A method of applying a one-component waterborne coating composition to a substrate using a high transfer efficiency applicator

Abstract

A method comprising applying a coating composition to a substrate by a high transfer efficiency applicator, wherein the coating composition has a pH greater than about 7 and comprises: A. a resin dispersion comprising a latex, a polyurethane, or a combination thereof; B. an optional crosslinker; C. an optional pigment; D. water; E. a water soluble solvent; and F. at least one rheology control agent selected from the group consisting of alkali swellable emulsions, layered silicates, and combinations thereof; wherein the coating composition has a viscosity of about 20 to about 100 cps, the viscosity determined using ASTM 7867-13 with a cone and plate or parallel plate at a shear rate of 1000 s ‑1 and wherein the coating composition has a wet film thickness of at least about 20 microns and no visible sagging when measured at about 45 degrees and without visible sagging.

Description

Technical Field

[0001] In summary, this disclosure relates to applying a one-component waterborne coating composition to a substrate (base) using a high-transfer-efficiency applicator. More specifically, this disclosure relates to spraying a particular composition using a high-transfer-efficiency applicator, said composition comprising at least one rheology control agent selected from alkali-swellable emulsions, layered silicates, and combinations thereof. Background Technology

[0002] Inkjet printing is a non-impact printing method that uses an electrical signal to deposit ink droplets onto a substrate (typically paper or textile fabric). The advantage of this application method is that it allows for digital printing on substrates tailored to individual needs. Droplets can be ejected onto the substrate using various inkjet application methods, including continuous printing and drop-on-demand printing. In drop-on-demand printing, the energy for ejecting the ink droplets can come from a thermistor, piezoelectric crystal, sound, or a solenoid valve. These methods utilize high-efficiency applicators.

[0003] In the automotive industry, car bodies are typically covered with a series of topcoats (finish coats), including an electrocoating layer, a primer, a colored base coat that provides color, and a clear topcoat that provides additional protection and a glossy finish. Currently, most car bodies are coated with a single-color base coat, which is applied in a single spray operation. The coating is applied using pneumatic spraying or rotary equipment that produces a wide jet of paint droplets with a broad droplet size distribution. This has the advantage of producing a uniform, high-quality coating in a relatively short time through an automated process.

[0004] However, this method has many drawbacks. If the car body is to be painted with multiple colors—for example, if a second color is used to create a pattern such as stripes, or if an entire area of ​​the car body (such as the roof) is painted a different color—the first coating needs to be masked off, and the car body then needs to go through the painting process again to add the second color. After this second painting operation, the masking must be removed. This is both time-consuming and labor-intensive, significantly increasing operating costs.

[0005] A second drawback of current spraying technology is that paint droplets are sprayed as wide droplet jets with a broad range of droplet sizes. As a result, many droplets fail to land on the vehicle, either because they are sprayed near the edges and thus over-spray the substrate, or because the smaller droplets have too low momentum to reach the body. This excessive overspray must be removed from the spraying operation and safely handled, leading to significant waste and additional costs.

[0006] Applying a coating using a high-transfer-efficiency applicator can provide a solution for applying two colors to a vehicle while minimizing overspray. This is achieved by generating uniformly sized droplets that can be directed to specific points on the substrate, such as specific locations on the vehicle body, thereby minimizing or completely eliminating overspray droplets. Furthermore, digital printing can be used to print patterns or two shades onto the vehicle body, either as a second color digitally printed on top of a previously applied base coat of a different color, or directly onto a vehicle substrate coated with a primer or clear coat.

[0007] However, conventional inkjet inks are typically formulated for printing on porous substrates such as paper and textiles, where the ink is rapidly absorbed into the substrate, facilitating drying and treatment of the substrate shortly after printing. Furthermore, while prints such as those on fabrics with printed text, images, or patterns offer sufficient durability for these applications, automotive coatings require significantly higher levels of physical durability (such as abrasion and shatter resistance) and long-term weather and lightfastness. Additionally, inkjet inks known in the art are formulated to have low viscosity, typically independent of shear rate or Newtonian viscosity, usually below 20 cps. This is because the energy available for ejecting microdroplets in each nozzle of the printhead is limited, and it also avoids clogging that could result from ink thickening in the printhead channels.

[0008] In contrast, automotive coatings typically exhibit significant non-Newtonian shear behavior and extremely high viscosity at low shear rates to help prevent pigment settling and ensure rapid and uniform curing of the coating immediately after application, while having relatively low viscosity at high shear rates to facilitate spraying and atomize the sprayed material into microdroplets.

[0009] Furthermore, even though existing technologies are suitable for some horizontal surface applications, there are other applications, such as vertical surface applications, where existing technologies result in unacceptable sagging. Because high-efficiency application requires very low viscosity without any shear-thinning behavior, standard methods for imparting sagging resistance to sprayed coatings cannot be used. Therefore, opportunities for improvement remain. Summary of the Invention

[0010] This disclosure provides a method for applying a one-component waterborne coating composition to a substrate using a high-transfer-efficiency applicator to form a coating disposed on the substrate, the method comprising the following steps:

[0011] To provide the coating composition to a high-transfer-efficiency applicator; and

[0012] A coating composition is applied to a substrate using a high-transfer-efficiency applicator to form a coating on the substrate, wherein, based on the total weight of the coating composition, the loss of volatiles after application using the high-transfer-efficiency applicator is less than about 0.5% by weight of active ingredients.

[0013] The coating composition has a pH greater than about 7 and comprises:

[0014] A. A resin dispersion, comprising latex, polyurethane, or combinations thereof;

[0015] B. Optional crosslinking agent;

[0016] C. Optional pigments;

[0017] D. Water;

[0018] E. Water-soluble solvents; and

[0019] F. At least one rheology control agent selected from alkali-swellable emulsions, layered silicates, and combinations thereof;

[0020] The coating composition described herein has a viscosity of about 20 to about 100 cps, which is determined using ASTM 7867-13 with a conical or parallel plate at 1000 s. -1 The shear rate was measured, and

[0021] When measured at approximately 45 degrees Celsius, the coating composition has a wet film thickness of at least approximately 20 micrometers and no visible sagging. Detailed Implementation

[0022] The following detailed description is merely exemplary in nature and is not intended to limit the method. Furthermore, it is not intended to be bound by the foregoing background art or any theory presented in the following detailed description.

[0023] In general, embodiments of this disclosure relate to one-component waterborne coating compositions and methods for their formation and application. For the sake of brevity, conventional techniques associated with the formation of one-component waterborne coating compositions may not be described in detail herein. Furthermore, the various tasks and process steps described herein can be combined into a more comprehensive procedure or process with additional steps or functions not described in detail herein. In particular, the various steps in the manufacture of one-component waterborne coating compositions are well known; therefore, for the sake of brevity, many conventional steps are only briefly mentioned or will be omitted entirely without providing well-known process details.

[0024] This disclosure provides a method for applying a one-component waterborne coating composition to a substrate using a high-transfer-efficiency applicator to form a coating disposed on the substrate, the method comprising the following steps:

[0025] To provide the coating composition to a high-transfer-efficiency applicator; and

[0026] A coating composition is applied to a substrate using a high-transfer-efficiency applicator to form a coating on the substrate, wherein, based on the total weight of the coating composition, the loss of volatiles after application using the high-transfer-efficiency applicator is less than about 0.5% by weight of active ingredients.

[0027] The coating composition has a pH greater than about 7 and comprises:

[0028] A. A resin dispersion, comprising latex, polyurethane, or combinations thereof;

[0029] B. Optional crosslinking agent;

[0030] C. Optional pigments;

[0031] D. Water;

[0032] E. Water-soluble solvents; and

[0033] F. At least one rheology control agent selected from alkali-swellable emulsions, layered silicates, and combinations thereof;

[0034] The coating composition described herein has a viscosity of about 20 to about 100 cps, which is determined using ASTM 7867-13 with a conical or parallel plate at 1000 s. -1 The shear rate was measured, and

[0035] When measured at approximately 45 degrees Celsius, the coating composition has a wet film thickness of at least approximately 20 micrometers and no visible sagging.

[0036] Provides single-component waterborne coating compositions:

[0037] The method includes the step of providing a coating composition to a high transfer efficiency applicator. There are no particular limitations on the providing step, and it can be any providing step known in the art. For example, the providing step can be described as providing one or more components (all or part) of the composition, combining these components to form the composition, and then providing the complete composition. Alternatively, the providing step can be described as delivering one or more components of the composition, or the composition as a whole, to the high transfer efficiency applicator by pumping, flowing, moving, or other means. The providing step can be described as a continuous or batch process. Similarly, the providing step may include continuous sub-steps 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 can be a step understood by those skilled in the art.

[0038] Apply a single-component waterborne coating composition:

[0039] The method further includes the step of applying the coating composition to a substrate using a high transfer efficiency applicator to form a coating on the substrate. There are no particular limitations on the application step. In various embodiments, the application step is further defined as spraying, for example, spraying using a high transfer efficiency applicator. Alternatively, the application step may be further defined as printing.

[0040] Typically, the application step is further defined as spraying or printing via, using, or through an applicator. During the application step, the volatile loss after application via a high-transfer-efficiency applicator is less than about 0.5% by weight of active ingredient, based on the total weight of the coating composition. In various embodiments, this amount is less than about 0.4, 0.3, 0.2, or 0.1% by weight of active ingredient, based on the total weight of the coating composition. Generally, the term "volatile" is defined as a substance that evaporates, resulting in a loss of weight of the coating composition. The volatile loss after application will be determined by the increase in solids (in percentage) before application and after baking, wherein in each case the solids percentage will be determined by gravimetric analysis according to ASTM D2369-10. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​above and values ​​between the values ​​above, are expressly considered herein.

[0041] In some embodiments, the application step generates coating composition droplets that impact the substrate. In various embodiments, at least about 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or even higher percentages of the coating composition droplets ejected from the high-transfer-efficiency applicator contact the substrate. Without being bound by theory, it is believed that the increased number of droplets in contact with the substrate relative to the number of droplets that do not contact the substrate and thus enter the environment improves the application efficiency of the coating composition, reduces waste generation, and minimizes maintenance.

[0042] In various embodiments, at least about 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or even higher percentages of the paint composition droplets expelled from the 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%. While conventional applicators rely on atomization to form a “mist” of atomized droplets of paint composition with a dispersed particle size distribution, the monodisperse droplets and / or flow formed by the high-transfer-efficiency applicator can be directed to the substrate, thereby resulting in improved transfer efficiency relative to conventional applicators. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein.

[0043] In various embodiments, at least about 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or even higher percentages of the paint composition droplets expelled from the high-transfer-efficiency applicator remain as single droplets after exiting the applicator. Without being bound by theory, it is believed that the formation of satellite droplets can be reduced or eliminated by applying the paint composition using a high-transfer-efficiency applicator. The formation of satellite droplets can be reduced by taking into account the impact velocity and nozzle diameter. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the described values, are expressly considered herein for use.

[0044] In various implementations, liquid paint is ejected from one or more nozzles of a high transfer efficiency applicator in an engineered / controlled manner to produce a fine stream, which may or may not break into droplets. This stream is targeted at the substrate, causing the droplets to reach specific locations to form a continuous film or pattern on the object. Therefore, in many implementations, there is virtually no overspray (droplets not reaching their target) and transfer efficiency is nearly 100% (all paint reaches the target location on the substrate). As those skilled in the art will understand, there are some tolerances due to the start-up and shutdown of the high transfer efficiency applicator. This type of device can be described as a stream-on-demand, overspray-free, or ultra-high transfer efficiency applicator. These devices differ from spray atomization devices and technologies in which energy, such as pneumatic, hydraulic, or centrifugal energy, is introduced to produce partially controlled, randomly distributed droplet size, trajectory, and velocity, and some of these additional mechanisms, such as electrostatic and / or shaping air, subsequently guide the paint droplet cloud to the substrate. There is always some overspray and transfer efficiency loss compared to conventional paint spraying.

