Glass with film layer, pillar assembly and vehicle

Abstract

This application relates to a glass with a film layer, a pillar assembly, and a vehicle. The aforementioned glass with a film layer includes: a glass substrate and an anti-fogging film layer disposed on a first surface of the glass substrate. The glass substrate has a visible area, and the anti-fogging film layer at least covers the visible area. The anti-fogging film layer includes a substrate layer and a resin functional layer stacked together. The substrate layer is closer to the glass substrate than the resin functional layer. The resin functional layer is made of a first polymer and a second polymer. The first polymer has pyrrolidone groups, and the second polymer has hydroxyl groups. The aforementioned glass with a film layer can improve anti-fogging performance in environments with large temperature differences or high humidity, maintaining the usability of intelligent modules such as cameras.

Description

Technical Field

[0001] This application relates to the field of glass, and in particular to a glass with a film layer, a pillar assembly, and a vehicle. Background Technology

[0002] With the development of vehicle intelligence, more and more vehicles are equipped with cameras or other intelligent modules such as facial recognition around their bodies to observe and monitor the surrounding environment, achieving purposes such as identity recognition for unlocking, vehicle anti-theft, and in-vehicle surround view. The cleanliness of the glass cover corresponding to the camera or other intelligent module directly affects the clarity of observation. In actual use, the glass cover in this location is prone to fogging in environments with large temperature differences or high humidity, thus affecting the use of the camera and other intelligent modules. Summary of the Invention

[0003] Based on this, some embodiments of this application provide a glass with a film layer that can improve the anti-fogging effect in environments with large temperature differences or high humidity, thus maintaining the use of smart modules such as cameras.

[0004] In addition, some other embodiments of this application also provide a pillar assembly and a vehicle including the glass with the above-described film layer.

[0005] A type of glass with a film layer, comprising:

[0006] A glass substrate, wherein the glass substrate has a visible area;

[0007] An anti-fogging film layer is disposed on the first surface of the glass substrate and at least covers the visible area;

[0008] The anti-fogging film layer includes a substrate layer and a resin functional layer stacked together. The substrate layer is closer to the glass substrate than the resin functional layer. The resin functional layer is made of a first polymer and a second polymer. The first polymer has pyrrolidone groups, and the second polymer has hydroxyl groups.

[0009] In some embodiments, the thickness of the resin functional layer is greater than or equal to 5 μm.

[0010] In some embodiments, the thickness of the resin functional layer is 5 μm to 100 μm.

[0011] In some embodiments, one or more of the following conditions are met:

[0012] (1) The mass ratio of the first polymer to the second polymer is 1:(0.01~0.5);

[0013] (2) The first polymer comprises a polymer of vinylpyrrolidone compounds such as N-vinyl-2-pyrrolidone and N-vinylethyl-2-pyrrolidone; optionally, the first polymer comprises one or more of vinylpyrrolidone-vinyl acetate copolymer and poly(methyl methacrylate-co-N-vinylpyrrolidone);

[0014] (3) The second polymer includes one or more of the following: cellulose polymers, chitosan polymers, cyclodextrin polymers and polyvinyl alcohol polymers.

[0015] In some embodiments, the cellulose polymer includes one or more of cellulose, methylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, methyl-2-hydroxyethylcellulose, and hydroxypropylmethylcellulose;

[0016] The chitosan polymers include one or more of chitosan and hydroxypropyl chitosan;

[0017] The cyclodextrin polymers include one or more of cyclodextrin and 2-hydroxypropyl-β-cyclodextrin;

[0018] The polyvinyl alcohol polymers include one or more of polyvinyl alcohol and polyvinyl butyral.

[0019] In some embodiments, the material of the substrate layer includes one or more of cellulose acetate and polyethylene terephthalate.

[0020] In some embodiments, the material of the substrate layer includes cellulose acetate.

[0021] In some embodiments, the thickness of the substrate layer is greater than 10 μm.

[0022] In some embodiments, the thickness of the substrate layer is 10 μm to 200 μm.

[0023] In some embodiments, the anti-fogging film layer has an anti-fogging time of greater than or equal to 70 seconds in a 35°C water bath anti-fogging test.

[0024] In some embodiments, the anti-fogging film layer has an anti-fogging time of greater than or equal to 80 seconds in a 35°C water bath anti-fogging test.

[0025] In some embodiments, the anti-fogging film layer has an anti-fogging time of greater than or equal to 90 seconds in a 35°C water bath anti-fogging test.

[0026] In some embodiments, the anti-fogging film layer has an anti-fogging time of greater than or equal to 100 seconds in a 35°C water bath anti-fogging test.

[0027] In some embodiments, the change in visible light transmittance of the glass substrate before and after the anti-fogging film layer is applied is less than or equal to 2%.

[0028] In some embodiments, the change in visible light transmittance of the glass substrate before and after the anti-fogging film layer is applied is less than or equal to 1%.

[0029] In some embodiments, an adhesive layer is further included, which is disposed between the anti-fogging film layer and the glass substrate, wherein the anti-fogging film layer is disposed on the glass substrate via the adhesive layer.

[0030] In some embodiments, the adhesive layer is made of one or more of polyvinyl butyral, ethylene-vinyl acetate copolymer, silicone resin, unsaturated polyester, polyurethane, and polyacrylate resin.

[0031] In some embodiments, the adhesive layer is made of polyvinyl butyral.

[0032] In some embodiments, a heating layer or heating wire is further included, the heating layer or heating wire being disposed on the first surface of the glass substrate, and the anti-fogging film layer being disposed on the side of the heating layer or heating wire away from the glass substrate.

[0033] In some embodiments, a self-cleaning coating is also included, which is disposed on a second surface of the glass substrate, the second surface being disposed opposite to the first surface, the self-cleaning coating at least covering the visible area.

