Coating with embedded pigments

Abstract

A hardened coating is disclosed, the hardened coating comprising a film-forming component and a pigment component comprising a pigment. The pigment component may be applied to at least a portion of a surface of the film-forming component that is at least partially unhardened when the pigment component is applied, such that the pigment becomes embedded in the film-forming component, where the pigment component itself does not form a film.

Description

[0001] Cross - reference to related applications

[0002] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 386,196, filed on Dec. 6, 2022, entitled "Coatings with Embedded Pigments", which is hereby incorporated by reference in its entirety. Field of the Invention

[0003] The present disclosure generally relates to a hardened coating in which pigments are embedded, a method of making the hardened coating, and a substrate coated with the hardened coating. Background of the Invention

[0004] Coatings can be applied to a wide variety of substrates to provide color and other visual effects, such as designs and patterns, and / or performance effects, such as corrosion resistance. Improved coatings and methods of applying them are always desired. Summary of the Invention

[0005] The present disclosure describes a hardened coating that includes a film-forming component and a pigment component that includes pigments, where the pigment component is applied to at least a portion of the surface of the film-forming component that is at least partially unhardened when the pigment component is applied, such that the pigments become embedded in the film-forming component, and where the pigment component itself does not form a film. Methods of making such layers and substrates coated with such layers are also within the scope of the present disclosure.

[0006] The present disclosure further describes a hardened coating that is formed by: (a) applying a film-forming component to at least a portion of a substrate; (b) applying a pigment component that includes pigments to at least a portion of the surface of the film-forming component that is at least partially unhardened when the pigment component is applied, such that the pigments become embedded in the film-forming component; and (c) hardening the coating; where the pigment component itself does not form a film. Methods of making such layers and substrates coated with such layers are also within the scope of the present disclosure. Brief Description of the Drawings

[0007] Figure 1a 、 Figure 1b and Figure 1c depict cross-sectional views of the hardened coatings described herein.

[0008] Figure 2 show scanning electron microscope (SEM) cross-sections of the coatings of Examples 14 and 15. Detailed Description

[0009] Unless otherwise specified, the temperature and pressure conditions are ambient temperature (22 °C), 45% relative humidity, and standard pressure of 101.3 kPa (1 atm).

[0010] Unless otherwise specified, any term in parentheses refers to the term with and without the material in parentheses. Thus, as used herein, the terms “(meth)acrylate” and similar terms are intended to include acrylate, methacrylate, or both.

[0011] It should be understood that the present disclosure can assume various alternative variations and sequences of steps, unless expressly provided to the contrary. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximations that can vary depending upon the desired properties to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0012] Although the numerical ranges and parameters setting forth the broad scope of the present disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0013] Moreover, it should be understood that any numerical range recited herein is intended to include all subranges subsumed therein. For example, a range of “1 to 10” is intended to include all subranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0014] All ranges are inclusive and combinable. For example, the term “a range of 0.06 to 0.25 wt% or 0.06 to 0.08 wt%” will include each of 0.06 to 0.25 wt%, 0.06 to 0.08 wt%, and 0.08 to 0.25 wt%. Further, when ranges are given, any endpoints and / or the numbers recited within those ranges can be combined within the scope of the present disclosure.

[0015] Unless otherwise specified, the plural encompasses the singular and vice versa. As used herein, terms such as “comprising” and the like mean “including but not limited to”. Similarly, as used herein, the terms “on”, “applied on / onto”, “formed on / onto”, “deposited on / onto”, “overlapped”, and “provided on / onto” mean formed, overlapped, deposited, or provided on a surface but not necessarily in contact with the surface. For example, a coating “formed on” a substrate does not exclude the presence of one or more other coatings of the same or different compositions between the formed coating and the substrate.

[0016] As used herein, unless explicitly and unambiguously limited to a single reference, the articles "a / an" and "the" include plural references and shall be construed to include "one or more." Thus, reference to "a" hardening coating, "a" film-forming component, "a" pigment component containing "a" pigment, etc. refers to one or more of these items.

[0017] As used herein, the term "abrasion-resistant particle" refers to a particle that imparts abrasion resistance and scratch resistance and, as non-limiting examples, may include diamond; crystalline materials such as polycrystalline materials, single-crystalline materials, or combinations thereof; amorphous materials; ceramic materials; glass-ceramic materials; superabrasives; minerals; carbon-based materials; or any combination thereof.

[0018] As used herein, an "adhesive layer" refers to a coating that can bond two materials together by adhering to their respective surfaces; as a non-limiting example, the adhesive layer can produce a joint having a lap shear strength of at least 20.0 MPa, which is measured according to ASTM D1002-10 using a 2024-T3 aluminum substrate with a thickness of 1.6 mm and is measured in tensile mode at a tensile rate of 1.3 mm per minute using an INSTRON 5567 machine.

[0019] As used herein, the term "ASTM" refers to the publications of ASTM International, West Conshohocken, PA.

[0020] As used herein, a "primer coat" refers to a coating applied to a primer, another primer coat, and / or directly to a substrate, optionally including components (such as colorants) that affect color and / or provide other visual effects.

[0021] As used herein, the term "luminance" refers to the luminance of a coating applied to a substrate, as determined using a BYK-MacI metallic color spectrophotometer instrument manufactured by BYK-Gardner, at 15° (L* 15° )

[0022] As used herein, the term "transparent coating" refers to a coating that is at least substantially transparent, if not completely transparent, and may or may not include a colorant. The term "substantially transparent" refers to a coating in which at least a portion of the surface beyond the coating is visible to the naked eye when viewed through the coating. The term "completely transparent" refers to a coating in which the entire surface beyond the coating is visible to the naked eye when viewed through the coating. The transparent coating may be substantially free of pigments. Substantially free of pigments may refer to a "colored transparent coating", which may be a coating composition comprising less than 3 wt%, such as less than 2 wt%, less than 1 wt% or 0 wt% of pigments and / or dyes based on the total solids.

[0023] As used herein, the term "coating" or "coating layer" refers to a finished product obtained by applying one or more coating compositions to a substrate and hardening or curing the composition. Primer layers, base coats, top coats, and transparent coatings may all be coatings according to the present disclosure.

[0024] As used herein, the term "colorant" refers to any substance that imparts color and / or other opacity and / or other visual effects to a coating composition, and may include, but is not limited to, dyes and pigments.

[0025] As used herein, the transitional term "comprising" (and other equivalent terms, such as "containing" and "including") is "open-ended" and open to include unspecified substances. Although described in terms of "comprising", the terms "consisting essentially of" and "consisting of" are also within the scope of the present disclosure. As used herein, "consisting essentially of" means the named materials or steps listed, and those materials or steps that do not materially affect the basic properties of the disclosure; "consisting of" means only the named materials or steps.

[0026] As used herein, the terms "crosslinking agent", "crosslinker", "curing agent", etc. refer to molecules or polymers containing functional groups that react with the functional groups of polymers and / or resins in a coating composition.

[0027] As used herein, terms such as "curable", "cured", and "hardenable" when used in conjunction with a composition refer to the ability of at least a portion of the polymerizable and / or crosslinkable components of the composition to undergo a reaction. Curing, hardening, and similar terms are used interchangeably herein.

[0028] As used herein, the terms "curing potential", "hardening potential", or similar terms refer to the amount of reactions that can potentially occur in a composition, which is determined by the amount of reactive functional groups present in the composition and, in some cases, the amount of crosslinking agent. Partial curing / hardening of X% of the curing / hardening potential indicates that X mol% of the reactive functional groups present have reacted, where X is less than all the groups capable of undergoing the reaction. Thus, a film-forming component or a curable composition that is "at least partially unhardened" means partially cured / hardened; that is, this means that not all of the polymerizable or crosslinkable components have reacted.

[0029] As used herein, the terms "dry", "dried", "drying", and similar terms refer to the removal of volatile compounds from a film or a composition.

[0030] As used herein, the term "dye" refers to a colored substance, which may include organic compounds that can impart color to a composition.

[0031] As used herein, the term "dry film thickness" refers to the thickness of a coating after curing and / or hardening, and can be measured using a Fischer coating thickness gauge (Fischerscope MMS Permascope) in accordance with ASTM D7091-21, "Standard practice for nondestructive measurement of dry film thickness of nonmagnetic coatings applied to ferrous metals and nonmagnetic, nonconductive coatings applied to non-ferrous metals".

[0032] As used herein, the terms "embed", "embedded", and similar terms refer to being partially or completely enclosed in a matrix such as a film-forming component. Pigments according to the present disclosure can be completely embedded or only partially embedded in the film-forming component.

[0033] As used herein, the term "conductive particle" refers to a material that can be used as a pair of electrodes or a current collector, such as conductive carbon, metal, metal oxide, graphene, or a combination thereof, and can be in various forms, such as nanoparticles, microparticles, nanowires, microfilaments, nanotubes, microtubes, or other forms or combinations of these forms.

[0034] As used herein, the terms "electrocoat", "ecoat", "e - coat", etc. refer to a coating applied by a process of depositing charged particles from a suspension to coat a conductive component. During this process, the coating is applied to the component with a certain film thickness, which is adjusted by the amount of voltage applied. The deposition can be self - limiting and can slow down due to the component being electrically insulated by the applied coating.

