Glass piece with communication window for sensor and camera systems

Abstract

The invention relates to a glass piece (10), in particular a vehicle glass piece, comprising at least:-a first glass sheet (1) having an outer side surface (I) and an inner side surface (II), in which-a coating (4) made of diamond-like carbon (DLC) is arranged on the outer side surface (I) by atmospheric pressure chemical vapor deposition (AP-CVD), preferably by atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD).

Description

Technical Field

[0001] The invention relates to the field of glazing, in particular for sensor and camera systems, glazing arrangements, methods for producing glazing and the use thereof. Background Art

[0002] Motor vehicles, aircraft, helicopters and ships are increasingly equipped with various sensors or camera systems. Examples include camera systems such as video cameras, night vision cameras, residual light amplifiers, laser rangefinders or passive infrared detectors. Vehicle recognition systems are also increasingly used, for example, to collect tolls.

[0003] Camera systems can use light in the ultraviolet (UV), visible (VIS) and infrared wavelength ranges (IR). With these, objects, vehicles and people can be accurately identified even in adverse weather conditions, such as darkness and fog. In motor vehicles, these cameras can be placed behind the windshield in the passenger compartment, behind the rear window, but also behind the side windows or other glass elements. In road traffic, they also offer the possibility of timely identification of dangerous situations and obstacles.

[0004] For example, high-value sensors and complex camera systems necessary for modern traffic sign recognition or automated driving (so-called vision-based driver assistance systems FAS or advanced driver assistance systems ADAS) require very high, undisturbed and low-scatter through vision in the area where their beam paths pass through the glass pane.

[0005] Normal fogging and icing can have a significant adverse effect on such a beam path. Suitable ventilation or heating systems, known for example from DE 10 2012 018 001 A1, offer a remedy.

[0006] Furthermore, minute defects and scratches on the outer surface (outer side) of the glass sheet are particularly disturbing and detrimental to the complex optical system. These can be caused, for example, by sand particles hitting or by abrasion caused by a wiper blade moving over it.

[0007] Therefore, for many applications, it is desirable to provide a glass sheet surface with improved scratch resistance. For example, soda-lime glass, which is commonly used in vehicle glazing, does not inherently have high scratch resistance, especially when exposed to sand particles combined with moving wiper blades.

[0008] Here, a remedy is provided by full surface coating of the outer surface of the glass element with a layer of diamond-like carbon (DLC), as disclosed, for example, in US 2003190476 A1. This layer can significantly improve the scratch resistance of the glass surface.

[0009] Diamond-like carbon (DLC) is composed of sp 3 -hybridized carbon and sp 2 - A mixture of hybrid carbons and characterized by an amorphous structure. Diamond-like carbon thin layers are in principle very suitable for improving the scratch resistance of surfaces since they have a low coefficient of friction and a sufficiently high hardness.

[0010] Methods for producing DLC ​​layers are well known. For example, WO 2016 / 171627 A1 describes coating a substrate wherein the thin layer comprises a carbon layer such as DLC. The DLC layer is applied by physical vapor deposition, for example by high-power pulsed magnetron sputtering. WO 2019 / 020481 A1 further describes a method for depositing a DLC layer by a PECVD magnetron process.

[0011] This process allows high-quality DLC layers to be provided for large flat glass areas. However, modern vehicle glazing often has curvatures and / or is heat-strengthened. During manufacturing, the coating is usually applied over the entire surface to a flat, planar glass sheet, which is then trimmed and subsequently subjected to appropriate heat treatment, for example during bending.

[0012] One problem with DLC layers is their temperature sensitivity. At high temperatures, diamond-like carbon graphitizes (i.e., undergoes a transformation: the carbon atoms change from sp 3 Coordination changes to sp 2 Coordination) and burns into CO2 at temperatures >400°C. Since the glass bending process and the glass hardening process (annealing) require temperatures of up to 700°C, the pure DLC layer on the glass will burn and disappear if they are not protected from oxidation. In order to avoid oxidation, complex techniques using protective layers and release layers are necessary to prevent the DLC layer from burning off during the temperature treatments used for bending or annealing. Such methods are described in WO2004 / 071981, US7060322B2, US8443627 or US8580336B2.

[0013] The washing processes described hitherto in the prior art for removing the annealing protective coating used to protect the DLC layer during the heat treatment are complex and have various disadvantages. Firstly, the removal of the protective layer in this way can be carried out unreliably and incompletely, in particular due to the geometry of the curved glass sheets. The exposed substrate with the applied DLC layer must then undergo a drying step. In addition, the washing medium used is accordingly contaminated with the components of the washed-off protective layer and must be disposed of in a complex and expensive manner that is environmentally compatible and compliant with the requirements.

[0014] WO 2021 / 043838 A1 and WO 2021 / 112144 A1 avoid bending of the DLC layer on the glass by inserting a transparent element (preferably a polycrystalline element or a chalcogenide glass) pre-coated with a DLC layer over the entire surface into a recess in the glass sheet.

[0015] DE 10 2012 200 969 A1 describes a carbon deposition process for coatings with anti-fingerprint properties using an open jet of atmospheric plasma, wherein flat operating elements of household appliances, in particular glass ceramic plates, are coated over their entire surface. Here, by varying the process parameters, different amorphous carbon structures can be selectively changed from graphite-like to diamond-like structures.

