Silicone modified polyurea coating composition

Abstract

This application relates to a coating composition that combines fouling release and / or de-icing performance with flexibility and durability. The coating composition includes a polyurea component and a polysiloxane component. The polyurea component includes an isocyanate component, an amine-functional resin, and an aliphatic copolymer. Corresponding methods for coating a substrate are also featured.

Description

[Technical field]

[0001] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT This disclosure was made with Government support under Government Contract No. NCMS FY2017 Marine Coatings 201853. The U.S. Government may have certain rights in aspects of this disclosure.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 294,871, filed December 30, 2021, the entire disclosure of which is incorporated herein by reference.

[0003] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Coating compositions for application to a substrate, and methods of coating a substrate, are described herein. [Background technology]

[0004] Outdoor structures such as wind turbines, bridges, towers, tanks, pipes, and fleet vehicles such as rail cars are constantly exposed to the elements and must be designed to withstand extreme temperature changes, wind shear, precipitation, icing, and other environmental hazards without significant damage or the need for regular maintenance, which can be time-consuming and costly. Similarly, marine structures such as ship hulls and offshore oil rigs and wind turbines are exposed to seawater and extreme weather and environmental conditions, making them susceptible to corrosion, marine fouling, abrasion, and impact. More effective treatment and coating systems are continually sought to meet the specification requirements of these industrial structures. Summary of the Invention

[0005] The present disclosure is directed to a coating composition. The coating composition may include a polyurea component including an isocyanate component, an amine-functional resin, and an aliphatic copolymer, and a polysiloxane component. The present disclosure is also directed to a method for coating a substrate. The method may include applying to at least a portion of the substrate a coating composition described herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] Provided herein are coating compositions and methods that can be applied to substrates for improved fouling release and / or de-icing performance. The present disclosure relates to coating compositions that can combine fouling release and de-icing performance with flexibility and durability. In some cases, the coatings described herein can be formed quickly and can significantly reduce the time required to recoat a substrate, which can reduce downtime and return a product to service.

[0007] Many conventional fouling release / de-icing coatings are soft and offer little protection from abrasion and impact. Many conventional epoxy coatings may offer some protection from abrasion and impact, but are unable to prevent or minimize marine fouling and icing. The coating compositions described herein may exhibit excellent durability and desirable properties such as high contact angles (water and diiodomethane), low ice accretion strength, high marine fouling release, high abrasion resistance, and high Young's modulus.

[0008] Described herein are coating compositions that may include a polyurea component and a polysiloxane component, with an equivalent ratio of isocyanate component to amine functional resin ranging from 1.01:1 to 1.4:1. The polyurea component may include an isocyanate component, an amine functional resin, and an aliphatic copolymer. The amine functional resin may include a difunctional amine, a triamine, and an aliphatic diamine chain extender. The aliphatic copolymer component may include a silicone copolymer. The isocyanate component may include a prepolymer formed from isophorone diisocyanate and a polyether diamine.

[0009] The coating compositions described herein may include an amine-functional resin in an amount of 16-43 wt% (e.g., 20-40 wt%, 18-32 wt%, or 30-35 wt%). The compositions may include 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, or 43% of the amine-functional resin. All percentages of the amine-functional resin are expressed as weight percent based on the total solids weight of the composition. In some cases, the amine-functional resin may include a difunctional amine, triamine, aliphatic diamine chain extender, or a combination thereof.

[0010] In some cases, the coating composition may include an equivalent ratio of isocyanate component to amine-functional resin of 1.01:1 to 1.4:1 (e.g., 1.08:1, 1.13:1, or 1.25:1). The composition may include an equivalent ratio of isocyanate component to amine functional resin of 1.01:1, 1.02:1, 1.04:1, 1.05:1, 1.06:1, 1.08:1, 1.1:1, 1.12:1, 1.14:1, 1.15:1, 1.16:1, 1.18:1, 1.2:1, 1.22:1, 1.24:1, 1.25:1, 1.26:1, 1.28:1, 1.3:1, 1.32:1, 1.34:1, 1.35:1, 1.36:1, 1.38:1, or 1.4:1.

[0011] The coating compositions described herein may include a difunctional amine in an amount of 8-25% by weight (e.g., 10-22%, 12-18%, or 15-20%). The compositions may include 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or 25% difunctional amine. All percentages of difunctional amine are expressed as weight percent based on the total solids weight of the composition. In some cases, the difunctional amine may include an aspartic acid ester.

