Vehicle glazing

Abstract

The present invention relates to a vehicle glazing comprising an outermost layer comprising 0.5 to 20 atomic% cerium, based on all components, and to a process for producing such a vehicle glazing comprising the step of sputtering a sputtering target comprising cerium oxide in order to provide a cerium oxide-containing layer directly or indirectly on a first surface, the invention also relates to the use of a cerium oxide-containing layer as a durable and long-life hydrophobic surface on a vehicle glazing, and to a vehicle comprising a vehicle glazing comprising an outermost layer containing 0.5 to 20 atomic% cerium, based on all components.

Description

Technical Field

[0001] This invention relates to vehicular glazing, particularly vehicular glazing with a durable and long-life hydrophobic surface, to processes for producing such vehicular glazing, and to the use of a cerium oxide layer as a durable and long-life hydrophobic surface on vehicular glazing. Background Technology

[0002] The goal is to easily remove water from vehicle glass so that light transmission through the glass to occupants or sensors is not impaired. Glass surfaces are typically hydrophilic, allowing water to "coat" the surface. This water layer is difficult to remove and can impair occupant or machine vision through the glass. To reduce water sheeting, glass surfaces can be made more hydrophobic. The use of hydrophobic surfaces prevents water sheeting and may cause water to form droplets, which are easier to remove. Therefore, hydrophobic surfaces are associated with improved visual acuity through the glass.

[0003] There is also a desire to reduce the weight of existing vehicles (especially electric vehicles) in order to improve fuel efficiency and range.

[0004] Water droplets on hydrophobic surfaces can be more easily removed by wiper blades. This allows for the use of lightweight wiper blades and lower-power, lighter wiper motors, thus reducing motor energy consumption and overall vehicle weight, thereby allowing for improved fuel efficiency and mileage.

[0005] Furthermore, the use of hydrophobic coatings allows for the elimination of windshield wipers, reducing vehicle weight by eliminating the need for wipers, wiper motors, and related wiring. This weight reduction is particularly desirable, for example, in electric vehicles such as electric cars.

[0006] Furthermore, compared to hydrophilic surfaces, it is easier to remove water droplets from glass components (such as side windows) that are not wiped by wiper blades through air resistance, because removing water droplets from such surfaces requires less energy.

[0007] Coatings on substrates (especially glass substrates) can be used to modify the properties of the substrate. Various methods can be used to deposit coatings on glass substrates, such as liquid-based methods including spin coating, dip coating, and spray coating, as well as chemical vapor deposition (CVD) and physical vapor deposition (PVD). Physical vapor deposition is also known as sputtering. Coatings have been used in the past to impart hydrophobicity to glass surfaces, such as sol-gel formulations using mixed organic-inorganic precursors, modified silanes with sol-gel additives, or modified silanes chemically cross-linked after surface treatment. Other products include reactive silicone fluids, coating the surface with easy-to-clean polymer coatings or polymer resins to provide a low-maintenance, non-stick surface.

[0008] However, many of these prior hydrophobic coatings do not adhere to the glass sufficiently for the lifespan of the vehicle or glass component and disperse into the environment over time. This is particularly concerning when the coating includes environmentally harmful substances. One class of substances considered environmentally harmful are perfluorinated and polyfluoroalkyl substances (PFAS). Some PFAS are undesirable because they are classified as persistent organic pollutants (POPs), which are organic substances that persist in the environment and accumulate in living organisms, causing harm. Other PFAS are not currently banned but are undesirable to consumers. Therefore, there is a need for hydrophobic coatings that do not allow PFAS to enter the environment. Furthermore, existing hydrophobic coatings have short lifespans due to their low durability, meaning they must be applied repeatedly in a time-consuming manner, thus repeatedly releasing them into the environment, further increasing their potential environmental damage. Summary of the Invention

[0009] Therefore, the object of the present invention is to solve the problems of known products or methods and to produce vehicle glass parts with long-term low water-surface adhesion and low likelihood of introducing harmful substances into the environment.

[0010] In a first aspect, the present invention provides a vehicle glass component having a durable and long-life hydrophobic surface, comprising:

[0011] A glass substrate having a first surface and a second surface; and

[0012] A cerium oxide-containing layer directly or indirectly on the first surface, wherein:

[0013] The cerium oxide-containing layer is the outermost layer on the first surface; and

[0014] Based on all components, the cerium oxide-containing layer contains 0.5 to 20 atomic percent cerium.

[0015] The inventors have discovered that the cerium-containing outermost layer as described in this invention provides a coating that offers excellent hydrophobic properties, thus providing vehicle glass components with low water-to-surface adhesion. Furthermore, the cerium-containing outermost layer is more durable than existing hydrophobic coatings, thus providing long-lasting hydrophobicity and is less likely to disperse into the environment. In addition, the cerium-containing layer is PFAS-free and achieves excellent hydrophobic properties without the use of perfluoroalkyl or polyfluoroalkyl substances, thus making it less likely to cause environmental harm.

[0016] According to the present invention, a vehicle glass component has a durable surface if the surface durability reaches the following levels: when subjected to an oil friction 50 test as detailed herein, the surface achieves a score of 5 or less, preferably 3 or less, more preferably 0; and / or when subjected to a microbrush test as detailed herein, it achieves a score of 5 or less, preferably 3 or less, more preferably 0; and / or passes the dry abrasion resistance test according to ASTM D6037.