[0045] The high-transfer-efficiency applicator can itself be any applicator known in the art. For example, in various embodiments, the applicator is described in one or more of the following patent numbers: US 20150375258 A1, US 20040217202 A1, US 2009 / 0304936 A1, US 7,824,015 B2, US 8,091,987 B2, and WO 2018 / 206309 A1, each of which is expressly incorporated herein by reference in its entirety for use in various non-limiting embodiments. The applicator is alternatively described as a printhead.

[0046] In one embodiment, the high transfer efficiency applicator includes a nozzle defining a nozzle orifice and may have a nozzle diameter of about 0.00002 m to about 0.0004 m. In another embodiment, the applicator may be fluidly connected to a reservoir configured to contain a coating composition. For example, the high transfer efficiency applicator may be configured to receive a coating composition from a reservoir and to discharge the coating composition through a nozzle orifice to a substrate to form a coating. It should be understood that the ranges of nozzle diameter, viscosity, density, surface tension, and relaxation time may be defined by any range described herein or any range known in the art. In the various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein.

[0047] A high-efficiency transfer applicator can be configured to discharge the coating composition through a nozzle orifice at an impact velocity of about 0.2 m / s to about 20 m / s. Alternatively, a high-efficiency transfer applicator can be configured to discharge the coating composition through a nozzle orifice at an impact velocity of about 0.4 m / s to about 10 m / s. The nozzle orifice can have a nozzle diameter of about 0.00004 m to about 0.00025 m. The coating composition can be discharged from the high-efficiency transfer applicator as droplets with a particle size of at least 10 micrometers. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein.

[0048] Consider using one, two, three, or even more applicators in combination with each other. Each applicator can be independent as described herein or can be any applicator known in the art.

[0049] In various embodiments, the high-transfer-efficiency applicator includes a plurality of nozzles, each nozzle defining a nozzle orifice. The plurality of nozzles may be arranged linearly 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 certain nozzle distance. The distance between the high-transfer-efficiency applicator and the substrate may be substantially the same as the nozzle distance.

[0050] In one embodiment, the plurality of nozzles are spaced apart from each other to form a rectangular array, and the plurality of nozzles may be configured to alternately discharge the coating composition between adjacent nozzles in the rectangular array to reduce sagging of the coating composition.

[0051] In various embodiments, the high-transfer-efficiency applicator includes fifty nozzles aligned along the y-axis. However, it should be understood that the applicator may include any number of nozzles. Each nozzle can be actuated independently of the other nozzles to apply the coating composition to the substrate. During spraying, independent actuation of the nozzles can control the placement of each droplet of the coating composition on the substrate.

[0052] Two or more applicators can be joined together to form a printhead assembly. In some embodiments, the applicators are aligned together such that the y-axis of each applicator is parallel to the other y-axis. Furthermore, the nozzles of each applicator can be aligned with each other along an x-axis perpendicular to the y-axis, forming an "array". A nozzle can be equidistant from other nozzles directly adjacent to it, relative to both the x-axis and y-axis. This nozzle configuration is suitable for applying the same paint composition to a substrate via each applicator as the printhead assembly moves along the x-axis. Without being bound by theory, it is assumed that equal spacing between nozzles relative to both the x-axis and y-axis results in uniform application of the same paint composition to the substrate. Uniform application of the same paint composition is suitable for single-color application, two-tone application, etc.

[0053] Alternatively, a set of nozzles along the first y-axis can be closely spaced from another set of nozzles relative to the spacing of each nozzle along the y-axis of a single high-transfer-efficiency applicator. This nozzle configuration may be suitable for applying different paint compositions to a substrate through each high-transfer-efficiency applicator. Different paint compositions used in the same high-transfer-efficiency applicator assembly may be suitable for markings, designs, logos, stripes, camouflage appearances, etc.

[0054] The nozzle of a high-transfer-efficiency applicator can have any configuration known in the art, such as linear, recessed relative to the substrate, convex relative to the substrate, circular, etc. The nozzle configuration may need to be adjusted to facilitate the application of the high-transfer-efficiency applicator to substrates with irregular configurations, such as vehicles including mirrors, trim panels, contours, spoilers, etc.

[0055] High-efficiency transfer applicators can be configured to blend individual droplets to form a desired color. A high-efficiency transfer applicator may include nozzles to apply cyan, magenta, yellow, and black paint compositions. The properties of the paint compositions can be modified to promote blending. Furthermore, agitation sources such as air motion or acoustic generators can be used to promote blending of the paint compositions. The agitation source may be coupled to or disconnected from the high-efficiency transfer applicator.

[0056] Determining the appropriate properties of a coating composition for use in a high-efficiency transfer applicator may depend on the performance of the high-efficiency transfer applicator. The performance of the high-efficiency transfer applicator may include, but is not limited to, the nozzle diameter of the high-efficiency transfer applicator, the impact velocity of the coating composition produced by the high-efficiency transfer applicator, the speed of the high-efficiency transfer applicator, the distance between the high-efficiency transfer applicator and the substrate, the droplet size of the coating composition produced by the high-efficiency transfer applicator, the emission rate of the high-efficiency transfer applicator, and the orientation of the high-efficiency transfer applicator relative to gravity.

[0057] In the implementation scheme, the substrate is a vehicle, automobile, or motor vehicle. "Vehicle," "automobile," or "motor vehicle" includes: automobiles, such as cars, vans, minivans, buses, SUVs (sports utility vehicles); trucks; semi-trucks; tractors; motorcycles; trailers; ATVs (all-terrain vehicles); pickup trucks; heavy-duty transport vehicles, such as bulldozers, mobile cranes, and excavators; aircraft; small boats; ships; and other modes of transport. The coating composition can also be used to coat substrates in industrial applications (such as buildings; fences; tiles; fixed structures; bridges; pipes; cellulosic materials (e.g., wood, paper, fibers, etc.)). The coating composition can also be used to coat substrates in consumer product applications (such as helmets, baseball bats, bicycles, and toys). It should be understood that the term "substrate," as used herein, can also refer to a coating applied to an article that is also considered a substrate.

[0058] Various substrates can include two or more discrete parts made of different materials. For example, a vehicle may include a metal body section and a plastic trim section. Due to the limitation of the baking temperature (80°C) for plastic relative to metal (140°C), the metal body section and the plastic trim section can often be coated in separate facilities, increasing the possibility of part mismatch. A coating composition suitable for a plastic substrate can be applied to the plastic substrate using a high-transfer-efficiency applicator after applying and baking a coating composition suitable for the metal substrate, without masking the substrate and wasting a portion of the coating composition using low-transfer-efficiency application methods such as conventional spray atomization. A first high-transfer-efficiency applicator can be used to apply the coating composition suitable for the plastic substrate, and a second high-transfer-efficiency applicator can be used to apply the coating composition suitable for the metal substrate. The first and second high-transfer-efficiency applicators can form a high-transfer-efficiency applicator assembly.

[0059] Single-component waterborne coating composition:

[0060] There are no particular limitations on the one-component waterborne coating composition itself, and it can be any one-component waterborne coating composition known in the art that includes the components described herein. For example, the composition can be described as a "1K" composition that does not require a hardener, catalyst, or activator for curing. For example, the composition can be cured by exposure to air.

[0061] Throughout this disclosure, the terms "substantially composed of" or "substantially composed of" may describe embodiments that do not contain any alternative monomers, polymers, additives, reactants, fillers, solvents, etc., as determined by those skilled in the art. The term "free of" may be described as including, based on the total weight of the composition, less than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% by weight. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly intended to be used herein.

[0062] The composition is a single-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, whether integers or fractions, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly considered herein.

[0063] In various embodiments, the composition is, includes, substantially consists of, 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 rheology control agent selected from alkali-swellable emulsions, layered silicates, and combinations thereof. For example, the term "substantially consists of" can describe embodiments that do not contain any resin or polymer not described herein or described herein as optional, any crosslinking agent not described herein or described herein as optional, any water-soluble solvent not described herein or described herein as optional, and any rheology control agent not described herein or described herein as optional. The term "does not contain" or "does not include" can describe that, based on the total weight of the composition, the composition contains less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% by weight (e.g., % by weight of active ingredient). Alternatively, the term "does not contain" or "does not include" can describe that the composition is completely free of the compound.

[0064] Generally, any percentage by weight of a component as described herein refers to the percentage by weight of the “active ingredient” and not the total percentage by weight of components that may include solvents such as water. However, it is understood that percentage by weight can refer to the total weight of components that include any solvent, such as water. As those skilled in the art will understand, some components may be approximately 100% active ingredient, such that the percentage by weight of the active ingredient and the percentage by weight of the total components are substantially the same.

[0065] resin dispersion

[0066] The composition comprises a resin dispersion, which may be, include, consist substantially of, or consist of latex, polyurethane, or a combination thereof. For example, the term "consistent substantially of" can describe an embodiment that is free of latex, polyurethane, or any other polymer known in the art, wherein "free of" is as described above. The dispersion itself is a system in which distributed particles of one material are dispersed in a continuous phase of another material. The two phases may be in the same or different physical states. Alternatively, the resin dispersion may be described as an emulsion, which is a homogeneous mixture of two immiscible liquids. In this disclosure, latex may include a polymer, which may 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, combinations of the above may be used. If it is an emulsion, the emulsion may be of any type known in the art, such as an oil-in-water emulsion, a water-in-oil emulsion, etc. In various embodiments, water, a water-soluble cosolvent (such as any water-soluble cosolvent described herein), or a combination of water and one or more such solvents may be used as the continuous phase, wherein the dispersed phase may be latex, polyurethane, or a combination thereof.

[0067] In various embodiments, based on the total weight of the composition, the resin dispersion 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, about 16 to about 24% by weight of active ingredient, etc. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein for use.

[0068] latex:

[0069] It is possible to use zero, one, two, three, four, five, or even more individual latexes in the composition. In various embodiments, the term "latex" refers to a dispersion of polymer particles in water. For example, latex polymers typically require a co-dispersant (e.g., a surfactant) to produce a dispersion or emulsion of polymer particles in water. There are no particular limitations on the latex and it can be any latex known in the art.

[0070] In various embodiments, the latex may be a reaction product of one or more of the following monomers, a reaction product comprising one or more of the following monomers, substantially composed of a reaction product of one or more of the following monomers, or composed of a reaction product of one or more of the following monomers to form a polymer that may be a dispersed phase and / or a continuous phase. These monomers may 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 epoxides, α-epoxides, 2-hydroxyethyl (meth)acrylate, (meth)acrylonitrile, and maleic anhydride. Itaconic acid, isodecyl methacrylate, dodecyl methacrylate, n-butyl methacrylate, methyl methacrylate, hexyl methacrylate, methacrylic acid, N-vinylcaprolactam, stearyl methacrylate, hydroxy-functional caprolactone (meth)acrylate, octadecyl methacrylate, isooctyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl methacrylate, hydroxypropyl methacrylate, hydroxyisopropyl methacrylate, hydroxybutyl methacrylate, hydroxyisobutyl methacrylate, tetrahydrofurfuryl methacrylate and combinations thereof.

[0071] In other embodiments, the latex may be, include, consist substantially of, or consist of: one or more (meth)acrylated urethanes (i.e., urethane (meth)acrylates), (meth)acrylated epoxy resins (i.e., epoxy (meth)acrylates), (meth)acrylated polyesters (i.e., polyester (meth)acrylates), (meth)acrylated (meth)acrylated acrylics, (meth)acrylated silicones, (meth)acrylated amines, (meth)acrylated amides; (meth)acrylated polysulfones; (meth)acrylated polyesters, (meth)acrylated polyethers (i.e., polyether (meth)acrylates), vinyl (meth)acrylates, and (meth)acrylated oils.

