Coating composition and related method

Abstract

A method for preparing a coated article is disclosed. The method includes preparing a substrate having a partially dehydrated, water-containing coating layer. The method further includes supplying the coating composition to a high-efficiency applicator, which includes a plurality of nozzles, each configured to apply the flow of the coating composition to the substrate without substantially atomizing it. The coating composition is an aqueous fluid exhibiting a near-Newtonian viscosity profile and includes a binder, a crosslinking agent, and a thickener. The method further includes applying the coating composition to the substrate by placing a plurality of lines of the coating composition onto the partially dehydrated, water-containing coating layer of the substrate via the plurality of nozzles using the high-efficiency applicator, thereby forming an overspray-free coating layer thereon.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 63 / 489,694, filed on 10 March 2023, the contents of which are incorporated herein by reference. This disclosure generally relates to aqueous coating compositions, more specifically to aqueous, overspray-free coating compositions, and to systems and methods for preparing overspray-free coatings using the same. [Background technology]

[0002] Inkjet printing is a non-impact printing process in which droplets of ink are deposited onto a substrate, typically paper or fabric, in response to an electronic signal. Digital printing, a specific application of this process, allows for precise adjustments to individual requirements. The droplets can be ejected onto the substrate by various inkjet application methods, including continuous and drop-on-demand printing. In drop-on-demand printing, the energy for ejecting the ink droplets can originate from a thermal resistor, piezoelectric crystal, acoustic, or solenoid valve. These methods utilize high transfer efficiency applicators. In the automotive industry, car bodies are typically coated with a series of finishes, each with a specific function, including electrodeposition, a primer, a colored base coat, and a clear top coat that provides additional protection and a glossy finish. Currently, most car bodies are painted in a single color with a base coat applied in a single spray application. The coating is applied with a pneumatic spray or rotary device that produces a wide jet of paint droplets with a broad droplet size distribution. This has the advantage of producing a uniform, high-quality coating in a relatively short time through an automated process. However, this process has many drawbacks. When the car body is painted in multiple colors, for example, if the second color is used in a pattern like stripes, or if an entire part of the car body, such as the roof, is painted in a different color, it is necessary to mask the first coating and then put the car body through a second paint spraying process to add the second color. After the second painting process, the masking must be removed. This is both time-consuming and labor-intensive, and adds a considerable cost to the work.

[0003] The second drawback of current spraying technology is that paint droplets are sprayed in a wide jet with a broad range of droplet sizes. As a result, many droplets either overspray the substrate because they are sprayed near the edges, or smaller droplets do not land on the vehicle at all because they have too little momentum to reach the vehicle body. This excessive overspray must be removed from the spraying process and disposed of safely, which leads to the generation of a large amount of waste and incurs additional costs for waste materials, cleaning, and disposal. Applying coatings using a high-efficiency applicator can provide a solution for applying two colors to a vehicle and for minimizing overspray by generating uniformly sized droplets that can be directed towards specific points on the substrate, such as specific locations on the vehicle body, thereby minimizing or completely eliminating oversprayed droplets. In addition, using digital printing, patterns or two-tone designs can be printed onto the vehicle body as a digitally printed second color, either on top of a previously sprayed base coat of a different color, or directly onto a primed or clear-coated vehicle substrate.

[0004] However, conventional inkjet inks are typically formulated to print on porous substrates such as paper and cloth, where the ink is rapidly absorbed into the substrate, thus facilitating drying and handling of the substrate immediately after printing. In addition, while printed articles have sufficient durability for these applications, such as printed text and images or patterned textiles, the durability requirements for automotive coatings are far more stringent in terms of both physical durability, such as resistance to abrasion and chipping, and long-term durability against weathering and lightfastness. Furthermore, inkjet inks known in the art are formulated to have a low, generally shear-independent, i.e., Newtonian viscosity, typically less than 20 cps. Such a viscosity profile is chosen due to the limited amount of energy available to eject ink droplets at each nozzle of the printhead, and also to avoid thickening of the ink (e.g., due to shear) that could clog the channels of the printhead.

[0005] On the other hand, automotive coatings typically exhibit significant non-Newtonian shear behavior. At low shear rates, they have extremely high viscosity, which helps avoid pigment sedimentation and ensures rapid and uniform application of the coating immediately after application. At high shear rates, however, they have relatively low viscosity, facilitating spraying and atomization into droplets.

[0006] Furthermore, while current technology is suitable for some horizontal applications, other applications remain, such as vertical applications, where sagging occurs at an unacceptable level with current technology. Because high-efficiency applicators require very low viscosities with limited shear thinning behavior, standard approaches to imparting sagging resistance to spray-applied coatings cannot be used.

[0007] More specifically, the limitations imposed by zero-overspray applicators (continuous flow) or high-resolution drop-on-demand (i.e., "inkjet" printheads) typically require very low high-shear viscosity. In contrast to atomization, viscosity increases do not occur because solvent evaporation does not occur after the paint is sprayed from the applicator and before it collides with the substrate. As a result, the coating will sag on non-horizontal surfaces. To achieve adequate sagging resistance, rheological modifiers must be incorporated at a high level such that sagging is prevented while the yield stress prevents flow and leveling that would result in coating defects specific to zero-overspray applicators. These defects include nozzle line and stripe overlap visibility. The former is due to incomplete flow and leveling of the flow or droplets released from adjacent nozzles, resulting in visible parallel lines in the direction of printhead movement. The latter is a result of the application of a second paint stripe (with the width of the nozzle array) adjacent to a first stripe that was applied earlier. Adhesion can be improved by changing the index (distance between adjacent stripes), but this requires high levels of rheological modifiers to prevent sagging, and overlapping regions exhibit visible peaks or valleys that cannot be eliminated by index optimization. In addition, due to particle size limitations for these small nozzle dispensers, some rheological modifiers cannot be used due to filter and nozzle clogging. Therefore, there remains an opportunity for improvement. [Overview of the project]

[0008] A method for preparing painted articles is provided. The method is: Prepare a substrate having a partially dehydrated, water-containing coating layer on it; A coating composition for application without overspray, with a near-Newtonian viscosity profile and a viscosity of 500 Pa at all shear rates from 0.1 / sec to 10 / sec, or from 0.1 / sec to 100 / sec. *Prepare a coating composition that exhibits a shear viscosity of less than 1 second and is an aqueous fluid containing a binder, a crosslinking agent, and a thickening agent; Supplying a coating composition to a high-efficiency applicator comprising multiple nozzles, each configured to apply the flow of the coating composition to a substrate without substantially atomizing it; and The method includes applying a coating composition to a substrate by using a high-efficiency applicator to place multiple lines of the coating composition onto a partially dehydrated, water-containing coating layer on the substrate via multiple nozzles, thereby forming an overspray-free coating layer thereon.

[0009] Coating compositions used in the method are also provided. A system is also provided. The system includes a high-efficiency applicator that supplies the coating composition. This disclosure is described below, along with the diagrams shown below. In the diagrams, similar numbers represent similar elements. [Brief explanation of the drawing]

[0010] [Figure 1A] This is a top view of a high-efficiency coating device that applies a coating composition to a substrate. [Figure 1B] This is a side view of Figure 1A. [Figure 2A] This is a side view showing the position of the edge nozzle of a high-efficiency coating device on a substrate on which paint (coating composition) is placed. [Figure 2B] This is a side view of the substrate in Figure 2A, which is tilted during the process of determining the sag, and shows the angle of the substrate compared to the horizontal plane. [Figure 3A] This is a side view of a high-efficiency coating device including multiple nozzles for applying a coating composition to a substrate, where a single nozzle line can be defined as having a periodically repeating pattern with spacings corresponding to the spacing between nozzles on a nozzle plate. [Figure 3B]FIG. 3A is a side view showing stripes of a coating composition applied to a substrate, and each stripe is a single pass of about 50 nozzles. [Figure 3C] FIG. 3A is an enlarged view of a single pass where there are defects where each nozzle impinged on the substrate. [Figure 4] Photograph showing stripe overlap defects in the substrate on which the comparative composition is disposed. [Figure 5] Schematic cross-sectional view of a coated article according to an embodiment of the present disclosure. [Figure 6A] Plot showing the results of a controlled shear rate flow sweep exemplifying the rheology profiles of representative and comparative coating compositions. [Figure 6B] Plot showing the results of a time sweep experiment exemplifying the recovery behavior of representative and comparative coating compositions. [Figure 7A] Plot showing the results of a controlled shear rate flow sweep exemplifying the rheology profile of a representative coating composition. [Figure 7B] Plot showing the results of a time sweep experiment exemplifying the recovery behavior of a representative coating composition. [Figure 8A] Plot showing the results of a controlled shear rate flow sweep exemplifying the rheology profile of an additional representative coating composition. [Figure 8B] Plot showing the results of a time sweep experiment for the representative coating composition of FIG. 8A.

DETAILED DESCRIPTION OF THE INVENTION

[0011] The following detailed description is merely representative in nature and is not intended to limit the present composition or method. Also, it is not intended to be bound by any theory presented in the preceding background art or the following detailed description.

[0012] Generally, this disclosure provides coating compositions, methods for preparing coating compositions, methods for applying coating compositions to a substrate (for example, to form a coating thereon), and coated articles prepared by such application methods. This disclosure further provides devices and systems for carrying out the methods and / or utilizing the coating compositions.

[0013] For simplicity, well-known and conventional techniques relating to compositions, methods, processes, devices, systems, and articles, as well as their various parts and components, may be introduced or otherwise described at various levels in the embodiments herein. For example, conventional techniques relating to the formation of coating compositions may not be described in detail herein, because the various steps in the manufacture of such compositions are well-known and can be readily understood and anticipated by those skilled in the art, considering the embodiments and examples provided herein. Similarly, various tasks and process steps described herein may be incorporated into more comprehensive procedures or processes having additional steps or functions not otherwise described, for example, because they are well-known and readily recognized by those skilled in the art. Such conventional steps may be described only briefly or may be omitted entirely without providing details of the well-known process.

[0014] A method for preparing painted articles is provided. The method is: Prepare a substrate having a partially dehydrated, water-containing coating layer on it; A coating composition for application without overspray, with a near-Newtonian viscosity profile and a shear rate of 500 Pa at all shear rates from 0.1 / sec to 10 / sec, or from 0.1 / sec to 100 / sec. * Prepare a coating composition that exhibits a shear viscosity of less than 1 second and is an aqueous fluid containing a binder, a crosslinking agent, and a thickening agent; A coating composition is supplied to a high-efficiency applicator comprising multiple nozzles, each configured to apply a flow of the coating composition (e.g., continuous, droplet, or both) onto a substrate without substantially atomizing it; and The method includes applying a coating composition to a substrate by using a high-efficiency applicator to place multiple lines of the coating composition onto a partially dehydrated, water-containing coating layer on the substrate via multiple nozzles, thereby forming an overspray-free coating layer thereon. The steps and components of the method are described below.

[0015] A coating composition suitable for use in the method is provided. The coating composition is particularly suitable for application without overspray, maintaining low sagging while providing a good overlap appearance. The coating composition is formulated as a fluid having a near-Newtonian viscosity profile, with a relatively low and substantially shear-independent ("Newtonian") low shear viscosity, and an even lower and increasingly shear-dependent (non-Newtonian) high shear viscosity. The specific near-Newtonian viscosity profile of the coating composition allows for improved overlap performance while maintaining good sagging performance and is still suitable for the ejection requirements of high-efficiency applicators. These and other advantages will be understood by considering the embodiments and examples provided herein. The coating composition is formulated for aqueous applications, i.e., it is a hydrous composition containing water as a carrier (e.g., solvent, diluent, etc.). The individual components of the coating composition and the desired use / application method determine the appropriate amount of water to be used. Generally, aqueous coating compositions typically contain about 30 to about 90 mass percent (mass%) of water relative to the total mass of the coating composition. In certain embodiments, the coating composition also contains up to about 30 mass percent of organic solvents. However, typically, the total amount of such organic solvents and other volatile organic compounds (VOCs) is targeted to be less than about 15 or less than about 10 mass percent relative to the total mass of the coating composition.

[0016] As will be described in more detail below, the coating composition is not particularly limited in its form prior to application. The coating composition may be formulated and used as a one-component (i.e., "1K") composition. Alternatively, the coating composition may be a two-component (i.e., "2K") composition.

[0017] Generally, coating compositions include a binder, a crosslinking agent, and a thickener, in addition to a water-based carrier medium in which the components are arranged. The term “binder” is used herein to refer to a component that forms a film in a coating composition, which typically includes one or more polymers (e.g., resins or elastomers), such as acrylic polymers, polyester polymers, polyurethane polymers, polyether polymers, and various oligomers and combinations thereof. The term “binder” is also understood to include latex particles and the like that can be used to prepare the coating of this embodiment. Thus, the coating composition may include acrylic polymers, polyester polymers, polyester-polyurethane polymers, latex polymers, melamine resins, or combinations thereof. It should be understood that other polymers may also be included in the coating composition.

[0018] Typically, polymers suitable as or for use as binders contain crosslinkable functional groups, such as isocyanate-reactive groups. The term “crosslinkable functional group” means a functional group located within an oligomer, in a polymer, within the polymer's main chain, within a side chain from the polymer's main chain, at the end of the polymer's main chain, or a combination thereof, which can crosslink with other crosslinkable functional groups (during the curing step) to produce a coating in the form of a crosslinked structure. Typical crosslinkable functional groups include hydroxyl, thiol, isocyanate, thioisocyanate, acetoacetoxy, carboxyl, primary amine, secondary amine, epoxy, anhydride, ketimine, aldimine, or functional combinations thereof. Several other functional groups that can generate hydroxyl or amine groups, such as orthoesters, orthocarbonates, or cyclic amides with open ring structures, may also be suitable as crosslinkable functional groups.

