Methods of applying a coating composition to a substrate

Abstract

This invention discloses a method comprising applying a coating composition to a substrate using a high-transfer-efficiency applicator, wherein the coating composition comprises a polyamide wax; wherein, when measured at approximately 45 degrees Celsius, the composition has a wet film thickness of at least approximately 30 micrometers, and exhibits no visible sagging after curing, wherein the curing time is approximately 10,000 seconds. ‑1 After a high shear rate of approximately 20 seconds, the rate decreases to approximately 1 second. ‑1 The viscosity measured at the shear rate recovers to approximately 1 second within about 5 seconds. ‑1 The steady-state viscosity reached when the shear rate is continuously sheared for more than about 100 seconds is within about 95%; and wherein when the complex viscosity measured at about 30°C is about 800 to about 8000 mPa·s, the complex viscosity of the coating composition measured at a temperature of about 60°C decreases to about 60 to about 500 mPa·s.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 260,721, filed August 30, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] In general, the present invention relates to a method of applying a coating composition to a substrate (base) using a high-transfer-efficiency applicator to form a coating thereon. More specifically, this disclosure relates to the use of a particular polyamide wax that allows the composition to be applied by a high-transfer-efficiency applicator and to cure with excellent physical and aesthetic properties. Background Technology

[0004] 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 jetted onto the substrate using various inkjet application methods, including continuous printing and drop-on-demand printing. In drop-on-demand printing, the energy for jetting the ink droplets can come from a thermistor, piezoelectric crystal, sound, or a solenoid valve. These methods utilize high-efficiency applicators.

[0005] 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.

[0006] 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.

[0007] 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.

[0008] Applying a coating using a high-transfer-efficiency applicator can provide a solution for applying two colors to a vehicle and minimizing overspray. This is achieved by generating droplets of uniform size 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.

[0009] 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 droplets in each nozzle of the printhead is limited, and it also avoids potential clogging caused by ink thickening in the printhead channels.

[0010] 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.

[0011] Furthermore, even though existing technologies are suitable for some horizontal surface applications, there are other applications, such as vertical surface applications, where existing technologies sag to unacceptable levels. Because high-transfer-efficiency applicators require very low viscosity and have limited shear-thinning behavior, standard methods for imparting anti-sag properties to applied coatings cannot be used.

[0012] More specifically, the limitations imposed by zero-overlap spray applicators (continuous flow) or high-resolution on-demand dripping (i.e., “inkjet” printheads) typically require very low viscosity under high shear. Unlike spray atomization, there is no viscosity increase because no solvent evaporation occurs after the paint is ejected from the applicator and before it impacts the substrate. Therefore, the coating will sag on non-horizontal surfaces. To achieve sufficient anti-sagging properties, rheology modifiers must be added at such high levels that, while preventing sagging, yield stress hinders flow and leveling, leading to coating defects characteristic of zero-overlap spray applicators. These defects include visible nozzle lines and streak overlap. The former is due to incomplete flow and leveling of the streams or droplets ejected from adjacent nozzles, resulting in visible parallel lines in the printhead movement direction. The latter is caused by the application of a second paint streak (with the width of the nozzle array) adjacent to the previously applied first streak. While changing the index (the distance between adjacent streaks) can improve coalescence, with the high levels of rheology modifiers required to prevent sagging, the overlap regions exhibit visible peaks or valleys that cannot be eliminated by index optimization. Furthermore, due to the particle size limitations of these small nozzle applicators, some rheology control agents cannot be used due to filter and nozzle clogging. Therefore, there is still an opportunity for improvement. Summary of the Invention

[0013] This disclosure provides a method for applying a one-component solvent-based 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:

[0014] To provide the coating composition to a high-transfer-efficiency applicator; and

[0015] 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.

[0016] The coating composition comprises:

[0017] A. Resins, comprising acrylic, polyester, or combinations thereof;

[0018] B. Melamine crosslinking agent;

[0019] C. Optional pigments;

[0020] D. Organic solvents; and

[0021] E. Polyamide wax, comprising (i) a fatty acid derived from C16-C48 fatty acids; and (ii) a reaction product of a polyamine having two or more amine functional groups, and present in an amount of about 0.1 to about 4% by weight based on the total weight of the coating composition;

[0022] When measured at approximately 45 degrees Celsius, the composition has a wet film thickness of at least approximately 30 micrometers and exhibits no visible sagging after curing at approximately 60 degrees Celsius or higher for at least 5 minutes.

[0023] During the application of approximately 10,000 seconds -1 After a high shear rate of approximately 20 seconds, the rate decreases to approximately 1 second. -1 The viscosity measured at the shear rate recovers to approximately 1 second within about 5 seconds. -1 The steady-state viscosity reached when the shear rate is continuously sheared for more than about 100 seconds is within about 95%; and

[0024] When the complex viscosity measured at about 30°C is about 800 to about 8000 mPa·s, the complex viscosity of the coating composition measured at about 60°C decreases to about 60 to about 500 mPa·s.

[0025] This disclosure also provides a method for applying a two-component solvent-based 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:

[0026] To provide the coating composition to a high-transfer-efficiency applicator; and

[0027] 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.

[0028] The coating composition comprises:

[0029] A. Hydroxyl-functionalized resins;

[0030] B. Isocyanate crosslinking agent;

[0031] C. Optional pigments;

[0032] D. Organic solvents; and

[0033] E. Polyamide wax, comprising (i) a fatty acid derived from C16-C48 fatty acids; and (ii) a reaction product of a polyamine having two or more amine functional groups, and present in an amount of about 0.1 to about 4% by weight based on the total weight of the coating composition;

[0034] When measured at approximately 45 degrees Celsius, the composition has a wet film thickness of at least approximately 30 micrometers and exhibits no visible sagging after curing at approximately 60 degrees Celsius or higher for at least 5 minutes.

[0035] During the application of approximately 10,000 seconds -1 After a high shear rate of approximately 20 seconds, the rate decreases to approximately 1 second.-1 The viscosity measured at the shear rate recovers to approximately 1 second within about 5 seconds. -1 The steady-state viscosity reached when the shear rate is continuously sheared for more than about 100 seconds is within about 95%; and

[0036] When the complex viscosity measured at about 30°C is about 800 to about 8000 mPa·s, the complex viscosity of the coating composition measured at about 60°C decreases to about 60 to about 500 mPa·s. Attached Figure Description

[0037] This patent or application document contains at least one color drawing. The Patent Office will, upon request and after payment of the necessary fees, provide a copy of this patent or patent application publication with the color drawing.

[0038] The present disclosure will now be described in conjunction with the following accompanying drawings, wherein the same numerals denote the same elements and:

[0039] Figure 1A This is a top view of a high-transfer-efficiency applicator for applying coating compositions to a substrate;

[0040] Figure 1B yes Figure 1A Side view;

[0041] Figure 2A It is a side view of a substrate on which paint (coating composition) is applied, showing the position of the edge nozzle of the high-transfer-efficiency applicator;

[0042] Figure 2B It was tilted during the process of determining the sag. Figure 2A A top view of the substrate, showing the angle of the substrate relative to a horizontal surface;

[0043] Figure 3A It is a side view of a high-transfer-efficiency applicator comprising multiple nozzles for applying a coating composition to a substrate, wherein a single nozzle line can be defined as having a periodically repeating pattern, the spacing of which is consistent with the spacing between nozzles on a nozzle plate;

[0044] Figure 3B yes Figure 3A A top view showing stripes of a coating composition applied to a substrate, wherein each stripe is a single pass of approximately 50 nozzles;

[0045] Figure 3C yes Figure 3B A magnified top view of a single pass, showing defects at each point where the nozzle impacts the substrate; Figure 3C yes Figure 3B A magnified top view of a single pass, showing that each nozzle impacts the substrate at a defective location.

[0046] Figure 4 This is a photograph showing the flow chart of a theoretical comparative embodiment;

[0047] Figure 5 The photograph shows the sag of the comparative composition, in which no rheology control agent was incorporated, resulting in very poor anti-sag properties;

[0048] Figure 6 The photograph shows a comparative composition with visible nozzle line defects;

[0049] Figure 7 These are photographs of comparative compositions showing stripe overlap defects;

[0050] Figure 8 The graph shows the viscosity recovery measurement results of Examples 1, 9 and 12 over time, wherein the viscosity was measured according to ASTM 2196 at a specified shear rate.