[0034] In some embodiments, the self-cleaning coating material comprises a fluorinated material and silica particles in a mass ratio of (2~20):(0.01~0.5).

[0035] In some embodiments, the water contact angle of the self-cleaning coating is greater than or equal to 110°, and the oil contact angle is greater than or equal to 90°.

[0036] In some embodiments, the thickness of the self-cleaning coating is less than 200 nm.

[0037] In some embodiments, the thickness of the self-cleaning coating is less than 100 nm.

[0038] In some embodiments, the thickness of the self-cleaning coating is 5 nm to 100 nm.

[0039] A column assembly comprising the aforementioned glass with a film layer.

[0040] In some embodiments, a smart module is also included, which is disposed corresponding to the visible area in the glass with the film layer. The smart module includes one or more of a camera module, a face recognition module, and a display module.

[0041] A vehicle comprising the aforementioned glass with a film or the aforementioned pillar assembly.

[0042] The aforementioned glass with a film layer includes a glass substrate and an anti-fogging film layer disposed on the surface of the glass substrate. The anti-fogging film layer covers at least the visible area. The substrate layer in the anti-fogging film layer serves as a carrier to support the resin functional layer. On the other hand, the adhesion of the resin functional layer to the glass substrate is relatively weak, and the resin functional layer is prone to generating large internal stress during long-term anti-fogging tests involving water absorption and release, which can lead to peeling and detachment. The addition of a substrate layer helps to improve the adhesion between the glass substrate and the functional layer, enabling it to continuously perform its anti-fogging function in environments with large temperature differences or high humidity, without the risk of peeling and detachment. The resin functional layer consists of a first polymer with pyrrolidone groups and a second polymer with hydroxyl groups. Both polymers are hydrophilic, but the second polymer, rich in polar hydroxyl groups, contributes more to the anti-fogging properties of the coating. The first polymer, with pyrrolidone groups, is a polymer of vinylpyrrolidone compounds, such as N-vinyl-2-pyrrolidone or N-vinylethyl-2-pyrrolidone. Vinylpyrrolidone is often copolymerized with other monomers to achieve the desired functionality, such as ethyl acetate monomers, which can effectively inhibit the polymer's solubility in water and improve the coating's water resistance. The combined use of the first and second polymers achieves a complementary synergistic effect, leveraging their respective advantages to achieve better anti-fogging performance while maintaining water resistance.

[0043] Therefore, the aforementioned glass with a film layer can absorb water molecules on the glass surface in foggy environments with large temperature differences and high humidity, thus preventing fogging and ensuring the high definition of smart modules such as cameras in the visible area. Attached Figure Description

[0044] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0045] Figure 1 This is a schematic diagram of a glass structure with a film layer according to some embodiments of this application. Detailed Implementation

[0046] To facilitate understanding of this application, a more comprehensive description of the application will be provided below in conjunction with specific embodiments. Preferred embodiments of the application are given in the specific embodiments. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0048] Unless otherwise stated or in case of conflict, the terms or phrases used in this application shall have the following meanings:

[0049] In this application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" and "second" may explicitly or implicitly include at least one of those features.

[0050] In this application, "one or more" refers to any one, any two, or any two or more of the listed items. "Several" refers to any two or more.

[0051] The terms "optionally" and similar expressions used in this application refer to embodiments of this application that may provide certain beneficial effects under certain circumstances. However, other embodiments may also be optional in the same or other circumstances. Furthermore, the description of one or more optional embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this application.

[0052] When a numerical range is disclosed in this application, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed in this application should be understood to include any and all subranges to which they are included.

[0053] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0054] The terms "comprising" and "having," and any variations thereof, used in the embodiments of this application, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the steps or units listed, but may optionally include steps or units not listed, or may optionally include other steps or modules inherent to such processes, methods, products, or devices.

[0055] In this application, the reference to "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this application can be combined with other embodiments.

[0056] In this application, "above" and "below" both include the number itself. For example, "thickness above 20 μm" means that the thickness is greater than or equal to 20 μm.

[0057] In a first aspect, this application provides a glass with a film layer, comprising:

[0058] A glass substrate, wherein the glass substrate has a visible area;

[0059] Anti-fogging film layer, the anti-fogging film layer is set in the visible area;

[0060] The anti-fogging film layer includes a substrate layer and a resin functional layer stacked together. The substrate layer is closer to the glass substrate than the resin functional layer. The resin functional layer is made of a first polymer and a second polymer. The first polymer has pyrrolidone groups and the second polymer has hydroxyl groups.

[0061] The aforementioned glass with a film layer includes a glass substrate and an anti-fogging film layer disposed on the surface of the glass substrate. The anti-fogging film layer covers at least the visible area. The substrate layer in the anti-fogging film layer serves two purposes: firstly, it acts as a carrier, supporting the resin functional layer; secondly, since the adhesion of the resin functional layer to the glass substrate is relatively weak, the substrate layer helps to improve the adhesion between the glass substrate and the functional layer, enabling it to perform its anti-fogging function in environments with large temperature differences or high humidity. The resin functional layer material includes a first polymer with pyrrolidone groups and a second polymer with hydroxyl groups. Both the first and second polymers are hydrophilic, but the second polymer contains abundant polar hydroxyl groups, which contribute more to the anti-fogging properties of the coating. The first polymer has pyrrolidone groups; for example, the first polymer may be a polymer of vinylpyrrolidone compounds, such as N-vinyl-2-pyrrolidone or N-vinylethyl-2-pyrrolidone. Vinylpyrrolidone is often copolymerized with other monomers to achieve the desired functionality, such as ethyl acetate monomers, which can effectively inhibit the dissolution of the polymer in water and improve the water resistance of the coating. Therefore, the aforementioned glass with a film layer can absorb water molecules on the glass surface in foggy environments with large temperature differences and high humidity, thus preventing fogging and ensuring the high definition of smart modules such as cameras in the visible area.