[0012] The coating compositions described herein may include a triamine in an amount of 5-15% by weight (e.g., 5-12%, 10-15%, or 8-14%). The compositions may include 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% triamine. All percentages of triamine are expressed as weight percent based on the total solids weight of the composition. In some cases, the triamine may include a polyetheramine.

[0013] The coating compositions described herein may include an aliphatic diamine chain extender in an amount of 3.6-12 wt % (e.g., 4-10%, 6-9.5%, or 8.5-9%). The compositions may include 3.6%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, or 12% of an aliphatic diamine chain extender. All percentages of the aliphatic diamine chain extender are expressed as weight percent based on the total solids weight of the composition. In some cases, the aliphatic diamine chain extender may include ethyl cyanide.

[0014] The coating compositions described herein may include a polysiloxane component in an amount of up to 60% by weight (e.g., up to 15%, up to 30%, or up to 50%). The compositions may include 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60% of the polysiloxane component. All percentages of the polysiloxane component are expressed in weight percent based on the total solids weight of the composition. The polysiloxane component may include an amine-functional silicone, a silicone polyether copolymer, a phenyl silicone, or a combination thereof. The amine-functional silicone fluid may include a monofunctional, difunctional, or trifunctional amine. Optionally, the polysiloxane component may include a polydimethylsiloxane, a phenylmethylpolysiloxane, a polyphenylmethyldimethylsiloxane, or a combination thereof.

[0015] The polyurea component may further include a tin compound. In some examples, the tin compound may include an organotin compound. In some examples, the tin compound may include less than 1% by weight of the composition (e.g., up to 0.8%, up to 0.5%, or up to 0.2%) based on the total solid weight of the composition. The composition may include 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or up to 1% of the tin compound. All percentages of the tin compound are expressed as weight percent based on the total solid weight of the composition. Optionally, the tin compound may include dibutyltin dilaurate (DBDL) and / or dibutyltin diacetate (DBDA). In some examples, the composition may be free of tin or organotin compounds.

[0016] The coating compositions described herein may further include a biocide. The biocide may limit the growth of bacteria on the coated substrate and / or destroy bacteria on the substrate. In some examples, the biocide may include a silver or copper-containing compound. In some examples, the composition may be free of a biocide.

[0017] The coating composition may further comprise additives in an amount up to 30% by weight (e.g., 1-3%, 2-10%, or 5-25%). The composition may comprise 1%, 2%, 4%, 5%, 6%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, or 30% of the additives. All percentages of additives are expressed as weight percent based on the total solids weight of the composition. The additives may include wetting agents, dispersants, UV absorbers, hindered amine light stabilizers (HALS), organoclay derivatives, fumed silica, pigments, or combinations thereof.

[0018] The coating compositions described herein may include a polyurea component and a polysiloxane component, with an equivalent ratio of the isocyanate component to the amine-functional resin ranging from 1.01:1 to 1.2:1. In some examples, the polysiloxane component may comprise up to 60% by weight of the composition. The polyurea component may include an isocyanate component, an amine-functional resin, and an aliphatic copolymer. In some examples, the composition may include 16-43% by weight of the amine-functional resin. The amine-functional resin may include a difunctional amine, a triamine, and an aliphatic diamine chain extender. In some examples, the amine-functional resin may include 8-25% by weight of the difunctional amine, 5-15% by weight of the triamine, and 3.6-12% by weight of the aliphatic diamine chain extender. The aliphatic copolymer component may include a silicone copolymer. Optionally, the aliphatic copolymer component may include a silicone polyether copolymer. The isocyanate component may include a prepolymer formed from isophorone diisocyanate and a polyether diamine.

[0019] In some examples, the coating composition may include an isocyanate component, 16-43 wt% amine-functional resin, and a polyurea component including an aliphatic copolymer, and up to 60 wt% polysiloxane component, where the equivalent ratio of the isocyanate component to the amine-functional resin is in the range of 1.01:1 to 1.2:1, and the amine-functional resin includes 8-25 wt% difunctional amine, 5-15 wt% triamine, and 3.6-12 wt% aliphatic diamine chain extender. Optionally, the coating composition may further include an organotin compound in an amount of less than 1 wt% and / or up to 10 wt% of the additive, where the additive includes a wetting agent, a dispersant, a UV absorber, a hindered amine light stabilizer (HALS), an organoclay derivative, a fumed silica, a pigment, a biocide, or a combination thereof.

