Method for applying to substrate, one liquid type aqueous coating composition using high transfer efficiency applicator

Abstract

To provide a method for applying to a substrate, a coating composition and capable of reducing sag.SOLUTION: There is provided a method for applying to a substrate, a coating composition through a high transfer efficiency applicator, in which the coating composition has a pH of greater than almost 7, and comprises: A. a resin dispersion including, a latex, polyurethane or a combination thereof; B. an optionally selected cross linking agent; C. an optionally selected pigment; D. water; E. a water soluble solvent; F. and at least one rheology control agent which is selected from an alkali swellable emulsion, a layering silicate, and a combination thereof. The coating composition has viscosity of almost 20-almost 100 cps in a shear speed of 1000 sec-1 when being measured using ASTM 7867-13 and by a circular cone flat plate or a parallel plate method, and the coating composition has a wet film thickness of at least 20 micron without visible sag, when measured at almost 45 degree.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates, in general terms, to a method for applying a one-component aqueous coating composition to a substrate using a high-transfer-efficiency applicator. More specifically, this disclosure relates to spraying a particular composition through a high-transfer-efficiency applicator, the composition comprising an alkali-swellable emulsion, a layered silicate, and at least one rheology control agent selected from a combination thereof. [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 electronic signals. This coating process has the advantage of enabling digital printing of substrates that can be tailored to individual requirements. The droplets can be ejected onto the substrate by various inkjet coating methods, such as continuous printing and drop-on-demand printing. In drop-on-demand printing, the energy for ejecting the ink droplets can be obtained from thermal resistors, piezoelectric crystals, acoustic or solenoid valves. These methods utilize high-transfer-efficiency coating devices. In the automotive industry, car bodies are typically covered with a series of finishes, including electrodeposition coating, primer coating, a colored base coat, and a clear top coat that provides additional protection and a glossy finish. Most modern car bodies are painted in a single color with a base coat applied in a single spray action. The coating is applied using pneumatic spraying or rotary equipment that produces a wide spray 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 painting a car body in multiple colors, for example, if a second color is used for a pattern such as stripes, or if an entire section 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 this second painting process, the masking must be removed. This requires both time and effort, and significantly increases the cost of the work. The second drawback of current spraying technology is that paint droplets are sprayed with a wide droplet size and a broad spray pattern. As a result, many droplets do not adhere to the vehicle, either because droplets are sprayed near the edges, overspraying the substrate, or because smaller droplets have too little momentum to reach the vehicle body. This excessive overspray needs to be removed from the spraying process and safely disposed of, leading to a large amount of waste and additional costs.

[0003] By applying the coating using a high-transfer-efficiency applicator, a solution is provided for applying two colors to a vehicle and for minimizing overspray by generating uniformly sized droplets that can be directed to specific points on the substrate (e.g., specific locations on the vehicle body), thereby minimizing or completely eliminating overspray. In addition, using digital printing, patterns or two-tone designs can be printed on the vehicle body either as a second color digitally printed on top of a pre-sprayed base coat of a different color, or as a second color printed directly onto a vehicle substrate that has been primed or clear-coated. However, conventional inkjet inks are typically formulated to print on porous substrates such as paper and textiles, where the ink is rapidly absorbed into the substrate, thereby facilitating drying and handling of the substrate immediately after printing. In addition, while printed articles, such as printed text and images or patterned textiles, have sufficient durability to these coatings, the durability requirements for automotive coatings are far higher 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 have low viscosity, are generally shear-independent, i.e., Newtonian, and are typically formulated to be less than 20 cps. This is due to the limited amount of energy available at each nozzle of the printhead in order to eject droplets and to avoid thickening of the ink in the printhead channels, which could lead to clogging. In contrast, automotive coatings typically exhibit significant non-Newtonian shear behavior. At low shear rates, they have extremely high viscosity, which is useful in avoiding pigment sedimentation and ensuring rapid and uniform curing of the coating immediately after application. However, at high shear rates, they have relatively low viscosity, facilitating spraying and atomization of the spray onto droplets. Furthermore, even if current technology is suitable for some horizontal surface coatings, other applications remain where current technology results in unacceptable levels of sag (drooping), such as vertical surface coatings. High transfer efficiency coatings require very low viscosity that does not exhibit shear-fluidizing behavior, making it impossible to use standard approaches to impart sag resistance to spray-coated coatings. Therefore, opportunities for improvement remain. [Overview of the project]

[0004] This disclosure provides a method for applying a one-component aqueous coating composition to a substrate using a high-transfer-efficiency applicator to form a coating layer on the substrate, the method being described as follows: A step of providing a coating composition to a high-transfer-efficiency applicator, A process of applying a coating composition to a substrate through a high-transfer-efficiency applicator to form a coating layer on the substrate, wherein the loss of volatile matter after application through the high-transfer-efficiency applicator is less than approximately 0.5% by mass (active ingredient) based on the total weight of the coating composition, Includes, The coating composition has a pH greater than approximately 7, and A. A resin dispersion containing latex, polyurethane, or a combination thereof, B. Optional crosslinking agents, C. Optional pigments and D. Water and, E. Water-soluble solvents, F. At least one rheology control agent selected from alkali-swelling emulsions, layered silicates, and combinations thereof, Includes, The coating composition, when measured using the conical plate or parallel plate method according to ASTM 7867-13, has a viscosity of approximately 20 to approximately 100 cps at a shear rate of 1000 sec⁻¹. The coating composition has a wet film thickness of at least 20 microns without visible sag when measured at approximately 45 degrees Celsius. [Modes for carrying out the invention]

[0005] The following detailed description is illustrative and not intended to limit the method. Furthermore, it is not intended to be bound by any theory shown in the background art described above or in the embodiments for carrying out the invention described below.

[0006] Embodiments of this disclosure generally relate to one-component aqueous coating compositions and methods for forming and applying such compositions. For simplicity, prior art related to the formation of one-component aqueous coating compositions may not be described in detail herein. Furthermore, various tasks and process steps described herein may be incorporated into more comprehensive procedures or processes having additional steps or functions not described herein. In particular, various steps in the manufacture of one-component aqueous coating compositions are well known, and therefore, for simplicity, many prior steps are either briefly described herein or omitted entirely without providing well known process details.

[0007] This disclosure provides a method for applying a one-component aqueous coating composition to a substrate using a high-transfer-efficiency applicator to form a coating layer on the substrate, the method being described as follows: A step of providing a coating composition to a high-transfer-efficiency applicator, A process of applying a coating composition to a substrate through a high-transfer-efficiency applicator to form a coating layer on the substrate, wherein the loss of volatile matter after application through the high-transfer-efficiency applicator is less than approximately 0.5% by mass (active ingredient) based on the total weight of the coating composition, Includes, The coating composition has a pH greater than approximately 7, and A. A resin dispersion containing latex, polyurethane, or a combination thereof, B. Optional crosslinking agents, C. Optional pigments and D. Water and, E. Water-soluble solvents, F. At least one rheology control agent selected from alkali-swelling emulsions, layered silicates, and combinations thereof, Includes, The coating composition, when measured using the conical plate or parallel plate method according to ASTM 7867-13, has a viscosity of approximately 20 to approximately 100 cps at a shear rate of 1000 sec⁻¹. The coating composition has a wet film thickness of at least 20 microns without visible sag when measured at approximately 45 degrees Celsius.

[0008] Providing a one-component aqueous coating composition: The method of the present invention includes the step of providing a coating composition to a high-efficiency applicator. The providing step is not particularly limited and may be any step known in the art. For example, the providing step can be described as providing all or part of one or more components of the composition, combining these components to form a composition, and then providing the finished composition. Alternatively, the providing step can be described as delivering one or more components of the composition or the entire composition to a high-efficiency applicator by pumping, flowing, moving, or other means. The providing step can be described as a continuous process or a batch process. Similarly, the providing step may include continuous and / or batch sub-steps. In various embodiments, the providing step is described as pumping the composition to the applicator under pressure. The providing step may be one that is understood by those skilled in the art.

[0009] Application of a one-component aqueous coating composition: The method of the present invention also includes the step of applying a coating composition to a substrate through a high-transfer-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-transfer-efficiency applicator. Alternatively, the application step may be further defined as printing. Typically, the coating process is further defined as spraying or printing through, using, or by a high-transfer-efficiency applicator. During the coating process, the loss of volatiles after coating through a high-transfer-efficiency applicator is less than about 0.5% by mass (active ingredient) based on 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% by mass (active ingredient) based on the total mass of the coating composition. Typically, the term "volatiles" is defined as substances that evaporate, resulting in a loss of mass of the coating composition. The loss of volatiles after coating is determined by the increase in solids content (%) after coating compared to before coating, and the solids content in each case is determined by gravimetric measurement according to ASTM D2369-10. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein. In certain embodiments, the coating process generates droplets of the coating composition that collide with the substrate. In various embodiments, at least about 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or more of the coating composition droplets released from a high-efficiency applicator come into contact with the substrate. While not bound by theory, an increase in the number of droplets that come into contact with the substrate relative to the number of droplets that enter the environment without contacting the substrate is thought to improve the efficiency of coating composition application, reduce waste generation, and reduce maintenance. In various embodiments, at least about 99.5, 99.6, 99.7, 99.8, 99.9%, or more of the droplets of the coating composition discharged from a high-transfer-efficiency applicator are monodisperse such 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 a high-transfer-efficiency applicator can direct the monodisperse droplets and / or flow formed toward the substrate, thereby resulting in improved transfer efficiency compared to conventional applicators. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein. In various embodiments, at least about 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or more of the droplets of the coating composition discharged from a high-efficiency applicator remain as single droplets after discharge from the high-efficiency applicator. While not bound by theory, it is believed that satellite droplet formation can be reduced or eliminated by applying the coating composition using a high-efficiency applicator. Satellite droplet formation can be reduced by considering impact velocity and nozzle diameter. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the values ​​and those between them, are obviously conceivable for use herein.

[0010] In various embodiments, the liquid paint is ejected from one or more nozzles of a high transfer efficiency applicator in an engineered / regulated manner to produce a fine stream, which may or may not break into droplets. This stream targets a substrate such that the droplets reach a specific location and, in some cases, form a continuous film or pattern on the target. As a result, in many embodiments, there is substantially no overspray (droplets that miss their target), and a transfer efficiency of nearly 100% is achieved (all of the paint goes to the targeted location on the substrate). As will be appreciated by those skilled in the art, some allowance is provided for the start-up and stop of the high transfer efficiency applicator. This type of device can be described as a drop-on-demand, stream-on-demand, overspray-free, or ultra-high transfer efficiency applicator. These devices are different from spray atomization devices and techniques (where energy such as air energy, hydraulic energy, or centrifugal energy is introduced to produce a partially controlled, random distribution of droplet sizes, trajectories, and velocities, and some additional mechanisms, such as electrostatic and / or shaping air, direct the cloud of paint droplets towards the substrate). With conventional paint spraying, there is always some overspray and loss of transfer efficiency.

