Easily-deicing glass, vehicle and deicing method thereof

Abstract

The invention provides glass easy to deice, a vehicle and a deicing method of the vehicle. The easy-to-deice glass comprises an inner glass plate, a middle bonding layer and an outer glass plate, the outer glass plate is provided with a first surface and a second surface, the inner glass plate is provided with a third surface and a fourth surface, and the second surface and the third surface are bonded together through the middle bonding layer; the first surface of the outer glass plate is provided with an ice dredging coating; the ice-phobic coating comprises a first coating, and the first coating is in direct contact with the first surface of the outer glass plate; the first coating is a long alkyl chain modified polyurethane layer; and an electric heating device is arranged between the first surface of the outer glass plate and the fourth surface of the inner glass plate.

Description

Technical Field

[0001] This invention relates to an easy-to-de-ice glass, a vehicle, and a de-icing method thereof, belonging to the field of vehicle glass technology. Background Technology

[0002] In winter, after a vehicle passes through a low-temperature environment, moisture in the air condenses on the glass surface, forming a layer of ice. During snowfall, snow can also accumulate on the glass, causing a thick layer of ice to form at the base. In recent years, freezing rain has become common in some regions, covering vehicle surfaces with thick layers of ice. These issues make windshield de-icing particularly important, and it has become an essential preparation for driving.

[0003] Currently used de-icing methods often cause some damage to the glass. For example, physical de-icing methods, such as using boiling water to melt the ice quickly, can cause the glass to crack due to thermal expansion and contraction; while using a snowplow leaves scratches on the glass surface. Besides common physical de-icing methods, electric heating de-icing has also seen some development in recent years, such as using air conditioning and wire-heated de-icing. Although these methods effectively improve de-icing efficiency, they still require a long time to defrost. Furthermore, with the rise of new energy vehicles, range anxiety is a serious issue, and prolonged electric heating de-icing will further reduce the vehicle's range, exacerbating range anxiety. In addition to the energy consumption of electric heating, the heating systems of new energy vehicles are equipped with a low voltage of 13.5V, further reducing de-icing efficiency. De-icing the windshield can take nearly an hour, reducing the practicality of the electric heating system.

[0004] To address the aforementioned problems, there is a need to develop a method that consumes little or no energy and achieves passive de-icing by reducing the adhesion between ice and glass, or by using minimal external force. For example, applying an anti-icing coating to the surface of a vehicle's windshield can effectively reduce the adhesion between ice and glass, achieving passive de-icing. This technology is commonly used in aircraft de-icing and cable de-icing; however, such coatings are opaque and cannot be directly applied to automotive glass surfaces. Furthermore, national standards impose strict requirements on the transparency of automotive windshields, requiring a light transmittance of ≥70%.

[0005] Therefore, a method for rapid de-icing of windshields is provided to save energy, shorten de-icing time, reduce potential damage to the glass, and thus improve travel safety and convenience. Summary of the Invention

[0006] To address the aforementioned technical problems, the present invention aims to provide a glass that is easy to de-ice, which can achieve rapid de-icing through a combination of heating and an anti-icing coating.

[0007] To achieve the above objectives, in a first aspect, the present invention provides an easy-to-de-ice glass, wherein the easy-to-de-ice glass includes an inner glass plate, an intermediate adhesive layer, and an outer glass plate;

[0008] The outer glass plate has a first surface and a second surface, the inner glass plate has a third surface and a fourth surface, and the intermediate adhesive layer bonds the second surface and the third surface together.

[0009] The first surface of the outer glass panel is provided with an ice-repellent coating; the ice-repellent coating includes a first coating layer, which is in direct contact with the first surface of the outer glass panel.

[0010] The first coating is a long alkyl chain modified polyurethane layer;

[0011] An electric heating device is provided between the first surface of the outer glass plate and the fourth surface of the inner glass plate.

[0012] In the above-mentioned easy-to-de-ice glass, preferably, the ice-repellent coating further includes a second coating, which is disposed on the side of the first coating away from the outer glass plate, that is, the second coating is located on the outermost surface of the easy-to-de-ice glass;

[0013] The second coating is a nano-silica layer. More preferably, this silica coating is formed by spraying nano-silica onto the surface of the long alkyl chain modified polyurethane layer during the preparation process, while the long alkyl chain modified polyurethane layer is not completely dry, so that the silica is partially embedded in the long alkyl chain modified polyurethane layer.

[0014] In this application, a spraying process can be used to apply the anti-icing coating. The process includes: glass pretreatment (polishing, cleaning) → filtered compressed air drying → coating spraying → high-temperature curing and / or ultraviolet curing. When the anti-icing coating comprises two layers, the second layer is applied after the first layer is completed. For the specific spraying method, existing spraying processes can be referenced.

[0015] In this application, specifically, the glass pretreatment can be carried out by polishing with polishing powder (e.g., cerium oxide) mixed with water using a polishing machine. The mass ratio of polishing powder such as cerium oxide to water can be controlled to be 2-5%, and the water contact angle of the glass after polishing should be <5°.

[0016] In the above-mentioned easy-to-de-ice glass, preferably, the overall light transmittance of the de-icing coating is 70%-95%.

[0017] In the above-mentioned easy-to-de-ice glass, preferably, the thickness of the de-icing coating is 3μm-10μm.