[0016] WO 2018 / 054595 A1 describes a method for ablating and patterning functional coatings on curved surfaces using a laser. Summary of the invention

[0017] The object of the present invention is now to provide an improved glazing unit having a scratch-resistant coating on the outer surface, which glazing unit can be produced simply and economically.

[0018] The scratch-resistant coating protects the through-viewing area of ​​optical sensors or camera systems, in particular via the glass surface, so that their optical properties are hardly impaired.

[0019] According to the invention, this object is achieved by a glazing unit in accordance with claim 1. Preferred embodiments emerge from the subclaims.

[0020] The glazing according to the present invention is in particular a vehicle glazing and comprises at least the following features:

[0021] - a first glass sheet having an outer surface and an inner surface,

[0022] in,

[0023] A coating made of diamond-like carbon (DLC) is arranged on the outer side surface of the first glass sheet.

[0024] In the following, the coating according to the invention made of diamond-like carbon (DLC) is also referred to as DLC coating or simply as coating.

[0025] In an advantageous embodiment of the glazing according to the invention, the coating made of diamond-like carbon (DLC) has a higher scratch resistance than the outer side surface of the first glass sheet, ie the outer side surface without the coating.

[0026] The first glass sheet is advantageously monolithic, ie, the first glass sheet is advantageously formed of a continuous material. In particular, the first glass sheet has no openings or recesses filled with different materials. Thus, the outer side surface of the first glass sheet forms a continuous and uniform surface.

[0027] In an advantageous embodiment of the glazing according to the invention, the DLC coating is arranged in sections on the outer side surface and preferably not on the entire surface.

[0028] In another advantageous embodiment of the glazing according to the invention, the area of ​​the DLC coating is 0.1% to 95%, preferably 0.1% to 30%, particularly preferably 0.5% to 10% of the area of ​​the outer surface of the first glass sheet. Here, the "area of ​​the DLC coating" refers to the area of ​​the outer surface of the first glass sheet that is provided with the DLC coating. Here, the "area of ​​the first glass sheet" refers to the total area of ​​the outer surface of the first glass sheet.

[0029] In a further advantageous embodiment of the glazing according to the invention, the DLC coating consists of closed areas which do not comprise any uncoated areas.

[0030] The coating of the invention contains or consists of diamond-like carbon, which is generally referred to herein and hereinafter as DLC. Coatings made of diamond-like carbon are well known. In DLC coatings, hydrogen-free or hydrogen-containing amorphous carbon is the main component, wherein the carbon can be composed of sp 3 -hybridized carbon and sp 2 - a mixture of hybrid carbons. Optionally, sp 3 -hybridized carbon or sp 2 -Hybridized carbon may be the main component. Examples of DLC include DLCs known as ta-C and a:CH. The DLC layer may be doped or undoped. Doping elements include silicon, metals, oxygen, nitrogen or fluorine.

[0031] In an advantageous embodiment, the carbon of the DLC coating comprises sp 3 -hybridized carbon and sp 2 - A mixture of hybridized carbon or composed of sp 3 -hybridized carbon and sp 2 - a mixture of hybrid carbons, preferably sp 3 - The proportion of hybridized carbon is at least 20%, particularly preferably sp 3 - The proportion of hybridized carbon is at least 40%.

[0032] DLC coatings have advantageous properties such as high scratch resistance while having high transparency. For example, scratch resistance is measured using an Erichsen hardness tester or an Erichsen scratch tester.

[0033] The DLC coating according to the invention is advantageously deposited on the outer surface of the first glass sheet using an atmospheric pressure chemical vapor deposition (AP-CVD) process, in particular an atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) process.

[0034] Layer deposition processes in atmospheric pressure plasmas are sufficiently known, wherein the plasma is preferably generated by a discharge between electrodes and at least one organic coating precursor compound is fed into the region of the relaxing plasma and deposited as a plasma polymer layer on the substrate. Reference is made here merely by way of example to WO 2018141802 A1.

[0035] Advantageously, said at least one organic coating precursor compound is chosen from the group consisting of acyclic or cyclic, non-functionalized or functionalized hydrocarbons.

[0036] In a preferred embodiment, the at least one organic coating precursor compound is selected from tetramethylsilane (TMS), alkanes with 1-10 carbon atoms, alkynes with 2-10 carbon atoms, benzene or a mixture thereof. Examples of alkynes with 2 to 10 carbon atoms are acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne and isomers thereof. Examples of alkanes with 1-10 carbon atoms are methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane and isomers thereof. The at least one organic coating precursor compound is particularly selected from tetramethylsilane (TMS), methane (CH4), acetylene (C2H2) or a combination thereof. Of course, a mixture of the above coating precursor compounds can also be used as a coating precursor compound.

[0037] In particular, the organic coating precursor compound consists of acetylene (C2H2).

[0038] Preferably nitrogen, neon, argon, krypton, xenon or a shaping gas is used as an inert gas or process gas.

[0039] In an advantageous embodiment of the glazing according to the invention, the thickness d of the coating made of diamond-like carbon is 1 nm to 20 nm, preferably 2 nm to 10 nm, particularly preferably 3 nm to 10 nm. DLC coatings of this thickness have good scratch resistance and high optical transparency.

[0040] The terms "inner surface" and "outer surface" are used to distinguish between the surfaces of the glass sheet. In the installed position, the outer surface preferably faces the external space, for example, the external space around the vehicle in the case of a vehicle glazing, and the inner surface preferably faces the internal space, for example, the interior of the vehicle in the case of a vehicle glazing.