[0072] In one embodiment, the resin dispersion may be, include, consist substantially of, or consist of a polyester-modified acrylic dispersion containing epoxy groups. A non-limiting example is available from Allnex under the trade name... Purchased from VTW 1686 / 40WA.

[0073] In another embodiment, the resin dispersion may be composed of, include, substantially consist of, or consist of a styrene-acrylic latex dispersion. This dispersion can be formed by a two-step emulsion polymerization process.

[0074] In one embodiment, the resin dispersion may be a latex, include a latex, consist substantially of a latex, or consist of a latex. In various embodiments, the latex is present in an amount of active ingredient 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 weight, based on the total weight of the dispersion. In other embodiments, the latex (e.g., alone or as a whole) is present in amounts of about 1 to about 50, about 1 to about 45, about 1 to about 35, about 1 to about 30, about 1 to about 25, about 1 to about 20, about 1 to about 15, about 1 to about 10, about 1 to about 5, about 5 to about 50, about 10 to about 45, about 15 to about 40, about 20 to about 35, about 25 to about 30, about 15 to about 20, about 15 to about 25, about 15 to about 30, about 10 to about 20, about 10 to about 25, about 10 to about 30, about 10 to about 35, about 18 to about 22, about 18 to about 20, about 16 to about 20, about 16 to about 22, about 16 to about 24% by weight of active ingredient, etc., based on the total weight of the composition. In other embodiments, the latex (e.g., alone or as a whole) is present in amounts such as 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 weight of active ingredient, based on the total weight of the composition. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein for use.

[0075] Polyurethane:

[0076] The resin dispersion may also be a polyurethane, include polyurethane, consist substantially of polyurethane, or consist of polyurethane. It is conceivable to use zero, one, two, three, four, five, or even more individual polyurethanes in the composition. There are no particular limitations on the polyurethane and it may be any polyurethane known in the art. In various embodiments, the polyurethane is a reaction product of a polyol and an isocyanate.

[0077] In various embodiments, the polyol is selected from polyester polyols, polyether polyols, and polycarbonate polyols. Polysulfide polyols, polycaprolactone polyols, and acrylic polyols are also considered. 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.

[0078] Polyols can be derived from the reaction of an initiator with an epoxide. The initiator can include any initiator known in the art. In various embodiments, the initiator is selected from ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, butanediol, pentanediol, hexanediol, heptahydrate, glycerol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, glycerol, alkyl glucoside, pentaerythritol, sorbitol, naphthyldiamine, aniline, condensation products of aniline and formaldehyde, alkylamines, triisopropanolamine, alkylene diamines, diamine alkanes, sucrose, toluene diamine, and combinations thereof.

[0079] The epoxide that reacts with an initiator to form a polyol can be selected from ethylene oxide, propylene oxide, butane oxide, pentane oxide, tetrahydrofuran, mixtures of epoxide and tetrahydrofuran, epihaloalcohols, aralkylene oxides, and combinations thereof. In various embodiments, the epoxide is selected from ethylene oxide, propylene oxide, and combinations thereof. However, it is also contemplated that any suitable epoxide known in the art may be used.

[0080] Polyols may include organic functional groups selected from carboxyl, amino, urethane, amide, and epoxy groups. Polyols may also include epoxide end-capping. If a polyol includes epoxide end-capping, the epoxide end-capping typically includes, but is not limited to, ethylene oxide, propylene oxide, butane oxide, pentane oxide, and combinations thereof. More typically, epoxide end-capping includes ethylene oxide. If a polyol includes epoxide end-capping, the epoxide end-capping may be less than or equal to 25% by weight, more typically 10 to 20% by weight, based on the total weight of the polyol. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein for use.

[0081] 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 mg KOH / g, and a nominal functionality 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, whether integers or fractions, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly considered herein.

[0082] Polyols may also include addition polymers dispersed therein. More specifically, polyols may include dispersions or solutions of addition or condensation polymers (i.e., grafted polyols). Dispersions may include styrene, acrylonitrile, and combinations thereof. Furthermore, polyols may also include emulsions comprising water or any other polar compounds known in the art.

[0083] Alternatively, polyurethane can be described as a reaction product of a compound having one or more hydroxyl groups (e.g., a monohydric alcohol, dihydric alcohol, trihydric alcohol, tetrahydric alcohol, or polyhydric alcohol) with an isocyanate. Non-limiting suitable compounds include ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanediol, trimethylpentanediol, ethylbutylpropylene glycol, bis(trimethylolpropane), trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, polyethylene glycol, and polypropylene glycol. If desired, a monohydric alcohol (e.g., butanol, octanol, lauryl alcohol, ethoxylated or propoxylated phenol) may also be included with the polyhydric alcohol to control the molecular weight.

[0084] In some embodiments, low molar mass polyols, such as polyhydric alcohols, defined by empirical structural formulas, are used to form polyurethanes. Non-limiting examples of polyols include ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanediol, trimethylpentanediol, ethylbutylpropylene glycol, bis(trimethylolpropane), trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, polyethylene glycol, and polypropylene glycol. In other embodiments, oligomeric or polymeric polyols with a number-average molar mass, for example, up to 8000, 5000, or 2000, and / or, for example, corresponding hydroxyl-functionalized polyethers, polyesters, or polycarbonates, are used. In all the various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly considered herein for use.

[0085] Isocyanates can also react with hydroxyl-functionalized resins; there are no particular limitations on the hydroxyl-functionalized resins, and they can be any hydroxyl-functionalized resin known in the art. In various embodiments, the resin can be, includes, consists substantially of, or is composed of aliphatic or aromatic dicarboxylic acids, polyols, diols, aromatic or aliphatic cyclic anhydrides, and cyclic alcohols. Non-limiting examples of suitable alicyclic polycarboxylic acids are tetrahydrophthalic acid, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, nethylenetetrahydrophthalic acid, tricyclodecanedicarboxylic acid, nethylenedihydrophthalic acid, camphoric acid, cyclohexanetetracarboxylic acid, and cyclobutanetetracarboxylic acid. Alicyclic polycarboxylic acids can be used not only in their cis form, but also in their trans form and as mixtures of both. Other non-limiting examples of suitable polycarboxylic acids may include aromatic and aliphatic polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, halophthalic acids (such as tetrachlorophthalic acid 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.

[0086] Suitable non-limiting polyols include ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanediol, trimethylpentanediol, ethylbutylpropylene glycol, di-trimethylolpropane, 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 with the polyol if desired. Alternatively, low molar mass polyols, such as polyols, as defined by empirical structural formulas, may be used. In other embodiments, oligomeric or polymeric polyols with a number-average molar mass, for example, up to 8000, 5000, or 2000, and / or, for example, corresponding hydroxyl-functionalized polyethers, polyesters, or polycarbonates, are used. In all non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​mentioned above and values ​​in between, are expressly considered for use herein.

[0087] The resin dispersion may also include an amine, which may be of any type known in the art, and may react with isocyanates to form polyureas or may not react with isocyanates. The amine may include, but is not limited to, primary and secondary aliphatic and / or cyclic aliphatic amines. The amine may include any additional functional groups known in the art, including but not limited to hydroxyl, thiol, alkyl, cyclic, aromatic groups, and combinations thereof. It should be understood that the amine may also include, and may be, any type of amide known in the art. The amide may include, but is 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.

[0088] Regarding isocyanates, there are no particular limitations on the type of isocyanate, and it can be any isocyanate described in this disclosure. In various embodiments, the isocyanate comprises at least one isocyanate and may comprise more than one isocyanate. The isocyanate can be, comprises, substantially consists of, or consists of aromatic isocyanates, aliphatic isocyanates, and / or combinations thereof. In one embodiment, the isocyanate is an aromatic isocyanate or comprises aromatic isocyanates, such as polymeric MDI. If the isocyanate is an aromatic isocyanate or comprises aromatic isocyanates, then the aromatic isocyanate typically corresponds to the formula R'(NCO). z , where R' is an aromatic polyvalent organic group and z is an integer corresponding to the valence of R'. Typically, z is at least 2.

[0089] In various embodiments, the isocyanate may be, include, consist substantially of, or consist of the following substances: 1,4-diisocyanate-phenylene, 1,3-diisocyanate-o-xylene, 1,3-diisocyanate-p-xylene, 1,3-diisocyanate-m-xylene, 2,4-diisocyanate-1-chlorobenzene, 2,4-diisocyanate-1-nitrobenzene, 2,5-diisocyanate-1-nitrobenzene, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4,4'-di(2 ... Phenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; triisocyanates such as 4,4',4”-triphenylmethane triisocyanate, polymethylene polyphenylene polyisocyanate and 2,4,6-toluene triisocyanate; tetraisocyanates such as 4,4'-dimethyl-2,2'-5,5'-diphenylmethane tetraisocyanate; toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, mixtures of their corresponding isomers and combinations thereof.

[0090] If the isocyanate is an aromatic isocyanate or includes aromatic isocyanates, then the isocyanate may be, include, consist substantially of, or consist of modified polyvalent aromatic isocyanates, i.e., products obtained by the chemical reaction of aromatic diisocyanates and / or aromatic polyisocyanates. Examples include, but are not limited to, urea, biuret, urethane, carbodiimide, urea ketone imide, and isocyanurate and / or diisocyanates and / or polyisocyanates containing urethane groups, such as modified diphenylmethane diisocyanate. The urethane groups of isocyanates can be formed by reacting a base isocyanate as described above with low molecular weight diols, triols, diallyl glycols, trialkyl glycols, polyoxyethylene glycols, diethylene glycols, dipropylene glycols, polyoxypropylene glycols, and combinations thereof, with a number average molecular weight of up to 1500 g / mol; diethylene glycol, dipropylene glycol, polyoxypropylene glycol, polyoxypropylene glycol, and / or polyoxypropylene polyoxyethylene glycol or polyoxypropylene polyoxyethylene triol. Isocyanates may also include one or more prepolymers containing isocyanate groups.

[0091] Isocyanates can be, include, consist substantially of, or consist of modified benzene and toluene diisocyanates, used alone or as reaction products with: polyoxyethylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, polyester alcohol, polycaprolactone, and combinations thereof. In various embodiments, isocyanates can be, include, consist substantially 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. Isocyanate compositions may also include stoichiometric or non-stoichiometric reaction products of the aforementioned isocyanates.

[0092] Alternatively, the isocyanate may be a liquid polyisocyanate comprising one or more carbodiimide groups. In various embodiments, crude polyisocyanates may also be used, such as crude toluene diisocyanate obtained by phosgenation of a mixture of toluene diamines or crude diphenylmethane isocyanate obtained by phosgenation of crude isocyanates.

[0093] The NCO content of the isocyanate is not limited and typically ranges from 5% to 35% by weight. The NCO content, expressed as a percentage by weight, is determined by standard chemical titration analysis known to those skilled in the art. In various non-limiting embodiments, all values ​​and ranges, whether integers or fractions, including the values ​​described above and those between them, are expressly considered herein for their application.

[0094] In other embodiments, non-limiting examples of suitable polyisocyanates include aromatic, aliphatic, or alicyclic diisocyanates, triisocyanates, or tetraisocyanates, including polyisocyanates having isocyanurate structural units, such as isocyanurates of hexamethylene diisocyanate and isocyanurates of isophorone diisocyanate; adducts of two molecules of diisocyanate such as hexamethylene diisocyanate with a diol such as ethylene glycol; urea diketone of hexamethylene diisocyanate; urea diketone or isophorone diisocyanate of isophorone diisocyanate; adducts of trimethylolpropane with m-tetramethylxylene diisocyanate. Other polyisocyanates disclosed herein are also suitable for the production of polyurethanes.

[0095] Other polyurethanes can be prepared as follows: first, an NCO-functional hydrophilic polyurethane prepolymer is formed by the addition reaction of a polyol-type compound with a polyisocyanate; the polyurethane prepolymer thus formed is converted into an aqueous phase; and then the water-dispersed NCO-functional polyurethane prepolymer is reacted with an NCO reactive chain extender such as a polyamine, a hydrazine derivative, or water.