[0051] Figure 9 Line graphs showing the complex viscosity as a function of temperature for Examples 1, 9, and 12 are provided, where the complex viscosity was measured according to ASTM D4440; and

[0052] Figure 10 The results of Optimap surface profile measurements for Examples 1, 9, and 12 are shown immediately after printing (wet) and after curing. Detailed Implementation

[0053] The following detailed description is merely exemplary in nature and is not intended to limit this disclosure. Furthermore, it is not intended to be bound by the foregoing background information or any theories presented in the following detailed description.

[0054] In general, embodiments of this disclosure relate to one-component and two-component solvent-based coating compositions and methods for forming them. For the sake of brevity, conventional techniques associated with the formation of such 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 such compositions are well known, and therefore, for the sake of brevity, many conventional steps are only briefly mentioned or will be omitted entirely without providing well-known process details.

[0055] This disclosure provides a method for applying a one-component solvent-based 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:

[0056] To provide the coating composition to a high-transfer-efficiency applicator; and

[0057] 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.

[0058] The coating composition comprises:

[0059] A. Resins, comprising acrylic, polyester, or combinations thereof;

[0060] B. Melamine crosslinking agent;

[0061] C. Optional pigments;

[0062] D. Organic solvents; and

[0063] E. Polyamide wax, comprising (i) a fatty acid derived from C16-C48 fatty acids; and (ii) a reaction product of a polyamine having two or more amine functional groups, and present in an amount of about 0.1 to about 4% by weight based on the total weight of the coating composition;

[0064] When measured at approximately 45 degrees Celsius, the composition has a wet film thickness of at least approximately 30 micrometers and exhibits no visible sagging after curing at approximately 60 degrees Celsius or higher for at least 5 minutes.

[0065] During the application of approximately 10,000 seconds -1 After a high shear rate of approximately 20 seconds, the rate decreases to approximately 1 second. -1 The viscosity measured at the shear rate recovers to approximately 1 second within about 5 seconds. -1 The steady-state viscosity reached when the shear rate is continuously sheared for more than about 100 seconds is within about 95%; and

[0066] Wherein, when the complex viscosity measured at about 30°C is about 800 to about 8000 mPa·s, the complex viscosity of the coating composition measured at about 60°C decreases to about 60 to about 500 mPa·s. 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.

[0067] This disclosure also provides a method for applying a two-component solvent-based 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:

[0068] To provide the coating composition to a high-transfer-efficiency applicator; and

[0069] 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.

[0070] The coating composition comprises:

[0071] A. Hydroxyl-functionalized resins;

[0072] B. Isocyanate crosslinking agent;

[0073] C. Optional pigments;

[0074] D. Organic solvents; and

[0075] E. Polyamide wax, comprising (i) a fatty acid derived from C16-C48 fatty acids; and (ii) a reaction product of a polyamine having two or more amine functional groups, and present in an amount of about 0.1 to about 4% by weight based on the total weight of the coating composition;

[0076] When measured at approximately 45 degrees Celsius, the composition has a wet film thickness of at least approximately 30 micrometers and exhibits no visible sagging after curing at approximately 60 degrees Celsius or higher for at least 5 minutes.

[0077] During the application of approximately 10,000 seconds -1 After a high shear rate of approximately 20 seconds, the rate decreases to approximately 1 second. -1 The viscosity measured at the shear rate recovers to approximately 1 second within about 5 seconds. -1 The steady-state viscosity reached when the shear rate is continuously sheared for more than about 100 seconds is within about 95%; and

[0078] Wherein, when the complex viscosity measured at about 30°C is about 800 to about 8000 mPa·s, the complex viscosity of the coating composition measured at about 60°C decreases to about 60 to about 500 mPa·s. 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.

[0079] Throughout this disclosure, the terms "consistently composed of" or "essentially 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 describe comprising less than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% by weight of the relevant element, 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 ​​above and values ​​between the values ​​above, are expressly intended to be used herein.

[0080] This disclosure includes the step of applying a coating composition to a substrate. There are no particular limitations on the application step. In various embodiments, the application step is further defined as spraying, for example, spraying through a high-transfer-efficiency applicator. Alternatively, the application step may be further defined as printing. This step is described in more detail below.

[0081] Furthermore, there are no particular limitations on the coating composition, and it can be any composition known in the art that includes the components described herein. For example, the composition can be described as a one-component or "1K" composition that does not require a hardener, catalyst, or activator for curing. For example, the composition can be cured by exposure to air. Alternatively, the composition can be described as a two-component or "2K" composition.

[0082] The coating composition can be used to coat any type of substrate known in the art. In embodiments, the substrate is a vehicle, automobile, or motor vehicle. “Vehicle” or “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.

[0083] Various substrates can include two or more discrete parts made of different materials. For example, a vehicle may include a metal body and a plastic trim. Due to the limited baking temperature (80°C) of plastic relative to metal (140°C), the metal body and plastic trim are often coated in separate facilities, increasing the possibility of part mismatch. A coating composition suitable for a metal substrate can be applied to a 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.

[0084] 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 step known in the art. For example, the providing step can be described as providing one or more components of the composition, all or part of them, 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.

[0085] 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. Typically, the application step is further defined as by spraying or printing via, using, or through an applicator. During the application step, after application with a high-transfer-efficiency applicator, the loss of volatiles is less than about 0.5% by weight, 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, based on the total weight of the coating composition. Typically, the term "volatiles" is defined as substances that evaporate, resulting in a loss of weight of the coating composition. After application, the loss of volatiles will be determined by the increase in solids (in percentage) before and after application, wherein in each case the percentage of solids 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.

[0086] In some embodiments, the application step generates coating composition droplets that impact the substrate. In various embodiments, at least about 99, 99.1, 99.2, 99.3, 99.4, 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.

[0087] 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 upon contact with the substrate. Without being bound by theory, it is believed that applying the paint composition using a high-transfer-efficiency applicator can minimize or eliminate splashing of the paint composition due to impact with the substrate. In various non-limiting embodiments, all values ​​and ranges, whether integers or fractions, including the values ​​described above and values ​​between the described values, are expressly considered herein.

[0088] 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 or streams upon contact with the substrate. 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.

[0089] 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.

[0090] 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: US20150375258 A1, US20040217202 A1, US2009 / 0304936A1, US 7,824,015 B2, US 8,091,987 B2, WO 2018 / 206309A1, each of which is expressly incorporated herein by reference in its entirety for use in various non-limiting embodiments. The applicator can be or is described as a printhead.

[0091] 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.

[0092] 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.

[0093] Consider using one, two, three, or even more applicators in combination with each other. Each applicator can be used independently as described herein or can be any applicator known in the art.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] In one implementation, for example, Figure 1A and 1B As shown, the high-transfer-efficiency applicator sprays a stream of composition 14 onto the substrate 16. Figure 1A The diagram illustrates spaces 18 between strips 20 of composition 14 disposed on substrate 16. These spaces 18 are preferably minimized or eliminated. However, those skilled in the art will understand that overlap of the strips 20 may unintentionally lead to overlap and undesirable accumulation of the composition, forming "hills" or protrusions on the substrate. These are also preferably minimized.

[0103] exist Figures 3A-3C The image shows a single nozzle line, which can be defined as having a periodically repeating pattern with a spacing consistent with the spacing between the nozzles of a high-transfer-efficiency applicator. This defect can be straight or curved. The defect may have interruptions. The defect may appear smooth or it may be raised. Figure 3B In this context, each stripe represents a single pass of approximately 50 nozzles. Figure 3C It shows Figure 3A A magnified view relative to a single pass of a high-transfer-efficiency applicator. A defect exists where each nozzle jet of the composition impacts the substrate 16. Figure 4 The image shows a photograph of a theoretically comparative composition that does not contain polyamide wax. Figure 5 The photograph shows the sag of a comparative composition in which the absence of a rheology control agent resulted in very poor anti-sagging properties. Figure 6 The photograph shows a substrate on which a comparative composition is arranged, revealing visible nozzle line defects. Figure 7 The photograph shows a substrate on which a comparative composition is arranged, revealing a stripe overlap defect.

[0104] Coating composition:

[0105] Now consider the composition itself. The composition is solvent-based and may be a one-component composition or a two-component composition. Each is described below.

[0106] Single-component composition:

[0107] In various embodiments, the composition is, includes, substantially consists of, or consists of: a resin comprising acrylic, polyester, or combinations thereof; a melamine crosslinking agent; optional pigment; an organic solvent; and at least one polyamide wax. For example, the term "substantially consists of" may describe an embodiment free of resins or polymers not described herein or described as optional components, crosslinking agents not described herein or described as optional components, pigments not described herein or described as optional components, organic solvents not described herein or described as optional components, and sag control agents and / or rheology control agents not described herein or described as optional components. The terms "free of" or "without" may describe that the composition contains less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% by weight (e.g., % by weight of active ingredient) of a compound, based on the total weight of the composition. Alternatively, the terms "free of" or "without" may describe that the composition is completely free of the compound.