[0018] In the aforementioned easily de-icing glass, preferably, the surface water contact angle of the de-icing coating is 95°-140°. When the de-icing coating only has a long alkyl chain modified polyurethane layer and no nano silica coating, if the surface water contact angle of the de-icing coating is lower than 95°, its de-icing ability will be insufficient. When the de-icing coating includes both a long alkyl chain modified polyurethane layer and a silica coating, if the surface water contact angle of the de-icing coating is higher than 140°, the optical properties of the coating, such as light transmittance, will decrease. Moreover, it is difficult to achieve both optical and mechanical properties when the surface water contact angle of the de-icing coating reaches above 140°.

[0019] In the above-mentioned easily de-icing glass, preferably, the surface pencil hardness of the de-icing coating is 4H-6H.

[0020] In the above-mentioned easy-to-de-ice glass, preferably, the de-icing coating is a smooth and transparent coating.

[0021] In the aforementioned easily de-icing glass, preferably, the thickness of the de-icing coating satisfies: d MAX -d MIN ≤0.5μm, where d MAX This refers to the maximum thickness of the ice-repellent coating, d MIN This refers to the minimum thickness of the icing-repellent coating. By controlling the thickness variation of the icing-repellent coating within the above range, a high degree of uniformity can be achieved, thereby meeting the optical distortion requirements of automotive windshields during use, ensuring that its refractive power MAX ≤ 75 mdpt and its refractive power fluctuation ROC ≤ 100 mdpt.

[0022] In the aforementioned easily de-icing glass, preferably, the long-alkyl chain modified polyurethane includes one or a combination of two or more of hexadecane-modified polyurethane, octadecane-modified polyurethane, octadecylamine-modified polyurethane, and polydimethylsiloxane-modified polyurethane. Compared with ordinary polyurethane, using long-alkyl chain modified polyurethane as the base layer of the de-icing coating allows the de-icing coating to retain its de-icing properties even after the nanoparticles on the coating surface are detached by wipers and dust. Although the performance is somewhat reduced, it does not completely fail, thereby increasing the service life of the de-icing coating. The long-alkyl chain modified polyurethane modification method of the present invention can refer to the method of modifying polyurethane with compounds containing long alkyl chains.

[0023] In the aforementioned easily de-icing glass, preferably, the nano-silica is obtained by grafting and modifying nano-silica with vinyltriethoxysilane (VTEO). The mass ratio of vinyltriethoxysilane to nano-silica is 0.8-1.5:1, i.e., mVTEO:mSiO2 = x, x = 0.8-1.5. This grafting and modification process can be carried out by dispersing VTEO and nano-silica in an appropriate amount of ethanol at a suitable temperature and then using ultrasound. Because nano-silica has active hydroxyl groups on its surface and a very high specific surface area, it is prone to agglomeration. This application preferably uses VTEO to react with the active hydroxyl groups on the surface of nano-silica to reduce its surface energy, thereby improving its dispersibility and reducing the final particle size of silica in the coating, thus improving the optical performance of the coating. While modifying the surface of nano-silica, VTEO also ensures that the silica is bound within its cross-linked spatial network after the coating cures, increasing its overall strength. Furthermore, VTEO can react with polyurethane, which has many active hydroxyl and amino functional groups. Under heating, the vinyl double bonds of VTEO open and combine with it to form new chemical bonds. This invention enhances the bonding force between the nano-silica top layer, the long alkyl chain modified polyurethane bottom layer, and the glass substrate by forming a double cross-linked network between A-PU and VTEO. This improves the mechanical properties and service life of the de-icing coating, making the de-icing glass provided by this invention suitable for use in high-wear environments. At the same time, the improved optical performance also enables it to meet automotive-grade optical performance requirements.

[0024] Furthermore, this application can improve the optical properties of the coating, such as light transmittance, by controlling the concentration and particle size of nano-silica and by increasing the dispersion performance of nano-silica through VETO.

[0025] In the above-mentioned easy-to-de-ice glass, preferably, the particle size of the nano-silica is 15nm-60nm.

[0026] In the aforementioned easily de-icing glass, preferably, the raw materials for the long-alkyl chain modified polyurethane layer include a long-alkyl chain compound and a silane coupling agent, and the molar ratio of the long-alkyl chain compound to the silane coupling agent is between 2 and 3; the long-alkyl chain compound includes one or more combinations of hexadecane, octadecane, octadecylamine, and polydimethylsiloxane. Thus, the long-alkyl chain compound in this application gives the first coating hydrophobic properties, and the silane coupling agent can promote the adhesion between the first coating and the outer glass plate and / or the second coating. More preferably, in this application, the silane coupling agent is one or more combinations of aminosilane coupling agents KH-550, KBM-603, and A-1130.

[0027] In the aforementioned easily de-icing glass, preferably, the raw material for the long alkyl chain modified polyurethane layer further includes a solvent, wherein the solvent includes one or more combinations of ethyl acetate, butyl acetate, amyl acetate, toluene, and methyl benzoate. Thus, this application can control the viscosity and flowability of the coating used to form the long alkyl chain modified polyurethane layer, making it adaptable to different coating processes such as spraying, scraping, and rolling.

[0028] In the aforementioned easily de-icing glass, preferably, the electric heating device includes a transparent conductive layer with a sheet resistance of 0.5Ω-2Ω. In this application, the transparent conductive layer is a silver-based coating with a total thickness of 100nm-300nm. This silver-based coating refers to a transparent conductive film based on silver, which can be a single-layer film or a multi-layer film. More preferably, the transparent conductive layer is a triple-silver coating or a quadruple-silver coating.