[0017] According to the invention, if the surface achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55°, the vehicle glass component has a long-life hydrophobic surface after a test selected from the list of the following: the oil friction 50 test as detailed herein, the oil friction 500 test as detailed herein, the microbrush test as detailed herein, or the dry abrasion resistance test according to ASTM D6037.

[0018] Preferably, the first surface does not include a layer containing perfluoroalkyl or polyfluoroalkyl substances.

[0019] Preferably, the glass substrate is a soda-lime-silica glass substrate. Alternatively, other glass compositions, such as borosilicates, aluminosilicates, and boroaluminosilicates, can be used.

[0020] The cerium oxide-containing layer is the outermost layer on the first surface. When the cerium oxide-containing layer is the outermost layer on the first surface, the cerium oxide-containing layer is directly exposed to the environment of the vehicle glass component.

[0021] The cerium oxide-containing layer is located on the first surface, because the first surface includes the cerium oxide-containing layer. The first surface can be substantially completely coated with the cerium oxide-containing layer. In this case, the entire vehicle glass component is coated, thereby providing a hydrophobic effect to the entire glass component. When the vehicle glass component is a fixed vehicle glass component (such as a car windshield, rear window, or sunroof), it is desirable for the entire vehicle glass component to be coated such that the first surface is substantially completely coated with the cerium oxide-containing layer.

[0022] When a vehicle windshield is equipped with a wiper, it may be desirable for the area swept by the wiper blade to include the cerium oxide layer to improve wiper efficiency. Alternatively, the area swept by the wiper blade may not include the cerium oxide layer, and other areas may include the cerium oxide layer.

[0023] In some implementations, the vehicle glass is equipped with a camera or sensor. Particularly advantageous is that, in cases where the vehicle glass is equipped with a camera or sensor that receives electromagnetic radiation, the electromagnetic radiation must penetrate to reach the first surface area of ​​the camera or sensor (defined herein as the sensor area) where the cerium oxide-containing layer is disposed.

[0024] Water droplets in the sensor region can reduce the sensitivity of the camera or sensor, leading to image quality degradation and potential malfunction of any autonomous driving assistance systems associated with the camera or sensor. The cerium oxide-containing layer improves the hydrophobicity of the sensor region, thereby reducing the energy required to remove water droplets and thus reducing the number of water droplets that might otherwise be present in the sensor region and could cause degradation of the camera or sensor sensitivity.

[0025] Particularly preferred is that when the sensor area is not within the area swept by the wipers on the vehicle's windshield, the sensor area is provided with the cerium oxide layer to allow water droplets to be effectively removed by wind resistance alone.

[0026] In some embodiments, the vehicle glass is adapted such that the first surface including the cerium oxide layer is positioned facing the exterior of the vehicle. This is particularly advantageous given the hydrophobicity of the vehicle exterior. However, in other embodiments, the vehicle glass is adapted such that the first surface including the cerium oxide layer is positioned facing the interior of the vehicle. This is particularly advantageous when hydrophobic surfaces are desired inside vehicles (such as multi-occupant vehicles and public transport vehicles), as such surfaces are easier to clean. Furthermore, hydrophobic surfaces on the inner surfaces of the glass, such as those provided by the cerium oxide layer, reduce the effects of condensation, as water droplets condensing on the inner surfaces are easily displaced by gravity alone. In some embodiments, the vehicle glass includes cerium oxide layers on both the outer and inner surfaces.

[0027] Preferably, the cerium in the cerium-containing layer is uniform. A uniformly cerium-containing cerium oxide layer comprises cerium atoms dispersed across and throughout the coating layer to a uniform degree. Preferably, the cerium atoms are within and constitute an amorphous or semi-amorphous coating layer applied to the first surface, such as a coating layer provided by sputtering. Preferably, the cerium atoms are not within nanoparticles, and preferably the cerium-containing layer does not contain particles and / or nanoparticles. Due to the reduced surface roughness, a uniformly cerium-containing layer free of particles and / or nanoparticles is less likely to be abraded by wiper blades. Furthermore, some nanoparticles may be unacceptable to consumers.

[0028] Advantageously, the vehicle glass components are corrosion-resistant, as demonstrated by a relatively low increase in haze after weathering. Weathering can be accelerated by high humidity, heating, or hot / cold cycling, and for testing purposes, weathering can be simulated by maintaining the glass at elevated temperatures for a predetermined period of time in high humidity. Typically, after 50 days at 98% relative humidity and 60°C, the measured haze of the coated glass (using, for example, a haze meter) will be 25% or less, preferably 20% or less, more preferably 15% or less, even more preferably 10%, and most preferably 5% or less. Preferably, after 50 days at 98% relative humidity and 60°C, the corrosion-resistant coated glass substrate exhibits a haze increase of 55% or less, more preferably 35% or less, and most preferably 24% or less. The haze increase can be calculated by comparing the measured haze before and after weathering.

[0029] Typically, the thickness of the cerium oxide-containing layer can be 1 nm or higher, preferably 10 nm or higher, more preferably 20 nm or higher, and most preferably 30 nm or higher. A coating that is too thin may not be durable or effective enough. Preferably, the thickness of the cerium oxide-containing layer is 500 nm or less, preferably 250 nm or less, more preferably 100 nm or less, and most preferably 50 nm or less. A coating that is too thick may crack during heat treatment or toughening processes, making production potentially uneconomical.

[0030] Therefore, preferably, the cerium oxide-containing layer has a thickness in the range of 1 nm to 500 nm, more preferably 5 to 250 nm, and more preferably 10 to 100 nm. Such thicknesses are advantageous because they provide a good balance between corrosion resistance, durability, and production economics.