[0108] Two-component composition:

[0109] In various embodiments, the composition is, includes, substantially consists of, or consists of: a hydroxyl-functionalized resin; an isocyanate crosslinking agent; an optional pigment; an organic solvent; and at least one polyamide wax. For example, the term "substantially consists of" may describe an embodiment free of resins or polymers not described herein or described as optional components, crosslinking agents not described herein or described as optional components, pigments not described herein or described as optional components, organic solvents not described herein or described as optional components, and sag control agents and / or rheology control agents not described herein or described as optional components. The terms "free of" or "without" may describe that the composition contains less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% by weight (e.g., % by weight of active ingredient) of a compound based on the total weight of the composition. Alternatively, the terms "free of" or "without" may describe that the composition is completely free of the compound. 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.

[0110] Resins comprising acrylic, polyester, or combinations thereof

[0111] Relative to a one-component composition, the resin may be, include, substantially consist of, or consist of acrylics, polyesters, or combinations thereof. For example, the term "substantially consist of" may describe an embodiment that does not contain acrylics, polyesters, or any other polymers known in the art, wherein "does not" is as described above. For example, the composition and / or resin itself may contain acrylics and not polyesters and / or any other polymers. Alternatively, the composition and / or resin itself may contain polyesters and not acrylics and / or any other polymers. The composition and / or resin itself may include both acrylics and polyesters and not any other polymers.

[0112] In various embodiments, the acrylic system may be, include, consist substantially of, or consist of the following substances: reaction products of one or more of the following monomers, including but 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-hydroxyethyl (meth)acrylate, and α-hydroxyethyl (meth)acrylate. - Epoxides, 2-hydroxyethyl methacrylate, methacrylonitrile, maleic anhydride, itaconic acid, isodecanyl 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.

[0113] In other embodiments, the acrylic system 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 acrylic systems, (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.

[0114] In various embodiments, the polyester can be, include, consist substantially of, or consist of any polyester known in the art. For example, the polyester 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, inner methylenetetrahydrophthalic acid, tricyclodecanedicarboxylic acid, inner ethylhexahydrophthalic 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 the two forms.

[0115] 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 with alicyclic polycarboxylic acids, may be suitable. Combinations of polyols may also be suitable.

[0116] 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 monomers 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.

[0117] Polyesters 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. Suitable hydroxycarboxylic acids include glycolic acid, lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and hydroxypyvalicacid. 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, the branched copolyester polymer can be prepared by polymerizing a monomer mixture including a chain extender and a hyperbranched monomer in one step, or by first polymerizing the hyperbranched monomer and then polymerizing the chain extender. It should be understood that the branched copolyester polymer can be formed from an acrylic core having the aforementioned chain extenders.

[0118] In various embodiments, the resin comprising acrylics, polyesters, or combinations thereof is used in amounts of about 10 to about 40, about 15% to about 35%, or about 20% to about 30% based on the total weight percentage 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.

[0119] Hydroxyl-functionalized resins:

[0120] There are no particular limitations on hydroxyl-functionalized resins, and they can be any resin known in the art. In various embodiments, the resin can be, include, consist substantially of, or consist 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, inner methylenetetrahydrophthalic acid, tricyclodecanedicarboxylic acid, inner ethylhydrophthalic 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 are also suitable.

[0121] Suitable non-limiting polyols include ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanediol, trimethylpentanediol, ethylbutylpropylene glycol, dimethylolpropane, 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 defined by empirical structural formulas, may be used. In other embodiments, oligomeric or polymeric polyols with number-average molar masses, such as up to 8000, 5000, or 2000, and / or, for example, corresponding hydroxyl-functionalized polyethers, polyesters, or polycarbonates, are used.

[0122] In various embodiments, the hydroxyl-functionalized resin is used in amounts of about 10% to about 50%, about 10% to about 40%, about 12% to about 30%, or about 15% to about 25% by weight, based on the total weight percentage 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.

[0123] The compositions disclosed herein may include crosslinking agents. The term "crosslinking agent" refers to a component having "crosslinking functional groups" that are: located in each molecule of a compound, oligomer, or polymer; in the polymer backbone; side-attached to the polymer backbone; located at the end of the polymer backbone; or combinations thereof, wherein these functional groups are capable (during the curing step) of crosslinking with crosslinkable functional groups to produce a coating in the form of a crosslinked structure. Those skilled in the art will recognize that certain combinations of crosslinking functional groups and crosslinkable functional groups will be excluded because they cannot crosslink and produce a film-forming crosslinked structure.

[0124] Isocyanate crosslinking agent:

[0125] There are no particular limitations on the isocyanate crosslinking agent, and it can be any isocyanate crosslinking agent known in the art. In various embodiments, the isocyanate crosslinking agent can 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; diisocyanates such as hexamethylene diisocyanate and diols such as ethylene glycol; urea diketone of hexamethylene diisocyanate; urea diketone or isophorone diisocyanate of isophorone diisocyanate; and adducts of trimethylolpropane and m-tetramethylxylene diisocyanate.

[0126] In various embodiments, isocyanates such as oligomers based on hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), or toluidine diisocyanate (TDI), such as isocyanurates, biuret, urethane, and adducts of the aforementioned isocyanates with polyols, and mixtures thereof, can be used. 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. In various embodiments, as chosen by those skilled in the art, monofunctional isocyanates are considered for use herein. In other embodiments, as chosen by those skilled in the art, end-capped isocyanates are considered for use herein.

[0127] In various embodiments, the isocyanate crosslinking agent is used in an amount of about 3 to about 6, or about 3, 4, 5, or 6% by weight, based on the total weight percentage of the composition. 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.

[0128] Optional crosslinking agent:

[0129] In various embodiments, a melamine crosslinking agent is used instead of an isocyanate crosslinking agent. Alternatively, both an isocyanate crosslinking agent and a melamine crosslinking agent may be used. In various embodiments, this optional crosslinking agent may be any melamine crosslinking agent known in the art, including any melamine crosslinking agent known in the art, substantially composed of any melamine crosslinking agent known in the art, or composed of any melamine crosslinking agent known in the art.

[0130] Melamine resins can be partially or fully 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 have an average degree of condensation high to 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., called... BMP5503 (molecular weight 690, polydispersity 1.98, 56% butyl, 44% amino) high-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.

[0131] 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.

[0132] In various embodiments, the optional crosslinking agent, such as a melamine crosslinking agent, is present in an amount of about 0 to about 30%, about 5 to about 30%, about 12 to about 25%, or about 15 to about 20% by weight, based on the total weight percentage of the composition. In other embodiments, this amount is about 5 to about 25%, about 10 to about 20%, or about 10 to about 15% by weight, based on the total weight percentage 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.

[0133] In an exemplary embodiment, the coating composition comprises a product with a trade name. 303 melamine-formaldehyde resin is commercially available from Cytec Industries Inc., West Patterson, NJ.

[0134] Optional pigments:

[0135] Any pigment known in the art for use in coating compositions may be used in said coating compositions. 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 reds, organic maroons, 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.

[0136] 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.

[0137] As described above, the coating composition may also contain extender pigments. While extender pigments are generally 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 may have a particle size of about 0.01 to about 44 micrometers. Extender pigments may 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, shale silicate (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.

[0138] Based on the total weight of the coating composition, the coating composition may contain an amount of about 0.1 to about 50%, or about 1 to about 20%, or about 1 to about 10% by weight of an extender pigment. In some embodiments, the coating composition contains magnesium silicate (talc), barium sulfate, or a combination thereof. In various embodiments, containing barium sulfate as an extender pigment results in a coating composition having a greater shear viscosity compared to containing talc as an extender pigment. 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.

[0139] In various implementation schemes, 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.

[0140] Organic solvents:

[0141] The composition may also include an organic solvent. Non-limiting examples of suitable organic solvents may include aromatic hydrocarbons, such as toluene and xylene; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, and diisobutyl ketone; and esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, and combinations thereof. In embodiments, the evaporation rate of the solvent may affect the suitability of the coating composition for printing. Certain co-solvents having increasing or decreasing evaporation rates may be incorporated into the coating composition, thereby increasing or decreasing the evaporation rate of the coating composition.