[0062] Specifically, a fogging environment characterized by large temperature differences and high humidity refers to a situation where water vapor condenses into water droplets and forms fog when the environment reaches the dew point temperature. Large temperature differences and high humidity make it easier to reach the dew point temperature. For example, if the ambient humidity is 95%, and the temperature difference between the inside and outside of the glass is greater than 1 degree Celsius, water droplets will easily condense on the glass, forming fog.

[0063] In some embodiments, the glass substrate is curved glass, for example, the glass substrate is obtained by heat treatment of a flat glass plate at a high temperature of at least 560°C and bending.

[0064] In some embodiments, the visible area in the glass with the film layer can serve as the field of view of a camera, or as the display area for facial recognition, etc. When the glass with the film layer is applied to the pillar assembly, the pillar assembly is further provided with one or more of a camera module, a facial recognition module, and a display module, thereby endowing the pillar assembly with intelligent functions for observing and monitoring the surrounding environment, and realizing purposes such as identity recognition unlocking, vehicle anti-theft, and vehicle surround view.

[0065] In some embodiments, the glass substrate further includes a non-visible area, which is provided with an ink layer. Specifically, the visible light transmittance of the non-visible area is less than or equal to 5%. The non-visible area helps to shield and protect the components inside the vehicle, ensuring an aesthetically pleasing appearance.

[0066] Specifically, the first polymer includes polymers of vinylpyrrolidone compounds such as N-vinyl-2-pyrrolidone and N-vinylethyl-2-pyrrolidone. Polymers containing vinylpyrrolidone compounds are highly hydrophilic polymers, capable of forming strong interactions with water molecules and exhibiting strong water absorption. They are often copolymerized with other monomers to achieve desired functionality, such as copolymerization with ethyl acetate monomers and / or methacrylate monomers. While this may reduce the overall water absorption, it effectively inhibits polymer dissolution in water, improves the coating's water resistance, and prevents performance degradation caused by excessive water absorption by the resin layer. It can also enhance the coating's cohesion and adhesion, making the coating adhere more firmly to the substrate. Specifically, copolymers of N-vinylethyl-2-pyrrolidone, for example, refer to copolymers of N-vinyl-2-pyrrolidone with ethyl acetate monomers and / or methacrylate monomers. In some embodiments, the molecular weight of the first polymer is between 50,000 and 2,000,000. This specific molecular weight ensures that the polymer's solubility in water is inhibited, preventing it from being easily carried away and lost by water.

[0067] In some embodiments, the first polymer includes one or more of vinylpyrrolidone-vinyl acetate copolymer and poly(methyl methacrylate-co-N-vinylpyrrolidone).

[0068] The second polymer contains abundant polar hydroxyl groups in its molecular structure, which further endows the resin functional layer with good hydrophilicity and water retention. The use of the first and second polymers together achieves a complementary synergistic effect, leveraging the advantages of both to achieve better anti-fogging performance while meeting water resistance requirements.

[0069] Specifically, the second polymer includes one or more of cellulose polymers, chitosan polymers, cyclodextrin polymers, and polyvinyl alcohol polymers. Cellulose polymers include one or more of cellulose, methylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, methyl-2-hydroxyethylcellulose, and hydroxypropyl methylcellulose. Chitosan polymers include one or more of chitosan and hydroxypropyl chitosan. Cyclodextrin polymers include one or more of cyclodextrin and 2-hydroxypropyl-β-cyclodextrin. Polyvinyl alcohol polymers include one or more of polyvinyl alcohol and polyvinyl acetate.

[0070] In some embodiments, the mass ratio of the first polymer to the second polymer is 1:(0.01~0.5). For example, the mass ratio of the first polymer to the second polymer may be, but is not limited to, 1:0.01, 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, or any range of two of these values. At a certain addition ratio, the first polymer and the second polymer can simultaneously achieve properties such as anti-fogging and water resistance.

[0071] In some embodiments, the thickness of the resin functional layer is greater than or equal to 5 μm. Specifically, the thickness of the resin functional layer is 5 μm to 100 μm. Optionally, the thickness of the resin functional layer is 20 μm to 100 μm. For example, the thickness of the resin functional layer can be, but is not limited to, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, or any combination of these values. By optimizing the thickness of the resin functional layer and its material composition, its anti-fogging effect can be further improved. Under otherwise constant conditions, a thicker resin functional layer results in a better anti-fogging effect, but a thicker resin functional layer also increases the cost. At the thickness specified above, a good anti-fogging effect and cost advantage can be achieved.

[0072] In some embodiments, the resin functional layer can be a single layer or multiple layers. The materials of the multiple resin functional layers can be the same or different, as long as the total thickness of the resin functional layers is greater than 5 μm, for example, 5 μm to 100 μm. It can be understood that multiple layers refer to two or more layers.

[0073] In some embodiments, the material of the resin functional layer further includes additives. Specifically, the additives include one or more of plasticizers, curing agents, ultraviolet absorbers, antioxidants, light stabilizers, inorganic fillers, leveling agents, coupling agents, and wetting agents. Specifically, in some embodiments, the additives include one or more of ultraviolet absorbers, inorganic fillers, plasticizers, antioxidants, and light stabilizers. The addition of the above-mentioned additives helps improve its anti-aging properties and film-forming properties, ensuring the normal operation of the intelligent module under complex driving conditions.

[0074] In some embodiments, the preparation step of the resin functional layer includes: dispersing a first polymer, a second polymer, and optional additives in a solvent, then applying the mixture to a substrate layer, and curing it to prepare the resin functional layer. Specifically, the curing method includes one or a combination of room temperature curing, thermal curing, and photocuring.