[0031] The cerium oxide-containing layer typically has a refractive index in the range of 2.28 to 2.44.

[0032] In some embodiments, the cerium oxide-containing layer is preferably the only layer on the first surface. However, in alternative embodiments, an underlayer is preferably provided between the cerium oxide-containing layer and the first surface. Preferably, the underlayer comprises silicon oxide. Such an underlayer can improve the adhesion and durability of the cerium oxide-containing layer. Preferably, the silicon oxide-containing underlayer is directly on the first surface. This further improves the adhesion and durability of the coating on the substrate.

[0033] In a preferred embodiment, the silicon oxide-containing substrate is directly on the first surface, and the cerium oxide-containing layer is directly on the silicon oxide-containing substrate. This layer arrangement provides excellent adhesion and durability of the coating in an efficient manner.

[0034] Preferably, the cerium oxide-containing layer contains 1 to 10 atomic percent cerium, more preferably 2 to 8 atomic percent cerium, based on all components. This range has been shown to provide excellent hydrophobicity.

[0035] Preferably, the cerium oxide-containing layer contains a substoichiometric amount of oxygen.

[0036] Preferably, the cerium oxide-containing layer further comprises titanium, and the cerium oxide-containing layer preferably comprises 50 to 95 atomic percent titanium based on titanium and cerium, more preferably 70 to 90 atomic percent titanium based on titanium and cerium, and even more preferably 75 to 85 atomic percent titanium based on titanium and cerium.

[0037] The inventors have discovered that layers containing cerium oxide and titanium are particularly effective, corrosion-resistant, and cleanable coatings with excellent durability. Furthermore, the inventors have discovered that such coatings can be easily deposited by sputtering.

[0038] Preferably, when the cerium oxide-containing layer is a layer comprising cerium oxide and titanium, i.e., Ce x Ti y O z In this case, the atomic ratio of Ce in the base layer, based on Ce and Ti (calculated as x / (x+y)), is 0.5 to 0.95, more preferably 0.50 to 0.90, more preferably 0.55 to 0.85, more preferably 0.60 to 0.80, and even more preferably 0.62 to 0.67. The inventors have discovered that such a range provides a particularly durable and long-lasting hydrophobic coating.

[0039] Preferably, the cerium oxide-containing layer contains less than 10 atomic% silicon based on all components; more preferably, the cerium-containing layer contains less than 1 atomic% silicon based on all components; and more preferably, the cerium-containing layer is substantially free of silicon.

[0040] Preferably, the cerium oxide-containing layer contains less than 10 atomic% aluminum based on all components; more preferably, the cerium-containing layer contains less than 1 atomic% aluminum based on all components; and more preferably, the cerium-containing layer is substantially free of aluminum.

[0041] Preferably, the vehicle glass exhibits a water contact angle greater than 30°, more preferably greater than 50°, and even more preferably greater than 60°. Such a water contact angle is associated with low water-surface adhesion. Therefore, according to this specification, the substrate is hydrophobic when it exhibits a water contact angle greater than 30°, more preferably greater than 50°, even more preferably greater than 60°, and even more preferably greater than 70°.

[0042] Preferably, the vehicle glass is a curved and / or reinforced vehicle glass.

[0043] Vehicle glass components are typically bent to fit the vehicle's openings and increase the visual appeal of the glass. These bending techniques can be employed, for example, through sag bending, press bending, or cold bending.

[0044] The bent vehicle glass includes a radius of curvature in at least one direction. Preferably, the bent coated glass sheet includes a radius of curvature of 500 mm to 20,000 mm in at least one direction. More preferably, the heat-bent coated glass sheet includes a radius of curvature of 1,000 mm to 8,000 mm in at least one direction. The vehicle glass can be bent as known to those skilled in the art, for example, preferably as described in US10995029B2, EP3538498B1, US11434161B2, WO2018220394A1, and WO2020021273A1.

[0045] Preferably, the vehicle glass is a reinforced vehicle glass, meaning that the vehicle glass includes at least one glass substrate that has been reinforced, making it less susceptible to damage than an annealed glass substrate. Reinforced vehicle glass is particularly advantageous because this reinforcement enhances user safety. In some cases, it may be necessary to use reinforced vehicle glass to meet regulatory requirements. Reinforcement can be achieved by thermally toughening or chemically toughening the glass substrate of the vehicle glass.

[0046] In some embodiments, the vehicle includes at least one heat-toughened glass substrate. The strength of the heat-toughened glass substrate is preferably at least four times that of annealed glass of similar thickness. Preferably, the strengthened vehicle glass component includes a heat-toughened glass substrate with a compressive stress of 400 to 1500 kg / m² on its surface. 2 Preferably 750 to 1500 kg / m 2 .

[0047] In some implementations, the vehicle glass component includes at least one chemically toughened glass substrate.

[0048] Vehicle glass can be laminated, where a glass substrate carrying a cerium oxide layer is attached to another glass substrate via an interlayer (typically an interlayer containing polyvinyl butyral (PVB)). Laminated vehicle glass is mandatory for certain vehicle openings, such as windshields. In cases where the vehicle glass is laminated, the surface carrying the cerium oxide layer is not adjacent to the interlayer. The interlayer can comprise a single ply or multiple plies. Plies can be provided to reduce sound transmission, or reduce the transmission of electromagnetic radiation at specific wavelengths, or reduce or increase the reflection of electromagnetic radiation at specific wavelengths. Laminated vehicle glass can be composite laminated vehicle glass—such vehicle glass comprises a chemically toughened glass substrate and an annealed or heat-toughened glass substrate attached together via an interlayer. Composite laminated vehicle glass typically has a chemically toughened glass substrate that is thinner than the annealed or heat-toughened glass substrate.