[0011] The high transfer efficiency applicator itself may be any known in the art. For example, in various embodiments, the applicator is as described in one or more of U.S. Patent Application Publication No. 20150375258 (A1), U.S. Patent Application Publication No. 20040217202 (A1), U.S. Patent Application Publication No. 2009 / 030493 (A1), U.S. Patent No. 7,824,015 (B2), U.S. Patent No. 8,091,987 (B2), International Publication No. 2018 / 206309 (A1), each of which is incorporated herein by reference in its entirety for use in various non-limiting embodiments. The applicator can alternatively be described as a print head. In one embodiment, a high-transfer-efficiency applicator includes a nozzle with a defined nozzle orifice, which may have a nozzle diameter of about 0.00002 m to about 0.0004 m. In another embodiment, the applicator may be in fluid communication with a reservoir configured to contain a coating composition. For example, the high-transfer-efficiency applicator may be configured to receive the coating composition from the reservoir and to discharge the coating composition onto the substrate through the nozzle orifice to form a coating layer. It should be understood that the ranges for nozzle diameter, viscosity, density, surface tension, and relaxation time may be determined by either those disclosed herein or those known in the art. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein. A high-efficiency applicator may be configured to discharge the coating composition through the nozzle orifice at an impact velocity of about 0.2 m / s to about 20 m / s. Alternatively, a high-efficiency applicator may be configured to discharge the coating composition through the nozzle orifice at an impact velocity of about 0.4 m / s to about 10 m / s. The nozzle orifice may have a nozzle diameter of about 0.00004 m to about 0.00025 m. The coating composition can be discharged from the high-efficiency applicator as droplets having a particle size of at least 10 microns. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein. It is conceivable that one, two, three, or more dispensers may be used in conjunction with each other. Each dispenser may be used independently as described herein or as any known in the art.

[0012] In various embodiments, the high transfer efficiency applicator includes a plurality of nozzles, each of the nozzles defining a nozzle orifice. The plurality of nozzles may be arranged in a linear configuration relative to each other along a first axis. For example, in various embodiments, the plurality of nozzles includes nozzle A and nozzle B adjacent to nozzle A. Nozzle A and nozzle B may be spaced apart from each other by a nozzle distance. The distance from the substrate of the high transfer efficiency applicator can be substantially the same as the nozzle distance. In one embodiment, the plurality of nozzles are spaced apart from each other so as to form a rectangular array, and the plurality of nozzles are configured to alternately discharge the coating composition between adjacent nozzles of the rectangular array to reduce sagging of the coating composition.

[0013] In various embodiments, the high transfer efficiency applicator includes 50 nozzles aligned along the y-axis. However, it should be understood that the applicator can include any number of nozzles. To apply the coating composition to the substrate, each nozzle may be operated independently of the other nozzles. During spraying, the independent operation of the nozzles can control the placement of each droplet of the coating composition on the substrate. Two or more applicators may be combined to form a print head assembly. In certain embodiments, the applicators described above are aligned such that the y-axis of each applicator is parallel to the other y-axes. Further, the nozzles of each applicator may be aligned with each other along the x-axis perpendicular to the y-axis, resulting in the formation of an "array". One nozzle may be equally spaced from other nozzles directly adjacent to the one nozzle with respect to the x-axis and the y-axis. This configuration of the nozzles can be suitable for applying the same coating composition to the substrate by each of the applicators when the print head assembly moves along the x-axis. Without being bound by theory, it is believed that equal spacing of the nozzles with respect to both the x-axis and the y-axis can result in a uniform application of the same coating composition on the substrate. Uniform application of the same coating composition can be suitable for single-color coating, two-tone color coating, etc. Alternatively, the spacing between a set of nozzles along the first y-axis and another set of nozzles may be narrower compared 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 by each high-efficiency applicator. Utilizing different coating compositions within the same high-efficiency applicator assembly may be suitable for logos, designs, markings, stripes, camouflage appearances, and the like. The nozzles of high-efficiency applicators can have any configuration known in the art, such as linear, concave, convex, or circular shapes relative to the substrate. Adjustments to the nozzle configuration may be necessary to facilitate the cooperation of high-efficiency applicators with substrates having irregular configurations, such as those found on vehicles, including mirrors, trim panels, contours, and spoilers.

[0014] A high-efficiency coating unit can be configured to compound individual droplets to form a desired color. The high-efficiency coating unit may include nozzles for applying cyan, magenta, yellow, and black coating compositions. The properties of the coating compositions can be modified to facilitate compounding. Furthermore, a stirring source, such as an air pump or an ultrasonic generator, can be used to further facilitate compounding of the coating compositions. The stirring source may be connected to or separate from the high-efficiency coating unit. The identification of suitable properties for a coating composition for use in a high-efficiency dispensing machine may depend on the properties of the high-efficiency dispensing machine. These properties include, but are not limited to, the nozzle diameter of the high-efficiency dispensing machine, the impact velocity of the coating composition applied by the high-efficiency dispensing machine, the speed of the high-efficiency dispensing machine, the distance of the high-efficiency dispensing machine from the substrate, the droplet size of the coating composition applied by the high-efficiency dispensing machine, the ejection rate of the high-efficiency dispensing machine, and the orientation of the high-efficiency dispensing machine with respect to gravity.

[0015] In 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, and SUVs (sports utility vehicles); trucks; semi-trucks; tractors; motorcycles; trailers; ATVs (all-terrain vehicles); pickup trucks; heavy machinery such as bulldozers, cranes, and earthmoving equipment; aircraft; boats; ships; and other forms of transport. The coating compositions can also be used to coat substrates in industrial applications such as buildings, fences, ceramic tiles, permanent structures, bridges, pipes, and cellulosic materials (e.g., wood, paper, and textiles). The coating compositions can also be used to coat substrates in consumer product applications such as helmets, baseball bats, bicycles, and toys. It should be understood that, as used herein, the term "substrate" may also refer to a coating layer placed on an article that is also considered a substrate. Various substrates may include two or more distinct parts made of different materials. For example, a vehicle may include a body part containing metal and a trim part containing plastic. Since the baking temperature of plastic (80°C) is limited compared to that of 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 incompatibility of the coated parts. A coating composition suitable for plastic substrates can be applied to the plastic substrate using a high-transfer-efficiency applicator after the application and baking of a coating suitable for metal substrates, without the need to mask the substrate or waste any portion of the coating composition by conventional low-transfer-efficiency application methods such as spray atomization. The coating composition suitable for plastic substrates may be applied using a first high-transfer-efficiency applicator, and the coating composition suitable for metal substrates may be applied using a second high-transfer-efficiency applicator. The first and second high-transfer-efficiency applicators may form a high-transfer-efficiency applicator assembly.

[0016] One-component aqueous coating composition: The one-component aqueous coating composition itself is not particularly limited and may be any known in the art containing the components described herein. For example, this composition can be described as a "1K" composition that does not require a curing agent, catalyst, or activator for curing. For example, this composition may be cured by exposure to air.

[0017] Throughout this disclosure, the terms “essentially consisting of” or “essentially consisting of” may describe embodiments that, as measured by those skilled in the art, do not include any alternative monomers, polymers, additives, reactants, fillers, solvents, etc. The term “not including” may describe the element in question as containing less than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% by mass, based on the total mass of the composition. In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein. The composition is a one-component aqueous coating composition having a pH greater than about 7. In various embodiments, the pH is about 7 to about 14, about 7.5 to about 13.5, about 8 to about 13, about 8.5 to about 12.5, about 9 to about 12, about 9.5 to about 11.5, about 10 to about 11, or about 10.5 to about 11. In other embodiments, the pH is about 8 to about 12, about 8 to about 11, about 8 to about 10, or about 8 to about 9. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein.

[0018] In various embodiments, the composition comprises, essentially comprises, or consists of: a resin dispersion comprising latex, polyurethane, or a combination thereof; an optional crosslinking agent; an optional pigment; water; a water-soluble solvent; and at least one rheological control agent selected from alkali-swellable emulsions, layered silicates, and combinations thereof. For example, the term “essentially comprises” may describe embodiments that do not include resins or polymers not described herein or described as optional, crosslinking agents not described herein or described as optional, pigments not described herein or described as optional, water-soluble solvents not described herein or described as optional, or rheological control agents not described herein or described as optional. The terms “does not include” or “is not present” may describe that the composition contains less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% by mass (e.g., mass% (active ingredient)) of the compound based on the total mass of the composition. Alternatively, the terms "does not contain" or "absent from" may indicate that the composition does not contain the compound at all.

[0019] Typically, the mass percentage of any component described herein refers to the mass percentage of the “active ingredient,” and not the total mass percentage of the component, which may include a solvent such as water. However, it is conceivable that the mass percentage may refer to the total weight of the component, which may include any solvent such as water. As will be understood by those skilled in the art, for some components, the mass percentage of the component (active ingredient) and the total mass percentage may be approximately the same, totaling about 100% (active ingredient).

[0020] resin dispersion The composition comprises a resin dispersion which is, contains, essentially consists of, or can consist of latex, polyurethane, or a combination thereof. For example, the term “essentially consists of” can describe embodiments which do not contain latex, polyurethane, or any other polymer known in the art, where “does not contain” is as described above. The dispersion itself is a system in which particles of one distributed material are dispersed in a continuous phase of another material. These two phases may be in the same state of matter or different states of matter. Alternatively, the resin dispersion can be described as an emulsion, which is a homogeneous mixture of two immiscible liquids. In this disclosure, latex may include a polymer which can be a dispersed phase in a liquid continuous phase such as water. Furthermore, polyurethane may be a dispersed phase or a liquid continuous phase. Alternatively, a combination of the above may be used. In the case of an emulsion, the emulsion may be any type known in the art, e.g., an o / w emulsion, a w / o emulsion, etc. In various embodiments, water, a water-soluble co-solvent as 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. In various embodiments, the resin dispersion exists in amounts such as approximately 1 to approximately 50, approximately 1 to approximately 45, approximately 1 to approximately 35, approximately 1 to approximately 30, 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% by mass (active ingredient), based on the total mass of the composition. In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the values ​​and those between them, are obviously conceivable for use herein.

[0021] latex: It is conceivable that 0, 1, 2, 3, 4, 5, or more individual latexes may be used in the 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 produce a dispersion or emulsion of polymer particles in water. The latex is not particularly limited and may be any known in the art. In various embodiments, to form a polymer that can be a dispersed phase and / or a continuous phase, the latex may be a reaction product of one or more of the following monomers, contain such reaction products, be essentially composed of such reaction products, or consist of such reaction products. Such monomers include, but are not limited to, (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, β-carboxyethyl (meth)acrylate, isobutyl (meth)acrylate, alicyclic epoxide, α-epoxide, 2-hydroxyethyl (meth)acrylate, (meth)acrylonitrile, maleic anhydride, itaconic acid, isodecyl (meth)acrylate Examples include caprolates, 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, octadecyl (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. In other embodiments, the latex is one or more of the following: (meth)acrylic urethane (i.e., urethane (meth)acrylate), (meth)acrylic epoxy (i.e., epoxy (meth)acrylate), (meth)acrylic polyester (i.e., polyester (meth)acrylate), (meth)acrylic (meth)acrylic, (meth)acrylic silicone, (meth)acrylic amine, (meth)acrylic amide; (meth)acrylic polysulfone; (meth)acrylic polyester, (meth)acrylic polyether (i.e., polyether (meth)acrylate), vinyl (meth)acrylate, and (meth)acrylic oil; contains, is essentially composed of, or can consist of.