[0035] As used herein, the term "film - forming component" refers to the film - forming ingredients of a coating composition and can include polymers, resins, cross - linking materials, or any combination thereof that can form a self - supporting continuous film on at least one level surface of a substrate upon curing. The coating composition can be thermosetting or thermoset, in which the components react to form irreversible covalent bonds, or thermoplastic, in which the reaction between the components does not form covalent bonds and can be reversed, such as by heating.

[0036] As used herein, the term "flop" or "flop index" refers to a measure of the change in reflectance of a coated substrate as it is rotated through a series of viewing angles, as measured using a spectrophotometer such as the BYK - Mac I spectrophotometer from BYK. Solid - color paints typically will have a flop index of 0, while paints containing metallic or pearlescent pigments will typically have a flop value that can be considered high or low depending on the pigment type. For example, non - transparent pigments typically cause the paint to have a low flop (less than 15), while paints with transparent and / or metallic pigments have a high flop (15 - 17). The flop index is a unitless value.

[0037] As used herein, the term "glass transition temperature" or "Tg" refers to the temperature at which a material (usually a polymer) transitions from a glassy state to a rubbery state as the temperature is increased. Any Tg values reported herein are determined using ASTM E1356 - 08(2014).

[0038] As used herein, the term "low - temperature curing" with respect to a coating means curing at a temperature of 140°C or lower (such as 80°C to 140°C).

[0039] As used herein, the term "magnetic particles" refers to particles having ferromagnetic, ferrimagnetic, superparamagnetic, and / or super - ferrimagnetic behavior, such as iron, cobalt, and nickel and their oxides and / or alloys, such as CoPt, FePt, FeNi, or FeCoAlNiCo, CoPt, FeCoCr, and combinations thereof.

[0040] Unless otherwise specified, as used herein, the term "molecular weight" refers to the weight-average molecular weight determined by gel permeation chromatography (GPC) using appropriate polystyrene standards. If the number-average molecular weight is specified, the weight is determined in the same GPC manner while calculating the number average based on the polymer molecular weight distribution data obtained thereby.

[0041] As used herein, "multicomponent" (which may be "two-component" or "2K") and like terms refer to a composition comprising a first component containing a functional material and at least one other component containing a functional material that reacts with the functional material in the first component. Generally, the components are maintained separately until use and react upon combination.

[0042] As used herein, terms such as "one-component", "1K", etc. refer to a composition in which all components are maintained in the same package after manufacture, during transportation and storage; a composition that is considered a 1-K coating composition even if a solvent is added to the 1-K composition to reduce its viscosity or solids.

[0043] As used herein, the term "organic solvent" refers to a carbon-based material capable of dissolving or dispersing other substances.

[0044] As used herein, the term "pigment component containing a pigment" refers to a component applied to at least a partially unhardened film-forming component. The "pigment" in the pigment component will be further described herein and is a pigment that imparts visual and / or performance effects. The pigment in the pigment component is distinguished from any pigment that may be included in the formulation of the film-forming component.

[0045] As used herein, the term "plasticizer" refers to a material such as an organic liquid that is typically colorless and non-volatile, which is added to an otherwise brittle pure polymer (a break or rupture without significant plastic deformation) or plastic to make it softer, more flexible, to increase its plasticity, to reduce its viscosity, to increase its tacky properties, and / or to reduce friction during handling during manufacture.

[0046] As used herein, the prefix "poly" refers to two or more. As a non-limiting example, polyisocyanate refers to a compound containing two or more isocyanate groups, and polyol refers to a compound containing two or more hydroxyl groups.

[0047] As used herein, the term "(poly)isocyanate" refers to blocked (or capped) (poly)isocyanates as well as unblocked (poly)isocyanates.

[0048] As used herein, the term "polymer" includes homopolymers (formed from one monomer) and copolymers formed from or containing two or more different monomer reactants or two or more different repeating units. In addition, the term "polymer" includes prepolymers and oligomers. "Polymer" and "resin" are used interchangeably herein.

[0049] As used herein, the term "powder coating" refers to a coating as a free-flowing dry powder that is typically applied electrostatically and then cured under heat or ultraviolet light. The powder may include thermoplastic and / or thermosetting polymers. The "gel bake" state of a powder coating composition refers to the point at which the powder turns into a liquid during heating.

[0050] As used herein, the term "primer" or "primer coat" refers to an undercoat that can be applied to a substrate to prepare the surface for the application of another coating.

[0051] As used herein, "reinforcing pigment" and like terms refer to particles that impart structural integrity (such as stiffness or strength) to a composition. Such particles can have many different shapes, such as spherical, hemispherical, flaky, rod-shaped, whisker-shaped, etc., and can include, for example, glass fibers, glass beads, and thermoplastic beads or particles.

[0052] As used herein, (retro)reflection and like terms refer to retroreflection or reflection. "Reflective" pigments or particles are those that reflect light in a specular manner (i.e., at the same angle with respect to the normal to the pigment surface but at an angle on the opposite side of the normal with respect to the direction of incidence of the incident light), which can include, for example, metallic flake pigments; or those that reflect or scatter light in a diffuse manner (in many directions), which can include, for example, titanium dioxide white pigments; "retroreflective" pigments or particles are those that return light back to the light source, and can include, for example, coated glass beads. "Luminescent pigments" are organic or inorganic compounds that absorb energy when relatively cool and emit energy as visible light.

[0053] As used herein, the term "average roughness" or "Ra" refers to the surface smoothness determined according to ISO method 4287 - 1997.

[0054] As used herein, "silicone" and like terms refer to polysiloxane polymers based on a structure containing alternating silicon and oxygen atoms. As used herein, "silicone" and "siloxane" are used interchangeably.

[0055] As used herein, the term "solvent-based coating" refers to a coating composition that uses hydrocarbon solvents as the carrier for the solid components and contains less than 40% by weight of water based on the total carrier weight. Solvent-based coatings can contain up to 80% solid components dispersed and / or dissolved in the solvent.

[0056] As used herein, "substrate" refers to an article on which a previous coating may or may not have been formed. This can include vehicle substrates, industrial substrates, structural substrates, etc. Examples of specific substrates include structures, vehicle or industrial protection structures such as electrical box housings, transformer enclosures or motor control housings; railcar containers, tunnels, oil or gas industry components (such as platforms, pipelines, tanks, vessels and their supports), ship components, automotive body components, aerospace components, pipelines, storage tanks or wind turbine components. "Structure" as used herein refers to buildings, bridges, oil derricks, oil platforms, water towers, power line towers, support structures, wind turbines, walls, piers, docks, levees, dams, transportation containers, trailers and any metal structure exposed to a corrosive environment. "Vehicle" refers to all types of vehicles such as, but not limited to, automobiles, trucks, buses, tractors, harvesters, heavy equipment, vans, golf carts, motorcycles, bicycles, trams, airplanes, helicopters, vessels of various sizes, etc. Medical devices are expressly excluded from the substrates of the present disclosure.

[0057] As used herein, the term "coated surface" refers to a part of the coating such as the outermost surface (see Figure 1a - element 110) or the innermost surface (see Figure 1c , element 120), typically reflecting the top or bottom 20 volume % of the cured coating, such as 15 volume % or 10 volume %.

[0058] As used herein, the term "total solids" or "solids" or "solids content" refers to the solids content as determined according to ASTM D2369 (2015).

[0059] As used herein, the term "topcoat" refers to the uppermost coating and may be applied over another coating such as a primer to provide a protective and / or decorative layer.

[0060] As used herein, unless otherwise specified, the term "viscosity" refers to the value determined at 25 °C and ambient pressure and reflects the resistance of a fluid to flow when subjected to shear stress and / or shear strain.

[0061] As used herein, the term "visual effect", unless otherwise specified, refers to the color, metallic appearance, luminescent appearance, flash appearance, Flop index and / or (retro)reflective effect imparted by pigments, dyes and / or particles, etc. when embedded in the coating surface.

[0062] As used herein, the term "volatile" refers to a material that is easily vaporized (easily evaporated) under the use conditions. A non-volatile material is not easily vaporized under the use conditions.

[0063] As used herein, the term "aqueous coating composition" refers to a coating composition in which the continuous phase comprises 40% or more water.

[0064] The present disclosure relates to a cured coating comprising a film-forming component and a pigment component containing pigments. The pigment component can be applied to at least a part of the surface of the film-forming component that is at least partially uncured, such that the pigments become embedded in the film-forming component. The pigment component itself does not form a film. Thus, the cured coating of the present disclosure is a single coating in which the pigments in the pigment component are embedded in the film-forming component and become fixed upon hardening or curing. This is different from a coating stack in which a first coating composition is deposited and a second coating composition containing pigments is deposited on top of the first coating composition. Additionally, while the present disclosure may include the application of additional coatings, due to the pigment particles embedded in the film-forming component, the use of a topcoat or other means to fix the particles in place can be avoided. Thus, the present disclosure may exclude additional layers deposited on the cured coating.

[0065] The film-forming component can be a powder coating composition, a solvent-based coating composition, an aqueous coating composition, an anion electrophoretic coating composition, a cation electrophoretic coating composition, a coating composition comprising greater than 95 wt% (such as greater than 97 wt%, or 95 wt% to 100 wt%) total solids measured according to ASTM D2369 (2015), or a low-temperature curing coating formulation. Any of the film-forming components described herein can be a single-component composition. Alternatively, the film-forming component can be a two-component or multi-component composition, where, as non-limiting examples, a polymer or resin having crosslinkable groups, and a crosslinking agent are thus in separate components.

