nano-scale near-infrared absorbing components is used to reduce the dynamic viscosity of the hydrophobic molecular fluid. The structural shrinkage pressure of the siloxane network formed by the curing of acidic silica sol matrix under temperature rise is used to drive the hydrophobic molecular fluid to migrate along the continuous micropores to the damaged area on the surface of the self-cleaning membrane.

7. A method for manufacturing a hydrophobic special coated glass door with self-cleaning function according to claim 6, characterized in that, The pumping efficiency of hydrophobic molecular fluids is evaluated using a self-healing index. Characterization: ,in, This is a self-repair evaluation index; The permeability constant of the top energy storage layer is determined based on its porosity; This represents the temperature rise per unit time of the self-cleaning film layer under solar radiation. This represents the dynamic viscosity of the hydrophobic molecular fluid at the current temperature.

8. The method for manufacturing a hydrophobic special coated glass door with self-cleaning function according to claim 1, characterized in that, In step S1, the solid content of the acidic silica sol base material is 8% to 12%, and the surface tension of the hybrid coating solution during coating is adjusted to 22mN / m to 28mN / m.

9. A method for manufacturing a hydrophobic special coated glass door with self-cleaning function according to claim 1, characterized in that, In step S2, the coating is performed using the dip-coating method, with a coating speed of 100 mm / min to 200 mm / min, so that the final surface energy of the self-cleaning film is less than 15 mN / m.

10. A method for manufacturing a hydrophobic special coated glass door with self-cleaning function according to claim 1, characterized in that, In step S2, the relative humidity of the coating environment is 40% to 60% to coordinate with the solvent partial pressure adjustment in step S3 to regulate the volatilization gradient of the components in the hybrid coating solution.

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