[0022] In one embodiment, the resin dispersion is a polyester-modified acrylic dispersion containing epoxy groups, contains, essentially consists of, or comprises such dispersion. One non-limiting example is commercially available from Allnex under the trade name Daotan® VTW 1686 / 40WA. In another embodiment, the resin dispersion may be a styrene-acrylic latex dispersion, contain such dispersion, consist essentially of such dispersion, or comprise such dispersion. This dispersion may be formed by a two-step emulsion polymerization process. In one embodiment, the resin dispersion may be latex, contain latex, be essentially latex, or consist of latex. In various embodiments, the latex 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 (active ingredient) based on the total mass of the dispersion. In other embodiments, latex (for example, individually or as a whole) is present in amounts 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, and about 16 to about 24% by mass (active ingredient), based on the total mass of the composition. In other embodiments, latex is present (either individually or as a whole) in amounts of about 1 to about 30, about 3 to about 30, about 3 to about 25, 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, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30% by mass (active ingredient), based on the total mass of the composition. In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein.

[0023] Polyurethane: The resin dispersion may be polyurethane, contain polyurethane, be essentially polyurethane, or consist of polyurethane. It is conceivable that 0, 1, 2, 3, 4, 5 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 is a reaction product of a polyol and an isocyanate. In various embodiments, the polyol is selected from polyester polyols, polyether polyols, and polycarbonate polyols. It has also been conceived that polythioether polyols, polycaprolactones, and acrylic polyols may be used. In one embodiment, the polyol is further defined as a polyester polyol. In another embodiment, the polyol is a polyester polyol. In yet another embodiment, the polyol is an aromatic polyester or a polyether polyol. Polyols can be derived from the reaction of an initiator with an alkylene oxide. Examples of initiators include any initiator known in the art. In various embodiments, initiators are 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. The alkylene oxide that reacts with the initiator to form a polyol can be selected from ethylene oxide, propylene oxide, butylene oxide, amylene oxide, tetrahydrofuran, alkylene oxide-tetrahydrofuran mixtures, epihalohydrins, aralkylene oxides, and combinations thereof. In various embodiments, the alkylene oxide is selected from ethylene oxide, propylene oxide, and combinations thereof. However, it is also conceivable that any suitable alkylene oxide known in the art may be used. Polyols may contain organic functional groups selected from carboxyl groups, amine groups, carbamate groups, amide groups, and epoxy groups. Polyols may also contain alkylene oxide caps. When polyols contain alkylene oxide caps, typically, but not limited to, ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and combinations thereof, the alkylene oxide cap is ethylene oxide. More typically, the alkylene oxide cap is ethylene oxide. When polyols contain alkylene oxide caps, the alkylene oxide cap may be 25% by mass or less, more typically 10-20% by mass, based on the total mass of the polyol. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein.

[0024] In various embodiments, the polyol has a number-average molecular weight of 200 to 10,000 g / mol, a hydroxyl value of 10 to 1,000 mgKOH / g, and a nominal number of functional groups of 1 to 8. In various embodiments, the polyol also typically has a viscosity of 20 to 50,000 centipoise at 77°F. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein. Polyols may also include addition polymers dispersed therein. More specifically, polyols may include dispersions or solutions of addition or condensation polymers, i.e., graft polyols. Dispersions may include styrene, acrylonitrile, and combinations thereof. Furthermore, polyols may also include emulsions containing water or any other polar compound known in the art.

[0025] Alternatively, polyurethanes can be described as reaction products of isocyanates with compounds having one or more hydroxyl groups (e.g., monools, diols, triols, tetraols, or polyols). Non-limiting suitable compounds 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. If desired, monohydric alcohols, such as butanol, octanol, lauryl alcohol, and ethoxylated or propoxylated phenols, may also be included along with polyhydric alcohols to control molecular weight. In certain embodiments, low molar polyols, such as polyhydric alcohols, defined empirically and by structural formula, are used to form polyurethanes. Non-limiting 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 other embodiments, oligomer or polymer polyols and / or, for example, corresponding hydroxyl-functionalized polyethers, polyesters, or polycarbonates are used, with number-average molar masses of, for example, up to 8000, or up to 5000, or up to 2000. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein.

[0026] The isocyanate may also react with a hydroxyl-functionalized resin, which is not particularly limited and may be any known in the art. In various embodiments, the resin may be, contain, essentially consist of, or consist of aliphatic or aromatic dicarboxylic acids, polyols, diols, aromatic or aliphatic cyclic anhydrides, and cyclic alcohols. Non-limited examples of suitable 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 cis form but also in trans form and mixtures of both forms. Further non-limiting examples of suitable polycarboxylic acids include aromatic and aliphatic polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, halogenophthalic acid (e.g., 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 be suitable. Combinations of polyols may also be suitable. Suitable polyhydric alcohols, non-limiting examples, 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. Monohydric alcohols, such as butanol, octanol, lauryl alcohol, ethoxylated or propoxylated phenols, may also be included, if desired, along with the polyhydric alcohols. Alternatively, low molar polyols, such as polyhydric alcohols, as defined by empirical and structural formulas, can be used. In other embodiments, oligomers or polymer polyols with a number-average molar mass of, for example, up to 8000, or up to 5000, or up to 2000, and / or, for example, corresponding hydroxyl-functionalized polyethers, polyesters, or polycarbonates are used. In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the values ​​and those between them, are obviously conceivable for use herein.

[0027] Examples of resin dispersions include amines, which may be any type known in the art and may or may not react with isocyanates to form polyureas. Examples of amines, but not limited to, include primary and secondary aliphatic and / or cyclic aliphatic amines. Amines may include, but are not limited to, hydroxyl groups, thiol groups, alkyl groups, cyclic groups, aromatic groups, and combinations thereof, any addition functional groups known in the art. It should be understood that amines may also include amides, and amides may be any type known in the art. Examples of amides include, but are not limited to, polyesteramides obtained from polymers of unsaturated or saturated carboxylic acids or anhydrides and polyfunctional unsaturated or saturated amino alcohols, and combinations thereof.

[0028] Returning to the reference to isocyanates, isocyanates are not particularly limited and may be any of those described herein. In various embodiments, the isocyanate comprises at least one isocyanate, and may comprise two or more isocyanates. The isocyanate may be an aromatic isocyanate, an aliphatic isocyanate, and / or a combination thereof, may comprise, be essentially composed of, or consist of. In one embodiment, the isocyanate is an aromatic isocyanate such as polymer MDI, or comprises an aromatic isocyanate. If the isocyanate is an aromatic isocyanate, or comprises an aromatic isocyanate, the aromatic isocyanate is typically of the formula R'(NCO) z This corresponds to the formula where R' is an aromatic polyvalent organic group and z is an integer corresponding to the valency of R'. Typically, z is at least 2.

[0029] In various embodiments, the 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, and 2,4-toluenediisocyanate. A mixture of annetes and 2,6-toluene diisocyanate, 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 Polymethylene polyphenylene polyisocyanates and 2,4,6-toluene diisocyanates, tetraisocyanates, e.g., 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, corresponding mixtures of these isomers, and combinations thereof, comprising these, essentially consisting of these, or being able to consist of these. If the isocyanate is an aromatic isocyanate or contains an aromatic isocyanate, the isocyanate may be a modified polyvalent aromatic isocyanate, i.e., a product obtained by a chemical reaction of an aromatic diisocyanate and / or an aromatic polyisocyanate, contain such product, essentially consist of such product, or consist of such product. Examples, but not limited to, include polyisocyanates such as urea, biuret, allophanate, carbodiimide, and uretonimine; diisocyanates containing isocyanurates and / or urethane groups; and / or polyisocyanates such as modified diphenylmethane diisocyanate. The urethane groups of the isocyanates may be formed by the reaction of the above-mentioned base isocyanates with low molecular weight diols, triols, dialkylene glycols, trialkylene glycols, polyoxyalkylene glycols, diethylene glycols, dipropylene glycols, polyoxyethylene glycols, polyoxypropylene glycols, polyoxypropylene glycols, and / or polyoxypropylene polyoxyethylene glycols or triols with a number average molecular weight of up to 1500 g / mol, and combinations thereof. The isocyanates may also contain one or more prepolymers containing isocyanate groups. The isocyanates are, contain, essentially consist of, or consist of modified benzene and toluene diisocyanate, used individually, or in reaction products with polyoxyalkylene glycol, diethylene glycol, dipropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene polyoxyethylene glycol, polyesterol, polycaprolactone, and combinations thereof. In various embodiments, the isocyanates are, contain, essentially consist of, or consist of isocyanates 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 compositions may also include stoichiometric or non-stoichiometric reaction products of the above isocyanates. Alternatively, the isocyanate may be a liquid polyisocyanate containing one or more carbodiimide groups, contain the polyisocyanate, essentially consist of the polyisocyanate, or consist of the polyisocyanate. In various embodiments, crude polyisocyanates such as crude toluene diisocyanate obtained by phosgenation of a mixture of toluenediamines, or crude diphenylmethane isocyanate obtained by phosgenation of a crude isocyanate, may also be used.

[0030] Isocyanates are not limited by their NCO content, but typically have an NCO content of 5 to 35% by mass. Measurement of the NCO content in mass percent is carried out by standard chemical titration analysis known to those skilled in the art. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein.

[0031] In further embodiments, non-limiting examples of suitable polyisocyanates include aromatic, aliphatic, or alicyclic di-, tri-, or tetra-isocyanates having isocyanurate structural units, such as isocyanurates of hexamethylene diisocyanate and isocyanurates of isophorone diisocyanate; adducts of two molecules, such as a diisocyanate like hexamethylene diisocyanate and a diol like ethylene glycol; uretidiones of hexamethylene diisocyanate; uretidiones of isophorone diisocyanate or isophorone diisocyanate; and adducts of trimethylolpropane and m-tetramethylxylenediisocyanate. Other polyisocyanates disclosed herein may also be suitable for the production of polyurethanes.

[0032] Other polyurethanes can be produced by first forming an NCO-functional hydrophilic polyurethane prepolymer through 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.

[0033] In other embodiments, the polyurethane may be a polyester-polyurethane polymer, contain the polymer, be essentially composed of the polymer, or consist of the polymer. The polyester in the polyester-polyurethane polymer may 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. Non-limiting examples of suitable 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 cis form but also in trans form and mixtures of both forms. Further non-limiting examples of suitable polycarboxylic acids include aromatic and aliphatic polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, halogenophthalic acid (e.g., 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 be suitable. Combinations of polyols may also be suitable.