[0041] In an advantageous embodiment of the glazing according to the invention, the DLC coating has a sufficient transmittance T both at an angle α of 0° and at an angle α of −80° to +80°. L to ensure unobstructed vision for complex optical sensor and camera systems, especially in terms of light sensitivity and dynamics.

[0042] In an advantageous embodiment, the glazing according to the invention has a transmission T of at least 70% in the region of the DLC coating in the visible spectral range at an angle α=0°. L In particular, the glass according to the invention has, in the region of the DLC coating, a transmission T of at least 75% in the visible spectral range at an angle α=0°. L The term "visible spectral range" refers to the spectral range from 400 nm to 750 nm. The transmittance is preferably determined in accordance with standard DIN EN 410.

[0043] In an advantageous embodiment of the glazing according to the invention, using the example of a composite glass sheet, the inner surface of a first glass sheet is planarly connected to the outer surface of a second glass sheet via at least one thermoplastic intermediate layer, for example by lamination.

[0044] The glazing according to the invention may have further thin layers, for example, IR-reflecting layers which protect the interior of the vehicle from solar radiation, or heat radiation-reflecting layers, also referred to as low-emissivity layers, emissivity-reducing layers or low-E layers. The low-E layer has in particular the function of reflecting thermal radiation, i.e. in particular IR radiation having a longer wavelength than the IR component of the solar radiation. In the case of low external temperatures, the low-E coating reflects heat back into the interior and reduces the cooling of the interior. In the case of higher external temperatures, the low-E coating reflects the thermal radiation of the heated composite glass sheet outwards and reduces the heating of the interior. On the inside surface (inner surface) of the second glass sheet (inner glass sheet), the coating according to the invention particularly effectively reduces the emission of thermal radiation from the glass sheet into the interior in summer and reduces the dissipation of heat to the external environment in winter.

[0045] Furthermore, the glazing can have further functional elements, for example electrically controllable optical functional elements, such as lighting elements (for example OLED) or shading elements (for example electrochromic functional elements or PDLC, SPD or guest-host cell elements).

[0046] In principle, all electrically insulating substrates which are thermally and chemically stable and dimensionally stable under the conditions of production and use of the glass pane according to the invention are suitable as the first glass pane and, if applicable, as the second glass pane.

[0047] The first glass sheet preferably contains glass or consists of glass, particularly preferably flat glass, float glass, quartz glass, borosilicate glass, soda-lime glass, or contains or consists of a transparent plastic, preferably a rigid transparent plastic, in particular polyethylene, polypropylene, polycarbonate, polymethyl methacrylate, polystyrene, polyamide, polyester, polyvinyl chloride and / or mixtures thereof. If present, the second glass sheet preferably contains glass or consists of glass, particularly preferably flat glass, float glass, quartz glass, borosilicate glass, soda-lime glass, or contains or consists of a transparent plastic, preferably a rigid transparent plastic, in particular polyethylene, polypropylene, polycarbonate, polymethyl methacrylate, polystyrene, polyamide, polyester, polyvinyl chloride and / or mixtures thereof.

[0048] The first glass sheet and / or the second glass sheet are preferably transparent, in particular for use of the glass sheet as a windshield or rear window of a vehicle or other uses where high light transmittance is desired.

[0049] The first glass sheet and / or, if present, the second glass sheet are advantageously monolithic, ie they do not have in each case recesses or inserts, for example of a different (transparent) material.

[0050] The thickness of the glass sheets can vary widely and can thus be optimally adapted to the requirements of the individual case. Preferably used are glass sheets with a standard thickness of 1.0 mm to 25 mm, preferably 1.4 mm to 5.9 mm for vehicle glazing and preferably 4 mm to 25 mm for furniture, electrical appliances and buildings, in particular electric radiators. The size of the glass sheets can vary widely and is governed by the size of the application according to the invention. For example, in the field of vehicle construction and construction, the first glass sheet and the optional second glass sheet have a thickness of 200 cm. 2 Up to 20m 2 of conventional area.

[0051] The glass sheet can have any desired three-dimensional shape. Preferably, the three-dimensional shape has no shadow areas, so that it can be coated with IR layers or low-E layers, for example by cathode sputtering. Preferably, the substrate is planar or slightly or highly curved in one or more spatial directions. In particular, planar substrates are used. The glass sheet can be colorless or colored.

[0052] A plurality of glass sheets are connected to each other by at least one intermediate layer. The intermediate layer preferably comprises at least one thermoplastic, preferably polyvinyl butyral (PVB), ethylene vinyl acetate (EVA) and / or polyethylene terephthalate (PET). However, the thermoplastic intermediate layer may also comprise, for example, polyurethane (PU), polypropylene (PP), polyacrylate, polyethylene (PE), polycarbonate (PC), polymethyl methacrylate, polyvinyl chloride, polyacetic acid resin, casting resin, acrylate, fluorinated ethylene-propylene, polyvinyl fluoride and / or ethylene-tetrafluoroethylene, or copolymers or mixtures thereof. The thermoplastic intermediate layer may be formed by one or even by a plurality of superimposed thermoplastic films, wherein the thickness of the thermoplastic film is preferably 0.25 mm to 1 mm, typically 0.38 mm or 0.76 mm.

[0053] Another aspect of the present invention includes a glazing arrangement comprising:

[0054] - a glazing unit according to the invention, and

[0055] At least one optical sensor or at least one camera system, the beam path of which is guided at least in sections and preferably completely onto or through the region of the DLC coating.