[0096] In other embodiments, the polyurethane can be, include, substantially consist of, or consist of a polyester-polyurethane polymer. The polyester in the polyester-polyurethane polymer can be linear or branched. Useful polyesters can include aliphatic or aromatic dicarboxylic acids, polyols, diols, aromatic or aliphatic cyclic anhydrides, and esterification products of cyclic alcohols. Non-limiting examples of suitable alicyclic polycarboxylic acids are tetrahydrophthalic acid, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, nethylenetetrahydrophthalic acid, tricyclodecanedicarboxylic acid, nethylenehexahydrophthalic acid, camphoric acid, cyclohexanetetracarboxylic acid, and cyclobutanetetracarboxylic acid. Alicyclic polycarboxylic acids can be used not only in their cis form, but also in their trans form and as mixtures of both forms. Other non-limiting examples of suitable polycarboxylic acids may include aromatic and aliphatic polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, halophthalic acids (such as tetrachloro or tetrabromophthalic acid), adipic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, trimellitic acid, and pyromellitic acid. Combinations of polyacids, such as combinations of polycarboxylic acids with alicyclic polycarboxylic acids, may be suitable. Combinations of polyols may also be suitable.

[0097] Non-limiting examples of suitable polyesters include branched copolyester polymers. The branched copolyester polymers and methods of production described in U.S. Patent No. 6,861,495, which is incorporated herein by reference, are suitable. Monomers having multiple functional groups, such as those of the AxBy type (x and y being 1 to 3 independently), including those having one carboxyl group and two hydroxyl groups, two carboxyl groups and one hydroxyl group, one carboxyl group and three hydroxyl groups, or three carboxyl groups and one hydroxyl group, can be used to produce branched structures. Non-limiting examples of such monomers include 2,3-dihydroxypropionic acid, 2,3-dihydroxy-2-methylpropionic acid, 2,2-dihydroxypropionic acid, 2,2-bis(hydroxymethyl)propionic acid, etc.

[0098] Branched copolyester polymers can conventionally be polymerized from a monomer mixture containing a chain extender selected from hydroxycarboxylic acids, lactones of hydroxycarboxylic acids, and combinations thereof; and one or more branched monomers. Some suitable hydroxycarboxylic acids include glycolic acid, lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and hydroxypyvaleric acid. Some suitable lactones include caprolactone, valerolactone; and lactones of the corresponding hydroxycarboxylic acids such as 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and hydroxyvaleric acid. In some embodiments, caprolactone may be used. In embodiments, branched copolyester polymers can be prepared by polymerizing a monomer mixture including a chain extender and hyperbranched monomers in one step, or by first polymerizing the hyperbranched monomers and then polymerizing the chain extender. It should be understood that branched copolyester polymers can be formed from an acrylic core having the aforementioned chain extenders.

[0099] Polyester-polyurethane polymers can be produced from polyesters and polyisocyanates. Polyesters can be polymeric or oligomeric organic substances having at least two hydroxyl functional groups or two thiol functional groups and mixtures thereof. Polyesters and polycarbonates with terminal hydroxyl groups can be effectively used as diols.

[0100] A non-limiting example of a polyester-polyurethane polymer is a polyurethane dispersion resin formed from a linear polyester glycol resin (the reaction product of monomers 1,6-hexanediol, adipic acid, and isophthalic acid) and isophorone diisocyanate. This polyester-polyurethane polymer has a weight-average molecular weight of about 30,000, a solids content of about 35% by weight, and a particle size (e.g., Dv50) of about 250 nanometers, the particle size being determined using any device known in the art, such as a Malvern Mastersizer.

[0101] 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 weight-average molecular weight of about 75,000, a solids content of about 35% by weight, and a particle size (e.g., Dv50) of about 180 nanometers, the particle size being determined using any device known in the art, such as a Malvern Mastersizer.

[0102] In another embodiment, the resin dispersion may be a polyurethane dispersion resin formed from a slightly branched polyester polyol and hexamethylene diisocyanate, for example, having a solids content of about 40% by weight.

[0103] In other embodiments, the resin dispersion may be, include, consist substantially of, or consist of a polyurethane dispersion resin formed from a linear polyester glycol resin (e.g., a reaction product of monomers 1,6-hexanediol, adipic acid, and isophthalic acid) and isophorone diisocyanate, for example, having a solids content of about 35% by weight.

[0104] In another embodiment, the polyurethane is selected from polyurethanes formed from branched polyester polyols and hexamethylene diisocyanates; polyurethanes formed from linear polyester diol resins and isophorone diisocyanates, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; polyurethanes formed from linear polycarbonate-polyester polyols and isophorone diisocyanates; polyester-polyurethane polymers; and combinations thereof.

[0105] In another embodiment, the resin dispersion may be a polyurethane dispersion resin formed from linear polycarbonate-polyester polyol and isophorone diisocyanate, comprising, substantially consisting of, or composed of the following substances.

[0106] In yet another embodiment, the resin dispersion may be, include, consist substantially of, or consist of a trade name. U 241 is a polyester-polyurethane polymer, which is available from Covestro AG, Leverkusen, Germany.

[0107] In one embodiment, the resin dispersion may be, include, substantially consist of, or consist of polyurethane. In various embodiments, based on the total weight of the dispersion, the polyurethane is present in an amount of about 1 to about 100, about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55% by weight of active ingredient. In various embodiments, based on the total weight of the dispersion, 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 weight of active ingredient. In other embodiments, based on the total weight of the composition, the polyurethane (e.g., alone 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, about 16 to about 24% by weight of active ingredient, etc. In various embodiments, the amount is from about 1 to about 15, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% by weight of active ingredient, based on the total weight of the composition. In other embodiments, the polyurethane (alone or as a whole) is present in amounts from about 1 to about 20, from about 2 to about 19, from about 3 to about 18, from about 4 to about 17, from about 5 to about 16, from about 6 to about 15, from about 7 to about 14, from about 8 to about 13, from about 9 to about 12, from about 10 to about 11, or from about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% by weight of active ingredient, based on the total weight of the dispersion. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly considered herein for use.

[0108] Optional crosslinking agent:

[0109] The coating composition also includes an optional crosslinking agent. In various embodiments, the optional crosslinking agent may be, include, consist substantially of, or consist of any melamine crosslinking agent known in the art.

[0110] Melamine resins can be partially or completely etherified with one or more alcohols such as methanol or butanol. A non-limiting example is hexamethoxymethyl melamine. Non-limiting examples of suitable melamine resins include monomeric melamines, polymeric melamine-formaldehyde resins, or combinations thereof. Monomeric melamines include low molecular weight melamines in which each triazine core contains, on average, three or more hydroxymethyl groups etherified with a C1 to C5 monohydric alcohol such as methanol, n-butanol, or isobutanol, and has an average degree of condensation of at most about 2, and in some embodiments, the average degree of condensation is in the range of about 1.1 to about 1.8, and has a proportion of not less than about 50% by weight of mononucleates. 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... 301 (degree of polymerization 1.5, 95% methyl and 5% hydroxymethyl), 350 (degree of polymerization 1.6, 84% methyl and 16% hydroxymethyl), 303, 325, 327, 370, and XW3106 are all monomeric melamines. Suitable polymeric melamines include those supplied by Solutia Inc., St. Louis, Mo., and are called... BMP5503 (molecular weight 690, polydispersity 1.98, 56% butyl, 44% amino) is a highly amino (partially alkylated, -N, -H) melamine, or supplied by Cytec Industries Inc., West Patterson, NJ. 1158. Cytec Industries Inc. also offers 1130@80% solids (degree of polymerization 2.5) 1133 (48% methyl, 4% hydroxymethyl, and 48% butyl), all of which are polymeric melamines. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly considered herein for use.

[0111] The coating composition may include more than one type of crosslinking agent having the same or different crosslinking functional groups. Typical crosslinking functional groups may include hydroxyl, thiol, isocyanate, thioisocyanate, acetoacetoxy, carboxyl, primary amine, secondary amine, epoxy, acid anhydride, ketimine, aldolimine, orthoester, orthocarbonate, cyclic amide, or combinations thereof.

[0112] 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 weight of the active ingredient, based on the total weight percentage of the composition. In other embodiments, the 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 weight of the active ingredient, based on the total weight 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 weight of the active ingredient, based on the total weight of the composition. In all the various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein for use.

[0113] In an exemplary embodiment, the coating composition includes, under the trade name 303 Melamine-formaldehyde resin purchased from Cytec Industries Inc., West Patterson, NJ.

[0114] Optional isocyanate crosslinking agent:

[0115] In various implementations, a melamine crosslinking agent is used instead of a capped isocyanate crosslinking agent. Alternatively, both a capped isocyanate crosslinking agent and a melamine crosslinking agent can be used. Alternatively, a melamine crosslinking agent can be used without the capped isocyanate crosslinking agent.

[0116] The composition may or may not contain a capped isocyanate crosslinking agent. There are no particular limitations on the capped isocyanate crosslinking agent, and it may be any capped isocyanate crosslinking agent known in the art, such as any capped isocyanate crosslinking agent as described above. In various embodiments, the capped isocyanate crosslinking agent may be, include, consist substantially of, or consist of: one or more isocyanates, such as, but not limited to, aromatic, aliphatic, or alicyclic diisocyanates, triisocyanates, or tetraisocyanates, including polyisocyanates having isocyanurate structural units, such as isocyanurates of hexamethylene diisocyanate and isocyanurates of isophorone diisocyanate; adducts of two molecules of diisocyanate such as hexamethylene diisocyanate with diols such as ethylene glycol; urea diketone of hexamethylene diisocyanate; urea diketone or isophorone diisocyanate of isophorone diisocyanate; adducts of trimethylolpropane with m-tetramethylxylene diisocyanate.

[0117] In various embodiments, isocyanates can be used, such as oligomers based on hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), or toluidine diisocyanate (TDI), such as isocyanurates, biuret, urethane, and adducts of the aforementioned isocyanates with polyols and mixtures thereof. These can react with polyols, such as hydroxyl-containing polyesters, polyethers, acrylates, and polyurethanes and mixtures thereof, which can be solvent-based, solvent-free, or water-dilutable. This end-capped isocyanate crosslinking agent can be used in any amount, for example, in the amount described above relative to other optional crosslinking agents.

[0118] Optional pigments

[0119] The coating composition also includes optional pigments. Therefore, the composition may contain pigments or not. Any pigment known in the art for use in coating compositions may be used in said coating composition. Non-limiting examples of suitable pigments include metal oxides, metal hydroxides, effect pigments (including flake metals), chromates (such as lead chromate), sulfides, sulfates, carbonates, carbon black, silica, talc, kaolin, phthalocyanine blue and phthalocyanine green, organic red, organic maroon, pearlescent pigments, other organic pigments and dyes, and combinations thereof. If desired, chromate-free pigments such as barium metaborate, zinc phosphate, aluminum triphosphate, and combinations thereof may also be used.

[0120] Other non-limiting examples of suitable effect pigments include bright aluminum flakes, very fine aluminum flakes, medium-grained aluminum flakes, and bright medium-coarse aluminum flakes; mica flakes coated with titanium dioxide pigment (also known as pearlescent pigments); and combinations thereof. Non-limiting examples of suitable colored pigments include titanium dioxide, zinc oxide, iron oxide, carbon black, monoazo red toner, iron oxide red, quinacridone maroon, transparent oxide red, dioxazine carbazole violet, iron blue, indanone blue, chromium titanate, titanium yellow, monoazo permanent orange, iron yellow, monoazo benzimidazolone yellow, transparent yellow oxide, isoindoline yellow, tetrachloroisoindoline yellow, anthrone orange, lead chromate yellow, phthalocyanine green, quinacridone red, perylene maroon, quinacridone violet, pre-darkened chrome yellow, indigo thiocyanate, transparent oxide red flakes, molybdate orange, molybdate orange red, and combinations thereof.