[0019] In some embodiments, the binder of the coating composition comprises a resin dispersion that is, contains, is essentially, or can contain latex, polyurethane, its derivatives, or a combination thereof. Examples of such combinations and derivatives include polyester-polyurethane, styrene-acrylic latex dispersions, etc. The resin dispersion itself is a system in which distributed particles of one resin material are dispersed in a continuous phase of another material. The two phases may be the same or different states of matter. Alternatively, the resin dispersion may be described as an emulsion, which is a homogeneous mixture of two immiscible liquids. In this disclosure, latex may include a polymer that is a continuous phase of liquid, for example, a phase dispersed in water. Furthermore, polyurethane may be a dispersed phase or a continuous phase of liquid. Alternatively, a combination of the above may be used. If the intended dispersion is an emulsion, the emulsion may be any type known in the art, for example, an o / w emulsion, a w / o emulsion, etc. In various embodiments, water, a water-soluble co-solvent, such as any of those described herein, or a combination of water and one or more such solvents can be used as the continuous phase, in which case the dispersed phase may be latex, polyurethane, or a combination thereof.

[0020] In various embodiments, the resin dispersion is present in the coating composition in mass% of approximately 1 to 50, 1 to 45, 1 to 35, 1 to 30, 1 to 25, 1 to 20, 1 to 15, 1 to 10, 1 to 5, 5 to 50, 10 to 45, 15 to 40, 20 to 35, 25 to 30, 15 to 20, 15 to 25, 15 to 30, 10 to 20, 10 to 25, 10 to 30, 18 to 22, 18 to 20, 16 to 20, 16 to 22, 16 to 24, etc., relative to the total mass of the coating composition. In various embodiments, all values ​​and ranges of values, including the values ​​described above and both integers and fractions between them, are explicitly intended for use herein. In some embodiments, the above amounts refer to the mass % solids content of the coating composition.

[0021] In some embodiments, the binder of the coating composition comprises a resin dispersion that is, contains, is essentially, or can be a latex. It is intended that zero, one, two, three, four, five, or more individual latexes may be used as the binder and therefore in the coating composition. In various embodiments, the term “latex” means a dispersion of polymer particles in water. For example, latex polymers typically require a secondary dispersant (e.g., a surfactant) to create a dispersion or emulsion of polymer particles in water. The latex is not particularly limited and may be any known in the art.

[0022] In some embodiments, the latex comprises reaction products of one or more of the following monomers to form a polymer that may be a dispersed phase and / or a continuous phase: These monomers include (meth)acrylamide, N-substituted (meth)acrylamide, octyl (meth)acrylate, nonylphenol ethoxylate (meth)acrylate, isononyl (meth)acrylate, 1,6-hexanediol (meth)acrylate, isobornyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, beta-carboxyethyl (meth)acrylate, isobutyl (meth)acrylate, alicyclic epoxide, alpha-epoxide, 2-hydroxyethyl (meth)acrylate, (meth)acrylonitrile, maleic anhydride, itaconic acid, and isodecyl (meth)acrylate. These include dodecyl (meth)acrylate, n-butyl (meth)acrylate, methyl (meth)acrylate, hexyl (meth)acrylate, (meth)acrylic acid, N-vinyl caprolactam, stearyl (meth)acrylate, hydroxyfunctional caprolactone ester (meth)acrylate, octodecyl (meth)acrylate, isooctyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyisopropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyisobutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and combinations thereof.

[0023] In some embodiments, the latex may be or comprise one or more of the following: (meth)acrylated urethane (i.e., urethane (meth)acrylate), (meth)acrylated epoxy (i.e., epoxy (meth)acrylate), (meth)acrylated polyester (i.e., polyester (meth)acrylate), (meth)acrylated (meth)acrylic, (meth)acrylated silicone, (meth)acrylated amine, (meth)acrylated amide; (meth)acrylated polysulfone; (meth)acrylated polyester, (meth)acrylated polyether (i.e., polyether (meth)acrylate, vinyl (meth)acrylate, and (meth)acrylated oil). In some embodiments, the resin dispersion may include an epoxy-group-containing polyester-modified acrylic dispersion, such as Daotan® VTW 1686 / 40WA, commercially available from Allnex. In other embodiments, the resin dispersion may include a styrene-acrylic latex dispersion. Such dispersions can be formed by a two-step emulsion polymerization method.

[0024] In some embodiments, latex is present (e.g., individually or as a whole) in mass% amounts of the active form, such as about 1 to about 50, about 1 to about 45, about 1 to about 35, about 1 to about 30, about 1 to about 25, about 1 to about 20, about 1 to about 15, about 1 to about 10, about 1 to about 5, about 5 to about 50, about 10 to about 45, about 15 to about 40, about 20 to about 35, about 25 to about 30, about 15 to about 20, about 15 to about 25, about 15 to about 30, about 10 to about 20, about 10 to about 25, about 10 to about 30, about 10 to about 35, about 18 to about 22, about 18 to about 20, about 16 to about 20, about 16 to about 22, about 16 to about 24, etc., relative to the total mass of the composition.

[0025] In some embodiments, the binder of the coating composition includes a polyurethane (i.e., a polyurethane dispersion resin), a resin dispersion containing, essentially being, or potentially being made of a polyurethane dispersion. It is intended that zero, one, two, three, four, five, or more individual polyurethanes may be used in the composition. The polyurethane is not particularly limited and may be any known in the art. In various embodiments, the polyurethane in the polyurethane dispersion resin is a reaction product of a polyol and an isocyanate. Other polyurethanes can be produced by first forming an NCO-functional hydrophilic polyurethane prepolymer by an addition reaction between a polyol-type compound and a polyisocyanate, converting the thus formed polyurethane prepolymer into an aqueous phase, and then reacting the aqueous-dispersed NCO-functional polyurethane prepolymer with an NCO-reactive chain extender such as a polyamine, a hydrazine derivative, or water.

[0026] As those skilled in the art will understand, polyurethanes can be described in relation to the reaction products of isocyanates with compounds having one or more hydroxyl groups (e.g., monools, diols, triols, tetrols, or polyols). Therefore, with respect to typical polyurethanes, those skilled in the art will understand their range based on examples of such reactive components, e.g., polyols and isocyanates, used to prepare many suitable polyurethanes for polyurethane dispersion resins. Polyols are typically selected from polyester polyols, polyether polyols, and polycarbonate polyols. Polythioether polyols, polycaprolactones, and acrylic polyols are also intended to be used. In individual embodiments, the polyol is further defined as a polyester polyol. In certain embodiments, the polyol is a polyester polyol. In certain embodiments, the polyol is an aromatic polyester or polyether polyol. Other suitable examples of polyols include the polyhydric alcohols described herein. Monohydric alcohols such as butanol, octanol, lauryl alcohol, and ethoxylated or propoxylated phenols may also be included along with polyhydric alcohols. Alternatively, polyols with low molar masses, as defined experimentally and structurally, such as polyhydric alcohols, may be used. In other embodiments, oligomeric or polymeric polyols having a number average molar mass of, for example, 8000 or less, or 5000 or less, or 2000 or less, and / or, for example, corresponding hydroxyl-functionalized polyethers, polyesters, or polycarbonates are used.

[0027] Polyols can be derived from the reaction of an initiator with an alkylene oxide. The initiator may include any initiator known in the art. In various embodiments, the initiator is selected from ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, butanediol, pentanediol, hexanediol, heptanediol, glycerol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, hexanetriol, alkyl glucoside, pentaerythritol, sorbitol, diaminenaphthalene, aniline, condensation products of aniline and formaldehyde, alkylamines, triisopropanolamine, alkylenediamine, diaminealkane, sucrose, toluenediamine, and combinations thereof.

[0028] The alkylene oxide reacted with the initiator to form the polyol may be selected from ethylene oxide, propylene oxide, butylene oxide, amylene oxide, tetrahydrofuran, alkylene oxide-tetrahydrofuran mixtures, epihalohydrins, aralkylene oxides, and combinations thereof. In some embodiments, the alkylene oxide is selected from ethylene oxide, propylene oxide, and combinations thereof. However, it is also intended that any suitable alkylene oxide known in the art may be used.

[0029] The polyol itself may contain additional organic functional groups selected from, for example, carboxyl groups, amine groups, carbamate groups, amide groups, and epoxy groups. The polyol may also contain an alkylene oxide cap. If the polyol contains an alkylene oxide cap, the alkylene oxide cap typically includes ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and combinations thereof. More typically, the alkylene oxide cap contains ethylene oxide. If the polyol contains an alkylene oxide cap, the amount of the alkylene oxide cap may be 25% or less of the total mass of the polyol, for example, 10-20% by mass.

[0030] The polyol may also contain an addition polymer dispersed therein. More specifically, the polyol may comprise a dispersion or solution of an addition or condensation polymer, i.e., a grafted polyol. The dispersion may comprise styrene, acrylonitrile, and combinations thereof. The polyol may comprise an emulsion containing water or any other polar compound known in the art. In certain embodiments, low molar polyols, such as polyhydric alcohols, defined experimentally and by structural formula, are used to form polyurethanes. Examples of polyhydric alcohols include ethylene glycol, propanediol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanedimethanol, trimethylpentanediol, ethylbutylpropanediol, ditrimethylolpropane, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, polyethylene glycol, and polypropylene glycol. In some embodiments, oligomeric or polymeric polyols with a number average molar mass of, for example, 8000 or less, or 5000 or less, or 2000 or less, and / or, for example, corresponding hydroxyl-functionalized polyethers, polyesters, or polycarbonates are used.

[0031] Since isocyanates can also react with hydroxyl-functional resins, such hydroxyl-functional resins can also be used as polyols to prepare polyurethanes. Such resins are not particularly limited and may be any known in the art, such as aliphatic or aromatic dicarboxylic acids, polyols, diols, aromatic or aliphatic cyclic anhydrides, and cyclic alcohols. Suitable examples of alicyclic polycarboxylic acids include tetrahydrophthalic acid, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tricyclodecanedicarboxylic acid, endoethylenehexahydrophthalic acid, camphoric acid, cyclohexanetetracarboxylic acid, and cyclobutanetetracarboxylic acid. Alicyclic polycarboxylic acids can be used not only in their cis form but also in their trans form, and mixtures of both forms can also be used. Further examples of suitable polycarboxylic acids include aromatic and aliphatic polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, halogenophthalic acid, such as tetrachloro- or tetrabromophthalic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, trimellitic acid, and pyromellitic acid. Combinations of polyacids, such as combinations of polycarboxylic acids and alicyclic polycarboxylic acids, may also be suitable. Combinations of polyols (e.g., polyhydric alcohols) can also be used.

[0032] The isocyanate is not particularly limited and may be any suitable for use in preparing the polyurethane resin dispersion. The isocyanate may be mono or polyisocyanate, aromatic isocyanate, aliphatic isocyanate, and / or a combination thereof. In some embodiments, the isocyanate is or contains an aromatic isocyanate, e.g., polymeric MDI. If the isocyanate is or contains an aromatic isocyanate, the aromatic isocyanate is typically of the formula R'(NCO) zCorresponding to this, R' in the formula is a polyvalent aromatic organic group, and z is an integer corresponding to the valence of R'. Typically, z is at least 2.

[0033] Other examples of suitable isocyanates include 1,4-diisocyanatobenzene, 1,3-diisocyanato-o-xylene, 1,3-diisocyanato-p-xylene, 1,3-diisocyanato-m-xylene, 2,4-diisocyanato-1-chlorobenzene, 2,4-diisocyanato-1-nitrobenzene, 2,5-diisocyanato-1-nitrobenzene, m-phenylenediisocyanate, p-phenylenediisocyanate, 2,4-toluenediisocyanate, 2,6-toluenediisocyanate, 2,4- and 2, A mixture of 6-toluene diisocyanates, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-biphenylenediisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, triisocyanates, e.g., 4,4',4"-triphenylmethane triisocyanate. This includes polymethylene polyphenylene polyisocyanates and 2,4,6-toluene diisocyanates, tetraisocyanates, such as 4,4'-dimethyl-2,2'-5,5'-diphenylmethane tetraisocyanate, toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanates, mixtures of their corresponding isomers, and combinations thereof.

[0034] Modified polyvalent aromatic isocyanates, such as products obtained by chemical reactions of aromatic diisocyanates and / or aromatic polyisocyanates, can also be used. Examples include polyisocyanates, urea, biuret, allophanate, carbodiimide, uretonimine, and isocyanurates and / or diisocyanates and / or polyisocyanates, such as urethane groups containing modified diphenylmethane diisocyanate. Urethane groups of isocyanates can be formed by reactions of the base isocyanates described above with low molecular weight polyols described herein, etc. Similarly, isocyanates may also include one or more prepolymers containing isocyanate groups.