[0056] The area of ​​the DLC coating enables particularly good and undisturbed communication of the optical sensor or camera system through the glass element and is often also referred to as the communication window. The passage area of ​​the beam path through the glass element and in particular through the outer side surface of the first glass sheet is often referred to as the camera window or camera area.

[0057] In an advantageous embodiment of the glazing arrangement according to the invention, the area of ​​the DLC coating (i.e. the communication window) completely encompasses the passage area of ​​the beam path through the first pane of glass (i.e. the camera window). Particularly preferably, the passage area of ​​the beam path (camera window) substantially coincides with the area of ​​the DLC coating (communication window).

[0058] In an advantageous embodiment of the arrangement of the glazing according to the invention, the angle α between the surface normal on the inner surface of the first pane and the center of the beam path of the optical sensor or camera system is 0° to 80°, preferably 10° to 75°, particularly preferably 30° to 75°. Preferably, the center of the beam path is substantially horizontal. Low values ​​of 10° to 30° are usually used for commercial vehicles, in particular agricultural utility vehicles such as tractors, trucks or buses. Values ​​between 30° and 75° are usually used for passenger cars, values ​​between 50° and 75° are preferably used for sports cars. The angles mentioned are understood to be the angles between the surface normal of the glazing and the center of the beam path. If the center of the beam path is horizontal, the angle α corresponds to the inclination of the glazing relative to the vertical in the installed position.

[0059] The camera system according to the invention is preferably a high-performance camera system, in particular with regard to dynamics and range, in particular for a vision-based driver assistance system (FAS) or an advanced driver assistance system (ADAS).

[0060] The invention also comprises a method for producing a glazing element according to the invention, the method comprising at least the following steps in the order shown:

[0061] a) annealing or bending at least one first glass sheet at a temperature exceeding 400° C., preferably exceeding 500° C., and

[0062] b) Depositing a coating made of diamond-like carbon (DLC) on the outer surface of the first glass sheet by atmospheric pressure chemical vapor deposition (AP-CVD), preferably by atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD).

[0063] The temperature treatment in step a) can be carried out in various ways, for example, by heating the glass piece using a furnace or a radiant heater. Alternatively, the temperature treatment can also be carried out by light irradiation, for example, using a lamp or a laser as a light source.

[0064] The first glass sheet can be bent in step a) typically at a temperature of 500° C. to 700° C.

[0065] In an advantageous embodiment, the temperature treatment is performed as a thermal prestressing process. In this case, the heated substrate is rapidly cooled by the air flow. Compressive stress is generated at the surface of the glass sheet; tensile stress is generated in the core of the glass sheet. The characteristic stress distribution increases the fracture strength of the glass sheet. The bending process can also precede the prestressing.

[0066] In an advantageous further development of the method according to the invention, before step b), an adhesive layer is deposited on the first glass sheet, preferably by atmospheric pressure chemical vapor deposition (AP-CVD), particularly preferably by atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD). The adhesive layer is preferably based on silicon oxide or consists of silicon oxide. The DLC coating is subsequently deposited, in particular substantially uniformly, on the adhesive layer.

[0067] In an advantageous further development of the method according to the invention, the DLC coating is output from the plasma nozzle and deposited on a sub-region of the outer surface of the first glass sheet (i.e. only locally). If present, the adhesive layer may also be output from the plasma nozzle and deposited on a sub-region of the outer surface of the first glass sheet (i.e. only locally).

[0068] Since the deposition of the DLC coating is only partially completed, the plasma nozzle is preferably moved in a track over the immediate area of ​​the outer side surface of the first glass sheet and the DLC coating is deposited.

[0069] In an advantageous further development of the method according to the invention, all steps for producing the glass element according to the invention after step b) are carried out at a temperature below 400° C., preferably below 300° C., particularly preferably below 200° C. In other words, the glass element according to the invention with the DLC coating is no longer heated to 400° C. or above 400° C., preferably no longer heated to 300° C. or above 300° C. and particularly preferably no longer heated to 200° C. or above 200° C. This has the effect that the DLC coating does not burn off or become damaged due to the influence of the temperature.

[0070] In an intermediate step between steps a) and b) or in a further step c), a composite glass sheet can be produced by bonding (laminating) the first glass sheet, the thermoplastic interlayer and the second glass sheet.

[0071] The bonding of the first glass sheet and the second glass sheet is preferably carried out under the effect of heat, vacuum and / or pressure.Methods known per se for producing glass sheets can be used.

[0072] For example, the so-called autoclave method can be carried out at a high pressure of about 10 bar to 15 bar and a temperature of 130° C. to 145° C. for about 2 hours. The vacuum bag or vacuum ring method known per se operates, for example, at about 200 mbar and 80° C. to 110° C. The first glass sheet, the thermoplastic interlayer and the second glass sheet can also be pressed between at least one pair of rollers in a calender to form a glass sheet. This type of equipment is known for producing glass sheets and usually has at least one heating channel upstream of the press. For example, the temperature during the pressing operation is 40° C. to 150° C. The combination of calender and autoclave method has proven to be particularly useful in practice. Alternatively, vacuum laminators can also be used. They consist of one or more heatable and evacuable chambers in which the first glass sheet and the second glass sheet are laminated, for example, at a low pressure of 0.01 mbar to 800 mbar and a temperature of 80° C. to 170° C. within about 60 minutes.