[0020] Also disclosed herein are methods for coating a substrate. Examples of suitable substrates can include metal, plastic, concrete, asphalt, wood, geotextile, fiberglass composite, and / or carbon fiber composite. In some examples, metal substrates can include iron, steel, steel alloy, galvanized metal, and / or aluminum. The method of coating a substrate can include applying a coating composition described herein to at least a portion of the substrate. In some examples, at least a portion of the substrate can include a first coating and / or a primer.

[0021] Optionally, the method may further include preparing at least a portion of the substrate prior to applying the coating composition. In some examples, preparing at least a portion of the substrate may include grit blasting, sand blasting, priming, and / or electrocoating at least a portion of the substrate. In some examples, preparing at least a portion of the substrate may include applying a release agent to at least a portion of the substrate.

[0022] Methods for applying the coating composition may include extrusion and / or spraying. The coating may be sprayed by air purged spray, mechanical purged spray, atomized air spray, non-atomized air spray, non-atomized airless spray, non-atomized airless spray, or other means known to those skilled in the art.

[0023] The substrate may comprise a coating composition as described herein. Suitable substrates for use in the methods described herein include metal, plastic, concrete, asphalt, wood, geotextile, glass fiber composites, and / or carbon fiber composites. Suitable metal substrates include, for example, ferrous metal, aluminum, aluminum alloys, and other metal and alloy substrates. Ferrous metal substrates used in the practice of the present disclosure may include iron, steel, and alloys thereof. Non-limiting examples of useful steel materials include hot-rolled and cold-rolled steel, galvanized (zinc-coated) steel, electrogalvanized steel, stainless steel, pickled steel, and combinations thereof. Combinations or composites of ferrous and non-ferrous metals may also be used.

[0024] The substrate may comprise a vehicle, a structure, or an industrial protective structure (e.g., electrical box enclosures, transformer housings, motor control enclosures, rail car containers), a tunnel, a bridge, an oil or gas industry component (e.g., platforms, pipes, tanks, vessels, and their supports), a marine component, an autobody part, an aerospace component, a pipeline, a storage tank, a wind turbine component, a roof structural component, a pile, an abutment, a seawall, and a general steel specimen. The article may comprise a substrate comprising a coating composition described herein.

[0025] As used herein, "structure" refers to buildings, bridges, oil rigs, oil platforms, water towers, power transmission towers, support structures, wind turbines, walls, piers, docks, dikes, dams, shipping containers, trailers, and any metal structure exposed to a corrosive environment. "Vehicle" in its broadest sense refers to all types of vehicles, including, but not limited to, cars, trucks, buses, tractors, harvesters, heavy duty equipment, vans, golf carts, motorcycles, bicycles, rail cars, airplanes, helicopters, and boats of all sizes.

[0026] In some examples, the coated substrate may have desirable fouling release properties. Biofouling, the attachment of marine organisms to a ship's hull, can be detrimental to marine vessels and ships. Attached marine organisms can increase the roughness of the ship's surface, increasing frictional resistance and impeding ship movement. Organisms can damage the ship's hull and increase the rate of corrosion of the ship. In some examples, the coated substrate may exhibit a maximum barnacle attachment force of 0.2 MPa when subjected to a barnacle removal peeling test, as described below. For example, the maximum barnacle attachment force may be 0.1 MPa, 0.15 MPa, or 0.2 MPa. In a barnacle removal peeling test, the substrate may be exposed to conditions favorable for barnacle attachment for a specified period of time, such as 30 days. The force required to remove the barnacles may be recorded as a maximum average load force. The barnacle removal peeling test may include a barnacle breakage test to ensure that the recorded removal force is due to the attachment of the barnacles to the substrate and not due to a defective portion of the barnacle.

[0027] In some examples, the coated substrate may have desirable de-icing properties. Ice build-up on surfaces such as wind turbine blades can impair performance and cause turbine overload and / or rotor imbalance. Ice splashing, large flakes of ice falling off structures, poses a hazard to the surroundings. In some examples, the coated substrate may exhibit a maximum mean load force of 400N when subjected to the ice accretion test described below. For example, the maximum mean load force may be 250N, 275N, 300N, 325N, 350N, 375N, or 400N.