[0142] In various embodiments, based on the total weight of the liquid carrier in the coating composition, the organic solvent content is greater than about 50% by weight, or greater than 60% by weight, or greater than 70% by weight, or greater than 80% by weight, or greater than 90% by weight. 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.

[0143] Polyamide wax:

[0144] The polyamide wax can be any polyamide wax known in the art. For example, the polyamide wax can be any polyamide wax described in US4778843 and / or US7837776, the disclosure of which is expressly and entirely incorporated herein by reference in various non-limiting embodiments.

[0145] In various embodiments, the polyamide wax is a combination, mixture, or blend of the following, comprising, substantially consisting of, or consisting of: (1) a reaction product of a specific polyamine with a carboxylic acid having at least two carboxyl moieties and (2) a low-volatility liquid alcohol with a water solubility of less than 10 mg / L at 25°C. Typically, the molar ratio between the amine functional group and the carboxyl functional group is from about 4:1 to about 1:1. Typical ranges are from about 1:5:1.0 to about 3:1, most typically about 2:1. 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] For example, any carboxylic acid having at least two carboxyl groups can be used. Dimer acids are typical in various embodiments, with C16 and C18 fatty acid dimers being particularly typical. Such dimers can be fully hydrogenated, partially hydrogenated, or completely unhydrogenated. Typical examples of dimers include products arising from the dimerization of C16 to C18 unsaturated fatty acids. The fatty acids may or may not be dimers.

[0147] Generally, when used, dimer acids typically have an average of about 18, typically about 28 to about 48, and more typically up to about 40 carbon atoms. The most typical dimer acids have 32 to 36 carbon atoms. In various embodiments, the acid has about 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, or 48 carbon atoms, although the acid may have an odd number of carbon atoms between the above values. Typical dimer acids can be prepared from C18 fatty acids such as oleic acid. Examples of dimer acids are described in U.S. Patent Nos. 2,482,760, 2,482,761, 2,731,481, 2,793,219, 2,964,545, 3,157,681, and 3,256,304, the entire disclosure of which is incorporated herein by reference in various non-limiting embodiments. 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.

[0148] In various embodiments, commercially available dimer fatty acids include mixtures of monomeric acids, dimer acids, and trimer acids. Typically, suitable dimer acids have a dimer content of at least about 80%, about 85%, about 90%, or about 95%. The dimer content can even be about 96%, 97%, 98%, 99%, or about 100%. 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.

[0149] Now consider polyamines, compounds that typically have two or more amine functional groups. Most typically, polyamines from the polyethylene polyamine family, which have two or more amine functional groups, can be used.

[0150] In various embodiments, diamines, triamines, and polyamines, and combinations thereof, are most suitable. Representative, non-limiting amines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and other members of this series as known to those skilled in the art. Branched polyamines and polyamines prepared with different alkyl groups can also be used. In various embodiments, triamines are typical, particularly diethylenetriamine (DETA). These reactions may also produce imidazolines and other byproducts. While the above are typical, other compositions with different molar ratios of raw materials can also be used. Additionally, alternative commercial dimer fatty acids can be reacted with various amines to generate reactive polymers.

[0151] In the foregoing, the term "consistently composed of" describes various non-limiting embodiments in which the total weight of the wax or composition as a whole contains or does not contain less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% of one or more compounds. For example, these one or more compounds may be or include other waxes, other amines, other carboxyl-containing compounds, organically modified clays, finely crushed (pyrolytic) silica, etc. In 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.

[0152] In other embodiments, the polyamide wax may be a reaction product of a polycarboxylic acid, an active hydrogen compound, and a monocarboxylic acid end-capping agent. Any of the aforementioned compounds may also be used.

[0153] In various embodiments, each carboxylic acid group of the polycarboxylic acid has at least about 5 carbon atoms, typically about 6 to about 36 carbon atoms, and most typically about 16 to about 20 carbon atoms. In various embodiments, the polycarboxylic acid may have any number of carbon atoms from about 5 to at most about 36, wherein all intermediate values ​​are considered. In fact, all values ​​and ranges of values, whether integers or fractions, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are explicitly considered for use herein.

[0154] While polycarboxylic acids having more than two carboxylic acid groups can be used, the amount of such acids can be limited to avoid excessive crosslinking, which may result in the reaction product being insoluble in the organic composition. This generally means that less than about 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5% by weight of the polycarboxylic acid may have three or more carboxylic acid groups. In the 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.

[0155] Exemplary but non-limiting polycarboxylic acids include sebacic acid, poly(butadiene)ic acid, dodecanedicarboxylic acid, and mixtures thereof. Particularly typical polycarboxylic acids are oligomers of fatty acids having about 16 to about 22 carbon atoms, typically about 16 to about 18 carbon atoms, or, for example, about 16, 17, 18, 19, 20, 21, or 22 carbon atoms. Exemplary but non-limiting fatty acids include those derived from soybean oil, castor oil, tall oil, corn oil, cottonseed oil, kapok seed oil, linseed oil, and mixtures thereof. More typically, they are oligomers of fatty acids consisting essentially of dimer fatty acids. Typically, dimer fatty acids constitute at least about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or even about 100% by weight of the oligomeric fatty acid. Oligomeric fatty acids also typically have a low monomer content, such as less than about 10% by weight, more typically less than about 4% by weight. 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.

[0156] The preparation of oligomeric fatty acids, including the low monomer content oligomers described below, is well known in the art and is disclosed, for example, in U.S. Patent Nos. 2,793,219 and 2,955,121, the contents of which are expressly incorporated herein by reference in various non-limiting embodiments.

[0157] In addition, suitable oligosaccharides are commercially available, such as certain oligosaccharides that are available under the name Empol from Emery Industries (a subsidiary of National Distillers & Chemical Corporation) and under the name Sylvadym T-18 from Arizona Chemical Company.

[0158] In various implementation schemes, the active hydrogen compound has the general formula X. m -RY n In this context, R represents a group comprising about 2 to about 12 carbon atoms and may include non-reactive groups such as ethers, alkoxy groups, or halogen groups; X and Y are independently selected from primary amino, secondary amino, and hydroxyl groups; and m and n are at least 1, the sum of (m+n) is at least 2, and typically m and n are each 1. 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 for use herein.

[0159] In various embodiments, at least about 90%, typically at least about 95%, and most typically all X and Y groups involved in the reaction are primary amines, secondary amines, or mixtures thereof. Typically, R represents a group containing about 6 to about 12 carbon atoms, and more typically R represents a group containing about 6 to about 8 carbon atoms. 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.

[0160] In various embodiments, the active hydrogen compound may have about three or more active groups. However, the amount of the active hydrogen compound having about three or more active groups is generally not selected to the extent that the reaction product crosslinks to an environment insoluble in the organic composition in which it is to be used. Typically, this means that the amount of the active hydrogen compound having about three or more active hydrogen groups is less than about 10% molar, typically less than about 2% molar, and most typically it is substantially absent. 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] Exemplary but non-limiting active hydrogen compounds include polyamines such as 1,2-diaminoethane, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,12-diaminododecane, 3,3-diaminopropyl-N-methylamine, N-alkyl-1,3-diaminopropane, wherein the alkyl group is a long carbon chain, such as cocoyl or shea butter alkyl, soybean alkyl, oleyl, stearyl, and mixtures thereof, and amino alcohols such as ethanolamine, 6-aminohexanol, aminoethylethanolamine, and combinations thereof.

[0162] The diol that may constitute a part of the active hydrogen compound may be selected from 1,2-ethylene glycol, 1,2- and 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, and combinations thereof. In various embodiments, the amount of diol is limited such that at least about 90 mol% of the total active hydrogen groups involved in the reaction are primary and / or secondary amino groups. Typical active hydrogen compounds are diamines, particularly diamines having about 6 to about 12 carbon atoms, the most typical diamine being 1,6-diaminohexane. 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.

[0163] End-capping agents are commonly used to terminate the reaction product of a polycarboxylic acid and an active hydrogen compound, and can be a monocarboxylic acid, which may be unsaturated and hydroxylated. Monocarboxylic acids typically have about 8 to about 22 carbon atoms. While some benefits can be achieved using monocarboxylic acids with fewer carbon atoms, such smaller monocarboxylic acids can be limited to less than about 20% molar of the total end-capping agent used, typically less than about 10% molar, and most commonly absent. 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.

[0164] The structure of the end-capping agent has a significant impact on the properties of polyamide waxes. For example, end-capping agents containing unsaturated, especially monounsaturated, monocarboxylic acid sites, such as oleic acid, can improve the efficiency of polyamide waxes compared to saturated monocarboxylic acid analogs.