[0073] Of course, lamination in step b) after application of the coating made of diamond-like carbon can only be carried out under temperature and process conditions which do not damage the coating.

[0074] The invention also includes the use of glazing according to the invention or the arrangement of glazing according to the invention in buildings, in particular in passageways, windows, roofs or facades; as built-in components in furniture and electrical appliances; in land, air or water sports equipment, in particular in trains, ships and motor vehicles, for example as windshields, rear windows, side windows and / or roof panels. Such uses include optical sensors and camera systems, in particular for vision-based driver assistance systems FAS or advanced driver assistance systems ADAS, whose beam path passes through the coated communication window. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] In the following, the invention is explained in more detail with reference to the accompanying drawings and exemplary embodiments. The drawings are schematic diagrams and are not drawn to scale. The drawings do not limit the invention in any way.

[0076] The accompanying drawings depict:

[0077] Figure 1A is a plan view of an embodiment of a glass element according to the present invention,

[0078] Figure 1B yes Figure 1A Schematic cross-sectional view of the layer structure of a glass piece,

[0079] Figure 1C is a schematic diagram of the arrangement of glass elements according to the present invention, wherein Figure 1A A cross-sectional view of a glass piece along the section line A-A',

[0080] Figure 2Ais a flow chart of an embodiment of a method according to the present invention,

[0081] Figure 2B is based on Figure 1A-Figure 1C Example of the invention A detailed view during step S2 during the production of a glazing 10 according to the invention, and

[0082] Figure 3A is a plan view of another embodiment of a glass element according to the present invention,

[0083] Figure 3B yes Figure 3A Schematic cross-sectional view of the layer structure of a glass piece,

[0084] Figure 3C is a schematic diagram of the arrangement of glass elements according to the present invention, wherein Figure 3A A cross-sectional view of a glass piece along the section line A-A',

[0085] Figure 4A is a flow chart of an embodiment of a method according to the present invention,

[0086] Figure 4B is based on Figure 3A-3C Example of the invention A detailed view during step S2 during the production of a glazing 10 according to the invention, and

[0087] Figure 4C is based on Figure 3A-3C Example of the invention Detailed view during step S3 during the production of a glazing 10 according to the invention. DETAILED DESCRIPTION

[0088] Figure 1A A plan view of an exemplary embodiment of a glazing 10 according to the invention is depicted, which has a coating area (communication window) 5 according to the invention. Figure 1B A schematic cross-sectional view of the layer structure of the glass element 10 is depicted, Figure 1C A schematic diagram of a glass arrangement 100 according to the present invention is depicted, wherein a Figure 1A A cross-sectional view of the glass member 10 taken along the section line AA'.

[0089] The glazing 10 comprises a first glass sheet 1 and a second glass sheet 2 connected to each other via a thermoplastic interlayer 3. The glazing 10 is, for example, a vehicle glass sheet, in particular a windshield of a passenger vehicle. The first glass sheet 1 is intended to face the outside of the vehicle, for example in the installed position; the second glass sheet 2 is intended to face the inside, for example in the installed position. The first glass sheet 1 and the second glass sheet 2 are, for example, made of soda-lime glass. The thickness of the first glass sheet 1 is, for example, 2.1 mm, and the thickness of the second glass sheet 2 is, for example, 1.6 mm. The thermoplastic interlayer 3 is made of polyvinyl butyral (PVB) and has a thickness of 0.76 mm.

[0090] Figure 1A A plan view of the outer side surface I of a first glass sheet 1 is depicted. Located behind the glass element 10 in this plan view is a camera system, the beam path of whose reception area is directed onto and through the glass element 10, more precisely onto the inner side surface IV of the second glass sheet 2. The through area of ​​the beam path has the reference numeral 7 and is also referred to as the camera window.

[0091] A coating 4 made of a diamond-like carbon (DLC) layer is arranged in a region 5, also referred to as a communication window, on the outer (first) surface I of the first glass sheet 1. The DLC coating 4 is more scratch-resistant than the outer surface I of the first glass sheet 1 in the region surrounding the coating 4.

[0092] Figure 1B Depicted Figure 1A Schematic cross-sectional view of the layer structure of a glass element 10 in the region of the coating 4. The thickness d of the coating 4 is 5 nm here, for example.

[0093] Of course, the glass element 10 can have additional layers or features typical for windshields. For example, additional functional layers, such as IR-reflecting layers or IR-absorbing layers, or so-called low-E layers, can be arranged on surfaces II, III and IV. In addition, heatable layers, prints or wires can be arranged in or on the glass element 10. In addition, other functional elements such as antennas or electrically controllable optical functional elements such as lighting elements or shading elements (PDLC, SPD, electrochromic, guest-host system, etc.) can be arranged in or on the glass element 10.

[0094] In this example, the glass element 10 has, in particular on the inner surface II of the first glass sheet 1, an opaque black printing (not shown here) which extends in strips at the upper, lower and side edges of the glass sheet, ie is implemented in the shape of a frame.

[0095] Figure 1CAn exemplary embodiment of a glazing arrangement 100 according to the invention is depicted with a glazing 10. Furthermore, a camera system 6 is arranged on the inner surface IV of the second glazing 2, which camera system can be used, for example, for a vision-based driver assistance system.

[0096] The beam path 8 of the camera system 6 is guided completely through the area 5 coated with the coating 4. In particular, the beam path 8 of the camera system 6 passes through the outer surface I of the first glass sheet 1 in the area 5 formed by the coating 4 (also called the camera window) throughout its entire passage area 7.