[0035] Examples of additional isocyanates include modified benzene and toluene diisocyanates, which are used, for example, individually or in reaction products with polyoxyalkylene glycols, diethylene glycols, dipropylene glycols, polyoxyethylene glycols, polyoxypropylene glycols, polyoxypropylene polyoxyethylene glycols, polyesterols, polycaprolactones, and combinations thereof. In various embodiments, the isocyanate may be an isocyanate selected from 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, modified 2,4'-diphenylmethane diisocyanate, modified 4,4'-diphenylmethane diisocyanate, and combinations thereof. The isocyanate composition used to prepare the polyurethane dispersion resin may also include stoichiometric or non-stoichiometric reaction products of the above-mentioned isocyanates.

[0036] In other embodiments, suitable polyisocyanates include aromatic, aliphatic, or alicyclic di-, tri-, or tetra-isocyanates, for example, polyisocyanates having isocyanurate structural units, such as isocyanurates of hexamethylene diisocyanate and isocyanurates of isophorone diisocyanate; diisocyanates, such as hexamethylene diisocyanate and diols, such as ethylene glycol; uretidione of hexamethylene diisocyanate; uretidione of isophorone diisocyanate or isophorone diisocyanate; and adducts of trimethylolpropane and meta-tetramethylxylene diisocyanate. Other polyisocyanates disclosed herein may also be suitable for producing polyurethanes.

[0037] Alternatively, the isocyanate may be a liquid polyisocyanate containing one or more carbodiimide groups. In various embodiments, unrefined polyisocyanates, such as unrefined toluenediisocyanate obtained by phosgenation of a mixture of toluenediamines, or unrefined diphenylmethane isocyanate obtained by phosgenation of an unrefined isocyanate, may also be used. It will be understood that suitable isocyanates are not particularly limited in terms of NCO content, but typically have an NCO content of 5 to 35 mass percent. The determination of the NCO content by mass percent is achieved by standard chemical titration analysis known to those skilled in the art. In some embodiments, the polyurethane may be a polyester-polyurethane polymer. In other words, the resin dispersion may be a dispersion containing at least a polyester-polyurethane resin.

[0038] The polyester in polyester-polyurethane polymers can be linear or branched. Useful polyesters include esterification products of aliphatic or aromatic dicarboxylic acids, polyols, diols, aromatic or aliphatic cyclic anhydrides, and cyclic alcohols. Suitable examples of alicyclic polycarboxylic acids are tetrahydrophthalic acid, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tricyclodecanedicarboxylic acid, endoethylenehexahydrophthalic acid, camphoric acid, cyclohexanetetracarboxylic acid, and cyclobutanetetracarboxylic acid. Alicyclic polycarboxylic acids can be used not only in their cis form but also in their trans form, and can also be used as mixtures of both forms. Further examples of suitable polycarboxylic acids include aromatic and aliphatic polycarboxylic acids, such as phthalic acids, isophthalic acids, terephthalic acids, halogenophthalic acids, such as tetrachloro- or tetrabromophthalic acids, adipic acids, glutaric acids, azelaic acids, sebacic acids, fumaric acids, maleic acids, trimellitic acids, and pyromellitic acids. Combinations of polyacids, such as combinations of polycarboxylic acids and alicyclic polycarboxylic acids, may also be suitable.

[0039] Suitable examples of polyesters include branched copolyester polymers. Branched copolyester polymers and manufacturing processes described in U.S. Patent No. 6,861,495, incorporated herein by reference, may be suitable. Polyesters prepared from monomers having polyfunctional groups such as AxBy type (where x and y are independently 1 to 3), for example, those having one carboxyl group and two hydroxyl groups, two carboxyl groups and one hydroxyl group, one carboxyl group and three hydroxyl groups, or three carboxyl groups and one hydroxyl group, can be used to create branched structures. Examples of such monomers include 2,3-dihydroxypropionic acid, 2,3-dihydroxy-2-methylpropionic acid, 2,2-dihydroxypropionic acid, 2,2-bis(hydroxymethyl)propionic acid, and the like.

[0040] Branched copolyester polymers can conventionally be polymerized from monomer mixtures containing hydroxycarboxylic acids, hydroxycarboxylic acid lactones, and combinations thereof; and one or more branched monomers. Some suitable hydroxycarboxylic acids include glycolic acid, lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and hydroxypyvalic acid. Some suitable lactones include caprolactone, valerolactone; and corresponding hydroxycarboxylic acid lactones such as 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and hydroxypyvalic acid. In certain embodiments, caprolactone can be used. In several embodiments, branched copolyester polymers can be produced by polymerizing a monomer mixture containing a chain extender and a hyper-branching monomer in a single step, or by polymerizing the hyper-branching monomer first, followed by the chain extender. It should be understood that branched copolyester polymers can be formed from an acrylic core using the above-mentioned branching monomers.

[0041] Polyester-polyurethane polymers can be produced from polyesters and polyisocyanates. The polyester can be a polymeric or oligomeric organic species having at least two hydroxyl functionalities or two mercapto functionalities, or mixtures thereof. Polyesters and polycarbonates having terminal hydroxyl groups can be effectively used as diols. In some embodiments, the resin dispersion comprises a polyester-polyurethane polymer formed from a linear polyester diol resin (a reaction product of monomers 1,6-hexanediol, adipic acid, and isophthalic acid) and isophorone diisocyanate. This polyester-polyurethane polymer has a mass-average molecular weight of about 30,000, a solids content of about 35% by mass, and a particle size of about 250 nanometers (e.g., Dv50) determined using any apparatus known in the art, such as a Malvern Mastersizer.

[0042] In some embodiments, the resin dispersion comprises a polyester-polyurethane polymer formed from linear polycarbonate-polyester and isophorone diisocyanate. This polyester-polyurethane polymer has a mass-average molecular weight of about 75,000, a solids content of about 35% by mass, and a particle size of about 180 nanometers (e.g., Dv50) determined using any apparatus known in the art, such as a Malvern Mastersizer. In some embodiments, the resin dispersion includes a polyester-polyurethane polymer, for example, about 40% by mass, which is a solid, formed from a slightly branched polyester polyol and hexamethylene diisocyanate.

[0043] In some embodiments, the resin dispersion comprises a polyester-polyurethane polymer, which is solid, for example, about 35% by mass, formed from a linear polyester diol resin (e.g., a reaction product of the monomers 1,6-hexanediol, adipic acid, and isophthalic acid) and an isophorone diisocyanate. In another embodiment, the polyurethane is selected from: those formed from branched polyester polyols and hexamethylene diisocyanates; those formed from linear polyester diol resins and isophorone diisocyanates, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; those formed from linear polycarbonates, polyester polyols, and isophorone diisocyanates; polyester-polyurethane polymers; and combinations thereof.

[0044] In another embodiment, the resin dispersion is, contains, essentially consists of, or can consist of, a polyurethane dispersion resin formed from linear polycarbonate-polyester polyol and isophorone diisocyanate.

[0045] In some embodiments, the resin dispersion contains a polyester-polyurethane polymer having the trade name Bayhydrol® U 241, which is commercially available from Covestro AG in Leverkusen, Germany. The coating composition may contain this polyester-polyurethane polymer in an amount of about 0.1 to about 50%, or about 1 to about 20%, or about 1 to about 10% by mass, based on the total mass of the coating composition. In some embodiments, the resin dispersion contains, is essentially, or consists of polyurethane as a resin component. In such embodiments, the polyurethane is present in an amount of about 1 to about 100, about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55% by mass of the active material relative to the total mass of the resin dispersion.

[0046] In some embodiments, polyurethane is present in mass percent active amounts of approximately 1 to approximately 65, approximately 1 to approximately 60, approximately 1 to approximately 55, approximately 1 to approximately 45, approximately 1 to approximately 40, approximately 1 to approximately 25, approximately 1 to approximately 20, approximately 1 to approximately 15, approximately 1 to approximately 10, approximately 1 to approximately 5, approximately 5 to approximately 50, approximately 10 to approximately 45, approximately 15 to approximately 40, approximately 20 to approximately 35, approximately 25 to approximately 30, approximately 15 to approximately 20, approximately 15 to approximately 25, approximately 15 to approximately 30, approximately 10 to approximately 20, approximately 10 to approximately 25, approximately 10 to approximately 30, approximately 10 to approximately 35, approximately 18 to approximately 22, approximately 18 to approximately 20, approximately 16 to approximately 20, approximately 16 to approximately 22, and approximately 16 to approximately 24 mass% relative to the total mass of the binder. In various embodiments, this amount is about 1 to about 15% by mass of the active material relative to the total mass of the binder, for example, about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% by mass. In other embodiments, polyurethane is present in amounts of about 1 to about 20, about 2 to about 19, about 3 to about 18, about 4 to about 17, about 5 to about 16, about 6 to about 15, about 7 to about 14, about 8 to about 13, about 9 to about 12, about 10 to about 11, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% by mass of the active material relative to the total mass of the coating composition. It should be understood that amounts outside the above ranges are also available.

[0047] In some embodiments, the binder or resin dispersion contains an acrylic resin. Generally, suitable acrylic resins for binders include one or more of the following monomers: (meth)acrylamide, N-substituted (meth)acrylamide, octyl (meth)acrylate, nonylphenol ethoxylate (meth)acrylate, isononyl (meth)acrylate, 1,6-hexanediol (meth)acrylate, isobornyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, beta-carboxyethyl (meth)acrylate, isobutyl (meth)acrylate, alicyclic epoxide, alpha-epoxide, 2-hydroxyethyl (meth)acrylate, (meth)acrylonitrile, maleic anhydride, itaconic acid, isodecyl (meth)acrylate This includes methacrylate, dodecyl(meth)acrylate, n-butyl(meth)acrylate, methyl(meth)acrylate, hexyl(meth)acrylate, (meth)acrylic acid, N-vinylcaprolactam, stearyl(meth)acrylate, hydroxyfunctional caprolactone ester(meth)acrylate, octodecyl(meth)acrylate, isooctyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxymethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyisopropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxyisobutyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, etc., as well as reaction products of derivatives, modifiers, and combinations thereof.

[0048] In some embodiments, the binder or resin dispersion comprises one or more of the following: (meth)acrylated urethane (i.e., urethane (meth)acrylate), (meth)acrylated epoxy (i.e., epoxy (meth)acrylate), (meth)acrylated polyester (i.e., polyester (meth)acrylate), (meth)acrylated (meth)acrylic, (meth)acrylated silicone, (meth)acrylated amine, (meth)acrylated amide; (meth)acrylated polysulfone; (meth)acrylated polyester, (meth)acrylated polyether (i.e., polyether (meth)acrylate), vinyl (meth)acrylate, (meth)acrylated oil, etc., or a combination thereof.

[0049] The resin dispersion may also include amines of any type known in the art, which may or may not react with isocyanates to form polyureas. The amines may include primary and secondary aliphatic and / or cyclic aliphatic amines. The amines may include any additional functional groups known in the art, including hydroxyl groups, thiol groups, alkyl groups, cyclic groups, aromatic groups, and combinations thereof. It should be understood that the amines may also include amides of any type known in the art. The amides may include, or otherwise exist as, polymers of unsaturated or saturated carboxylic acids or anhydrides, and polyester amides obtained from polyfunctional unsaturated or saturated amino alcohols, and combinations thereof.

[0050] The coating composition contains a crosslinking agent. The term "crosslinking agent" means a component having a "crosslinkable functional group," i.e., a reactive functional group located within each molecule of a compound, oligomer, or polymer, within the main chain of a polymer, within the side chains from the main chain of a polymer, or at the ends of the main chain of a polymer, which can crosslink (e.g., covalently bond) with a crosslinkable functional group (e.g., during the curing step) to produce a coating in a crosslinked structural form, or a combination thereof. It will be recognized by those skilled in the art that certain combinations of crosslinkable functional groups and crosslinkable functional groups are excluded because they cannot crosslink and produce a crosslinked structure that forms a film. The coating composition may contain more than one crosslinking agent having the same or different crosslinking functional groups. Typical crosslinking functional groups include hydroxyl, thiol, isocyanate, thioisocyanate, acetoacetoxy, carboxyl, primary amine, secondary amine, epoxy, anhydride, ketimine, aldimine, orthoester, orthocarbonate, cyclic amide, or combinations thereof.

[0051] In some embodiments, the coating composition includes a melamine crosslinking agent. A suitable melamine crosslinking agent may be a melamine resin (e.g., hexamethoxymethylmelamine) partially or completely etherified with one or more alcohols such as methanol or butanol. Other examples of suitable melamine crosslinking agents include monomeric melamines, polymeric melamine-formaldehyde resins, and combinations thereof. Monomeric melamines include low molecular weight melamines having an average of three or more methylol groups etherified with a C1-C5 monohydric alcohol such as methanol, n-butanol, or isobutanol per triazine nucleus, an average degree of condensation in the range of about 2 or less, and in certain embodiments about 1.1 to about 1.8, and a mononuclear proportion of about 50 mass percent or more. In contrast, polymeric melamines have an average degree of condensation greater than about 1.9. Some such suitable monomeric melamines include alkylated melamines, such as methylated, butylated, isobutylated melamines, and mixtures thereof.

[0052] Several suitable monomeric melamines are commercially available. For example, Cytec Industries Inc., West Patterson, NJ offers Cymel® 301 (degree of polymerization 1.5, 95% methyl and 5% methylol), Cymel® 350 (degree of polymerization 1.6, 84% methyl and 16% methylol), 303, 325, 327, 370, and XW3106, all of which are monomeric melamines. Suitable polymeric melamines include the high-amino (partially alkylated, -N, -H) melamine known as Resimene® BMP5503 (molecular weight 690, polydispersity 1.98, 56% butyl, 44% amino) offered by Solutia Inc., St. Louis, Mo., or Cymel® 1158 offered by Cytec Industries Inc., West Patterson, NJ. Cytec Industries Inc. also offers Cymel® 1130 @ 80% solids (degree of polymerization 2.5) and Cymel® 1133 (48% methyl, 4% methylol and 48% butyl), both of which are polymerizable melamines.