[0165] Hydroxylation of saturated monocarboxylic acids can improve the ease of dispersion (incorporation) of polyamide waxes in a composition, but may reduce their efficiency in the composition. Due to the increased ease of dispersion, incorporating polyamide waxes capped with hydroxylated monocarboxylic acids into a composition may require less energy input compared to similar polyamide waxes capped with, for example, unsaturated and non-hydroxylated monocarboxylic acids. Therefore, monocarboxylic acid capping agents typically contain both unsaturated and hydroxylated components. More typically, monocarboxylic acid capping agents have a single unsaturated point (if aliphatic) or a single hydroxyl moiety, and even more typically, monocarboxylic acid capping agents have both a single unsaturated point (if aliphatic) and a single hydroxyl moiety.

[0166] End-capping agents may also have straight or branched chains, and may also include groups that do not react with other components used to prepare polyamide waxes, such as tertiary amino, alkoxy, halogen, ketone, etc.

[0167] Exemplary but non-limiting examples of unsaturated fatty acids include linoleic acid, linolenic acid, oleic acid, monocarboxylic acids derived from dehydrated castor oil, undecenoic acid, tall oil fatty acids, soybean fatty acids, and mixtures thereof. Aromatic acids such as benzoic acid, salicylic acid, and mixtures thereof may also be used as part of the total capping agent.

[0168] Hydroxylated monocarboxylic acids include ricinoleic acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, and mixtures thereof. The most typical end-capping agent is ricinoleic acid.

[0169] A portion of the capping agent may consist of a compound that is not an unsaturated and / or hydroxylated monocarboxylic acid. For example, a portion of the capping agent may consist of at least one non-hydroxylated saturated aliphatic monocarboxylic acid, such as octanoic acid, nonanoic acid, dodecanoic acid, octadecanoic acid, docosanoic acid, hydrogenated tallow acid, stearic acid, and mixtures thereof. In various embodiments, at least about 25% molar, typically at least about 50% molar, and most typically at least about 90% molar of the capping agent actually reacting may be said unsaturated and / or hydroxylated monocarboxylic acid. 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.

[0170] In various embodiments, the polyamide wax is a reaction product of an oligomer of a fatty acid having a carbon chain of about 16 to about 18 carbon atoms, a diamine having 6 to 12 carbon atoms, and an unsaturated and hydroxylated monocarboxylic acid having about 16 to about 22 carbon atoms as a capping agent, the most typical capping agent being ricinoleic acid. 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.

[0171] In various embodiments, the specific type and amount of reactants are selected to obtain a non-resin-like reaction product dispersible in the composition. Therefore, in various embodiments, the amount of active hydrogen compound reacting to form the reaction product can be from about 1.0 to about 4.0 per mole of the polycarboxylic acid, typically from about 1.0 to about 3.0, and most typically from about 1.0 to about 2.0 moles. 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.

[0172] The amount of the selected capping agent is typically sufficient to cap the active hydrogen compound terminus of the reaction product of the polycarboxylic acid and the active hydrogen compound. Typically, the amount of capping agent forming the reaction product is about 0.1 to about 4.0 moles of the polycarboxylic acid, typically about 0.17 to about 2.0 moles, and most typically about 0.3 to about 2.0 moles per mole of the reacted polycarboxylic acid. 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.

[0173] The molar amounts of each component in the reaction mixture may differ from the molar amounts of the polyamide wax formed. That is, one or more reactants may be used in excess. In various embodiments, an excess of about 2% to about 10% molar of an active hydrogen compound (e.g., a diamine) may be used to accelerate the reaction and compensate for losses due to co-distillation with the reaction water. In various embodiments, the number-average molecular weight (Mn) of the reaction product is about 500 to about 12,000, typically about 1,250 to about 8,500, and most typically about 1,250 to about 4,000. In various embodiments, the polyamide wax is not a polymer resin, but a compound with relatively low molecular 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.

[0174] Polyamide waxes can be prepared using known techniques. For example, the reactants can be loaded into a suitable reaction vessel equipped with a mechanical stirrer, thermometer, Bartlett modified Dean-Stark water separator, and nitrogen inlet. The vessel can be stirred and heated under a nitrogen cover. After the reaction is complete, which can be determined by the acid value (e.g., typically less than about 4), the polyamide is cooled and discharged. If grinding is required, the polyamide wax can be ground to a fine particle size. The desired or typical degree of particle size reduction depends on the specific polyamide wax, or more appropriately, on the melting point of the specific polyamide wax, where harder, higher-melting-point polyamide waxes tend to require finer particle sizes to achieve satisfactory dispersion in the composition.

[0175] In various implementation schemes, the typical general formula for polyamide waxes is as follows:

[0176] R'-C(O)-XRY-[-C(O)-R"-C(O)-XRY-] x --C(O)R'

[0177] Wherein R' is a residue of a monocarboxylic acid capping agent, R is a group comprising about 2 to about 12 carbon atoms, each of X and Y is a primary amino, secondary amino, or hydroxyl residue, R" is a residue of a polycarboxylic acid, and x is about 1 to about 17, typically about 1 to about 12, and most typically about 1 to about 5. 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.

[0178] In various embodiments, to improve efficiency and processing, the polyamide wax may first be pre-dispersed in a compatible organic solvent, especially at slightly elevated temperatures. Typically, the solvent contains at least about 10% by weight of an alcohol and usually at least about 25% by weight of an alcohol. Representative alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, isoamyl alcohol, and mixtures thereof, with 2-propanol being a typical alcohol. In various embodiments, the function of the alcohol solvent is to form hydrogen bonds with the polyamide wax to eliminate or significantly reduce intermolecular polyamide-polyamide interactions. 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.

[0179] By using an alcoholic solution of the polyamide wax, greater freedom can be exercised in selecting the amounts of reactants used to prepare the polyamide wax. For example, the amount of reacting groups from the active hydrogen compound can be reduced from about 90% amino to at least about 50% amino. However, even in this case, more amino groups are typically used, and therefore at least about 75% of the reacting groups from the active hydrogen compound are typically primary and / or secondary amino groups. 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.

[0180] The remaining portion of the solvent can be any organic solvent, which, together with the alcohol, will provide a fluid solution of the polyamide wax. Typical cosolvents include aromatic solvents such as benzene, toluene, xylene, ethylbenzene, naphthalene-containing solvents and mixtures thereof, and aliphatic solvents such as mineral oil, mineral oil, hexane, heptane and mixtures thereof, with toluene and xylene being the most typical cosolvents.

[0181] In various embodiments, a typical combination of solvents is 2-propanol and toluene in a weight ratio of about 1:1 to about 1:9, and most commonly about 1:1 to about 1:4. This combination provides a solution that remains fluid when stored at ambient temperature and acts as an effective thixotropic agent when used in organic solvent-based applications. In various embodiments, the amount of polyamide wax pre-dispersed in the solvent is about 5% to about 75% by weight, typically about 25% to about 50% 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.

[0182] In the foregoing, the term "consistently composed of" describes various non-limiting embodiments in which the total weight of the wax or composition as a whole contains or does not contain less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% of one or more compounds. For example, these one or more compounds may be or include other waxes, other amines, other carboxyl-containing compounds, organically modified clays, finely crushed (pyrolytic) silica, etc. In 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.

[0183] In various embodiments, the polyamide wax also comprises a low-volatility liquid alcohol with a water solubility of less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 mg / L. 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.

[0184] In other embodiments, the polyamine is selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and combinations thereof. In one embodiment, the polyamine is diethylenetriamine. In another embodiment, the fatty acid is derived from a C18 fatty acid. In a further embodiment, the C18 fatty acid is oleic acid. In another embodiment, the fatty acid contains about 28 to about 48 carbon atoms. In another embodiment, the fatty acid contains about 32 to about 36 carbon atoms.

[0185] In various embodiments, the polyamide wax is present in an amount of about 0.1 to about 4% by weight, based on the total weight of the coating composition. In other embodiments, the polyamide wax is present in an amount of about 0.1 to about 1.75, 0.2 to about 3.9, about 0.3 to about 3.8, about 0.4 to about 3.7, about 0.4 to about 1.4, about 0.5 to about 3.6, about 0.6 to about 3.5, about 0.7 to about 3.4, about 0.8 to about 3.3, about 0.9 to about 3.2, about 1 to about 3.1, about 1.1 to about 3, about 1.2 to about 2.9, about 1.3 to about 2.8, about 1.4 to about 2.7, about 1.5 to about 2.6, about 1.6 to about 2.5, about 1.7 to about 2.4, about 1.8 to about 2.3, about 1.9 to about 2.2, or about 2 to about 2.1% by weight, based on the total weight of the coating composition. 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.