[0028] Coatings on substrates can be damaged by abrasion during manufacturing and service. In some examples, the coatings described herein can be durable and the coated substrate can resist abrasion. The coated substrate can have less than 60 mg loss of coating for abrasion resistance as measured by ASTM D4060-14. For example, the coating loss can be less than 20 mg, 35 mg, 30 mg, 35 mg, 40 mg, 45 mg, 50 mg, 55 mg, or 60 mg for abrasion resistance as measured by ASTM D4060-14.

[0029] In some examples, the coated substrate may have desirable marine biofouling removal properties. Biofilms, which are thin sheets of bacteria, may form on the surfaces of marine vessels. Biofilms may result in material degradation, such as microbial corrosion of ferrous and non-ferrous metals, increased drag, and reduced efficiency from biofouling activity. In some examples, the coated substrate may exhibit a minimum average removal of at least 30% for Cellulophaga lytica (C. lytica) and at least 50% for Navicula incerta (N. incerta) when subjected to a microbial removal test with a 20 psi water jet, as described below.

[0030] As used herein, unless expressly specified otherwise, all numbers, such as those expressing values, ranges, amounts, or percentages, may be read as if preceded by the word "about" even if the term does not explicitly appear. Any numerical range recited herein is intended to include all subranges contained therein. The plural encompasses the singular and vice versa. For example, although the present disclosure is described in terms of "a" amine-functional resin, mixtures of such resins may also be used. Also, as used herein, the term "polymer" is meant to refer to prepolymers, oligomers, and both homopolymers and copolymers, and the prefix "poly" refers to two or more. Similarly, as used herein, the terms "on", "coated on / over", "formed on / on", "deposited on / on", "layered", and "provided on / on" refer to a surface that is applied, formed, deposited, layered, or provided to a surface, respectively, but not necessarily in contact with the surface. For example, a coating layer "formed on" a substrate does not exclude the presence of other coating layers, of the same or different composition, located between the formed coating and the substrate.

[0031] Although the numerical ranges and parameters setting forth the broad scope of the present disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements. When ranges are given, any of the endpoints of those ranges and / or any numerical values ​​within those ranges can be combined within the scope of the present disclosure.

[0032] As used herein, the meanings of "a," "an," and "the" include singular and plural referents unless the context clearly dictates otherwise.

[0033] As used herein, the terms "comprising," "having," "including," and "containing," unless otherwise indicated, are to be construed as open-ended terms (i.e., meaning "including, but not limited to") and do not limit the claimed disclosure to exclude any modifications or additions. Although various embodiments of the present invention have been described in terms of "comprising," embodiments that consist essentially of or consist of are also within the scope of the present invention. In this context, "consisting essentially of" means that any additional components do not materially affect the viscosity or other properties of the composition.

[0034] Each of the above-disclosed and below-disclosed features and examples, and combinations thereof, is believed to be encompassed by the present disclosure.

[0035] The following examples are intended to further illustrate the present disclosure.It is understood that the disclosure described herein is not necessarily limited to the examples described in this section.Components that are described elsewhere herein as suitable alternative materials for use in the present disclosure, but are not shown in the following examples, are expected to provide results comparable to those of the corresponding materials shown. EXAMPLES

[0036] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible, however, any numerical values ​​inherently contain certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0037] Comparative and exemplary deicing and fouling release coating compositions were prepared and evaluated for performance. The compositions evaluated are listed in Table 1. Examples 1 and 2 are comparative examples. Examples 3-4 are examples of coating compositions described herein. [Table 1]

[0038] Isocyanate-functional prepolymer #1 was synthesized according to the process described in US 8,691,929 (Example 1). Isocyanate-functional prepolymer #2 was synthesized according to the process described in US 8,691,929 (Example 2). Other additives included: Bentone 34 (clay derivative available from Akzo Nobel Chemicals, Amsterdam, Netherlands), BYK-9077 (solvent-free wetting and dispersing additive available from BYK Additives and Instruments, Wesel, Germany), pigments (e.g., TiO2), hydrophilic fumed silica, UV absorbers.