[0075] The substrate layer serves as a support structure for the resin functional layer, enabling it to adhere firmly. In some embodiments, a portion of the substrate layer not only provides support but also exhibits low water absorption and anti-fogging properties. Moisture absorbed in the resin functional layer is transferred to the substrate layer, further enhancing the anti-fogging performance and durability of the anti-fogging film. This type of substrate layer complements the resin functional layer, facilitating the achievement of ultra-thick film thickness processes and allowing for easier customization of film structures with superior anti-fogging performance to meet customer needs. Specifically, the substrate layer material includes one or more of cellulose acetate and polyethylene terephthalate. In one embodiment, the substrate layer material includes cellulose acetate. Cellulose acetate can absorb and release water using temperature and humidity changes. Experiments have shown that a substrate layer material including cellulose acetate is more adaptable to high-humidity environments, further improving the anti-fogging effect.

[0076] In some embodiments, the thickness of the substrate layer is 10 μm or more. For example, the thickness of the substrate layer may be, but is not limited to, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 80 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, or any range of two of these values. Optionally, the thickness of the substrate layer is 10 μm to 200 μm.

[0077] In some embodiments, the anti-fogging film layer exhibits an anti-fogging time of greater than or equal to 70 seconds in a 35°C water bath anti-fogging test. Optionally, the anti-fogging film layer exhibits an anti-fogging time of greater than or equal to 80 seconds in a 35°C water bath anti-fogging test. Optionally, the anti-fogging film layer exhibits an anti-fogging time of greater than or equal to 90 seconds in a 35°C water bath anti-fogging test. Optionally, the anti-fogging film layer exhibits an anti-fogging time of greater than or equal to 100 seconds in a 35°C water bath anti-fogging test.

[0078] In some embodiments, the change in visible light transmittance of the glass substrate before and after the application of the anti-fogging film is less than or equal to 2%. Optionally, the change in visible light transmittance of the glass substrate before and after the application of the anti-fogging film is less than or equal to 1%. Wherein, the change in visible light transmittance = |T1-T2|, where T1 is the visible light transmittance of the glass substrate, and T2 is the visible light transmittance of the glass substrate after the application of the anti-fogging film.

[0079] In some embodiments, the glass with the film layer further includes an adhesive layer disposed between the anti-fogging film layer and the glass substrate, wherein the anti-fogging film layer is disposed on the glass substrate via the adhesive layer. The adhesive layer further enhances the adhesion between the substrate layer and the glass substrate.

[0080] In some embodiments, the adhesive layer material includes one or more of polyvinyl butyral (PVB), ethylene-vinyl acetate copolymer (EVA), silicone resin, unsaturated polyester, polyurethane, and polyacrylate resin. In one embodiment, the adhesive layer material includes polyvinyl butyral. Experiments have shown that the inclusion of polyvinyl butyral in the adhesive layer, when used in conjunction with the anti-fogging film layer, is beneficial for further improving its anti-fogging effect.

[0081] In some embodiments, the thickness of the adhesive layer is 5 μm to 760 μm. For example, the thickness of the adhesive layer may be, but is not limited to, 5 μm, 10 μm, 20 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 500 μm, 600 μm, 700 μm, 760 μm, or any combination of these values.

[0082] In some embodiments, the glass with the film layer further includes a heating layer or heating wire, which is disposed on a first surface of the glass substrate, and the anti-fogging film layer is disposed on the side of the heating layer or heating wire away from the glass substrate. For example, the heating layer or heating wire can be a silver-plated heating layer or a silver-plated heating wire. The presence of a heating layer or heating wire on the glass substrate enables the glass substrate to defog and de-ice when heated, further contributing to maintaining a clear field of vision.

[0083] In some embodiments, the glass with the film layer further includes a self-cleaning coating. The self-cleaning coating is disposed on a second surface of the glass substrate, which is opposite to the first surface. The self-cleaning coating covers at least the visible area. By providing the self-cleaning coating, the glass substrate is less prone to dust adhesion and raindrop dripping, ensuring that the aforementioned smart module located in the visible area always maintains high definition. In conjunction with the anti-fogging film layer, the glass with the film layer is less prone to fogging in environments with high temperature differences and high humidity. At the same time, it is less prone to dust adhesion and raindrop dripping, thereby ensuring that the aforementioned smart module such as the camera maintains high definition in different environments.

[0084] In some embodiments, the thickness of the self-cleaning coating is less than 200 nm. For example, the thickness of the self-cleaning coating may be, but is not limited to, 200 nm, 180 nm, 150 nm, 120 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, or a range of any two of these values. Optionally, the thickness of the self-cleaning coating is less than 100 nm. Optionally, the thickness of the self-cleaning coating is greater than 5 nm.

[0085] In some embodiments, the water contact angle of the self-cleaning coating is 110° or greater, and the oil contact angle is 90° or greater. For example, the water contact angle of the self-cleaning coating may be, but is not limited to, 110°, 112°, 114°, 115°, 116°, 118°, 119°, 120°, 122°, or any combination thereof. The oil contact angle of the self-cleaning coating may be, but is not limited to, 90°, 91°, 92°, 93°, 94°, 95°, 96°, 97°, 98°, 99°, 100°, or any combination thereof. The self-cleaning coating has a certain degree of water and oil repellency, enabling it to quickly roll away dirt adhering to the glass surface with the film layer under the action of wind and rain, maintaining the clarity of the visible area and ensuring the normal use of the smart module.

[0086] In some embodiments, the self-cleaning coating material comprises a fluorinated material and silica particles in a mass ratio of (2~20):(0.01~0.5). Optionally, the self-cleaning coating material comprises a fluorinated material and silica particles in a mass ratio of (2~20):(0.2~0.4). By adding a certain amount of silica particles to the self-cleaning coating, it is beneficial to improve the water contact angle and oil contact angle of the self-cleaning coating.

