Vehicles with improved LIDAR detectability and RADAR transparent coatings

Abstract

The present invention relates to a vehicle having a frame or body, at least a part of the outer surface of the frame or body is covered with a coating, said coating comprising at least two layers, the outer two or three layers being (a) a base coat layer, (b) optionally a tinted clear coat layer on (a), and (c) a clear coat top layer on (a) or on (b), the base coat layer (a) consisting of a binder, spherical glass beads, pigment flakes and optionally further components, the median diameter D50 of said pigment flakes being greater than 35% of the median particle diameter D50 of said spherical glass beads. The present invention further relates to a Laser Imaging Detection and Ranging (LIDAR) process of the vehicle, and to the use of a vehicle or a coated substrate comprising said coating in a Laser Imaging Detection and Ranging (LIDAR) of said vehicle or coated substrate and / or for improving the visibility of said vehicle or coated substrate under visible light conditions and / or for creating a three-dimensional image of said vehicle or coated substrate.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to a vehicle having a coating useful in Light Detection and Ranging (LIDAR) and Radio Detection and Ranging (RADAR) technologies. The present invention further relates to a laser imaging detection and ranging process for said vehicle, and the use of said coating on said vehicle or substrate (i) in laser imaging detection and ranging of said coating on said vehicle or substrate, (ii) to improve the visibility of said coating on said vehicle or substrate under visible light conditions, and / or (iii) to create a three-dimensional image of said coating on said vehicle or substrate. The present invention further relates to a radio detection and ranging process, and the use of spherical glass beads as radio wave penetration enhancers in a coating layer.

[0002] [Background technology] Vehicles such as cars, bicycles, motorcycles and scooters are typically provided with a clear coat top layer to protect them, for example, from oxidation or weathering and to provide an overall coating with a glossy appearance. This glossy clear coat top layer, while it may be aesthetically attractive, reduces the detectability of the vehicle using light detection and ranging (LIDAR) technology. In order to properly determine the distance to the vehicle or the exact contour of the vehicle under different viewing angles using LIDAR technology, an increased Lambertian reflection of electromagnetic radiation at the LIDAR wavelength is preferred over specular reflection or retroreflection due to the disturbing effects of 100% specular reflection or 100% retroreflection. Lambertian reflection is a property that defines an ideal matte or diffuse reflecting surface. In this regard, reference is made to A. Hope, Experimental Methods in the Physical Sciences, 46, Chapter 6-Diffuse Reflectance and Transmittance, 2014, pp 179-219, which is incorporated herein by reference in its entirety. The apparent brightness of a Lambertian surface to an observer is the same regardless of the observer's viewing angle. By definition, 100% Lambertian reflection defines the whitest white, ie the most visible color.

[0003] WO 03 / 016964 discloses a retroreflective coating system comprising retroreflective microspheres for wet-on-wet application to automotive body panels. The retroreflective coating system is described as providing satisfactory gloss and retroreflectivity to optimally enhance visibility to others to ensure safety. Figure 4 of WO 03 / 016964 shows an embodiment in which a substrate is covered with a basecoat layer BC comprising binder, retroreflective microspheres and pigments, with a clearcoat layer CC on top of the basecoat layer.

[0004] RADAR sensors are used in vehicles for adaptive cruise control, as well as for blind spot, lane change, and cross traffic assistant. RADAR sensors for acquiring the surroundings are a key component for future vehicles with semi-autonomous and fully autonomous driving capabilities. Autonomous driving requires RADAR technology that reliably detects objects in the surrounding area. Automotive RADAR sensors are usually invisibly integrated behind the vehicle bumper. Vehicle bumpers are typically made of plastic and have a metallic coating layer on them that is the same color as the rest of the vehicle body, often containing metal flake pigments, such as aluminum flake pigments. The presence of these metal flake pigments adversely affects the transparency of the coating for the RADAR signal.

[0005] It is an object of the present invention to provide a glossy coating for vehicles that provides improved LIDAR detectability.

[0006] It is an object of the present invention to provide a glossy coating for vehicles that offers improved transparency to RADAR signals.

[0007] It is a further object of the present invention to provide a glossy coated substrate that provides improved LIDAR detectability.

[0008] It is a further object of the present invention to provide a glossy coated substrate that provides improved transparency to RADAR signals.

[0009] Another object of the present invention is to improve LIDAR detectability of a vehicle.

[0010] [Summary of the Invention] The inventors have unexpectedly determined that one or more of the objectives can be met by using a coating comprising retroreflective microspheres and high aspect ratio pigment flakes, particularly when the ratio of the median diameter D50 of the pigment flakes is greater than 35% of the median particle size D50 of the retroreflective microspheres.

[0011] Thus, in a first aspect, the present invention provides a vehicle having a frame or body, at least a portion of the outer surface of the frame or body being covered with a coating, said coating comprising at least two layers, the outer two or three layers being: (a) a base coat layer; (b) optionally, a tinted clearcoat layer over (a); (c) A top layer of clear coat on (a) or (b). and The base coat layer (a) is, based on the weight of the base coat layer (a), 14.95 to 98.95 weight percent of a binder; 1 to 85% by weight of spherical glass beads having a median particle size D50 of 1 μm to 150 μm as measured by laser diffraction and a refractive index of 1.7 to 2.8 as measured at a wavelength λ of 589 nm; 0.05-30% by weight of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes or combinations thereof, the pigment flakes having a median diameter D50 of 1 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, as measured by laser diffraction; 0-30% by weight of further components; It consists of: A vehicle is provided, wherein the median diameter D50 of the pigment flakes is greater than 35% of the median particle diameter D50 of the spherical glass beads.

[0012] The inventors have found that a vehicle having this coating has improved LIDAR detectability, especially at increasing angles of incidence, i.e., increasing angles from normal incidence. In other words, the coating not only improves the front view of the vehicle, but improves the overall LIDAR scannable profile of the vehicle.

[0013] Additionally, the inventors have found that a vehicle having this coating has improved RADAR signal transmission compared to a similar coating that does not include the spherical glass beads. For example, a plastic bumper as part of a vehicle frame or body covered with this coating has improved RADAR signal transmission compared to a plastic bumper covered with a similar coating that does not include the spherical glass beads.

[0014] In a second aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: (i) providing a LIDAR device comprising an electromagnetic radiation source, a receiver and optionally a Global Positioning System (GPS); (ii) transmitting electromagnetic radiation from an electromagnetic radiation source of the LIDAR device to the vehicle; (iii) scanning the electromagnetic radiation reflected by the coating of the vehicle with a receiver of the LIDAR device; (iv) from the difference between the transmitted electromagnetic radiation and the scanned reflected electromagnetic radiation, preferably as a function of time; the distance between the vehicle and the LIDAR device; Vehicle acceleration, Vehicle deceleration, the direction of vehicle movement, the speed of the vehicle, preferably relative to the speed of the LIDAR device, and 3D image of the vehicle and calculating one or more of: The present invention provides a process for vehicular laser imaging detection and ranging (LIDAR) as defined herein, comprising:

[0015] In a third aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: in laser imaging detection and ranging (LIDAR) of said vehicle or coated substrate; and / or to improve the visibility of said vehicle or coated substrate under visible light conditions; and / or for generating a three-dimensional image of the vehicle or coated substrate; At least two layers, the outer two or three of which are (a) a base coat layer; (b) optionally, a tinted clearcoat layer over (a); (c) A top layer of clear coat on (a) or (b). and The base coat layer (a) is, based on the weight of the base coat layer (a), 14.95 to 98.95 weight percent of a binder; 1 to 85% by weight of spherical glass beads having a median particle size D50 of 1 μm to 150 μm as measured by laser diffraction and a refractive index of 1.7 to 2.8 as measured at a wavelength λ of 589 nm; 0.05-30% by weight of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes or combinations thereof, the pigment flakes having a median diameter D50 of 1 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, as measured by laser diffraction; 0-30% by weight of additional ingredients It consists of: The present invention provides a use of a vehicle or coating substrate as defined herein, wherein the median diameter D50 of said pigment flakes is greater than 35% of the median particle size D50 of said spherical glass beads. [Brief description of the drawings]

[0016] [Figure 1A] FIG. 13 shows LIDAR test results of coated substrates. [Figure 1B] FIG. 13 shows LIDAR test results of coated substrates. [Figure 1C] FIG. 13 shows LIDAR test results of coated substrates. [Figure 1D] FIG. 13 shows LIDAR test results of coated substrates. [Figure 1E] FIG. 13 shows LIDAR test results of coated substrates. [Figure 1F] FIG. 13 shows LIDAR test results of coated substrates. [Figure 2A] FIG. 13 shows LIDAR test results of coated substrates. [Figure 2B] FIG. 13 shows LIDAR test results of coated substrates. [Figure 2C] FIG. 13 shows LIDAR test results of coated substrates. [Figure 2D] FIG. 13 shows LIDAR test results of coated substrates. [Figure 2E] FIG. 13 shows LIDAR test results of coated substrates. [Figure 3A] FIG. 13 shows LIDAR test results of coated substrates. [Figure 3B] FIG. 13 shows LIDAR test results of coated substrates. [Figure 3C] FIG. 13 shows LIDAR test results of coated substrates. [Figure 3D] FIG. 13 shows LIDAR test results of coated substrates.

[0017] definition As used herein, the term "pigment" refers to a particulate colorant, such as a globule or flake, that is insoluble in the binder or solvent used.

[0018] As used herein, the term "dye" refers to a colorant that is molecularly soluble in the binder or solvent used.

[0019] As used herein, the term "colorant" includes pigments and dyes.

[0020] As used herein, the term "titanium suboxide" refers to a compound of the formula Tin O 2n-1 (wherein n is an integer greater than 1).

[0021] The term "LIDAR" is an acronym for "Light Detection and Ranging" or "Laser Imaging Detection and Ranging" and refers to a method of determining the range to an object (variable distance), the object's speed, and a 3D representation of the object by targeting the object with electromagnetic radiation, typically laser light, and measuring the time it takes for the reflected electromagnetic radiation to return to a receiver.

[0022] The term "RADAR" is an acronym for "Radio Detection and Ranging" and refers to a method of determining the range, angle, and radial velocity of an object by targeting the object with radio waves and measuring the time it takes for the reflected radio waves to return to the receiver.

[0023] [Mode for carrying out the invention] vehicle In a first aspect, the present invention provides a vehicle having a frame or body, at least a portion of an exterior surface of the frame or body being covered with a coating, the coating comprising at least two layers, the outer two or three layers being: (a) a base coat layer; (b) optionally, a tinted clearcoat layer over (a); (c) A top layer of clear coat on (a) or (b). and The base coat layer (a) is, based on the weight of the base coat layer (a), 14.95 to 98.95 weight percent of a binder or resin; 1 to 85% by weight of spherical glass beads having a median particle size D50 of 1 μm to 150 μm as measured by laser diffraction and a refractive index of 1.7 to 2.8 as measured at a wavelength λ of 589 nm; 0.05-30% by weight of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes or combinations thereof, the pigment flakes having a median diameter D50 of 1 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, as measured by laser diffraction; 0-30% by weight of further components; It consists of: The median diameter D50 of said pigment flakes is greater than 35% of the median particle diameter D50 of said spherical glass beads.