[0039] The B-pack (amine) samples were prepared by first combining 50% of the amine-functional resin with BYK-9077 dispersant, UV absorber, and DBDL, if applicable. Under agitation, the pigment, if applicable, was added to the resin blend and milled with a Cowles blade under high shear for 30 minutes. Once the milling stage was complete, the remaining 50% of the amine-functional resin was added under low shear along with the amine-functional silicone and polysiloxane components, if applicable, and mixed for 10 minutes to complete the B-pack formulation. The samples were shaken for 10 minutes before every application operation to ensure a homogenous sample.

[0040] A-packs (isocyanates) were prepared by combining isocyanate-functional prepolymer #1 with 0-30% silicone copolymer of the total formulation weight, where applicable. Samples were stirred and mixed using an impeller blade in a nitrogen-rich environment. An alternative A-pack containing isocyanate-functional prepolymer #2, synthesized via the process described in US 8,691,929 (Example 2), was also used.

[0041] Substrates were coated via extrusion of the coating. Wet samples were first loaded into a 50 mL, 1:1, two-component cartridge (Nordson TAH 50 mL cartridge) and capped with an O-ring piston (Nordson EFD EPDM O-ring piston tall). Application was performed using a pneumatic gun (Cox A25 Dual Component 50 mL Pneumatic Cartridge Gun) set at an application pressure of 20-30 psi using a 6 inch static mix tip (Nordson 7701488). The sample was extruded and then quickly drawn down to approximately 20 mils. Coating thickness was controlled during drawdown using shims. Ferrous substrates (CRS steel, smooth finish Q-panel stock #QD-412, E-coatings CRS-ACT Product #26241) were prepared on a magnetic board to hold the sample in place and maintain a flat working surface. A non-ferrous substrate (4" x 8" pre-primed aluminum: Q-Panel Stock #AQ-48) was prepared using a vacuum drawdown plate. The de-icing samples were coated on both sides of the substrate with a one day interval between applications. The samples were allowed to cure for seven days before any testing was performed.

[0042] The coatings were evaluated for surface free energy, water and diiodomethane (DM) contact angles, de-icing power, abrasion resistance, and deposit release properties.

[0043] To evaluate the effectiveness of the formulation changes against icing, an icing test was developed. The test method used was described in the U.S. Army Corps of Engineers Engineer Research and Development Center Document No. ERDC / CRRELTR-06-11 (incorporated herein by reference). The fixture design described therein was modified to interface with existing test equipment and accept test panels approximately 0.032 inches thick. In general, the procedure was as follows: A 4 inch wide test panel was coated on both sides with the desired coating(s). After the appropriate cure time, five 1×4 inch strips were cut from the test panel. The test strips were taped into place in the center of the test fixture so that the fixture could be filled with 1 inch of water. Cold water was used to fill the test fixture, ensuring that both sides of the coated panel were in contact with 1 inch of water. The entire test fixture was placed in a −20° C. freezer overnight. The test fixture was then transferred to a tensile tester (e.g., INSTRON 5567) with an environmental chamber set at −20° C. The test fixture was mounted such that the fixed end of the tensile tester was connected to the test fixture and the movable jaw was connected to the test panel. This test setup creates relative movement between the test paper and the ice formed from the water. The tape holding the test paper and water in place was removed and using a constant extension rate, the maximum force required to remove the panel from the ice was recorded. Typically, five samples of each coating variation were tested and the average maximum load reported.

[0044] To evaluate the effectiveness of formulation modifications on fouling release, a barnacle removal peel test was developed. The test method used was described in Stafslien, Shane, et al., “An improved laboratory reattachment method for the rapid assessment of adult barnacle adhesion strength to fouling-release marine coatings,” J. Coat. Technol. Res., April 2012.

[0045] To evaluate the effectiveness of the formulation modifications on microbial release, a microbial removal test was developed using a 20 psi water jet. The test method used was described in Stafslien, Shane, et al., “Combinatorial materials research applied to the development of new surface coatings VI: An automated spinning water jet apparatus for the high-throughput characterization of fouling-release marine coatings,” Am. Inst. Physics, Rev. Scientific Instruments, 78, 072204, 2007, and Casse, Franck, et al., “Combinatorial materials research applied to the development of new surface coatings V. Application of a spinning water-jet for the semi-high throughput assessment of the attachment strength of marine fouling algae,” Biofouling, 23:2, 121, 2007.