[0121] Alternatively, the pigment may be described as an extender pigment. While extender pigments are often used to replace more expensive pigments in coating compositions, the extender pigments considered herein can increase the shear viscosity of the coating composition compared to coating compositions without extender pigments. This increase in shear viscosity improves the suitability of applying the coating composition to a substrate using a high-transfer-efficiency applicator. Extender pigments can have a particle size of about 0.01 to about 44 micrometers (e.g., Dv50, as determined using a Malvern Mastersizer). Extender pigments can have a variety of structures, including but not limited to nodular, flake, needle-like, and fibrous forms. Non-limiting examples of suitable extender pigments include white powder, barite, amorphous silica, pyrolytic silica, diatomaceous earth silica, kaolin, calcium carbonate, mica, wollastonite, magnesium silicate (talc), barium sulfate, kaolin, and aluminum silicate. In all non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein.

[0122] Based on the total weight of the coating composition, 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 weight. In other embodiments, the pigment is optionally 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 weight of active ingredient, based on the total weight of the composition. In other embodiments, the pigment is optionally present 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 weight of active ingredient, based on the total weight of the composition. In other embodiments, the optional pigment is present in amounts of about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, about 0.5 to about 0.6, or about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0% by weight of active ingredient, based on the total weight of the composition. In all the various non-limiting embodiments, all values ​​and ranges, whether integers or fractions, including the values ​​above and values ​​between the values ​​above, are expressly considered herein for use.

[0123] In some embodiments, the coating composition comprises magnesium silicate (talc), barium sulfate, or a combination thereof. In various embodiments, comprising barium sulfate as an extender pigment results in a coating composition with a higher shear viscosity compared to comprising talc as an extender pigment. In various embodiments, the optional pigments are selected from Pigment Yellow 213, PY 151, PY 93, PY 83, Pigment Red 122, PR 168, PR 254, PR 179, Pigment Red 166, Pigment Red 48:2, Pigment Violet 19, Pigment Blue 15:1, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Green 7, Pigment Green 36, Pigment Black 7, or Pigment White 6, and combinations thereof.

[0124] water

[0125] The composition also comprises water. In various embodiments, the amount of water 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 weight of active ingredient, based on the total weight 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 weight of active ingredient, based on the total weight of the composition. This amount of water may describe the total amount of water in the composition or the amount of water added to the composition, regardless of any water contained in, for example, dispersions, solvents, etc. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​above and values ​​between the values ​​above, are expressly considered herein.

[0126] Water-soluble solvents

[0127] The composition also contains a water-soluble solvent, which is not particularly limited and can be any solvent known in the art. In various embodiments, the water-soluble solvent can 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, methyl diethanolamine, methyl isocyanate, N-methyl-2-pyrrolidone, propionic acid, propylene glycol, pyridine, tetrahydrofuran, triethylene glycol, glycol ethers (ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), any and all isomers thereof, or combinations thereof. Alternatively, the composition may not contain any one or more of the solvents mentioned above, as long as at least one water-soluble solvent is used in the composition.

[0128] 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 weight of the active ingredient, based on the total weight of the composition. In other embodiments, the water-soluble solvent is present, based on the total weight of the composition, 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, about 16 to about 24% by weight of active ingredient, etc. In other embodiments, the water-soluble solvent is present in an amount 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 weight of the active ingredient, based on the total weight of the composition. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein for use.

[0129] At least one rheology control agent

[0130] The composition also includes at least one rheology control agent. For example, a rheology modifier that can increase the rheological properties of the coating composition can be used compared to a coating composition without a rheology modifier. Increased rheological properties of the coating composition improve its applicability to substrates using a high-efficiency applicator. In this disclosure, as described in more detail below, the at least one rheology control agent is used to reduce sagging and / or minimize sagging.

[0131] In various embodiments, based on the total weight of the composition, the at least one rheology control agent is present in an amount of up to 20, about 0.1 to 20, about 0.1 to 15, about 0.1 to 10, about 0.1 to 5, about 0.1 to 1, about 0.1 to 0.9, about 0.2 to 0.8, about 0.3 to 0.7, about 0.4 to 0.6, about 0.5 to 0.6, about 0.5 to 10, about 1 to 9.5, about 1.5 to 9, about 2 to 8.5, about 2.5 to 8, about 3 to 7.5, about 3.5 to 7, about 4 to 6.5, about 4.5 to 6, about 5 to 5.5, or about 0.01, 0.02, 0.03...0.1, 0.2, 0.3...1, 1.1, 1.2... up to and including 20% ​​by weight of active ingredient. In various embodiments, the at least one rheology control agent is present in an amount of about 0.01 to about 7% by weight. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein.

[0132] The at least one rheology control agent is selected from alkali-swellable emulsions, layered silicates, and combinations thereof. In various embodiments, the at least one rheology control agent is, includes, is substantially composed of, or is composed of alkali-swellable emulsions, layered silicates, and combinations thereof. For example, the term "substantially composed of" can describe embodiments that do not contain any alternative rheology control agents. In one embodiment, the at least one rheology control agent comprises an alkali-swellable emulsion but does not include layered silicates. In another embodiment, the at least one rheology control agent comprises layered silicates but does not include alkali-swellable emulsions. In yet another embodiment, both alkali-swellable emulsions and layered silicates are used.

[0133] There are no particular limitations on alkali-swellable emulsions (ASEs) and they can be any alkali-swellable emulsion known in the art. ASEs can include carboxyl-containing copolymers prepared by addition polymerization of olefinic unsaturated monomers and swollen or solubilized upon neutralization to thicken aqueous media. Depending on their chemical structure and primary thickening mechanism, these ASEs can be broadly classified as conventional (presumably non-associative) or associative. ASEs are typically copolymers of methacrylic acid and a non-water-soluble ester of that acid. ASEs typically thicken only in a neutralized state (pH > 7) by utilizing the ion repulsion mechanism between various carboxylic acid ester groups carried by the polymer chain. Typically, ASEs are manufactured as direct emulsions of alkali-swellable polymers in water, with the active ingredient content varying between about 10% and about 45% of the total weight. In one embodiment, the ASE is an acrylic polymer emulsion.

[0134] In various embodiments, the alkali-swellable emulsion is present in an amount of active ingredient 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 weight, based on the total weight of the at least one rheology control agent. In other embodiments, based on the total weight of the composition, the alkali-swellable emulsion is present in amounts of about 0.1 to about 20, about 0.1 to about 15, about 0.1 to about 10, about 0.1 to about 5, about 0.1 to about 1, about 0.1 to about 0.9, about 0.2 to about 0.8, about 0.3 to about 0.7, about 0.4 to about 0.6, about 0.5 to about 0.6, about 0.5 to about 10, about 1 to about 9.5, about 1.5 to about 9, about 2 to about 8.5, about 2.5 to about 8, about 3 to about 7.5, about 3.5 to about 7, about 4 to about 6.5, about 4.5 to about 6, about 5 to about 5.5, or about 0.1, 0.2, 0.3...1, 1.1, 1.2... up to and including about 20% by weight of active ingredient. It is contemplated that the alkali-swellable emulsion may not be used at all. In all non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​mentioned above and values ​​in between, are expressly considered for use herein.

[0135] Now consider layered silicates. There are no particular limitations on this compound; it can be any layered silicate known in the art. Layered silicates typically comprise octahedral planar layers or silicates composed of octahedral planar layers, with tetrahedral layers bonded vertically, wherein there is a characteristic repeating distance between the layers. For example, layered silicates can be classified based on their repeating distance. Layered silicates, Silicates and chlorite. The minerals in these clusters can be further divided into dioctahedral and trioctahedral. Layered silicates include kaolinite Al4(Si4O) 10 (OH)8 (dioctahedral) and serpentine Mg6 (Si4O) 10 )(OH)8(trioctahedron). Layered silicates typically form as weathering products and can exhibit perfect planar dissociation, making them suitable for classification as mica. These clusters may also include clay minerals. Chlorite comprises dioctahedral and trioctahedral Mg₅Al(AlSi₃O₃)₂. 10(OH)8. In various embodiments, layered silicates comprise two-dimensional (2D) layers of two molten silicate tetrahedral sheets or consist of two two-dimensional (2D) layers of two molten silicate tetrahedral sheets, each approximately 100 μm thick and 100 nm to 1000 nm long, with octahedral metal atom sheets (such as Mg or Al) sharing edges. The gaps between the sheets are called corridors, which are typically filled with cations to counteract excess negative charges. The stacking of the sheets results in regular van der Waals gaps between the layers. Isomorphic substitutions within the layers (e.g., Al) 3+ Mg 2+ or Fe 2+ Substitution, or Mg 2+ By Li 1+ Substitution generates negative charges, which are counteracted by alkali metal and alkaline earth metal cations located within the interstitial spaces. Layered silicates have two structures: tetrahedral substituted and octahedral substituted. In the case of tetrahedral substituted layered silicates, the negative charges are located on the surface of the silicate layers, thus the polymer matrix can interact with these more readily than with octahedral substituted materials. In various embodiments, MMT, lithium montmorillonite, and saponite are commonly used layered silicates.

[0136] In some embodiments, a lithium saponite propylene glycol solution comprising the synthetic layered silicate, water, and polypropylene glycol is used. The synthetic layered silicate is available from Altana AG of Wesel, Germany, under the trade name Laponite RD.

[0137] In one embodiment, the layered silicate is a synthetic foliated silicate.

[0138] 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 weight of active material, based on the total weight of the at least one rheology control agent. In other embodiments, the layered silicate is present, based on the total weight of the composition, in amounts of about 0.1 to about 20, about 0.1 to about 15, about 0.1 to about 10, about 0.1 to about 5, about 0.1 to about 1, about 0.1 to about 0.9, about 0.2 to about 0.8, about 0.3 to about 0.7, about 0.4 to about 0.6, about 0.5 to about 0.6, about 0.5 to about 10, about 1 to about 9.5, about 1.5 to about 9, about 2 to about 8.5, about 2.5 to about 8, about 3 to about 7.5, about 3.5 to about 7, about 4 to about 6.5, about 4.5 to about 6, about 5 to about 5.5, about 0.1 to about 0.6, or about 0.1, 0.2, 0.3...1, 1.1, 1.2... up to and including about 20% by weight of active material. In all non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​mentioned above and values ​​in between, are expressly considered for use herein.

[0139] In various embodiments, HEUR, namely hydrophobically modified ethylene oxide-urethane block copolymers, can be used. HEURs can be used with one or both of alkali-swellable emulsions, layered silicates, or combinations thereof, or without them. There are no particular limitations on HEURs, and any HEUR known in the art can be used. For example, polyalkylene glycols can be reacted with a hydrophobic end-capping agent or a hydrophobic bifunctional agent or a combination thereof, and a stoichiometric excess of diisocyanate relative to the total molar amount of the isocyanate reactive groups of the polyalkylene glycol and the end-capping agent or the hydrophobic bifunctional agent or the combination thereof, to form a polyurethane prepolymer having isocyanate functional groups. This prepolymer can then be converted into a hydrophobically modified alkylene oxide poly(urethane-urea-urethane), which may also contain additional functional groups such as amine functional groups. However, this disclosure is not limited to such HEURs, and any HEUR known in the art can be used. For example, any OH-functionalized compound and any isocyanate compound described herein can be used to form block copolymers.

[0140] Additional optional components:

[0141] The coating composition may contain or not contain one or more of various components, such as binders, dyes, additional rheology modifiers, carriers, catalysts, conventional additives, or combinations thereof. Conventional additives may include, but are not limited to, dispersants, antioxidants, UV stabilizers and absorbers, surfactants, wetting agents, leveling agents, defoamers, anti-cratering agents, or combinations thereof. In embodiments, based on the presence of certain components and / or the presence of certain components in specific amounts / ratios, the coating composition is suitable for application to a substrate using a high-transfer-efficiency applicator.