[0024] As will be appreciated by those skilled in the art, the phrase "base coat layer (a) consists of" means that the combined amounts of binder / resin, spherical glass beads, pigment flakes, and additional components total 100% by weight of base coat layer (a).

[0025] The term "vehicle" as used herein refers to a physical object used to transport people or goods. Non-limiting examples of vehicles in the context of the present invention are selected from the group consisting of cars, lorries, trucks, bicycles, mopeds, scooters, motorcycles, trains, trams, boats, ships, drones, skateboards, missiles, helicopters and aircraft. In a preferred embodiment, the vehicle is selected from cars, lorries, trucks, bicycles, mopeds, scooters and motorcycles.

[0026] The portion of the exterior surface of the frame or body to which the coating is applied may be, for example, a metal part, a carbon fiber part, a composite part, a plastic part, a truck tarpaulin, or canvas, and combinations thereof.

[0027] The portion of the exterior surface of the frame or body to which the coating is applied may be, for example, a metal exterior surface, a carbon fiber exterior surface, a composite exterior surface, a plastic exterior surface, a truck tarpaulin, or canvas, and combinations thereof.

[0028] In one embodiment, the portion of the exterior surface of the frame or body to which the coating is applied is a plastic part. In another embodiment, the portion of the exterior surface of the frame or body to which the coating is applied is a plastic part and the pigment flakes are selected from the group consisting of metallic pigment flakes.

[0029] In one embodiment, the coating is applied to at least a portion of an exterior surface of the frame or body plastic part, hi another embodiment, the coating is applied to at least a portion of an exterior surface of the frame or body plastic part and the pigment flakes are selected from the group consisting of metallic pigment flakes.

[0030] In one embodiment, at least a portion of the frame or body is made of plastic and at least a portion of its (i.e., the plastic frame or body part) exterior surface is covered with a coating. In another embodiment, at least a portion of the frame or body is made of plastic and at least a portion of its (i.e., the plastic frame or body part) exterior surface is covered with a coating, and the pigment flakes are selected from the group consisting of metallic pigment flakes.

[0031] In some embodiments, more than 1%, preferably more than 10%, more preferably more than 30%, even more preferably more than 50%, even more preferably more than 75%, and even more preferably more than 90% of the exterior surface of the frame or body is covered with the coating. In some embodiments, the entire exterior surface of the frame or body is covered with the coating.

[0032] coating As defined above, at least a portion of the exterior surface of the vehicle frame or body is covered with a coating, said coating comprising at least two layers, the outer two or three layers being (a) a basecoat layer, optionally (b) a tinted clearcoat layer over (a), and (c) a clearcoat top layer over (a) or (b). Although only the outer two or three layers of the coating are defined, the coating can also include additional layers between the exterior surface of the frame or body and the basecoat layer (a).

[0033] For example, if at least a portion of the frame or body of a "ready-to-use vehicle" comprises at least two exterior layers as defined above, the exterior surface of the frame or body typically already comprises a primer layer, one or more "first" basecoat layers different from the basecoat layer (a), and one or more (tinted) clearcoat (top) layers. The at least two exterior layers as defined above are then applied on top of the already present layers.

[0034] Thus, in one embodiment, the coating comprises the following layers in the following order: (i) optionally, one or more primer layers on the exterior surface of the frame or body; (ii) optionally, one or more "first" basecoat layers on the exterior surface of the frame or body, different from the basecoat layer (a) on (i); (iii) optionally, one or more clearcoat layers and / or tinted clearcoat layers on (i) or (ii) on the exterior surface of the frame or body; (iv) a basecoat layer (a) on (i), (ii), or (iii) on the frame or exterior surface of the vehicle; (v) optionally, a pigmented clearcoat layer (b) over the basecoat layer (a); and (vi) a top layer of clear coat (c) on a base coat layer (a) or on a tinted clear coat layer (b); Includes.

[0035] The coating can also be applied as a sticker, which is then applied onto at least a portion of the outer surface of the frame or body, or onto at least a portion of the outer coating layer of a different coating layer already present on the ready-to-use vehicle, if present.

[0036] The term "primer layer" is well known in the field of paints or coatings for vehicles and relates to an adhesion layer between the substrate to be coated, i.e. the outer surface of the frame or body, and the base coat layer (a) or "first" base coat layer. A primer layer is typically applied when there is insufficient adhesion between the substrate to be coated and the base coat layer. Thus, whether a primer layer is useful or even necessary depends on both the nature of the outer surface of the frame or body and the nature of the base coat layer.

[0037] The base coat layer (a) may be the only color layer of the coating. In some embodiments, color is provided only by the metallic pigment flakes, the pearlescent pigment flakes, or a combination thereof. However, the base coat layer (a) may also include additional colorants, such as dyes, organic pigments, and inorganic pigments, that are different from the metallic pigment flakes and the pearlescent pigment flakes defined herein.

[0038] If a "first" basecoat layer is present under the basecoat layer (a), this layer is typically a pigmented basecoat layer. The first basecoat layer can include metal pigment flakes, pearlescent pigment flakes, dyes, organic pigments, inorganic pigments, and combinations thereof. The "first" basecoat layer typically does not include spherical glass beads.

[0039] The clearcoat top layer (c) and the tinted clearcoat layer (b) can comprise two or more (tinted) clearcoat (top) layers applied on top of one another in a subsequent step. The basecoat layer (a) can also comprise two or more basecoat layers applied on top of one another in a subsequent step, provided that the basecoat layer (a) as a whole meets the requirements defined herein.

[0040] The terms "clearcoat top layer" and "clearcoat layer" are well known in the field of paints or coatings for vehicles and refer to a transparent layer over a pigmented basecoat layer, typically free of dyes and pigments. The clearcoat top layer is applied for various purposes, such as preventing oxidation or weathering of the basecoat layer, and / or to provide an overall coating with a glossy appearance. In a preferred embodiment, the clearcoat top layer (c) is free of dyes and pigments. In a preferred embodiment, the clearcoat top layer (c) is free of spherical glass beads. The term "tinted clearcoat layer" refers to a tinted clearcoat composition that is transparent and typically includes dyes, nanoscale pigments, and / or pigment flakes. In a preferred embodiment, the tinted clearcoat layer (b) is free of spherical glass beads.

[0041] In general, types of clearcoat compositions suitable for application in coatings include solvent-based and water-based clearcoat compositions, powder and powder slurry clearcoat compositions, and heat-curable and thermoplastic clearcoat compositions. The clearcoat composition may be radiation-curable. If the clearcoat composition is radiation-curable, it may include a cure initiator, such as a photoinitiator or a thermal initiator.

[0042] In a preferred embodiment, the total thickness of the base coat layer (a) is 1 μm to 300 μm, more preferably 2 μm to 75 μm, even more preferably 3 μm to 50 μm, even more preferably 4 μm to 40 μm, and even more preferably 5 μm to 20 μm. The total thickness of the base coat layer (a) is typically equal to or greater than the median particle size D90 of the spherical glass beads.

[0043] In a preferred embodiment, the spherical glass beads in the base coat layer (a) have a median particle size D50 of 1 μm to 25 μm, measured by laser diffraction, and a refractive index of 1.9 to 2.6, measured at a wavelength λ of 589 nm, and the pigment flakes selected from the group consisting of metal pigment flakes, pearlescent pigment flakes, or combinations thereof have a median particle size D50 of 2 μm to 75 μm, measured by laser diffraction, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, and the median particle size D50 of said pigment flakes is greater than 35% of the median particle size D50 of said spherical glass beads.

[0044] In a highly preferred embodiment, the spherical glass beads in the base coat layer (a) have a median particle size D50, measured by laser diffraction, of 1 μm to 15 μm and a refractive index, measured at a wavelength λ of 589 nm, of 2.0 to 2.3, and the pigment flakes selected from the group consisting of metal pigment flakes, pearlescent pigment flakes, or combinations thereof have a median particle size D50, measured by laser diffraction, of 3 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, and the median particle size D50 of said pigment flakes is greater than 45% of the median particle size D50 of said spherical glass beads.

[0045] The inventors have established that the improved Lidar detectability of the present coating is more pronounced when the coating is a metallic coating and / or has a dark color.

[0046] Binder or resin Binders and resins suitable for application in vehicle coatings are generally known to those skilled in the art. The suitability of the binder and resin type depends not only on their expected abrasion resistance, but also on the method of applying the precursor of the basecoat (a) layer to the vehicle, which is typically the case. On the one hand, precursor basecoat layer (a) compositions applied in water-based or aqueous form, and on the other hand, precursor basecoat layer (a) compositions applied based on organic solvents, typically require different binders and resins. Binders and resins suitable for both types of compositions are well known to those skilled in the art. The binder or resin may be radiation-curable. If the binder or resin is radiation-curable, further components may include a curing initiator, such as a photoinitiator or a thermal initiator.

[0047] Spherical Glass Beads As previously defined, the base coat layer (a) comprises spherical glass beads. In a preferred embodiment, the term "glass" in "spherical glass beads" as used herein refers to a non-crystalline, amorphous solid transparent material made of oxides. In another embodiment, the term "glass" in "spherical glass beads" refers to a solid transparent material made of oxides and containing some microcrystallinity. The refractive index of the spherical glass beads is closely related to the density of glass, although this relationship is not linear. Due to the nature of glass, the density is approximately an additive function of its composition. The density of spherical glass beads with a refractive index of 1.5 to 2.8 is typically 2.5 g / cm 3 ~4.5g / cm 3 It changes.

[0048] In a preferred embodiment, the spherical glass beads have a refractive index, measured at a wavelength λ of 589 nm, of 1.9 to 2.6, preferably 2.0 to 2.3.

[0049] In another embodiment, the spherical glass beads as defined herein comprise at least two types of spherical glass beads.

[0050] The oxides that can be used in the glass are the oxides of silicon, boron, aluminum, sodium, barium, vanadium, titanium, lanthanum, strontium, zirconium, potassium, magnesium, iron, calcium, zinc, lithium, barium, and lead. Spherical glass beads can include, for example, different combinations of silica (SiO2), boron oxide (B2O3), phosphorus pentoxide (P2O5), vanadium pentoxide (V2O5), arsenic trioxide (As2O3), germanium oxide (GeO2), calcium oxide (CaO), sodium oxide (Na2O), magnesium oxide (MgO), zinc oxide (ZnO), aluminum oxide (Al2O3), potassium oxide (K2O), iron oxide (Fe2O3), lead oxide (PbO), barium oxide (BaO), barium titanate (BaTiO3), titanium oxide (TiO2), lithium oxide (Li2O), strontium oxide (SrO), lanthanum oxide (La2O3), and zirconium oxide (ZrO2). Silica and boron oxide generally have the lowest density. Thus, glasses with a high weight percentage of these oxides generally result in glass beads with a low refractive index. The refractive index can be increased by adding oxides with higher molecular weights. Preferably, the spherical glass beads are free of PbO.