[0087] In some embodiments, the fluorinated material includes one or more of fluorocarbon materials and fluorosilicone materials. Specifically, the fluorinated material includes one or a combination of several of the following: 3,3,4,4,5,5,5-heptafluoropentyl(trimethoxy)silane, triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, nonafluorohexyltrimethoxysilane, perfluorooctyltrichlorosilane, perfluorooctyltriethoxysilane, perfluorodecyltrichlorosilane, perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorotetradecyl-1H,1H,2H,2H-triethoxysilane, perfluorohexadecyl-1H,1H,2H,2H-triethoxysilane, heptafluorodecyltriisopropoxysilane, and fluorinated silicone oil.

[0088] In some embodiments, the silica particles comprise hydrophobic fumed silica with a primary particle size of 10 nm to 20 nm. Specifically, the silica particles comprise one or more of Evonik Degussa's AEROSIL R202, AEROSIL R812, AEROSIL R812S, AEROSIL R972, AEROSIL R974, and AEROSIL R805.

[0089] It can be understood that primary grain size refers to the grain size of a single fine grain, also called the original grain size or initial grain size. When the crystal is very small, due to the large surface energy of the grains, the small grains are easily bonded together by weak interaction forces, leading to grain agglomeration. In other words, many small grains clump together to form larger secondary particles. The grain size of a single fine grain before agglomeration is called the primary grain size, while the grain size of the secondary particles formed after agglomeration is called the secondary grain size. This description also applies to amorphous particles.

[0090] In some embodiments, the self-cleaning coating can be applied to a glass substrate by methods such as spraying, coating, wiping, or vapor deposition, and then cured. Specifically, the curing method includes one or a combination of room temperature curing, thermal curing, and photocuring.

[0091] Specifically, the self-cleaning coating comprises fluorinated materials, solvents, and silica particles in a mass ratio of (2~20):(1000~2000):(0.01~0.5). Optionally, the self-cleaning coating comprises fluorinated materials, solvents, and silica particles in a mass ratio of (2~20):(1000~2000):(0.2~0.4).

[0092] In some embodiments, the solvent includes fluorinated ether solvents. Specifically, the solvent includes one or more of the following: ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,3,3,3-hexafluoroisopropylmethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,1,2,3,3-hexafluoropropylmethyl ether, 1,1,2,2-tetrafluoroethylethyl ether, 3-fluoro-4-methylanisole, 4-fluoro-2-methylanisole, heptafluoroisopropylethyl ether, isoflurane, heptafluoroalkyl, 1,-dichloro-2,2,2-trifluoroethylchlorodifluoromethyl ether, 2-chloro-1,1,2-trifluoroethyldifluoromethyl ether, 1,1,2,3,3,3-pentafluoropropyl-2,2,2-trifluoroethyl ether, perfluoroheptane, 2,2,3,3-tetrafluoropropyldifluoromethyl ether, and 2,6-difluoro-3-methylanisole. Self-cleaning coatings use solvents with low boiling points and strong dissolving power, which effectively reduce surface tension and improve the wettability of the coating.

[0093] Please see Figure 1The glass 100 with the film layer includes a glass substrate 110, an adhesive layer 120, an anti-fogging film layer 130, and a self-cleaning coating 140. The glass substrate 110 has a first surface 112 and a second surface 114 disposed opposite to each other, and the glass substrate 110 has a visible area 116 and a non-visible area 118. The adhesive layer 120 and the anti-fogging film layer 130 are sequentially stacked on the first surface 112 of the glass substrate 110. The anti-fogging film layer 130 includes a substrate layer 132 and a resin functional layer 134 stacked together, with the substrate layer 132 closer to the glass substrate 110. The self-cleaning coating 140 is disposed on the second surface 114 of the glass substrate 110, and the adhesive layer 120, the anti-fogging film layer 130, and the self-cleaning coating 140 all at least cover the visible area 116.

[0094] In some embodiments, the change in visible light transmittance of the glass substrate before and after the application of the anti-fogging film and self-cleaning coating is less than or equal to 2%. Optionally, the change in visible light transmittance of the glass substrate before and after the application of the anti-fogging film and self-cleaning coating is less than or equal to 1%. Wherein, the change in visible light transmittance = |T1-T3|, where T1 is the visible light transmittance of the glass substrate, and T3 is the visible light transmittance of the glass substrate after the application of the anti-fogging film and self-cleaning coating.

[0095] In some embodiments, the glass with the film can be the exterior trim glass of the A-pillar, B-pillar, C-pillar, etc. It is understood that in other embodiments, the glass with the film is not limited to being the exterior trim glass of pillars, but can also be used as windshield, rear window, side window, etc.

[0096] In some embodiments, the method for preparing glass with a film layer includes the following steps:

[0097] An anti-fogging film layer is formed on the first surface of the glass substrate;

[0098] A self-cleaning coating is provided on the second surface of the glass substrate, wherein the second surface is disposed opposite to the first surface.

[0099] Specifically, the step of forming an anti-fogging film layer on the first surface of the glass substrate includes: forming a resin functional layer on the substrate layer to obtain an anti-fogging film layer; and bonding the anti-fogging film layer, the adhesive layer and the glass substrate to form an anti-fogging film layer on the glass substrate.

[0100] In some embodiments, before applying the self-cleaning coating to the second surface of the glass substrate, a step of cleaning and activating the second surface of the glass substrate is included. Specifically, the cleaning and activation treatment includes one or more of cerium oxide polishing, plasma treatment, flame treatment, and dry ice treatment. This treatment helps to improve the adhesion between the self-cleaning coating and the glass substrate.

[0101] It is understood that the steps of setting an anti-fogging film layer on the first surface of the glass substrate and setting a self-cleaning coating on the second surface of the glass substrate are not sequential. The anti-fogging film layer can be set first, followed by the self-cleaning coating, or the self-cleaning coating can be set first, followed by the anti-fogging film layer, or both layers can be set simultaneously.