[0097] The central beam of the beam path 8 of the camera system 6 is oriented approximately horizontally here. The angle α between the normal to the glass element 10 (here shown as the normal to the inner surface IV of the second glass sheet 2 ) and the center of the beam path 8 of the camera system 6 is 73° here, for example.

[0098] The windshield of a passenger car is usually installed flat, for example, here the interval angle α relative to the vertical direction is 72°. Of course, in other vehicle types of applications, such as in buses or tractors, the installation angle can be smaller, for example 15°.

[0099] The communication window 5 is suitable for ensuring a through vision for a camera system 6 or other optical sensors. For this purpose, the camera window, i.e. the through region 7 through which the beam path 8 of the camera system 6 passes through the glass element 10, is arranged completely within the region 5 of the communication window provided with the coating 4. The coating 4 in the communication window 5 is optically hardly perceptible to the camera system 6 and does not interfere with the through vision through the glass element 10. On the contrary, due to its scratch resistance, the surface of the coating 4 is particularly smooth and has only a few scratches and defects that interfere with the optical signal. This is particularly important for use in vehicles and for camera systems 6 with high optical requirements, such as in the case of vision-based driver assistance systems (FAS) or advanced driver assistance systems (ADAS).

[0100] Figure 2A Describes a method for producing Figure 1A-Figure 1C Flow chart of an embodiment of a method for a glazing unit 10 according to the present invention.

[0101] For this purpose, in a first step S1, at least a first glass sheet 1 and a second glass sheet 2 are cut out of a larger flat glass sheet, bent at a temperature of about 640° C. and then laminated to one another via a thermoplastic intermediate layer 3, for example in an autoclave process at a temperature of about 120° C., to form a composite glass sheet.

[0102] Subsequently, in a second step S2 , a coating 4 made of diamond-like carbon is deposited in the local region 5 of the communication window, for example via a process for atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD).

[0103] Figure 2B The deposition process is schematically depicted, in which the coating 4 is output from the plasma nozzle 20 and deposited on the outer surface I of the first glass sheet 1. In this process, the plasma nozzle 20 and / or the glass piece can be moved on the outer surface I of the first glass sheet 1 by a robot, an XY translation stage, an XYZ translation stage or another lateral device, and the coating 4 made of diamond-like carbon according to the present invention can be locally deposited below the nozzle outlet.

[0104] Figure 3A A plan view of another exemplary embodiment of a glazing 10 having a communication window 5 according to the present invention is depicted. Figure 3B A schematic cross-sectional view of the layer structure of the glass element 10 is depicted, Figure 3C A schematic diagram of another glass device 100 according to the present invention is depicted, wherein a Figure 3A A cross-sectional view of the glass member 10 taken along the section line AA'.

[0105] Figure 4A Describes a method for producing Figure 3A-3C Flow chart of another embodiment of the method for a glazing unit 10 according to the present invention. Figure 4B and Figure 4C Detailed diagrams depicting selected steps.

[0106] Figure 3A-3C The glass element 10 and the glass element arrangement 100 correspond substantially to Figure 1A-Figure 1C Therefore, only the differences are dealt with here, and the rest is referred to for Figure 1A-Figure 1C The same applies to the description of Figure 4A-4C Description of the production process, which essentially corresponds to Figure 2A and Figure 2B production process.

[0107] Figure 3A The glass element 10 of the present invention relates to a single glass sheet, for example, a passenger car rear window made of a single glass sheet safety glass. Since the glass element 10 comprises only a single glass sheet, the so-called "first" glass sheet 1 here is this single glass sheet of the glass element 10. The outer side surface I of the glass element 10 is intended to face the outside of the vehicle, for example in the installed position. The (first) glass sheet 1 is made of, for example, heat-strengthened soda-lime glass. The thickness of the (first) glass sheet 1 is, for example, 2.1 mm.

[0108] Figure 3A A plan view of the outer surface I of the (first) glass sheet 1 is depicted. Located behind the glass element 10 in this plan view is a camera system, the beam path of whose reception field is directed onto and through the glass element 10, more precisely onto the inner surface II of the (first) glass sheet 1.

[0109] A coating 4 made of a diamond-like carbon layer is arranged in a region 5 (ie, the communication window) on the outer (first) surface I of the first glass sheet 1. The coating 4 is more scratch-resistant than the outer surface I of the first glass sheet 1 in the region surrounding the coating 4.

[0110] Figure 3B Depicted Figure 3A Schematic cross-sectional view of the layer structure of a glass element 10 in the region of the coating 4. The thickness d of the coating 4 is 5 nm here, for example.

[0111] Of course, the glass element 10 can have additional layers or features typical for rear windows. For example, additional functional layers, such as IR-reflecting or IR-absorbing layers or so-called low-E layers, can be arranged on the inner surface II. In addition, antenna conductors and / or heatable layers, prints or wires can be arranged in or on the glass element 10.

[0112] In this example, the glass piece 10 has an opaque black print (not shown here) on the inner surface II of the first glass sheet 1, which extends in the form of strips at the upper and lower edges of the glass sheet. Of course, the black print can also be implemented in the shape of a frame.

[0113] Figure 3C An exemplary embodiment of a glazing arrangement 100 according to the invention is depicted with a glazing 10. Furthermore, a camera system 6 is arranged on the inner surface II of the glazing 10, which can be used, for example, for a vision-based driver assistance system or as a rearview camera.