[0049] Laminated glass pieces can be provided as is known to those skilled in the art, for example, preferably as described in WO2021038214A1, WO2021180954A1, US20080318028A1, and US20010019759A1.

[0050] The glass component can be adapted for mounting in a vehicle opening by adding a seal, an encapsulation, or a fastener. The glass component can be adapted to hold the fastener through at least one hole (e.g., one, two, three, four, or more than four holes) drilled through the substrate. If the substrate has at least one hole drilled through it, the substrate can be toughened after drilling.

[0051] Considering their visible light transparency, coating sequence, film resistance, energy efficiency, and formability, vehicle glass components can be adapted to fit these openings. Typical vehicle glass components are provided with shielding strips, as known to those skilled in the art.

[0052] It is preferable to perform edge-work on the glass components to reduce the risk of injury to vehicle occupants, where the vehicle glass components can be opened after installation, such as side windows.

[0053] Vehicle glass components may be provided with a low emissivity and / or infrared radiation reflective coating to improve the energy efficiency of the glass component. In some embodiments, the second surface comprises a low emissivity and / or infrared radiation reflective coating. In some embodiments where the vehicle glass component is a laminated glass component, an additional substrate carries the low emissivity and / or infrared radiation reflective coating, such as an additional glass plate or interlayer.

[0054] According to a second aspect of the present invention, a process is provided for producing vehicle glass components according to a first aspect of the present invention, the process comprising:

[0055] A glass substrate having a first surface and a second surface is provided;

[0056] Provide sputtering targets containing cerium oxide; and

[0057] Sputtering a sputtering target containing cerium to provide a cerium oxide layer directly or indirectly on the first surface.

[0058] Preferably, the glass substrate is a soda-lime-silica glass substrate. Alternatively, other glass compositions, such as borosilicates, aluminosilicates, or boroaluminosilicates, can be used.

[0059] Preferably, the sputtering target comprises titanium, preferably 50 to 95 atomic percent titanium based on titanium and cerium, more preferably 70 to 90 atomic percent titanium based on titanium and cerium, and even more preferably 75 to 85 atomic percent titanium based on titanium and cerium. Including titanium in the sputtering target can improve the conductivity of the sputtering target, thereby improving the rate of the sputtering process.

[0060] Preferably, the sputtering of the sputtering target is carried out in an atmosphere having less than 10% by volume oxygen, more preferably less than 5% by volume oxygen, and even more preferably less than 1% by volume oxygen. A person skilled in the art can evaluate the sputtering atmosphere based on the flow rate of the sputtering atmosphere gas. Preferably, the sputtering of the sputtering target is carried out in an atmosphere containing a rare gas, preferably argon or krypton. Preferably, the sputtering atmosphere has more than 50% by volume rare gas, preferably argon, and even more preferably more than 90% by volume rare gas, preferably argon.

[0061] When the sputtering process is carried out in a low-oxygen atmosphere, oxygen atoms to be supplied to the coating can be obtained from the target material. A sputtering target containing a large proportion of oxygen can be considered "ceramic". Therefore, preferably, the sputtering target is a ceramic sputtering target.

[0062] Preferably, the sputtering step is a plasma sputtering step. When using plasma sputtering, films of uniform quality and high adhesion can be obtained. In some cases, large targets can be used, allowing films to be produced on large glass sizes. Plasma sputtering methods include DC sputtering, RF sputtering, magnetron sputtering, and reactive sputtering. Preferably, the cerium oxide-containing layer is produced by magnetron sputtering. First, argon gas and optionally oxygen are introduced into the vacuum chamber in sufficient quantities to allow a voltage to be applied to the cathode on which the target material is mounted. At this time, electrons escaping from the cathode collide with Ar gas atoms, thereby ionizing the Ar gas atoms into Ar. +Ions. At this point, as argon is excited, electrons are released, thus emitting energy. Therefore, a glow discharge is produced. Due to the glow discharge, plasma is formed where ions and electrons coexist. Ar in the plasma + Ions are accelerated toward the cathode target due to the large potential difference and collide with the target surface. As a result, target atoms are displaced and ejected toward the substrate, thus forming a coating layer.

[0063] Preferably, the process further includes a surface cleaning step prior to the sputtering of the sputtering target. Such a step can improve the durability and / or appearance of the coating. Preferably, surface cleaning includes one or more of the following: polishing with cerium oxide; cleaning with an alkaline aqueous solution; rinsing with deionized water; and plasma treatment. Alternatively or concurrently, other cleaning methods may be used, such as those known to those skilled in the art.

[0064] Preferably, the sputtering target is a cylindrical sputtering target. Cylindrical sputtering targets can be used to improve the uniformity of the resulting coating and / or to provide high-quality coatings in a repeatable manner.

[0065] Prior to applying the cerium oxide-containing layer, the substrate can be thermally toughened, chemically toughened, and / or bent. However, it is most preferred to toughen and / or bend the substrate by a heat treatment step after applying the cerium oxide-containing layer. Therefore, preferably, the process further includes a step of heat-treating the soda-lime-silicon glass substrate after the step of sputtering the sputtering target, preferably wherein the step of heat-treating the soda-lime-silicon glass substrate includes heating the soda-lime-silicon glass substrate to at least 450°C for at least 5 minutes.