[0053] In various embodiments, the melamine crosslinking agent is used in an amount of about 1 to about 30, about 2 to about 25, about 5 to about 25, or about 5 to about 20% by mass relative to the total mass active material in the coating composition. In other embodiments, this amount is about 1 to about 20, about 1 to about 15, about 1 to about 10, or about 1 to about 5% by mass relative to the total mass of the coating composition. In a typical embodiment, the coating composition contains a melamine-formaldehyde resin, trade name Cymel® 303, commercially available from Cytec Industries Inc. in West Patterson, NJ, as a crosslinking agent. Other crosslinking agents can also be used in the coating composition. For example, isocyanate-based crosslinking agents can be used. Alternatively, both isocyanate crosslinking agents and melamine crosslinking agents can be used.

[0054] Examples of isocyanate crosslinking agents are not particularly limited and may be any known in the art. In various embodiments, the isocyanate crosslinking agent is or comprises aromatic, aliphatic or alicyclic di-, tri- or tetra-isocyanates, including polyisocyanates having isocyanurate structural units, such as isocyanurates of hexamethylene diisocyanate and isocyanurates of isophorone diisocyanate; diisocyanates, such as hexamethylene diisocyanate and diols, such as ethylene glycol, as adducts of two molecules; urethidiones of hexamethylene diisocyanate; urethidiones of isophorone diisocyanate or isophorone diisocyanate; and adducts of trimethylolpropane and meta-tetramethylxylenediisocyanate.

[0055] In various embodiments, isocyanates such as oligomers based on hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), or toluidine diisocyanate (TDI), such as isocyanurates, biuretes, allophanates, and adducts of the above-mentioned isocyanates with polyhydric alcohols, and mixtures thereof, can be used as crosslinking agents. These can react with polyols such as polyesters, polyethers, acrylates, and polyurethanes containing OH groups, and mixtures thereof, and these polyols may be solvent-based, solvent-free, or water-dilutable. In various embodiments, monofunctional isocyanates are intended for use as selected by those skilled in the art. In other embodiments, blocked isocyanates are intended for use as selected by those skilled in the art.

[0056] Polyisocyanate functional adducts having isocyanurate structural units can also be used in or as crosslinking agents. Diisocyanates, such as hexamethylene diisocyanate or isophorone diisocyanate, and two adducts of diols, such as ethylene glycol; adducts of three molecules of hexamethylene diisocyanate and one molecule of water (commercially available from Bayer Corporation in Pittsburgh, Pennsylvania under the trade name Desmodur® N); adducts of one molecule of trimethylolpropane and three molecules of toluene diisocyanate (commercially available from Bayer Corporation in Pittsburgh, Pennsylvania under the trade name Desmodur® L); adducts of one molecule of trimethylolpropane and three molecules of isophorone diisocyanate or compounds such as 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatotoluene; and adducts of one molecule of pentaerythritol and four molecules of toluene diisocyanate.

[0057] In various embodiments, when used, the isocyanate crosslinking agent is present in an amount of about 1 to about 10, or about 2 to about 8, or about 3 to about 6, or about 3, 4, 5, or 6% by mass of the total mass of the coating composition as specified herein. Coating compositions contain thickeners. It is generally understood that the rheological properties of a coating composition can be greatly influenced by the choice of thickener used. Generally, thickeners are selected from rheological regulators, i.e., rheological modifiers, thixotropes, etc. Thickeners can be synthetic or natural, organic or inorganic. Organic thickeners may be associative, nonassociative, or solvent-based. Typically, thickeners are selected from associative synthetic organic thickeners, synthetic inorganic thickeners, and combinations thereof. Examples of associative synthetic organic thickeners generally include hydrophobic modified ethoxylated urethanes (HEUR), hydrophobic modified alkali-swellable emulsions (HASE), epoxy-functionalized polyurethanes, epoxy-functionalized acrylics, hydrophobic modified polyacrylate thickeners, hydrophobic modified polyether thickeners, hydrophobic modified cellulose ethers, and others known in the art.

[0058] In some embodiments, the coating composition comprises a nonionic associative HEUR thickener. The suitable HEUR is not particularly limited and may be any known in the art that is suitable for imparting the required rheological profile to the coating composition. For example, a suitable HEUR may be prepared by reacting a polyalkylene glycol, a hydrophobic capping agent and / or a hydrophobic bifunctional agent, and a diisocyanate in a stoichiometric excess of isocyanate reactive groups, the reaction of which forms a polyurethane prepolymer having isocyanate functionality. This prepolymer may then be converted to a hydrophobic modified alkylene oxide poly(urethane-urea-allophanate), which may further include additional functionality, such as amine functionality. HEUR can be used with or in the absence of an alkaline swelling emulsion or any other type of thickener.

[0059] In various embodiments, HEUR is present in amounts of about 0.01 to about 20, about 0.1 to about 20, about 0.1 to about 15, about 0.1 to about 10, about 0.1 to about 5, about 0.1 to about 1, about 0.1 to about 0.9, about 0.2 to about 0.8, about 0.3 to about 0.7, about 0.4 to about 0.6, about 0.5 to about 0.6, about 0.5 to about 10, about 1 to about 9.5, about 1.5 to about 9, about 2 to about 8.5, about 2.5 to about 8, about 3 to about 7.5, about 3.5 to about 7, about 4 to about 6.5, about 4.5 to about 6, about 5 to about 5.5, or about 0.01, 0.02, 0.03...0.1, 0.2, 0.3...1, 1.1, 1.2...about 20% by mass or less of the active form relative to the total mass of the composition. In various embodiments, HEUR is present in an amount of about 0.1 to about 10, or about 0.2 to about 8, or about 0.2 to about 6% by mass of the total mass of the coating composition. In some embodiments, the coating composition includes an inorganic thickener, and examples of such thickeners include phyllosilicates, also known as "layered silicates." A suitable layered silicate is not particularly limited and may be any known in the art that is suitable for imparting the rheological profile required for the coating composition.

[0060] Layered silicates typically contain planar layers in which octahedra are joined to upper and lower tetrahedra, or consist of such planar layers with characteristic repeating distances between the layers. For example, layered silicates can be classified as 7Å layered silicates, 10Å layered silicates, and chlorite based on their repeating distances. Minerals within these groups can be further divided into dioctahedrons and trioctahedrons. 7Å layered silicates include kaolinite Al4(Si4O 10 )(OH)8(dioctahedron) and serpentine Mg6(Si4O 10 It contains (OH)8 (trioctahedron). 10Å layered silicates usually occur as weathering products and can exhibit perfect planar cleavage, and are therefore sometimes known as mica. This group may also include clay minerals. Chlorite contains 2 and 3octahedron Mg5Al(AlSi3O 10It contains (OH)8. In various embodiments, the layered silicate comprises or consists of two condensed silicate tetrahedral sheets and octahedral sheets sharing edges of metal atoms such as Mg or Al, with dimensions of approximately 1 nm thickness and 100 nm to 1000 nm length, in a two-dimensional (2D) layer. In various embodiments, MMT, hectorite, and saponite are commonly used layered silicates.

[0061] In certain embodiments, a laponite propylene glycol solution containing synthetic layered silicate, water, and polypropylene glycol is used. The synthetic layered silicate is commercially available from Altana AG in Wesel, Germany, under the trade name Laponite RD. In one embodiment, the layered silicate is a synthetic phyllosilicate. In various embodiments, the layered silicate is present in an amount of about 0.01 to about 10, about 0.1 to about 8, about 0.1 to about 6, about 0.1 to about 5, about 1 to about 5, or about 1 to about 3% by mass of the active material relative to the total mass of the composition. It is also intended that no layered silicates be used at all. In various non-limiting embodiments, all values ​​and ranges of values, including the values ​​described above, as well as both integers and fractions between them, are explicitly intended for use herein. Furthermore, quantities outside the above ranges may also be used. In some embodiments, combinations of thickeners are used. In such embodiments, each thickener may be present in the amounts listed above individually for each type of thickener, or in the total amount listed above in total.

[0062] The coating composition may contain, or may not contain, one or more different components, such as binders, dyes, additional rheological modifiers, carriers, catalysts, conventional additives, or combinations thereof. Conventional additives may include, but are not limited to, dispersants, antioxidants, UV stabilizers and absorbers, surfactants, wetting agents, leveling agents, defoamers, anti-cratering agents, or combinations thereof. In some embodiments, the coating composition contains one or more pigments; cosolvents; catalysts; UV absorbers; leveling additives; wetting additives; or any combination thereof. In some embodiments, the coating composition includes a pigment. Any pigment known for use in coating compositions in the art can be used in the coating composition, provided that other parameters of the coating composition are achieved.

[0063] In various embodiments, the coating composition may or may not contain a pigment. Any pigment known in the art for use in coating compositions can be used in the coating composition. Non-limiting examples of suitable pigments include effect pigments containing metal oxides, metal hydroxides, metal flakes, chromates, e.g., lead chromate, sulfides, sulfates, carbonates, carbon black, silica, talc, clay, phthalocyanine blue and green, organo red, organo maroon, pearlescent pigments, other organic pigments and dyes, and combinations thereof. If desired, chromate-free pigments, e.g., barium metaborate, zinc phosphate, aluminum triphosphate, and combinations thereof can also be used.

[0064] Further non-limiting examples of suitable effect pigments include lustrous aluminum flakes, very fine aluminum flakes, medium-grain aluminum flakes, and lustrous medium-coarse aluminum flakes; mica flakes coated with titanium dioxide pigments, also known as pearl pigments; and combinations thereof. Non-limiting examples of suitable coloring pigments include titanium dioxide, zinc oxide, iron oxide, carbon black, monoazo red toner, red iron oxide, quinacridone maroon, clear red iron oxide, dioxazine carbazole violet, Prussian blue, indanthron blue, chromium titanate, titanium yellow, monoazo permanent orange, ferrite yellow, monoazo benzimidazolone yellow, clear yellow oxide, isoindoline yellow, tetrachloroisoindoline yellow, enthon orange, lead chromate yellow, phthalocyanine green, quinacridone red, perylene maroon, quinacridone violet, pre-darkened chrome yellow, thioindigo red, clear red iron oxide chip, molybdate orange, molybdate orange red, and combinations thereof.

[0065] Alternatively, the pigment may be described as an extender pigment. Extender pigments are generally used to replace higher-cost pigments in coating compositions, but the extender pigments intended herein can increase the shear viscosity of the coating composition compared to a coating composition without an extender pigment. An increase in the shear viscosity of the coating composition can improve the suitability of the coating composition for application to substrates using high-efficiency applicators. Extender pigments may have a particle size of approximately 0.01 to approximately 44 μm (e.g., Dv50 determined using a Malvern Mastersizer). Extender pigments may have various shapes, including but not limited to nodular, plate-like, needle-like, and fibrous. Non-limiting examples of suitable extender pigments include chalk, barite, amorphous silica, fumed silica, diatomaceous earth, clay, calcium carbonate, mica, wollastonite, magnesium silicate (talc), barium sulfate, kaolin, and aluminum silicate. In various non-limiting embodiments, all values ​​and ranges of values, including the values ​​described above and both integers and fractions between them, are expressly intended for use herein.

[0066] The coating composition may contain extender pigments in an amount of about 0.1 to about 50, or about 1 to about 20, or about 1 to about 10% by mass, relative to the total mass of the coating composition. In other embodiments, an optional pigment is present in an amount of about 1 to about 50, about 5 to about 50, about 10 to about 45, about 15 to about 40, about 20 to about 35, or about 25 to about 30% by mass of the active form, relative to the total mass of the composition. In other embodiments, an optional pigment is present in amounts of about 1 to about 20, about 2 to about 19, about 3 to about 18, about 4 to about 17, about 5 to about 16, about 6 to about 15, about 7 to about 14, about 8 to about 13, about 9 to about 12, about 10 to about 11, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 mass percent of the active compound relative to the total mass of the composition. In other embodiments, the optional pigment is present in amounts of about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, about 0.5 to about 0.6, or about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 mass percent of the active compound relative to the total mass of the coating composition. In various non-limiting embodiments, all values ​​and ranges of values, including the values ​​described above, both integers and fractions between them, are expressly intended for use herein.

[0067] In certain embodiments, the coating composition includes magnesium silicate (talc), barium sulfate, or a combination thereof. In various embodiments, the inclusion of barium sulfate as an extender pigment yields a coating composition with a higher shear viscosity compared to those containing talc as an extender pigment. In various embodiments, optional pigments are selected from Pigment Yellow 213, PY 151, PY 93, PY 83, Pigment Red 122, PR 168, PR 254, PR 179, Pigment Red 166, Pigment Red 48:2, Pigment Violet 19, Pigment Blue 15:1, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Green 7, Pigment Green 36, Pigment Black 7, or Pigment White 6, and combinations thereof.