[0051] Glass beads having a refractive index in the range of 1.5 to 2.51 and their compositions with respect to oxides are disclosed in WO 2014 / 109564, which is incorporated herein by reference in its entirety. PbO-free transparent glass beads having a refractive index greater than 2.15 are disclosed in U.S. Pat. No. 4,082,427, which is incorporated herein by reference in its entirety.

[0052] The spherical glass beads may be colored spherical glass beads, provided that they remain transparent. Both colored spherical glass beads made of colored transparent glass and spherical glass beads with a concentric transparent color coating are encompassed by the present invention. The color may be a natural color caused by the composition of oxides, or may be deliberately selected by adding components with a specific color. Colored glass beads with high refractive index and high transmittance are disclosed in WO 2014 / 109564.

[0053] Thus, in some embodiments, at least some of the spherical glass beads are spherical glass beads made of colored transparent glass and / or at least some of the spherical glass beads are provided with a concentric transparent colored coating.

[0054] Spherical glass beads have a median diameter D50, as measured by laser diffraction. The median diameter D50 is therefore the volume median based on a volume distribution. The median diameter D50 is the diameter below which half of the population of spherical glass beads lies. This volume median diameter is known in the art as Dv50 or D v0.5 It is often referred to as.

[0055] In a preferred embodiment, the spherical glass beads have a median particle size D50, measured by laser diffraction, of 1.5 μm to 100 μm, more preferably 2 μm to 50 μm, even more preferably 2.5 μm to 20 μm, even more preferably 3 μm to 10 μm, for example less than 3 μm to 10 μm, or less than 3 μm to 9.5 μm.

[0056] In another embodiment, the spherical glass beads have a median particle size D50, as measured by laser diffraction, of 10 μm to 150 μm, for example 15 μm to 150 μm, 20 μm to 150 μm, 25 μm to 150 μm, 30 μm to 150 μm, or 35 μm to 150 μm.

[0057] In a highly preferred embodiment, the spherical glass beads have a median particle size D50, as measured by laser diffraction, of 1 μm to 100 μm, e.g., 1 μm to 75 μm, 1 μm to 50 μm, 1 μm to 45 μm, 1 μm to 40 μm, 1 μm to 35 μm, 1 μm to 30 μm, 1 μm to 25 μm, 1 μm to 20 μm, 1 μm to 15 μm, 1 μm to 10 μm, 1 μm to less than 10 μm, 1 μm to 9.5 μm, 1 μm to 9 μm, or 1 to 8.

[0058] In a preferred embodiment, the spherical glass beads have a median particle size D50, as measured by laser diffraction, of 5 μm to 100 μm, more preferably 5 μm to 75 μm, even more preferably 5 μm to 50 μm, for example 5 μm to 45 μm, 5 μm to 40 μm, 5 μm to 35 μm, 5 μm to 30 μm, 5 μm to 25 μm, 5 μm to 20 μm, or 5 μm to 15 μm.

[0059] The diameters D10 and D90 are referred to in the art as Dv10 or D v0.1 and Dv90 or D v0.9 The D10 diameter is the diameter below which 10% of the population of spherical glass beads lies. Similarly, the D90 diameter is the diameter below which 90% of the population of spherical glass beads lies.

[0060] The span of the particle size distribution of spherical glass beads, as measured by laser diffraction, is:

number

[0061] In another embodiment, the spherical glass beads have a median particle size D50 of 1 μm to 100 μm, and a span of 0 to 1.9, preferably 0 to 1.5, more preferably 0 to 1, even more preferably 0 to 0.5, such as 0 to 0.2, or 0 to 0.1, as measured by laser diffraction.

[0062] In a preferred embodiment, the spherical glass beads have a median particle size D50 of 1 μm to 50 μm, and a span of 0 to 1.9, preferably 0 to 1.5, more preferably 0 to 1, even more preferably 0 to 0.5, such as 0 to 0.2, or 0 to 0.1, as measured by laser diffraction.

[0063] In another preferred embodiment, the spherical glass beads have a median particle size D50 of 1 μm to 25 μm, and a span of 0 to 1.9, preferably 0 to 1.5, more preferably 0 to 1, even more preferably 0 to 0.5, such as 0 to 0.2, or 0 to 0.1, as measured by laser diffraction.

[0064] In yet another preferred embodiment, the spherical glass beads have a median particle size D50 of 1 μm to 15 μm, and a span of 0 to 1.9, preferably 0 to 1.5, more preferably 0 to 1, even more preferably 0 to 0.5, such as 0 to 0.2, or 0 to 0.1, as measured by laser diffraction.

[0065] In yet another preferred embodiment, the spherical glass beads have a median particle size D50 of 1 μm to 10 μm, and a span of 0 to 1.9, such as 0 to 1.5, 0 to 1, 0 to 0.5, 0 to 0.2, or 0 to 0.1, as measured by laser diffraction.

[0066] In yet another preferred embodiment, the spherical glass beads have a median particle size D50, as measured by laser diffraction, of 1 μm to less than 10 μm, and a span of 0 to 1.9, such as 0 to 1.5, 0 to 1, 0 to 0.5, 0 to 0.2, or 0 to 0.1.

[0067] In yet another preferred embodiment, the spherical glass beads have a median particle size D50 of 1 μm to 8 μm, and a span of 0 to 1.9, such as 0 to 1.5, 0 to 1, 0 to 0.5, 0 to 0.2, or 0 to 0.1, as measured by laser diffraction.

[0068] As will be appreciated by those skilled in the art, span=0 corresponds to monodisperse spherical glass beads.

[0069] In a preferred embodiment, the spherical glass beads are not hemispherically coated with a light reflective coating, such as a hemispherical aluminum coating (HAC).

[0070] In one embodiment, at least a portion of the spherical glass beads are fluorochemically coated. In another embodiment, at least a portion of the spherical glass beads are silane coated. In another embodiment, at least a portion of the spherical glass beads are silicone coated.

[0071] In a preferred embodiment, the amount of spherical glass beads is 1.5 to 80% by weight, more preferably 2 to 70% by weight, even more preferably 3 to 65% by weight, based on the weight of the base coat layer (a).

[0072] In some embodiments, the amount of spherical glass beads is 1-80 wt%, 1-75 wt%, 1-70 wt%, 1-65 wt%, 1-60 wt%, 1-55 wt%, 1-50 wt%, 1-45 wt%, 1-40 wt%, 1-35 wt%, 1-30 wt%, 1-25 wt%, 1-20 wt%, 1-15 wt%, or 1-10 wt%, based on the weight of the base coat layer (a).

[0073] In other embodiments, the amount of spherical glass beads is 2-85 wt%, 5-85 wt%, 10-85 wt%, 15-85 wt%, 20-85 wt%, 25-85 wt%, or 30-85 wt%, based on the weight of base coat layer (a).

[0074] Pigment flakes The base coat layer (a) comprises 0.05% to 30% by weight, based on the weight of the base coat layer (a), of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or combinations thereof, said pigment flakes having a median diameter D50 of 1 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, as measured by laser diffraction.

[0075] In some embodiments, the pigment flakes are selected from the group consisting of metallic pigment flakes.

[0076] Metallic pigment flakes and pearlescent pigment flakes constitute two main types of (flake-like) special effect pigments. Metallic pigment flakes, also called metallic effect pigment flakes, consist of flaky metal particles used to give products metallic effect colors or functional properties such as corrosion resistance, heat resistance, and electrical conductivity. The small metal platelets behave like mirrors and can reflect incident light. Pearlescent pigment flakes simulate the luster of natural pearls and give materials additional color effects such as angular color dependence. Pearlescent pigments typically have several layers of materials with different refractive indices. Thin flakes of low refractive index materials such as mica, silica, alumina, or glass are typically used as substrates, which are coated with high refractive index materials. However, pearlescent pigment flakes without substrates are also encompassed by the present invention.

[0077] In a preferred embodiment, the pearlescent pigment flakes have several layers of materials with different refractive indexes, where a low refractive index material such as mica, silica, alumina, or glass is used as a substrate, which is coated with a material of higher refractive index.

[0078] Aspect Ratio The term "flake" or "platelet" as used herein refers to a pigment shape having a large surface area and a small thickness. Typically, flakes or platelets are characterized by their "aspect ratio", which is defined as the largest dimension, i.e., the maximum diameter of the surface, divided by the smallest dimension, i.e., the thickness.

[0079] The pigment flakes used herein have an aspect ratio of at least 10, preferably at least 15, more preferably at least 20, and even more preferably at least 30.

[0080] In one embodiment, the pigment flakes used herein have an aspect ratio of 10-500, preferably 15-250, and more preferably 20-100.

[0081] Median diameter of pigment flakes In a preferred embodiment, the median diameter of the pigment flakes is 1.5 to 65 μm, more preferably 2 to 50 μm, even more preferably 2.5 to 40 μm, even more preferably 3 to 35 μm, and most preferably 4 to 30 μm.

[0082] In another preferred embodiment, the median diameter of the pigment flakes is from 1 to 65 μm, for example from 1 to 50 μm, from 1 to 40 μm, from 1 to 35 μm, from 1 to 25 μm, from 1 to 20 μm, from 1 to 15 μm, or from 1 to 13 μm.

[0083] In another embodiment, the median diameter of the pigment flakes is from 1.5 to 75 μm, for example, from 3 to 75 μm, from 5 to 75 μm, from 7 to 75 μm, from 9 to 75 μm, or from 11 to 75 μm.

[0084] Pigment flake thickness In a preferred embodiment, the thickness of the pigment flakes is from 10 nm to 950 nm, more preferably from 15 nm to 850 nm, and even more preferably from 50 nm to 650 nm.

[0085] In another preferred embodiment, the thickness of the pigment flakes is from 10 nm to 200 nm, for example from 10 nm to 150 nm, from 10 nm to 100 nm, or from 10 nm to 50 nm.

[0086] In another preferred embodiment, the thickness of the pigment flake is from 200 nm to 980 nm, for example from 300 nm to 980 nm, from 400 nm to 980 nm, or from 500 nm to 980 nm.