[0029] In the aforementioned easily de-icing glass, preferably, the transparent conductive layer is disposed on the second surface of the outer glass plate and / or the third surface of the inner glass plate. More preferably, this application forms the transparent conductive layer on the third surface of the inner glass plate by means of magnetron sputtering or the like. The specific process can refer to existing coating processes, such as: cutting, breaking, and grinding flat glass → magnetron sputtering silver-based coating (such as triple silver coating) → high-temperature pressing of glass → high-temperature and high-pressure lamination in an autoclave.

[0030] In the aforementioned easy-to-de-ice glass, preferably, the heating voltage of the transparent conductive layer is 13.5V, and the heating power is 400W-450W.

[0031] In the above-mentioned easy-to-de-ice glass, preferably, the intermediate adhesive layer is polyvinyl butyral (PVB).

[0032] In the aforementioned easily de-icing glass, preferably, the electric heating device includes a heating wire; the diameter of the heating wire is 0.018mm-0.2mm, and the resistivity is 0.5Ω / m-270Ω / m. The heating wire is a tungsten wire or enameled wire. More preferably, the heating wire is a tungsten wire, the diameter of which is 0.02mm-0.2mm, and the resistivity is 30Ω / m-200Ω / m.

[0033] In the aforementioned easy-to-de-ice glass, preferably, the heating wires are generally wavy and are vertically arranged between the second surface of the outer glass plate and the intermediate adhesive layer, with a spacing of 2mm-5mm between the heating wires.

[0034] In the aforementioned easily de-icing glass, preferably, the heating wire is disposed between the intermediate adhesive layer and the second surface of the outer glass plate. Specifically, this application adds the heating wire onto the intermediate adhesive layer, which can be done by referring to the existing manufacturing process of heated glass, for example: cutting, breaking, and grinding flat glass → high-temperature pressing of glass → laying of intermediate adhesive layer and heating wire → high-temperature and high-pressure lamination in an autoclave.

[0035] The present invention also provides a vehicle including a window glass and a windshield wiper, the window glass including the aforementioned de-icing glass, and the windshield wiper extending from a first surface of the outer glass panel.

[0036] The present invention also provides a de-icing method for the aforementioned vehicle, the de-icing method comprising: energizing an electric heating device in the easily de-icing glass, and / or de-icing by means of external force, i.e., achieving the de-icing operation by means of a combination of energizing and / or external force.

[0037] In the above-mentioned method for de-icing vehicle glass, preferably, the external force is achieved by a windshield wiper, the compressive stress of the windshield wiper on the easily de-iced glass is 10N / cm-15N / cm, and the movement speed of the windshield wiper is 15 times / min-20 times / min.

[0038] In the above-mentioned de-icing method for vehicle glass, preferably, the external force can be achieved by a vibrator, and the vibration frequency of the vibrator is 100Hz-40000Hz.

[0039] The de-icing method provided by this invention can be achieved through the combined action of an anti-icing coating, electrically heated glass, and windshield wipers. The anti-icing coating reduces the adhesion between ice and glass, while electrically heating the glass and applying external force to the ice layer using the windshield wipers quickly removes the ice. In practical use, a "de-icing mode" can be added to the vehicle's windshield wipers. When the user selects this mode, the de-icing function can be activated for de-icing.

[0040] According to a specific embodiment of the present invention, when the de-icing glass is installed on a vehicle, the first surface of the outer glass panel of the de-icing glass faces outward and the second surface faces inward, the third surface of the inner glass panel faces outward and the fourth surface faces inward, and the de-icing coating is located on the outermost surface of the de-icing glass.

[0041] The de-icing glass provided by this invention is equipped with an electric heating device and an ice-repellent coating, which can quickly de-ice the glass with the assistance of external force (such as windshield wipers) when it encounters ice. Attached Figure Description

[0042] Figure 1 These are the results of the de-icing experiment in Example 1;

[0043] Figure 2 This is the result of the de-icing experiment in Example 2;

[0044] Figure 3 These are the results of the de-icing experiment in Example 3;

[0045] Figure 4 These are the results of the de-icing experiment in Example 4;

[0046] Figure 5 This is the result of the de-icing experiment in Example 5;

[0047] Figure 6 These are the results of the de-icing experiment in Example 6;

[0048] Figure 7 The results are from the de-icing experiment in Comparative Example 1;

[0049] Figure 8 The results are from the de-icing experiment in Comparative Example 2;

[0050] Figure 9 This is a diagram illustrating the testing mechanism of the adhesion test;

[0051] Figure 10 This is a diagram of the testing equipment for the adhesion test;

[0052] Figure 11 and Figure 12 This is a typical structural diagram of the de-icing glass provided by the present invention. Detailed Implementation

[0053] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0054] I. Specific construction process:

[0055] 1) Glass pretreatment: Polishing is carried out using a polishing machine with a mixture of cerium oxide polishing powder and water. The mass ratio of cerium oxide to water is 2%-5%, and the water contact angle after polishing is <5°.

[0056] 2) Use filtered compressed air to dry the glass;

[0057] 3) First coating: Spraying is carried out using a spray gun with a height of 15cm. Spraying parameters: flow rate of 160ml / min, spray width of 16cm, atomizing air pressure of 0.3MPa, moving speed of 600mm / s, and spacing between each spray layer of 8cm.

[0058] 4) Second coating spraying: Spraying is carried out using a spray gun with a height of 35cm. Spraying parameters: flow rate of 100ml / min, spray width of 30cm, atomizing air pressure of 0.15MPa, moving speed of 500mm / s, and spray spacing of 10cm between each spray. The second coating is sprayed while the first coating is not completely dry. With the help of a low-pressure spray gun and the above-mentioned spraying height, nano-silica can be evenly sprayed onto the surface of the first coating.