[0068] The composition may also include a co-solvent, i.e., an organic or solvent compatible with the aqueous coating composition. Non-limiting examples of suitable organic solvents include aromatic hydrocarbons; ketones, e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and diisobutyl ketone; esters, e.g., ethyl acetate, n-butyl acetate, isobutyl acetate, and combinations thereof. In some embodiments, the evaporation rate of the solvent may have a certain effect on the printability of the coating composition. Certain co-solvents can be incorporated into a coating composition to increase or decrease its evaporation rate. Typically, the coating composition does not contain or substantially contains volatile organic solvents.

[0069] In some embodiments, the cosolvent is selected from water-soluble solvents. In various embodiments, water-soluble solvents include methanol, propanol, butanol, ethanol, 1,2-butanediol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,4-dioxane, 1,5-pentanediol, 2-butoxyethanol, 2-propanol, acetaldehyde, acetic acid, acetone, acetonitrile, butyric acid, diethanolamine, diethylenetriamine, dimethoxyethane, dimethyl sulfoxide, dimethylformamide, ethylamine, ethylene glycol, formic acid, furfuryl alcohol, glycerol, methyl diethanolamine. The solvents may be ethanolamine, methyl isocyanide, n-methyl-2-pyrrolidone, propanoic acid, propylene glycol, pyridine, tetrahydrofuran, triethylene glycol, glycol ethers (ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), any and all isomers thereof, or combinations thereof. Alternatively, the composition may not contain one or more of the above solvents, as long as at least one water-soluble solvent is used in the composition. In some embodiments, for example, the composition is substantially free of small-chain alcohols.

[0070] In various embodiments, the cosolvent, including any one or more additional solvents selected for use, is present in amounts of about 0.1 to about 25, about 0.5 to about 25, about 2 to about 19, about 3 to about 18, about 4 to about 17, about 5 to about 16, about 6 to about 15, about 7 to about 14, about 8 to about 13, about 9 to about 12, about 10 to about 11, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 mass percent of the active material relative to the total mass of the composition. In various non-limiting embodiments, all values ​​and ranges of values, including the values ​​described above, both integers and fractions between them, are expressly intended for use herein.

[0071] The coating composition may further contain a catalyst. The coating composition may further contain a catalyst to shorten the curing time and enable curing of the coating composition at ambient or elevated temperatures. Ambient temperature is typically in the range of about 18°C ​​to about 35°C. Non-limiting examples of suitable catalysts include organometallic salts, e.g., dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dichloride, dibutyltin dibromide, zinc naphthenate; triphenylboron, tetraisopropyl titanate, triethanolamine titanate chelate, dibutyltin dioxide, dibutyltin dioctoate, tin octanoate, aluminum titanate, aluminum chelate, zirconium chelate, hydrocarbon phosphonium halides, e.g., ethyltriphenylphosphonium iodide and other such phosphonium salts, and other catalysts, or combinations thereof. Non-limiting examples of suitable acid catalysts include carboxylic acids, sulfonic acids, phosphoric acids, or combinations thereof. In some embodiments, examples of acid catalysts include acetic acid, formic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, p-toluenesulfonic acid, phosphoric acid, or combinations thereof. The coating composition may contain the catalyst in an amount of about 0.01 to about 5, or about 0.01 to about 1, or about 0.02 to about 0.5% by mass of the total mass of the coating composition.

[0072] The coating composition may further contain conventional additives. The coating composition may further contain UV stabilizers. Non-limiting examples of such UV stabilizers include UV absorbers, screeners, quenchers, and hindered amine light stabilizers. Antioxidants can also be added to the coating composition. Typical UV stabilizers include benzophenone, triazole, triazine, benzoates, hindered amines, and mixtures thereof. For hindered amine light stabilizers, for example, a blend of Tinuvin® 328 and Tinuvin® 123, both commercially available under the trade name Tinuvin® from Ciba Specialty Chemicals in Tarrytown, New York, can be used.

[0073] Non-limiting examples of suitable UV absorbers include hydroxyphenylbenzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole (benzotrazole), 2-(2-hydroxy-3,5-di-tert.amylphenyl)-2H-benzotriazole, 2[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2-hydroxy-3-tert.butyl-5-methylpropionate)-2H-benzotriazole, and reaction products of polyethylene ether glycol having a mass-average molecular weight of 300, 2-(2-hydroxy-3-tert.butyl-5-iso-octylpropionate)-2H-benzotriazole; hydroxyphenyl s -Triaazines, such as 2-[4((2,-hydroxy-3-dodecyloxy / tridecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4(2-hydroxy-3-(2-ethylhexyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine, 2-(4-octyloxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;Hydroxybenzophenone UV absorbers, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and 2-hydroxy-4-dodecyloxybenzophenone.

[0074] Non-limiting examples of suitable hindered amine light stabilizers include N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-dodecylsuccinimide, N(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecylsuccinimide, N-(2-hydroxyethyl)-2,6,6,6-tetramethylpiperidine-4-ol-succinate copolymer, 1,3,5-triazine-2,4,6-triamine, and N,N'”-[1,2- Tandiylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]bis[N,N'”-dibutyl-N',N'”-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)], poly-[[6-[1,1,3,3-tetramethylbutyl)-amino]-1,3,5-triazine-2,4-diyl][2,2,6,6-teto [(2,2,6,6-tetramethyl-4-piperidinyl)-imino]-1,6-hexane-diyl[(2,2,6,6-tetramethyl-4-piperidinyl)-imino]), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) This includes [3,5-bis(1,1-dimethylethyl-4-hydroxyphenyl)methyl]butylpropanediate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dione, and dodecyl / tetradecyl-3-(2,2,4,4-tetramethyl-2l-oxo-7-oxa-3,20-diazadispiro(5.1.11.2)henicosan-20-yl)propionate.

[0075] Non-limiting examples of suitable antioxidants include tetrakis[methylene(3,5-di-tert-butylhydroxyhydrocinnamate)]methane, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tris(2,4-di-tert-butylphenyl)phosphite, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and benzenepropanoic acid, and 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl esters. In certain embodiments, the antioxidant is a hydroperoxide decomposer, such as Sanko® HCA (9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide), triphenyl phosphate, and other organophosphorus compounds, such as Ciba Specialty Chemicals' Irgafos® TNPP, Ciba Specialty Chemicals' Irgafos® 168, GE Specialty Chemicals' Ultranox® 626, Asahi Denka's Mark PEP-6, Asahi Denka's Mark HP-10, Ciba Specialty Chemicals' Irgafos® P-EPQ, Albemarle's Ethanox 398, GE Specialty Chemicals' Weston 618, Ciba Specialty Chemicals' Irgafos® 12, Ciba Specialty Chemicals' Irgafos® 38, GE Specialty This includes Ultranox® 641 from Chemicals and Doverphos® S-9228 from Dover Chemicals.

[0076] The coating composition may further contain other additives known in the art, such as wetting agents, leveling and flow control agents, e.g., Resiflow® S (polybutylacrylate), BYK® 320 and 325 (high molecular weight polyacrylates) under their respective trade names, BYK® 347 (polyether-modified siloxane), leveling agents based on (meth)acrylic homopolymers; rheology control agents; thickeners, e.g., partially crosslinked polycarboxylic acids or polyurethanes; and defoaming agents. Other additives may be used in conventional amounts well known to those skilled in the art. In several embodiments, the wetting agents, leveling agents, flow control agents, and surfactants of the coating composition may affect the surface tension of the coating composition and thus may affect the printability of the coating composition. Certain wetting agents, leveling agents, flow control agents, and surfactants may be incorporated into the coating composition to increase or decrease the surface tension of the coating composition.

[0077] The coating composition is not particularly limited in terms of solids content and may have a solids content of about 5 to about 90, 5 to about 80, about 15 to about 70% by mass, about 15 to about 30, about 10 to about 35, or about 20 to about 25% by mass relative to the mass of the composition. In other embodiments, the solids content is about 5 to about 85, about 10 to about 80, about 15 to about 75, about 20 to about 70, about 25 to about 65, about 30 to about 60, about 35 to about 55, about 40 to about 50, or about 45 to about 50% by mass relative to the mass of the composition. The solids content can be determined in accordance with ASTM D2369-10. In certain embodiments, a higher solids content relative to the coating composition may be desired for coating compositions that do not atomize when using conventional spraying equipment.

[0078] The coating composition is formulated with a near-Newtonian viscosity profile as described above. In a typical embodiment, the coating composition is applied at 500 Pa at all shear rates from 0.1 / sec to 10 / sec, or from 0.1 / sec to 100 / sec. *It exhibits a shear viscosity of less than 1 / second. In some embodiments, the coating composition has a shear viscosity of 30-500 or 30-200 Pa at all shear rates from 0.1 / second to 10 / second, or from 0.1 / second to 100 / second. * It shows the shear viscosity in seconds.

[0079] In some embodiments, the near-Newtonian viscosity profile of a coating composition is defined according to the viscosity ratio between shear viscosities measured at two different shear rates, where a ratio of 1 is the model for the Newtonian profile. In some embodiments, for example, the near-Newtonian viscosity profile of a coating composition is indicated by a coating composition exhibiting a viscosity ratio (0.1 s⁻¹ / 10 s⁻¹) between the shear viscosity at a shear rate of 0.1 / s and the shear viscosity at a shear rate of 10 / s, which is less than 10, or less than 8, or less than 6, or less than 4, or less than 3, or less than 2, or less than 1.5. In these or other embodiments, the coating composition exhibits a viscosity ratio (0.1 s⁻¹ / 100 s⁻¹) (0.1 s⁻¹ / 100 s⁻¹), i.e., the ratio of the shear viscosity at a shear rate of 0.1 / s to the shear viscosity at a shear rate of 100 / s, which is less than 40, or less than 30, or less than 20, or less than 10, or less than 5, or less than 3, or less than 2, or less than 1.5.

[0080] In some embodiments, the coating composition includes a viscosity recovery of at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, within 30 seconds after exposure to a shear rate of 12,000 / second. In these or other embodiments, the coating composition includes a viscosity recovery of at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, within 15 seconds after exposure to a shear rate of 12,000 / second. In these or yet other embodiments, the coating composition includes a viscosity recovery of at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, within 2 seconds after exposure to a shear rate of 12,000 / second.

[0081] Viscosity can be determined according to standard methods known in the art. For example, ASTM 7867-13, which uses conical or parallel plates at various shear rates, can be used. The high-efficiency coating device itself may be any device known in the art. For example, in various embodiments, the coating device is as described in one or more of the following: U.S. Patent Application Publications 20150375258, 20040217202, 2009 / 0304936, U.S. Patent No. 7,824,015, U.S. Patent No. 8,091,987, and International Publication No. 2018 / 206309, each of which is explicitly incorporated herein in whole for use in various non-limiting embodiments. The coating device may also be described as a print head.

[0082] In one embodiment, a high-efficiency applicator includes a nozzle that defines a nozzle opening and may have a nozzle diameter of about 0.00002 m to about 0.0004 m. In another embodiment, the applicator may be fluidly coupled to a container configured to contain a coating composition. For example, a high-efficiency applicator may be configured to receive a coating composition from a container and also to discharge the coating composition onto a substrate through the nozzle opening to form a coating layer. It should be understood that the ranges for nozzle diameter, viscosity, density, surface tension, and relaxation time may be defined by any of the ranges described herein or any of those known in the art. In various non-limiting embodiments, all values ​​and ranges of values, including the values ​​described above, both integers and fractions between them, are explicitly intended for use herein.

[0083] A high-efficiency coating device may be configured to dispense the coating composition through the nozzle opening at an impact speed of approximately 0.2 m / s to approximately 20 m / s. Alternatively, the high-efficiency coating device may be configured to dispense the coating composition through the nozzle opening at an impact speed of approximately 0.4 m / s to approximately 10 m / s, or at a value outside these ranges. The nozzle opening may have a nozzle diameter of approximately 0.00004 m to approximately 0.00025 m. The coating composition can be dispensed from the high-efficiency applicator as droplets having a particle size of at least 10 μm. Alternatively, the coating composition may be dispensed from the high-efficiency applicator as a flow.

[0084] In various embodiments, a high-efficiency applicator includes a plurality of nozzles, each nozzle defining a nozzle opening. The plurality of nozzles may be arranged linearly along a first axis. For example, in various embodiments, the plurality of nozzles includes nozzle A and nozzle B adjacent to nozzle A. Nozzles A and B can be separated from each other by a nozzle distance. The distance of the high-efficiency applicator from the substrate may be substantially the same as the nozzle distance. Similarly, it is intended that one, two, three, or even more applicators may be used in relation to each other. Each applicator may be independently as described herein or any of those known in the art. In various embodiments, a high-efficiency coating device includes approximately 50 nozzles arranged along the y-axis. However, it should be understood that the device can include any number of nozzles. Each nozzle can be operated independently of the others to apply the coating composition to the substrate. During ejection, the independent operation of the nozzles can provide control over the placement of each droplet of the coating composition on the substrate. In one embodiment, a plurality of nozzles are spaced apart from one another to form a rectangular array, where the nozzles can be configured to reduce dripping of the coating composition by alternately dispensing the coating composition between adjacent nozzles in the rectangular array.