[0066] The inventors have discovered that cerium-containing layers produced by this method are suitable for such heat treatment because they do not undergo significant damage, as indicated by minimal changes in transparency, haze, and durability after heat treatment. Therefore, the cerium-containing layer is considered "heat-treatable." This is highly advantageous because the coating can be applied on a large scale by the glass manufacturer and then cut and toughened as required for vehicle glass components. Thus, high-quality hydrophobic glass can be supplied to vehicle glass manufacturers requiring minimal processing changes, and preferably no changes to the manufacturer's processing steps.

[0067] As described above, in some embodiments, the corrosion-resistant coated glass substrate may include an underlayer between the cerium oxide-containing layer and the first surface, and preferably the underlayer comprises silicon oxide. When the coated glass substrate includes an underlayer, this can be formed by a coating method that is the same as or different from the coating method used for the cerium oxide-containing layer.

[0068] In one embodiment, the underlayer, preferably a silicon oxide underlayer, is produced by sputtering, and the cerium oxide-containing layer is also produced by sputtering. This allows for the acquisition of high-quality products. Those skilled in the art are familiar with methods for providing layers such as underlayers via sputtering.

[0069] In alternative embodiments, the underlayer, preferably a silicon oxide underlayer, is produced by chemical vapor deposition (CVD), preferably “in-line” CVD during a float glass process, and the cerium oxide-containing layer is produced by sputtering. This allows for increased production speeds. The silicon oxide layer can be deposited using CVD (also known as pyrolysis deposition) as disclosed in US 2018118613 A1, which is incorporated herein by reference. Typically, pyrolysis deposition of the underlayer involves contacting the substrate surface with a precursor mixture comprising a silicon source, an oxygen source, and optionally a free radical scavenger. The silicon source may comprise oxygen-containing silicon compounds, such as alkoxysilanes (e.g., tetraethyl orthosilicate, TEOS) and / or silicon halides (e.g., silicon chloride). However, preferably, the silicon source comprises silanes, more preferably silane SiH4. Pyrolysis deposition of silicon oxide can advantageously be combined with the fabrication of the glass substrate in a known float glass manufacturing process. It has been found that the silicon oxide underlayer produced by CVD improves coating durability compared to a sputtered silicon oxide underlayer. Furthermore, compared to a cerium oxide-containing coating with a silicon oxide-containing underlayer produced by sputtering, the measured water contact angle of the cerium oxide-containing coating is improved by using a silicon oxide-containing underlayer produced by chemical vapor deposition.

[0070] In some embodiments, the underlayer can be applied to the first surface by applying a liquid coating precursor, preferably comprising a silazane, preferably a polysilazane, or an orthosilicate, preferably tetraethyl orthosilicate (TEOS). Methods for producing the underlayer from a liquid coating precursor comprising a polysilazane are disclosed, for example, in WO 2017187173 A1, which is incorporated herein by reference. The method of applying the liquid coating precursor to the surface is generally not critical, and various techniques can be used. Contacting the surface with the coating composition can include, for example, methods selected from: dip coating, spin coating, roll coating, spray coating, air atomization spraying, ultrasonic spraying, and / or slot die coating. Preferably, the liquid coating precursor is cured after application to provide a coating.

[0071] Aspects of the first implementation scheme can be applied to the second implementation scheme in any combination, and vice versa.

[0072] According to a third aspect of the invention, the use of a cerium oxide-containing layer as a durable and long-life hydrophobic surface on vehicle glass components is provided, wherein: the glass substrate includes a first surface and a second surface;

[0073] The cerium oxide-containing layer is directly or indirectly on the first surface;

[0074] The cerium oxide-containing layer is the outermost layer on the first surface; and

[0075] Based on all components, the cerium oxide-containing layer contains 0.5 to 20 atomic percent cerium.

[0076] Aspects of the first and second embodiments can be applied to the third embodiment in any combination, and vice versa.

[0077] According to a fourth aspect of the invention, a vehicle is provided, which includes vehicle glass components manufactured according to the first aspect or the second aspect.

[0078] Aspects of the first, second, and third implementation schemes can be applied to the fourth implementation scheme in any combination, and vice versa.

[0079] Those skilled in the art will understand that optional or preferred features of this invention may be applied to other aspects as needed and required. Attached Figure Description

[0080] The invention will now be described by way of example only and with reference to the accompanying drawings, in which:

[0081] Figure 1 A vehicle glass component according to an embodiment of the present invention is schematically shown;

[0082] Figure 2 A vehicle glass component according to an embodiment of the present invention is schematically shown, comprising a base layer.

[0083] Figure 3 schematically shown Figure 1 A cross-section of an alternative implementation scheme for vehicle glass components.

[0084] Figure 4 schematically shown Figure 1 A cross-section of an alternative implementation scheme for vehicle glass components. Detailed Implementation

[0085] Figure 1 A vehicle glass component 100 is schematically shown, comprising a soda-lime-silica glass substrate having a first surface 101. The first surface includes a cerium oxide-containing layer (not shown), wherein the cerium oxide-containing layer is the outermost layer on the first surface 101.

