Vehicle glazing

Abstract

The present invention relates to a vehicle glazing having an outermost layer comprising 0.5 to 20 atomic percent of cerium based on its total composition, and a method for producing such a vehicle glazing, which involves sputtering a sputtering target comprising cerium oxide to prepare a layer directly or indirectly on a first surface, and also relates to using the layer comprising cerium oxide as a durable and long-lasting water-repellent surface on the vehicle glazing, as well as to a vehicle having a vehicle glazing having an outermost layer comprising 0.5 to 20 atomic percent of cerium based on its total composition.

Description

[Technical Field]

[0001] The present invention relates to vehicle glazing, particularly vehicle glazing having a durable and long-lasting water-repellent surface, a method for manufacturing such vehicle glazing, and the use of a layer comprising cerium oxide as a durable and long-lasting water-repellent surface on vehicle glazing.

[0002] The ease with which water can be removed from vehicle glazing is desirable to prevent obstruction of light transmission to occupants or sensors through the glazing. Glass surfaces are typically hydrophilic, causing water to spread across the surface in a "sheet-like" manner. This water layer is difficult to remove and can obstruct the view of occupants or machinery through the glazing. To reduce water sheeting, the glazing surface can be made more hydrophobic. The use of a hydrophobic surface prevents water sheeting, allowing water to bead up into droplets, which can be removed more easily. Therefore, a hydrophobic surface is associated with improved visibility through the glazing.

[0003] Furthermore, it is desirable to reduce the weight of existing vehicles, especially electric vehicles, and improve their fuel efficiency and driving range.

[0004] Water droplets on water-repellent surfaces can be removed more easily by wiper blades. This allows for the use of lighter wiper blades and lower-power, lighter wiper motors, reducing motor energy consumption and overall vehicle weight, resulting in improved fuel efficiency and driving range.

[0005] Furthermore, the use of a water-repellent coating may eliminate the need for wipers, reducing the vehicle's weight by eliminating the need for wipers, wiper motors, and associated wiring. Such weight reduction is particularly desirable in electric vehicles, such as electric cars.

[0006] In addition, compared to hydrophilic surfaces, water droplets are more easily removed by air resistance from glazing surfaces that are not wiped by wiper blades, such as side lights. This is because less energy is required to remove water droplets from the surface.

[0007] Coatings on substrates, particularly glass substrates, can be used to modify the properties of the substrate. Multiple methods can be used to deposit coatings on glass substrates, including liquid-based methods such as spin coating, dip coating, and spray coating, as well as chemical vapor deposition (CVD) and physical vapor deposition (PVD). PVD is also known as sputtering. Conventionally, to make glazing surfaces water-repellent with water-repellent coatings, for example, sol-gel compositions of hybrid organic-inorganic precursors, modified silanes containing sol-gel additives, or modified silanes that are chemically crosslinked after surface treatment have been used. Other products include reactive silicone fluids for forming easy-to-clean polymer coatings on surfaces, and polymer resins for providing low-maintenance, non-stick surfaces.

[0008] However, many of these conventional water-repellent coatings do not adhere sufficiently durablely to the glazing for the entire lifespan of the vehicle or glazing, and are dispersed into the environment over time. This is particularly problematic if the coating contains substances harmful to the environment. One class of substances considered harmful is perfluoroalkyl and polyfluoroalkyl substances (PFAS). Certain PFAS are undesirable because they are classified as persistent organic pollutants (POPs). POPs are organic substances that remain in the environment and accumulate in living organisms, causing harm. Other PFAS are not currently banned, but are undesirable to consumers. Therefore, it is desirable to provide water-repellent coatings that do not release PFAS into the environment. Furthermore, the short lifespan of conventional water-repellent coatings is due to their low durability, requiring repeated application over time, and each time they are released into the environment, further increasing the potential for adverse environmental impacts. [Overview of the project]

[0009] Therefore, the object of the present invention is to solve problems with known products or methods and to provide a vehicle glazing that has a long lifespan, low water-surface adhesion, and is less likely to introduce harmful substances into the environment.

[0010] In a first aspect of the present invention, a vehicle glazing is provided having a durable and long-lasting water-repellent surface, comprising a glass substrate having a first surface and a second surface, and a layer comprising cerium oxide directly or indirectly disposed on the first surface, wherein the layer comprising cerium oxide is the outermost layer on the first surface, and the layer comprising cerium oxide comprises 0.5 to 20 atomic percent of cerium based on its total composition.

[0011] The inventors have found that an outermost layer comprising cerium oxide as described in the present invention provides a coating that exhibits excellent water-repellent properties, and therefore provides a vehicle glazing with low water-surface adhesion. Furthermore, the outermost layer comprising cerium oxide is far more durable than conventional water-repellent coatings, maintaining its water repellency over a long period of time and being less likely to spread into the environment. Moreover, the layer comprising cerium oxide does not contain PFAS, and the excellent water-repellent properties are obtained without the use of perfluoroalkyl or polyfluoroalkyl substances, thus causing less adverse environmental impact.

[0012] According to the present invention, vehicle glazing shall be durable if the surface satisfies the following conditions: achieving a score of 5 or less, preferably 3 or less, and more preferably 0, when subjected to the oil friction 50 test as detailed herein; and / or achieving a score of 5 or less, preferably 3 or less, and more preferably 0, when subjected to the minibrush test as detailed herein; and / or passing a dry abrasion scratch resistance test in accordance with ASTM D6037.