[0085] Two or more dispensers may be linked together to form a printhead assembly. In certain embodiments, the dispensers are aligned with each other such that the y-axis of each dispenser is parallel to the y-axis of the others. Furthermore, the nozzles of each dispenser may be aligned in a line with respect to the x-axis perpendicular to the y-axis, resulting in the formation of an "array". One nozzle can be equally spaced from other nozzles directly adjacent to it with respect to the x-axis and y-axis. This nozzle shape may be suitable for dispensing the same coating composition onto the substrate by each dispenser as the printhead assembly moves along the x-axis. Without being bound by theory, it is thought that equal nozzle spacing with respect to both the x-axis and y-axis can result in uniform dispensing of the same coating composition onto the substrate. Uniform dispensing of the same coating composition may be suitable for single-color dispensing, two-tone dispensing, etc. Alternatively, a pair of nozzles along the first y-axis may be spaced more closely together than another pair of nozzles, relative to the spacing between each nozzle along the y-axis of a single high-efficiency applicator. This nozzle configuration may be suitable for applying different coating compositions to a substrate using each high-efficiency applicator. Different coating compositions used within the same high-efficiency applicator assembly may be suitable for logos, designs, signs, stripes, camouflage appearances, and the like. The nozzles of high-efficiency applicators may have any shape known in the art, such as linear, concave relative to the substrate, convex relative to the substrate, or circular. Adjustment of the nozzle shape may be necessary to facilitate the operation of high-efficiency applicators on substrates with irregular shapes, such as those of vehicles, including mirrors, trim panels, contours, spoilers, etc.

[0086] A high-efficiency applicator may be configured to blend individual droplets to produce a desired color. The high-efficiency applicator may include nozzles for applying cyan, magenta, yellow, and black coating compositions. The properties of the coating compositions may be modified to facilitate blending. Furthermore, a stirring source, such as air movement or an ultrasonic generator, may be used to facilitate the blending of the coating compositions. The stirring source may be connected to or separate from the high-efficiency applicator.

[0087] Determining the properties of a coating composition suitable for use in a high-efficiency applicator may depend on the properties of the high-efficiency applicator. These properties include, but are not limited to, the nozzle diameter of the high-efficiency applicator, the impact velocity of the coating composition applied by the high-efficiency applicator, the speed of the high-efficiency applicator, the distance of the high-efficiency applicator from the substrate, the droplet size of the coating composition applied by the high-efficiency applicator, the firing rate of the high-efficiency applicator, and the orientation of the high-efficiency applicator relative to gravity.

[0088] The method includes the step of supplying a coating composition to a high-efficiency applicator. The supplying step is not particularly limited and may be any known in the art. For example, the supplying step may be described as preparing all or part of one or more components of the composition, combining these components to form the composition, and then supplying the finished composition. Alternatively, the supplying step may be described as pumping, flowing, moving, or otherwise delivering one or more components of the composition or the entire composition to the high-efficiency applicator. The supplying step may be described as a continuous process or a batch process. Similarly, the supplying step may include continuous substeps and / or batch substeps. In various embodiments, the supplying step is described as pumping the composition to the applicator under pressure. The supplying step will be understood by those skilled in the art. The coating composition can be used to coat any type of substrate known in the art, insofar as the conditions of the method can be met (i.e., the substrate has a partially dehydrated, water-containing layer on which the coating composition can be applied). Therefore, and as will be further described below, it will be recognized that the term “substrate” generally refers to the article to be coated and not strictly to the surface on which the coating is applied (i.e., the surface has a partially dehydrated, water-containing layer as described herein).

[0089] In several embodiments, the substrate is a vehicle, automobile, or motor vehicle. “Vehicle” or “automobile” or “motor vehicle” includes automobiles, such as passenger cars, vans, minivans, buses, SUVs (Sports-Specific Vehicles); trucks; semi-trucks; tractors; motorcycles; trailers; ATVs (All-Terrain Vehicles); pickup trucks; heavy-duty movers, such as bulldozers, mobile cranes, and earth movers; airplanes; boats; ships; and other means of transport. The coating compositions may also be used to coat substrates in industrial applications, such as buildings; fences; ceramic tiles; permanent structures; bridges; pipes; and cellulose materials (e.g., wood, paper, fibers, etc.). The coating compositions may also be used to coat substrates in consumer applications, such as helmets; baseball bats; bicycles; and toys. The term “substrate” as used herein should be understood to also mean a coating layer placed on an article that can be considered a substrate.

[0090] Various substrates may include two or more separate parts made of different materials. For example, a vehicle may include a body part containing metal and a trim part containing plastic. Due to the baking temperature limitations of plastic (80°C) compared to metal (140°C), the body part containing metal and the trim part containing plastic have traditionally been coated in separate facilities, which can increase the possibility of unsuitable coated parts. A coating composition suitable for plastic substrates can be applied to the plastic substrate using a high-efficiency applicator without the need to mask the substrate or waste portions of the coating composition by conventional low-efficiency application methods such as spray atomization, after the application and baking of a coating composition suitable for metal substrates. A coating composition suitable for plastic substrates can be applied using a first high-efficiency applicator, and a coating composition suitable for metal substrates can be applied using a second high-efficiency applicator. The first and second high-efficiency applicators can form a high-efficiency applicator assembly.

[0091] Alternatively, high-efficiency applicators can be used in line with conventional coating techniques. For example, in certain embodiments, one or more coatings are applied to a substrate by a conventional coating method (e.g., spraying), and then the coating composition is applied by a high-efficiency applicator. In this way, the coating prepared with the coating composition can be defined as an overspray-free coating compared to a conventional application method used for one or more other coatings applied to the substrate. This process is described in more detail below.

[0092] The method also includes the step of applying a coating composition to a substrate using a high-efficiency applicator to form a coating layer on the substrate. The application step is not particularly limited. In various embodiments, the application step may be further defined as spraying, for example, spraying through a high-efficiency applicator. Alternatively, the application step may be further defined as printing. In certain embodiments, the application step may be defined as digital printing. Typically, the coating step is further defined as spraying or printing through, using, or with a high-efficiency applicator. During the coating step, the loss of volatile substances after coating through a high-efficiency applicator is less than about 0.5 mass percent of the total mass of the coating composition. In various embodiments, this amount is less than about 0.4, 0.3, 0.2, or 0.1 mass percent of the total mass of the coating composition. Typically, the term "volatile substances" is defined as substances that cause a mass loss of the coating composition by evaporation. The loss of volatile substances after coating is determined by the increase in % solids after coating compared to before coating, where the % solids in each case is determined by gravimetric method according to ASTM D2369-10. In various non-limiting embodiments, all values ​​and ranges of values, including the values ​​described above, both integers and fractions between them, are expressly intended for use herein.

[0093] In certain embodiments, the coating step generates droplets or streams of the coating composition that affect the substrate. In various embodiments, at least about 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or even higher % of the coating composition discharged from a high-efficiency applicator comes into contact with the substrate. Without being bound by theory, an increase in the number of droplets that come into contact with the substrate compared to the number of droplets that do not come into contact with the substrate and enter the environment is considered to improve the efficiency of coating composition application, reduce waste generation, and lower maintenance.

[0094] In various embodiments, at least about 99.5, 99.6, 99.7, 99.8, 99.9, or more percent of the droplets of the coating composition discharged from a high-efficiency applicator are monodisperse, so that the droplets have a particle size distribution of less than about 20%, or less than about 15%, or less than about 10%, or less than about 5%, or less than 3%, or less than 2%, or less than 1%, or less than about 0.1%. Conventional applicators rely on atomization to form a "mist" of atomized droplets of the coating composition having a dispersed particle size distribution, but the monodisperse droplets and / or flow formed by a high-efficiency applicator can be directed toward the substrate, thereby resulting in improved coating efficiency compared to conventional applicators. In various non-limiting embodiments, all values ​​and ranges of values, including the values ​​described above, both integers and fractions between them, are explicitly intended for use herein.

[0095] In a typical embodiment, a coating composition is ejected from one or more nozzles of a high-efficiency applicator in an engineered / controlled manner, creating a narrow stream that may or may not split into droplets. This stream targets the substrate so that droplets reach specific locations and potentially form a continuous film or pattern on the object. As a result, in many embodiments, there is essentially no overspray (droplets that do not reach the target) and nearly 100% coating efficiency (all paint goes to the targeted location on the substrate). As will be recognized by those skilled in the art, starting and stopping the high-efficiency applicator is permissible to some extent. This type of device can be described as drop-on-demand, stream-on-demand, overspray-free, or ultra-high-efficiency applicator. These devices differ from atomizers and technologies in which energy, such as air pressure, water pressure, or centrifugal force, is introduced to create a partially controlled, random distribution of droplet size, trajectory, and speed, and some additional mechanism, such as electrostatics and / or shaping air, then guides the paint droplet cloud onto the substrate. Compared to traditional paint spraying, there is always some degree of overspray and loss of coating efficiency.

[0096] While known coating appearance characteristics, including gloss, image clarity, and orange peel, can be quantified using various instruments, this does not apply to the visibility of nozzle lines and stripe overlap. Coatings applied with high-efficiency applicators may have high gloss and high image clarity and lack orange peel, but they may still have visible nozzle lines and stripe overlap defects. In some embodiments, applying a coating composition to a substrate involves arranging continuous stripes of the coating composition that at least partially overlap on the substrate to form a continuous wet film. For example, in one such embodiment, a high-efficiency applicator 12 ejects a stream of composition 14 onto a substrate 16, as shown, for example, in Figures 1A and 1B. In Figure 1A, a gap 18 is shown between the stripes 20 of composition 14 arranged on the substrate 16. It is preferable to minimize or eliminate this gap 18. However, as will be understood by those skilled in the art, overlap of stripes 20 in conventional coating compositions can result in unintentional overlap defects due to the accumulation of the composition and the generation of types such as “hills” or raised areas and “valleys” or lower areas of the substrate. It is preferable, even in the present embodiments, to minimize and reduce overlap defects for the rheological profile of the coating composition.

[0097] In Figures 3A-3C, a single nozzle line is shown, which can be defined as having a periodically repeating pattern with an interval 18 that matches the interval 18 between nozzles of a high-efficiency applicator. In Figure 3B, each stripe is a single pass of ~50 nozzles. Figure 3C shows an enlarged view of Figure 3A relating to a single pass of a high-efficiency applicator. Defects exist where each nozzle jet of the composition has struck the substrate 16. This type of defect can be straight or winding, continuous or interrupted, and appear smooth or raised.

[0098] Typically, nozzle lines present a striped appearance in the applied coating, with visible line spacings having the same intervals 18 as the nozzles of the applicator 12. Stripe overlap defects are also parallel to the application direction (e.g., X), but the defects are independent of the applicator nozzle spacing and only exist where adjacent stripes applied consecutively overlap, visible over a length scale of 5–10 mm, i.e., perpendicular to the application direction. This is typically evaluated by comparison with a printed control coating of low viscosity and without rheology control agents, although surface profile measurements introduced below may be used to show that defects are visible when the height difference between high and low regions is greater than 1–2 μm.

[0099] For example, although not shown, it will be understood that Optimap™ PSD using phase step deflectometry can be used to determine the surface profile of one or more areas of a coating, for example, approximately 79 × 57 mm. Such a coating surface profile can be shown including areas of stripe overlap, and the color scale corresponds to differences in coating height (e.g., green represents the average coating surface height, red represents "hills" with heights greater than the average (e.g., up to 3 μm), and blue represents "valleys" with heights less than the surface average (e.g., down to 3 μm)). Thus, stripe overlap areas can be observed as defects parallel to the coating direction, becoming more visible as the hills and valleys become more pronounced.

[0100] As schematically shown (top-down) in Figure 3C, the stripes 20 represent lines of the coating composition deposited from a single nozzle parallel to the direction of application. The resulting application lines with spacing 18 may be visible immediately after application, but preferably become less visible over time as flow and leveling occur. However, if sufficient flow and leveling do not occur, the lines may remain visible after coating curing, resulting in an uneven and generally undesirable coating appearance. In certain embodiments, a coating layer without overspray is substantially free of visible application lines.

[0101] For illustrative purposes, Figure 4 is a photograph of the comparative composition placed on a substrate, showing visible stripe overlap defects. In some embodiments, the coating step is further defined as applying the coating composition through a nozzle in multiple lines on the substrate in a direction (X) along the substrate, where each line partially overlaps with an adjacent line to form overlapping and non-overlapping regions, the overlapping regions being visually smooth, and the thickness of the overlapping regions varying by less than approximately 1 μm compared to the thickness of the non-overlapping regions measured over a distance of 5 mm perpendicular to the direction (X) after the curing step. In some such embodiments, the overspray-free coating layer is prepared substantially free of visible stripe overlap defects. In a typical embodiment, the coating composition is applied to a wet film thickness of at least about 6, or at least about 8, or at least about 10, or at least about 12 μm or more. In other embodiments, greater wet film thicknesses (e.g., 25, 30 μm, or more) are available. In some embodiments, the wet film thickness can be measured at about 45 degrees without visible dripping. Higher or lower values ​​may also be achieved. In a typical embodiment, there is no visible dripping at all during the application of the coating composition.

[0102] In certain embodiments, the method is used to prepare a multilayer coating on a substrate. Multilayer coatings are used in a variety of applications and consist of various layers such as primer / surface layer, base coat layer, barrier coating layer, filler layer, top coat layer, clear coat layer, etc. For example, a morphological structure having a primer layer, filler layer and top coat layer, where the top coat layer includes a base coat and clear coat or is a pigmented one-coat top coat layer, is typical for vehicle coatings and vehicle repair coating structures. The various layers of a multilayer coating are applied sequentially. Between each application step, a certain drying time is usually required before the next layer can be applied. The actual minimum drying time required before a previously applied coating can be overlaid depends on various factors, such as the physical drying and reactivity of the applied coating composition, the amount and type of solvent contained in the coating composition, the presence of a curing catalyst, and external factors, such as the drying temperature and humidity during drying. In any case, before another coating layer is applied to a previously applied coating layer, the previously applied coating layer must be sufficiently dried so that it does not mix or react with other coating layers and has sufficient mechanical resistance. On the other hand, particularly with respect to the surface layer, it is desirable that, after drying, the mechanical resistance still allows for the removal of defects in the dried layer before further layers, such as a base coat or a base coat pigmented one-coat topcoat, are applied. Defects in the surface layer may also become visible after the application of another layer, thus degrading the appearance of the final coating. In other words, all of the above requirements affect the overall quality, especially the appearance, of each topcoat layer applied to a previously applied filler layer.