[0059] 5) High-temperature curing and UV curing:

[0060] Among them, the experiment of single-layer anti-icing coating: spraying was carried out in the same way as the first coating; after the single-layer anti-icing coating was sprayed, the next curing process was carried out directly.

[0061] Experiment on double-layer ice-repellent coating: After applying the first coating as described above, apply the second coating as described above, and then proceed to the curing process;

[0062] Single-layer or double-layer anti-icing coatings are cured by high temperature and ultraviolet light (the raw materials of the first and second coatings include photoinitiators): first, irradiate with an infrared lamp (4×1kw) for 15 minutes, and then cure with an ultraviolet lamp (4×16kw, 30% opening) for 5 minutes.

[0063] The typical structures of the de-icing glass provided by this invention are as follows: Figure 11 and Figure 12 As shown, where:

[0064] Figure 11 The typical structure of the de-icing glass shown includes a second de-icing coating 1, a first de-icing coating 2, an outer glass plate 3, an electric heating device 4 (tungsten wire), an intermediate adhesive layer 5, and an inner glass plate 7.

[0065] Figure 12 The typical structure of the de-icing glass shown includes a second de-icing coating 1, a first de-icing coating 2, an outer glass plate 3, an intermediate adhesive layer 5, an electric heating device 6 (triple silver coating), and an inner glass plate 7.

[0066] II. De-icing Experiment:

[0067] The test was conducted in accordance with the national standard "GB 11555-2009 Performance and Test Methods for Automotive Windshield Defrosting and Defogging Systems", and specifically included the following steps:

[0068] (1) Spray an ice-repellent coating onto the experimental windshield to make a windshield with an ice-repellent coating;

[0069] (2) The windshield is equipped with tungsten wire or enameled wire or transparent conductive layer (silver-based coating) for electric heating. It is connected to a regulated DC power supply with the corresponding voltage (13.5V / 36V) and the voltage across the glass is calibrated using a multimeter.

[0070] (3) The car was placed in a low-temperature test chamber for pre-cooling at -18℃ and kept at a constant temperature for 12-24 hours.

[0071] (4) After sufficient pre-cooling time, open the experimental chamber and evenly spray 500g (0.044g / cm³) of the solution. 2 Apply water to the surface of the windshield, then close the test chamber and continue to maintain the low temperature for 30-40 minutes;

[0072] (5) Set up a camera and heat the tungsten wire, enameled wire, or transparent conductive layer (silver-based coating) by electricity. After the initial heating for 2 minutes, start the wipers at the 3rd minute (121st second) and then wipe the wipers once per minute thereafter.

[0073] (6) When the de-icing area is ≥80% (A / B area is completely de-iced or defrosted by more than 80%), the de-icing process is considered complete. The heating system is then turned off and the temperature of the test chamber is restored to 20℃.

[0074] Example 1

[0075] This embodiment provides an easy-to-de-ice glass, which is the windshield of a car. The easy-to-de-ice glass includes an inner glass panel, an intermediate adhesive layer, and an outer glass panel.

[0076] The outer glass plate has a first surface and a second surface, the inner glass plate has a third surface and a fourth surface, and the intermediate adhesive layer bonds the second surface and the third surface together.

[0077] The first surface of the outer glass plate is provided with an ice-repellent coating; the ice-repellent coating is a single-layer ice-repellent coating, specifically a layer of octadecylamine-modified polyurethane (A-PU, the same in the following examples and comparative examples) with a thickness of 3.8 μm. The preparation process of A-PU and the coating used to prepare the ice-repellent coating is as follows;

[0078] 1) Hydroxyl-terminated polybutadiene (HTPB) and isophorone diisocyanate (IPDI) were added to a three-necked flask equipped with a mechanical stirrer, a condenser, and a nitrogen inlet at a molar ratio of 1:2. Then, 0.1% of the total mass of dibutyltin dilaurate (DBTDL) catalyst was added. Nitrogen gas was introduced and the reaction was carried out at 45°C for 3 hours to prepare the isocyanate-terminated polyurethane prepolymer (HTPB-IPDI).

[0079] 2) Heat to 75℃, add octadecylamine and KH-550 to HTPB-IPDI in a molar ratio of NCO:NH3 = 1:1, and continue the reaction for 3.5h to synthesize A-PU, where NCO represents HTPB-IPDI, NH3 represents octadecylamine and KH550, and the molar ratio of octadecylamine to KH-550 is 7:3;

[0080] 3) Disperse A-PU and photoinitiator 1173 in a methyl benzoate solution at a mass ratio of 99:1 to obtain a mixed solution with a concentration of 20wt% for A-PU and photoinitiator 1173. Additives BYK111 and BYK3550 are added to the mixed solution, with each additive accounting for 1% of the total mass of the mixed solution. The mixture is ultrasonically dispersed for 10 minutes to obtain a uniform coating.

[0081] The third surface of the inner glass plate is provided with a transparent conductive layer, specifically a three-silver coating with a thickness of 200nm, a sheet resistance of 1.85Ω, and a heating power of 411.2W.

[0082] The contact angle, adhesion, and light transmittance of the icing-repellent coating are shown in Table 1.

[0083] In this embodiment, an A-PU coating is sprayed onto the windshield, and the de-icing test process specifically includes:

[0084] Begin the de-icing process by spraying water onto the glass surface to freeze, and pre-cool for 40 minutes.