[0013] According to the present invention, a vehicle glazing shall have a long-lasting water-repellent surface if the surface satisfies the following conditions: achieving 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 a test selected from the list consisting of oil friction 50, oil friction 500, minibrush as described herein, or dry abrasion scratch resistance in accordance with ASTM D6037.

[0014] Preferably, the first surface does not include a layer comprising a perfluoroalkyl or polyfluoroalkyl substance.

[0015] Preferably, the glass substrate is a soda-lime silica glass substrate. Alternatively, other glass compositions such as borosilicate, aluminosilicate, or boroaluminosilicate may be used.

[0016] The cerium oxide layer is the outermost layer on the first surface. When the cerium oxide layer is the outermost layer on the first surface, the cerium oxide layer is directly exposed to the vehicle glazing environment.

[0017] A layer comprising cerium oxide is present on a first surface, and the first surface comprises a layer comprising cerium oxide. The first surface may be coated substantially entirely with a layer comprising cerium oxide. In this case, the entire vehicle glazing is provided by the coating, and a water-repellent effect is imparted to the entire glazing. When the vehicle glazing is a fixed vehicle glazing such as an automotive windshield, taillight, or roof light, it is desirable that the entire vehicle glazing be provided by the coating, and that the first surface be coated substantially entirely with a layer comprising cerium oxide.

[0018] When a wiper is provided in a vehicle glazing, it may be desirable to include a layer containing cerium oxide in the area swept by the wiper blade to improve wiper efficiency. Alternatively, the area swept by the wiper blade may not contain a layer containing cerium oxide, while other areas may contain a layer containing cerium oxide.

[0019] In some embodiments, a camera or sensor is provided in the vehicle glazing. Particularly beneficial is the provision of a cerium oxide layer in a first surface region (defined herein as the sensor region) that the electromagnetic radiation must pass through to reach the camera or sensor, when the vehicle glazing is provided with a camera or sensor that receives electromagnetic radiation.

[0020] Water droplets in the sensor area can degrade the clarity of the camera or sensor, potentially leading to image quality degradation and malfunctions in autonomous driving assistance systems associated with the camera or sensor. A layer containing cerium oxide improves the water repellency of the sensor area, reducing the energy required to remove water droplets and thus decreasing the number of water droplets that may be present in the sensor area, thereby preventing degradation of camera or sensor clarity.

[0021] Particularly preferable is a layer comprising cerium oxide in the sensor area when the sensor area is not within the area of ​​vehicle glazing swept by the wiper, thereby enabling effective removal of water droplets by air pressure alone.

[0022] In some embodiments, the vehicle glazing is adapted such that a first surface comprising a layer comprising cerium oxide is disposed facing the outside of the vehicle. This is particularly beneficial considering the water repellency outside the vehicle. However, in other embodiments, the vehicle glazing is adapted such that a first surface having a layer comprising cerium oxide is disposed facing the inside of the vehicle. This is particularly beneficial when a water-repellent surface is desired inside the vehicle, for example in multi-passenger vehicles or public transportation vehicles, since the surface can be more easily cleaned. Further, the water-repellent surface on the inner surface of the glazing provided by the layer comprising cerium oxide reduces the effect of condensation, and water droplets condensed on the inner surface move easily by gravity alone. In some embodiments, the vehicle glazing comprises a layer comprising cerium oxide on both the outer and inner surfaces.

[0023] Preferably, the layer comprising cerium oxide is homogeneous with respect to cerium. A layer comprising cerium oxide that is homogeneous with respect to cerium has cerium atoms uniformly dispersed throughout the coating layer. Preferably, the cerium atoms are present within an amorphous or semi-amorphous coating layer applied to the first surface, which includes those provided by sputtering. Preferably, the cerium atoms do not exist within nanoparticles, and the layer comprising cerium oxide does not comprise particles and / or nanoparticles. A layer that is homogeneous with respect to cerium and does not contain particles and / or nanoparticles may be less prone to wear by a wiper blade since the surface roughness is reduced. Further, certain nanoparticles may not be acceptable to consumers.

[0024] Advantageously, the vehicle glazing has corrosion resistance, as indicated by a relatively low increase in haze after weathering. Weathering is accelerated by high humidity, heating or heating / cooling cycles, and for test purposes, weathering can be simulated by holding the glass at high temperature and high humidity for a predetermined period. Usually, the measured haze of the coated glass (e.g., using a haze meter) is 25% or less, preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and most preferably 5% or less after 50 days at 98% relative humidity and 60 °C. Preferably, the corrosion-resistant coated glass substrate has a haze increase of 55% or less, more preferably 35% or less, and most preferably 24% or less after 50 days at 98% relative humidity and 60 °C. The haze increase can be calculated by comparing the measured haze before and after weathering.

[0025] Generally, the thickness of the layer comprising cerium oxide can be 1 nm or more, preferably 10 nm or more, more preferably 20 nm or more, and most preferably 30 nm or more. If the coating is too thin, sufficient durability and effects may not be obtained. The thickness of the layer comprising cerium oxide is preferably 500 nm or less, preferably 250 nm or less, more preferably 100 nm or less, and most preferably 50 nm or less. If the coating is too thick, cracks may occur during heat treatment or strengthening steps, and the manufacturing cost may increase.

[0026] Therefore, preferably, the thickness of the layer comprising cerium oxide is in the range of 1 nm to 500 nm, preferably 5 to 250 nm, and more preferably 10 to 100 nm. Such a thickness is advantageous because it provides a good balance of corrosion protection, durability, and manufacturing economy.