[0046] Abrasion resistance was collected using a Taber 5150 instrument based on ASTM D4060-14 with a CS-17 abrasive disk under vacuum at 60 RPM for 1000 cycles with a weight of 1 kg. The abrasive disk was resurfaced with an S-11 abrasive disk for 50 cycles every 500 test cycles. Abrasion resistance was recorded as the weight loss (mg) of the coating after 1000 test cycles. Surface free energy and contact angle were collected using a Kruss DSA 100 instrument via ASTM 7490-13.

[0047] Table 2 provides the characteristics of the test panel. [Table 2]

[0048] Exemplary embodiments of the preferred compositions and methods As used hereinafter, any reference to a composition, article, or method shall be understood as a reference to each of those compositions, articles, or methods in isolation (e.g., "Exemplary Embodiments 1-4 shall be understood as Exemplary Embodiments 1, 2, 3, or 4").

[0049] Exemplary embodiment 1 is a coating composition that includes an isocyanate component, an amine-functional resin, and a polyurea component that includes an aliphatic copolymer, and a polysiloxane component.

[0050] Exemplary embodiment 2 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the equivalent ratio of isocyanate component to amine functional resin ranges from 1.01:1 to 1.4:1.

[0051] Exemplary embodiment 3 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the amine functional resin is in the range of 16-43 weight percent.

[0052] Exemplary embodiment 4 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the aliphatic copolymer component comprises a silicone copolymer.

[0053] Exemplary embodiment 5 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the aliphatic copolymer component comprises a silicone polyether copolymer.

[0054] Exemplary embodiment 6 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the isocyanate component comprises a prepolymer formed from isophorone diisocyanate and a polyether diamine.

[0055] Exemplary embodiment 7 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the amine functional resin comprises a difunctional amine, a triamine, an aliphatic diamine chain extender, or a combination thereof.

[0056] Exemplary embodiment 8 is the coating composition of any preceding or subsequent exemplary embodiment, wherein the difunctional amine is in the range of 8 to 25 weight percent, based on the total solids weight of the composition.

[0057] Exemplary embodiment 9 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the difunctional amine comprises an aspartic acid ester.

[0058] Exemplary embodiment 10 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the triamine is in the range of 5 to 15 weight percent, based on the total solids weight of the composition.

[0059] Exemplary embodiment 11 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the triamine comprises a polyetheramine.

[0060] Exemplary embodiment 12 is the coating composition of any preceding or subsequent exemplary embodiment, wherein the aliphatic diamine chain extender is in the range of 3.6 to 12 weight percent, based on the total solids weight of the composition.

[0061] Exemplary embodiment 13 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the aliphatic diamine chain extender comprises ethyl cyanide.

[0062] Exemplary embodiment 14 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the polysiloxane component comprises up to 60 weight percent, based on the total solids weight of the composition.

[0063] Exemplary embodiment 15 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the polysiloxane component comprises an amine functional silicone, a silicone polyether copolymer, a phenyl silicone, or a combination thereof.

[0064] Exemplary embodiment 16 is the coating composition of any preceding or subsequent exemplary embodiment, wherein the polysiloxane component comprises polydimethylsiloxane, phenylmethylpolysiloxane, polyphenylmethyldimethylsiloxane, or combinations thereof.

[0065] Exemplary embodiment 17 is a coating composition as described in any preceding or subsequent exemplary embodiment, further comprising a tin compound, the tin compound optionally comprising an organotin compound.

[0066] Exemplary embodiment 18 is the coating composition of any preceding or subsequent exemplary embodiment, wherein the organotin compound comprises less than 1 weight percent of the composition, based on the total solids weight of the composition.

[0067] Exemplary embodiment 19 is a coating composition as described in any preceding or subsequent exemplary embodiment, further comprising a biocide.

[0068] Exemplary embodiment 20 is a coating composition as described in any preceding or subsequent exemplary embodiment, wherein the biocide comprises silver and / or copper.

[0069] Exemplary embodiment 21 is a coating composition comprising an isocyanate component, 16-43 wt. % of an amine-functional resin, and a polyurethane component comprising an aliphatic copolymer, and up to 60 wt. % of a polysiloxane component, wherein the equivalent ratio of the isocyanate component to the amine-functional resin is in the range of 1.01:1 to 1.4:1.

[0070] Exemplary embodiment 22 is the coating composition of any preceding or subsequent exemplary embodiment, wherein the amine functional resin comprises 8 to 25 weight percent of a difunctional amine, 5 to 15 weight percent of a triamine, and 3.6 to 12 weight percent of an aliphatic diamine chain extender.