[0102] Secondly, this application provides a column assembly including the glass with a film layer as described in the first aspect.

[0103] In some embodiments, the column assembly further includes a smart module, which is disposed corresponding to a visible area in the film-coated glass. The smart module includes one or more of a camera module, a face recognition module, and a display module. Specifically, the visible area in the film-coated glass can serve as the field of view of the camera or as the display area for face recognition.

[0104] Thirdly, this application provides a vehicle including the glass with a film layer as described in the first aspect or the pillar assembly as described in the second aspect.

[0105] Specifically, the vehicle includes a body and a pillar assembly, with the pillar assembly mounted on the body.

[0106] Specifically, when glass with a coating is used in vehicles, the side with the anti-fogging coating faces inwards, while the side with the self-cleaning coating faces outwards. The inner anti-fogging coating can absorb water molecules on the glass surface in foggy environments with large temperature differences and high humidity, thus delaying fogging. The outer self-cleaning coating has a certain degree of water and oil repellency, making it less prone to dust adhesion and rain dripping. Under the action of wind and rain, it can quickly roll away dirt adhering to the glass surface, maintaining the clarity of the visible area and ensuring that the smart module maintains high definition for normal use.

[0107] Specifically, the vehicle can be any vehicle commonly used in this field, without any particular limitation. For example, the vehicle can be, but is not limited to, cars, trucks, buses, pickup trucks, etc.

[0108] To make the objectives and advantages of this application clearer, the following detailed description of the film-coated glass and its effects, in conjunction with specific embodiments, is provided. It should be understood that the specific embodiments described herein are for illustrative purposes only and should not be construed as limiting the scope of this application. Unless otherwise specified, the following embodiments do not include components other than unavoidable impurities. Unless otherwise specified, the drugs and instruments used in the embodiments are conventionally chosen in the art. Experimental methods not specifying specific conditions in the embodiments are implemented under conventional conditions, such as those described in literature, books, or methods recommended by the manufacturer.

[0109] Example 1

[0110] This embodiment provides a glass with a film layer, including a glass substrate. The glass substrate has a visible area and a non-visible area. The first surface of the glass substrate, corresponding to the visible area, is sequentially provided with an adhesive layer, a substrate layer, and a resin functional layer. The second surface of the glass substrate, corresponding to the visible area, is provided with a self-cleaning coating. The adhesive layer is a 380 μm thick polyvinyl butyral adhesive layer (PVB adhesive layer). The substrate layer is made of cellulose acetate and has a thickness of 120 μm. The resin functional layer comprises a first polymer, vinylpyrrolidone-vinyl acetate copolymer, and a second polymer, hydroxyethyl cellulose, in a mass ratio of 1:0.25, with a thickness of 20 μm. The self-cleaning coating comprises a fluorinated material, 3,3,4,4,5,5,5-heptafluoropentyl(trimethoxy)silane, and silica particles (primary particle size 14 nm) in a mass ratio of 2:0.2.

[0111] The preparation steps of the glass with the film layer in this embodiment are as follows:

[0112] (1) Preparation of self-cleaning coating: 3,3,4,4,5,5,5-heptafluoropentyl (trimethoxy)silane, ethyl nonafluorobutyl ether, and silica particles (with a primary particle size of 14 nm) are mixed in a mass ratio of 2:1000:0.2 and stirred to obtain the self-cleaning coating.

[0113] (2) The non-visible area of ​​the glass substrate is shielded, and the above-mentioned self-cleaning coating is sprayed on the outer side of the visible area of ​​the glass substrate and cured to form a self-cleaning coating.

[0114] (3) Prepare an anti-fogging film layer. The anti-fogging film layer includes a substrate layer and a resin functional layer. The substrate layer is made of cellulose acetate and has a thickness of 120 μm. The resin functional layer is made of a first polymer, vinylpyrrolidone-vinyl acetate copolymer, and a second polymer, hydroxyethyl cellulose, with a mass ratio of 1:0.25 and a thickness of 20 μm.

[0115] (4) The substrate layer of the anti-fogging film is bonded to the inner side of the visible area of ​​the glass substrate through the PVB adhesive layer. The bonding is carried out at a temperature of 135°C and a pressure of 1.2MPa to obtain glass with an anti-fogging film and a self-cleaning coating.

[0116] Example 2

[0117] This embodiment provides a glass with a film layer, similar to the glass with a film layer in Example 1, except that the mass ratio of fluorine-containing material to silica particles in the self-cleaning coating is 2:0.01; the substrate layer is made of polyethylene terephthalate (PET). Other parameters are the same as in Example 1 and will not be repeated.

[0118] The preparation steps of the glass with the film layer in this embodiment are the same as those in Embodiment 1, and will not be repeated here.

[0119] Example 3

[0120] This embodiment provides a glass with a film layer, similar to the glass with a film layer in Embodiment 1, except that the thickness of the resin functional layer is 30 μm. Other parameters are the same as in Embodiment 1 and will not be repeated.

[0121] The preparation steps of the glass with the film layer in this embodiment are the same as those in Embodiment 1, and will not be repeated here.

[0122] Example 4

[0123] This embodiment provides a glass with a film layer, similar to the glass with a film layer in Embodiment 1, except that the mass ratio of fluorine-containing material to silica particles in the self-cleaning coating is 2:0.5; the substrate layer is made of polyethylene terephthalate; and the thickness of the resin functional layer is 30 μm. Other parameters are the same as in Embodiment 1 and will not be repeated.

[0124] The preparation steps of the glass with the film layer in this embodiment are the same as those in Embodiment 1, and will not be repeated here.

[0125] Example 5

[0126] This embodiment provides a glass with a film layer, similar to the glass with a film layer in Example 1, except that the substrate layer is made of polyethylene terephthalate, the resin functional layer is 30 μm thick, and the adhesive layer is a polyacrylate adhesive layer. Other parameters are the same as in Example 1 and will not be repeated.