[0142] In various embodiments, the coating composition may also comprise a dye. Non-limiting examples of suitable dyes include triphenylmethane dyes, anthraquinone dyes, xanthones and related dyes, azo dyes, reactive dyes, phthalocyanine compounds, quinacridone compounds, and fluorescent whitening agents and combinations thereof. Based on the total weight of the coating composition, the coating composition may contain 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 weight. In some embodiments, the coating composition comprises 10% of a black dye solution, such as Sol. Orasol Negro RL. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein.

[0143] In various embodiments, in addition to those described above, the coating composition may also contain additional rheology modifiers. Many different types of rheology modifiers that can be used in the coating composition may be used. Non-limiting examples of suitable rheology modifiers include urea-based compounds, acrylic alkaline emulsions, and combinations thereof. Based on the total weight of the coating composition, the coating composition may contain an amount of additional rheology modifier of about 0.01 to about 5%, or about 0.05 to about 1%, or about 0.05 to about 0.5% by weight. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein.

[0144] The term "binder" refers to a film-forming component of a coating composition. Typically, a binder may include polymers, oligomers, or combinations thereof, which are essential for forming a coating with desired properties such as hardness, protection, adhesion, etc. Additional components, such as carriers, pigments, catalysts, rheology modifiers, antioxidants, UV stabilizers and absorbers, leveling agents, defoamers, anti-cratering agents, or other conventional additives, may not be included in the term "binder" unless any of these additional components is a film-forming component of the coating composition. One or more of these additional components may be included in the coating composition. In some embodiments, the binder comprises a polymer. Based on the total weight of the coating composition, the coating composition may contain about 5 to about 70% by weight, or about 10 to about 50% by weight, or about 15 to about 25% by weight of the binder. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein.

[0145] The coating composition may also contain a catalyst. The coating composition may further contain a catalyst to reduce curing time and allow the coating composition to cure at ambient temperature or elevated temperatures. Ambient temperature generally refers to a temperature in the range of about 18°C ​​to about 35°C. Non-limiting examples of suitable catalysts may include organometallic salts such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dichloride, dibutyltin dibromide, zinc naphthenate; triphenylboron, tetraisopropyl titanate, triethanolamine titanate chelate, dibutyltin dioxide, dibutyltin dioctanoate, tin octanoate, aluminum titanate, aluminum chelates, zirconium chelates, phosphonium halides such as ethyltriphenylphosphonium iodide and other such phosphonium salts and other catalysts or combinations thereof. Non-limiting examples of suitable acid catalysts may include carboxylic acids, sulfonic acids, phosphoric acid, 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 combinations thereof. Based on the total weight of the coating composition, the coating composition may contain a 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 weight. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​above and values ​​between the values ​​above, are expressly considered herein for use.

[0146] The coating composition may also contain conventional additives. The coating composition may also contain UV stabilizers. Non-limiting examples of such UV stabilizers include UV absorbers, shielding agents, quenchers, and hindered amine light stabilizers. Antioxidants may also be added to the coating composition. Typical UV stabilizers may include benzophenone, triazoles, triazines, benzoates, hindered amines, and mixtures thereof. Mixtures of hindered amine light stabilizers may be used, such as… 328 and 123, they can all be obtained from Ciba Specialty Chemical, Tarrytown, New York, under the trade name. Purchased.

[0147] Non-limiting examples of suitable ultraviolet absorbers include hydroxyphenylbenzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, the reaction product of 2-(2-hydroxy-3-tert-butyl-5-methylpropionate)-2H-benzotriazole with polyethyl ether glycol of weight average molecular weight 300, and 2-(2-hydroxy-3-tert-butyl-5-isooctylpropionate)-2H-benzotriazole; hydroxyphenyltriazines, such as 2-[4(( [2-Hydroxy-3-dodecyloxypropyl)-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-octoxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; hydroxybenzophenone UV absorbers, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-dodecyloxybenzophenone.

[0148] 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-tetramethylpiperidin-4-ol-succinic acid copolymer, 1,3,5-triazine-2,4,6-triamine, N,N'”-[1 ,2-Ethyldimethylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-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-triazin-2,4-diyl][2 [2,6,6-Tetramethylpiperidinyl)-imino]-1,6-hexane-diyl[(2,2,6,6-tetramethyl-4-piperidinyl)-imino]), sebacate bis(2,2,6,6-tetramethyl-4-piperidinyl), sebacate bis(1,2,2,6,6-pentamethyl-4-piperidinyl), sebacate bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl), [3,5-bis(1,1-dimethylethyl-4-hydroxy] [1,2,2,6,6-pentamethyl-4-piperidinyl]butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl), 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dione, and 3-(2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazabispiro(5.1.11.2)eicosano-20-yl)propionate dodecyl ester / tetradecyl ester.

[0149] Non-limiting examples of suitable antioxidants include tetra[methylene(3,5-di-tert-butylhydroxycinnamate)]methane, octadecyl 3,5-di-tert-butyl-4-hydroxycinnamate, 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 phenylpropionic acid, and 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl esters. In some embodiments, the antioxidant includes a hydroperoxide decomposing agent, such as... HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), triphenyl phosphate and other organophosphorus compounds, such as those from Ciba Specialty Chemicals. TNPP, from CibaSpecialty Chemicals 168. From GE Specialty Chemicals 626, Mark PEP-6 from Asahi Denka, Mark HP-10 from Asahi Denka, and from Ciba Specialty Chemicals. P-EPQ, Ethanox 398 from Albemarle, Weston 618 from GE Specialty Chemicals, and Ciba Specialty Chemicals 12. From CibaSpecialty Chemicals 38. From GE Specialty Chemicals 641 and from Dover Chemicals S-9228.

[0150] The coating composition may also contain other additives known in the art, such as wetting agents, leveling agents, and flow control agents, for example, each with a trade name. S (polybutyl acrylate), 320 and 325 (high molecular weight polyacrylate), 347 (polyether-modified siloxane), a leveling agent based on (meth)acrylic acid homopolymer; a rheology control agent; a thickener, such as partially crosslinked polycarboxylic acid or polyurethane; and a defoamer. These other additives can be used in conventional amounts familiar to those skilled in the art. In embodiments, the wetting agents, leveling agents, flow control agents, and surfactants of the coating composition affect the surface tension of the coating composition, and thus may affect the suitability of the coating composition for printing. 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.

[0151] There are no particular limitations on the solids content of the coating composition, and it may have a solids content of about 5 to about 90, or 5 to about 80, about 15 to about 70% by weight, about 15 to about 30, about 10 to about 35, or about 20 to about 25% by weight, based on the weight 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 weight, based on the weight of the composition. The solids content can be determined according to ASTM D2369-10. In some embodiments, a higher solids content is expected in the coating composition because conventional spraying equipment is not used to atomize the coating composition. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​above and values ​​between the values ​​above, are expressly considered herein.

[0152] In one embodiment, the ASE is an acrylic alkaline 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 is used. This dispersion may have, for example, a solids content of 46% by weight, a Tg of -7°C, an acid value of 12, and a hydroxyl value of 7. In another embodiment, the polyurethane dispersion resin is formed from a slightly branched polyester polyol and hexamethylene diisocyanate. In another embodiment, the polyurethane dispersion resin is formed from a linear polyester glycol resin (e.g., the reaction product of monomers 1,6-hexanediol, adipic acid, and isophthalic acid) and isophorone diisocyanate. In another embodiment, the polyurethane dispersion resin is formed from a linear polycarbonate-polyester polyol and isophorone diisocyanate. In another embodiment, hexa(methoxymethyl)melamine (HMMM) melamine-formaldehyde resin is used. In another embodiment, a high-imino melamine-formaldehyde resin is used. In another embodiment, a dispersion of amorphous carbon black pigment is used. In yet another embodiment, a dispersion of micronized talc-based pigment is used.

[0153] Physical properties:

[0154] In various embodiments, the coating composition has a viscosity of about 20 to about 100 cps, said viscosity being determined using ASTM 7867-13 with a cone or parallel plate at 1000 s. -1The viscosity was determined at a shear rate 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, whether integers or fractions, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly considered as used herein.

[0155] In other embodiments, the coating composition has a wet film thickness of at least about 20, 25, 30 micrometers or greater when measured at about 45 degrees Celsius, without visible sagging. For example, the wet film thickness when measured at about 45 degrees Celsius could be about 30 micrometers to about 150 micrometers, or about 40 to about 120 micrometers, without visible sagging. In other embodiments, the wet film thickness could 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 micrometers. In all the various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly considered herein.

[0156] To assess sagging, the following procedure is typically used:

[0157] Orient the substrate panel horizontally before applying the coating;

[0158] Four separate strips of paint composition with varying thicknesses, each 40 mm wide, were applied to a horizontal substrate using a Rea Jet DOD 2.0 32-nozzle printhead. After application, the substrate was tilted at approximately 45 degrees to the horizontal. After approximately 5 minutes at room temperature, with the angle maintained, the substrate was baked at approximately 140°C for approximately 30 minutes. Any sagging was indicated by dripping at the bottom edge of the coating and assessed visually.

[0159] In various implementations, ASTM D4400-18 is used to determine sagging. Typically, both the ASTM D4400 method and the printing method are performed at a 45-degree angle. In one implementation, the following conditions are used: ASTM D4400-18 w / ASM-2 and ASM-1 anti-sagging apparatus, on a coil-coated plate, at 45 degrees, rapid evaporation at room temperature for 4 minutes and baking at 140°C for 30 minutes.

[0160] The composition may also have a yield stress greater than about 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 about 0.1 to about 2.5, about 0.5 to about 2.5, about 1 to about 2.5, about 1.5 to about 2.5, about 2 to about 2.5, about 0.5 to about 2, about 0.5 to about 1.5, about 0.5 to about 1, about 1 to about 2, about 1 to about 1.5, or about 1.5 to about 2 Pa. Typically, the yield stress is measured using a controlled stress scan on a rheometer with a conical-plate geometry. The samples were sheared at each shear stress from 0.01 Pa to 10,000 Pa, and the shear rate and viscosity were measured. The viscosity data and first derivatives were then plotted against shear stress on a log-log scale. The yield stress value was determined by the stress with the lowest first derivative (i.e., the maximum negative slope of the viscosity-stress curve). In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are expressly considered herein.

[0161] In various embodiments, the coating composition is in 0.1s -1 The coating composition has viscosities of approximately 400 to 10,000, approximately 400 to 1,000, approximately 500 to 900, approximately 600 to 800, approximately 600 to 700, approximately 1,000 to 9,500, approximately 1,500 to 9,000, approximately 2,000 to 8,500, approximately 2,500 to 8,000, approximately 3,000 to 7,500, approximately 3,500 to 7,000, approximately 4,000 to 6,500, approximately 4,500 to 6,000, or approximately 5,000 to 5,500 mPa·s, wherein the viscosity is determined using ASTM D7867. In other embodiments, the coating composition has a viscosity of approximately 1000 s. -1 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, wherein the viscosity is determined using ASTM D7867. In other embodiments, the coating composition has a viscosity of about 10,000 mPa·s. -1 After 5 seconds of shearing, in 1 second -1The viscosities are approximately 50 to approximately 1,000, approximately 100 to approximately 950, approximately 150 to approximately 900, approximately 200 to approximately 850, approximately 250 to approximately 800, approximately 300 to approximately 750, approximately 350 to approximately 700, approximately 400 to approximately 650, approximately 450 to approximately 600, or approximately 500 to approximately 550 mPa·s, wherein the viscosities are determined using ASTM D7867. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​above and values ​​between the values ​​above, are expressly considered herein.

[0162] Curing of the coating composition:

[0163] In various embodiments, the method further includes a step of curing the coating composition on the substrate. For example, the coating composition may be free from visual defects caused by incomplete flow and leveling of the individual nozzle lines after the curing step.