[0034] Examples of suitable non-limiting polyesters include branched copolyester polymers. Branched copolyester polymers and methods for producing the same as described in U.S. Patent No. 6,861,495, incorporated herein by reference, may be suitable. Branched structures can be created using monomers having polyfunctional groups such as AxBy (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. Examples of such non-limiting monomers include 2,3-dihydroxypropionic acid, 2,3-dihydroxy2-methylpropionic acid, 2,2-dihydroxypropionic acid, and 2,2-bis(hydroxymethyl)propionic acid. Branched copolyester polymers can be polymerized by conventional methods from a monomer mixture containing a hydroxycarboxylic acid, a hydroxycarboxylic acid lactone, and a chain extender selected from combinations thereof, and one or more branched monomers. Suitable hydroxycarboxylic acids include glycolic acid, lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and hydroxypivalic acid. Suitable lactones include caprolactone, valerolactone, and the corresponding hydroxycarboxylic acid lactones (e.g., 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and hydroxypivalic acid). In certain embodiments, caprolactone can be used. In embodiments, branched copolyester polymers can be produced by polymerizing a monomer mixture containing a chain extender and a highly branched monomer in a single step, or by polymerizing the highly branched monomer first, followed by the chain extender. It should be understood that branched copolyester polymers can be formed from acrylic cores having the above-mentioned extension monomers.

[0035] Polyester polyurethane polymers can be produced from polyester and polyisocyanates. The polyester can be a polymer or oligomeric organic species having at least two hydroxyl functional groups or two mercapto functional groups, or a mixture thereof. Polyesters and polycarbonates having terminal hydroxyl groups can be effectively used as diols. One non-limiting example of a polyester-polyurethane polymer is a polyurethane dispersion resin formed from a linear polyester diol resin (a reaction product of the monomer 1,6-hexanediol, adipic acid, and isophthalic acid) and an 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) when measured using any apparatus known in the art, such as a Malvern Mastersizer. Another non-limiting example of a polyester-polyurethane polymer is a polyurethane dispersion resin 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) when measured using any apparatus known in the art, such as a Malvern Mastersizer.

[0036] In another embodiment, the resin dispersion is a polyurethane dispersion resin formed from a slightly branched polyester polyol and hexamethylene diisocyanate, for example, having a solid content of about 40% by mass, contains the resin, is essentially composed of the resin, or can consist of the resin. In further embodiments, the resin dispersion is a polyurethane dispersion resin formed from a linear polyester diol resin (for example, a reaction product of the monomer 1,6-hexanediol, adipic acid, and isophthalic acid) and an isophorone diisocyanate, for example, having a solid content of about 35% by mass, contains the resin, is essentially composed of the resin, or can consist of the resin. In another embodiment, the polyurethane is selected from: those formed from a branched polyester polyol and hexamethylene diisocyanate; those formed from a linear polyester diol resin and isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; those formed from a linear polycarbonate-polyester polyol and isophorone diisocyanate; polyester-polyurethane polymers; and combinations thereof. In another embodiment, the resin dispersion is a polyurethane dispersion resin formed from a linear polycarbonate-polyester polyol and isophorone diisocyanate, contains the resin, is essentially composed of the resin, or can consist of the resin. In yet another embodiment, the resin dispersion is a polyester-polyurethane polymer traded as Bayhydrol® U241, commercially available from Covestro AG (Leverkusen, Germany), contains the polymer, is essentially composed of the polymer, or can consist of the polymer.

[0037] In one embodiment, the resin dispersion may be polyurethane, contain polyurethane, be essentially polyurethane, or consist of polyurethane. In various embodiments, 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 (active ingredient), based on the total mass of the dispersion. In various embodiments, this amount is about 30 to about 50, for example, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50% by mass (active ingredient), based on the total mass of the dispersion. In other embodiments, polyurethane (for example, individually or as a whole) is present in amounts 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, and about 16 to about 24% by mass (active ingredient), based on the total mass of the composition. In various embodiments, this amount is about 1 to about 15, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% by mass (active ingredient), based on the total mass of the composition. In other embodiments, polyurethane is present (either individually or as a whole) in an amount 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 (active ingredient), based on the total mass of the composition. In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the values ​​and those between them, are obviously conceivable for use herein.

[0038] Optional crosslinking agent: The coating composition also includes an optional crosslinking agent. In various embodiments, this optional crosslinking agent may be any melamine crosslinking agent known in the art, contain such crosslinking agent, consist essentially of such crosslinking agent, or consist of such crosslinking agent.

[0039] Melamine resins may be partially or completely etherified with one or more alcohols such as methanol or butanol. A non-limiting example is hexamethoxymethylmelamine. Non-limiting examples of suitable melamine resins include monomeric melamines, polymeric melamine-formaldehyde resins, or combinations thereof. Monomeric melamines include low molecular weight melamines containing, on average, three or more methylol groups etherified with C1-C5 monohydric alcohols such as methanol, n-butanol, or isobutanol per triazine nucleus, with an average degree of condensation of up to about 2, in a particular embodiment ranging from about 1.1 to about 1.8, and a mononuclear ratio of about 50% by mass 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. Many of these suitable monomeric melamines are commercially available. For example, Cytec Industries Inc. (West Patterson, NJ) supplies 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 monomer melamines. Preferred polymer melamines include high-amino (partially alkylated, -N, -H) known as Resimene® BMP5503 (molecular weight 690, polydispersity 1.98, 56% butyl, 44% amino) supplied by Solutia Inc. (St. Louis, Mo), or Cymel® 1158 provided by Cytec Industries Inc. (West Patterson, NJ). Cytec Industries Inc. also supplies Cymel® 1130, 80% solids (degree of polymerization 2.5), and Cymel® 1133 (48% methyl, 4% methylol, and 48% butyl), both of which are polymerized melamines.In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the values ​​and those between them, are obviously conceivable for use herein.

[0040] The coating composition may contain two or more types of crosslinking agents having the same or different crosslinking functional groups. Typical crosslinking functional groups include hydroxyl, thiol, isocyanate, thioisocyanate, acetoacetoxy, carbonyl, primary amine, secondary amine, epoxy, anhydride, ketimine, aldimine, orthoester, orthocarbonate, cyclic amide, or combinations thereof. In various embodiments, an optional crosslinking agent, such as a melamine crosslinking agent, is used in an amount of about 10 to about 30%, about 12 to about 25%, or about 15% to about 20% by mass (active ingredient), based on the total mass of the composition. In other embodiments, this amount is about 10 to about 25%, about 10 to about 10%, about 10 to about 15%, about 15 to about 30%, about 15 to about 25%, about 20 to about 30%, or about 20 to about 25% by mass (active ingredient), based on the total mass of the composition. In other embodiments, the crosslinking agent 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 (active ingredient), based on the total mass of the composition. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein. In exemplary embodiments, the coating composition comprises a melamine-formaldehyde resin traded as Cymel® 303, which is commercially available from Cytec Industries Inc. (West Patterson, NJ).

[0041] Optional isocyanate crosslinking agents: In various embodiments, blocked isocyanate crosslinkers are not used, and melamine crosslinkers are used instead. Alternatively, both blocked isocyanate crosslinkers and melamine crosslinkers can be used. Alternatively, melamine crosslinkers can be used, eliminating the blocked isocyanate crosslinkers. The composition may or may not contain a blocked isocyanate crosslinking agent. This blocked isocyanate crosslinking agent is not particularly limited and may be any known in the art, such as those described above. In various embodiments, this blocked isocyanate crosslinking agent may be, contain, essentially consist of, or consist of one or more isocyanates, for example, aromatic, aliphatic or alicyclic di-, tri- or tetra-isocyanates, such as polyisocyanates having isocyanurate structural units, such as isocyanurate of hexamethylene diisocyanate and isocyanurate of isophorone diisocyanate; adducts of two molecules of a diisocyanate such as hexamethylene diisocyanate and a diol such as ethylene glycol; uretidione of hexamethylene diisocyanate; uretidione of isophorone diisocyanate or isophorone diisocyanate; or adducts of trimethylolpropane and m-tetramethylxylenediisocyanate. 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 isocyanates with polyhydric alcohols, as well as mixtures thereof, can be used. These can react with polyols, such as OH group-containing polyesters, polyethers, acrylates, and polyurethanes, as well as mixtures thereof, and the polyols may be solvent-based, solvent-free, or water-dilutable. This blocked isocyanate crosslinking agent can be used in any amount, for example, the amounts described above with respect to other optional crosslinking agents.

[0042] Optional pigments: The coating composition may also include optional pigments. Therefore, the composition may or may not contain pigments. Any pigment known in the art for use in coating compositions may be used in the coating composition. Non-limiting examples of suitable pigments include effect pigments including metal oxides, metal hydroxides, metal flakes, chromates such as lead chromate, sulfides, sulfates, carbonates, carbon black, silica, talc, China clay, phthalocyanine blue and green, organic red, organic maroon, pearlescent pigments, other organic pigments and dyes, and combinations thereof. Chromate-free pigments such as barium metaborate, zinc phosphate, aluminum triphosphate, and combinations thereof may also be used as needed. Further non-limiting examples of suitable effect pigments include luminous aluminum flakes, ultrafine aluminum flakes, medium-particle aluminum flakes, and luminous medium-coarse aluminum flakes; mica flakes coated with titanium dioxide pigment, also known as pearl pigments; and combinations thereof. Suitable coloring pigments, though not limited to these, include titanium dioxide, zinc oxide, iron oxide, carbon black, monoazo red toner, red iron oxide, quinacridone maroon, clear red iron oxide, dioxazine carbazole violet, iron blue, indanthron blue, chromium titanate, titanium yellow, monoazo permanent orange, ferrite yellow, monoazo benzimidazolone yellow, clear yellow iron oxide, isoindoline yellow, tetrachloroisoindoline yellow, antantron orange, lead chromate yellow, phthalocyanine green, quinacridone red, perylene maroon, quinacridone violet, pre-darkened chromium yellow, thioindigo red, clear red iron oxide chip, molybdate orange, molybdate oren red, and combinations thereof.

[0043] Pigments can also be described as extender pigments. Extender pigments are generally used to replace high-cost pigments in coating compositions, but the extender pigments intended herein may increase the shear viscosity of the coating composition compared to coating compositions without extender pigments. An increase in the shear viscosity of the coating composition can improve the suitability of the coating composition for coating onto substrates using high-transfer-efficiency applicators. Extender pigments may have a particle size of about 0.01 to about 44 microns (e.g., Dv50 measured using a Malvern Mastersizer). Extender pigments may have a variety of configurations, including but not limited to nodular, platelet, needle-like, and fibrous forms. Non-limiting examples of suitable extender pigments include chalk, barite, amorphous silica, fumed silica, diatom silica, china 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, both in whole and in part, including the values ​​and those between them, are obviously conceivable for use herein. The coating composition may contain an extender pigment 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 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 (active ingredient), based on the total mass of the composition. In other embodiments, optional pigments are 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 (active ingredient), based on the total mass of the composition. In other embodiments, optional pigments are 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% by mass (active ingredient), based on the total mass of the composition. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein. In certain embodiments, the coating composition comprises 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 the case in which talc is included as an extender pigment. In various embodiments, the optional pigment is selected from Pigment Yellow 213, PY151, PY93, PY83, Pigment Red 122, PR168, PR254, PR179, 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.