[0127] The preparation steps of the glass with the film layer in this embodiment are the same as those in Embodiment 1, and will not be repeated here.

[0128] Example 6

[0129] This embodiment provides a glass with a film layer, similar to the glass with a film layer in Embodiment 1, except that it does not contain a self-cleaning coating, the thickness of the resin functional layer is 30 μm, and the adhesive layer is a polyacrylate adhesive layer. Other steps are the same as in Embodiment 1 and will not be repeated.

[0130] The preparation steps of the glass with the film layer in this embodiment are the same as those in Embodiment 1, and will not be repeated here.

[0131] Example 7

[0132] This embodiment provides a glass with a film layer, similar to the glass with a film layer in Embodiment 1, except that the mass ratio of the first polymer and the second polymer in the resin functional layer is 1:0.5. Other parameters are the same as in Embodiment 1 and will not be repeated.

[0133] The preparation steps of the glass with the film layer in this embodiment are the same as those in Embodiment 1, and will not be repeated here.

[0134] Example 8

[0135] This embodiment provides a glass with a film layer, similar to the glass with a film layer in Embodiment 1, except that the mass ratio of the first polymer and the second polymer in the resin functional layer is 1:0.05. Other parameters are the same as in Embodiment 1 and will not be repeated.

[0136] The preparation steps of the glass with the film layer in this embodiment are the same as those in Embodiment 1, and will not be repeated here.

[0137] Example 9

[0138] This embodiment provides a glass with a film layer, similar to the glass with a film layer in Embodiment 1, except that the second polymer in the resin functional layer is methylcellulose. Other parameters are the same as in Embodiment 1 and will not be repeated.

[0139] The preparation steps of the glass with the film layer in this embodiment are the same as those in Embodiment 1, and will not be repeated here.

[0140] Example 10

[0141] This embodiment provides a glass with a film layer, similar to the glass with a film layer in Example 1, except that the first polymer in the resin functional layer is poly(methyl methacrylate-co-N-vinylpyrrolidone). Other parameters are the same as in Example 1 and will not be repeated.

[0142] The preparation steps of the glass with the film layer in this embodiment are the same as those in Embodiment 1, and will not be repeated here.

[0143] Comparative Example 1

[0144] Comparative Example 1 provides a glass with a film layer, which differs from the glass with a film layer in that it does not contain a self-cleaning coating, an anti-fogging film layer, or an adhesive layer.

[0145] Comparative Example 2

[0146] Comparative Example 2 provides a glass with a film layer, similar to the glass with a film layer in Example 1, except that the mass of silica in the self-cleaning coating is 0; and the thickness of the resin functional layer in step (3) is 5 μm. Other parameters are the same as in Example 1 and will not be repeated.

[0147] The preparation steps of the glass with the film layer in Comparative Example 2 are the same as those in Example 1, and will not be repeated here.

[0148] Comparative Example 3

[0149] Comparative Example 3 provides a glass with a film layer, similar to the glass with a film layer in Example 1, except that the material of the resin functional layer does not contain the first polymer. Other parameters are the same as in Example 1 and will not be repeated.

[0150] The preparation steps of the glass with the film layer in Comparative Example 3 are the same as those in Example 1, and will not be repeated here.

[0151] Comparative Example 4

[0152] Comparative Example 4 provides a glass with a film layer, similar to the glass with a film layer in Example 1, except that the material of the resin functional layer does not contain a second polymer. Other parameters are the same as in Example 1 and will not be repeated.

[0153] The preparation steps of the glass with the film layer in Comparative Example 4 are the same as those in Example 1, and will not be repeated here.

[0154] Comparative Example 5

[0155] Comparative Example 5 provides a glass with a film layer, similar to the glass with a film layer in Example 1, except that it does not contain a substrate layer, and the resin functional layer is bonded to the inner side of the visible area of ​​the glass substrate through a PVB adhesive layer. Other parameters are the same as in Example 1 and will not be repeated.

[0156] The preparation steps of the glass with the film layer in Comparative Example 5 are the same as those in Example 1, and will not be repeated here.

[0157] The thickness of each layer in the above embodiments and comparative examples was measured using a step meter.

[0158] The main process parameters for preparing the films in the above embodiments and comparative examples are shown in Tables 1 and 2 below.

[0159] Table 1. Main process parameters of each embodiment

[0160]

[0161] Table 2 Main process parameters for each comparative example

[0162]

[0163] The following is the specific test section:

[0164] The glass samples with film layers of each embodiment and each comparative example were subjected to the following tests, and the test results are shown in Table 3.

[0165] (1) Contact angle: The contact angle of the sample was measured using a German Krüss MSA portable contact angle measuring instrument. 3 μL of liquid was dropped into the sample. The water and oil droplets were provided by deionized water and diiodomethane, respectively.

[0166] The contact angles in Table 3 below refer to the average value obtained by measuring three different points of the same sample.

[0167] (2) 35℃ water bath anti-fogging test: Place the glass sample with the film layer in an environment of 20℃ and 50%RH for 1 hour, and then transfer it to a container of more than 100mL containing 35℃ water. Record the time (s) when fogging begins.

[0168] (3) Water splash anti-fog test: Place the glass sample with the film layer in an environment of 50℃ and 95%RH for 12 hours. After taking it out, continuously splash 5℃ cold water in the visible area for 1 minute and observe whether fog forms on the surface of the visible area.

[0169] Table 3 Test results of the films on the glass of each embodiment and comparative example.

[0170]

[0171] As can be seen from Table 3:

[0172] Without an anti-fogging film, the anti-fogging effect is poor. After applying a self-cleaning coating to the glass substrate, the water contact angle of the glass with the film reaches over 110° and the oil contact angle is over 90°. Furthermore, by optimizing the amount of silica particles added, the water and oil contact angles can be moderately improved within a certain range.