[0087] Types of pigment flakes In a preferred embodiment, the pigment flakes defined herein are (A) metal or mica flakes, optionally coated with at least one layer of one or more components selected from the group consisting of metal oxides, metals, metal sulfides, titanium suboxides, titanium oxynitrides, FeO(OH), SiO2, B2O3, GeO2, MgF2, metal alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and binders; (B) flakes comprising Al2O3, SiO2, glass, ceramic, graphite, or mica platelets, coated with at least one layer of one or more components selected from the group consisting of metal oxides, metals, metal sulfides, titanium suboxides, titanium oxynitrides, FeO(OH), SiO2, B2O3, GeO2, metal alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and binders; and (C) Flakes comprising Al2O3 platelets doped with one or more components selected from the group consisting of TiO2, ZrO2, SiO2, SnO2, In2O3, ZnO, and iron oxide, coated with at least one layer of one or more components selected from the group consisting of metal oxides, metals, metal sulfides, titanium suboxides, titanium oxynitrides, FeO(OH), SiO2, B2O3, GeO2, metal alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and binders. The compound is selected from (A), (B), (C), or a combination thereof.

[0088] In a preferred embodiment, the pigment flake is a synthetic pigment flake. As will be appreciated by those skilled in the art, the term "synthetic" in "synthetic pigment flake" means that the pigment flake is not a naturally occurring pigment flake, but rather a chemically produced pigment flake or a chemically / physically treated naturally occurring pigment flake. One advantage of using synthetic pigment flakes is that they can be produced with very smooth surfaces and high aspect ratios, thereby enhancing reflective properties.

[0089] The pigment flakes (A) can have zero to multiple coating layers, for example 1, 2, 3, 4, or 5 coating layers.

[0090] In an embodiment, the metal in the metal pigment flake (A) is selected from the group consisting of aluminum, silver, and gold, preferably aluminum. In an embodiment, the metal pigment flake (A) is an aluminum flake without a coating. An example of an aluminum pigment flake without a coating (A) is Decomet® aluminum flake (Schlenk, Germany). Decomet® aluminum pigment flakes typically have a median diameter (D50) of 10 μm to 15 μm and a thickness of less than 50 nm.

[0091] In one embodiment, the pigment flake (A) is an uncoated mica flake.

[0092] In one embodiment, the pigment flake (A) is a mica flake with several coating layers, such as a mica flake coated with TiO2, Fe2O3, and SnO2. An example is Iriodin® Silver-Grey SW pigment flake (Merck, Germany).

[0093] In one embodiment, the metal pigment flake (A) is an aluminum pigment flake coated with at least one layer of one or more components selected from the group consisting of metal oxides, SiO2, B2O3, and GeO2. In one embodiment, the metal pigment flake (A) is an aluminum flake coated with a SiO2 layer.

[0094] An example of a suitable aluminum pigment flake (A) coated with a SiO2 layer is Aquamet® aluminum flake (Schlenk, Germany). Aquamet® aluminum flakes typically have a median diameter (D50) of 5 μm to 50 μm and a thickness of 20 nm to 1 μm.

[0095] An example of a suitable aluminum pigment flake (A) coated with MgF2 is SpectraFlair pigment (VIAVI Solutions Inc., USA), which typically has a median diameter (D50) of 14 μm to 35 μm and a thickness of 250 nm to 900 nm.

[0096] In an embodiment, the flake (A) is coated with an outer layer comprising a SiO2 layer and one or more colorants and a binder for fixing the one or more colorants. An example of a suitable aluminum pigment flake (A) coated with an outer layer comprising a SiO2 layer and one or more colorants and a binder is Toyal flake (Toyo Aluminium KK, Japan). Toyal flake may have a median diameter (D50) of about 10 μm and a thickness of less than 1 μm, for example about 100 nm.

[0097] Examples of metal oxides that can be applied to the coating layer on the metal pigment flakes (A) are selected from the group consisting of TiO2, ZrO2, SnO2, ZnO, MnO2, MgO, Ce2O3, Fe2O3, Fe3O4, FeTiO5, Cr2O3, CoO, CO3O4, VO2, V2O3, NiO, and combinations thereof.

[0098] Examples of suitable aluminum pigment flakes (A) coated with (i) a first layer of SiO2, B2O3, MnO2, MgO, GeO2, or Al2O3, (ii) a second Fe2O3 layer on top of the first layer, and optionally (iii) a third layer of TiO2, ZrO2, or Al2O3 on top of the second layer are disclosed in U.S. Patent Application Publication No. 2019 / 044679, the entirety of which is incorporated herein by reference.

[0099] The pigment flakes (B) and (C) can have one to several coating layers, for example 2, 3, 4, or 5 coating layers.

[0100] Examples of metal oxides that can be applied to the coating layer on the metal pigment flakes (A) are selected from the group consisting of TiO2, ZrO2, SnO2, ZnO, MnO2, MgO, Ce2O3, Fe2O3, Fe3O4, FeTiO5, Cr2O3, CoO, CO3O4, VO2, V2O3, NiO, and combinations thereof.

[0101] In one embodiment, the pigment flake (B) comprises glass platelets, the glass being a borosilicate glass. In a highly preferred embodiment, the pigment flake (B) comprises Al2O3 platelets.

[0102] In an embodiment, the pigment flake (B) or (C) is coated with one or more layers of a metal oxide, for example at least one layer of a metal oxide selected from the group consisting of TiO2, ZrO2, SnO2, ZnO, MnO2, MgO, Ce2O3, Fe2O3, Fe3O4, FeTiO5, Cr2O3, CoO, CO3O4, VO2, VO3, NiO, and combinations thereof. In a preferred embodiment, the pigment flake (B) or (C) is coated with one or more layers of a metal oxide selected from the group consisting of TiO2, Fe2O3, Fe3O4, SnO2, ZrO2, Cr2O3, and combinations thereof, for example coated with one layer of a metal oxide selected from the group consisting of TiO2, Fe2O3, and combinations thereof.

[0103] An example of a pigment flake (B) comprising Al2O3 platelets coated with different layers of metal oxide, SiO2, and organic dye as a topcoat is disclosed in EP 2799398, the entirety of which is incorporated herein by reference.

[0104] Examples of pigment flakes (B) comprising Al2O3 platelets coated with a metal oxide selected from the group consisting of TiO2, Fe2O3, and combinations thereof, and their preparation are disclosed in U.S. Pat. No. 6,267,810, the entirety of which is incorporated herein by reference.

[0105] An example of a pigment flake (B) comprising Al2O3 platelets coated with a TiO2 or Fe2O3 layer is Xirallic® pigment (Merck, Germany). Xirallic® pigments typically have a median diameter (D50) of 5 μm to 50 μm and a thickness of up to 1 μm.

[0106] In another embodiment, the pigment flakes (B) or (C) are titanium suboxide (Ti n O 2n-1 , n is an integer greater than 1, e.g., a layer of an oxide (Ti3O5, Ti2O3), a layer of titanium oxynitride, a layer of FeO(OH), or a thin semi-transparent metal layer comprising, e.g., Al, Fe, Cr, Ag, Au, Pt, or Pd, or a combination thereof.

[0107] In yet another embodiment, the pigment flakes (B) or (C) are coated with a layer of a metal sulfide, for example a sulfide of tungsten, molybdenum, cerium, lanthanum, or a rare earth element.

[0108] In another embodiment, the pigment flakes (B) or (C) are coated with one or more colorants, such as Prussian Blue or Carmine Red, and an outer layer of a binder to fix the colorants.

[0109] As will be appreciated by those skilled in the art, these different layers can be combined, provided that the colorant and binder layer(s), if present, is always the outer layer.

[0110] Examples of pigment flakes (C) comprising titanium oxide-doped, metal oxide-coated Al2O3 platelets and their preparation are disclosed in EP 0763573, the entirety of which is incorporated herein by reference.

[0111] Examples of pigment flakes (C) comprising metal oxide-coated Al2O3 platelets doped with TiO2, ZrO2, SiO2, SnO2, In2O3, or ZnO are disclosed in EP 2799398, the entirety of which is incorporated herein by reference.

[0112] The ratio of the diameter of the pigment flakes to the diameter of the spherical glass beads In a preferred embodiment, the median diameter D50 of the pigment flakes is greater than 36% of the median particle size D50 of the spherical glass beads, more preferably greater than 38%, such as greater than 40, greater than 45, greater than 50%, greater than 55%, greater than 60%, greater than 70%, greater than 90%, greater than 110%, or greater than 130%.

[0113] In another preferred embodiment, the median diameter D50 of the pigment flakes is 35% to 400% of the median particle diameter D50 of the spherical glass beads, more preferably 40% to 400%, for example 45% to 400%, 50% to 400%, 55% to 400%, 60% to 400%, 70% to 400%, 90% to 400%, 110% to 400%, or 130% to 400%.

[0114] In yet another embodiment, the median diameter D50 of the pigment flakes is 35% to 350%, more preferably 35% to 300%, such as 35% to 250%, 35% to 225%, 35% to 200%, 35% to 175%, 35% to 150%, 35% to 125%, 35% to 100%, or 35% to 75% of the median particle size D50 of the spherical glass beads.

[0115] Amount of pigment flakes In a preferred embodiment, the amount of said pigment flakes in the base coat layer (a) is 0.1 to 25% by weight, for example 0.5 to 20% by weight, 1 to 18% by weight, 2 to 16% by weight, 3 to 14% by weight, or 5 to 13% by weight, based on the weight of the base coat layer (a).

[0116] In one embodiment, the amount of the pigment flakes in the base coat layer (a) is 0.1 to 24 wt. %, for example 0.1 to 20 wt. %, 0.1 to 18 wt. %, 0.1 to 16 wt. %, 0.1 to 14 wt. %, or 0.1 to 13 wt. %, based on the weight of the base coat layer (a).

[0117] In another embodiment, the amount of the pigment flakes in the base coat layer (a) is 0.5 to 30% by weight, for example 1 to 30% by weight, 2 to 30% by weight, 5 to 30% by weight, 8 to 30% by weight, or 10 to 30% by weight, based on the weight of the base coat layer (a).

[0118] The amount of the pigment flakes in the base coat layer (a) is preferably 1 part by weight per 1 to 30 parts by weight of the spherical glass beads, preferably 1 part by weight per 1 to 15 parts by weight of the spherical glass beads, and more preferably 1 part by weight per 1 to 10 parts by weight of the spherical glass beads.

[0119] Further ingredients As defined above, the base coat layer (a) comprises 0-30 wt. % of additional components. As recognized by those skilled in the art, the "additional" components are different from the other components defined in the base coat layer (a). In other words, the additional components do not include the binder, the spherical glass beads, and the pigment flakes.

[0120] In some embodiments, the additional component is selected from the group consisting of thickeners, foam control agents, luminescent agents, UV absorbers, preservatives, dyes, cure initiators, organic pigments, inorganic pigments other than metallic pigment flakes and pearlescent pigment flakes, and combinations thereof.

[0121] In some embodiments, the amount of the additional component is 0.01 to 25 wt%, 0.02 to 20 wt%, 0.05 to 18 wt%, 0.1 to 16 wt%, 0.2 to 14 wt%, 0.25 to 12 wt%, 0.30 to 10 wt%, or 0.35 to 8 wt%, based on the weight of the base coat layer (a).