[0027] The layer comprising cerium oxide usually has a refractive index in the range of 2.28 to 2.44.

[0028] In some embodiments, it is preferred that the layer comprising cerium oxide is the only layer on the first surface. However, in other embodiments, it is preferred that an underlayer is provided between the layer comprising cerium oxide and the first surface. Preferably, the underlayer comprises silicon oxide. Such a substrate can improve the adhesion and durability of the cerium oxide layer. Preferably, the silicon oxide substrate is placed directly on the first surface. This further improves the adhesion and durability of the coating on the substrate.

[0029] In one preferred embodiment, a substrate comprising silicon oxide is directly placed on the first surface, and a layer comprising cerium oxide is directly placed on top of the silicon oxide substrate. This layer arrangement provides excellent adhesion and durability of the coating layer in an efficient manner.

[0030] Preferably, the cerium oxide layer comprises 1 to 10 atomic percent of cerium based on the total composition, and more preferably 2 to 8 atomic percent of cerium based on the total composition. Such a range has been shown to provide excellent water repellency.

[0031] Preferably, the layer comprising cerium oxide contains oxygen in a quasi-stoichiometric ratio.

[0032] Preferably, the layer comprising cerium oxide further comprises titanium, preferably the layer comprising cerium oxide comprises 50 to 95 atomic percent of titanium based on titanium and cerium, more preferably 70 to 90 atomic percent of titanium based on titanium and cerium, and even more preferably 75 to 85 atomic percent of titanium based on titanium and cerium.

[0033] The inventors found that a layer comprising cerium oxide and titanium is a highly durable coating with particularly excellent corrosion resistance and cleanability. Furthermore, the inventors found that such a coating can be easily formed by sputtering.

[0034] Preferably, cerium oxide and titanium, i.e., Ce x Ti y O zWhen the layer comprising is a layer comprising cerium oxide, the atomic ratio of Ce (calculated as x / (x+y)) based on Ce and Ti in the base layer is 0.5 to 0.95, more preferably 0.50 to 0.90, 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 found that such a range provides a particularly durable and long-lasting water-repellent coating.

[0035] Preferably, the cerium oxide layer contains less than 10 atomic percent silicon based on the total components, preferably the cerium layer contains less than 1 atomic percent silicon based on the total components, and more preferably the cerium layer is substantially silicon-free.

[0036] Preferably, the cerium oxide layer contains less than 10 atomic percent of aluminum based on the total composition, preferably the cerium layer contains less than 1 atomic percent of aluminum based on the total composition, and more preferably the cerium layer is substantially free of aluminum.

[0037] Preferably, vehicle glazing exhibits a water contact angle greater than 30°, preferably greater than 50°, and more preferably greater than 60°. Such a water contact angle is associated with low water-surface adhesion. Therefore, as used herein, a substrate is considered water-repellent if it exhibits a water contact angle greater than 30°, preferably greater than 50°, more preferably greater than 60°, and even more preferably greater than 70°.

[0038] It is preferable that the vehicle glazing is bent and / or reinforced vehicle glazing.

[0039] Vehicle glazing is often bent to fit vehicle openings and to enhance its aesthetic appeal. Vehicle glazing can be bent by methods such as sag bending, press bending, and cold bending.

[0040] The bent vehicle glazing has a radius of curvature in at least one direction, preferably the bent coated glass sheet has a radius of curvature of 500 mm to 20,000 mm in at least one direction, and more preferably the heat-bent coated glass sheet has a radius of curvature of 1,000 mm to 8,000 mm in at least one direction. The vehicle glazing can be bent in a manner known to those skilled in the art, and preferably in the manner described in U.S. Patent No. 1,09950292, European Patent No. 3,538498, U.S. Patent No. 1,1434161, International Patent Publication No. 2018220394, and International Patent Publication No. 2020021273.

[0041] Preferably, the vehicle glazing is a reinforced vehicle glazing, that is, the vehicle glazing comprises at least one glass substrate that is reinforced to be more resistant to damage than an annealed glass substrate. Reinforced vehicle glazing is particularly advantageous because such reinforcement improves user safety. In some cases, the use of reinforced vehicle glazing may be required to meet legal regulations. Reinforcement can be achieved by thermally or chemically strengthening the glass substrate of the vehicle glazing.

[0042] In some embodiments, the vehicle comprises at least one heat-strengthened glass substrate. The heat-strengthened glass substrate preferably has at least four times the strength of annealed glass of equivalent thickness. Preferably, the strengthened vehicle glazing has a surface load of 400 to 1500 kg / m². 2 Preferably 750-1500 kg / m 2 It comprises a heat-strengthened glass substrate having compressive stress.

[0043] In some embodiments, the vehicle glazing comprises at least one chemically strengthened glass substrate.

[0044] Vehicle glazing can be laminated vehicle glazing, in which a glass substrate having a cerium oxide layer is bonded to another glass substrate, often by an intermediate layer containing polyvinyl butyral (PVB). Laminated vehicle glazing is mandatory in certain vehicle openings, such as automotive windshields. When vehicle glazing is laminated vehicle glazing, the surface having the cerium oxide layer is not adjacent to the intermediate layer.

[0045] The intermediate layer may consist of a single intermediate layer ply or multiple intermediate layer plies. Intermediate layer plies may be provided to reduce sound transmission, to reduce transmission of electromagnetic waves of a specific wavelength, or to reduce or increase reflection of electromagnetic waves of a specific wavelength. Laminated vehicle glazing may be composite laminated vehicle glazing, in which a chemically strengthened glass substrate and an annealed or heat-strengthened glass substrate are bonded by an intermediate layer. In composite laminated vehicle glazing, the chemically strengthened glass substrate is usually thinner than the annealed or heat-strengthened glass substrate.