[0066] The film-forming component can be a thermosetting coating composition and can comprise a film-forming polymer or resin having functional groups that react with itself ("self-crosslink") or with a crosslinking agent. Suitable film-forming resins include, for example, acrylic polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyether polymers, polysiloxane polymers, polyepoxy polymers, epoxy resins, vinyl resins, copolymers thereof, and mixtures thereof. Generally, these polymers can be any polymers of these types prepared by any method known to those skilled in the art. The functional groups on the film-forming resin can include, for example, carboxylic acid groups, amine groups, epoxy groups, hydroxyl groups, thiol groups, urethane groups, amide groups, urea groups, isocyanate groups (including blocked isocyanate groups), mercaptan groups, and combinations thereof. Mixtures of film-forming resins can also be used to prepare the film-forming component of the present invention.

[0067] The film-forming component can be a thermoplastic coating composition and can include a film-forming polymer such as a thermoplastic olefin such as a poly(meth)acrylate, polyethylene, polypropylene, polystyrene, polybutene, thermoplastic polyurethane, polycarbonate, acrylonitrile-based material or a condensation polymer, non-limiting examples including polyesters and polyamides such as nylon and the like.

[0068] As Figure 1a shown, the cross-section of the cured coating 100 of the present disclosure applied to a substrate (130) can be considered to have: an outermost surface 110 that includes 20% or less, such as 15% or less or 10% or less of the volume of the cured coating; an innermost surface 120 adjacent to the substrate 130 that includes 20% or less, such as 15% or less or 10% or less of the volume of the cured coating; and an innermost surface 120 and a body 140 that include the remainder.

[0069] When the pigment component is applied to the film-forming component, the pigments in the pigment component become embedded in the film-forming component because the film-forming component is at least partially uncured. Based on the volume of the pigments in the pigment component, as determined by cross-sectional microscopy, the pigments in the pigment component can be embedded in the film-forming component (such as the surface of the film-forming component) from 10% to 100% by volume, such as 20% to 100%, or 50% to 100%, or 70% to 100%. Figure 1b Pigments 150 embedded in the outermost surface 110 of the cured coating 100 are shown. The pigments are Figure 1b shown as having different levels of embedding - some pigments are embedded more than others. When the pigments are positioned as Figure 1b shown, the pigments can affect the visual appearance of the cured coating.

[0070] The pigments in the pigment component can account for less than 25% by weight, such as less than 20% by weight, or less than 15% by weight, or less than 10% by weight, or 1% to 25% by weight of the cured coating.

[0071] The pigments of the pigment composition can be substantially evenly distributed on the surface or a part of the surface of the cured coating, and can provide a substantially uniform visual effect to the surface of the coating. As used in this context, "substantially" means that the visual effect is uniform to the naked eye. For example, the visual effect can be a metallic visual effect, a color effect, a luminescent effect, and / or a (retro)reflective effect. The pigments can be substantially evenly distributed on all surfaces (100%), most surfaces (99% - 50%), some surfaces (49% - 1%), and / or can be distributed on the surface in a predetermined pattern, where the surface can be the outermost surface (shown as 110 in FIG. 1). The pigments can be embedded in the cured coating such that each pigment particle is surrounded by the film-forming resin and thus insulated from each other. Alternatively, as a non-limiting example, when conductivity is desired, the pigment particles can be in contact with each other.

[0072] Depending on the pigment composition, the degree of "hardness" of the film-forming component when applying the pigment composition, the application method, the type of film-forming component, etc., certain pigments may cause the pigments (160) to be located on or near the innermost surface (120) of the cured coating, as Figure 1c shown. Particularly suitable can be effect pigments that provide some performance-enhancing effects to the coating, such as corrosion-inhibiting pigments. It can also be the case where the pigments in the pigment composition become distributed throughout the cured coating (as shown in the figure), including the surface (110, 120) and / or the bulk (140) region.

[0073] As pointed out above, the pigment composition is applied before the film-forming component is fully cured or hardened; (that is, "at least partially uncured"). The pigment composition can be applied when the film-forming component does not exceed 75% of the curing / hardening potential of the film-forming component (such as not exceeding 65%, or not exceeding 50%, or 0% to 75%, such as 0% to 65% or 0% to 50%).

[0074] Any type of pigment can be included in the pigment composition. The pigments in the pigment composition can include visual effect pigments that produce visual effects (such as color effects), or pigments, metallic pigments, luminescent pigments, (retro)reflective pigments, and / or particles, etc. The pigments can be performance effect pigments that produce specific performance characteristics, such as corrosion-inhibiting pigments, radar reflective pigments, LiDAR reflective pigments, conductive pigments, and / or filler pigments. It should be understood that some pigments can impart both visual and performance properties to the cured coating.

[0075] Suitable color - imparting pigments are well - known and include organic and / or inorganic materials such as titanium dioxide, zinc oxide, iron oxide, carbon black, carbazole dioxazine crude pigments, azo, monoazo, bisazo, naphthol AS, salt type (lakes), benzimidazolone, condensed, metal complexes, isoindolinone, isoindoline, and polycyclic phthalocyanines, quinacridone, perylene, violanthrone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylium, quinophthalone pigments, diketopyrrolopyrrole red (“DPPBO

[0076] Red”), monoazo red, iron oxide red, quinacridone maroon, transparent red oxide, cobalt blue, iron blue, iron oxide yellow, chromium titanate, titanium yellow, nickel titanate yellow, transparent yellow oxide, lead chromate yellow, bismuth vanadium yellow, pre - dark chrome yellow, transparent red oxide flakes, iron oxide red, molybdate orange, molybdate orange - red, radar - reflective pigments, LiDAR - reflective pigments, corrosion - inhibiting pigments, and combinations thereof.

[0077] Metal pigments can be in any form, such as spherical, flake, or pellet form, and can contain, for example, aluminum, stainless steel, zinc, copper, and their alloys and their flakes, interference pigments such as mica coated with titanium dioxide, muscovite, phlogopite, silver nickel, platinum, bronze, brass, titanium, tungsten, including their oxides and their alloys.

[0078] Luminescent pigments are commercially available, as are (retro)reflective particles such as (retro)reflective microspheres.

[0079] The pigments in the pigment composition can include conductive pigments, radar - reflective pigments or LiDAR - reflective pigments or infrared - reflective pigments. LiDAR, radar - reflective pigments or infrared - reflective pigments can include, but are not limited to, nickel manganese ferrite black (Pigment Black 30), chromite iron brown black (CI Pigment Green 17, CI Pigment Brown 29 and 35), Pigment Blue 28, Pigment Blue 36, Pigment Green 26, Pigment Green 50, Pigment Brown 33, Pigment Brown 24, Pigment Black 12, and Pigment Yellow 53 and combinations thereof. As indicated above, all of these materials are commercially available.

[0080] The pigments in the pigment component may include corrosion-inhibiting pigments. Any suitable corrosion-inhibiting pigments known in the art can be used, including, for example, calcium strontium, zinc phosphosilicate; double orthophosphates, where one of the cations is represented by zinc, non-limiting examples being Zn-Al, Zn-Ca, Zn-K, Zn-Fe, Zn-Ca-Sr, Ba-Ca, Sr-Ca and combinations thereof; combinations of phosphate anions with anti-corrosion effective anions, non-limiting examples being silicates, molybdates and borates; modified phosphate pigments modified by organic corrosion inhibitors and combinations thereof. Non-limiting examples of modified phosphate pigments include aluminum(III) zinc(II) phosphate, basic zinc phosphate, zinc phosphomolybdate, zinc calcium phosphomolybdate, zinc borophosphate, zinc strontium phosphosilicate, calcium barium phosphosilicate, calcium strontium zinc phosphosilicate and combinations thereof. Other non-limiting examples of corrosion-inhibiting pigments that can be used in coating formulations include zinc 5-nitroisophthalate, calcium 5-nitroisophthalate, calcium cyanurate, metal salts of dinonylnaphthalenesulfonic acid and combinations thereof. Particularly suitable corrosion-inhibiting pigments include magnesium oxide, such as nanoscale magnesium oxide (5 nm - 100 nm), micron-scale magnesium oxide (1 micron - 5 microns), silicon dioxide, lithium salts, such as lithium nitrate, lithium sulfate, lithium fluoride, lithium bromide, lithium chloride, lithium hydroxide, lithium carbonate, lithium iodide or combinations of any of these.

[0081] The pigments in the pigment component may have a median particle size in the range of 2 μm - 75 μm, such as 2 μm - 50 μm, 2 μm - 40 μm, 2 μm - 30 μm, 2 μm - 25 μm, 2 μm - 10 μm, 5 μm - 75 μm, 5 μm - 50 μm, 5 μm - 40 μm, 5 μm - 30 μm, 5 μm - 25 μm or 5 μm - 10 μm. The median particle size is measured or reported herein in accordance with ISO 13320-1 (1999).