[0164] Other implementation plans

[0165] In one embodiment, the resin dispersion is present in an amount of about 15 to about 30% by weight, based on the total weight of the composition; the crosslinking agent is melamine, present in an amount of about 2 to about 7% by weight, based on the total weight of the composition; the pigment is present in an amount of about 0.1 to about 20% by weight, based on the total weight of the composition; water is present in an amount of about 15 to about 70% by weight, based on the total weight of the composition; a water-soluble solvent is present in an amount of about 5 to about 20% by weight, based on the total weight of the composition; and the at least one rheology control agent is present in an amount of about 0.01 to about 5% by weight, based on the total weight of the composition; wherein the coating composition has a viscosity of about 35 to about 95 cps, the viscosity being determined using ASTM 7867-13 with a cone or parallel plate at a shear rate of 1000 s⁻¹, and wherein, when measured at about 45 degrees, the coating composition has a wet film thickness of at least about 20 micrometers without visible sagging, determined using ASTM D4400-18.

[0166] In another embodiment, the resin dispersion is present in an amount of about 19 to about 22% by weight, based on the total weight of the composition, and comprises: an acrylic latex dispersion, present in an amount of about 9 to about 11% by weight and being an acrylic dispersion containing epoxy groups, which is a polyester-modified acrylic dispersion; a first polyurethane dispersion, present in an amount of about 4.5 to about 5.5% by weight and formed from branched polyester polyol and hexamethylene diisocyanate, based on the total weight of the composition; a second polyurethane dispersion, present in an amount of about 3 to about 4% by weight and formed from linear polyester glycol resin and isophorone diisocyanate, wherein the linear polyester glycol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; and a second polyurethane dispersion, present in an amount of about 1 to about 2% by weight and formed from branched polyester polyol and hexamethylene diisocyanate, based on the total weight of the composition. A third polyurethane dispersion formed from polycarbonate-polyester polyol and isophorone diisocyanate; a crosslinking agent is melamine, present in an amount of about 3.9 to about 4.6% by weight based on the total weight of the composition; a pigment is an emulsion, present in an amount of about 8 to about 16% by weight based on the total weight of the composition; water is present in an amount of about 35 to about 45% by weight based on the total weight of the composition; a water-soluble solvent is butanol, present in an amount of about 6 to about 7% by weight based on the total weight of the composition; and the at least one rheology control agent is an alkali-swellable emulsion, the alkali-swellable emulsion being an acrylic copolymer emulsion, present in an amount of about 4 to about 5% by weight based on the total weight of the composition, and the composition is free of layered silicates; wherein the coating composition has a viscosity of about 35 to about 70 cps, the viscosity being determined using ASTM... 7867-13 The coating composition is determined using a conical or parallel plate at a shear rate of 1000 s⁻¹, and wherein, when measured at approximately 45 degrees, the coating composition has a wet film thickness of at least approximately 20 micrometers and no visible sagging, as determined using ASTM D4400-18.

[0167] In another embodiment, the resin dispersion is present in an amount of about 28 to about 29% by weight based on the total weight of the composition, and comprises: an acrylic latex dispersion present in an amount of about 8 to about 9% by weight based on the total weight of the composition and being a styrene-acrylic latex dispersion; a first polyurethane dispersion present in an amount of about 12 to about 13% by weight based on the total weight of the composition and formed of a branched polyester polyol and hexamethylene diisocyanate; and a second polyurethane dispersion present in an amount of about 8 to about 9% by weight based on the total weight of the composition and formed of a linear polyester glycol resin and isophorone diisocyanate, wherein the linear polyester glycol is a reaction mixture of 1,6-hexanediol, adipic acid, and isophthalic acid. The product comprises: a crosslinking agent of melamine, present in an amount of about 2 to 3% by weight based on the total weight of the composition; a pigment of an emulsion, present in an amount of about 5 to 6% by weight based on the total weight of the composition; water present in an amount of about 40 to 50% by weight based on the total weight of the composition; a water-soluble solvent of butanol, present in an amount of about 7 to 8% by weight based on the total weight of the composition; and at least one rheology control agent of an alkali-swellable emulsion, wherein the alkali-swellable emulsion is an acrylic copolymer emulsion, present in an amount of about 2.5% by weight based on the total weight of the composition, and wherein the composition is free of layered silicates; wherein the coating composition has a viscosity of about 90 to 95 cps, the viscosity being determined by ASTM 7867-13 using a cone or parallel plate at 1000 s. -1 The coating composition was measured at a shear rate of less than about 0.5 Pa, and the coating composition had a wet film thickness of at least about 20 micrometers with no visible sagging when measured at about 45 degrees, using ASTM D4400-18.

[0168] In another embodiment, the resin dispersion is present in an amount of about 19 to about 20% by weight based on the total weight of the composition, and comprises: an acrylic latex dispersion present in an amount of about 9 to about 10% by weight based on the total weight of the composition and being an acrylic dispersion containing epoxy groups, which is a polyester-modified acrylic dispersion; a first polyurethane dispersion present in an amount of about 4 to about 5% by weight based on the total weight of the composition and being formed from a branched polyester polyol and hexamethylene diisocyanate; a second polyurethane dispersion present in an amount of about 3 to about 4% by weight based on the total weight of the composition and being formed from a linear polyester glycol resin and isophorone diisocyanate, wherein the linear polyester glycol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; and a second polyurethane dispersion present in an amount of about 1 to about 2% by weight based on the total weight of the composition and being formed from a linear polycarbonate. A third polyurethane dispersion formed from ester-polyester polyol and isophorone diisocyanate; a crosslinking agent of melamine, present in an amount of about 3 to 4% by weight based on the total weight of the composition; a pigment of emulsion, present in an amount of about 15 to 17% by weight based on the total weight of the composition; water present in an amount of about 30 to 35% by weight based on the total weight of the composition; a water-soluble solvent of butanol, present in an amount of about 6 to 7% by weight based on the total weight of the composition; and the at least one rheology control agent comprising an alkali-swellable emulsion and about 0.1 to 0.5% by weight of layered silicate based on the total weight of the composition, wherein the alkali-swellable emulsion is an acrylic copolymer emulsion, present in an amount of about 3 to 3.5% by weight based on the total weight of the composition; wherein the coating composition has a viscosity of about 70 to 75 cps, the viscosity being determined using ASTM 7867-13 with a conical or parallel plate at 1000 s. -1 The coating composition was measured at a shear rate of less than about 2 Pa, and the coating composition had a wet film thickness of at least about 20 micrometers with no visible sagging when measured at about 45 degrees, using ASTM D4400-18.

[0169] In another embodiment, the resin dispersion is present in an amount of about 27 to about 28% by weight based on the total weight of the composition, and comprises: an acrylic latex dispersion, present in an amount of about 8 to about 9% by weight based on the total weight of the composition, and being a styrene-acrylic latex dispersion; a second polyurethane dispersion, present in an amount of about 6.5 to about 7.5% by weight based on the total weight of the composition, and formed from a linear polyester glycol resin and isophorone diisocyanate, wherein the linear polyester glycol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; a crosslinking agent, melamine, present in an amount of about 2 to about 3% by weight based on the total weight of the composition; and a pigment, an emulsion, and a base The composition contains, by weight, about 1 to about 2%; water contains, by weight, about 15 to about 20%; a water-soluble solvent is butanol, containing, by weight, about 7 to about 8%; and the at least one rheology control agent comprises an alkali-swellable emulsion and, by weight, about 0.1 to about 0.5% of layered silicate, the alkali-swellable emulsion being an acrylic copolymer emulsion, containing, by weight, about 3 to about 3.5%; wherein the coating composition has a viscosity of about 90 to about 95 cps, the viscosity measured using ASTM 7867-13 with a cone or parallel plate at 1000 s. -1 The coating composition was determined at a shear rate of at least about 1 Pa, and the coating composition had a wet film thickness of at least about 20 micrometers with no visible sagging when measured at about 45 degrees, using ASTM D4400-18.

[0170] In another embodiment, based on the total weight of the composition, the resin dispersion is present in an amount of about 19 to about 22% by weight and comprises: an acrylic latex dispersion, said acrylic latex dispersion being 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 said 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.

[0171] In another embodiment, based on the total weight of the composition, the acrylic latex dispersion is present in an amount of about 9 to about 11% by weight; based on the total weight of the composition, the first polyurethane dispersion is present in an amount of about 4.5 to about 5.5% by weight; based on the total weight of the composition, the second polyurethane dispersion is present in an amount of about 3 to about 4% by weight; and based on the total weight of the composition, the third polyurethane dispersion is present in an amount of about 1 to about 2% by weight, wherein the alkali-swellable emulsion is an acrylic copolymer emulsion and the layered silicate is a synthetic layered silicate.

[0172] In another embodiment, based on the total weight of the composition, the resin dispersion is present in an amount of about 28 to about 29% by weight and comprises: an acrylic latex dispersion, said acrylic latex dispersion being a styrene-acrylic latex dispersion; a first polyurethane dispersion formed from a branched polyester polyol and hexamethylene diisocyanate; and a second polyurethane dispersion formed from a linear polyester diol resin and isophorone diisocyanate, wherein said linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid.

[0173] In another embodiment, based on the total weight of the composition, an acrylic latex dispersion is present in an amount of about 8 to about 9% by weight; a first polyurethane dispersion is present in an amount of about 12 to about 13% by weight; and a second polyurethane dispersion is present in an amount of about 8 to about 9% by weight, wherein the alkali-swellable emulsion is an acrylic copolymer emulsion and the layered silicate is a synthetic layered silicate.

[0174] In another embodiment, based on the total weight of the composition, the resin dispersion is present in an amount of about 19 to about 20% by weight and comprises: an acrylic latex dispersion, said acrylic latex dispersion being 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, said linear polyester diol being 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.

[0175] In another embodiment, based on the total weight of the composition, the acrylic latex dispersion is present in an amount of about 9 to about 10% by weight; based on the total weight of the composition, the first polyurethane dispersion is present in an amount of about 4 to about 5% by weight; and based on the total weight of the composition, the second polyurethane dispersion is present in an amount of about 3 to about 4% by weight; and based on the total weight of the composition, the third polyurethane dispersion is present in an amount of about 1 to about 2% by weight, wherein the alkali-swellable emulsion is an acrylic copolymer emulsion and the layered silicate is a synthetic layered silicate.

[0176] In other embodiments, based on the total weight of the composition, the resin dispersion is present in an amount of about 27 to about 28% by weight and comprises: an acrylic latex dispersion, said acrylic latex dispersion being a styrene-acrylic latex dispersion; and a second polyurethane dispersion formed from a linear polyester diol resin and isophorone diisocyanate, wherein said linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid.

[0177] In another embodiment, the acrylic latex dispersion is present in an amount of about 8 to about 9% by weight, based on the total weight of the composition; and the second polyurethane dispersion is present in an amount of about 6.5 to about 7.5% by weight, based on the total weight of the composition, wherein the alkali-swellable emulsion is an acrylic copolymer emulsion and the layered silicate is a synthetic layered silicate.

[0178] In one embodiment, the resin dispersion comprises a latex and does not contain polyurethane. In another embodiment, the resin dispersion comprises a polyurethane and does not contain a latex. In other embodiments, the latex is selected from polyester-modified acrylic dispersions containing epoxy groups, styrene-acrylic latex dispersions, and combinations thereof; the polyurethane is selected from polyurethanes formed from branched polyester polyols and hexamethylene diisocyanate; polyurethanes formed from linear polyester diol resins and isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; polyurethanes formed from linear polycarbonate-polyester polyols and isophorone diisocyanate; polyester-polyurethane polymers; and combinations thereof.

[0179] In another embodiment, the alkali-swellable emulsion is an acrylic copolymer emulsion and the layered silicate is a synthetic layered silicate.