[0086] Figure 2 schematically shown Figure 1A cross-section of an embodiment of a vehicle glass component 100 includes: a substrate 111 of soda-lime-silica glass having a first surface 101, and a cerium oxide-containing layer 121 directly on the first surface 101, wherein the cerium oxide-containing layer 121 is the outermost layer on the first surface 101. While the cerium oxide-containing layer 121 in this embodiment is directly on the first surface 101, in an alternative embodiment of the invention, the vehicle glass component further includes an underlayer between the cerium oxide-containing layer 121 and the first surface 101. In this embodiment, a low emissivity and / or infrared radiation reflective coating 122 is adjacent to a second surface 102 of the glass substrate 110. In an alternative embodiment, the low emissivity and / or infrared radiation reflective coating 122 may be omitted. An additional layer containing cerium oxide may be on the outer surface of the coating 122.

[0087] Figure 3 schematically shown Figure 1 A cross-section of an alternative embodiment of the vehicle glass component 100 includes: a substrate of soda-lime-silica glass 111 having a first surface 101, and a cerium oxide-containing layer 121 directly on the first surface 101, wherein the cerium oxide-containing layer 121 is the outermost layer on the first surface 101. While the cerium oxide-containing layer 121 in this embodiment is directly on the first surface 101, in an alternative embodiment of the invention, the vehicle glass component also includes an underlayer between the cerium oxide-containing layer 121 and the first surface 101. In this embodiment, a low emissivity and / or infrared radiation reflective coating 122 is adjacent to a second surface 102 of the glass substrate 111. In an alternative embodiment, the low emissivity and / or infrared radiation reflective coating 122 may be omitted. This embodiment also includes an additional glass substrate 112 attached to the soda-lime-silica glass substrate 111 via an interlayer 131. The additional cerium oxide layer may be on the outer surface of the additional glass substrate 112.

[0088] Figure 4 schematically shown Figure 1A cross-section of an alternative embodiment of the vehicle glass component 100 includes: a soda-lime-silica glass substrate 111 having a first surface 101, and a cerium oxide-containing layer 121 directly on the first surface 101, wherein the cerium oxide-containing layer 121 is the outermost layer on the first surface 101. While the cerium oxide-containing layer 121 in this embodiment is directly on the first surface 101, in an alternative embodiment of the invention, the vehicle glass component also includes an underlayer between the cerium oxide-containing layer 121 and the first surface 101. This embodiment also includes a further glass substrate 112 attached to the soda-lime-silica glass substrate 111 via an interlayer 131. In this embodiment, a low emissivity and / or infrared radiation reflective coating 122 is interposed between the further glass substrate 112 and the interlayer 131. The additional cerium oxide layer may be on the outer surface of the further glass substrate 112.

[0089] The present invention is further illustrated by the following embodiments, but the present invention is not limited to the following embodiments.

[0090] An embodiment of the invention is prepared by sputtering a rotatable ceramic target comprising 65 wt% TiO2 and 35 wt% CeO2 (corresponding to 80.0 atomic% titanium and 20.0 atomic% cerium based on cerium and titanium, and corresponding to 26.7 atomic% titanium, 6.7 atomic% cerium, and 66.7 atomic% oxygen based on all components), wherein the rotatable ceramic target is 23 inches in length and 5.914 inches in diameter. This forms a structure comprising cerium, titanium, and oxygen (CeTiO2). x () layer.

[0091] By including CeTiO x Examples 1 to 3 were prepared by directly sputtering a layer onto a soda-lime-silicon glass substrate, while examples 1 to 3 were prepared by sputtering a layer containing CeTiO2 directly onto a soda-lime-silicon glass substrate. x Examples 4 to 6 were prepared by sputtering a layer onto a silicon oxide-containing substrate. In these examples, a silicon oxide-containing substrate with a thickness of 20 to 30 nm was prepared using chemical vapor deposition. Comparative Example 1 (CE1) was uncoated float glass, and Comparative Example 2 (CE2) was commercially available PFAS.

[0092] The features of the embodiment are as follows:

[0093] Water contact angle—The average water contact angle (n=5) of a 10×10 cm sample was measured using FTA200 and FTA32 software (both available from First Ten Angstroms, Newark, CA, USA) with deionized water (50 μl deionized water droplets). Samples coated with glass substrates were tested after deposition and then again after the durability evaluation step to evaluate the long-term properties of the hydrophobicity.

[0094] Table 1 depicts the average water contact angle of the examples measured after deposition (AD).

[0095] Table 1

[0096]

[0097] As can be seen from Table 1, compared with untreated glass with a water contact angle of 25°, CeTiO₂… x Substrates with unusually high water contact angles greater than 60° can be obtained. High water contact angles are associated with lower water-surface energy, resulting in easier removal of water from the surface.

[0098] In fact, a high water contact angle can be achieved with a coating only 10 nm thick. Meanwhile, a 50 nm thick CeTiO₂ coating can also be used. x The coating achieves an exceptionally high water contact angle, and the presence of a silica underlayer significantly improves the aging performance of this coating.

[0099] Therefore, in embodiments where a silicon oxide underlayer is desired, CeTiO is preferred. x The layer thickness is greater than 10 nm, preferably 25 nm or greater, more preferably 50 nm or greater, for example, greater than 10 nm to 500 nm, preferably 25 nm to 250 nm, more preferably 50 nm to 100 nm. Note that the water contact angle increases to a stable value with aging.