[0082] The pigments in the pigment component may account for 0.1 wt% - 100 wt% of the pigment component, such as 1 wt% - 90 wt%, 1 wt% - 75 wt%, or 10 wt% - 70 wt%, where wt% is based on the total weight of the pigment component. The pigments may include 100% of the pigment component, such as dry pigment particles. The pigment component may be in the form of a slurry of the pigment in a suitable slurry medium. The slurry medium can be selected based on the type of pigment used, the type of film-forming component to which the pigment component is to be applied and / or the application method of the pigment component. The pigment component may also be in the form of a "rinsing liquid" or "immersion liquid". Non-limiting examples of suitable media for forming the slurry or rinsing liquid include water; C3-C 12 ketones, such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); alcohols, such as isopropyl alcohol, butanol and 2-ethylhexanol; monomethyl ethers, monoethyl ethers and monohexyl ethers of ethylene glycol or propylene glycol, such as propylene glycol methyl ether; C2-C 12Aldehydes, such as acetaldehyde, cinnamaldehyde, and vanillin; esters, such as ethyl acetate, butyl acetate, phthalates, sebacates, adipates, terephthalates, dibenzoates, glutarates, or azelates; or any combination thereof. "Slurry", "spray", "rinsing liquid", and "immersion liquid" are used interchangeably herein because they all contain pigments in a carrier; a slurry generally refers to a higher solids content than a rinsing liquid or an immersion liquid.

[0083] The medium or carrier in the slurry, rinsing liquid, spray, or immersion liquid (non-limiting examples include MEK or MIBK) may cause the uncured resin of the electrophoretic coating to swell. The swelling can help embed pigments, such as aluminum flakes or zinc powder. This helps enhance the color effect in the outermost part of the cured coating when the pigment is a pigment that imparts a visual effect.

[0084] The pigments used in the pigment component of the present invention can be pigments that are generally incompatible with certain coating compositions. For example, aluminum, silver, and zinc may hydrolyze or oxidize when used in aqueous electrophoretic coating compositions. According to the present disclosure, this is avoided because the pigments are not dispersed in the film-forming component or composition in the same way as in a conventional formulation. As another non-limiting example, in the case of directly adding magnesium oxide to an aqueous electro-depositable coating composition, the magnesium oxide dissolves in the water in the composition and causes the pH in the bath to increase, resulting in the bath becoming unstable. Due to this stability problem, magnesium oxide cannot be directly incorporated into the water-based solution for electrophoretic coating. Another non-limiting example of "incompatibility" of pigments may be size-related, such as when the pigments are too large to pass through certain nozzles. When the pigments have a particle size greater than 5 μm, such as greater than 8 μm or greater than 10 μm as measured according to ISO 13320-1, they may be too large to pass through certain nozzles.

[0085] Two precision applicators can be used, where the second applicator has a nozzle with a larger orifice. Thus, the film-forming component can be precisely applied using the first applicator, and the pigment component can be applied using the second applicator. In this way, larger pigments can be precisely applied to at least a partially uncured film-forming component.

[0086] The pigment component can be applied by any tool known in the art, such as spraying, electrostatic spraying, rinsing, dipping, vibrating jetting, screw conveyors, and / or augers. Alternatively, or in combination with any of these methods, the pigment component can be applied to the surface of a substrate to which the film-forming component has already been applied. In this way, as the coating forms and the coating composition hardens, the pigments and / or particles in the pigment component become embedded in the film-forming component. The pigment component can be applied in a predetermined pattern or shape. For example, the pigment component can be applied using a stepper motor with an axis attached to a reservoir of pigments and / or particles, just after the film-forming component is applied. The rotation frequency of the motor can be used to control the amount of vibration and, thus, the mass flow rate of the pigment component from the reservoir due to the vibration.

[0087] Another non-limiting advantage of the present disclosure is the ability to achieve effects such as visual effects, where the amount of pigment required to achieve the effect can be significantly lower than the amount used in traditional formulations. When the film-forming component comprises a powder coating, the pigment component can be applied to the outermost surface of the powder coating. Upon hardening, the layer will have the color of the pigment. This avoids the traditional methods of grinding the pigment with all the other powder coating components or dry-blending the pigment with the powder coating composition; thus, compared to traditional powder coatings, the hardened coatings of the present invention use less pigment and also allow for a more uniform distribution of the pigment and / or greater visual effects. Another non-limiting particularly suitable application is to apply the film-forming component, such as an electrophoretic coating formulation, and then apply the pigment component, where the pigment includes flake pigments such as aluminum. This achieves better orientation of the flakes, and thus less flakes can be used to achieve better visual effects.

[0088] The pigment component and / or the hardened coating can be substantially free (less than 3 wt%), essentially free (less than 1 wt%), and / or completely free of wear-resistant particles, conductive particles, reinforcing particles, (retro)reflective particles, and / or magnetic particles.

[0089] Substrates to which the hardened coating according to the present disclosure can be applied include a wide range of substrates, including metal alloys, polymers, glass fibers, composites, or combinations thereof. Such substrates can include vehicle substrates, industrial substrates, structural substrates, etc. The substrate can be in the form of a sheet, plate, rod, bar, or any desired shape, and can be in the form of a vehicle component, such as a body, door, trunk lid, fender, hood, or bumper. The thickness of the substrate can vary as needed. The substrate can include an adhesive layer that allows the substrate to be attached to another surface.

[0090] Transportation components typically made of thermoplastic and thermosetting materials include bumpers and trim pieces.

[0091] The metal substrates to which the coating components can be applied can include rigid metal substrates such as ferrous metals, aluminum, aluminum alloys, copper, and other metal and alloy substrates. Ferrous metal substrates can include iron, steel, and their alloys. Non-limiting examples of useful steel materials include cold-rolled steel, galvanized (zinc-coated) steel, electro-galvanized steel, stainless steel, pickled steel, zinc-iron alloys, and combinations thereof. Combinations or composite materials of ferrous and non-ferrous metals can also be used, such as hot-dip galvanized steel assembled with an aluminum substrate.

[0092] The coating can be applied directly to the metal substrate; "direct to metal" means that there is no intermediate coating between the substrate of the present disclosure and the coating.

[0093] Direct to substrate can be a bare metal substrate, which is the original metal substrate that has not been treated with any pretreatment compositions (such as conventional phosphating baths, heavy metal rinsing solutions, etc.). The bare metal substrates that can be used herein can be the cut edges of substrates that are otherwise treated and / or coated on the rest of their surfaces. Alternatively, before applying the film-forming components or hardening coatings of the present disclosure, the substrate can undergo processing steps known in the art, such as cleaning, etching, pretreatment, etc. Those skilled in the art will understand that such processing is not "coating", and the application of the coatings of the present invention is still considered to be direct to metal.

[0094] When the film-forming component is an electrophoretic coating composition, the film-forming component can be applied by: optionally pretreating the current collector or substrate; at least partially immersing the current collector into a bath containing the film-forming component; and electrodepositing the film-forming component onto a portion of the current collector or substrate immersed in the bath.

[0095] After electrodeposition, the substrate can be dried for 15 minutes to 1 hour (but not fully cured), after which the pigment component can be applied to the partially uncured electrophoretic coating. When the pigment component is in powder form, the pigment component can be applied electrostatically, such as by using an electrostatic spray gun. When the pigment component is in slurry form, a spray gun, brush, or roller can be used to apply the pigment component. Alternatively, the substrate can be immersed in a rinsing solution containing the pigment component, or the rinsing solution can be cascaded onto the substrate. Then the substrate can be baked, such as baked at 90°C to 125°C, such as 95°C to 120°C or 100°C to 115°C for 15 minutes to 60 minutes, such as 20 minutes to 45 minutes or 30 minutes to 40 minutes.

[0096] When the film-forming component is an electrophoretic coating composition, the film-forming component may include pigments. The pigments may include iron oxide, lead oxide, strontium chromate, carbon black, pulverized coal, titanium dioxide, barium sulfate, colored pigments, phyllosilicate pigments, metallic pigments, thermally conductive electrically insulating fillers, flame-retardant pigments, or any combination thereof, as described in paragraphs [0051-0064] of International Patent Application No. PCT / US22 / 3497, at the levels described in paragraph

[0086] , the specific sections of the patent application being incorporated herein by reference.

[0097] When the film-forming component is an electrophoretic coating composition, the film-forming component may include pigments, the pigments including inorganic platelet pigments having an average equivalent spherical diameter of at least 0.2 micrometers and up to 5.0 micrometers, as described in paragraphs [0080-0081] of International Publication Application WO 2019 / 243973, the specific sections of the patent application being incorporated herein by reference. An electrophoretic coating composition as described in paragraph

[0057] of International Publication Application WO 2019 / 126498 may also be used, the specific sections of the application being incorporated herein by reference.

[0098] When the film-forming component is an electrophoretic coating composition, the film-forming component may include phyllosilicate pigments and dispersants as disclosed in paragraphs [0038-0050] of International Publication Application WO 2021 / 127327, the specific sections of the patent application being incorporated herein by reference.

[0099] When the film-forming component is an electrophoretic coating composition, the film-forming component may be compatible with the pigment component to allow the pigments to be more effectively incorporated. Acids may help dissolve cationic electrophoretic coatings or other amine-functional coatings and allow them to be more readily water-dispersible or soluble. When the film-forming component comprises an anionic electrophoretic coating or an acid-functional coating, amines may allow the pigments to be more effectively incorporated and allow them to be more readily water-dispersible or soluble.

[0100] When the film-forming component is an electrophoretic coating composition, the film-forming component may include groups containing active hydrogen and cationic salt groups and may be made cationic and water-dispersible by at least partially neutralizing the acid with a resin. Suitable resins for neutralizing the acid include organic acids and inorganic acids. Non-limiting examples of suitable organic acids include formic acid, acetic acid, methanesulfonic acid, and lactic acid. Non-limiting examples of suitable inorganic acids include phosphoric acid and aminosulfonic acid. Based on the total amine in the film-forming component containing cationic salt groups, the total amount of resin for neutralizing the acid of the film-forming component containing cationic salt groups containing active hydrogen may be 20%, such as 35%, or 50%, or 60% or 80%.