[0085] The glass with the silver-based coating is powered on with a voltage of 13.5V. After power is applied, the wipers are activated at 121 seconds and wipe back and forth once. Then, the wipers are activated again every 60 seconds to wipe back and forth once.

[0086] De-icing is complete when ≥80% of the AB zone is cleared. (Specific details are as follows...) Figure 1 As shown.

[0087] according to Figure 1 It can be seen that:

[0088] After heating the triple silver coating for 7 minutes, the ice layer began to melt;

[0089] When heated for 20 minutes, the ice layer that has begun to melt is detached from the overall ice layer by the combined action of the wipers and the A-PU coating and is more easily carried away by the wipers. However, a lot of ice layer is still attached to the glass.

[0090] After heating for 30 minutes, although there is still floating ice on the glass, increasing the number of wipers can remove the floating ice, and the de-icing area is ≥80%. The floating ice present at this time can be considered as de-icing and is not counted in the un-de-iced area. This means that the de-icing is completed, indicating that the coating with A-PU can quickly and efficiently complete the de-icing under the combined action of the wipers and the heating of the silver-based coating.

[0091] Example 2

[0092] This embodiment provides an easy-to-de-ice glass for automobile windshields. The difference between this easy-to-de-ice glass and Embodiment 1 is that: no transparent conductive layer is provided; a tungsten wire is provided in the intermediate adhesive layer; the diameter of the tungsten wire is 0.05 mm; the resistivity is 33 Ω / m; the tungsten wire is wavy and vertically arranged between the second surface of the outer glass plate and the intermediate adhesive layer; the spacing between the heating wires is 2.5 mm; and the heating power of the tungsten wire is 405.8 W. Other aspects are the same as in Embodiment 1.

[0093] The contact angle, adhesion, and light transmittance of the icing-repellent coating are shown in Table 1.

[0094] In this embodiment, an A-PU coating is sprayed onto the windshield, and the de-icing test process specifically includes:

[0095] Begin the de-icing process by spraying water onto the glass surface to freeze, and pre-cool for 30 minutes.

[0096] The windshield wipers are heated using a tungsten filament and then activated at 121 seconds to complete one round trip. This process is repeated every 60 seconds.

[0097] De-icing is complete when ≥80% of the AB zone is cleared. (Specific details are as follows...) Figure 2 As shown.

[0098] according to Figure 2 It can be seen that:

[0099] After heating with a tungsten wire for 8 minutes, the ice began to melt.

[0100] When heated for 20 minutes, the ice layer that has begun to melt is detached from the overall ice layer by the combined action of the wipers and the A-PU coating and is more easily carried away by the wipers. However, a lot of ice layer is still attached to the glass.

[0101] When the de-icing area is ≥80% after heating for 27 minutes, it means that de-icing is complete, indicating that the coating with A-PU can quickly and efficiently complete de-icing under the combined action of the wiper and tungsten wire heating.

[0102] Example 3

[0103] This embodiment provides an easy-to-de-ice glass for automotive windshields. The difference between this easy-to-de-ice glass and that of Embodiment 1 is that the de-icing coating is a double-layer de-icing coating. The first coating consists of long-alkyl chain modified polyurethane (A-PU), and the second coating consists of hydrophobic nano-silica (SiO2). The nano-silica has a particle size of 60 nm and is dispersed and modified using vinyltriethoxysilane (VTEO) in the following manner:

[0104] SiO2, photoinitiator 1173, and VTEO in a mass ratio of 50:1:49 were dispersed in anhydrous ethanol solution and sonicated for 10 min to obtain a homogeneous mixture, which allowed VTEO to be attached to SiO2 for modification; wherein the sum of the masses of SiO2, photoinitiator 1173, and VTEO accounted for 3% of the total mass of the mixture.

[0105] The thickness of the first coating is 4.3 μm, and the thickness of the second coating is 0.5 μm; otherwise, it is the same as in Example 1.

[0106] The contact angle, adhesion, and light transmittance of the icing-repellent coating are shown in Table 1.

[0107] In this embodiment, a double-layer coating of A-PU and 60nm SiO2 is sprayed onto the windshield. The de-icing experiment process specifically includes:

[0108] Begin the de-icing process by spraying water onto the glass surface to freeze, and pre-cool for 30 minutes.

[0109] The glass with the triple silver coating was powered on at 13.5V. After powering on, the wipers were activated at 121 seconds and wiped back and forth once. Then, the wipers were activated again every 60 seconds to wipe back and forth once.

[0110] De-icing is complete when ≥80% of the AB zone is cleared. (Specific details are as follows...) Figure 3 As shown.

[0111] according to Figure 3 It can be seen that:

[0112] After heating the silver-based coating for 7 minutes, the ice layer began to melt.

[0113] When heated for 20 minutes, the ice layer that has begun to melt is detached from the overall ice layer by the combined action of the wipers and the double-layer coating and is more easily carried away by the wipers. However, a lot of ice layer is still attached to the glass.

[0114] After heating for 26 minutes, although there is still some floating ice attached to the glass, increasing the number of wipers can remove the floating ice, and the de-icing area is ≥80%, which means that de-icing is completed. This indicates that the de-icing coating with a double-layer structure can quickly and efficiently complete de-icing under the combined action of the wipers and the heating of the silver-based coating.

[0115] Example 4

[0116] This embodiment provides an easy-to-de-ice glass for automobile windshields. The difference between this easy-to-de-ice glass and Embodiment 3 is that the particle size of the nano-silica is 35nm; otherwise, it is the same as Embodiment 3.