[0122] In some embodiments, the amount of the additional component is 0-25 wt%, 0-20 wt%, 0-18 wt%, 0-16 wt%, 0-14 wt%, 0-12 wt%, 0-10 wt%, or 0-8 wt%, based on the weight of the base coat layer (a).

[0123] In other embodiments, the amount of the further component is 0.01-30 wt%, 0.02-30 wt%, 0.05-30 wt%, 0.1-30 wt%, 0.2-30 wt%, 0.25-30 wt%, 0.30-30 wt%, or 0.35-30 wt%, based on the weight of the base coat layer (a).

[0124] Base coat layer (a) typically comprises one or more thickeners as part of further components.Thickeners can provide the composition, for example, water-based or organic solvent-based composition, that is applied to the vehicle with the necessary rheology to produce high-quality base coat layer (a).Without wishing to be bound by any theory, it is believed that thickeners do not have any particular advantageous properties in the dried, cured or ready-to-use coating on the vehicle.

[0125] In one embodiment, the further component comprises a thickener, the amount of the thickener being 0.01 to 3 wt. %, more preferably 0.01 to 2 wt. %, even more preferably 0.01 to 1 wt. %, based on the weight of the base coat layer (a).

[0126] As will be appreciated by those skilled in the art, the type of thickener present in the basecoat (a) depends on the way in which the "precursor basecoat layer (a) composition" is applied to the vehicle. Precursor compositions applied in water-based or aqueous form on the one hand and compositions applied based on organic solvents on the other hand typically require different thickeners to obtain the required rheological properties.

[0127] Thickener for water-based or aqueous compositions One preferred group of thickeners for the aqueous precursor basecoat layer (a) composition are ASE polymers (alkali swellable emulsions, these polymers are produced using emulsion polymerization). In one embodiment, the hydrophilic monomers of the ASE polymers are selected from the group consisting of (meth)acrylic acid, maleic acid, and combinations thereof. In another embodiment, the hydrophobic monomers of the ASE polymers are selected from the group consisting of esters of (meth)acrylic acid and C1-C4-alcohols, in particular ethyl acrylate, butyl acrylate, and methyl methacrylate.

[0128] Another preferred group of thickeners for the waterborne precursor basecoat layer (a) composition are HASE polymers (hydrophobically modified alkali swellable emulsions, these polymers are produced using emulsion polymerization). The hydrophilic and hydrophobic monomers of the HASE polymers can be the same as those described for the ASE polymers. The preferred hydrophobic associative monomers are (meth)acrylic acid and C8-C 22 - (meth)acrylic acid ester monomers of alcohols and / or (substituted) vinyl alcohols with C8-C 22 - is a vinyl ester monomer of alkyl acid.

[0129] Yet another preferred group of thickeners for the aqueous precursor basecoat layer (a) composition are hydrophobically modified ethoxylated urethane (HEUR) polymers. Unlike ASE or HASE type thickeners, HEUR polymers are non-ionic and soluble at any pH. This solubility is due to the ethylene oxide backbone of the polymer, which is water-soluble and constitutes the majority of the polymer structure. Therefore, HEUR polymers require hydrophobic moieties in the composition to interact with the ethylene oxide backbone to provide structure.

[0130] Examples of ASE polymers include Rheovis® 1125 (available from BASF Corporation), ACULYN™ 33, ACULYN™ 38, ACUSOL™ 810A, ACUSOL™ 830, ACUSOL™ 835, ACUSOL™ 842 (all available from DOW Chemical), and Carbopol® Aqua 30 polymer (manufactured by Lubrizol Corporation).

[0131] Examples of HASE polymers include ACULYN™ Excel, ACRYSOL™ TT615, ACULYN™ 22, ACULYN™ 88, ACUSOL™ 801S, ACUSOL™ 805S, ACUSOL™ 820, and ACUSOL™ 823 (all available from DOW Chemical).

[0132] Examples of HEUR polymers include ACUSOL™ 880, ACUSOL™ 882, ACULYN™ 44, and ACULYN™ 46N (all available from DOW Chemical).

[0133] In yet another embodiment, the thickener for the waterborne precursor basecoat layer (a) composition is selected from the group consisting of ASE polymers, HASE polymers, HEUR polymers, liquid acrylic crosslinked or copolymer dispersions, acrylate crosspolymers, crosslinked polyacrylic acid polymers, crosslinked polyacrylic acid copolymers, non-ionic aqueous emulsions of modified ethylene vinyl acetate copolymer waxes, modified ureas or urea modified polyamides, and combinations thereof.

[0134] Thickener for organic solvent-based compositions Examples of thickeners that can be used in the organic solvent-based precursor basecoat layer (a) composition are preferably selected from the group consisting of (modified) hydrogenated castor oil, clays, modified clays, sulfonic acid calcium complexes, organophilic phyllosilicates, silica gels, synthetic amorphous silicas, acrylic acid type gelling agents, modified cellulose-based materials, polyurea dispersions, solutions of urea modified polyamides, polyurethane dispersions, and combinations thereof. Examples of modified clays include BENTONE® LT and BENTONE® 38 (Elementis Global). Examples of silica gels include HDK® N20 (Wacker Chemical Corporation) or AEROSIL® (Evonik). Examples of organophilic phyllosilicates include Claytone 40 (Byk). An example of modified hydrogenated castor oil is Efka® RM 1900 (BASF). An example of hydrogenated castor oil is Efka® RM 1920 (BASF). An example of a solution of a non-polar urea modified polyamide in isobutanol / monophenyl glycol is Rheobyk-431 (Byk). An example of a medium polar urea modified polyamide in isobutanol / solvent naphtha is Rheobyk-430 (Byk). An example of a synthetic amorphous silica is Zeothix® (Huber).

[0135] In a preferred embodiment, the organic solvent based precursor basecoat layer (a) composition comprises two thickeners, more preferably: Organophilic phyllosilicates and modified hydrogenated castor oil, or Calcium sulfonate complexes and polyurea dispersions Includes.

[0136] Preferred thickeners in base coat layer (a) In a preferred embodiment, the base coat layer (a) comprises, as part of further components, one or more thickeners selected from the group consisting of ASE polymers, HASE polymers, HEUR polymers, liquid acrylic crosslinked or copolymer dispersions, acrylate crosspolymers, crosslinked polyacrylic acid polymers, crosslinked polyacrylic acid copolymers, non-ionic aqueous emulsions of modified ethylene vinyl acetate copolymer waxes, modified urea or urea modified polyamides, (modified) hydrogenated castor oils, clays, modified clays, sulfonic acid calcium complexes, organophilic phyllosilicates, silica gels, synthetic amorphous silicas, acrylic acid type gelling agents, modified cellulose materials, polyurea dispersions, solutions of urea modified polyamides, polyurethane dispersions, and combinations thereof.

[0137] Laser Imaging Detection and Ranging (LIDAR) Process A second aspect of the present invention is (i) providing a LIDAR device comprising an electromagnetic radiation source, a receiver and optionally a Global Positioning System (GPS); (ii) transmitting electromagnetic radiation from an electromagnetic radiation source of the LIDAR device to the vehicle; (iii) scanning the electromagnetic radiation reflected by the coating of the vehicle with a receiver of the LIDAR device; (iv) from the difference between the transmitted electromagnetic radiation and the scanned reflected electromagnetic radiation, preferably as a function of time; the distance between the vehicle and the LIDAR device; Vehicle acceleration, Vehicle deceleration, the direction of vehicle movement, the speed of the vehicle, preferably relative to the speed of the LIDAR device, and 3D image of the vehicle and calculating one or more of: The present invention relates to a vehicular laser imaging detection and ranging (LIDAR) process as defined above, including:

[0138] As will be appreciated by those skilled in the art, calculating the vehicle's speed, acceleration, deceleration and direction of travel requires steps (ii) and (iii) to be performed as a function of time.

[0139] If the LIDAR device is also equipped with GPS, the distance between the vehicle and the LIDAR device can also be shown on the map and a 3D image of the vehicle can be identified on the map.

[0140] In a preferred embodiment, the electromagnetic radiation transmitted and scanned in steps (ii) and (iii), respectively, has a wavelength between 740 nm and 2500 nm, preferably between 750 nm and 1800 nm, more preferably between 780 nm and 1600 nm, e.g. 905 nm or 1550 nm.

[0141] In an embodiment, the electromagnetic radiation transmitted and scanned in steps (ii) and (iii), respectively, has a wavelength between 740 nm and 2200 nm, for example between 740 nm and 2000 nm, between 740 nm and 1800 nm, between 740 nm and 1700 nm, between 740 nm and 1650 nm, and between 740 nm and 1600 nm.

[0142] In another embodiment, the electromagnetic radiation transmitted and scanned in steps (ii) and (iii), respectively, has a wavelength between 750 nm and 2500 nm, for example between 780 nm and 2500 nm, between 800 nm and 2500 nm, between 825 nm and 2500 nm, between 850 nm and 2500 nm, and between 875 nm and 2500 nm.

[0143] The LIDAR device may be a mobile device, such as a LIDAR gun for checking the speed of vehicles, a device fixed to a certain infrastructure element, for example to determine traffic density, or a mobile device placed on another vehicle.

[0144] Radio Detection and Ranging (RADAR) Process Another aspect of the present invention is a method for producing a (i) providing a vehicle as previously defined with a RADAR device within a frame or body, said RADAR device comprising a radio source and a receiver, the vehicle optionally being equipped with a Global Positioning System (GPS); (ii) transmitting radio waves from a radio source of the RADAR device through at least a portion of the exterior surface of the frame or body of the vehicle that is covered with the coating as previously defined, to an object outside the vehicle; (iii) scanning with a receiver of the RADAR device for radio waves reflected by objects outside the vehicle; (iv) from the difference between the transmitted radio waves and the scanned reflected radio waves, preferably as a function of time; the distance between the object and the RADAR device, Acceleration of the object relative to the RADAR device, The deceleration of the object relative to the RADAR device, the direction of movement of the object relative to the RADAR device, and The velocity of the object, preferably relative to the velocity of the RADAR device and calculating one or more of: The present invention relates to the radio detection and ranging (RADAR) process, including

[0145] As used herein, the expression "RADAR device within a frame or body" means that the frame or body is positioned between the RADAR device and objects outside the vehicle, e.g., the RADAR device is positioned inside the vehicle behind the bumper to scan objects outside the vehicle in front of the bumper.

[0146] In this RADAR process, the portion of the exterior surface of the frame or body to which the coating is applied is preferably a plastic part, such as a plastic bumper. In a preferred embodiment of this RADAR process, the portion of the exterior surface of the frame or body to which the coating is applied is a plastic part, such as a plastic bumper, and the pigment flakes are selected from the group consisting of metallic pigment flakes. The RADAR device, which comprises a radio wave source and a receiver, is preferably positioned within the frame or body of the vehicle behind the plastic bumper.