[0114] The beam path 8 of the camera system 6 is guided substantially completely through the area 5 coated with the coating 4. In particular, the beam path 8 of the camera system 6 passes through the outer surface I of the first glass sheet 1 in the area 5 (communication window) formed by the coating 4 throughout its entire passage area 7. In the example depicted, the area 5 and the passage area 7 (for example) coincide. Figure 1A-Figure 1C Compared to the exemplary embodiment of FIG. 4 , an adhesive layer 9 made of silicon oxide, for example, is arranged between the outer side surface I of the first glass sheet 1 and the coating 4.

[0115] The central beam of the beam path 8 of the camera system 6 is oriented approximately horizontally here.

[0116] The communication window 5 is suitable for ensuring a through vision for a camera system 6 or other optical sensors. For this purpose, the camera window, i.e. the through region 7 through which the beam path 8 of the camera system 6 passes through the glass element 10, is arranged in line with the region 5 of the communication window provided with the coating 4. The coating 4 in the communication window 5 is optically hardly perceptible to the camera system 6 and does not interfere with the through vision through the glass element 10. On the contrary, due to its scratch resistance, the surface of the coating 4 is particularly smooth and has only a few scratches and defects that interfere with the optical signal. This is particularly important for use in vehicles and for camera systems 6 with high optical requirements, such as in the case of vision-based driver assistance systems (FAS) or advanced driver assistance systems (ADAS).

[0117] Figure 4A Describes a method for producing Figure 3A-3C Flow chart of an embodiment of a method for a glazing unit 10 according to the present invention.

[0118] For this purpose, in a first step S1, at least a (first) glass sheet 1 is cut out of a larger flat glass sheet, bent at a temperature of, for example, about 690° C., and then quenched (thermal strengthening), for example by a stream of cold air. Thus, a thermally strengthened single glass sheet of a single glass sheet safety glass is created.

[0119] Subsequently, in a second step S2, an adhesion enhancing layer 9 (hereinafter also referred to as adhesion layer 9 in an abbreviated manner) is deposited in a local area of ​​the communication window 5 by a process for atmospheric pressure plasma enhanced CVD deposition. The adhesion layer 9 is, for example, based on silicon oxide and here, for example, is made of silicon oxide.

[0120] Figure 4B The deposition process is schematically depicted, wherein the bonding layer 9 is output from the plasma nozzle 20 and deposited on the outer side surface I of the (first) glass sheet 1. In this process, the plasma nozzle 20 and / or the glass piece 10 can be moved on the outer side surface I of the first glass sheet 1 by a robot, an XY stage, an XYZ stage or another lateral device; and, for example, a silicon oxide layer can be locally deposited below the nozzle outlet.

[0121] Subsequently, in a third step S3 , a coating 4 made of diamond-like carbon is deposited in a localized area of ​​the communication window 5 and on the adhesive layer 9 by a process for atmospheric pressure plasma enhanced CVD deposition.

[0122] Figure 4CThe deposition process is schematically depicted, in which a coating 4 of an adhesive layer 9 is output and deposited from a plasma nozzle 20. Here, too, the plasma nozzle 20 and / or the glass piece 10 can be moved on the adhesive layer 9 on the outer surface I of the first glass sheet 1 by a robot, an XY stage, an XYZ stage or another lateral device; and a coating 4 made of diamond-like carbon can be locally deposited below the nozzle outlet.

[0123] Of course, after application of the coating 4, the glass element 10 is no longer exposed to high temperatures, such as occur during bending of the glass. Therefore, the diamond-like carbon layer of the coating 4 no longer presents any risk of damage.

[0124] Table 1 below shows production parameters and measurement results from a study of four samples 1-4 coated with DLC coatings in an AP-PECVD process.

[0125] Table 1:

[0126]

[0127] The DLC coatings of samples 1-4 were deposited by atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) on 2.1 mm thick transparent float glass sheets of the type SGG Planiclear (PLC) of Saint-Gobain Glass. Acetylene (C2H2) was used as the coating precursor compound (precursor). In each case, the transmittance T was measured at an angle α of 2° with a standard light source D65. L Scratch resistance was measured with an Erickson 413 hardness tester and a 1 mm diameter tip at a normal force of 10 N.

[0128] As shown in Table 1, the AP-PECVD method is able to produce DCL coatings with good to excellent scratch resistance.

[0129] The glazing 10 according to the invention with the correspondingly coated communication window 5 is better suited than glazings from the prior art for low-interference and low-distortion through-viewing and operation of highly sensitive optical sensors and camera systems and meets the requirements of modern vision-based driver assistance systems.

[0130] Due to the deposition process using atmospheric pressure chemical vapor deposition (AP-CVD) or atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) according to the present invention, the DLC coating can be performed after bending and annealing of the glass piece. That is, after the DLC coating, the glass piece no longer needs to be heated to the critical temperature for the DLC coating. Expensive techniques required to avoid oxidation, which use protective layers and release layers to prevent the DLC coating from burning off during the temperature treatment for bending or annealing, are eliminated.

[0131] The method according to the invention allows targeted, rapid, localized and therefore economical deposition of DLC coatings.