[0101] When the film-forming component is an electrophoretic coating composition, the film-forming component may include an anionic polymer, which may be at least partially neutralized by, for example, treatment with a base to form a water-dispersible anionic salt group-containing polymer before or during dispersion in a dispersion medium containing water. As used herein, the term "anionic salt group-containing polymer" refers to an anionic polymer that includes at least partially neutralized anionic functional groups such as carboxylic acid groups and / or phosphate groups that confer a negative charge. Suitable bases include amines, such as, for example, tertiary amines. Non-limiting examples of suitable amines include trialkylamines and dialkanolamines, such as triethylamine, diethylethanolamine, and dimethylethanolamine. Based on the total carboxylic acid and / or phosphate groups in the film-forming component containing anionic groups, the total amount of resin-neutralizing amine used to neutralize the anionic groups in the film-forming component may be 20%, such as 35%, or 50%, or 60%, or 80%.

[0102] The cured electrophoretic coating may have a dry film thickness of 0.012 mm to 0.038 mm (0.5 mils to 1.5 mils), such as 0.015 mm to 0.036 mm (0.6 mils to 1.4 mils) or 0.016 mm to 0.033 mm (0.65 mils to 1.3 mils), as determined using a Fischer coating thickness gauge in accordance with ASTM D7091-21.

[0103] When the film-forming component is a powder coating composition, such as a powder coating containing greater than 95 wt% total solids as measured in accordance with ASTM D2369 (2015), the powder coating composition may be applied to a substrate by any tool known in the art, such as electrostatic spraying. A potential of 10 kV to 150 kV (such as 20 kV to 125 kV or 50 kV to 100 kV) may be applied to the substrate, where the amperage is limited to 1 mA to 20 mA, such as 2 mA to 17 mA or 5 mA to 15 mA, and the flow rate is 1 psi to 50 psi, such as 2 psi to 40 psi or 5 psi to 35 psi, and the atomization is 1 psi to 50 psi, such as 2 psi to 40 psi or 5 psi to 35 psi. The resulting coated substrate may be baked at a temperature greater than the Tg of the powder coating composition for a period of time sufficient to reach a "gel bake" state. Then, a pigment component may be applied and the coating may be hardened, such as by heating. For example, the coated substrate may be baked at 90 °C to 250 °C (such as 100 °C to 225 °C or 120 °C to 215 °C) for 5 minutes to 60 minutes, such as 10 minutes to 45 minutes or 14 minutes to 40 minutes. Alternatively, the pigment component may be applied before reaching the gel bake state.

[0104] The dry film thickness of the cured coating formed from the powder film-forming agent can be in the range of 0.5 mils to 6 mils, such as 0.75 mils to 5 mils or 1 mil to 4 mils, as determined using a Fischer coating thickness gauge in accordance with ASTM D7091-21.

[0105] When the film-forming component comprises an aqueous coating composition (aqueous paint), the aqueous coating composition can comprise an aqueous composition including a continuous phase comprising water and a dispersed phase comprising a film-forming resin, an optional crosslinking agent, and optional additives as described herein. When the film-forming component comprises a solvent-based coating composition (solvent-based paint), the solvent-based coating composition can comprise an organic solvent in which a film-forming resin, an optional crosslinking agent, and optional other additives as described herein are dissolved and / or dispersed. The liquid film-forming component can be applied by any means known in the art such as dipping, rolling, brushing, spraying, etc. Depending on the chemical nature of the film-forming component used, curing or hardening can be accomplished as needed by any means known in the art such as by heating.

[0106] The dry film thickness of the cured coating formed from the liquid film-forming component can be at least 0.5 μm, such as at least 1 μm, at least 2 μm, at least 5 μm, and at least 7 μm, as determined using a Fischer coating thickness gauge in accordance with ASTM D7091-21, and can be up to 65 μm, such as up to 60 μm, up to 55 μm, and up to 52 μm, as well as from 0.5 μm to 60 μm, such as from 0.5 μm to 65 μm, such as from 0.5 μm to 60 μm, 0.5 μm to 55 μm, 0.5 μm to 52 μm, 1 μm to 65 μm, 1 μm to 60 μm, 1 μm to 55 μm, 5 μm to 65 μm, 5 μm to 60 μm, and 5 μm to 55 μm. The dry film thickness can be any value or range between (and including) any of the values recited above.

[0107] The cured coating described herein can be part of a multi-layer coating, stack, or system including one or more of a primer coating, a base coat, a top coat, and a clear coat. The cured coating of the present disclosure can be deposited on top of and / or beneath other coatings.

[0108] When the film-forming component has suitable rheological properties, the film-forming component can be applied to the substrate using a precision applicator, after which a pigment component is applied, and optionally the pigment component applied outside the area applied by the defined precision applicator to the substrate is removed. The pigment component can be applied with or without precision application.

[0109] As a non-limiting example, suitable rheological properties of the film-forming component can include at 0.1 s -1(Low shear rate) and the viscosity measured at 25 °C, which may be from 1,000 cps to 30,000 cps, such as from 2,000 cps to 25,000 cps, from 2,000 cps to 20,000 cps, and from 3,000 cps to 15,000 cps, is measured at 25 °C using an Anton Paar MCR 301 rheometer with a double-gap cylinder equipped with a DG26.7 measuring system. If the viscosity of the coating composition measured at 0.1 s -1 is too high or too low, it may not flow properly through the precision applicator, individual streams may not merge as desired, and / or the coating composition may run unacceptably on a vertical substrate. At 0.1 s -1 the viscosity of the coating composition can be any value or range between (and including) any of the values described above.

[0110] As a non-limiting example, suitable rheological properties of the film-forming component may alternatively include the viscosity measured at 1000 s -1 (high shear rate, unless otherwise stated, high shear rate means 1000 s -1 ), at 25 °C, which may be from 25 cps to 150 cps, from 35 cps to 140 cps, from 40 cps to 130 cps, and from 50 cps to 125 cps, and is measured at 1000 s -1 using an Anton Paar MCR 301 rheometer with a double-gap cylinder equipped with a DG26.7 measuring system. If the viscosity of the coating composition measured at 1000 s -1 is too high or too low, it may not flow properly through the precision applicator, individual streams may not merge as desired, and / or the coating composition may run unacceptably on a vertical substrate. At 1000 s -1 the viscosity of the coating composition can be any value or range between (and including) any of the values described above.

[0111] Suitable rheological properties of the film-forming component may alternatively include a shear-thinning rheological profile, in other words, the viscosity of the coating composition is higher at low shear rates than at high shear rates. The film-forming component may have a viscosity measured at 0.1 s -1 (low shear rate, unless otherwise stated, low shear rate means 0.1 s -1 ), which may be the viscosity measured at 1000 s -16 to 1,200 times, such as 20 to 1,000 times, 30 to 750 times or 40 to 1,200 times (this is called the viscosity ratio) of the viscosity of the coating composition measured at a high shear rate, is measured at 25 °C using an Anton Paar MCR 301 rheometer with a double-gap cylinder equipped with a DG26.7 measurement system. If the shear thinning property of the coating composition is too high or too low, it may not flow properly through the precision applicator, separate streams may not merge as desired, and / or the coating composition may sag unacceptably on a vertical substrate. The shear thinning property of the coating composition can be any value or range between (and including) any of the values described above.

[0112] The film-forming component can include various other additives, such as additional binders, carriers, water, catalysts, conventional additives, or combinations thereof. Conventional additives can include, but are not limited to, dispersants, antioxidants and absorbers, wetting agents, leveling agents, defoamers, anti-cratering agents, thermoplastic resins, plasticizers, wear-resistant particles, fillers (and including, but not limited to, mica, talc, clay, and inorganic minerals), metal oxides, metal flakes, and various forms of carbon, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow and surface control agents, thixotropic agents, rheology modifiers, reactive diluents, catalysts, reaction inhibitors, corrosion inhibitors, other conventional aids, and combinations thereof. As noted above, the film-forming component itself can include pigments, which can be the same as or different from the pigments in the pigment component.

[0113] Compared to a coating containing the same pigments in the film-forming component itself, the hardened coatings described herein can impart improved corrosion resistance to the substrate. Pigments particularly suitable for imparting corrosion resistance in the pigment component can include magnesium oxide, zinc, silver, mica, aluminum, and combinations thereof.

[0114] Compared to a coating containing the same pigments in the film-forming component, at the same loading based on the total composition weight, the hardened coatings described herein can have improved color. For example, the pigments in the pigment component can be flake pigments and provide a stronger metallic luster, the color can be more uniform, and / or the color can be brighter. The color characteristics can be measured using a BYK-MacI metallic color spectrophotometer instrument manufactured by BYK-Gardner. When forming a hardened coating using a powder film-forming component according to the present disclosure, such as the brightness indicated by the luminance of the hardened coating at 15° (L* 15° ) can be greater than 55, such as greater than 75, or in the range of 55 to 95, such as 75 to 92 or 78 to 91. This is a significant achievement because the L* 15° of conventional powder coatings is typically around 50 or lower. The present disclosure can be used to achieve an L* that was previously only achievable with liquid coatings through powder coatings.15° Value

[0115] The hardened coatings described herein may have a measurable flop index. The flop index can be measured using a BYK-Mac I spectrophotometer from BYK. Specifically, the flop index can be calculated by measuring the luminance of the reflected light at angles of 15°, 45°, and 110° relative to the surface of the hardened coating and then substituting these values into Equation 1:

[0116]

[0117] L* 15° = luminance of the reflected light measured at a 15° angle

[0118] L* 45° = luminance of the reflected light measured at a 45° angle

[0119] L* 110° = luminance of the reflected light measured at a 110° angle

[0120] The flop index of an object surface without metallic texture is zero.