[0186] In various embodiments, the coating composition further comprises a polyethylene wax in combination with a polyamide wax. There are no particular limitations on the polyethylene wax, and it can be any polyethylene wax known in the art. In one embodiment, the polyethylene wax is selected from LDPE wax, HDPE wax, and combinations thereof. Specific polyethylene waxes used herein can have any molecular weight, degree and length of polymer branching, and monomer / polymer composition, as long as they are still considered by those skilled in the art to be polyethylene waxes. Changing any of these factors can alter the physical properties of the polyethylene wax, such as viscosity, hardness, melting point, reactivity, etc. In various embodiments, the polyethylene wax is described as a homopolymer polyethylene wax, which can also be functionalized by adding acid and ester functional groups to the polyethylene wax through oxidation. Oxidized polyethylene waxes, which are polar and have different compatibility with homopolymer polyethylene waxes, can also be used. In various embodiments, the polyethylene wax is an anionic polyethylene wax emulsion. In various embodiments, the polyethylene wax has a melting point of about 105 to about 125°C, about 110 to about 120°C, about 110 to about 115°C, about 110 to about 125°C, about 115 to about 125°C, or about 115 to about 120°C. 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.

[0187] The amount of polyethylene wax may be zero or may be included herein. In various embodiments, the amount of polyethylene wax used is about 0.025 to about 1, about 0.03 to about 0.1, about 0.04 to about 0.09, about 0.05 to about 0.08, about 0.06 to about 0.06, 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, or about 0.5 to about 0.6% by weight, based on the total weight of 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.

[0188] Other optional components:

[0189] The coating composition may contain various components, such as binders, dyes, 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 fact that the coating composition contains certain components and / or contains certain components in specific amounts / ratios, the coating composition is suitable for application to a substrate using a high-transfer-efficiency applicator.

[0190] 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.

[0191] 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.

[0192] As described above, the coating composition may also include a catalyst. The coating composition may also contain a catalyst to reduce curing time and allow the coating composition to cure at ambient temperature. 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.

[0193] As described above, 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. Acquired through commercial purchase.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] The coating composition may also contain other additives known in the art for use in coating compositions. Non-limiting examples of such additives may include wetting agents, leveling agents, and flow control agents, such as those marketed under their respective trade names. 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.

[0198] The coating composition may have a solids content of about 5 to about 90%, or 5 to about 80%, or about 15 to about 70% by weight. The solids content may be determined according to ASTM D2369-10. In some embodiments, a higher solids content is desirable because the coating composition is not atomized using conventional spraying equipment. In all 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.

[0199] The coating composition may be substantially dye-free. As used herein, the term "substantially" means that the coating composition may contain an insignificant amount of dye, such that the color and / or properties of the coating composition are not affected by the added insignificant amount of dye and are still considered substantially dye-free. In embodiments, a substantially dye-free coating composition contains no more than 5% by weight, or no more than 1% by weight, or no more than 0.1% by weight of dye. 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.

[0200] In various embodiments, the composition is free of clay and silica. The term "free of" may describe that the composition contains less than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% by weight of clay and / or silica, based on the total weight of the composition. Alternatively, the composition may be completely free of clay or silica. There are no particular limitations on the clay and it may be quaternary ammonium-surface-functionalized clay particles. Similarly, there are no particular limitations on the silica and it may be an organophilic layered silicate, amorphous silica such as CAS:92797-60-9, AEROSIL R-805VV90, and combinations thereof. 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.

[0201] In various embodiments, based on the total weight of the composition, the composition contains no or less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% by weight of at least one polyurea crystal sag control agent. This agent is typically a reaction product of an amine and an isocyanate. Neither the amine nor the isocyanate is particularly limited and can be any amine and isocyanate known in the art or as described above. For example, the amine can be a primary or secondary amine. Amines typically contain hydroxyl and / or ether groups. In various embodiments, the amine is a monoamine, diamine, triamine, or polyamine. In various embodiments, the use of diamines, triamines, and / or polyamines requires the use of a monofunctional isocyanate.

[0202] In various embodiments, the method further includes the step of curing the coating composition on a substrate, wherein the high-transfer-efficiency applicator includes a plurality of nozzles, wherein the application step is further defined as applying the coating composition to the substrate in multiple lines through the nozzles, and wherein the coating composition is free from visible appearance defects due to incomplete flow and leveling of the individual nozzle lines after the curing step.

[0203] In other embodiments, the method further includes the step of curing a coating composition on a substrate, wherein the high-transfer-efficiency applicator includes a plurality of nozzles, and wherein the application step is further defined as applying the coating composition to the substrate in multiple lines along the direction (X) via the nozzles, wherein each line partially overlaps with an adjacent line to form overlapping and non-overlapping areas, wherein the overlapping areas are visually smooth such that the thickness of the overlapping areas varies by less than about 1 micrometer after the curing step compared to the thickness of the non-overlapping areas measured at a distance of 5 mm perpendicular to the direction (X).

[0204] In various embodiments, the high-transfer-efficiency applicator includes a nozzle with a defined diameter, and the step of applying the coating composition to the substrate via the high-transfer-efficiency applicator results in minimized nozzle clogging, wherein the coating composition contains no components whose average particle size is greater than about 10% of the nozzle diameter. The nozzle and nozzle diameter can be any nozzle and nozzle diameter described in this disclosure or known in the art.

[0205] In one implementation scheme

[0206] A. The resin is a hydroxyl-functional acrylic resin with a Mw of 5500 and a hydroxyl content of 97 mg KOH / g;

[0207] B. The melamine crosslinking agent includes

[0208] Methylated and isobutylated melamine-formaldehyde resins; and

[0209] Methylated imino-type (triether) melamine-formaldehyde resin;

[0210] C. The optional pigment is a 20% carbon black dispersion; and

[0211] D. The organic solvent is a naphthalene-poor aromatic solvent; and the coating composition further comprises a hydroxylated acrylic polyol having a modified hydroxyl content of 4.5%. The polyamide wax may be any polyamide wax described herein.

[0212] In another implementation scheme,

[0213] A. The resin is a hydroxyl-functional branched acrylic resin with a Mw of 34,500 and a hydroxyl content of 54 mg KOH / g;

[0214] B. The melamine crosslinking agent includes

[0215] Methylated and isobutylated melamine-formaldehyde resins; and

[0216] Methylated imino-type (triether) melamine-formaldehyde resin;

[0217] C. The optional pigment is a 20% carbon black dispersion; and

[0218] D. The organic solvent is a naphthalene-poor aromatic solvent; wherein the coating composition further comprises a hydroxylated acrylic polyol having a modified hydroxyl content of 4.5%. The polyamide wax may be any polyamide wax described herein.

[0219] Sagging assessment:

[0220] In various embodiments, the coating composition, after curing at a temperature of about 60°C or higher for at least about 5, 10, 15, 20, 25, or 30 minutes, has a wet film thickness of at least about 30 micrometers when measured at about 45 degrees Celsius, without visible sagging. For example, the wet film thickness when measured at about 45 degrees Celsius can 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 can 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 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.

[0221] To assess sagging, the following procedure is typically used:

[0222] Orient the substrate panel horizontally before applying the coating;

[0223] Three consecutive stripes of the coating composition are applied to a horizontal substrate panel using a high-transfer-efficiency applicator, such that the composition overlaps to provide a continuous coating surface with a target wet film thickness (typically 30 microns or more) and a width of approximately 150 mm across the substrate.

[0224] After applying the composition, tilt the panel so that the width edge of the approximately 150mm coated substrate forms an angle of approximately 20 to approximately 45 degrees with the horizontal, for example, as shown below. Figure 2B As shown;

[0225] After about 10 minutes at room temperature, bake the panel at about 140°C for about 30 minutes while keeping the panel angle unchanged;

[0226] If sagging is present, it is evidenced by dripping at the bottom edge of the coating and assessed visually, for example, as shown in the image. Figure 4 and 5 As shown;

[0227] If nozzle line visibility exists, it will be observed as thin lines parallel to each other and thin lines parallel to the application direction and having the same spacing (approximately 1 mm) as adjacent nozzles in the applicator, as shown in Figure 3, for example.