[0103] The wet-on-wet coating method described herein is defined as applying a first layer, such as a filler layer, and then conditioning (e.g., evaporating) the surface layer, after which the surface layer is not polished, in particular not completely polished, for the purpose of leveling the surface of the surface layer, for example, by removing unwanted structures from it. In other words, the wet-on-wet coating process is not a polishing process. Furthermore, both the time and conditions for evaporating the filler prior to the application of the topcoat layer, such as temperature, air circulation, or humidity, should not be limited by the term wet-on-wet coating method.

[0104] Typically, the substrate comprises at least a partially dehydrated, water-containing basecoat layer (e.g., an aqueous basecoat), and the step of applying the coating composition to the substrate comprises placing the coating composition on the partially dehydrated, water-containing basecoat layer, and the application of the coating composition thereto is a wet-on-wet process. In some such embodiments, the method further comprises the step of preparing at least a partially dehydrated, water-containing basecoat layer on the substrate.

[0105] For example, in some embodiments, the method is performed before applying the coating composition. Applying a water-based primer film to the substrate; Conditioning the aqueous primer film to provide a partially dehydrated primer layer; Placing a water-based basecoat film on a partially dehydrated primer layer; and Conditioning the water-based basecoat film to form a partially dehydrated water-based basecoat layer. This includes the following. As will be readily apparent, the parameters for deploying a coating onto a substrate in an inline wet-on-wet process are not limited, and many techniques and various parameters can be selected (depending on the substrate material, the coating used, etc.). Individual such parameters will be understood by considering the following examples.

[0106] Similarly, in some embodiments, a clear coat is applied over a coating layer without overspray to prepare a painted article. Therefore, in each embodiment, the method for preparing a painted article is as follows: A step of preparing a partially dehydrated primer layer on a substrate; A step of preparing a partially dehydrated basecoat layer on top of a primer layer; A step of preparing a partially dehydrated, overspray-free coating layer on a base coat layer with a coating composition; Prepare a clear coat layer on a coating layer without overspray. Includes inline wet-on-wet processes, including step-by-step processes. In this inline wet-on-wet process, the primer, base coat, and coating composition are all aqueous coating compositions. In a typical embodiment, the clear coat is a solvent-based composition, such as a 2k solvent-based clear coat.

[0107] After the final coating application, the multi-layer coating is typically subjected to finishing conditions, for example, to fully cure the various coatings. Referring to Figure 5, the entire schematic cross-section of an article prepared with the multilayer coating described above is shown in 22. The coated article 22 includes a component layer 24, a primer or surface layer 26, a base coat layer 28, a coating layer 30 without overspray according to the embodiments herein, and a clear coat layer 32. The component layer 24 is understood to represent the component to be coated, such as a vehicle panel. Therefore, the component layer 24 generally represents the substrate to be coated at the beginning of the coating method herein. When applying a primer (e.g., a coating that subsequently gives a primer or surface layer 26) to the component layer 24, the term “substrate” may refer to the component coated with the primer (i.e., the combination of layers 24 and 26 before final curing) with respect to the next topcoat step (e.g., the step of applying a basecoat that subsequently gives a basecoat layer 28). Similarly, when a component is coated with both a primer and a basecoat, the component that is primer-primed and coated with a basecoat (i.e., the combination of layers 24, 26, and 28 before final curing) may be referred to as the “substrate” with respect to the next topcoat step (e.g., the step of applying a coating composition).

[0108] In some embodiments, layers 26 and 28 are both prepared from a water-containing / aqueous coating. In certain embodiments, one or two or each of layers 28, 30, and 32 are prepared by wet-on-wet application to their respective primers. In each such embodiment, the primer used to prepare the primer layer 26 is at least partially dehydrated after application and before the application of the base coat topcoat. In a typical embodiment, preparing the painted article 22 involves subjecting the fully coated components to curing conditions, i.e., curing the clear coat to give the final clear coat layer 32 while simultaneously fully curing the primers to also give the final layers 26, 28, and 30.

[0109] Drooping rating: To evaluate sagging, the following procedure is typically used: Prior to coating application, the substrate panel is oriented horizontally; A high-efficiency coating device is used to apply four consecutive stripes of the coating composition to a horizontal substrate panel, so that the compositions overlap to provide a continuous coated surface having a target wet film thickness (typically 30 μm or more) and a coated substrate width of approximately 180 mm; After the composition is applied, the panel is tilted so that the coated substrate width of approximately 180 mm is at an angle of approximately 45 degrees from the horizontal, as shown in Figure 2B, for example. After maintaining the same panel angle for approximately 5 minutes at room temperature, the panel is dehydrated at 82°C for 5 minutes, followed by spraying with a clear coat and final baking to ensure complete curing. Drip, if present, is indicated by droplets at the bottom edge of the coating and is visually assessed; Although not shown herein, if present, nozzle line visibility can be observed as thin lines parallel to each other and to the dispensing direction, with the same spacing (~1 mm) as adjacent nozzles within the dispensing apparatus;

[0110] If present, stripe overlap visibility is visually evaluated in the area where the coating is applied in a series of coating passes. It can be seen that a thickness variation of just 1 μm over a distance of 5 mm parallel to the coating direction results in stripe overlap visibility, as shown in Figure 4, for example.

[0111] The use of coating compositions can reduce or eliminate nozzle clogging. For example, high-efficiency "stream-on-demand" or "drop-on-demand" applicators typically include an array of narrow-diameter nozzles, each having a nozzle diameter of approximately 20 μm to 200 μm. Typically, for reliable fluid ejection, the particle size of the coating composition components is expected to be no more than approximately 10% of the nozzle diameter. While some components of the coating composition may have an average size that meets this criterion, a small amount of excessively large particles will eventually lead to nozzle clogging. The result is either a partially clogged nozzle that can produce erroneous droplets or flows, or a completely clogged nozzle that prevents fluid ejection. In either case, it results in coating defects. Clogging can be evaluated in two ways: (1) blockage of a filter installed prior to the applicator, and (2) discontinuities during coating application followed by microscopic examination of debris within the nozzle. [Examples]

[0112] The following embodiments illustrating the embodiments of this disclosure are intended to be illustrative and are not intended to limit the present invention. All parts and percentages are reported on a mass basis unless otherwise indicated. Where provided, molecular weights (both number and mass-average molecular weights) referred to herein may be determined by conventional methods known in the art. For example, the molecular weight for polyaspartate resins can be determined by gel permeation chromatography (GPC), for example, using a polystyrene standard and tetrahydrofuran (THF) eluent. Unless otherwise indicated, molecular weights are reported as mass-average molecular weight (Mw).

[0113] material Unless otherwise stated, all solvents, substrates, and reagents are purchased or otherwise obtained from various commercial suppliers (e.g., BASF, Covestro, Evonik, Sigma-Aldrich, VWR, Alfa Aesar, etc.) and used as received (i.e., without further purification) or in the form conventionally used in the art.

[0114] (Examples 1-7 and Comparative Examples (CE) 1-2) Coating formulation: A coating composition without overspray was prepared using the materials and parameters listed in Table 1 below. After preparation, the coating composition without overspray was evaluated as described below. A single coating composition was prepared and dispensed into two samples, which were used in Examples 2 and 3. [Table 1]

[0115] The thickener (C1) is a hydrophobic, modified ethylene oxide urethane (HEUR) rheology modifier that does not contain APEO or solvents. The thickener (C2) is a layered silicate rheology control agent supplied as a solution of water and polypropylene glycol. The thickening agent (C3) is an acrylic alkali swelling emulsion (ASE).

[0116] The crosslinking agent (B) is a highly methylated methoxymethyl functional monomeric melamine crosslinking agent. The binder (A1) is a polyurethane dispersion resin formed from a linear polyester diol resin (a reaction product of monomer 1,6-hexanediol, adipic acid, and isophthalic acid) and isophorone diisocyanate. It is approximately 35% solid by mass. The binder (A2) is a glycol ether polyester, 80% by mass solid, with an acid value of ~7. The binder (A3) is a styrene-acrylic latex dispersion formed by a two-step emulsion polymerization method, with a solid content of 46% by mass, a Tg of -7C, an acid value of ~12, and a hydroxyl value of ~7.

[0117] The polyol is polypropylene glycol 425. The pigment is a dispersion of amorphous carbon black pigment similar to the carbon black pigment commercially available from Birla Carbon under the trade name Raven 5000 Ultra II. The catalyst is a dodecylbenzenesulfonic acid (DDBSA) / aminomethylpropanol (AMP) solution. The UV absorber is a commercially available UV absorber. The leveling additive is a commercially available leveling additive.

[0118] The wetting additive is a commercially available silicone-free wetting additive.

[0119] The amine is aminomethylpropanol. Cosolvent 1 is isotridecanol. Cosolvent 2 is ethylene glycol monobutyl ether. Cosolvent 3 is N-butanol. Cosolvent 4 is N-methyl-2-pyrrolidone. Cosolvent 5 is petroleum spirit.

[0120] Viscosity analysis The nine formulated coating compositions from Examples 1-7 and Comparative Examples 1-2 were evaluated using controlled shear rate flow sweep and time sweep experiments to assess their demonstrable shear viscosity reduction behavior. ASTM D2196 can be used to determine viscosity. The evaluation results are shown in Table 2 below. [Table 2] Regarding controlled shear rate flow sweep experiments, the results for Examples 1-2 and Comparative Examples 1-2 are plotted in Figure 6A, and the results for Examples 3-7 are plotted in Figure 7A. As clearly shown, Examples 1-7 each exhibit near-Newtonian viscosity profiles. Comparative Examples 1-2 exhibit non-Newtonian viscosity profiles. Regarding the time sweep experiment, the viscosity recovery performance results for Examples 1-2 and Comparative Examples 1-2 are plotted in Figure 6B, and the results for Examples 3-7 are plotted in Figure 7B. The representative coating compositions (Examples 1-7) show faster viscosity recovery than the comparative coating compositions (Comparative Examples 1-2).

[0121] Preparation of multilayer coatings Nine formulated coating compositions from Examples 1-7 and Comparative Examples 1-2 were used in an inline wet-on-wet multilayer coating process to prepare four-layer coatings. The sagging, popping, and overlap visibility of the as-applied coating compositions were evaluated. The process parameters for multilayer coating preparation are shown in Table 3 below. The application parameters and performance results are further described in Table 4 below.

[0122] [Table 3]

[0123] [Table 4]

[0124] In Table 4 above, each "+" is a positive indicator of subjectively better performance, as understood and appreciated by those skilled in the art. Each "-" is a negative indicator of subjectively worse performance, as understood and appreciated by those skilled in the art. If more than one "+" or "-" symbol is used, this means even better or worse performance, as understood and appreciated by those skilled in the art. The data described above shows that representative compositions exhibit good performance and can be used to successfully prepare coatings without overspray, and that some representative coatings provide superior performance and appearance compared to comparative coating compositions.

[0125] (Examples 8-13) Coating formulation: A coating composition without overspray was prepared using the materials and parameters listed in Table 5 below. After preparation, the coating composition without overspray was further evaluated as described below.

[0126] During the evaluation, the coating composition prepared using the formulation of Example 2 was evaluated together with Examples 8-13 and reported as Example 2B. [Table 5]

[0127] The formulated coating compositions of Examples 8-13 and 2B were evaluated for the shear-thinning behavior described above. The formulated coating compositions were then used in an inline wet-on-wet multilayer coating process to prepare a four-layer coating in the same manner as described above. The as-applied coating compositions were evaluated for the overlap visibility and 90-degree sag described above, and the performance is reported as high (H), medium / low (M), and low (L), where low (L) sag is most desirable here.

[0128] The results of the viscosity and coating evaluations are set forth in Table 6 below.

Table 6

[0129] The results of the controlled shear rate flow sweep experiments and time sweep experiments for Examples 2B and 8-13 were plotted and are shown in FIGS. 8A and 8B, respectively. As clearly shown, Examples 8-13 and 2B each exhibit a near-Newtonian viscosity profile and a fast viscosity recovery time. Further, the coating compositions can be optimized for high recovery and low sag, enabling improved coating and reduced defects in the coatings formed therefrom. ]>

[0130] The present disclosure may be further described by the following aspects. Aspect 1. A method of preparing a coated article, comprising: providing a substrate having thereon a partially dehydrated aqueous coating layer; providing a coating composition for spray-free coating, the coating composition being an aqueous fluid having a near-Newtonian viscosity profile and exhibiting a shear viscosity of less than 500 Pa at all shear rates from 0.1 / sec to 10 / sec, or from 0.1 / sec to 100 / sec, and comprising a binder, a crosslinking agent, and a thickening agent; * sec, and an aqueous fluid comprising a binder, a crosslinking agent, and a thickening agent; Supplying a coating composition to a high-efficiency applicator comprising multiple nozzles, each configured to apply the flow of the coating composition to a substrate without substantially atomizing it; and By using a high-efficiency coating device, the coating composition is applied to the substrate by placing multiple lines of the coating composition onto a partially dehydrated, water-containing coating layer on the substrate via multiple nozzles, thereby forming a coating layer without overspray. A method that includes the act of doing so.