[0071] Exemplary embodiment 23 is a coating composition as described in any preceding or subsequent exemplary embodiment, further comprising an organotin compound in an amount less than 1 weight percent.

[0072] Exemplary embodiment 24 is a coating composition as described in any preceding or subsequent exemplary embodiment, further comprising an additive in an amount of up to 30 wt.%, wherein the additive comprises a wetting agent, a dispersant, a UV absorber, a hindered amine light stabilizer (HALS), an organoclay derivative, a fumed silica, a pigment, a biocide, or a combination thereof.

[0073] Exemplary embodiment 25 is a coating composition comprising an isocyanate component, 8-25 wt. % of a difunctional amine, 5-15 wt. % of a triamine, 3.6-12 wt. % of an aliphatic diamine chain extender, and a polyurea component comprising an aliphatic copolymer, and up to 60 wt. % of a polysiloxane component, wherein the equivalent ratio of the isocyanate component to the total amount of the difunctional amine, triamine, and aliphatic diamine chain extender is in the range of 1.01:1 to 1.4:1.

[0074] Exemplary embodiment 26 is a coating composition as described in any preceding or subsequent exemplary embodiment, further comprising an organotin compound in an amount less than 1 weight percent.

[0075] Exemplary embodiment 27 is the coating composition of any preceding exemplary embodiment, further comprising an additive in an amount up to 10 wt.%, wherein the additive comprises a wetting agent, a dispersant, a UV absorber, a hindered amine light stabilizer (HALS), an organoclay derivative, a fumed silica, a pigment, a biocide, or a combination thereof.

[0076] Exemplary embodiment 28 is a substrate comprising a coating composition as described in any preceding exemplary embodiment.

[0077] Exemplary embodiment 29 is a substrate as described in any preceding or subsequent exemplary embodiment, wherein the coated substrate, when subjected to an ice test, exhibits a maximum average load force of 400 N.

[0078] Exemplary embodiment 30 is a substrate as described in any preceding or subsequent exemplary embodiment, wherein the coated substrate, when subjected to a barnacle removal peel test, exhibits a maximum barnacle adhesion force of 0.2 MPa.

[0079] Exemplary embodiment 31 is a substrate as described in any preceding or subsequent exemplary embodiment, wherein the coating has less than 60 mg loss in abrasion resistance as measured by ASTM D4060-14.

[0080] Exemplary embodiment 32 is a substrate as described in any preceding or subsequent exemplary embodiment, wherein the coated substrate exhibits at least a 30% minimum average removal of C. lytica when subjected to a microbial removal test with a 20 psi water jet.

[0081] Exemplary embodiment 33 is a substrate as described in any preceding exemplary embodiment, wherein the coated substrate exhibits at least a 50% minimum average removal of N. incerta when subjected to a microbial removal test with a 20 psi water jet.

[0082] Exemplary embodiment 34 is an article comprising a substrate as described in any preceding exemplary embodiment.

[0083] Exemplary embodiment 35 is a method for coating a substrate, the method comprising applying to at least a portion of the substrate a coating composition as described in any preceding exemplary embodiment.

[0084] Exemplary embodiment 36 is a method as described in any preceding or subsequent exemplary embodiment, wherein the substrate comprises metal, plastic, concrete, asphalt, wood, geotextile, fiberglass composite, and / or carbon fiber composite.

[0085] Exemplary embodiment 37 is a method as described in any preceding or subsequent exemplary embodiment, wherein the metal substrate comprises iron, steel, a steel alloy, galvanized metal, and / or aluminum.

[0086] Exemplary embodiment 38 is the method of any preceding or subsequent exemplary embodiment, wherein at least a portion of the substrate includes a first coating and / or a primer.

[0087] Exemplary embodiment 39 is the method of any preceding or subsequent exemplary embodiment, further comprising preparing at least a portion of the substrate prior to applying the coating composition.

[0088] Exemplary embodiment 40 is the method of any preceding or subsequent exemplary embodiment, where preparing at least a portion of the substrate includes grit blasting, sand blasting, priming, and / or electrocoating at least a portion of the substrate.

[0089] Exemplary embodiment 41 is the method of any preceding or subsequent exemplary embodiment, where preparing at least a portion of the substrate includes applying a release agent to at least a portion of the substrate.