[0228] If stripe overlap visibility exists, it will be visually evaluated in areas where multiple coating passes have been applied. It was found that a thickness variation of only 1 micrometer over a distance of 5 mm parallel to the application direction will result in stripe overlap visibility, as shown in Figure 3-4, for example.

[0229] The use of the coating compositions of this invention can reduce or eliminate nozzle clogging. For example, high-efficiency "on-demand" or "drop-on-demand" applicators typically include an array of fine-diameter nozzles, each with a nozzle diameter of about 20 to 200 micrometers. For reliable fluid jetting, it is generally expected that the particle size of any component of the coating composition must not exceed about 10% of the nozzle diameter. While some components of the coating composition may have an average size that meets this standard, nozzle clogging will occur over time if a small number of excessively large particles are present. The result is either partial nozzle clogging, which may cause droplets or flow to become disoriented, or complete nozzle clogging, which prevents fluid jetting. In either case, this leads to coating defects. Clogging can be assessed in two ways: (1) clogging of the filter installed before the applicator and (2) missing lines during coating application followed by microscopic examination of debris in the nozzle.

[0230] While well-known coating appearance properties, including gloss, image sharpness, and "orange peel" effect, can be quantified using various instruments, this is not the case for the visibility of nozzle lines and streaks. Coatings applied using high-efficiency transfer applicators can have high gloss, high image sharpness, and no orange peel effect, but visible nozzle lines and streaks still exist. Figure 3C The illustration shows that item 20 represents a paint line deposited from a single nozzle parallel to the application direction. While the lines may be visible immediately after application, they can remain visible after the coating has cured if sufficient flow and leveling have not occurred, resulting in an uneven and generally undesirable coating appearance. Typically, nozzle line visibility presents as a striped appearance, with the distance between visible lines being the same as the nozzle spacing on the applicator. Stripe overlap defects are also parallel to the application direction, but this defect is independent of the applicator nozzle spacing. It only exists where adjacent stripes applied sequentially and adjacent to each other overlap and are visible on a 5-10 mm length scale perpendicular to the application direction. Although usually evaluated by comparison with a printed control coating with low viscosity and no rheology control agent, the defect is visible when the height difference between high and low areas is greater than 1-2 micrometers.

[0231] Viscosity evaluation:

[0232] In other embodiments, the coating composition is applied for approximately 10,000 seconds. -1 After a high shear rate of approximately 20 seconds, the rate decreases to approximately 1 second. -1 The viscosity measured at the shear rate recovers to approximately 1 second within about 5 seconds. -1 The viscosity is approximately 95% of the steady-state viscosity reached when the shear rate is continuously sheared for more than approximately 100 seconds. More specifically, this viscosity can be measured using ASTM 2196. 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.

[0233] In various embodiments, the high shear rate may vary by about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25% compared to any value herein. Similarly, in other embodiments, the high shear rate application time may vary by about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25 seconds compared to any value herein. In other embodiments, the recovery of about 95% may vary by about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% compared to any value herein. In other embodiments, the measurement result of more than about 100 seconds may vary by about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25% compared to any value herein. In other embodiments, the continuous shear value may vary by about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25% compared to any value herein. Finally, in other embodiments, the value less than 5 seconds may vary by approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 seconds compared to any value herein. 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.

[0234] In other embodiments, the coating composition has a complex viscosity measured at about 60°C, and when the complex viscosity measured at about 30°C is about 800 to about 8000 mPa·s, the complex viscosity of the coating composition measured at about 60°C decreases to about 60 to about 500 mPa·s. In various embodiments, the 30°C and / or 60°C may each vary independently by about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, or 25%. In other embodiments, the 60 and / or 500 mPa·s may each vary independently by about 1%, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20%, or 25% compared to any value herein. In other embodiments, the 80 and / or 8000 mPa·s may vary independently by about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25% compared to any value herein. In various embodiments, the range of about 60 to about 500 mPa·s can alternatively be about 70 to about 490, about 80 to about 480, about 90 to about 470, about 100 to about 460, about 110 to about 450, about 120 to about 440, about 130 to about 430, about 140 to about 420, about 150 to about 410, about 160 to about 400, about 170 to about 390, about 180 to about 380, about 190 to about 370, about 200 to about 360, about 210 to about 350, about 220 to about 340, about 230 to about 330, about 240 to about 320, about 250 to about 310, about 260 to about 300, about 270 to about 290, or about 280 to about 290 mPa·s. In other embodiments, the range of about 800 to about 8000 can alternatively be about 1000 to about 7500, about 1500 to about 7000, about 2000 to about 6500, about 2500 to about 6000, about 3000 to about 5500, about 3500 to about 5000, or about 4000 to about 4500 mPa·s. In other embodiments, the value can be 800, 810, 820, etc., up to about 8000 mPa·s. 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.

[0235] In other embodiments, the coating composition has a 1000s -1 The high shear rate viscosity measured at approximately 20 to approximately 70 mPa·s and at approximately 1 s -1 The low shear viscosity was measured at a shear rate of approximately 800 to approximately 8000 mPa·s. In various embodiments, the viscosity was measured at 1000 s. -1The measured high shear rate viscosity can be 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 55 mPa·s. The low shear viscosity can be any of the above-described viscosities independently. In various non-limiting embodiments, all values ​​and ranges of values, whether integers or fractions, including the values ​​described above and values ​​between the above-described values, are expressly considered herein for use.

[0236] Example

[0237] The following describes the preparation and evaluation of a series of examples to determine various physical properties. Examples of the invention include Examples 1-6. Examples 1-3 contain only polyamide wax as a rheology control agent. Examples 4 and 5 contain a combination of polyamide wax and polyethylene wax. Example 6 contains a combination of polyamide wax and a strong sag control agent. Comparative examples include Examples 7-12, which do not contain the polyamide wax of this disclosure. The amounts of the various components of the examples are listed in the table below, where, unless otherwise stated, the values ​​for the examples are weight percentages based on 100% total weight.

[0238]

[0239]

[0240] *The method for producing the polyamide wax solution to be incorporated into Examples 1 and 6 is as follows: Polyamide wax 1 is slowly added to the high-solids enamel resin while stirring at 2000 rpm for about 15 minutes using a high-speed disperser, until the material thickens and no longer moves when the temperature reaches between 40°C and 50°C. Xylene is added to the mixture and stirred until homogeneous.

[0241] The grinding method used to incorporate polyamide wax 4 into Example 2 is as follows: Alkyd resin, melamine-formaldehyde resin 2, high-solids enamel resin, dipropylene glycol methyl ether, and polyamide wax 4 are mixed and stirred for 5 minutes to combine. The mixture is then ground in a media mill using ceramic media with a diameter of 0.8 mm, while maintaining a temperature below 40°C.

[0242]

[0243]

[0244] The components used in the examples are described in more detail below.

[0245]

[0246]

[0247] After formation, Examples 1-6 and Comparative Examples 7-12 of the present invention are evaluated as described below to determine various physical properties.

[0248]

[0249] In these embodiments, each "+" is a positive indicator, indicating subjectively better performance as understood and evaluated by those skilled in the art. Each "-" is a negative indicator, indicating subjectively worse performance as understood and evaluated by those skilled in the art. If more than one "+" or "-" sign is used, this respectively means even better or worse performance as understood and evaluated by those skilled in the art. "0" indicates performance between + and -.

[0250] Streak overlap visibility was visually assessed in areas where multiple coating passes were applied consecutively. It was found that a thickness variation of only 1 micrometer over a distance of 5 mm parallel to the application direction would result in visible streak overlap.

[0251] To evaluate sagging at 20°, the following procedure is typically used: The substrate panel is horizontally oriented before coating application. Using a high-transfer-efficiency applicator, three consecutive stripes of the coating composition are applied to the horizontal substrate panel, such that the composition overlaps to provide a continuous coated surface with the target wet film thickness (typically 30 micrometers or greater) and a width of approximately 150 mm across the substrate. After application, the panel is tilted so that the approximately 150 mm wide edge of the coated substrate forms an angle of approximately 20° with the horizontal. After approximately 3–10 minutes at room temperature, the panel is baked at approximately 140°C for approximately 30 minutes while maintaining the panel angle. If sagging is present, it is indicated by dripping at the bottom edge of the coating and is visually evaluated as described in detail above.

[0252] Nozzle line visibility refers to the presence of fine lines that are parallel to each other and parallel to the application direction, and whose spacing is the same as the spacing between adjacent nozzles in the applicator (approximately 1 mm).