[0147] In this RADAR process, the portion of the exterior surface of the frame or body to which the coating is applied is preferably the exterior surface of a plastic part, such as the exterior surface of a plastic bumper. In a preferred embodiment of this RADAR process, the portion of the exterior surface of the frame or body to which the coating is applied is the exterior surface of a plastic part, such as the exterior surface of a plastic bumper, and the pigment flakes are selected from the group consisting of metallic pigment flakes. The RADAR device, which comprises a radio wave source and a receiver, is preferably positioned within the frame or body of the vehicle behind the plastic bumper.

[0148] As will be appreciated by those skilled in the art, calculating the velocity, acceleration, deceleration and direction of movement of an object requires steps (ii) and (iii) to be performed as a function of time.

[0149] The distance between the object and the RADAR device can be processed into a (real-time) image of the vehicle's surroundings that is shown on a video screen inside the vehicle.

[0150] If the vehicle is also equipped with GPS, the distance between the object and the RADAR device can also be shown on the map.

[0151] In a preferred embodiment, the radio waves transmitted and scanned in steps (ii) and (iii), respectively, have a wavelength between 3.5 mm and 14.5 mm. In another preferred embodiment, the radio waves transmitted and scanned in steps (ii) and (iii), respectively, have a wavelength between 12.1 mm and 12.6 mm (Short Range RADAR, SRR). In yet another preferred embodiment, the radio waves transmitted and scanned in steps (ii) and (iii), respectively, have a wavelength between 3.6 mm and 4.0 mm (Long Range RADAR, LRR).

[0152] Method for coating an exterior surface of a vehicle frame or body The base coat layer (a) is typically provided on the outer surface of the vehicle frame or body in the form of an organic solvent-based composition or in the form of an aqueous or water-based composition, such compositions being referred to below as "precursor base coat layer (a) compositions."

[0153] These organic solvent-based, aqueous or water-based precursor basecoat layer (a) compositions therefore contain a solvent in addition to the solid components of the basecoat layer (a) in the relative amounts defined above. The amount of solvent in the organic solvent-based, aqueous or water-based composition is typically 15 to 75 wt. %, for example 25 to 65 wt. %, based on the weight of the precursor basecoat layer (a) composition.

[0154] In other words, the precursor basecoat layer (a) composition comprises, based on the weight of the precursor basecoat layer (a) composition: (A) 15 to 75% by weight of water, an aqueous solvent, or an organic solvent; (B) 25 to 85% by weight of a solid composition; may consist of, The solid composition (B) is, based on the weight of the solid composition (B), 14.95 to 98.95 weight percent of a binder; 1 to 85% by weight of spherical glass beads having a median particle size D50 of 1 μm to 150 μm as measured by laser diffraction and a refractive index of 1.7 to 2.8 as measured at a wavelength λ of 589 nm; 0.05 to 30% by weight of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or combinations thereof, the pigment flakes having a median diameter D50 of 1 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, as measured by laser diffraction; 0-30% by weight of further components; It consists of: The median diameter D50 of the pigment flakes is greater than 35% of the median particle diameter D50 of the spherical glass beads.

[0155] The solvent may be, for example, an aqueous solvent or water. As used herein, the term "aqueous solvent" includes at least 70% by weight water, preferably at least 80% by weight water, more preferably at least 90% by weight water, even more preferably at least 95% by weight water, such as at least 96% by weight, at least 97% by weight, or at least 98% by weight, based on the weight of the aqueous solvent.The remaining solvent in the aqueous solvent is not particularly limited, but is typically a water-miscible organic solvent, such as an alcohol (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol), a polyhydric alcohol (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerol, hexanetriol, or thiodiglycol), a glycol derivative, such as an ether or ester (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol, The solvent may be selected from the group consisting of dimethyl ether, dimethylsulfoxide, dimethyl ether ...

[0156] The organic solvent may be a mixture of organic solvents. Preferred organic solvents are selected from the group consisting of aliphatic and aromatic solvents, ketones, esters, glycoethers, alcohols, halogenated hydrocarbons, and combinations thereof. Highly preferred organic solvents are selected from the group consisting of xylene (mixture of isomers), toluene, ethylbenzene, naphtha, 1,2,4-trimethylbenzene, mesitylene, n-propylbenzene, isopentyl acetate, n-butyl acetate, (2-methoxymethylethoxy)propanol, 2-butoxyethyl acetate, 2-methylbutyl acetate, isobutanol, 1-butanol, 1-ethoxypropan-2-ol, 2,6-dimethyl-4-heptanone, 2-methoxy-1-methylethyl acetate, 4,6-dimethyl-heptan-2-one, 4-methyl-2-pentanone, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, 2-(2-butoxyethoxy)ethanol, 2-butoxyethanol, 5-methylhexan-2-one, ethyl acetate, and combinations thereof.

[0157] Alternatively, the "precursor basecoat layer (a) composition" can be a reactive system in which the solvent comprises a liquid reactive organic monomer, such as a low molecular weight acrylate, and the binder comprises a reactive polymeric organic resin that can be dispersed or dissolved in the solvent. Thus, the solvent and resin may both constitute a liquid phase in the precursor basecoat layer (a) composition and together form the binder in the basecoat layer (a) upon curing.

[0158] In one aspect, the present invention provides a method of coating at least a portion of an exterior surface of a vehicle frame or body, comprising the steps of: i) providing a frame or body for a vehicle, said frame or body having an exterior surface, at least a portion of said exterior surface may already include a different coating layer; ii) applying a precursor basecoat layer (a) composition as defined previously onto at least a portion of the outer surface of the frame or body of step (i) or onto an outer coating layer of a different coating layer of step (i) to obtain a precursor basecoat layer (a); iii) optionally at least partially drying and curing the precursor basecoat layer (a) of step (ii) to obtain a basecoat layer (a); iv) optionally applying a precursor tinted clearcoat layer (b) composition onto at least a portion of the precursor basecoat layer (a) of step (ii) or onto at least a portion of the basecoat layer (a) of step (iii) to obtain a precursor tinted clearcoat layer (b), optionally followed by at least partial drying and curing to obtain a tinted clearcoat layer (b); v) applying a precursor clearcoat layer (c) composition onto at least a portion of the precursor basecoat layer (a) of step (ii), onto at least a portion of the basecoat layer (a) of step (iii), onto the precursor tinted clearcoat layer (b) of step (iv), or onto the tinted clearcoat layer (b) of step (iv), followed by drying and curing to obtain a top clearcoat layer (c); The present invention relates to a method comprising the steps of:

[0159] Step (ii) of applying the precursor basecoat layer (a) composition can include applying a single layer in one step or applying multiple layers on top of each other in subsequent steps. Subsequent layers can be applied "wet-on-wet", meaning that the subsequent layer is applied on a previous layer from which at least some to substantially all of the solvent has evaporated, but which has not (fully) cured. This means that an intermediate drying step is applied between the application of subsequent layers, even when the subsequent layers are applied "wet-on-wet".

[0160] It is also possible to allow the previous layer to completely dry and cure before applying the subsequent layer, and it is within the skill of one of ordinary skill in the art to select appropriate drying conditions.

[0161] In an embodiment, step (ii) involves applying two or more layers, for example 2, 3, 4, or 5 layers.

[0162] In one embodiment, step (ii) comprises n subsequent steps resulting in n layers, where layer x is applied at least partially on layer x-1, where x is an integer from 2 to n, and n is an integer from 2 to 5.

[0163] Steps (iv) and (v) of applying the precursor (tinted) clearcoat composition may involve applying a single layer in one step, or multiple layers applied on top of each other in subsequent steps. Subsequent layers may be applied "wet-on-wet," meaning that a subsequent layer is applied over a previous layer that has not been (fully) dried or cured.

[0164] In some embodiments, the precursor clearcoat layer (c) composition applied in step (v) is applied to a layer that is not completely dried and cured, i.e., applied "wet-on-wet." Selecting appropriate drying conditions is within the skill of one of ordinary skill in the art.

[0165] The geometry of the outer surface of the frame or body to be coated is not limited in any way, so long as it can be coated, for example, by spraying. In some embodiments, the outer surface of the frame or body to be coated is flat. In other embodiments, the outer surface of the frame or body to be coated is curved. In further embodiments, the outer surface of the frame or body to be coated includes flat and curved portions.

[0166] Step (ii) of applying the precursor basecoat layer (a) composition is preferably carried out using powder coating, electrostatic spraying, curtain coating, a spray gun, a high-speed rotating bell, a high-speed rotating disk, or using a spray can with a propellant. In a preferred embodiment, the spraying is carried out without the use of a propellant.

[0167] In another preferred embodiment, the outer two or three coating layers as defined previously are applied to a sticker, which is then applied onto at least a portion of the outer surface of the frame or body, or onto at least a portion of the outer coating layer of a different coating layer already present on the vehicle, if present.

[0168] use In a third aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: in laser imaging detection and ranging (LIDAR) of said vehicle or coated substrate; and / or to improve the visibility of said vehicle or coated substrate under visible light conditions; and / or for generating a three-dimensional image of the vehicle or coated substrate; The coating comprises at least two layers, the outer two or three of which are: (a) a base coat layer; (b) optionally, a tinted clearcoat layer over (a); (c) A top layer of clear coat on (a) or (b). and The base coat layer (a) is, based on the weight of the base coat layer (a), 14.95 to 98.95 weight percent of a binder; 1 to 85% by weight of spherical glass beads having a median particle size D50 of 1 μm to 150 μm as measured by laser diffraction and a refractive index of 1.7 to 2.8 as measured at a wavelength λ of 589 nm; 0.05 to 30% by weight of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or combinations thereof, the pigment flakes having a median diameter D50 of 1 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, as measured by laser diffraction; 0-30% by weight of additional ingredients It consists of: The use of a vehicle or coating substrate as defined herein, wherein the median diameter D50 of said pigment flakes is greater than 35% of the median particle size D50 of said spherical glass beads.

[0169] In another aspect, the present invention relates to the use of spherical glass beads having a median particle size D50 of 1 μm to 150 μm, measured by laser diffraction, and a refractive index of 1.7 to 2.8, measured at a wavelength λ of 589 nm, as a radio wave transmission enhancer in a coating layer comprising a binder and metal pigment flakes, wherein the metal pigment flakes have a median particle size D50 of 2 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, measured by laser diffraction, and the median particle size D50 of the metal pigment flakes is greater than 35% of the median particle size D50 of the spherical glass beads.

[0170] The preferred embodiments defined in the context of the first, second and third aspects also apply to this further aspect.