[0100] Oil Rub – Using a Sheen Instruments Ltd 903 wet rub tester, an oil-soaked felt pad is passed over the coated side of the sample under an applied load of 0.9 kg. The sample is placed on the apparatus with the coating on top and secured using clamps. A square felt block (1.2 cm square) cut from an Erichsen felt strip (DIN 68 861) is immersed in microscopic impregnation oil from Merck Chemicals Ltd. It is placed on glass and rubbed back and forth across the sample surface 50 or 500 times. The scratches on the sample are examined and compared with an image from a reference sample to be rated according to an oil rub test layering scale from 0 to 9, with lower scores being better. If all coating is removed, the sample is rated 10. Table 3 depicts the oil rub results and average water contact angle after the test. The water contact angle was measured before and after the test. Preferably, when subjected to the oil friction 50 and / or oil friction 500 tests as detailed herein, the vehicle glass component according to the invention achieves a score of 5 or less, preferably 3 or less, more preferably 0. Preferably, after the oil friction 50 and / or oil friction 500 tests as detailed herein, the vehicle glass component according to the invention achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55°.

[0101] Mini-brush test—Using a Sheen Instruments Ltd wet abrasion tester 903, a moistened mink brush is passed over the coated side of the sample under a given load. The sample is placed on the apparatus with the coating on top and secured with clamps. A water droplet approximately 2.5 cm in diameter is placed on the sample, directly below the brush head. The brush is placed on the glass and rubbed back and forth across the sample surface 500 times. The scratches on the sample are examined and compared with an image from a reference sample to be rated on a scale of 0 to 4, with lower scores indicating better performance. A score of 0 can be given for imperceptible abrasion. A score of 1 or 2 is considered a pass, and a score of 3 or 4 is considered a failure. The water contact angle is measured before and after the test. Preferably, when subjected to the mini-brush test detailed herein, the vehicle glass component according to the invention achieves a score of 5 or less, preferably 3 or less, more preferably 0. Preferably, the vehicle glass component according to the invention achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55° after oil friction 50 and / or oil friction 500 tests as detailed herein.

[0102] Alkali Corrosion Testing — The examples and comparative examples were subjected to alkali corrosion testing, in which the heat-treated samples were immersed in 1M NaOH at 23°C for 2 hours.

[0103] The haze variation was evaluated according to ASTM D1003 (BYK Gardner Haze-gard plus), as shown in Table 2; and the transmittance variation was evaluated, as shown in Table 3.

[0104] Table 2

[0105]

[0106] Table 3

[0107]

[0108] Table 2 shows that all measured samples exhibited extremely low haze both initially and after the alkaline corrosion test, indicating the excellent corrosion resistance provided by the CeTiOx coating. Similarly, Table 3 shows the effect of increasing CeTiO2... x The thickness of the coating reduces transmittance, but the presence of the silicon oxide underlayer increases or only slightly reduces transmittance. The change in transmittance caused by the alkaline corrosion test is negligible. Preferably, the vehicle glass component according to the invention achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55° after the alkaline immersion corrosion test detailed herein.

[0109] Acid corrosion test—Acid corrosion tests were performed on the examples and comparative examples, in which the heat-treated samples were immersed in 1M HCl at 23°C for 2 hours. Haze changes were evaluated according to ASTM D1003 (BYK Gardner Haze-gard plus), as shown in Table 4, and transmittance changes were evaluated, as shown in Table 5.

[0110] Table 4

[0111]

[0112] Table 4 shows that all measured samples exhibited extremely low haze both initially and after acid corrosion testing, demonstrating the excellent corrosion resistance provided by the CeTiOx coating.

[0113] Table 5

[0114]

[0115] Table 5 shows that the transmittance change caused by acid corrosion testing is negligible.

[0116] Therefore, CeTiO can be used. x The coating is used to produce a heat-treated coated glass substrate with excellent corrosion resistance, and preferably, the vehicle glass exhibits a haze increase of 1% or less after immersion in 1M NaOH or 1M HCl at 23°C for 2 hours. Preferably, the vehicle glass according to the invention achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55° after the acid immersion corrosion test detailed herein.

[0117] Preferably, the vehicle glass component according to the invention passes EN1096A on the surface bearing the cerium oxide coating and achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55° after one or more tests according to EN1096 A.

[0118] Preferably, the vehicle glass component according to the invention passes EN1096B for the surface bearing the cerium oxide coating and achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55° after one or more tests according to EN1096 B.

[0119] Preferably, the vehicle glass component according to the invention passes the dry abrasion and scratch resistance test ASTM D6037 applied to the surface bearing the cerium oxide coating, and achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55° after one or more tests according to ASTM D6037.

[0120] Preferably, the vehicle glass component according to the invention passes a scratch test according to ASTM E 2546 or ISO 14577 on the surface bearing the cerium oxide coating, and achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55° after one or more tests according to ASTM D6037 or ISO 14577.

[0121] Preferably, the vehicle glass component according to the invention has passed accelerated UV aging tests according to ASTM D 523 and / or ASTM D 2244 on the surface bearing the cerium oxide coating, and achieves a water contact angle of at least 30°, preferably at least 40°, more preferably at least 50°, and even more preferably at least 55° after one or more tests according to ASTM D 523 or ASTM D 2244.

[0122] Furthermore, the coated glass substrate responds very well to heat treatment, thus providing a heat-treatable coated glass substrate that can be heat-treated to produce a heat-treatable coated glass substrate with a durable and long-life hydrophobic surface and excellent corrosion resistance.

[0123] This manual covers vehicle glass components such as side windows, rooflights, windshields, side windows, quarterlights, etc. In addition, such vehicle glass components include other exterior glass areas of the vehicle, such as spandrels and finishers, as well as other interior glass areas of the vehicle, such as displays, consoles, fascia pieces, etc.