[0173] Furthermore, the comparison of Examples 1 to 4 shows that the thicker the resin functional layer in the anti-fogging film, the better the anti-fogging effect. Cellulose acetate, as the substrate layer, enhances the anti-fogging properties of the film compared to the PET substrate layer.

[0174] The comparison between Example 1 and Comparative Examples 3-4 shows that the anti-fogging effect is significantly worse when the resin functional layer does not contain the first polymer or the second polymer. The comparison between Example 1 and Comparative Example 5 shows that the anti-fogging film layer does not contain the substrate layer, resulting in a poorer anti-fogging effect and peeling of the coating.

[0175] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0176] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A type of glass with a film layer, characterized in that, include: A glass substrate, wherein the glass substrate has a visible area; An anti-fogging film layer is disposed on the first surface of the glass substrate and at least covers the visible area; The anti-fogging film layer includes a substrate layer and a resin functional layer stacked together. The substrate layer is closer to the glass substrate than the resin functional layer. The resin functional layer is made of a first polymer and a second polymer. The first polymer has pyrrolidone groups, and the second polymer has hydroxyl groups.

2. The glass with a film layer according to claim 1, characterized in that, The thickness of the resin functional layer is greater than or equal to 5 μm.

3. The glass with a film layer according to claim 2, characterized in that, The thickness of the resin functional layer is 5μm~100μm.

4. The glass with a film layer according to any one of claims 1 to 3, characterized in that, One or more of the following conditions must be met: (1) The mass ratio of the first polymer to the second polymer is 1:(0.01~0.5); (2) The first polymer comprises a polymer of vinylpyrrolidone compounds such as N-vinyl-2-pyrrolidone and N-vinylethyl-2-pyrrolidone; (3) The second polymer includes one or more of the following: cellulose polymers, chitosan polymers, cyclodextrin polymers and polyvinyl alcohol polymers.

5. The glass with a film layer according to claim 4, characterized in that, The first polymer includes one or more of vinylpyrrolidone-vinyl acetate copolymer and poly(methyl methacrylate-co-N-vinylpyrrolidone).

6. The glass with a film layer according to claim 4, characterized in that, The cellulose polymers include one or more of cellulose, methylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, methyl-2-hydroxyethylcellulose, and hydroxypropylmethylcellulose; The chitosan polymers include one or more of chitosan and hydroxypropyl chitosan; The cyclodextrin polymers include one or more of cyclodextrin and 2-hydroxypropyl-β-cyclodextrin; The polyvinyl alcohol polymers include one or more of polyvinyl alcohol and polyvinyl butyral.

7. The glass with a film layer according to claim 1, characterized in that, The substrate layer is made of one or more of cellulose acetate and polyethylene terephthalate.

8. The glass with a film layer according to any one of claims 1-3 and 5-7, characterized in that, The thickness of the substrate layer is greater than 10 μm.

9. The glass with a film layer according to claim 8, characterized in that, The thickness of the substrate layer is 10μm~200μm.

10. The glass with a film layer according to any one of claims 1-3 and 5-7, characterized in that, The anti-fogging film layer has an anti-fogging time of greater than or equal to 70 seconds in a 35°C water bath anti-fogging test.

11. The glass with a film layer according to claim 10, characterized in that, The anti-fogging film layer has an anti-fogging time of greater than or equal to 90 seconds in a 35°C water bath anti-fogging test.

12. The glass with a film layer according to any one of claims 1-3 and 5-7, characterized in that, The change in visible light transmittance of the glass substrate before and after the anti-fogging film layer is applied is less than or equal to 2%.

13. The glass with a film layer according to claim 12, characterized in that, The change in visible light transmittance of the glass substrate before and after the anti-fogging film layer is applied is less than or equal to 1%.

14. The glass with a film layer according to claim 1, characterized in that, It also includes an adhesive layer disposed between the anti-fogging film layer and the glass substrate, wherein the anti-fogging film layer is disposed on the glass substrate through the adhesive layer.

15. The glass with a film layer according to claim 14, characterized in that, The adhesive layer is made of one or more of the following materials: polyvinyl butyral, ethylene-vinyl acetate copolymer, silicone resin, unsaturated polyester, polyurethane, and polyacrylate resin.

16. The glass with a film layer according to any one of claims 1-3, 5-7, 11 or 13-15, characterized in that, It also includes a heating layer or heating wire, which is disposed on the first surface of the glass substrate, and the anti-fogging film layer is disposed on the side of the heating layer or heating wire away from the glass substrate.

17. The glass with a film layer according to any one of claims 1-3, 5-7, 11 or 13-15, characterized in that, It also includes a self-cleaning coating disposed on a second surface of the glass substrate, the second surface being disposed opposite to the first surface, the self-cleaning coating at least covering the visible area.

18. The glass with a film layer according to claim 17, characterized in that, The self-cleaning coating consists of fluorine-containing materials and silica particles in a mass ratio of (2~20):(0.01~0.5).

19. The glass with a film layer according to claim 17, characterized in that, The self-cleaning coating has a water contact angle greater than or equal to 110° and an oil contact angle greater than or equal to 90°; and / or, The thickness of the self-cleaning coating is less than 200 nm.

20. A column assembly, characterized in that, Including the glass with a film layer as described in any one of claims 1 to 19.

21. The column assembly according to claim 20, characterized in that, It also includes a smart module, which is configured to correspond to the visible area in the glass with the film layer. The smart module includes one or more of a camera module, a face recognition module, and a display module.

22. A vehicle, characterized in that, Including the glass with a film layer as described in any one of claims 1 to 19.

23. A vehicle, characterized in that, Includes the column assembly as described in claim 20 or 21.

Images