[0180] In another embodiment, based on the total weight of the composition, the resin dispersion is present in an amount of about 10 to about 35% by weight of active ingredient; the crosslinking agent is melamine, present in an amount of about 2 to about 8% by weight of active ingredient based on the total weight of the composition; the pigment is present in an amount of about 0.1 to about 20% by weight of active ingredient based on the total weight of the composition; water is present in an amount of about 15 to about 70% by weight of active ingredient based on the total weight of the composition; the water-soluble solvent is present in an amount of about 5 to about 25% by weight of active ingredient based on the total weight of the composition; and the at least one rheology control agent is present in an amount of about 0.01 to about 7% by weight of active ingredient based on the total weight of the composition; wherein the coating composition has a viscosity of about 35 to about 95 cps, the viscosity being determined using ASTM 7867-13 with a cone or parallel plate at 1000 s. -1 The coating composition was measured at a shear rate of at least about 20 micrometers with no visible sagging when measured at about 45 degrees Celsius, using ASTM D4400-18.

[0181] In other embodiments, the resin dispersion is present in an amount of about 12 to about 20% by weight of active ingredient based on the total weight of the composition, and comprises: an acrylic latex dispersion being an acrylic dispersion containing epoxy groups and present in an amount of about 3 to about 5% by weight of active ingredient based on the total weight of the composition; a first polyurethane dispersion formed of branched polyester polyol and hexamethylene diisocyanate and present in an amount of about 1.5 to about 2.5% by weight of active ingredient based on the total weight of the composition; a second polyurethane dispersion formed of linear polyester glycol resin and isophorone diisocyanate and present in an amount of about 1 to about 2% by weight of active ingredient based on the total weight of the composition, wherein the linear polyester glycol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; and an active latex dispersion formed in an amount of about 0.5 to about 1.5% by weight of active ingredient based on the total weight of the composition. The composition contains a third polyurethane dispersion formed from linear polycarbonate-polyester polyol and isophorone diisocyanate; a crosslinking agent, melamine, is present in an amount of about 3 to 4% by weight based on the total weight of the composition; a pigment dispersion is present in an amount of about 0.5 to 4.5% by weight of active ingredient (the active ingredient is only carbon black) based on the total weight of the composition; water is present in an amount of about 55 to 70% by weight of active ingredient based on the total weight of the composition; a water-soluble solvent, butanol, is present in an amount of about 10 to 20% by weight of active ingredient based on the total weight of the composition; and the at least one rheology control agent is an alkali-swellable emulsion, which is an acrylic copolymer emulsion, present in an amount of about 0.1 to 2% by weight of active ingredient based on the total weight of the composition; wherein the coating composition has a viscosity of about 35 to 70 cps, the viscosity being determined using ASTM... 7867-13 The coating composition is determined using a conical or parallel plate at a shear rate of 1000 s⁻¹, and wherein, when measured at approximately 45 degrees, the coating composition has a wet film thickness of at least approximately 20 micrometers and no visible sagging, as determined using ASTM D4400-18.

[0182] coating:

[0183] This disclosure also provides the coating itself, which is formed by applying a coating composition to a substrate. There are no particular limitations on the physical properties of the coating. Typically, the coating has a wet film thickness of about 1 to about 10, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mils. Typically, the coating 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 mils. One or more of these measurements may be performed according to ASTM D7091-13.

[0184] In other embodiments, for example, when the coating composition is used to form a single coating or outer layer of a coating system, the coating may have solvent resistance to at least 5 MEK back-and-forth wiping cycles or at least 10 MEK back-and-forth wiping cycles, or at least 20, 35, 30, 35, 40, 45, 50, 55, 6, 65, 70, 75, 80, 85, 90, 95, or 100 MEK back-and-forth wiping cycles, performed on a non-porous substrate according to ASTM D4752. In other embodiments, according to ASTM 5026-15, the coating may have a film tensile modulus of at least 100 MPa, or at least 100 MPa, or at least 200 MPa. In other embodiments, according to ASTM D5026-15, the coating may have a film tensile modulus of at least 0.2 mmol / cm². 3 or at least 0.5 mmol / cm 3 or at least 1.0 mmol / cm 3 The crosslinking density. In other embodiments, according to ASTM 2813, the coating may have a gloss value of at least 75, or at least 88, or at least 92 at a 20-degree specular angle. In other embodiments, according to ASTM D7869, after 2000 hours of weather exposure, the coating may have a gloss retention rate of at least 50%, or at least 70%, or at least 90% of the initial gloss value. In various non-limiting embodiments, all values ​​and value ranges, including integers and fractions, including and between the values ​​described above. In various non-limiting embodiments, all values ​​and value ranges, whether integers or fractions, including the values ​​described above and values ​​between the values ​​described above, are described above.

[0185] The coating may be cured, uncured, or partially cured. There are no particular restrictions on the type of curing of the coating, and any curing mechanism associated with any one or more of the components described above may be used. Curing may be carried out partially or completely under ambient conditions, such as using condensation curing or free radical curing, or any other suitable curing as commonly understood by those skilled in the art, and / or at elevated temperatures, such as in an oven at temperatures up to about 400°F. The coating may be rapidly evaporated to remove water and / or solvents, and such rapid evaporation may or may not affect (fully or partially) the curing.

[0186] Throughout this disclosure, the term "about" may mean that a value may optionally vary by ±1, 2, 4, 5, 6, 7, 8, 9, or 10%. However, in other embodiments, "about" may also mean the exact value.

[0187] Example

[0188] A series of coating compositions of the present invention and comparative coating compositions are described below. After formation, each composition was evaluated to determine various physical properties, which are also described below.

[0189]

[0190]

[0191]

[0192] In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including those stated in the above embodiments and those between the above values, are hereby explicitly considered for use herein, independent of those specific embodiments.

[0193] The following section provides further description of some of the compounds used in the above embodiments:

[0194]

[0195]

[0196] The data above indicate that compositions 2, 3, and 4 exhibit excellent performance, especially compared to compositions 1, 5, and 6. Compositions 2, 3, and 4 also possess high yield stress and low shear viscosity, which are manifestations of superior performance. Compositions 7-10, as other examples, were evaluated and demonstrated to provide sufficient sag control. Composition 11 was evaluated and demonstrated good sag performance without any thickener.

[0197] Although at least one exemplary embodiment has been shown in the foregoing detailed description, it should be understood that numerous variations exist. It should also be understood that the one or more exemplary embodiments are merely examples and are not intended to limit the scope, applicability, or construction in any way. Rather, the foregoing detailed description will provide those skilled in the art with a simple roadmap for implementing the exemplary embodiments. It should be understood that various changes can be made to the function and arrangement of the elements described in the exemplary embodiments without departing from the scope set forth in the appended claims.

Claims

1. A method for applying a one-component waterborne coating composition to a substrate using a high-transfer-efficiency applicator to form a coating disposed on the substrate, the method comprising the following steps: The coating composition is supplied to a high-transfer-efficiency applicator; and A coating composition is applied to a substrate using a high-transfer-efficiency applicator to form a coating on the substrate, wherein, based on the total weight of the coating composition, the loss of volatiles after application using the high-transfer-efficiency applicator is less than 0.5% by weight of active ingredients. The coating composition has a pH greater than 7 and comprises: (A) A resin dispersion, including an acrylic latex dispersion, a polyurethane dispersion, or a combination thereof; (B) Optional crosslinking agent; (C) Optional pigments; (D) Water; (E) Water-soluble solvents; and (F) At least one rheology control agent selected from alkali-swellable emulsions, layered silicates, and combinations thereof; The coating composition described herein has a viscosity of 20 to 100 cps, which is determined using ASTM 7867-13 with a cone or parallel plate at 1000 s. -1 The shear rate was measured. The coating composition is in 0.1 s -1 The viscosity ranges from 2,000 to 6,500 mPa·s, and the viscosity was determined using ASTM D7867. When measured at 45 degrees, the coating composition has a wet film thickness of at least 20 micrometers and no visible sagging. When measured at 45 degrees, the wet film thickness of the coating composition is at least 71 micrometers without thick edges.

2. The method according to claim 1, wherein: A. Based on the total weight of the composition, the resin dispersion is present in an amount of 10 to 35% by weight of active ingredient; B. The crosslinking agent is melamine, present in an amount of 2 to 8% by weight of active ingredient based on the total weight of the composition; C. Based on the total weight of the composition, the pigment is present in an amount of 0.1 to 20% by weight of active ingredient; D. Based on the total weight of the composition, the water is present in an amount of 15 to 70% by weight of the active ingredient; E. Based on the total weight of the composition, the water-soluble solvent is present in a total amount of 5 to 25% by weight of the active ingredient; and F. Based on the total weight of the composition, the at least one rheology control agent is present in an amount of 0.01 to 7% by weight of active ingredient; The coating composition described herein has a viscosity of 35 to 95 cps, which is determined using ASTM 7867-13 with a cone or parallel plate at 1000 s. -1 The shear rate was measured, and When measured at 45 degrees, the coating composition has a wet film thickness of at least 20 micrometers and no visible sagging.

3. The method according to claim 1, wherein: A. Based on the total weight of the composition, the resin dispersion is present in an amount of 12 to 20% by weight of active ingredient and comprises: An acrylic latex dispersion, which contains 3 to 5% by weight of active ingredient based on the total weight of the composition and is a polyester-modified acrylic dispersion containing epoxy groups; The first polyurethane dispersion, based on the total weight of the composition, is present in an amount of 1.5 to 2.5% by weight of active material and is formed from branched polyester polyol and hexamethylene diisocyanate; The second polyurethane dispersion, based on the total weight of the composition, is present in an amount of 1 to 2% by weight of active material 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 third polyurethane dispersion, based on the total weight of the composition, is present in an amount of 0.5 to 1.5% by weight of active material and is formed from linear polycarbonate-polyester polyol and isophorone diisocyanate; B. The crosslinking agent is melamine, present in an amount of 3 to 4% by weight of active ingredient based on the total weight of the composition; C. Based on the total weight of the composition, the pigment dispersion is present in an amount of 0.5 to 4.5% by weight of active ingredient; D. Based on the total weight of the composition, the water is present in an amount of 55 to 70% by weight of the active ingredient; E. The water-soluble solvent is butanol, present in an amount of 10 to 20% by weight of the 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 0.1 to 2% by weight of active ingredient based on the total weight of the composition; The coating composition described herein has a viscosity of 35 to 70 cps, which is determined using ASTM 7867-13 with a cone or parallel plate at 1000 s. -1 The shear rate was measured, and When measured at 45 degrees, the coating composition has a wet film thickness of at least 20 micrometers and no visible sagging, as determined using ASTM D4400-18.

4. The method of claim 1, wherein the resin dispersion comprises an acrylic latex dispersion and does not contain a polyurethane dispersion.

5. The method of claim 1, wherein the resin dispersion comprises a polyurethane dispersion and does not contain an acrylic latex dispersion.

6. The method according to claim 1, wherein: The acrylic latex dispersion is selected from polyester-modified acrylic dispersions containing epoxy groups, styrene-acrylic latex dispersions, and combinations thereof; and The polyurethane dispersion is selected from polyurethanes formed from branched polyester polyols and hexamethylene diisocyanate; polyurethanes formed from linear polyester diol resins and isophorone diisocyanate, wherein the linear polyester diol is a reaction product of 1,6-hexanediol, adipic acid, and isophthalic acid; polyurethanes formed from linear polycarbonate-polyester polyols and isophorone diisocyanate; polyester-polyurethane polymers; and combinations thereof.

7. The method according to any one of the preceding claims, wherein the alkali-swellable emulsion is an acrylic copolymer emulsion and the layered silicate is a synthetic layered silicate.

8. The method according to any one of claims 1-6, wherein the coating composition is substantially composed of (A)-(F).

9. The method according to claim 7, wherein the coating composition is substantially composed of (A)-(F).

10. A coating formed by the method of any one of the preceding claims.

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