[0117] The contact angle, adhesion, and light transmittance of the icing-repellent coating are shown in Table 1.

[0118] In this embodiment, a double-layer coating of A-PU and 35nm SiO2 is sprayed onto the windshield. The de-icing experiment specifically includes:

[0119] Begin the de-icing process by spraying water onto the glass surface to freeze, and pre-cool for 30 minutes.

[0120] The glass with the triple silver coating was powered on at 13.5V. After powering on, the wipers were activated at 121 seconds and wiped back and forth once. Then, the wipers were activated again every 60 seconds to wipe back and forth once.

[0121] De-icing is complete when ≥80% of the AB zone is cleared. (Specific details are as follows...) Figure 4 As shown.

[0122] according to Figure 4 It can be seen that:

[0123] After heating the silver-based coating for 7 minutes, the ice layer began to melt.

[0124] When heated for 20 minutes, the ice layer that has begun to melt is detached from the overall ice layer by the combined action of the wipers and the double-layer coating and is more easily carried away by the wipers. However, a lot of ice layer is still attached to the glass.

[0125] When the de-icing area is ≥80% after heating for 25 minutes, it means that de-icing is complete, indicating that the de-icing coating with a double-layer structure can quickly and efficiently complete de-icing under the combined action of the wiper and the heating of the silver-based coating.

[0126] Example 5

[0127] This embodiment provides an easy-to-de-ice glass, which is the windshield of a car. The difference between this easy-to-de-ice glass and that of Embodiment 3 is that the particle size of the nano-silica is 15nm; otherwise, it is the same as that of Embodiment 3.

[0128] The contact angle, adhesion, and light transmittance of the icing-repellent coating are shown in Table 1.

[0129] In this embodiment, a double-layer coating of A-PU and 35nm SiO2 is sprayed onto the windshield. The de-icing experiment specifically includes:

[0130] Begin the de-icing process by spraying water onto the glass surface to freeze, and pre-cool for 30 minutes.

[0131] The glass with the triple silver coating was powered on at 13.5V. After powering on, the wipers were activated at 121 seconds and wiped back and forth once. Then, the wipers were activated again every 60 seconds to wipe back and forth once.

[0132] De-icing is complete when ≥80% of the AB zone is cleared. (Specific details are as follows...) Figure 5 As shown.

[0133] according to Figure 5 It can be seen that:

[0134] After heating the silver-based coating for 7 minutes, the ice layer began to melt.

[0135] When heated for 20 minutes, the ice layer that has begun to melt is detached from the overall ice layer by the combined action of the wipers and the double-layer coating and is more easily carried away by the wipers. However, a lot of ice layer is still attached to the glass.

[0136] When the de-icing area is ≥80% after heating for 25 minutes, it means that de-icing is complete, indicating that the de-icing coating with a double-layer structure can quickly and efficiently complete de-icing under the combined action of the wiper and the heating of the silver-based coating.

[0137] Example 6

[0138] This embodiment provides a glass, which is a windshield of an automobile. The difference between this glass and that of Example 3 is that vinyltriethoxysilane (VTEO) was not used for dispersion modification; otherwise, it is the same as that of Example 3.

[0139] The contact angle, adhesion, and light transmittance of the ice-repellent layer are shown in Table 1.

[0140] This embodiment uses a two-layer coating of A-PU and 15nm undispersed modified SiO2 sprayed onto the windshield. The de-icing experiment specifically includes:

[0141] Begin the de-icing process by spraying water onto the glass surface to freeze, and pre-cool for 30 minutes.

[0142] The windshield wipers are heated using a tungsten filament and then activated at 121 seconds to complete one round trip. This process is repeated every 60 seconds.

[0143] De-icing is complete when ≥80% of the AB zone is cleared. (Specific details are as follows...) Figure 6 As shown.

[0144] according to Figure 6 It can be seen that:

[0145] After heating the silver-based coating for 7 minutes, the ice layer began to melt;

[0146] When heated for 20 minutes, the ice that has begun to melt is detached from the main ice layer by the windshield wipers and is more easily carried away by the wipers, but there is still a lot of ice attached to the glass.

[0147] If the de-icing area is ≥80% after heating for 26 minutes, the de-icing is complete.

[0148] Comparative Example 1

[0149] This comparative example provides a glass for a car windshield, which differs from Example 1 in that it does not have an anti-icing coating; otherwise, it is the same as Example 1.

[0150] The contact angle, adhesion, and light transmittance of the icing-repellent coating are shown in Table 1.

[0151] This comparative example uses ordinary windshields without anti-icing coatings, and its de-icing experiment process specifically includes:

[0152] Begin the de-icing process by spraying water onto the glass surface to freeze, and pre-cool for 30 minutes.

[0153] The glass with the triple silver coating was powered on at 13.5V. After powering on, the wipers were activated at 121 seconds and wiped back and forth once. Then, the wipers were activated again every 60 seconds to wipe back and forth once.

[0154] De-icing is complete when ≥80% of the AB zone is cleared. (Specific details are as follows...) Figure 7 As shown.

[0155] according to Figure 7 It can be seen that:

[0156] After heating the triple silver coating for 7 minutes, the ice layer began to melt;

[0157] When heated for 20 minutes, the ice that has begun to melt is detached from the main ice layer by the windshield wipers and is more easily carried away by the wipers, but there is still a lot of ice attached to the glass.

[0158] If the de-icing area is ≥80% after heating for 42 minutes, the de-icing is complete.

[0159] Comparative Example 2

[0160] This comparative example provides a glass for a car windshield, which differs from Example 2 in that it does not have an anti-icing coating; otherwise, it is the same as Example 2.