[0121] The hardened coatings described herein may have a flop index, measured as described above, greater than 8, such as greater than 10, or from 8 to 22, such as from 10 to 20 or from 8 to 15.

[0122] The hardened coatings described herein may form a smooth coating or film. As used herein, "smooth" means an average roughness Ra of less than 5 μm, such as less than 3 μm, less than 1.8 μm, less than 1 μm, or less than 0.5 μm, as measured according to ISO method 4287-1997.

[0123] It should be understood that, where not mutually exclusive, the various features of the present disclosure described, shown, and / or claimed herein may be used in combination with each other. In addition, the following examples are presented to illustrate the general principles of the coatings and coated substrates provided by the present disclosure. Unless otherwise indicated, all listed amounts are described in parts by weight. The present disclosure should not be considered limited to the specific examples presented.

[0124] Examples

[0125] Example 1 (Galvanic protection via zinc powder)

[0126] The CRS substrates obtained from ACT Industies were evaluated. The 4”×12” panels were treated by spray application of Chemkleen Surface Prep 1, an alkaline cleaner commercially available from PPG Industries, Inc. The panels were spray cleaned and degreased in ST-1 (125°F) at 10 psi - 15 psi using a Vee-jet nozzle for 120 seconds and rinsed with deionized water by immersion in a deionized water bath (75°F) for 30 seconds, and then spray rinsed with deionized water using a Melnor Rear-Trigger 7-Pattern nozzle (available from Home Depot) set to the shower mode.

[0127] After spray cleaning and degreasing, the panels were rinsed with deionized water spray rinse solution for 30 seconds using a Melnor Rear-Trigger 7-Pattern nozzle set to the shower mode (75°F), and then hot air dried at a high setting at a temperature of about 50°C - 55°C using a high-speed handheld hair dryer (model 078302-300-000) manufactured by OSTER until the panels were dry (about 1 minute - 5 minutes). The panels were cut into 4”×6” size using a panel cutter.

[0128] The 4”×6” CRS panels were immersed in a bath containing CR840, a cationic electrophoretic coating commercially available from PPG, diluted with water to 20% theoretical solids non-volatile weight. The bath temperature was 90°F and the panels served as the cathode electrically connected to the anode. When a 200-volt potential was applied between the electrodes and the current was limited to 5 amperes, the coating composition was electrodeposited onto the panels. The coating temperature was limited to 36°C. The coated panels were dried (1 hour - 2 hours under ambient conditions), and then a suspension of 25 grams of zinc powder (ultra-pure zinc powder UP6 from pure zinc metal) in 250 grams of methoxypropanol, ethylene glycol ether solvent (Dowanol PM available from Dow Chemical Company) was sprayed onto the film. After the zinc spray application, the panels were dried under ambient conditions for about 5 minutes - 10 minutes and then baked in an electric furnace at 177°C for 30 minutes. A smooth film with a film thickness of approximately 19 microns (ISO method 4287-1997) was achieved.

[0129] The galvanized protection was evaluated by monitoring the formation of white rust (i.e., zinc corrosion products) under a 500-hour salt spray test according to ASTM B 117 (2019). The galvanized protection was rated by the white rust on the surface of the coated panels, the scribes, and (if applicable) the gravel impact marks. White rust indicates that the zinc-rich coating oxidizes in a sacrificial manner to protect the base metal of the substrate. Red rust indicates the oxidation of the substrate.

[0130] The results of the visually determined salt spray test showed that white rust was dominant along the scribe lines and little red rust was detected.

[0131] Example 2 (Aluminum particle embedding)

[0132] As described in Example 1, the cationic acrylic electrocoat POWERCRON 935, commercially obtained from PPG, was applied to cold-rolled steel sheets (ACT part number 26241) via an electro-deposition process. The control samples were baked at 177 °C for 30 minutes directly after electro-deposition.

[0133] The pigment component in slurry form was applied to the partially uncured electrocoated film. The slurry was prepared by mixing 15 grams of aluminum pigment (HYDROLAN 2153, from Eckart) and 150 grams of methyl ethyl ketone. The slurry was directly sprayed on top of the vertically hung panel using a standard liquid paint spray gun (Binks 2100 spray gun). The panel was sprayed within 30 minutes after the electro-deposition process. Then the sample was baked at 177 °C for 30 minutes. Then the panel was cut into 2.5”×1.75” and placed in a weatherometer set up using ASTM D7869-13. The gloss retention rate is reported in Table 1. Example A is the control without embedded aluminum, and Example B is the panel with aluminum as described above. For the panels with embedded aluminum, the gloss retention rate is higher.

[0134] Table 1: Gloss Retention Rate of Acrylic Electrocoat

[0135]

[0136] Example 3 : Anticorrosive Acrylic Electrocoat

[0137] The cationic acrylic electrocoat CR 935, commercially obtained from PPG, was applied to cold-rolled steel sheets (ACT part number 26241) via an electro-deposition process and baked at 177 °C for 30 minutes.

[0138] Panels were prepared as described in Example 1 and then sprayed with a silver mica slurry, which was prepared by mixing 15 grams of silver mica pigment (Mearlin Sparkle 139X from BASF) and 150 grams of methyl ethyl ketone and directly sprayed on top of the uncured electrocoated panel using a standard liquid paint spray gun (3M Accuspray gun with 1.2mm nozzle side). The panel was sprayed within 30 minutes after the electro-deposition process. Then the sample was baked at 177 °C for 30 minutes (Example C is the control without applying mica pigment, and Example D includes applying mica pigment as described above).

[0139] The substrate was evaluated for scribing corrosion after 500 hours of salt spray testing according to ASTM B 117 (2019). As shown in Table 2, an improvement in scribing corrosion was observed, where a smaller number indicates an improvement.

[0140] Table 2

[0141]

[0142] Example 4: Electrodepositable coating composition

[0143] The electrodepositable coating composition was prepared similarly to that described in Examples 4, 5A, and 5B of U.S. Patent No. 10,947,408.

[0144] Powder MgO particle embedding in anionic electrophoretic coating

[0145] The electrodepositable coating composition (similar to Example 5B of U.S. Patent No. 10,947,408) was electrodeposited onto a 2024T3 bare aluminum alloy test panel (ACT Test Panel Technologies) at a bath temperature of 85°F, a current of 0.2 amperes, and a voltage of 130 volts for 90 seconds according to ASTM D7091-21, resulting in a dry film thickness of 0.51 ± 0.02 mils (Example E, Table 3). After electrodeposition, the panel was dried for 15 minutes to 1 hour. Powdered magnesium oxide particles (MAGCHEM 10-325) were added to a fluidizing hopper (Nordson HR-1-4) and fluidized with clean, dry air. The powder was then electrostatically applied to a vertically grounded test panel at 75 kV (Example F, Table 3) at a flow rate of 30 psi and an atomization of 30 psi (via a Nordson Encore electrostatic spray gun). The panel was then baked in an electric furnace at 225°F for 30 minutes. According to ASTM D7091-21, using a Positector 6000 magnetic flux meter, the panel had a dry film thickness of 0.70 ± 0.07 mils.

[0146] After baking the panel, a "X" measuring 10 cm × 10 cm was scribed on the panel. The "X" was scribed into the panel surface to a sufficient depth to penetrate any surface coating and expose the underlying metal. Then, the scribed test panel was placed in a 5% sodium chloride neutral salt spray cabinet according to ASTM B117 (2019) (except that the pH value and salt concentration were checked weekly instead of daily). After 504 hours of neutral salt spray exposure, the test panel was evaluated according to the rating shown in Table 3. The panel was rated according to the following scribed corrosion rating, with a rating scale of 0 to 100, where the number represents the percentage of the scribed area showing visible corrosion. The lower the number, the less corrosion and thus the better the corrosion inhibition. The lightness of the scribe was also evaluated on a rating scale of 0 to 100 representing the percentage of the scribe (i.e., dull or loss of gloss). Both values were the average of two repetitions. The lower the number, the better the performance.

[0147] Table 3: Powder Salt Spray Performance

[0148]

[0149] 1 Magchem 10-325, available from Martin Marietta Magnesia Specialties

[0150] It can be seen that compared with Example E without embedded MgO, both the scribed corrosion and the scribed lightness of Example F were greatly improved when MgO particles were embedded in the surface. As pointed out in the specification, it is usually not possible to directly incorporate MgO particles into the aqueous electrophoretic coating bath, and therefore, it is not possible to compare with directly adding MgO to the electrophoretic coating composition. The present disclosure allows the use of MgO together with the aqueous electrophoretic coating.