[0131] Embodiment 2. The method of Embodiment 1, wherein the application of a coating composition to a substrate comprises arranging partially overlapping continuous stripes of the coating composition on the substrate to form a continuous wet film; the method further comprises conditioning the wet film by at least partially flushing and / or dehydrating to give an overspray-free coating layer; (i) the wet film is substantially free of visible sagging; (ii) the overspray-free coating layer is substantially free of visible stripe overlap defects; or (iii) both (i) and (ii).

[0132] Embodiment 3. The partially dehydrated water-containing coating layer of a substrate is further defined as a partially dehydrated aqueous basecoat layer; the method of Embodiment 1 or 2 further comprises preparing a partially dehydrated aqueous basecoat layer by applying a film of aqueous basecoat onto a substrate and then conditioning the film of aqueous basecoat to form a partially dehydrated aqueous basecoat layer.

[0133] Embodiment 4. The method of Embodiment 3, wherein applying the aqueous basecoat to the substrate includes applying the aqueous basecoat film onto a partially dehydrated water-containing primer layer by a wet-on-wet process. Embodiment 5. The method of Embodiment 4, further comprising preparing a partially dehydrated primer layer on the substrate by placing a film of aqueous primer on the substrate and conditioning the film of aqueous primer to give a partially dehydrated, water-containing primer layer. Appearance 6. Furthermore, Placing the clear coat film on a coating layer without overspray; and The clear coat is cured to form a clear coat layer on top of a coating layer that is free from overspray. A method that includes any one of embodiments 1 to 5.

[0134] Embodiment 7. The method of Embodiment 6, wherein applying a coating composition to a substrate gives a film of the coating composition without overspray, the method further comprises conditioning the film of the coating composition without overspray to give a partially dehydrated, watery, overspray-free coating layer, and arranging a clear coat film comprises applying a clear coat to the partially dehydrated, watery, overspray-free coating layer by a wet-on-wet process. Embodiment 8. The coating composition withstands 200 Pa at all shear rates from 0.1 / sec to 10 / sec, or from 0.1 / sec to 100 / sec. * A method exhibiting a shear viscosity of less than 1 second, as described in any one of embodiments 1 to 7. Appearance 9. The coating composition is subjected to 30-200 Pa at all shear rates from 0.1 / sec to 10 / sec, or from 0.1 / sec to 100 / sec. * A method, one of embodiments 1 to 8, that exhibits shear viscosity in seconds.

[0135] Embodiment 10. The near-Newtonian viscosity profile of the coating composition is less than 10, or less than 8, or less than 6, or less than 4, or less than 3, or less than 2, or less than 1.5, and the viscosity ratio of the shear viscosity at a shear rate of 0.1 / second to the shear viscosity at a shear rate of 10 / second (0.1 second -1 / 10 seconds -1 One of the methods of embodiments 1 to 9, including ). Embodiment 11. The near-Newtonian viscosity profile of the coating composition is less than 40, or less than 30, or less than 20, or less than 10, or less than 5, or less than 3, or less than 2, or less than 1.5, and the viscosity ratio of the shear viscosity at a shear rate of 0.1 / second to the shear viscosity at a shear rate of 100 / second (0.1 second -1 / 100 seconds -1 One of the methods from embodiments 1 to 10, including ). Embodiment 12. Any one of Embodiments 1 to 11, wherein the coating composition exhibits viscosity recovery of at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95% within 30 seconds after exposure to a shear rate of 12,000 / second.

[0136] Embodiment 13. Any one of Embodiments 1 to 12, wherein the coating composition exhibits viscosity recovery of at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95% within 2 seconds after exposure to a shear rate of 12,000 / second. Embodiment 14. Any one of Embodiments 1 to 13, wherein the binder comprises: (i) acrylic resin; (ii) polyester resin; (iii) polyurethane resin; or (iv) any combination of (i) to (iii). Embodiment 15. Any one of Embodiments 1 to 14, wherein the crosslinking agent comprises a melamine-based crosslinking agent.

[0137] Embodiment 16. Any one of Embodiments 1 to 15, wherein the thickener comprises: (i) an organic thickener; (ii) an inorganic thickener; or (iii) both (i) and (ii). Embodiment 17. A method from any one of Embodiments 1 to 16, comprising an associative organic thickener containing a hydrophobically modified ethylene oxide-urethane copolymer (HEUR). Embodiment 18. Any one of Embodiments 1 to 17, wherein the thickening agent comprises an inorganic thickening agent containing a phyllosilicate. Embodiment 19. Any one of Embodiments 1 to 18, wherein the coating composition further comprises a pigment, a cosolvent, a catalyst, a UV absorber, a leveling additive, a wetting additive, or a combination thereof. Embodiment 20. Any one of Embodiments 1 to 19, wherein the base material is a component of a vehicle. Embodiment 21. A painted article prepared using any one of the methods described in Embodiments 1 to 20.

[0138] While at least one representative embodiment has been presented in the detailed description above, it should be understood that a vast number of variations exist. It should also be understood that one or more representative embodiments are merely examples and are not intended to limit their scope, applicability, or configuration in any sense. Rather, the detailed description above provides a useful guide for carrying out the representative embodiments. It should be understood that various modifications can be made to the function and arrangement of the elements described in the representative embodiments without departing from the scope set forth in the appended claims. Furthermore, all combinations of the above-mentioned components, compositions, method steps, compounding steps, etc., are explicitly intended for use in various non-limiting embodiments herein, even if such combinations are not explicitly described in the same or similar paragraphs.

[0139] With respect to any group of markashes used in this specification to describe individual features or aspects of various embodiments, different, special, and / or unexpected results may be obtained from each member of each group of markashes, independent of all other markash members. Each member of a group of markashes may be used individually and / or in combination to provide appropriate support for specific embodiments within the scope of the appended claims.

[0140] Furthermore, all ranges and subranges used to describe various embodiments of the present invention, individually and collectively, fall within the scope of the appended claims, and even if integer and / or fractional values ​​within a range are not explicitly stated herein, it is understood that all ranges, including such values, are described and intended. As will be readily apparent to those skilled in the art, the ranges and subranges enumerated herein adequately describe and enable various embodiments of the present invention, and such ranges and subranges may further represent related 1 / 2, 1 / 3, 1 / 4, 1 / 5, and so on. As merely one example, the range "0.1 to 0.9" may further represent the lower 1 / 3, i.e., 0.1 to 0.3, the middle 1 / 3, i.e., 0.4 to 0.6, and the upper 1 / 3, i.e., 0.7 to 0.9, which, individually and collectively, fall within the scope of the appended claims and may be used individually and / or collectively, providing appropriate support for specific embodiments within the scope of the appended claims. In addition, with respect to words that define or modify a range, such as "at least," "greater than," "less than," "less than or equal to," etc., such words should be understood to include subranges and / or upper or lower limits. As another example, the range "at least 10" essentially includes the subranges at least 10 to 35, at least 10 to 25, 25 to 35, etc., and each subrange may be used individually and / or in combination to provide appropriate support for specific embodiments within the scope of the attached claims. Individual numbers within the disclosed range may be used to provide appropriate support for specific embodiments within the scope of the attached claims. For example, the range "1 to 9" includes various individual integers such as 3, as well as individual numbers including decimals (or fractions), such as 4.1, which may be used to provide appropriate support for specific embodiments within the scope of the attached claims. Finally, the term “about” relating to the individual numbers and ranges described herein is understood to be used to specify values ​​within standard tolerances, equivalent functions, potency, final fills, etc., as understood by those skilled in the art who have the relevant conventional techniques and processes for formulating and / or utilizing compounds and compositions as described herein.Therefore, the term "approximately" can specify a percentage value or range of values ​​that is within 10, 5, 1, 0.5, or 0.1.

[0141] While this disclosure has described its individual embodiments, it will be apparent that numerous other forms and modifications are obvious to those skilled in the art. The appended claims and this disclosure should generally be construed to include all such obvious forms and modifications that fall within the true scope of this disclosure.

Claims

1. A method for preparing painted articles, To prepare a substrate having a partially dehydrated, water-containing coating layer thereon; A coating composition for application without overspray, having a near-Newtonian viscosity profile and a viscosity of 500 Pa at all shear rates from 0.1 / sec to 10 / sec, or from 0.1 / sec to 100 / sec. * Prepare a coating composition that exhibits a shear viscosity of less than 1 second and is an aqueous fluid containing a binder, a crosslinking agent, and a thickening agent; Supplying a coating composition to a high-efficiency applicator comprising multiple nozzles, each configured to apply the flow of the coating composition to a substrate without substantially atomizing it; and By using a high-efficiency coating device, the coating composition is applied to the substrate by placing multiple lines of the coating composition onto a partially dehydrated, water-containing coating layer on the substrate via multiple nozzles, thereby forming a coating layer without overspray. A method that includes doing so.

2. The method according to claim 1, wherein the application of the coating composition to a substrate comprises arranging partially overlapping continuous stripes of the coating composition on the substrate to form a continuous wet film; the method further comprises conditioning the wet film by at least partially flushing and / or dehydrating to give an overspray-free coating layer; (i) the wet film is substantially free of visible sagging; (ii) the overspray-free coating layer is substantially free of visible stripe overlap defects; or (iii) both (i) and (ii).

3. The method according to claim 1, wherein a partially dehydrated, water-containing coating layer of a substrate is further defined as a partially dehydrated aqueous basecoat layer; the method further comprises preparing a partially dehydrated aqueous basecoat layer by applying a film of aqueous basecoat onto a substrate and then conditioning the film of aqueous basecoat to form a partially dehydrated aqueous basecoat layer.

4. The method according to claim 3, wherein applying the aqueous basecoat to the substrate includes applying the aqueous basecoat film onto a partially dehydrated water-containing primer layer by a wet-on-wet process.

5. The method according to claim 4, further comprising preparing a partially dehydrated primer layer on the substrate by placing a film of aqueous primer on the substrate and conditioning the film of aqueous primer to give a partially dehydrated primer layer.

6. Furthermore, Placing a clear coat film on a coating layer without overspray; and The clear coat is cured to form a clear coat layer on top of a coating layer that is free from overspray. The method according to any one of claims 1, including the method described in claim 1.

7. The method according to claim 6, wherein the coating composition is applied to a substrate to give a film of the coating composition without overspray, the method further comprises conditioning the film of the coating composition without overspray to give a partially dehydrated, watery, overspray-free coating layer, and the placement of a clear coat film comprises applying a clear coat to the partially dehydrated, watery, overspray-free coating layer by a wet-on-wet process.

8. The coating composition withstands 200 Pa at all shear rates from 0.1 / sec to 10 / sec, or from 0.1 / sec to 100 / sec. * The method according to any one of claims 1 to 7, which exhibits a shear viscosity of less than a second.

9. The coating composition exhibits a shear rate of 30 to 200 Pa at all shear rates from 0.1 / sec to 10 / sec, or from 0.1 / sec to 100 / sec. * The method according to any one of claims 1 to 7, exhibiting a shear viscosity in seconds.

10. (i) The near-Newtonian viscosity profile of the coating composition is less than 10, or less than 8, or less than 6, or less than 4, or less than 3, or less than 2, or less than 1.5, and the viscosity ratio of the shear viscosity at a shear rate of 0.1 / s to the shear viscosity at a shear rate of 10 / s (0.1 seconds -1 / 10 seconds -1 (ii) The viscosity ratio of the shear viscosity at a shear rate of 0.1 / s to the shear viscosity at a shear rate of 100 / s, wherein the near-Newtonian viscosity profile of the coating composition is less than 40, or less than 30, or less than 20, or less than 10, or less than 5, or less than 3, or less than 2, or less than 1.5 (0.1 / s -1 / 100 seconds -1 (v) The method according to any one of claims 1 to 7, comprising: (iii) the coating composition exhibits viscosity recovery of at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95% within 30 seconds after exposure to a shear rate of 12,000 / second; (iv) the coating composition exhibits viscosity recovery of at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95% within 2 seconds after exposure to a shear rate of 12,000 / second; or any combination of (v)(i) to (iv).

11. The method according to any one of claims 1 to 7, wherein (I) the binder comprises (i) an acrylic resin; (ii) a polyester resin; (iii) a polyurethane resin; or (iv) any combination of (i) to (iii); (II) the crosslinking agent comprises a melamine-based crosslinking agent; (III) the thickener comprises (i) an organic thickener; (ii) an inorganic thickener; or (iii) both (i) and (ii); or (IV) any combination of (I) to (IV).

12. The method according to any one of claims 1 to 7, wherein the thickener comprises (i) an associative organic thickener containing a hydrophobically modified ethylene oxide-urethane copolymer (HEUR); (ii) an inorganic thickener containing a phyllosilicate; or (iii) both (i) and (ii).

13. The method according to any one of claims 1 to 7, wherein the coating composition further comprises a pigment, a cosolvent, a catalyst, a UV absorber, a leveling additive, a wetting additive, or a combination thereof.

14. The method according to any one of claims 1 to 7, wherein the base material is a component of a vehicle.

15. A painted article prepared by the method described in any one of claims 1 to 7.

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