[0046] Laminated glazing can be provided in ways known to those skilled in the art, preferably as described in, for example, International Patent Publication No. 2021038214, International Patent Publication No. 2021180954, U.S. Patent Publication No. 20080318028, and U.S. Patent Publication No. 20010019759.

[0047] Glazing can be adapted for mounting to a vehicle opening by adding seals, encapsulation, or fasteners. Glazing can be adapted to hold fasteners by drilling at least one hole in the substrate (e.g., one, two, three, four, or more than four holes). If at least one hole is drilled in the substrate, the substrate can be reinforced after drilling.

[0048] Vehicle glazing, taking into consideration visible light transmittance, sheet resistance of the coating sequence, energy efficiency, moldability, etc., is typically provided with a shielding strip, as is known to those skilled in the art, to be adaptable to these openings.

[0049] The glazing is preferably edged, and in vehicle glazing that may be opened after installation, such as side lights, it reduces the risk of injury to vehicle occupants.

[0050] Vehicle glazing may include a low-emissivity and / or infrared-reflective coating to improve the energy efficiency of the glazing. In some embodiments, a second surface is provided with a low-emissivity and / or infrared-reflective coating. In embodiments where the vehicle glazing is a laminated glazing, an additional substrate may carry the low-emissivity and / or infrared-reflective coating, such as an additional glass sheet or an intermediate layer.

[0051] A second aspect of the present invention provides a method for manufacturing vehicle glazing according to the first aspect, comprising the steps of: preparing a glass substrate having a first surface and a glass substrate having a second surface; preparing a sputtering target comprising cerium oxide; and sputtering the cerium-containing sputtering target to form a layer comprising cerium oxide directly or indirectly on the first surface.

[0052] The glass substrate is preferably a soda-lime silica glass substrate. Alternatively, other glass compositions, such as borosilicate glass, aluminosilicate glass, or borate aluminosilicate glass, may be used.

[0053] The sputtering target preferably comprises titanium, more preferably comprising 50 to 95 atomic percent of titanium based on titanium and cerium, more preferably comprising 70 to 90 atomic percent of titanium based on titanium and cerium, and even more preferably comprising 75 to 85 atomic percent of titanium based on titanium and cerium. Including titanium in the sputtering target improves the conductivity of the sputtering target, which can thereby increase the speed of the sputtering process.

[0054] The sputtering step of the sputtering target is preferably carried out in an atmosphere of less than 10 volume% oxygen, more preferably less than 5 volume% oxygen, and even more preferably less than 1 volume% oxygen. The sputtering atmosphere can be evaluated by those skilled in the art based on the flow rate of the sputtering atmosphere gas. The sputtering step of the sputtering target is preferably carried out in an atmosphere containing a noble gas, preferably argon or krypton. The sputtering atmosphere is preferably more than 50 volume% of a noble gas, preferably argon, and even more preferably more than 90 volume% of a noble gas, preferably argon.

[0055] When the sputtering step is performed in a low-oxygen atmosphere, oxygen atoms supplied to the coating may come from the target. A sputtering target that contains a lot of oxygen can be considered a "ceramic." Therefore, the sputtering target is preferably a ceramic sputtering target.

[0056] The sputtering step is preferably a plasma sputtering step. Plasma sputtering allows for the acquisition of films of uniform quality and high adhesion. In some cases, large targets can be used, enabling film deposition on large glass sizes. Plasma sputtering methods include DC sputtering, RF sputtering, magnetron sputtering, and reactive sputtering. Preferably, layers comprising cerium oxide are manufactured by magnetron sputtering. First, appropriate amounts of argon gas and, if necessary, oxygen gas are introduced into a vacuum chamber so that a voltage can be applied to the cathode on which the target material is placed. At this time, electrons emitted from the cathode collide with gas atoms of Ar gas, and Ar gas atoms are destroyed. + It is ionized into ions. In this process, argon is excited, electrons are released, and energy is released. Therefore, a glow discharge occurs. The glow discharge creates a plasma in which ions and electrons coexist. Ar in the plasma + The ions are accelerated toward the cathode target by the large potential difference and collide with the target surface. As a result, target atoms are ejected and released toward the substrate, forming a coating layer.

[0057] The process preferably further includes a step of cleaning the surface of the sputtering target before the sputtering step. Such a step may improve the durability and / or appearance of the coating layer. Surface cleaning preferably includes one or more of the following: polishing with ceria, washing with an alkaline aqueous solution, rinsing with deionized water, and plasma treatment. In addition, or instead, other cleaning methods known to those skilled in the art may be used.

[0058] The sputtering target is preferably a cylindrical sputtering target. By using a cylindrical sputtering target, the uniformity of the resulting coating layer can be improved, and high-quality coatings can be repeatedly and stably provided.

[0059] The substrate may be thermally strengthened, chemically strengthened, and / or bent before the application of the cerium oxide layer. However, it is most preferable that the substrate be strengthened and / or bent by a heat treatment step after the application of the cerium oxide layer. Therefore, the process preferably further includes a step of heat treating the soda-lime silica glass substrate after the sputtering step of the sputtering target, and preferably the heat treatment step of the soda-lime silica glass substrate includes heating the soda-lime silica glass substrate at at least 450°C for at least 5 minutes.