[0132] Reference numerals:

[0133] 1 First glass sheet

[0134] 2 Second glass sheet

[0135] 3 Thermoplastic middle layer

[0136] 4 Coatings made of diamond-like carbon

[0137] 5 Coating 4 area, communication window

[0138] 6 Camera System

[0139] 7 Transmission area of ​​beam path 8, camera window

[0140] 8 Beam Path

[0141] 9 Adhesive layer

[0142] 10 Glass pieces

[0143] 20 plasma nozzles

[0144] 100 Glass Pieces Arrangement

[0145] I. First / outer surface of the first glass sheet 1

[0146] II Second / inner surface of the first glass sheet 1

[0147] III. First / outer side of the second glass sheet 2

[0148] IV The second / inner surface of the second glass sheet 2

[0149] d Thickness of coating 4

[0150] F1 Area of ​​the outer surface I of the first glass sheet 1

[0151] F4 coating 4 area

[0152] DLC Diamond-like Carbon

[0153] AP-CVD atmospheric pressure chemical vapor deposition

[0154] AP-PECVD atmospheric pressure plasma enhanced chemical vapor deposition

[0155] Steps S1, S2, and S3

[0156] T L Transmittance

[0157] A-A' hatch line

Claims

1. A glass component (10), in particular a vehicle glass, comprising at least: - a first glass sheet (1) having an outer surface (I) and an inner surface (II), in, - the first glass sheet (1) comprises or consists of soda-lime glass, and A coating (4) made of diamond-like carbon (DLC) is arranged on said outer surface (I).

2. The glass element (10) according to claim 1, wherein: The coating (4) is arranged on the outer surface (I) of the first glass sheet (1) by atmospheric pressure chemical vapor deposition (AP-CVD), preferably by atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD).

3. The glass element (10) according to claim 1 or 2, wherein: The first glass sheet (1) is monolithic and preferably has a continuous and uniform outer surface (I).

4. The glass element (10) according to any one of claims 1 to 3, wherein: The coating (4) is arranged in some sections on the outer side surface (I), and preferably, the coating (4) is not arranged on the entire surface of the outer side surface (I).

5. The glass element (10) according to any one of claims 1 to 4, wherein: The area (F4) of the coating (4) is 0.1% to 95%, preferably 0.1% to 30%, particularly preferably 0.5% to 10%, of the area (F1) of the outer surface (I) of the first glass sheet (1).

6. The glass element (10) according to any one of claims 1 to 5, wherein: The diamond-like carbon of the coating (4) includes sp 3 -hybridized carbon and sp 2 - A mixture of hybridized carbon or composed of sp 3 -hybridized carbon and sp 2 -hybridized carbon mixture, where sp 3 The proportion of hybridized carbon is at least 20%, preferably at least 40%.

7. The glass element (10) according to any one of claims 1 to 6, wherein: The coating (4) is undoped or doped, preferably doped with silicon, metal, oxygen, nitrogen or fluorine.

8. The glass element (10) according to any one of claims 1 to 7, wherein: The thickness d of the coating (4) is 1 nm to 20 nm, preferably 2 nm to 10 nm, particularly preferably 3 nm to 10 nm, in particular 3 nm to 9 nm.

9. The glass element (10) according to any one of claims 1 to 8, wherein: The coating (4) has a higher scratch resistance than the outer surface (I) of the first glass sheet (1).

10. The glass element (10) according to any one of claims 1 to 9, wherein: The inner surface (II) of the first glass sheet (1) is preferably connected planarly to the outer surface (III) of the second glass sheet (2) via at least one thermoplastic intermediate layer (3) by lamination.

11. A glass arrangement (100), comprising at least: a) A glazing unit (10) according to any one of claims 1 to 10, and b) At least one optical sensor or at least one camera system (5), the beam path (8) of which is guided through the region (5) of the coating (4).

12. The glazing arrangement (10) according to claim 11, wherein: The region (5) of the coating (4) completely encompasses a passage region (7) of the beam path (8), and preferably, the passage region (7) substantially coincides with the region (5) of the coating (4).

13. A method for manufacturing a glass element (10) according to any one of claims 1 to 10, comprising at least the following steps in the order shown: a) annealing or bending at least one first glass sheet (1), preferably at a temperature exceeding 400° C., preferably exceeding 500° C., b) depositing a coating (4) made of diamond-like carbon (DLC) on the outer surface (I) of the first glass sheet (1) by atmospheric pressure chemical vapor deposition (AP-CVD), preferably by atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD).

14. The method according to claim 13, wherein: Prior to step b), an adhesive layer (9) is deposited on the outer surface (I) of the first glass sheet (1), preferably by atmospheric pressure chemical vapor deposition (AP-CVD), particularly preferably by atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD), and in step b), the coating (4) is deposited, in particular substantially uniformly, on the adhesive layer (9).

15. The method according to claim 13 or 14, wherein: The coating (4) is output from a plasma nozzle (20) and deposited on a sub-region of the outer surface (I) of the first glass sheet (1).

16. The method according to any one of claims 13 to 15, wherein: After step b), all subsequent steps for producing the glass element (10) are carried out at a temperature below 400°C, preferably below 300°C, particularly preferably below 200°C.

17. Use of a glazing (10) according to any one of claims 1 to 10 or a glazing arrangement (100) according to claim 11 or 12 in a moving device travelling on land, in the air or on water, in particular in a motor vehicle, for example as a windshield, rear window, side windows and / or roof panel and functional individual parts, as well as as a built-in component of furniture, electrical appliances and buildings, with an optical sensor and camera system (6), in particular for a vision-based driver assistance system (FAS) or an advanced driver assistance system (ADAS), the beam path (8) of the optical sensor and camera system passing through the area (6) of the coating (4).

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