[0151] Example 5 : Embedding of Liquid MgO Slurry in Anionic Electrophoretic Coating

[0152] At a bath temperature of 85°F, the electrodepositable coating composition of Example 4 was electrodeposited onto a T3 bare aluminum alloy test panel (the above ACT test panel technology) at a current of 0.2 amperes and a voltage of 170 volts for 90 seconds, achieving a dry film thickness of 0.93 ± 0.04 mils as determined by ASTM D7091-21 (Example G, Table 4). The panel was dried for 15 minutes to 1 hour and then the slurry was applied. The slurry contained 10% (by weight) magnesium oxide particles (MagCHEM 10-325) in acetone, which was stirred with a tongue depressor before spraying. The slurry was applied to the vertically electrocoated test panel with an HVLP spray gun, either 2 passes (2 passes, Example H, Table 4), or 4 passes (4 passes, Example I, Table 4). Upon hardening, the dry film thickness of the hardened coating as determined by ASTM D7091-21 was 1.03 mils and 0.75 mils respectively.

[0153] The panel was baked in an electric furnace at 225°F for 30 minutes. After baking, the panel was scribed inwardly with a 10 cm × 10 cm "X" that was scratched into the panel surface to a sufficient depth to penetrate any surface coating and expose the underlying metal. The scribed test panel was then placed in a 5% sodium chloride neutral salt fog cabinet according to ASTM B117 (2019) (except that the pH value and salt concentration were checked weekly instead of daily). The test panel was evaluated after 504 hours of neutral salt fog exposure according to the ratings shown in Table 5 below. The panel was rated as described in Example 4.

[0154] Table 5: Slurry Salt Spray Performance

[0155]

[0156] 10-325, available from Martin Marietta Magnesia Specialties

[0157] Compared to over 50% corrosion of the control (Example G), minimal corrosion (<5%) was observed for the panels coated with MgO slurry (Examples H and I).

[0158] Example 6 : Anti-Corrosion Epoxy Electrocoating

[0159] CRS substrates from the ACT industry were evaluated. Panels measuring 4” × 12” were treated with a spray application of Chemkleen Surface Prep 1, an alkaline cleaner commercially available from PPG Industries, Inc. The panels were spray cleaned and degreased for 120 seconds at 10 psi - 15 psi in ST-1 (125°F) using a Vee-jet nozzle and rinsed with deionized water by immersion in a deionized water bath (75°F) for 30 seconds, and then spray rinsed with deionized water using a Melnor Rear-Trigger 7-Pattern nozzle (available from Home Depot) set to the shower mode.

[0160] After spray cleaning and degreasing (but without pretreatment), the panels were spray rinsed with deionized water for 30 seconds using a Melnor Rear-Trigger 7-Pattern nozzle set to the shower mode (75°F), and then hot air dried at a high setting at a temperature of approximately 50°C - 55°C using a high-speed hand-held hair dryer (model 078302-300-000) manufactured by OSTER until the panels were dry (about 1 minute - 5 minutes).

[0161] A commercially available epoxy electrocoating FrameCoat II from PPG was applied using the above electrodeposition process. Control samples were baked at 177°C for 25 minutes directly after the electrodeposition process (Example J). Panels prepared according to the present disclosure were sprayed with an aluminum paste, which was prepared by mixing 15 grams of aluminum pigment (HYDROLAN 2153) in methyl ethyl ketone and applied to the panels before baking at 177°C for 25 minutes (Example K).

[0162] The substrates were evaluated for scribed corrosion by scribing the surface and testing the surface using a salt spray test for 500 hours according to ASTM B 117 (2019). The results are shown in Table 6.

[0163] In addition, flexibility was evaluated according to ASTM D522 (2010) with a 180° bend on a 1 / ”" mandrel. No visual cracks or delamination of the film were observed. After measuring the film thickness, cure was evaluated by a diacetone rubbing test. The baked panels were wiped with a WYPALL X80 disposable paper towel soaked with acetone manufactured by Kimberly-Clark. Rubbing was considered double rubbing (one forward rub and one backward rub constitute double rubbing). Rubbing was continued until 50 rubs were counted or visible scratches / indentations were observed. In both samples, more than 50 rubs were achieved with no scratches / indentations observed. However, when the pigment component was applied, scribed corrosion was greatly improved.

[0164] Table 6

[0165]

[0166] Examples 7 - 13 (powder coating)

[0167] According to the disclosure herein, the panel is coated only with a commercial PPG black hybrid powder primer with product code PCF 90202, and the powder primer is dry blended (“dry blend”) with the pigment component, or the pigment component is coated after the powder primer. As indicated in Table 7, the pigments used are XIRALLIC pigments available from Merck or MEARLIN 139X available from Sun Chemical.

[0168] The PCF 90202 conventional powder is electrostatically sprayed by adding the powder to the application cup, and the powder is electrostatically applied to a grounded cold rolled steel sheet (ACT part number 26241) at 75 kV at a flow rate of 10 psi and an atomization of 10 psi (via an Encore LT manual electrostatic spray gun). Dry blend samples are prepared by mixing the pigments indicated in Table 7 with the base powder in a bag or mixing cup to the level required to achieve the pigment load also shown in Table 7. The container is then shaken vigorously for three minutes to thoroughly mix the pigments in the base powder and the dry blend applied using the same electrostatic procedure described above. For the panels prepared according to the present disclosure, the pigment component is directly sprayed on top of the PCF 90202 (identified as “embedded” in Table 7) at a flow rate of 30 psi and an atomization of 30 psi using a 75 kV Encore LT manual electrostatic spray gun setting. The pigment load of these panels is calculated based on the deposited weight. Specifically, the weight of the powder is measured immediately after applying the PCF-90202 and then again after applying the pigment component (the powder-coated panel minus the initial weight of the panel).

[0169] All panels are baked in an electric furnace at 191 °C for 20 minutes directly after application, and a cured film thickness of approximately 3 mils is produced. The color of the cured film is evaluated using a BYK-Mac I metallic color spectrophotometer instrument manufactured by BYK-Gardner.

[0170] The L* data of the panels are provided in Table 7. All panels prepared according to the present disclosure have a much higher brightness level, as indicated by higher L* values, visible at all angles, compared to other panels. This indicates that the pigments have a greater sparkle relative to the dark substrate because the pigments are concentrated at the surface of the coating. Figure 2SEM cross-sections of Examples 12 and 13 are shown to highlight the local concentration of the pigment. The SEM samples were prepared by mounting the samples into an epoxy film and microtoming the film. The samples were then coated with Au / Pd for 40 seconds and analyzed in a Quanta 250FEG SEM under high vacuum.

[0171] Table 7: BYK Mac Data

[0172]

[0173] The use of the cured coatings of the present disclosure opens up new color spaces for powder coatings, as indicated by higher L* values (brightness), compared to the case where the pigment is mixed with other coating components.

[0174] Examples 14 - 17

[0175] Panels were coated with a commercial PPG powder coating as indicated in Table 8, followed by coating with the indicated pigment components. The powder coating was electrostatically applied to a grounded cold-rolled steel sheet (ACT part number 26241) at 75 kV at a flow rate of 10 psi and an atomization of 10 psi (via an Encore LT manual electrostatic spray gun). The pigment component (dry pigment) was directly sprayed on top of the powder coating using an Encore LT manual electrostatic spray gun with a 75 kV setting at a flow rate of 30 psi and an atomization of 30 psi. The panels were baked in an electric furnace at 191 °C for 20 minutes, and the dry film thickness was approximately 3 mils as determined by ASTM D7091-21. The smoothness of the cured film was evaluated using a handheld Mitutoyo sj-210 (Mitutoyo America Corporation) with a cut-off wavelength of 0.8 mm according to ISO method 4287-1997. The results are shown in Table 8, where "Ra" represents "arithmetic mean roughness"; these values represent the average of three panels.

[0176] Table 8

[0177]

[0178] 2 Available from PPG

[0179] 3 Available from Merck kGaA

[0180] 4 Available from Sun Chemical

[0181] As the data shows, Example 14 has a relatively rough or "drawn" surface, Example 17 has a less rough or "sanitary" finished surface, while Examples 15 and 16 have a smooth or "flawless" finished surface.

[0182] Examples 18 and 19

[0183] Apply the commercially available film-forming component epoxy electrocoat FrameCoat II from PPG on the grounded cold-rolled steel sheet (ACT part number 26241) using the above electro-deposition process. Prepare the pigment component slurry by mixing 15 grams of aluminum pigment (Sparkle silver 3122-AR, Silberline Manufacturing Co., Inc.) in 150 grams of methyl ethyl ketone or acetone. Spray the slurry directly on top of the unhardened electrocoated panel using a standard liquid paint spray gun (3M Accuspray gun with a 1.2 mm nozzle side). Spray the panel within 30 minutes after the electro-deposition process. Then bake the sample at 177 °C for 30 minutes. The results are shown in Table 9.

[0184] Table 9

[0185] Examples Effect pigments Slurry medium Average roughness (Ra) 18 <![CDATA[Sparkle silver 3122-AR 15 > Methyl ethyl ketone 1.66 19 <![CDATA[Sparkle silver 3122-AR 15 > Acetone 2.78

[0186] 15 Available from Silberline Manufacturing Co., Inc.

[0187] As the data shows, Examples 18 and 19 will be considered to have a somewhat smooth finished surface.

[0188] Examples 20 - 23 (precision application)

[0189] When conventional effect pigments are included in a precision coating composition, the nozzles for precision application may become clogged. Therefore, precision coatings are limited to base colors (i.e., without effect pigments).