[0060] The inventors have found that layers comprising cerium oxide produced by this method are suitable for such heat treatment. Specifically, changes in transparency, haze, and durability after heat treatment are minimal, and they do not suffer significant damage. Therefore, layers comprising cerium oxide are considered "heat-treatable." This is highly beneficial, as the coating can be applied on a large scale by glass manufacturers and then cut and strengthened to the shapes required for vehicle glazing. Thus, high-quality water-repellent glass can be provided to vehicle glazing manufacturers with minimal changes to the manufacturing steps, preferably no changes to the manufacturing steps at all.

[0061] As described above, in some embodiments, a glass substrate having a corrosion-resistant coating may have a base layer between the layer comprising cerium oxide and the first surface, preferably the base layer comprising silicon oxide. When the glass substrate having a coating has a base layer, the base layer may be formed by the same or a different coating method as the coating method for the layer comprising cerium oxide.

[0062] In one embodiment, the underlayer, preferably a silicon oxide underlayer, is produced by sputtering, and the layer comprising cerium oxide is also produced by sputtering. This allows for the production of a high-quality product. Skilled workers are familiar with the method of forming layers such as underlayers by sputtering.

[0063] In another embodiment, the underlayer, preferably a silicon oxide underlayer, is fabricated by chemical vapor deposition, preferably "online" chemical vapor deposition in a float process, and the layer comprising cerium oxide is fabricated by sputtering. This can improve the production rate of the product. The deposition of the silicon oxide layer by chemical vapor deposition, i.e., pyroretic deposition, can be carried out in the manner disclosed in U.S. Patent Publication No. 2018118613, which is incorporated herein by reference. Typically, pyroretic deposition of the underlayer involves contacting a precursor mixture comprising a silicon source, an oxygen source, and optionally a radical scavenger, with the substrate surface. The silicon source may comprise an oxygen-containing silicon compound such as, for example, silicon alkoxide (e.g., tetraethyl orthosilicate (TEOS)) and / or silicon halide (e.g., silicon chloride), but is preferably a silane, more preferably a monosilane (SiH4). Pyrolytic deposition of silicon oxide can be advantageously carried out in combination with the production of glass substrates in well-known float glass manufacturing processes. It was found that silicon oxide underlayers fabricated by chemical vapor deposition (CVM) improve coating durability compared to silicon oxide underlayers fabricated by sputtering. Furthermore, the measured water contact angle of a cerium oxide coating with a silicon oxide underlayer fabricated by CVM was improved compared to a cerium oxide coating with a silicon oxide underlayer fabricated by sputtering.

[0064] In some embodiments, the underlayer may be applied to the first surface by coating a liquid coating precursor comprising a liquid coating precursor, preferably silazane, more preferably polysilazane, or orthosilicate, preferably tetraethyl orthosilicate (TEOS). A method for preparing an underlayer from a liquid coating precursor containing polysilazane is disclosed, for example, in International Patent Publication 2017187173, incorporated herein by reference. The method of coating the surface with the liquid coating precursor is usually not important, and various techniques can be used. Methods for bringing the coating composition into contact with the surface may include, for example, dip coating, spin coating, roll coating, spray coating, air atomization spray, ultrasonic spray, and / or slot die coating. Preferably, the liquid coating precursor is cured after coating to form a coating.

[0065] Aspects of the first embodiment may be applied to the second embodiment in any combination, and vice versa.

[0066] A third aspect of the present invention provides a layer comprising cerium oxide for use as a durable and long-lasting water-repellent surface on vehicle glazing. Here, the glass substrate has a first surface and a second surface, the layer comprising cerium oxide is disposed directly or indirectly on the first surface, the layer comprising cerium oxide is the outermost layer on the first surface, and the layer comprising cerium oxide comprises 0.5 to 20 atomic percent of cerium based on its total composition.

[0067] Aspects of the first and second embodiments may be applied to the third embodiment in any combination, and vice versa.

[0068] A fourth aspect of the present invention provides a vehicle equipped with vehicle glazing according to the first aspect or manufactured according to the second aspect.

[0069] The aspects of the first, second, and third embodiments may be applied to the fourth embodiment in any combination, and vice versa.

[0070] Those skilled in the art will understand that any or preferred features of each aspect of the present invention can be applied to other aspects as needed and required.

[0071] The present invention will be described below with reference to the accompanying drawings, for illustrative purposes only. [Brief explanation of the drawing]

[0072] [Figure 1] A schematic diagram of a vehicle glazing according to one embodiment of the present invention is shown. [Figure 2] A schematic diagram shows a vehicle glazing according to one embodiment of the present invention, which includes a base layer. [Figure 3] A schematic cross-section of another embodiment of the vehicle glazing shown in Figure 1 is provided. [Figure 4] A schematic cross-section of another embodiment of the vehicle glazing shown in Figure 1 is provided. [Modes for carrying out the invention]

[0073] Figure 1 schematically shows a vehicle glazing 100 comprising a soda-lime silica glass substrate and a first surface 101. The first surface has a layer (not shown) comprising cerium oxide, and the cerium oxide layer is the outermost layer on the first surface 101.