[0044] water The composition also contains water. In various embodiments, the amount of water used is about 1 to about 99, 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 (active ingredient), based on the total mass of the composition. In other embodiments, water is present in an amount of about 40 to about 90, about 45 to about 85, about 50 to about 80, about 55 to about 75, about 60 to about 70, or about 65 to about 70% by mass (active ingredient), based on the total mass of the composition. The above amounts of water may refer to the total amount of water in the composition, or to the amount of water added to the composition independently of the water contained in the composition (e.g., dispersion, solvent, etc.). In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the values ​​and those between them, are obviously conceivable for use herein.

[0045] water-soluble solvent The composition also includes a water-soluble solvent, which is not particularly limited and may be any solvent known in the art. In various embodiments, the water-soluble solvent may be 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, methyldiethanolamine, methyl isocyanide, n-methyl-2-pyrrolidone, propanoic acid, propylene glycol, pyridine, tetrahydrofuran, triethylene glycol, glycol ethers (such as ethylene glycol monobutyl ether and diethylene glycol monobutyl ether), and 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 various embodiments, the water-soluble solvent is present in an amount of about 1 to about 99, 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 (active ingredient) based on the total mass of the composition. In other embodiments, the water-soluble solvent is present in amounts such as approximately 1 to approximately 50, approximately 1 to approximately 45, approximately 1 to approximately 35, approximately 1 to approximately 30, 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% by mass (active ingredient), based on the total mass of the composition. In other embodiments, the water-soluble solvent is present in amounts of about 1 to about 25, about 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% by mass (active ingredient), based on the total mass of the composition. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein.

[0046] at least one rheological regulator The composition also includes at least one rheology modifier. For example, a rheology modifier can be used that can increase the rheology of the coating composition compared to a coating composition without a rheology modifier. An increase in the rheology of the coating composition can improve the suitability of the coating composition for coating onto a substrate using a high-transfer-efficiency coater. In this disclosure, at least one rheology modifier is used to reduce and / or minimize sag, as described in more detail below. In various embodiments, at least one rheology control agent is present in quantities of approximately 0.01 to 20, 0.1 to 20, 0.1 to 15, 0.1 to 10, 0.1 to 5, 0.1 to 1, 0.1 to 0.9, 0.2 to 0.8, 0.3 to 0.7, 0.4 to 0.6, and 0.5 to 0.6 based on the total mass of the composition. , are present in amounts of approximately 0.5 to approximately 10, approximately 1 to approximately 9.5, approximately 1.5 to approximately 9, approximately 2 to approximately 8.5, approximately 2.5 to approximately 8, approximately 3 to approximately 7.5, approximately 3.5 to approximately 7, approximately 4 to approximately 6.5, approximately 4.5 to approximately 6, approximately 5 to approximately 5.5, or approximately 0.01, 0.02, 0.03…0.1, 0.2, 0.3…1, 1.1, 1.2… up to a maximum of approximately 20% by mass (active ingredient). In various embodiments, at least one rheology control agent is present in amounts of approximately 0.01 to approximately 7. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein. At least one rheology control agent is selected from alkali-swelling emulsions, layered silicates, and combinations thereof. In various embodiments, at least one rheology control agent is an alkali-swelling emulsion, a layered silicate, and a combination thereof, includes, essentially consists of, or comprises these. For example, the term essentially consists of may describe embodiments that do not include any alternative rheology control agent. In one embodiment, at least one rheology control agent includes an alkali-swelling emulsion but does not include a layered silicate. In another embodiment, at least one rheology control agent includes a layered silicate but does not include an alkali-swelling emulsion. In yet another embodiment, both alkali-swelling emulsions and layered silicates are used.

[0047] Alkali-swelling emulsions (ASEs) are not particularly limited and may be any known in the art. ASEs may include carboxyl-containing copolymers prepared by addition polymerization of ethylenically unsaturated monomers, which thicken aqueous media by swelling or solubilization upon neutralization. These ASEs can be broadly classified into either conventional (possibly non-associative) or associative types based on their chemical structure and main thickening mechanism. ASEs are typically copolymers of methacrylic acid and water-insoluble esters of methacrylic acid. ASEs typically thicken only in a neutralized (pH > 7) state using an ionic repulsion mechanism between various carboxylate groups supported on the polymer chain. Typically, ASEs are prepared in the form of direct emulsions of alkali-swelling polymers in water, with active ingredient content varying from about 10% to about 45% of the total mass. In one embodiment, the ASE is an acrylic polymer emulsion. In various embodiments, the alkali swelling emulsion is present in amounts of about 1 to about 99, 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 (active ingredient), based on the total mass of at least one rheology control agent. In other embodiments, the alkali-swelling emulsion is present in amounts of approximately 0.1 to 20, 0.1 to 15, 0.1 to 10, 0.1 to 5, 0.1 to 1, 0.1 to 0.9, 0.2 to 0.8, 0.3 to 0.7, 0.4 to 0.6, 0.5 to 0.6, 0.5 to 10, 1 to 9.5, 1.5 to 9, 2 to 8.5, 2.5 to 8, 3 to 7.5, 3.5 to 7, 4 to 6.5, 4.5 to 6, 5 to 5.5, or approximately 0.1, 0.2, 0.3…1, 1.1, 1.2…up to a maximum of approximately 20% by mass (active ingredient), based on the total mass of the composition. It is conceivable that the alkali swelling emulsion may not be used at all. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein.

[0048] Referring to phyllosilicates here, this compound is not particularly limited and may be any one known in the art. Phyllosilicates typically include or consist of planar layers of octahedra tetrahedrally bonded above and below with a characteristic repeat distance between the t-o-t layers. For example, phyllosilicates can be classified into 7 Å layer silicates, 10 Å layer silicates, and chlorites based on their repeat distance. Minerals within the above classification can be further divided into dioctahedral and trioctahedral. Examples of 7 Å layer silicates include kaolinite Al4(Si4O 10 )(OH)8 (dioctahedral) and serpentine Mg6(Si4O 10 )(OH)8 (trioctahedral). 10 Å layer silicates are usually formed as weathering products and can exhibit perfect planar cleavage (minerals) known as mica. This classification may also include clay minerals. Chlorites include dioctahedral and trioctahedral Mg5Al(AlSi3O 10 )(OH)8. In various embodiments, the phyllosilicate includes or consists of a two-dimensional (2D) layer of two molten silicate tetrahedral sheets having dimensions of about 1 nm in thickness and 100 nm to 1000 nm in length, and an edge-sharing octahedral sheet of metal atoms such as Mg or Al. The gap between the two sheets is called a gallery and is usually filled with cations that neutralize the excess negative charge. Stacking the sheets creates a regular van der Waals gap between the layers. Isomorphic substitution within the layer (e.g., substitution of Al 3+ by Mg 2+ or Fe 2+ , or substitution of Mg 2+ by Li 1+ ) generates a negative charge, which is neutralized by alkali and alkaline earth cations inside the gap. Phyllosilicates have two types of structures: tetrahedral substitution and octahedral substitution. In the case of tetrahedral substitution phyllosilicates, since the negative charge is present on the surface of the silicate layer, the polymer matrix can interact with the negative charge more easily than in the case of octahedral substitution materials. In various embodiments, MMT, hectorite, and saponite are commonly used phyllosilicates. In certain embodiments, a laponite propylene glycol solution is used, comprising a synthetic layered silicate, water, and polypropylene glycol. The synthetic layered silicate is commercially available from Altana AG (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 1 to about 99, 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 (active ingredient), based on the total mass of at least one rheology control agent. In other embodiments, the layered silicate is present in amounts of approximately 0.1 to 20, approximately 0.1 to 15, approximately 0.1 to 10, approximately 0.1 to 5, approximately 0.1 to 1, approximately 0.1 to 0.9, approximately 0.2 to 0.8, approximately 0.3 to 0.7, approximately 0.4 to 0.6, approximately 0.5 to 0.6, approximately 0.5 to 10, approximately 1 to 9.5, approximately 1.5 to 9, approximately 2 to 8.5, approximately 2.5 to 8, approximately 3 to 7.5, approximately 3.5 to 7, approximately 4 to 6.5, approximately 4.5 to 6, approximately 5 to 5.5, approximately 0.1 to 0.6, or approximately 0.1, 0.2, 0.3...1, 1.1, 1.2... up to a maximum of approximately 20% by mass (active ingredient), based on the total mass of the composition. It is conceivable that layered silicates may not be used at all. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein.

[0049] In various embodiments, HEUR, i.e., hydrophobic modified ethylene oxide-urethane block copolymer, may be used. HEUR may be used with or without one or both of the following: alkali-swellable emulsion, layered silicate, or a combination thereof. HEUR is not particularly limited and may be any known in the art. For example, polyalkylene glycol may be reacted with a hydrophobic capping agent or hydrophobic difunctional substance or a combination thereof, and a diisocyanate in stoichiometric excess relative to the total moles of isocyanate-reactive groups of the polyalkylene glycol and the capping agent or hydrophobic difunctional substance or a combination thereof, to form an isocyanate-functional polyurethane prepolymer. This prepolymer may then be converted to a hydrophobic modified alkylene oxide poly(urethane-urea-allophanate), which may further include additional functionalities such as amine functionalities. However, the present disclosure is not limited to such HEUR, and any known in the art may be used. For example, block copolymers can be formed using any OH-functionalized compound and any isocyanate compound described herein.

[0050] Additional optional components: 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 include, but are not limited to, dispersants, antioxidants, UV stabilizers and absorbers, surfactants, wetting agents, leveling agents, defoamers, anti-denting agents, or combinations thereof. In embodiments, the coating composition is suitable for application to substrates using a high-transfer-efficiency applicator, provided that the coating composition contains specific components and / or specific components in specific amounts / ratios.

[0051] In various embodiments, the coating composition may further contain dyes. Non-limiting examples of suitable dyes include triphenylmethane dyes, anthraquinone dyes, xanthene and related dyes, azo dyes, reactive dyes, phthalocyanine compounds, quinacridone compounds, and fluorescent whitening agents, and combinations thereof. The coating composition may contain the dye in an amount of about 0.01 to about 5, or about 0.05 to about 1, or about 0.05 to about 0.5% by mass, based on the total mass of the coating composition. In certain embodiments, the coating composition contains a 10% black dye solution, e.g., Sol.Orasol Negro RL. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein.

[0052] In various embodiments, the coating composition may further contain additional rheological modifiers in addition to those described above. A number of different types of rheological modifiers can be used in the coating composition. Non-limiting examples of suitable rheological modifiers include urea compounds, acrylic alkali emulsions, and combinations thereof. The coating composition may contain additional rheological modifiers in an amount of about 0.01 to about 5, or about 0.05 to about 1, or about 0.05 to about 0.5% by mass, based on the total mass of the coating composition. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein.