[0190] As indicated in Table 10, the electrophoretic coating primer substrate is coated with a colored base coat and cured or dried as indicated in Table 10. The second coating as indicated in Table 10 is applied over a 3×3 inch [7.6×7.6 cm] square area via a precision applicator, with a dry film thickness of 30 µm - 80 µm as determined by ASTM D7091-21. The effect pigment as indicated in Table 10 is applied by electrostatic powder spraying to the already precisely applied but uncured coating. In this way, the effect pigment is applied only to the uncured precisely applied coating. Then, the sample is subjected to a period of ambient post-curing or heat flash time. Any remaining pigment is removed by an air knife, a feather duster, or other non-destructive method. When the unadhered pigment has been satisfactorily removed, the sample is transparently coated and cured, as indicated in Table 10.

[0191] Table 10

[0192]

[0193] 16 Deltron coatings are available from PPG

[0194] 17 Available from PPG

[0195] 18 Envirobase coatings are available from PPG

[0196] 19 Available from Sun Chemical

[0197] 20 Steel panels coated with ED6280C are available from PPG

[0198] The method according to the present disclosure allows the placement of the effect pigment only on specific portions of the coated panel (the portions where the coating is precisely applied). This represents an advancement over conventional methods of adding the effect pigment to the entire formulation; according to the present disclosure, a reduced amount of the effect pigment can be used, and the effect pigment is better aligned at the surface of the coating. Thus, using the single coating composition and method described herein, the effect pigment is successfully incorporated into the precisely applied coating, which was not achievable previously.

[0199] Although specific embodiments of the present disclosure have been described above for purposes of illustration, it will be apparent to those skilled in the art that various modifications can be made to the details of the present disclosure without departing from the scope defined in the appended claims.

Claims

1. A hardened coating, comprising: a. A film-forming component; and b. A pigment component containing pigments; wherein the pigment component is applied to at least a part of the surface of the film-forming component that is at least partially unhardened when the pigment component is applied, such that the pigments become embedded in the film-forming component; wherein the pigment component itself does not form a film.

2. A hardened coating formed by: a. Applying a film-forming component to at least a part of a substrate; b. Applying a pigment component containing pigments to at least a part of the surface of the film-forming component that is at least partially unhardened when the pigment component is applied, such that the pigments become embedded in the film-forming component; and c. Hardening the coating; wherein the pigment component itself does not form a film.

3. The coating according to claim 1 or 2, wherein the pigments in the pigment component are incompatible with the film-forming component and / or with the desired application method.

4. The coating according to any one of the preceding claims, wherein the pigments are concentrated in a part of the coating, such as 75 wt% or more, 80 wt% or more, 85 wt% or more, 90 wt% or more, or 95 wt% or more of the pigments are in 25% of the coating, such as 15% of the coating, or 10% of the coating, such as the surface of the coating, such as the innermost surface or the outermost surface.

5. The coating according to any one of the preceding claims, wherein the pigments are distributed substantially uniformly on the surface or a part of the surface of the coating, and provide a substantially uniform visual effect to the surface of the coating, such as a metallic visual effect, a color effect, a luminescent effect, and / or a (retro)reflective effect, and wherein the pigments are distributed substantially uniformly on all the surfaces (100%), most of the surfaces (99% - 50%), some of the surfaces (49% - 1%), and / or can be distributed on the surface in a predetermined pattern, and wherein the surface can be the outermost surface.

6. The coating according to any one of the preceding claims, wherein the pigments in the pigment component account for less than 25 wt% of the weight of the hardened coating, such as less than 20 wt%, or less than 15 wt%, or less than 10 wt%, or 1 wt% to 25 wt%.

7. The coating according to any one of the preceding claims, wherein the pigment component comprises dry pigment particles, a slurry of pigment particles, and / or a liquid carrier such as a liquid carrier containing water and / or an organic solvent, or a rinsing liquid or immersion liquid containing pigment particles dispersed in a carrier such as a carrier containing water and / or an organic solvent.

8. The coating according to claim 7, wherein the carrier comprises a plasticizer and / or a solvent, such as water; C3-C 12 ketones, such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohols, such as isopropyl alcohol, butanol and 2-ethylhexanol; monomethyl ethers, monoethyl ethers or monohexyl ethers of ethylene glycol or propylene glycol, such as propylene glycol methyl ether; C2-C 12 aldehydes, such as acetaldehyde, cinnamaldehyde and vanillin; esters, such as ethyl acetate, butyl acetate, phthalate, sebacate, adipate, terephthalate, dibenzoate, glutarate or azelate; or any combination thereof.

9. The coating according to any one of the preceding claims, wherein the pigments are embedded in the coating such that, based on the volume of the pigments, 10 vol% to 100 vol%, such as 20 vol% to 100 vol%, or 50 vol% to 100 vol%, or 70 vol% to 100 vol% of the pigments are embedded in the coating, as determined by cross-sectional microscopy.

10. The coating according to any one of the preceding claims, wherein the pigment has a visual effect and / or a performance effect, such as a corrosion-inhibiting pigment, a color-imparting pigment, a metallic pigment, a radar-reflecting pigment, a LIDAR-reflecting pigment, a filler pigment, a luminescent pigment, a (retro)reflective pigment, a reinforcing particle, or a combination thereof, such as a metallic-effect pigment in any form, such as in the form of spheres, flakes or agglomerates, such as aluminum, stainless steel, zinc, copper, and their alloys and their flakes, an interference pigment, such as mica coated with titanium dioxide, muscovite, phlogopite or biotite, mica, gold, silver, nickel, platinum, bronze, brass, titanium, tungsten, including their oxides and alloys.

11. The coating according to any one of the preceding claims, wherein the pigment and / or the cured coating is substantially free of, essentially free of, and / or completely free of wear-resistant particles, conductive particles, reinforcing particles, (retro)reflective particles, and / or magnetic particles, and when the film-forming component is thermoplastic.

12. The coating according to any one of the preceding claims, wherein the pigment component comprises a corrosion-inhibiting pigment, and the corrosion-inhibiting pigment comprises nano-scale magnesium oxide (5 nm - 100 nm as determined according to ISO 13320-1 (1999)), micro-scale magnesium oxide (1 micron - 5 microns as determined according to ISO 13320-1 (1999)), silica, lithium salts, such as lithium nitrate, lithium sulfate, lithium fluoride, lithium bromide, lithium chloride, lithium hydroxide, lithium carbonate, lithium iodide, or a combination of any of these.

13. The coating according to any one of the preceding claims, wherein the film-forming component comprises a thermosetting resin, a thermoplastic resin, a crosslinkable resin and its crosslinking agent, a self-crosslinking resin, or any combination thereof, and wherein the film-forming component may comprise one component or multiple components.

14. The coating according to any one of the preceding claims, wherein the film-forming component comprises a powder coating composition, a solvent-based coating composition, an aqueous coating composition, an anion electrophoretic coating composition, a cation electrophoretic coating composition, a coating composition comprising greater than 95 wt% total solids as measured according to ASTM D2369 (2015), or a low-temperature curing coating formulation.

15. The coating according to any one of the preceding claims, wherein when the pigment component is applied, the at least partially uncured film-forming component is cured to no more than 75% of its curing potential, such as no more than 65%, or no more than 50%, or 0% to 75%, such as 0% to 65% or 0% to 50%.

16. The coating according to any one of the preceding claims, wherein the film-forming component comprises a powder coating composition, and the powder coating composition may be in a gel-baked state when the pigment component is applied and provides a substantially uniform effect, such as a visual effect, such as a color effect and / or a metallic effect, to the outermost surface of the coating or a portion thereof upon curing.

17. The coating according to claim 16, wherein the coating comprises platelet pigments and has a flop index greater than 8, such as greater than 10 or from 8 to 22, such as from 10 to 20 or from 8 to 15, and / or a brightness greater than 55, such as greater than 75 or in the range of 55 to 95, such as 75 to 92 or 78 to 91, as indicated by the luminance at 15° (L* 15° ), and both the flop index and the brightness are determined using a BYK-Mac I spectrophotometer.

18. A coating according to any one of claims 1 to 15, wherein the film-forming component comprises an electrocoating formulation, and wherein the pigment in the pigment component provides a substantially uniform effect, such as a visual effect, such as a color effect and / or a metallic effect, to the outermost surface or a part thereof of the coating, or the pigment is within the body and / or the innermost surface of the coating and provides corrosion resistance.

19. A coating according to any of the preceding claims, wherein the hardened coating has a surface roughness or Ra of less than 5 μm, such as less than 3, less than 1.8, less than 1 or less than 0.5, as measured according to ISO method 4287-1997.

20. A substrate at least partially coated with a coating according to any of the preceding claims, such as a metal substrate, a polymer substrate, a composite material or a combination thereof.

21. A substrate according to claim 20, wherein the film-forming component comprises an electrocoating, such as an anion electrocoating or a cation electrocoating, and the pigment in the pigment component comprises metal flakes and / or a corrosion inhibitor; the film-forming component comprises a primer, and the pigment component comprises a corrosion inhibitor; the film-forming component comprises a powder coating formulation, and the pigment component comprises a visual effect pigment.

22. A substrate according to claim 20 or 21, wherein the substrate comprises one or more additional coatings, such as a primer layer, an undercoat, a topcoat, a clear coat and / or an adhesive layer, under and / or over the hardened coating.

23. A substrate according to claims 20 to 22, wherein the substrate forms at least a part of a vehicle, an article, a consumer electronic device, a consumer appliance or a structure.

Images