[0253] If the coating performance is poor from the beginning or deteriorates (degrades) over time, nozzle clogging must be considered. If coating degradation occurs (missing or incorrectly oriented nozzle lines, reduced flow rate, pressure buildup), nozzle clogging can be confirmed by: (1) clogging of the filter installed before the applicator and (2) missing nozzle lines during coating application, followed by microscopic examination of debris in the nozzle. If no nozzle clogging is observed during prolonged coating application, the nozzle clogging is considered minimal (+++++). On the other hand, if nozzle clogging is observed at the start of application, the nozzle clogging is considered most severe (-----).

[0254] In addition, Examples 1, 9 and 12 were evaluated to determine their physical properties. Figure 8The viscosity recovery plot and test procedure are shown. The plot displays the viscosity recovery measurement results, where the viscosity was measured according to ASTM 2196 at a specified shear rate. For example, the sample was tested in a rheometer at 10000 s⁻¹. -1 Shearing at a shear rate of 20 seconds. Then reduce the shear rate to 1 second. -1 And measure the change in viscosity over time. The viscosity reaches its steady-state value (usually within 1 second). -1 At least 95% of the time (100 seconds or longer) is considered the time required for viscosity recovery.

[0255] Figure 9 The relationship between complex viscosity and temperature, as measured according to ASTM D4440, is shown.

[0256] Figure 10 The results of Optimap surface profile measurements for the same embodiment, performed immediately after printing (wet) and after curing, are shown. Optimap TM PSD uses phase-step deflection measurement to determine the surface profile of an area of ​​approximately 79 x 57 mm. Here, the surface profile of the coating, including the stripe overlap area, is shown. For each image, the stripe overlap area is identified by a red arrow. The color scale corresponding to the coating height differences is shown on the left. Green represents the average coating surface height, while red (to white) represents "hills" with a higher height than the average, and blue (to black) represents "valleys" with a lower height than the surface average. Because the Optimap must be placed in direct contact with the coating, the height profile around the edges of the wet coating is distorted due to the coating thinning when in contact with the gasket supporting the Optimap. However, an undistorted image of the stripe overlap area is still obtained at the center of the image. The stripe overlap area is observed to be a defect parallel to the application direction and becomes more visible as the hills and valleys become more pronounced. For Example 1, the height of the stripe overlap "hills" is 30 micrometers higher than the average, significantly exceeding that of Comparative Examples 12 (approximately 4 micrometers) and 9 (approximately 3 micrometers).

[0257] The above and Figure 8 , 9 The data given in section 10 indicate that, for the embodiments including polyamide wax, an optimal balance was achieved with minimal stripe overlap visibility, no nozzle line visibility, and anti-sagging properties without any nozzle clogging. Given... Figure 8 The rapid viscosity recovery observed in Example 1 compared to the alternative rheology control additives used in Examples 12 and 9 after applying a high shear rate is unexpected. Based on this rapid viscosity recovery, in Figure 10 The post-printing (wet) examples illustrate the expected poor flow and leveling immediately after application. However, the expected viscosity during oven heating for coating curing is as follows, prior to significant solvent evaporation. Figure 9 The measurement results show that as the temperature decreases, this results in significant leveling of Example 1 containing polyamide wax, without the significant sagging that occurred before curing due to the viscosity being too low as in Example 9.

[0258] 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 single-component solvent-based automotive 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. The coating composition comprises: A. Resins, including acrylic, polyester, or combinations thereof; B. Melamine crosslinking agent; C. Optional pigments; D. Organic solvents; and E. Polyamide wax comprising (i) and (ii) reaction products: (i) a fatty acid derived from C16-C48 fatty acids; (ii) a polyamine having two or more amine functional groups, and the polyamide wax being present in an amount of 0.1 to 4% by weight based on the total weight of the coating composition; When measured at 45 degrees, the composition has a wet film thickness of at least 30 micrometers and no visible sagging after curing at 60°C or higher for at least 5 minutes; The composition is applied for 10,000 seconds. -1 High shear rate for 20 seconds followed by 1 second -1 The viscosity measured by the shear rate recovers to a rate of 1 second within 5 seconds. -1 The viscosity reached at a shear rate greater than 100 seconds is within 95% of the steady-state viscosity, measured according to ASTM 2196 at a specified shear rate; and When the complex viscosity measured at 30°C is 800 to 8000 mPa·s, the complex viscosity of the coating composition measured at 60°C decreases to 60 to 500 mPa·s, and the complex viscosity is measured according to ASTM D4440.

2. The method according to claim 1, wherein the polyamide wax further comprises a low-volatility liquid alcohol with a water solubility of less than 10 mg / L.

3. The method according to claim 1 or 2, wherein the polyamine is selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

4. The method according to claim 1 or 2, wherein the polyamine is diethylenetriamine.

5. The method according to any one of claims 1-4, wherein the fatty acid is derived from C18 fatty acids.

6. The method according to claim 5, wherein the C18 fatty acid is oleic acid.

7. The method according to any one of claims 1-6, wherein the fatty acid comprises 28 to 48 carbon atoms.

8. The method according to any one of claims 1-7, wherein the fatty acid comprises 32 to 36 carbon atoms.

9. The method according to any one of claims 1-8, wherein the polyamide wax is present in an amount of 0.1 to 1.75% by weight based on the total weight of the coating composition.

10. The method according to any one of claims 1-9, wherein the coating composition has a [temperature] of 1000 s -1 The high shear rate viscosity measured at 20 to 70 mPa·s and at 1 s -1 The low shear viscosity of 800 to 8000 mPa·s was measured at shear rates.

11. The method according to any one of claims 1-10, wherein the coating composition further comprises polyethylene wax.

12. The method according to any one of claims 1-11, further comprising the step of curing the coating composition on a substrate, wherein the high transfer efficiency applicator comprises a plurality of nozzles, wherein the application step is further defined as applying the coating composition to the substrate in multiple lines through the nozzles, and wherein the coating composition is free from visible appearance defects due to incomplete flow and leveling of the individual nozzle lines after the curing step.

13. The method according to any one of claims 1 to 11, further comprising the step of curing a coating composition on a substrate, wherein the high transfer efficiency applicator comprises a plurality of nozzles, wherein the application step is further defined as applying the coating composition to the substrate in multiple lines along the substrate in direction X via the nozzles, wherein each line partially overlaps with an adjacent line to form overlapping and non-overlapping areas, wherein the overlapping areas are visually smooth such that the thickness of the overlapping areas varies by less than 1 micrometer after the curing step compared to the thickness of the non-overlapping areas measured at a distance of 5 mm perpendicular to direction X.

14. A method for applying a two-component solvent-based automotive coating composition to a substrate using a high-transfer-efficiency applicator to form a coating disposed on the substrate, the method comprising the steps of: 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. The coating composition comprises: A. Hydroxyl-functionalized resins; B. Melamine crosslinking agent; C. Optional pigments; D. Organic solvents; and E. Polyamide wax comprising (i) and (ii) reaction products: (i) a fatty acid derived from C16-C48 fatty acids; (ii) a polyamine having two or more amine functional groups, and the polyamide wax being present in an amount of 0.1 to 4% by weight based on the total weight of the coating composition; When measured at 45 degrees, the composition has a wet film thickness of at least 30 micrometers and no visible sagging after curing at 60°C or higher for at least 5 minutes; The coating composition is applied for 10,000 seconds. -1 High shear rate for 20 seconds followed by 1 second -1 The viscosity measured by the shear rate recovers to a rate of 1 second within 5 seconds. -1 The viscosity reached when continuously sheared at a shear rate greater than 100 seconds is within 95% of the steady-state viscosity, wherein the viscosity is measured according to ASTM 2196 at a specified shear rate; and When the complex viscosity measured at 30°C is 800 to 8000 mPa·s, the complex viscosity of the coating composition measured at 60°C decreases to 60 to 500 mPa·s, and the complex viscosity is measured according to ASTM D4440.

15. The method of claim 14, wherein the polyamide wax further comprises a low-volatility liquid alcohol with a water solubility of less than 10 mg / L.

16. The method according to claim 14 or 15, wherein the polyamine is selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

17. The method according to any one of claims 14 to 16, wherein the fatty acid is derived from C18 fatty acids.

18. The method according to any one of claims 14 to 17, wherein the fatty acid comprises about 28 to about 48 carbon atoms.

19. The method according to any one of claims 14 to 18, wherein the polyamide wax is present in an amount of about 0.1 to about 1.75% by weight based on the total weight of the coating composition.

20. The method according to any one of claims 14 to 19, wherein the coating composition further comprises polyethylene wax.

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