[0074] Figure 2 schematically shows a cross-section of one embodiment of the vehicle glazing 100 of Figure 1, comprising a soda-lime silica glass substrate 111, a first surface 101, and a layer 121 comprising cerium oxide directly disposed on the first surface 101. The cerium oxide layer 121 is the outermost layer on the first surface 101. In this embodiment, the cerium oxide layer 121 is directly disposed on the first surface 101, but in other embodiments of the present invention, a further underlayer may be provided between the cerium oxide layer 121 and the first surface 101. In this embodiment, a low-emissivity and / or infrared-reflective coating 122 is adjacent to the second surface 102 of the glass substrate 110. In other embodiments, the low-emissivity and / or infrared-reflective coating 122 may be omitted. Furthermore, a cerium oxide layer may be provided on the outer surface of the coating 122.

[0075] Figure 3 schematically shows a cross-section of another embodiment of the vehicle glazing 100 of Figure 1, comprising a soda-lime silica glass substrate 111, a first surface 101, and a layer 121 comprising cerium oxide directly disposed on the first surface 101. The cerium oxide layer 121 is the outermost layer on the first surface 101. In this embodiment, the cerium oxide layer 121 is directly disposed on the first surface 101, but in other embodiments of the present invention, a further underlayment can be provided between the cerium oxide layer 121 and the first surface 101. In this embodiment, the low emissivity and / or infrared reflective coating 122 is adjacent to the second surface 102 of the glass substrate 111. In other embodiments, the low emissivity and / or infrared reflective coating 122 may be omitted. This embodiment further includes an additional glass substrate 112 bonded to the soda-lime silica glass substrate 111 by an intermediate layer 131. Furthermore, a layer comprising cerium oxide can be provided on the outer surface of the additional glass substrate 112.

[0076] Figure 4 schematically shows a cross-section of another embodiment of the vehicle glazing 100 of Figure 1, comprising a soda-lime silica glass substrate 111, a first surface 101, and a layer 121 comprising cerium oxide directly disposed on the first surface 101. The cerium oxide layer 121 is the outermost layer on the first surface 101. In this embodiment, the cerium oxide layer 121 is directly disposed on the first surface 101, but in other embodiments of the present invention, a further underlayment can be provided between the cerium oxide layer 121 and the first surface 101. This embodiment further includes an additional glass substrate 112 bonded to the soda-lime silica glass substrate 111 by an intermediate layer 131. In this embodiment, a low-emissivity and / or infrared-reflective coating 122 is placed between the additional glass substrate 112 and the intermediate layer 131. Furthermore, a layer comprising cerium oxide may be provided on the outer surface of the additional glass substrate 112.

[0077] The present invention will be further illustrated by the following embodiments, but will not be limited thereto.

[0078] An embodiment of the present invention was prepared by sputtering a rotating ceramic target measuring 23 inches in length and 5.914 inches in diameter (containing 65 wt% TiO2 and 35 wt% CeO2, corresponding to 80.0 atomic% titanium and 20.0 atomic% cerium based on cerium and titanium, and 26.7 atomic% titanium, 6.7 atomic% cerium, and 66.7 atomic% oxygen based on the total composition). A CeTiOx layer comprising cerium, titanium, and oxygen was formed.

[0079] Examples 1-3 were prepared by directly sputtering a layer containing CeTiOx onto a soda-lime silica glass substrate, while Examples 4-6 were prepared by sputtering a layer containing CeTiOx onto a silicon oxide-containing underlayer. The silicon oxide-containing underlayer was fabricated to a thickness of 20-30 nm using chemical vapor deposition in these examples.

[0080] Comparative Example 1 (CE1) is uncoated float glass, and Comparative Example 2 (CE2) is a commercially available PFAS.

[0081] The characteristic evaluations of each example are as follows. Water contact angle - For a 10 cm × 10 cm sample, deionized water (50 μl deionized water droplets) was used, and an average water contact angle (n = 5) was measured using FTA200 and FTA32 software (both manufactured by First Ten Angstroms, Newark, California, USA). Samples of the coated glass substrate were tested after film formation and after the durability evaluation step to evaluate the long-life characteristics of water repellency.

[0082] Table 1 shows the average water contact angles of each example measured after film formation (AD).

[0083] [Table 1]

[0084] From Table 1, it can be seen that by using CeTiO x a substrate with a surprisingly high water contact angle exceeding 60° can be obtained compared to the water contact angle of 25° of the untreated glass. The high water contact angle is related to the reduction of water-surface energy, making it easier to remove water from the surface.

[0085] In fact, a high water contact angle can be obtained even with a coating thickness of only 10 nm. On the other hand, with a 50 nm CeTiO x coating, a surprisingly high water contact angle is obtained, and the durability performance of such a coating is significantly improved by the presence of the silicon oxide underlayer.

[0086] Therefore, in embodiments where a silicon oxide underlayer is desired, CeTiO xThe layer thickness is preferably greater than 10 nm, more preferably 25 nm or more, and more preferably 50 nm or more, for example, from more than 10 nm to 500 nm, preferably 25 nm to 250 nm, and more preferably 50 nm to 100 nm. The water contact angle was confirmed to increase to a stable value over time.