[0053] The term “binder” refers to the film-forming elements of a coating composition. Typically, a binder may include polymers, oligomers, or combinations thereof that are essential for forming a coating with desired properties such as hardness, protection, and adhesion. Additional components such as carriers, pigments, catalysts, rheology modifiers, antioxidants, UV stabilizers and absorbers, leveling agents, defoamers, anti-denting agents, or other conventional additives may not be included in the term “binder” unless any of these additional components are film-forming elements of the coating composition. One or more of these additional components may be included in the coating composition. In certain embodiments, the binder includes polymers. A coating composition may contain the binder in an amount of about 5 to about 70% by mass, or about 10 to about 50% by mass, or about 15 to about 25% by mass, based on the total mass of the coating composition. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein.

[0054] 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 at ambient temperature or high temperature. Ambient temperature typically refers to a temperature 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 octoate, aluminum titanate, aluminum chelate, zirconium chelate, hydrocarbon phosphonium halides, e.g., ethyltriphenylphosphonium iodide, and other such phosphonium salts, as well as 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, the acid catalyst may include, for example, acetic acid, formic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, p-toluenesulfonic acid, phosphoric acid, or a combination thereof. The coating composition may contain the catalyst in an amount of about 0.01 to about 5, or about 0.05 to about 1, or about 0.05 to about 0.5% by mass, based on the total mass of the coating composition. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein.

[0055] 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, UV blockers, UV quenchers, and hindered amine light stabilizers. Antioxidants can also be added to the coating composition. Typical UV stabilizers include benzophenone, triazole, triazine, benzoate, hindered amine, and mixtures thereof. All of these can be hindered amine light stabilizer formulations such as Tinuvin® 328 and Tinuvin® 123, which are commercially available from Ciba Specialty Chemicals (Tarrytown, New York) under the trade name Tinuvin®. Non-limiting examples of suitable UV absorbers include hydroxyphenylbenzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amyl-phenyl)-2H-benzotriazole, 2[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, reaction products of 2-(2-hydroxy-3-tert-butyl-5-methylpropionate)-2H-benzotriazole with polyethylene ether glycol having a mass-average molecular weight of 300, and 2-(2-hydroxy-3-tert-butyl-5-iso-octylpropionate)-2H-benzotriazole; hydroxyphenyl s-triazines, for example, 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, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and 2-hydroxy-4-dodecyloxybenzophenone. 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, N,N'”-[1,2-ethanol Dibutylbis[[[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-tetramethylbutyl] [(methylpiperidinyl)-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-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[ Examples include 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-diazardispiro(5.1.11.2)henicosan-20-yl)propionate.

[0056] Examples of suitable antioxidants that are not limited 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 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7~C9 branched alkyl esters of benzenepropanoic acid. In certain embodiments, the antioxidant may be a hydroperoxide decomposer, such as Sanko® HCA (9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide), triphenyl phosphate, and other organophosphorus compounds, such as Irgafos® TNPP from Ciba Specialty Chemicals, Irgafos® 168 from Ciba Specialty Chemicals, Ultranox® 626 from GE Specialty Chemicals, Mark PEP-6 from Asahi Denka, Mark HP-10 from Asahi Denka, Irgafos® P-EPQ from Ciba Specialty Chemicals, Ethanox 398 from Albemarle, Weston 618 from GE Specialty Chemicals, Irgafos® 12 from Ciba Specialty Chemicals, Irgafos® 38 from Ciba Specialty Chemicals, and GE Specialty Examples include Ultranox® 641 from Chemicals and Doverphos® S-9228 from Dover Chemicals.

[0057] The coating composition may include other additives known in the art, such as wetting agents, leveling agents and flow control agents, for example, Resiflow® S (polybutyl acrylate), BYK® 320 and 325 (high molecular weight polyacrylate), BYK® 347 (polyether-modified siloxane), leveling agents based on (meth)acrylic homopolymers; rheology modifiers; thickeners, such as partially crosslinked polycarboxylic acids or polyurethanes; and defoamers. Other additives may be used in conventional amounts well known to those skilled in the art. In 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, therefore, 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.

[0058] The coating composition is not particularly limited in terms of solids content and may have a solids content of about 5 to about 90, or 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, based on 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, based on the mass of the composition. The solids content can be determined according to ASTM D2369-10. In certain embodiments, since the coating composition is not atomized using a conventional spraying device, a high solids content may be desirable for the coating composition. In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein.

[0059] In one embodiment, ASE is an acrylic alkali emulsion. In another embodiment, the layered silicate is provided as a solution of water and polypropylene glycol. In another embodiment, a polyester-modified acrylic dispersion containing epoxy groups is used. In another embodiment, a styrene-acrylic latex dispersion formed by a two-step emulsion polymerization process is used. This dispersion may have, for example, 46% by mass solids, a Tg of about -7°C, an acid value of about 12, and a hydroxyl value of about 7. In another embodiment, the polyurethane dispersion resin is formed from a slightly branched polyester polyol and a hexamethylene diisocyanate. In another embodiment, the polyurethane dispersion resin is formed from a linear polyester diol resin (e.g., a reaction product of the monomer 1,6-hexanediol, adipic acid, and isophthalic acid) and an isophorone diisocyanate. In another embodiment, the polyurethane dispersion resin is formed from a linear polycarbonate-polyester polyol and an isophorone diisocyanate. In another embodiment, hexa(methoxymethyl)melamine (HMMM) melamine formaldehyde resin is used. In yet another embodiment, high iminomelamine formaldehyde resin is used. In yet another embodiment, a dispersion of amorphous carbon black pigment is used. In yet another embodiment, a dispersion of finely powdered talc-based pigment is used.

[0060] Physical properties: In various embodiments, the coating compositions have a viscosity of about 20 to about 100 cps at a shear rate of 1000 sec⁻¹, as measured by the conical or parallel plate method using ASTM 7867-13. For example, compositions may have viscosities of about 25 to about 95, about 30 to about 90, about 35 to about 85, about 40 to about 80, about 45 to about 75, about 50 to about 70, about 55 to about 65, or about 60 to about 65 cps. In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein. In other embodiments, the coating composition has a wet film thickness of at least about 20, 25, 30 microns or more, without visible sag, when measured at about 45 degrees. For example, this wet film thickness may be about 30 to about 150 microns, or about 40 to about 120 microns, without visible sag, when measured at about 45 degrees. In other embodiments, the wet film thickness may be about 35 to about 145, about 40 to about 140, about 45 to about 135, about 40 to about 130, about 45 to about 125, about 50 to about 120, about 55 to about 115, about 60 to about 110, about 65 to about 105, about 70 to about 100, about 75 to about 95, about 80 to about 90, or about 85 to about 90 microns. In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the values ​​and those between them, are obviously conceivable for use herein.

[0061] The following procedure is commonly used to evaluate sag. Orient the substrate panel horizontally before applying the coating; Using a Rea Jet DOD 2.0 32-nozzle printhead, four stripes of coating composition with different thicknesses, each 40 mm wide, are applied to a horizontal substrate panel. After application of the composition, the panel is tilted at an angle of approximately 45 degrees from the horizontal. Maintaining the same panel angle, the panel is baked at approximately 140°C for approximately 30 minutes after approximately 5 minutes at room temperature. If sag is present, it is visually evaluated using the droplet at the bottom edge of the coating as evidence. In various embodiments, sag is measured using ASTM D4400-18. Typically, both the ASTM D4400 method and the printing method are performed at a 45-degree angle. In one embodiment, the following are used: ASTM D4400-18, ASM-2 and ASM-1 Anti-Sag meters. On a coil-coated panel, bake at 45 degrees, 4 minutes at room temperature, and 30 minutes at 140 degrees.

[0062] The compositions may also have yield stresses greater than approximately 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or 2.5. In various embodiments, the yield strength is approximately 0.1 to approximately 2.5, approximately 0.5 to approximately 2.5, approximately 1 to approximately 2.5, approximately 1.5 to approximately 2.5, approximately 2 to approximately 2.5, approximately 0.5 to approximately 2, approximately 0.5 to approximately 1.5, approximately 0.5 to approximately 1, approximately 1 to approximately 2, approximately 1 to approximately 1.5, or approximately 1.5 to approximately 2 Pa. Typically, the yield stress is measured using a controlled stress sweep test on a cone-disk rheometer. The sample is sheared at shear stresses and shear rates from 0.01 Pa to 10,000 Pa, and its viscosity is measured. The viscosity data and first derivative are plotted against the shear stress on a log-log scale. The yield stress value is determined by the stress at which the first derivative is lowest (i.e., the negative slope of the viscosity-stress curve is maximum). In various non-limiting embodiments, all values ​​and ranges of values, both whole and in part, including the above values ​​and those between them, are obviously conceivable for use herein.

[0063] In various embodiments, the coating composition has a viscosity of about 400 to about 10,000, about 400 to about 1,000, about 500 to about 900, about 600 to about 800, about 600 to about 700, about 1,000 to about 9,500, about 1,500 to about 9,000, about 2,000 to about 8,500, about 2,500 to about 8,000, about 3,000 to about 7,500, about 3,500 to about 7,000, about 4,000 to about 6,500, about 4,500 to about 6,000, or about 5,000 to about 5,500 mPa·s at 0.1s⁻¹, as measured using ASTM D7867. In other embodiments, the coating composition has a viscosity of about 20 to about 100, about 25 to about 95, about 30 to about 90, about 35 to about 85, about 40 to about 80, about 45 to about 75, about 50 to about 70, about 55 to about 60, or about 60 to about 65 mPa·s at 1000 s⁻¹, as measured using ASTM D7867. In other embodiments, the coating composition has a viscosity of about 50 to about 1,000, about 100 to about 950, about 150 to about 900, about 200 to about 850, about 250 to about 800, about 300 to about 750, about 350 to about 700, about 400 to about 650, about 450 to about 600, or about 500 to about 550 mPa·s at 1 s⁻¹, after 5 seconds of shearing for 10,000 s⁻¹, as measured using ASTM D7867. In various non-limiting embodiments, all values ​​and ranges of values, both in whole and in part, including the above values ​​and those in between, are obviously conceivable for use herein.

[0064] Curing of the coating composition: In various embodiments, the method further includes a step of curing the coating composition on a substrate. For example, after the curing step, the coating composition may be free from visible defects due to incomplete flow and leveling from individual nozzles.

[0065] Additional embodiments: In one embodiment, the resin dispersion is present in an amount of about 15 to about 30% by mass based on the total mass of the composition; the crosslinking agent is melamine, present in an amount of about 2 to about 7% by mass based on the total mass of the composition; the pigment is present in an amount of about 0.1 to about 20% by mass based on the total mass of the composition; water is present in an amount of about 15 to about 70% by mass based on the total mass of the composition; the water-soluble solvent is present in a total amount of about 5 to about 20% by mass based on the total mass of the composition; at least one rheology control agent is present in an amount of about 0.01 to about 5% by mass based on the total mass of the composition; the coating composition has a viscosity of about 35 to about 95 cPs at a shear rate of 1000 sec⁻¹ when measured by the conical or parallel plate method using ASTM 7867-13, and the coating composition is ASTM Measurements using D4400-18 showed that when measured at approximately 45 degrees Celsius, the wet film thickness was at least approximately 20 microns without any visible sag.