Claims

1. A vehicle glass component having a durable and long-life hydrophobic surface, comprising: A glass substrate having a first surface and a second surface; and A cerium oxide-containing layer directly or indirectly on the first surface, wherein: The cerium oxide-containing layer is the outermost layer on the first surface; as well as Based on all components, the cerium oxide-containing layer contains 0.5 to 20 atomic percent cerium.

2. The vehicle glass component according to claim 1, wherein, The cerium oxide-containing layer contains Ce x Ti y O z Furthermore, the atomic ratio of Ce in the base layer, based on Ce and Ti, is 0.5 to 0.95, more preferably 0.50 to 0.90, more preferably 0.55 to 0.85, more preferably 0.60 to 0.80, and even more preferably 0.62 to 0.67, in x / (x+y) terms.

3. The vehicle glass component according to claim 1 or claim 2, wherein, The thickness of the cerium oxide-containing layer is 1 nm to 500 nm, preferably 5 nm to 250 nm, and more preferably 10 nm to 100 nm.

4. The vehicle glass component according to any of the preceding claims, wherein, The cerium oxide-containing layer is the only layer on the first surface.

5. The vehicle glass component according to any one of claims 1 to 3, further comprising an underlayer between the cerium oxide-containing layer and the first surface.

6. The vehicle glass component according to claim 5, wherein, The underlying layer comprises silicon oxide, preferably the silicon oxide-containing underlying layer is directly on the first surface, more preferably the silicon oxide-containing underlying layer is directly on the first surface, and the cerium oxide-containing layer is directly on the underlying layer.

7. The vehicle glass component according to any of the preceding claims, wherein, The cerium oxide-containing layer contains 1 to 10 atomic% cerium based on all components, preferably 2 to 8 atomic% cerium based on all components.

8. The vehicle glass component according to any of the preceding claims, wherein, The cerium oxide-containing layer further comprises titanium, preferably comprising 50 to 95 atomic percent titanium based on titanium and cerium, more preferably comprising 70 to 90 atomic percent titanium based on titanium and cerium, and even more preferably comprising 75 to 85 atomic percent titanium based on titanium and cerium.

9. The vehicle glass component according to any of the preceding claims, wherein, The cerium oxide-containing layer contains less than 10 atomic% silicon based on all components, preferably less than 1 atomic% silicon based on all components, and more preferably substantially free of silicon.

10. The vehicle glass component according to any of the preceding claims, wherein, The cerium oxide-containing layer contains less than 10 atomic% aluminum based on all components, preferably less than 1 atomic% aluminum based on all components, and more preferably substantially free of aluminum.

11. The vehicle glass component according to any of the preceding claims, wherein, The coated glass substrate exhibits the following water contact angle: greater than 30°, preferably greater than 50°, and even more preferably greater than 60°.

12. The vehicle glass component according to any of the preceding claims, wherein, The second surface comprises a coating with low emissivity and / or infrared radiation reflection.

13. The vehicle glass component according to claim 12, wherein, The low emissivity and / or infrared radiation reflective coating comprises a transparent conductive layer, preferably a transparent conductive silver layer or a transparent conductive metal oxide layer.

14. The vehicle glass component according to any one of the preceding claims, wherein, The vehicle glass is a curved and / or reinforced vehicle glass.

15. The vehicle glass component according to any of the preceding claims, wherein, The vehicle glass component is a laminated vehicle glass component.

16. The vehicle glass component according to any of the preceding claims, wherein, The vehicle glass component is a windshield, side window, rear window, or sunroof, preferably a car windshield, side window, rear window, or sunroof.

17. A process for producing vehicle glass components according to any one of claims 1-16, wherein, The process includes: Provide a glass substrate having a first surface; Provide sputtering targets containing cerium oxide; and Sputtering a cerium-containing sputtering target to provide a cerium oxide layer directly or indirectly on the first surface.

18. The process according to claim 17, wherein, The sputtering target contains titanium, preferably 50 to 95 atomic percent titanium based on titanium and cerium, more preferably 70 to 90 atomic percent titanium based on titanium and cerium, and even more preferably 75 to 85 atomic percent titanium based on titanium and cerium.

19. The process of any one of claims 17 to 18, further comprising a step of heat-treating the soda-lime-silicon glass substrate after the step of sputtering the sputtering target, preferably wherein the step of heat-treating the soda-lime-silicon glass substrate comprises heating the soda-lime-silicon glass substrate to at least 600°C for at least 5 minutes.

20. The method according to any one of claims 17 to 19, further comprising the step of bending the substrate.

21. The method according to claim 20, wherein, The step of bending the substrate occurs before the step of sputtering the sputtering target.

22. The method according to claim 21, wherein, The step of bending the substrate follows the step of sputtering the sputtering target.

23. The process according to any one of claims 17 to 22 further includes the step of applying an underlayer to the first surface, wherein the step of applying the underlayer preferably includes depositing a silicon oxide-containing layer by chemical vapor deposition, physical vapor deposition, or liquid deposition, preferably by chemical vapor deposition.

24. The use of cerium oxide-containing layers as durable and long-life hydrophobic surfaces on vehicle glass components, wherein: The glass substrate includes a first surface; The cerium oxide-containing layer is directly or indirectly on the first surface; The cerium oxide-containing layer is the outermost layer on the first surface; as well as Based on all components, the cerium oxide-containing layer contains 0.5 to 20 atomic percent cerium.

25. A vehicle comprising a glass element according to any one of claims 1 to 15, or a glass element produced according to any one of claims 15 to 22, preferably an automobile.

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