[0087] Oil friction - A felt pad impregnated with oil is passed over the coated surface of the sample using a Sheen Instruments Ltd Wet Abrasion Scrub Tester 903, applying a 0.9 kg load. The sample is placed in the apparatus with the coated surface facing upwards and secured with clamps. A 1.2 cm square felt piece cut from an Erichsen felt strip (DIN 68 861) is immersed in Merck Chemicals Ltd Microscope Immersion Oil. This is placed on a glass surface and rubbed back and forth 50 or 500 times over the sample surface. The samples were observed for the presence or absence of scratches and compared with images of a reference sample, and evaluated on an oil friction test peeling scale from 0 to 9, with lower scores indicating better quality. If the coating was completely removed, the sample score was 10. Table 3 shows the results of the oil friction test and the average water contact angle after the test. The water contact angle was measured before and after the test. The vehicle glazing according to the present invention preferably achieves a score of 5 or less, more preferably 3 or less, and even more preferably 0 in the oil friction 50 and / or oil friction 500 tests described in detail herein. Furthermore, the vehicle glazing according to the present invention preferably achieves a water contact angle of at least 30°, more preferably at least 40°, even more preferably at least 50°, and even more preferably at least 55° after the oil friction 50 and / or oil friction 500 tests described in detail herein.

[0088] Mini Brush Test - A moistened mink brush is passed over the coated surface side of the sample under a predetermined load using a Sheen Instruments Ltd Wet Abrasion Scrub Tester 903. The sample is placed in the apparatus with the coated surface facing upwards and secured with a clamp. A water droplet approximately 2.5 cm in diameter is placed on the sample, directly below the brush head. The brush is placed on glass and rubbed back and forth approximately 500 times over the sample surface. The sample is observed for the presence or absence of scratches and evaluated on a score from 0 to 4 by comparing it with an image of a reference sample, with a lower score indicating better condition. A score of 0 is given if no clear wear is observed. A score of 1 or 2 is considered a pass, and a score of 3 or 4 is considered a fail. The water contact angle was measured before and after the test. In the mini brush test described in detail here, it is desirable that the vehicle glazing according to the present invention preferably achieves a score of 5 or less, more preferably 3 or less, and even more preferably 0. Furthermore, it is desirable that the vehicle glazing according to the present invention achieves a water contact angle of preferably at least 30°, more preferably at least 40°, even more preferably at least 50°, and even more preferably at least 55° after the oil friction 50 and / or oil friction 500 tests described in detail herein.

[0089] Alkaline corrosion test - Examples and comparative examples were subjected to an alkaline corrosion test, and heat-treated samples were immersed in 1M NaOH at 23°C for 2 hours.

[0090] Changes in haze were evaluated according to ASTM D1003 (BYK Gardner Haze-gard plus), as shown in Table 2, and changes in transmittance were evaluated as shown in Table 3.

[0091] [Table 2]

[0092] [Table 3]

[0093] Table 2 shows that all measured samples exhibited extremely low haze both initially and after alkaline corrosion testing, and CeTiO x It can be seen that the coating provides excellent corrosion resistance. Similarly, from Table 3, CeTiO x Increasing the coating thickness reduces the transmittance, but the presence of a silicon oxide underlayer increases or only slightly reduces the transmittance. The change in transmittance due to the alkaline corrosion test is negligible. The vehicle glazing according to the present invention preferably 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.

[0094] Acid Corrosion Test - Examples and comparative examples were subjected to acid corrosion tests. Heat-treated samples were immersed in 1M HCl at 23°C for 2 hours. Changes in haze were evaluated according to ASTM D1003 (BYK Gardner Haze-gard plus) as shown in Table 4, and changes in transmittance were evaluated as shown in Table 5.

[0095] [Table 4]

[0096] Table 4 shows that all measured samples exhibited extremely low haze both initially and after acid corrosion testing, and CeTiO x This demonstrates excellent corrosion resistance due to the coating.

[0097] [Table 5]

[0098] Table 5 shows that the change in transmittance due to the acid corrosion test is negligible.

[0099] Therefore, CeTiO xThe coating can be used to manufacture heat-treated coated glass substrates with excellent corrosion resistance, and preferably the vehicle glazing exhibits a haze increase of 1% or less after immersion in 1M NaOH or 1M HCl at 23°C for 2 hours. The vehicle glazing according to the present invention preferably 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.

[0100] The vehicle glazing according to the present invention preferably passes EN1096 A on a surface having a 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 in accordance with EN1096 A.

[0101] The vehicle glazing according to the present invention preferably passes EN1096 B, which is applied to surfaces having a cerium oxide coating, and after one or more tests in accordance with EN1096 B, it preferably 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°.

[0102] The vehicle glazing according to the present invention preferably passes the ASTM D6037 dry abrasion resistance test applied to a surface having a cerium oxide coating, and after one or more tests in accordance with ASTM D6037, it preferably 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°.

[0103] The vehicle glazing according to the present invention preferably passes a scratch test in accordance with ASTM E 2546 or ISO 14577 applied to a surface having a cerium oxide coating, and after one or more tests in accordance with ASTM D6037 or ISO 14577, it preferably 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°.

[0104] The vehicle glazing according to the present invention preferably passes an accelerated ultraviolet degradation test in accordance with ASTM D 523 and / or ASTM D 2244 applied to a surface having a cerium oxide coating, and after one or more tests in accordance with ASTM D 523 or ASTM D 2244, it preferably 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°.

[0105] Furthermore, since the coated glass substrate responds very well to heat treatment, heat-treatable coated glass substrates are provided for manufacturing heat-treated coated glass substrates with a durable and long-lasting water-repellent surface and excellent corrosion resistance.

[0106] This specification relates to vehicle glazing, such as side lights, roof lights, windshields, side windows, and quarter lights. Furthermore, such vehicle glazing also includes 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, and fascia components.

Claims

1. Vehicle glazing having a durable and long-lasting water-repellent surface, A glass substrate having a first surface and a second surface, A layer comprising cerium oxide disposed directly or indirectly on the first surface, Equipped with, The layer comprising the cerium oxide is the outermost layer on the first surface, The layer comprising the cerium oxide comprises 0.5 to 20 atomic percent of cerium based on the total composition. Vehicle glazing with a durable and long-lasting water-repellent surface.