[0161] The contact angle, adhesion, and light transmittance of the icing-repellent coating are shown in Table 1.

[0162] This comparative example uses ordinary windshields without anti-icing coatings, and its de-icing experiment process specifically includes:

[0163] Begin the de-icing process by spraying water onto the glass surface to freeze, and pre-cool for 30 minutes.

[0164] The windshield wipers are heated using a tungsten filament and then activated at 121 seconds to complete one round trip. This process is repeated every 60 seconds.

[0165] De-icing is complete when ≥80% of the AB zone is cleared. (Specific details are as follows...) Figure 8 As shown.

[0166] according to Figure 8 It can be seen that:

[0167] After heating with a tungsten filament for 8 minutes, the ice began to melt;

[0168] When heated for 20 minutes, the ice that has begun to melt is detached from the main ice layer by the windshield wipers and is more easily carried away by the wipers, but there is still a lot of ice attached to the glass.

[0169] If the defrosting area is ≥80% after heating for 38 minutes, it means that the defrosting is complete.

[0170] The above embodiments and comparative examples were tested, and the test results are shown in Table 1:

[0171] Table 1

[0172]

[0173] In Table 1, the adhesion force refers to the force required to pull ice off the glass surface when it adheres to it.

[0174] Figure 9 and Figure 10 This describes the testing mechanism and equipment for adhesion testing. The testing equipment includes a bottom glass plate 3 and a hollow cubic mold 1, such as... Figure 10 As shown, the glass plate 3 has a length of 100mm, a width of 24mm, and a thickness of 5mm, and the internal side length of the hollow cube mold 1 is 24mm × 24mm.

[0175] The test was conducted in the following manner:

[0176] 1. Place the hollow cube mold 1 on one end of the glass plate 3 with the ice-repellent coating, inject water into the cavity 2 of the mold, and freeze it at -18℃ for 24 hours to obtain the sample to be tested.

[0177] 2. In an environment of -18℃, fix the glass plate 3, connect the tensile tester to the hollow cube mold 1, pull the tensile tester at a constant speed, record the value of the tensile force during the pulling process, and take the peak value of the tensile force as the adhesion test value.

[0178] The transmittance was tested by using a spectrophotometer to measure the transmittance spectrum in the wavelength range of 250nm-2500nm; the transmittance of visible light in the range of 380nm-780nm was calculated according to the ISO9050 standard. The transmittance measured in this experiment is the average value obtained by measuring three different points of the same icing coating.

[0179] Hardness was tested on glass with an ice-repellent coating using a pencil hardness tester.

[0180] According to the analysis in Table 1:

[0181] Example 1 is a windshield with an ice-repellent coating, while Comparative Example 1 is a regular windshield. By using the A-PU ice-repellent coating, the ice adhesion increased from 31.60 N / cm. 2 Reduced to 6.02 N / cm 2 The de-icing time was reduced from 42 minutes to 30 minutes, which shows that using an A-PU de-icing coating on the windshield can reduce the adhesion between ice and glass, thereby improving de-icing efficiency.

[0182] The de-icing method in Example 1 was to use an electric heating method with a silver-based coating to uniformly heat the entire glass surface. The de-icing method in Example 2 was to use a tungsten wire for heating. Since the tungsten wire heating is a single-line heating method, vertically arranged on the glass, it can break the ice layer on the glass into small pieces during the heating process, which is beneficial for the wipers to remove it from the surface. Therefore, by comparison, it can be seen that under the same heating power, the de-icing time of Example 2 (27 minutes) is shorter than that of Example 1 (30 minutes). In addition, Comparative Example 2, which only uses tungsten wire heating, has a shorter de-icing time (38 minutes) compared to Comparative Example 1, which only uses an electric heating method with a silver-based coating. This shows that the de-icing efficiency of using tungsten wire heating in combination with a wiper is higher than that of using a silver-based coating in combination with a wiper.

[0183] In the ice-repellent coating of the present invention, by using nano-silica as the second coating (i.e., the surface layer), microstructures can be constructed on the surface of the ice-repellent coating, specifically the microstructures shown in the Cassie model.

[0184] The Wenzel and Cassie models are general models for describing the state of liquids on microstructured surfaces.

[0185] In the Wenzel model, when ice forms in a wet state, the strong mechanical interlocking between the surface texture and the accumulated ice creates an anchoring effect, significantly enhancing ice adhesion and increasing the difficulty of de-icing. In contrast, the Cassie model, in a wet state, utilizes microstructures to prevent the substrate surface from becoming wet. When water condenses into ice on its surface, the contact state between the ice and the coating surface remains that of a liquid. This reduces the contact area between the ice layer and the solid surface, thus decreasing the adhesion between the ice and the coating surface. Simultaneously, the solid surface can trap a large amount of air, creating an "air cushion" between the ice and the substrate, further reducing adhesion.

[0186] The de-icing coating in Example 1 did not contain nano-silica, and the de-icing time was 30 min. However, in Examples 3-5, 60 nm, 35 nm, and 15 nm nano-silica were added respectively, and the de-icing times were 26 min, 25 min, and 25 min respectively. This shows that using nano-silica as the surface layer of the de-icing coating can improve the de-icing efficiency and further reduce the adhesion between ice and the glass surface.