[0066] In another embodiment, the resin dispersion comprises: an acrylic latex dispersion, which is an epoxy-group-containing polyester-modified acrylic dispersion, present in an amount of about 19 to about 22% by mass based on the total mass of the composition; a first polyurethane dispersion, which is present in an amount of about 4.5 to about 5.5% by mass based on the total mass of the composition, and is formed from a branched polyester polyol and a hexamethylene diisocyanate; and a second polyurethane dispersion, which is present in an amount of about 3 to about 4% by mass based on the total mass of the composition, and is formed from a linear polyester diol resin and an isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; and the total mass of the composition The composition comprises a third polyurethane dispersion formed from a linear polycarbonate-polyester polyol and isophorone diisocyanate, present in an amount of approximately 1 to approximately 2% by mass based on the total mass of the composition; a crosslinking agent is melamine, present in an amount of approximately 3.9 to approximately 4.6% by mass based on the total mass of the composition; a pigment is an emulsion, present in an amount of approximately 8 to approximately 16% by mass based on the total mass of the composition; water is present in an amount of approximately 35 to approximately 45% by mass based on the total mass of the composition; a water-soluble solvent is butanol, present in an amount of approximately 6 to approximately 7% by mass based on the total mass of the composition; at least one rheology control agent is an acrylic copolymer emulsion, present in an amount of approximately 4 to approximately 5% by mass based on the total mass of the composition, which is an alkali-swelling emulsion, and the composition does not contain layered silicates; the coating composition conforms to ASTM When measured using the conical plate or parallel plate method with 7867-13, the viscosity is approximately 35 to approximately 70 cps at a shear rate of 1000 sec⁻¹, and the coating composition has a wet film thickness of at least approximately 20 microns without visible sag when measured at approximately 45 degrees using ASTM D4400-18.

[0067] In another embodiment, the resin dispersion comprises: an acrylic latex dispersion, which is a styrene-acrylic latex dispersion, present in an amount of about 28 to about 29% by mass based on the total mass of the composition; an acrylic latex dispersion, which is a styrene-acrylic latex dispersion, present in an amount of about 8 to about 9% by mass based on the total mass of the composition; a first polyurethane dispersion, which is formed from a branched polyester polyol and a hexamethylene diisocyanate, present in an amount of about 12 to about 13% by mass based on the total mass of the composition; and a second polyurethane dispersion, which is formed from a linear polyester diol resin and an isophorone diisocyanate, present in an amount of about 8 to about 9% by mass based on the total mass of the composition, wherein the linear polyester diol is 1,6-hexanediol and adipine The composition comprises an acid and a second polyurethane dispersion which is a reaction product of isophthalic acid; the crosslinking agent is melamine, present in an amount of about 2 to about 3% by mass based on the total mass of the composition; the pigment is an emulsion, present in an amount of about 5 to about 6% by mass based on the total mass of the composition; water is present in an amount of about 40 to about 50% by mass based on the total mass of the composition; the water-soluble solvent is butanol, present in an amount of about 7 to about 8% by mass based on the total mass of the composition; at least one rheology control agent is an acrylic copolymer emulsion, present in an amount of about 2.5% by mass based on the total mass of the composition, which is an alkali-swelling emulsion, and the composition does not contain layered silicates; the coating composition conforms to ASTM When measured using the conical plate or parallel plate method with 7867-13, the coating composition has a viscosity of approximately 90 to approximately 95 cps at a shear rate of 1000 sec⁻¹, a yield stress of less than approximately 0.5 Pa, and, when measured at approximately 45 degrees using ASTM D4400-18, the coating composition has a wett film thickness of at least approximately 20 microns without visible sag.

[0068] In another embodiment, the resin dispersion comprises: an acrylic latex dispersion, which is an epoxy-group-containing polyester-modified acrylic dispersion, present in an amount of about 19 to about 20% by mass based on the total mass of the composition; a first polyurethane dispersion, which is present in an amount of about 4 to about 5% by mass based on the total mass of the composition, and is formed from a branched polyester polyol and a hexamethylene diisocyanate; and a second polyurethane dispersion, which is present in an amount of about 3 to about 4% by mass based on the total mass of the composition, and is formed from a linear polyester diol resin and an isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; and a second polyurethane dispersion, which is present in an amount of about 1 to about 2% by mass based on the total mass of the composition. The composition comprises a third polyurethane dispersion, present in % of a linear polycarbonate-polyester polyol and isophorone diisocyanate; a crosslinking agent, melamine, present in about 3 to about 4% by mass based on the total mass of the composition; a pigment, an emulsion, present in about 15 to about 17% by mass based on the total mass of the composition; water, present in about 30 to about 35% by mass based on the total mass of the composition; a water-soluble solvent, butanol, present in about 6 to about 7% by mass based on the total mass of the composition; at least one rheology control agent, an acrylic copolymer emulsion, present in about 3 to about 3.5% by mass based on the total mass of the composition, comprising an alkali-swelling emulsion, and a layered silicate, present in about 0.1 to about 0.5% by mass based on the total mass of the composition; the coating composition conforms to ASTM When measured using the conical plate or parallel plate method with 7867-13, the coating composition has a viscosity of approximately 70 to approximately 75 cps at a shear rate of 1000 sec⁻¹, a yield stress of at least approximately 2 Pa, and a wet film thickness of at least approximately 20 microns without visible sag when measured at approximately 45 degrees using ASTM D4400-18.

[0069] In another embodiment, the resin dispersion comprises: an acrylic latex dispersion, which is a styrene-acrylic latex dispersion, present in an amount of about 27 to about 28% by mass based on the total mass of the composition and: an acrylic latex dispersion, which is a styrene-acrylic latex dispersion, present in an amount of about 8 to about 9% by mass based on the total mass of the composition; and a second polyurethane dispersion, which is present in an amount of about 6.5 to about 7.5% by mass based on the total mass of the composition, and is formed from a linear polyester diol resin and isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; and the crosslinking agent is melamine, and the combination The composition contains approximately 2-3% by mass of the total mass of the product; the pigment is an emulsion and is present in approximately 1-2% by mass of the total mass of the composition; water is present in approximately 15-20% by mass of the total mass of the composition; the water-soluble solvent is butanol and is present in approximately 7-8% by mass of the total mass of the composition; at least one rheology control agent is an acrylic copolymer emulsion and comprises an alkali-swelling emulsion present in approximately 3-3.5% by mass of the total mass of the composition, and layered silicates are present in approximately 0.1-0.5% by mass of the total mass of the composition; the coating composition conforms to ASTM When measured using the conical plate or parallel plate method with 7867-13, the coating composition has a viscosity of approximately 90 to approximately 95 cps at a shear rate of 1000 sec⁻¹, a yield stress of at least approximately 1 Pa, and a wet film thickness of at least approximately 20 microns without visible sag when measured at approximately 45 degrees using ASTM D4400-18.

[0070] In another embodiment, the resin dispersion is present in an amount of about 19 to about 22% by mass based on the total mass of the composition and includes: an acrylic latex dispersion which is a polyester-modified acrylic dispersion containing epoxy groups; a first polyurethane dispersion formed from a branched polyester polyol and hexamethylene diisocyanate; a second polyurethane dispersion formed from a linear polyester diol resin and isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; and a third polyurethane dispersion formed from a linear polycarbonate-polyester polyol and isophorone diisocyanate. In another embodiment, the acrylic latex dispersion is present in an amount of about 9 to about 11% by mass based on the total mass of the composition; the first polyurethane dispersion is present in an amount of about 4.5 to about 5.5% by mass based on the total mass of the composition; the second polyurethane dispersion is present in an amount of about 3 to about 4% by mass based on the total mass of the composition; and the third polyurethane dispersion is present in an amount of about 1 to about 2% by mass based on the total mass of the composition, the alkali-swellable emulsion is an acrylic copolymer emulsion, and the layered silicate is a synthetic phyllosilicate.

[0071] In another embodiment, the resin dispersion is present in an amount of about 28 to about 29% by mass based on the total mass of the composition and comprises: an acrylic latex dispersion which is a styrene-acrylic latex dispersion; a first polyurethane dispersion formed from a branched polyester polyol and a hexamethylene diisocyanate; and a second polyurethane dispersion formed from a linear polyester diol resin and an isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid. In another embodiment, the acrylic latex dispersion is present in an amount of about 8 to about 9% by mass based on the total mass of the composition; the first polyurethane dispersion is present in an amount of about 12 to about 13% by mass based on the total mass of the composition; the second polyurethane dispersion is present in an amount of about 8 to about 9% by mass based on the total mass of the composition, the alkali-swellable emulsion is an acrylic copolymer emulsion, and the layered silicate is a synthetic phyllosilicate.

[0072] In another embodiment, the resin dispersion includes: an acrylic latex dispersion which is an epoxy-containing polyester-modified acrylic dispersion present in an amount of about 19 to about 20% by mass based on the total mass of the composition; a first polyurethane dispersion formed from a branched polyester polyol and hexamethylene diisocyanate; a second polyurethane dispersion formed from a linear polyester diol resin and isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; and a third polyurethane dispersion formed from a linear polycarbonate-polyester polyol and isophorone diisocyanate. In another embodiment, the acrylic latex dispersion is present in an amount of about 9 to about 10% by mass based on the total mass of the composition; the first polyurethane dispersion is present in an amount of about 4 to about 5% by mass based on the total mass of the composition; the second polyurethane dispersion is present in an amount of about 3 to about 4% by mass based on the total mass of the composition; and the third polyurethane dispersion is present in an amount of about 1 to about 2% by mass based on the total mass of the composition, the alkali-swellable emulsion is an acrylic copolymer emulsion, and the layered silicate is a synthetic phyllosilicate.

[0073] In a further embodiment, the resin dispersion is present in an amount of about 27 to about 28% by mass based on the total mass of the composition and comprises: an acrylic latex dispersion which is a styrene-acrylic latex dispersion; and a second polyurethane dispersion formed from a linear polyester diol resin and an isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid. In another embodiment, the acrylic latex dispersion is present in an amount of about 8 to about 9% by mass based on the total mass of the composition; the second polyurethane dispersion is present in an amount of about 6.5 to about 7.5% by mass based on the total mass of the composition; the alkali-swellable emulsion is an acrylic copolymer emulsion; and the layered silicate is a synthetic phyllosilicate.

[0074] In one embodiment, the resin dispersion contains latex but does not contain polyurethane. In another embodiment, the resin dispersion contains polyurethane but does not contain latex. In further embodiments, the latex is selected from epoxy-containing polyester-modified acrylic dispersions, styrene-acrylic latex dispersions, and combinations thereof, and the polyurethane is selected from those formed from branched polyester polyol and hexamethylene diisocyanate; those formed from linear polyester diol resin and isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; those formed from linear polycarbonate-polyester polyol and isophorone diisocyanate; polyester-polyurethane polymers; and combinations thereof. In another embodiment, the alkali-swelling emulsion is an acrylic copolymer emulsion, and the layered silicate is a synthetic phyllosilicate.