[0171] Further embodiments In a fourth aspect, the present invention provides a vehicle having a frame or body, at least a portion of an exterior surface of the frame or body being covered with a coating, the coating comprising at least two layers; or a coated substrate, the coating comprising at least two layers; The outer two or three layers are (a) a base coat layer; (b) optionally, a tinted clearcoat layer over (a); (c) A top layer of clear coat on (a) or (b). and The base coat layer (a) is, based on the weight of the base coat layer (a), 14.95 to 98.95 weight percent of a binder; 1 to 85% by weight of spherical glass beads having a median particle size D50 of 1 μm to less than 10 μm as measured by laser diffraction and a refractive index of 1.7 to 2.8 as measured at a wavelength λ of 589 nm; 0.05 to 30% by weight of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or combinations thereof, the pigment flakes having a median diameter D50 of 1 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, as measured by laser diffraction; 0-30% by weight of further components; Consists of:

[0172] In a fifth aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: (i) providing a LIDAR device comprising an electromagnetic radiation source, a receiver and optionally a Global Positioning System (GPS); (ii) transmitting electromagnetic radiation from an electromagnetic radiation source of the LIDAR device to the vehicle; (iii) scanning the electromagnetic radiation reflected by the coating of the vehicle with a receiver of the LIDAR device; (iv) from the difference between the transmitted electromagnetic radiation and the scanned reflected electromagnetic radiation, preferably as a function of time; The distance between the vehicle and the LIDAR device, Vehicle acceleration, Vehicle deceleration, the direction of vehicle movement, the speed of the vehicle, preferably relative to the speed of the LIDAR device, and 3D image of the vehicle and calculating one or more of: The present invention relates to a vehicular laser imaging detection and ranging (LIDAR) process as defined in a fourth aspect, comprising:

[0173] Another aspect of the present invention is a method for producing a (i) providing a vehicle as defined in the fourth aspect with a RADAR device within a frame or body, said RADAR device comprising a radio source and a receiver, the vehicle optionally comprising a Global Positioning System (GPS); (ii) transmitting radio waves from a radio wave source of the RADAR device through at least a portion of an exterior surface of the frame or body of the vehicle that is covered with a coating as defined in the fourth aspect to an object outside the vehicle; (iii) scanning with a receiver of the RADAR device for radio waves reflected by objects outside the vehicle; (iv) from the difference between the transmitted radio waves and the scanned reflected radio waves, preferably as a function of time; the distance between the object and the RADAR device, Acceleration of the object relative to the RADAR device, The deceleration of the object relative to the RADAR device, the direction of movement of the object relative to the RADAR device, and The velocity of the object, preferably relative to the velocity of the RADAR device and calculating one or more of: The present invention relates to the radio detection and ranging (RADAR) process, including:

[0174] In a sixth aspect, the present invention provides a method for producing a composition comprising the steps of: in laser imaging detection and ranging (LIDAR) of the vehicle or the coated substrate; and / or to improve the visibility of the vehicle or the coated substrate under visible light conditions; and / or for generating a three-dimensional image of the vehicle or the coated substrate; The use of a vehicle or coated substrate as defined in the fourth aspect.

[0175] In another aspect, the present invention relates to the use of spherical glass beads having a median particle size D50 of 1 μm to 150 μm, measured by laser diffraction, and a refractive index of 1.7 to 2.8, measured at a wavelength λ of 589 nm, as a radio wave transmission enhancer in a coating layer comprising a binder and metal pigment flakes, said metal pigment flakes having a median particle size D50 of 2 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, measured by laser diffraction.

[0176] Preferred embodiments defined in the context of the first, second and third aspects also apply to the fourth, fifth and sixth aspects.

[0177] Thus, the invention has been described with reference to certain specific embodiments outlined above, it being recognized that these embodiments are susceptible to various modifications and alternatives that are well known to those skilled in the art.

[0178] Moreover, to properly understand this specification and its claims, it should be understood that the verb "to comprise" and its conjugations are used in its open-ended sense to mean that the items following the word are included, but items not specifically mentioned are not excluded. Furthermore, reference to an element by the indefinite article "a" or "an" does not exclude the possibility that more than one element is present, unless the context clearly requires that one and only one element is present. Thus, the indefinite article "a" or "an" typically means "at least one." EXAMPLES

[0179] material Spherical Glass Beads Micro glass beads (AL) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., China, have a refractive index of about 2.2 measured at a wavelength λ of 589 nm, a median particle size D50 of 40.4 μm, a D10 diameter of 37.3 μm, and a D90 diameter of 44.1 μm measured by laser diffraction.

[0180] Micro glass beads (AS) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., China, have a refractive index of about 2.2 measured at a wavelength λ of 589 nm, a median particle size D50 of 20 μm, a D10 diameter of 16.3 μm, and a D90 diameter of 26.2 μm measured by laser diffraction.

[0181] Micro glass beads (BS) obtained from Swarco, Australia, having a refractive index of about 2.1 measured at a wavelength λ of 589 nm, a median particle size D50 of about 5 μm, and a D90 diameter of 10 μm measured by laser diffraction.

[0182] Micro glass beads (CL) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., China, have a refractive index of about 1.9 measured at a wavelength λ of 589 nm, a median particle size D50 of 40.4 μm, a D10 diameter of 34.9 μm, and a D90 diameter of 44 μm measured by laser diffraction.

[0183] Micro glass beads (CS) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., China, have a refractive index of about 1.9 measured at a wavelength λ of 589 nm, a median particle size D50 of 20 μm, a D10 diameter of 14.7 μm, and a D90 diameter of 25.1 μm measured by laser diffraction.

[0184] solvent Desalinated water Syrox S900 binder, Syrox S941 thinner, ACULYN™ Excel, AMP-Ultra® PC 2000, and the solvent portion of Acticide® MBL

[0185] Further ingredients Solid portion of AMP-Ultra® PC 2000, neutralizer obtained from Angus Chemical Company Acticide® MBL solid portion, preservative, obtained from Thor ACULYN™ Excel solids portion, HASE thickener, obtained from DOW Chemical

[0186] Binder Solid portions of Syrox S900 binder and Syrox S941 thinner obtained from Axalta Coating Systems

[0187] Pigment flakes Xirallic® T60-10 SW Crystal Silver, coated Al2O3 flakes (Al2O3, TiO2, SnO2) obtained from Merck KGaA, with a median diameter (D50) of approximately 18 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of more than 10. Xirallic® T61-10 WNT Crystal Silver, coated Al2O3 flakes (Al2O3, TiO2, SnO2) obtained from Merck KGaA, with a median diameter (D50) of approximately 11 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of more than 10 Iriodin® 9602 Silver-Grey SW (mica, TiO2, Fe2O3, and SnO2) obtained from Merck Performance Materials Germany GmbH, with a median diameter (D50) of approximately 22.3 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of greater than 10. Iriodin® 9612 Silver-Grey Fine Satin SW (mica, TiO2, Fe2O3, and SnO2) obtained from Merck Performance Materials Germany GmbH, with a median diameter (D50) of 7.2 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of more than 10.

[0188] Clearcoat Composition S5000 HS Top Clear / S6000 HS Activator Slow, clear coat precursor composition obtained from Axalta Coating Systems

[0189] composition Twelve waterborne precursor basecoat layer (a) compositions containing different types of spherical glass beads and different types of pigment flakes were prepared as follows.

[0190] In a first step, for each type of spherical glass beads, an "intermediate composition" was prepared by adding the following ingredients (see the "Materials" section) to a container at ambient temperature (approximately 20° C.) in the following order: (1) demineralized water, (2) preservative Acticide® MBL, (3) spherical glass beads, (4) AMP-Ultra® PC 2000 neutralizer to adjust pH, and (5) ACULYN™ Excel thickener. The resulting mixture was stirred in a Dispermill Orange-line 18 / 186 at ambient temperature for approximately 5 minutes.

[0191] Twelve waterborne precursor basecoat layer (a) compositions were prepared by placing Syrox S900 binder, Syrox S941 thinner, different types of pigment flakes (see Materials section) and the above intermediate compositions in a beaker and subsequently thoroughly mixing in a Dispermill Orange-line 18 / 186 at ambient temperature (about 20°C) for 5-10 minutes. The types and amounts of components in the different waterborne precursor basecoat layer (a) compositions (wt % based on the weight of the waterborne precursor basecoat layer (a) composition) are shown in Tables 1 and 2. Tables 1 and 2 also list the ratio [%] of the median diameter D50 of the pigment flakes to the median particle size D50 of the spherical glass beads in the different waterborne precursor basecoat layer (a) compositions.

[0192] [Table 1]

[0193] [Table 2]

[0194] Example 1 All waterborne precursor basecoat layer (a) compositions were applied over the entire surface to a flat white metal test plate (10.5 x 14.9 cm) with a vertical black bar (0.3 cm wide) at ambient temperature (approximately 20 °C) using a spray gun (DV1.2 Mini) with a 1.2 mm nozzle. Two types of layers were applied: a "normal layer" and a "mist layer". For the "normal layer", the spray gun was placed 30-40 cm away from the metal test plate and a pressure of 2.0 bar was applied. For the "mist layer", the spray gun was placed 40-50 cm away from the metal test plate and a pressure of 1.5 bar was applied. The mist layer is a very thin layer of droplets (i.e., not a complete layer) that is applied first to improve adhesion.

[0195] Drying was applied between the application of subsequent "regular layers". Some aqueous precursor basecoat layer (a) compositions were applied to the metal test plate as a mist layer, followed by drying, a subsequent regular layer was applied on top of the mist layer, followed by drying, a clear topcoat layer was applied again, followed by drying ("single basecoat layer" or "1L"). Other aqueous precursor basecoat layer (a) compositions were applied to the metal test plate as a mist layer with two subsequent regular layers, with intermediate and final drying, a clear topcoat layer was applied again, followed by drying ("double basecoat layer" or "2L"). The clear clearcoat top layer consisted of a clearcoat composition as defined in the "Materials" section. In summary, the coating substrate consisted of a metal test plate, a mist layer on top of the metal test plate, one or two layers of basecoat on top of the mist layer, and finally a clear clearcoat top layer.

[0196] The compositions of the dry basecoat layer (a) are shown in Tables 3 and 4. Tables 3 and 4 also list the ratio [%] of the median diameter D50 of the pigment flakes to the median particle size D50 of the spherical glass beads in the different dry compositions.