[0187] The nano-silica in the double-layer ice-repellent coating of Example 5 was dispersed and modified using VTEO, while the nano-silica in the double-layer ice-repellent coating of Example 6 was not dispersed and modified using VTEO. According to the data in Table 9, the ice adhesion of both is roughly the same, but their optical performance differs significantly. The transmittance of Example 5 is 80.8%, while that of Example 6 is 72.9%. This is because nano-silica is prone to agglomeration during use, resulting in nano- to micro-sized particles on the coating surface. The microstructure affects transmittance mainly due to light scattering caused by structural roughness in the visible light region, thus reducing the transmittance of the glass surface (excluding scattered light). This invention, by controlling the microstructure size to below 100 nm (approximately less than one-quarter of the visible light wavelength (320-780 nm), avoids visible light scattering and ensures that the ice-repellent coating has high light transmittance. Furthermore, using VTEO-modified nano-silica can reduce the surface energy of nano-silica, thereby reducing the agglomeration of nano-silica and decreasing the actual particle size of silica on the coating surface, thus reducing light scattering.

[0188] Examples 3-5 involved the addition of silica particles with diameters of 60 nm, 35 nm, and 15 nm, respectively. While the de-icing efficiency was roughly the same for silica particles of different sizes, their optical performance varied significantly. Example 3 used silica particles with a diameter of 60 nm but a transmittance of 70.6%; Example 4 used silica particles with a diameter of 30 nm and a transmittance of 77.8%; and Example 5 used silica particles with a diameter of 15 nm and a transmittance of 80.8%. This indicates that, in addition to adding VTEO for effective dispersion, reducing the particle size of silica on the glass surface can also effectively reduce the actual particle size of silica on the glass surface, thereby improving optical performance.

Claims

1. An easy-to-de-ice glass, wherein, The easy-to-de-ice glass includes an inner glass panel, an intermediate adhesive layer, and an outer glass panel; The outer glass plate has a first surface and a second surface, the inner glass plate has a third surface and a fourth surface, and the intermediate adhesive layer bonds the second surface and the third surface together. The first surface of the outer glass panel is provided with an ice-repellent coating; The ice-repellent coating includes a first coating that is in direct contact with the first surface of the outer glass plate. The first coating is a long alkyl chain modified polyurethane layer; An electric heating device is provided between the first surface of the outer glass plate and the fourth surface of the inner glass plate.

2. The de-icing glass according to claim 1, wherein, The de-icing coating further includes a second coating, which is disposed on the side of the first coating away from the outer glass plate; The second coating is a nano-silica layer.

3. The de-icing glass according to claim 1 or 2, wherein, The overall light transmittance of the ice-repellent coating is 70%-95%.

4. The de-icing glass according to claim 1 or 2, wherein, The thickness of the ice-repellent coating is 3μm-10μm.

5. The de-icing glass according to claim 1, 2, or 4, wherein, The thickness of the ice-repellent coating meets the following requirements: d MAX -d MIN ≤0.5μm, where d MAX This refers to the maximum thickness of the ice-repellent coating, d MIN This refers to the minimum thickness of the ice-repellent coating.

6. The de-icing glass according to claim 1 or 2, wherein, The surface water contact angle of the ice-repellent coating is 95°-140°.

7. The de-icing glass according to claim 1 or 2, wherein, The surface pencil hardness of the ice-repellent coating is 4H-6H.

8. The de-icing glass according to claim 1, wherein, The long alkyl chain modified polyurethane includes one or more combinations of hexadecane-modified polyurethane, octadecane-modified polyurethane, octadecylamine-modified polyurethane, and polydimethylsiloxane-modified polyurethane.

9. The de-icing glass according to claim 2, wherein, The nano-silica is obtained by grafting and modifying nano-silica with vinyltriethoxysilane, wherein the mass ratio of vinyltriethoxysilane to nano-silica is 0.8-1.5:

1.

10. The de-icing glass according to claim 8 or 9, wherein, The raw materials for the long alkyl chain modified polyurethane layer include long alkyl chain compounds and silane coupling agents, and the molar ratio of the long alkyl chain compound to the silane coupling agent is between 2 and 3; the long alkyl chain compound includes one or more of hexadecane, octadecane, octadecylamine, and polydimethylsiloxane.

11. The de-icing glass according to claim 10, wherein, The raw materials for the long alkyl chain modified polyurethane layer also include solvents, which include one or more of ethyl acetate, butyl acetate, amyl acetate, toluene, and methyl benzoate.

12. The de-icing glass according to claim 2, wherein, The particle size of the nano-silica is 15nm-60nm.

13. The de-icing glass according to claim 1 or 2, wherein, The electric heating device includes a transparent conductive layer with a sheet resistance of 0.5Ω-2Ω.

14. The de-icing glass according to claim 1 or 2, wherein, The electric heating device includes a heating wire with a diameter of 0.018mm-0.2mm and a resistivity of 0.5Ω / m-270Ω / m.

15. The de-icing glass according to claim 14, wherein, The heating wire is a tungsten wire or an enameled wire.

16. A vehicle, wherein, The vehicle includes a window glass and a windshield wiper, the window glass including de-icing glass as described in any one of claims 1-15, and the windshield wiper extending from a first surface of the outer glass panel.

17. A method for de-icing a vehicle, wherein, The vehicle is the vehicle of claim 16, and the de-icing method includes the steps of: heating the de-icing glass with electricity, and / or de-icing it with the aid of external force.

18. The vehicle de-icing method according to claim 17, wherein, The external force is achieved through the windshield wiper, and the compressive stress exerted by the windshield wiper on the de-icing glass is 10N / cm-15N / cm, and the windshield wiper's movement speed is 15 times / min-20 times / min.

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