2. The layer comprising the ceroxide is Ce ｘ Ti ｙ O ｚ The atomic ratio of Ce based on Ce and Ti in the base layer, calculated as x / (x+y), is 0.5 to 0.95, more preferably 0.50 to 0.90, preferably 0.55 to 0.85, more preferably 0.60 to 0.80, and even more preferably 0.62 to 0.

67. Vehicle glazing according to claim 1.

3. The thickness of the layer comprising the cerium oxide is 1 nm to 500 nm, preferably 5 nm to 250 nm, and more preferably 10 nm to 100 nm. Vehicle glazing according to claim 1 or 2.

4. The layer comprising the cerium oxide is the only layer on the first surface. Vehicle glazing according to any one of claims 1 to 3.

5. A base layer is further provided between the layer containing cerium oxide and the first surface. Vehicle glazing according to any one of claims 1 to 3.

6. The aforementioned base layer comprises silicon oxide, preferably the base layer comprising silicon oxide is directly disposed on the first surface, more preferably the base layer comprising silicon oxide is directly disposed on the first surface and the layer comprising cerium oxide is directly disposed on the base layer. Vehicle glazing according to claim 5.

7. The layer comprising the cerium oxide comprises 1 to 10 atomic percent of cerium based on the total composition, preferably 2 to 8 atomic percent of cerium based on the total composition. Vehicle glazing according to any one of claims 1 to 6.

8. The layer comprising cerium oxide further comprises titanium, preferably the layer comprising cerium oxide comprising 50 to 95 atomic percent of titanium based on titanium and cerium, more preferably comprising 70 to 90 atomic percent of titanium based on titanium and cerium, and even more preferably comprising 75 to 85 atomic percent of titanium based on titanium and cerium. Vehicle glazing according to any one of claims 1 to 7.

9. The layer comprising the cerium oxide comprises less than 10 atomic percent of silicon based on the total composition, preferably the layer comprising cerium comprises less than 1 atomic percent of silicon based on the total composition, and more preferably the layer comprising cerium is substantially silicon-free. Vehicle glazing according to any one of claims 1 to 8.

10. The cerium oxide layer comprises less than 10 atomic percent of aluminum based on its total composition, preferably the cerium layer comprises less than 1 atomic percent of aluminum based on its total composition, and more preferably the cerium layer is substantially aluminum-free. Vehicle glazing according to any one of claims 1 to 9.

11. The coated glass substrate exhibits a water contact angle greater than 30°, preferably greater than 50°, and more preferably greater than 60°. Vehicle glazing according to any one of claims 1 to 10.

12. The second surface has a low emissivity and / or infrared reflective coating. Vehicle glazing according to any one of claims 1 to 11.

13. The low emissivity and / or infrared reflective coating comprises a transparent conductive layer, preferably a transparent conductive silver layer or a transparent conductive metal oxide layer. Vehicle glazing according to claim 12.

14. The aforementioned vehicle glazing is a bent and / or reinforced vehicle glazing. Vehicle glazing according to any one of claims 1 to 13.

15. The aforementioned vehicle glazing is a laminated vehicle glazing. Vehicle glazing according to any one of claims 1 to 14.

16. The vehicle glazing is a windshield, side light, taillight, or roof light, preferably an automotive windshield, side light, taillight, or roof light. Vehicle glazing according to any one of claims 1 to 15.

17. The steps include preparing a glass substrate having a first surface, The steps include preparing a sputtering target comprising cerium oxide, The steps include: sputtering the sputtering target comprising cerium to prepare a layer comprising cerium oxide directly or indirectly on the first surface; A method for manufacturing vehicle glazing according to any one of claims 1 to 16, including

18. The sputtering target comprises titanium, preferably comprising 50 to 95 atomic percent of titanium based on titanium and cerium, more preferably comprising 70 to 90 atomic percent of titanium based on titanium and cerium, and even more preferably comprising 75 to 85 atomic percent of titanium based on titanium and cerium. The method according to claim 17.

19. The sputtering step of the sputtering target further includes a step of heat-treating the soda-lime silica glass substrate, preferably the heat-treating step of the soda-lime silica glass substrate further includes a step of heating the soda-lime silica glass substrate at at least 600°C for at least 5 minutes. The method according to claim 17 or 18.

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

21. The step of bending the substrate is performed before the sputtering step of the sputtering target. The method according to claim 20.

22. The step of bending the substrate is performed after the sputtering step of the sputtering target. The method according to claim 21.

23. The process further includes the step of applying a base layer to the first surface, preferably the step of applying the base layer, which includes forming a silica layer by chemical vapor deposition, physical vapor deposition, or liquid phase deposition, preferably by chemical vapor deposition. The method according to any one of claims 17 to 22.

24. Use of a layer comprising cerium oxide as a durable and long-lasting water-repellent surface on vehicle glazing, The glass substrate has a first surface, The layer comprising the cerium oxide is disposed directly or indirectly on the first surface. The layer comprising the cerium oxide is the outermost layer on the first surface, The layer comprising the cerium oxide is used to contain 0.5 to 20 atomic percent of cerium based on the total composition.

25. A vehicle comprising a glazing described in any one of claims 1 to 15, or a glazing manufactured by the method described in any one of claims 15 to 22, preferably an automobile. vehicle.

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