[0197] [Table 3]

[0198] [Table 4]

[0199] LIDAR detectability was determined by scanning the surface of the coated metal test plate with a Livox Tele-15 LIDAR instrument (Livox Technology Company Co., Ltd) at a wavelength of 905 nm at an angle of approximately 0 degrees (i.e., in a direction perpendicular to the coating surface). Scanning was performed under daylight conditions. The Tele-15 LIDAR instrument was positioned at a distance of approximately 20 meters from the surface of the coated metal test plate. The Tele-15 LIDAR instrument calculates reflectance values ​​of different areas of the surface of the scanned coated metal test plate based on the ratio of reflected laser energy to incident laser energy, and generates a point cloud from these data. Every point in the point cloud has a corresponding reflectance value between 0 and 255. Reflectance values ​​between 0 and 155 correspond to reflectance in the range of 0 to 100% in the Lambertian reflectance model, while values ​​between 151 and 255 correspond to retroreflection. Lambertian reflectance is a characteristic that defines an ideal matte or diffuse reflecting surface. The apparent brightness of a Lambertian surface to an observer is the same regardless of the observer's angle of view. The increased Lambertian reflectance of a surface is therefore highly relevant for LIDAR applications, as it allows for the detection of the complete object at different viewing angles.

[0200] Histograms were created by counting all points in the point cloud that had reflectance values ​​in the ranges 1 to 10, 11 to 20, 21 to 30, etc. The number counts in each range were then normalized based on the total number of points in the point cloud and expressed as a percentage.

[0201] Table 5 lists the different coated metal test plates tested, the ratio [%] of the median diameter D50 of the pigment flakes to the median particle size D50 of the spherical glass beads, the number of basecoat layers (a) applied, and the figure on which the histogram is shown.

[0202] [Table 5]

[0203] From Figures 1A-1F, it can be concluded that all coated metal substrates exhibit significant LIDAR detectability at an angle of about 0 degrees (i.e., perpendicular to the coating surface).

[0204] The more the "body" of the histogram shifts to higher reflectance values, the better the LIDAR detectability of the coated metal substrate. From each of Figures 1A-1F, it can be seen that the "body" of the histogram shifts to higher reflectance values ​​as the ratio of the median diameter D50 of the pigment flakes to the median particle size D50 of the spherical glass beads increases.

[0205] Thus, the inventors have unexpectedly discovered that a high ratio of the median diameter D50 of the pigment flakes to the median particle size D50 of the spherical glass beads increases LIDAR detectability.

[0206] Example 2 The LIDAR detectability of the coated white metal test plate prepared as described in Example 1 was determined by scanning the surface of the coated metal test plate with a Livox Tele-15 LIDAR device (Livox Technology Company Co., Ltd) at a wavelength of 905 nm and an angle of 15 degrees. Table 6 lists the different coated metal test plates tested, the ratio [%] of the median diameter D50 of the pigment flakes to the median particle diameter D50 of the spherical glass beads, the number of base coat layers (a) applied, and the figure in which the histogram is shown.

[0207] [Table 6]

[0208] From Figures 2A-2E, it can be concluded that all metal substrates exhibit significant LIDAR detectability even under a 15 degree angle. Also, from each of Figures 2A-2E, the "body" of the histograms shifts to higher reflectance values ​​as the ratio of the median pigment flake diameter D50 to the median spherical glass bead diameter D50 increases. Thus, the inventors unexpectedly found that even under a 15 degree angle, a higher ratio of the median pigment flake diameter D50 to the median spherical glass bead diameter D50 increases the LIDAR detectability.

[0209] Example 3 The LIDAR detectability was determined on a gray metal test plate (10.5×14.9 cm) prepared as described in Example 1, but with a vertical black bar (0.3 cm wide) across the entire surface, by scanning the surface of the coated metal test plate with a Livox Tele-15 LIDAR device (Livox Technology Company Co., Ltd) at a wavelength of 905 nm and an angle of about 0 degrees. Table 7 lists the different coated metal test plates tested, the ratio [%] of the median diameter D50 of pigment flakes to the median particle diameter D50 of spherical glass beads, the number of base coat layers (a) applied, and the figure in which the histogram is shown.

[0210] [Table 7]

[0211] From Figures 3A-3D, it can be concluded that all coated metal substrates exhibit significant LIDAR detectability at an angle of about 0 degrees (i.e., perpendicular to the coating surface).

[0212] Also, from each of Figures 3A-3D, the "body" of the histogram shifts to higher reflectance values ​​as the ratio of the median diameter D50 of the pigment flakes to the median particle size D50 of the spherical glass beads increases. From a comparison of Figures 1A to 3A, 1C to 3B, and 1F to 3C, it can be inferred that this shift is more pronounced when a darker substrate is coated.

Claims

1. A vehicle having a frame or body, wherein at least a portion of an outer surface of the frame or body is covered with a coating, the coating comprising at least two layers, the outer two or three layers being: (a) a base coat layer; (b) optionally, a tinted clearcoat layer over (a); (c) a top layer of clear coat on (a) or (b) and The base coat layer (a) comprises, based on the weight of the base coat layer (a), 14.95 to 98.95 wt. % of a binder; 1 to 85% by weight of spherical glass beads having a median particle size D50 of 1 μm to 150 μm as measured by laser diffraction and a refractive index of 1.7 to 2.8 as measured at a wavelength λ of 589 nm; 0.05 to 30% by weight of pigment flakes selected from the group consisting of metal pigment flakes, pearlescent pigment flakes, or combinations thereof, the pigment flakes having a median diameter D50 of 2 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, as measured by laser diffraction; 0-30% by weight of further ingredients; It consists of A vehicle, wherein the median diameter D50 of the pigment flakes is greater than 35% of the median particle diameter D50 of the spherical glass beads.

2. 2. The vehicle of claim 1, wherein the amount of the pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or a combination thereof in the base coat layer (a) is 1 part by weight per 1 to 30 parts by weight of the spherical glass beads.

3. 3. The vehicle according to claim 1 or 2, wherein the median diameter D50 of the pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or a combination thereof in the base coat layer (a) is greater than 36% of the median particle diameter D50 of the spherical glass beads.

4. 2. The vehicle of claim 1, wherein the spherical glass beads in the base coat layer (a) have a refractive index of 1.9 to 2.6 measured at a wavelength λ of 589 nm.

5. 2. The vehicle of claim 1, wherein the spherical glass beads in the base coat layer (a) have a median particle size D50 of 1.5 μm to 100 μm, as measured by laser diffraction.

6. 2. The vehicle of claim 1, wherein the additional components in the base coat layer (a) are selected from the group consisting of thickeners, foam control agents, luminescent agents, UV absorbers, preservatives, dyes, cure initiators, organic pigments, inorganic pigments other than the metallic pigment flakes and pearlescent pigment flakes, and combinations thereof.

7. The metallic pigment flakes and pearlescent pigment flakes are (A) Metal oxides, metals, metal sulfides, titanium suboxide, titanium oxynitride, FeO(OH), SiO ２ , B ２ O ３ , GeO ２ , MgF ２ , metal pigment flakes or mica pigment flakes optionally coated with at least one layer of one or more components selected from the group consisting of metal alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and a binder; (B) Metal oxides, metals, metal sulfides, titanium suboxide, titanium oxynitride, FeO(OH), SiO ２ , B ２ O ３ , GeO ２ , a metal alloy, a rare earth compound, and optionally coated with an outer layer comprising one or more colorants and a binder. ２ O ３ , SiO ２ , pigment flakes containing glass, ceramic, graphite, or mica platelets; (C) Metal oxides, metals, metal sulfides, titanium suboxide, titanium oxynitride, FeO(OH), SiO ２ , B ２ O ３ , GeO ２ , a metal alloy, a rare earth compound, and optionally coated with an outer layer comprising one or more colorants and a binder. ２ , ZrO ２ , SiO ２ , SnO ２ , In ２ O ３ Al doped with one or more components selected from the group consisting of ZnO and iron oxide. ２ O ３ Platelet-containing pigment flakes 10. The vehicle of claim 1, selected from the group consisting of:

8. The coating comprises the following layers in the following order: (i) optionally, one or more primer layers on the exterior surface of the frame or body; (ii) optionally, one or more "first" basecoat layers different from basecoat layer (a) on the outer surface of said frame or body; (iii) optionally, one or more clear coat layers and / or tinted clear coat layers on (i), or on (ii) the exterior surface of said frame or body; (iv) the base coat layer (a) on (i), (ii), or (iii) the outer surface of the frame or vehicle; (v) optionally, said tinted clear coat layer (b) on said base coat layer (a); and (vi) the clear coat top layer (c) on the base coat layer (a) or on the tinted clear coat layer (b); 10. The vehicle of claim 1, comprising:

9. The vehicle according to claim 1, wherein the total thickness of the base coat layer (a) is 1 μm to 300 μm.

10. 10. The vehicle of claim 1, wherein more than 1% of the exterior surface of the frame or body is covered with the coating.

11. 10. The vehicle of claim 1, selected from the group consisting of a car, a lorry, a truck, a bicycle, a moped, a scooter, a motorcycle, a train, a tram, a boat, a watercraft, a drone, a skateboard, a missile, a helicopter and an aircraft.

12. (i) providing a LIDAR device comprising an electromagnetic radiation source, a receiver, and optionally a Global Positioning System (GPS); (ii) transmitting electromagnetic radiation from the electromagnetic radiation source of the LIDAR device to the vehicle; (iii) scanning the electromagnetic radiation reflected by the coating of the vehicle with the receiver of the LIDAR device; (iv) from the difference between the transmitted electromagnetic radiation and the scanned reflected electromagnetic radiation; the distance between the vehicle and the LIDAR device; the acceleration of the vehicle; the deceleration of the vehicle; the direction of movement of the vehicle; the speed of the vehicle, and 3D image of the vehicle and calculating one or more of:

2. The vehicle laser image detection and ranging (LIDAR) process of claim 1, comprising:

13. in laser imaging detection and ranging (LIDAR) of the vehicle or coated substrate; and / or to improve the visibility of said vehicle or coated substrate under visible light conditions; and / or for generating a three-dimensional image of the vehicle or coated substrate; The coating comprises at least two layers, the outer two or three of which are: (a) a base coat layer; (b) optionally, a tinted clearcoat layer over (a); (c) a top layer of clear coat on (a) or (b) and The base coat layer (a) comprises, based on the weight of the base coat layer (a), 14.95 to 98.95 wt. % of a binder; 1 to 85% by weight of spherical glass beads having a median particle size D50 of 1 μm to 150 μm as measured by laser diffraction and a refractive index of 1.7 to 2.8 as measured at a wavelength λ of 589 nm; 0.05 to 30% by weight of pigment flakes selected from the group consisting of metal pigment flakes, pearlescent pigment flakes, or combinations thereof, the pigment flakes having a median diameter D50 of 1 μm to 75 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, as measured by laser diffraction; 0-30% by weight of further ingredients It consists of 2. Use of a vehicle or coated substrate according to claim 1, wherein the median diameter D50 of the pigment flakes is greater than 35% of the median particle diameter D50 of the spherical glass beads.

14. 13. The LIDAR process of claim 12, wherein the LIDAR uses electromagnetic radiation having a wavelength between 740 nm and 2500 nm.

15. The use described in claim 13, wherein the LIDAR uses electromagnetic radiation having a wavelength of 740 nm to 2500 nm.

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