[0075] In another embodiment, the resin dispersion is present in an amount of about 10 to about 35% by mass (active ingredient) based on the total mass of the composition; the crosslinking agent is melamine, present in an amount of about 2 to about 8% by mass (active ingredient) based on the total mass of the composition; the pigment is present in an amount of about 0.1 to about 20% by mass (active ingredient) based on the total mass of the composition; water is present in an amount of about 15 to about 70% by mass (active ingredient) based on the total mass of the composition; the water-soluble solvent is present in a total amount of about 5 to about 25% by mass (active ingredient) based on the total mass of the composition; at least one rheology control agent is present in an amount of about 0.01 to about 7% by mass (active ingredient) based on the total mass of the composition; the coating composition has a viscosity of about 35 to about 95 cPs at a shear rate of 1000 sec⁻¹ when measured by the conical or parallel plate method using ASTM 7867-13, and the coating composition is ASTM Measurements using D4400-18 showed that when measured at approximately 45 degrees Celsius, the wet film thickness was at least approximately 20 microns without any visible sag.

[0076] In a further embodiment, the resin dispersion comprises: an acrylic latex dispersion, which is a polyester-modified acrylic dispersion containing epoxy groups, present in an amount of about 12 to about 20% by mass (active ingredient) based on the total mass of the composition, and present in an amount of about 3 to about 5% by mass (active ingredient) based on the total mass of the composition; a first polyurethane dispersion, which is formed from a branched polyester polyol and a hexamethylene diisocyanate, present in an amount of about 1.5 to about 2.5% by mass (active ingredient) based on the total mass of the composition; and a second polyurethane dispersion, which is formed from a linear polyester diol resin and an isophorone diisocyanate, present in an amount of about 1 to about 2% by mass (active ingredient) based on the total mass of the composition, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; and The composition comprises: a third polyurethane dispersion present in an amount of approximately 0.5 to approximately 1.5% by mass (active ingredient), formed from linear polycarbonate-polyester polyol and isophorone diisocyanate; a crosslinking agent, melamine, present in an amount of approximately 3 to approximately 4% by mass (active ingredient) based on the total mass of the composition; a pigment dispersion present in an amount of approximately 0.5 to approximately 4.5% by mass (active ingredient) based on the total mass of the composition (this is carbon black only); water present in an amount of approximately 55 to approximately 70% by mass (active ingredient) based on the total mass of the composition; a water-soluble solvent, butanol, present in an amount of approximately 10 to approximately 20% by mass (active ingredient) based on the total mass of the composition; and at least one rheology control agent, an acrylic copolymer emulsion, present in an amount of 0.1 to approximately 2% by mass (active ingredient) based on the total mass of the composition, which is an alkali-swelling emulsion; and the coating composition conforms to ASTM When measured using the conical plate or parallel plate method with 7867-13, the viscosity is approximately 35 to approximately 70 cPs at a shear rate of 1000 sec⁻¹, and the coating composition has a wet film thickness of at least approximately 20 microns without visible sag when measured at approximately 45 degrees using ASTM D4400-18.

[0077] Coating layer: This disclosure also provides the coating layer itself, which is formed by applying a coating composition to a substrate. The physical properties of the coating layer are not particularly limited. Typically, the coating layer has a wet film thickness of about 1 to about 10, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mil. Typically, the coating layer has a dry film thickness of about 0.6 to about 2, about 0.7 to about 1.9, about 0.8 to about 1.8, about 0.9 to about 1.7, about 1 to about 1.6, about 1.1 to about 1.5, about 1.2 to about 1.4, or about 1.3 to about 1.4 mil. One or more of the above measurements may be performed in accordance with ASTM D7091-13.

[0078] In other embodiments, for example, when the coating composition is used to form a monocoat or an outer layer of a coating, the coating layer may have solvent resistance to at least 5 double MEK frictions, or at least 10 double MEK frictions, or at least 20, 35, 30, 35, 40, 45, 50, 55, 6, 65, 70, 75, 80, 85, 90, 95, or 100 double MEK frictions on a non-porous substrate according to ASTM D4752. In other embodiments, the coating layer may have a film tensile modulus of at least 100 MPa, or at least 100 MPa, or at least 200 MPa, according to ASTM 5026-15. In other embodiments, the coating layer may have a film tensile modulus of at least 0.2 mmol / cm³, according to ASTM D5026-15. 3 , or at least 0.5 mmol / cm³ 3 , or at least 1.0 millimoles / cm³ 3 It may have a crosslinking density. In other embodiments, the coating layer may have a gloss value of at least 75, or at least 88, or at least 92 at a reflectance angle of 20 degrees, according to ASTM 2813. In other embodiments, the coating layer may have a gloss retention rate of at least 50%, or at least 70%, or at least 90% of the initial gloss value after 2000 hours of weathering exposure according to ASTM D7869. In various non-limiting embodiments, all values ​​and ranges of values ​​are described both in whole and in part, including the values ​​and between them. The coating layer may be cured, uncured, or partially cured. The type of curing of the coating layer is not particularly limited, and any curing mechanism related to one or more of the above components can be used. Curing may be performed under ambient conditions, for example, by condensation curing or free radical curing, or by other suitable curing methods generally recognized by those skilled in the art, and / or at high temperatures, for example, in an oven at temperatures up to about 400°F, either partially or whole. The coating layer may be flushed to remove water and / or solvents, and this flushing may or may not cause curing, either whole or partially.

[0079] Throughout this disclosure, the term “about” means that the value may vary by an arbitrary range of ±1, 2, 4, 5, 6, 7, 8, 9, or 10%. However, in other embodiments, “about” may also mean an exact value. [Examples]

[0080] A series of coating compositions, both for the inventive and comparative products, are described below. After formation, each composition is evaluated to measure various physical properties. This is also described below. [Table 1] TIFF2022171643000002.tif228160 TIFF2022171643000003.tif41160 [Table 2] TIFF2022171643000005.tif228156

[0081] In various non-limiting embodiments, all values ​​and ranges of values, including the values ​​and intervals described in the above embodiments, both in whole and in part, are obviously conceivable for use herein, independently of these embodiments.

[0082] Some of the compounds used in the above examples are described below: [Table 3]

[0083] The data above shows that compositions 2, 3, and 4 exhibit superior performance, particularly when compared to compositions 1, 5, and 6. Compositions 2, 3, and 4 also possess high yield stress and low shear viscosity, which are indicators of superior performance. Compositions 7-10 are evaluated as additional examples demonstrating appropriate sag control. The evaluation of composition 11 shows the sag performance obtained without a thickener.

[0084] While at least one exemplary embodiment is shown 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 exemplary embodiments are merely examples and are not intended to limit the scope, applicability, or configuration. Rather, the detailed description above will provide a convenient roadmap for implementing the exemplary embodiments. It should be understood that various modifications may be made to the function and arrangement of the elements described in the exemplary embodiments without departing from the scope of the appended claims.

Claims

1. 1. A method for applying a one-part aqueous coating composition to a substrate using a high transfer efficiency applicator to form a coating layer disposed on the substrate, the method comprising: providing the coating composition to the high transfer efficiency applicator; applying the coating composition to the substrate through the high transfer efficiency applicator to form the coating layer on the substrate, wherein volatile loss after application through the high transfer efficiency applicator is less than about 0.5% by weight (active ingredient) based on a total weight of the coating composition; Including, the coating composition has a pH greater than about 7; and A. a resin dispersion comprising latex, polyurethane, or a combination thereof; B. an optional cross-linking agent; C. an optional pigment; D. Water; E. a water-soluble solvent; F. at least one rheology control agent selected from alkali swellable emulsions, layered silicates, and combinations thereof; Including, the coating composition has a viscosity of about 20 to about 100 at a shear rate of 1000 sec-1, as measured by cone and plate or parallel plate methods using ASTM 7867-13; the coating composition has a wet film thickness of at least 20 microns with no visible sag when measured at about 45 degrees; method.

2. A. the resin dispersion is present in an amount of about 10 to about 35% by weight (active ingredient), based on the total weight of the composition; B. the crosslinker is melamine and is present in an amount of about 2 to about 8% by weight (active ingredient), based on the total weight of the composition; C. the pigment is present in an amount of about 0.1 to about 20% by weight (active ingredient), based on the total weight of the composition; D. the water is present in an amount of about 15 to about 70% by weight (active ingredient), based on the total weight of the composition; E. the water-soluble solvent is present in an amount of about 5 to about 25% by weight (active ingredient), based on the total weight of the composition; and F. the at least one rheology control agent is present in an amount of about 0.01 to about 7% by weight (active ingredient), based on the total weight of the composition; the coating composition has a viscosity of about 35 to about 95 cps at a shear rate of 1000 sec-1 as measured by cone and plate or parallel plate methods using ASTM 7867-13; the coating composition has a wet film thickness of at least about 20 microns with no visible sag when measured at about 45 degrees using ASTM D4400-18; The method of claim 1.

3. A. the resin dispersion is present in an amount of about 12 to about 20% by weight (active ingredient) based on the total weight of the composition; and an acrylic latex dispersion, which is present in an amount of about 3 to about 5 weight percent (active ingredient), based on the total weight of the composition, and which is a polyester-modified acrylic dispersion containing epoxy groups; a first polyurethane dispersion formed from a branched polyester polyol and hexamethylene diisocyanate, present in an amount of about 1.5 to about 2.5 weight percent (actives), based on the total weight of the composition; a second polyurethane dispersion present in an amount of about 1 to about 2 weight percent (actives), based on the total weight of the composition, formed from a linear polyester diol resin and isophorone diisocyanate, the linear polyester diol being the reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; a third polyurethane dispersion present in an amount of about 0.5 to about 1.5 weight percent (active ingredient), based on the total weight of the composition, the third polyurethane dispersion being formed from a linear polycarbonate-polyester polyol and isophorone diisocyanate; Including, B. the crosslinker is melamine and is present in an amount of about 3 to about 4% (active ingredient) by weight, based on the total weight of the composition; C. the pigment dispersion is present in an amount of about 0.5 to about 4.5% by weight (active ingredient), based on the total weight of the composition; D. the water is present in an amount of about 55 to about 70% by weight (active ingredient), based on the total weight of the composition; E. the water soluble solvent is butanol and is present in an amount of about 10 to about 20% by weight (active ingredient), based on the total weight of the composition; and F. the at least one rheology control agent is an alkali swellable emulsion which is an acrylic copolymer emulsion and is present in an amount of about 0.1 to about 2 weight percent (active ingredient) based on the total weight of the composition; the coating composition has a viscosity of about 35 to about 70 cps at a shear rate of 1000 sec-1 as measured by the cone and plate or parallel plate method using ASTM 7867-13; the coating composition has a wet film thickness of at least about 20 microns with no visible sag when measured at about 45 degrees using ASTM D4400-18; The method of claim 1.

4. The method of claim 1 , wherein the resin dispersion comprises the latex and is free of the polyurethane.

5. The method of claim 1 , wherein the resin dispersion comprises the polyurethane and is free of the latex.