[0090] Exemplary embodiment 42 is a method according to any preceding or subsequent exemplary embodiment, where applying the coating composition comprises extrusion and / or spraying.

[0091] Exemplary embodiment 43 is a method according to any preceding or subsequent exemplary embodiment, wherein the spraying includes an air purged spray, a mechanical purged spray, an atomized air spray, a non-atomized air spray, an atomized airless spray, or a non-atomized airless spray.

[0092] Exemplary embodiment 44 is a method according to any preceding or subsequent exemplary embodiment, wherein the coated substrate, when subjected to an ice test, exhibits a maximum average load force of 400 N.

[0093] Exemplary embodiment 45 is a method according to any preceding or subsequent exemplary embodiment, wherein the coated substrate, when subjected to a barnacle removal peel test, exhibits a maximum barnacle adhesion force of 0.2 MPa.

[0094] Exemplary embodiment 46 is the method of any preceding or subsequent exemplary embodiment, wherein the coating has less than 60 mg loss in abrasion resistance as measured by ASTM D4060-14.

[0095] Exemplary embodiment 47 is a method according to any preceding or subsequent exemplary embodiment, wherein the coated substrate exhibits at least a 30% minimum average removal of C. lytica when subjected to a microbial removal test with a 20 psi water jet.

[0096] Exemplary embodiment 48 is a method according to any preceding exemplary embodiment, wherein the coated substrate exhibits at least a 50% minimum average removal of N. incerta when subjected to a microbial removal test with a 20 psi water jet.

[0097] Although particular embodiments of the present disclosure have been described above for purposes of illustration, it will be apparent to those skilled in the art that many changes can be made in the details of the invention without departing from the invention as defined in the appended claims.

Claims

1. 1. A coating composition comprising: a polyurea component comprising an isocyanate component, an amine-functional resin, and an aliphatic copolymer; and a polysiloxane component.

2. 2. The coating composition of claim 1, wherein the equivalent ratio of said isocyanate component to said amine functional resin ranges from 1.01:1 to 1.4:

1.

3. The coating composition of claim 1 or 2, wherein the amine functional resin is in the range of 16 to 43 weight percent.

4. The coating composition of any one of claims 1 to 3, wherein the aliphatic copolymer component comprises a silicone copolymer.

5. The coating composition of any one of claims 1 to 4, wherein the aliphatic copolymer component comprises a silicone polyether copolymer.

6. The coating composition of any one of claims 1 to 5, wherein the isocyanate component comprises a prepolymer formed from isophorone diisocyanate and a polyether diamine.

7. The coating composition of any one of claims 1 to 6, wherein the amine functional resin comprises a difunctional amine, a triamine, an aliphatic diamine chain extender, or a combination thereof.

8. The coating composition of claim 7 , wherein the difunctional amine comprises an aspartic acid ester.

9. 9. The coating composition of claim 7 or 8, wherein the triamine comprises a polyetheramine.

10. The coating composition of any one of claims 7 to 9, wherein the aliphatic diamine chain extender comprises ethyl cyanide.

11. The coating composition of any one of claims 1 to 10, wherein the polysiloxane component comprises up to 60% by weight, based on the total solids weight of the composition.

12. The coating composition of any one of claims 1 to 11, wherein the polysiloxane component comprises an amine-functional silicone, a silicone polyether copolymer, a phenyl silicone, or a combination thereof.

13. The coating composition of any one of claims 1 to 12, wherein the polysiloxane component comprises polydimethylsiloxane, phenylmethylpolysiloxane, polyphenylmethyldimethylsiloxane, or a combination thereof.

14. The coating composition of any one of claims 1 to 13, further comprising a tin compound, said tin compound optionally comprising an organotin compound.

15. The coating composition of any one of claims 1 to 14, further comprising a biocide.

16. 1. A coating composition comprising: A polyurea component comprising: Isocyanate component, 16 to 43 weight percent of an amine-functional resin, and a polyurea component comprising an aliphatic copolymer; up to 60% by weight of a polysiloxane component; A coating composition wherein the equivalent ratio of said isocyanate component to said amine functional fat ranges from 1.01:1 to 1.4:

1.

17. The amine functional resin is 8 to 25% by weight of a difunctional amine, 5 to 15% by weight of a triamine, and 17. The coating composition of claim 16 comprising 3.6 to 12 weight percent of an aliphatic diamine chain extender.

18. 18. The coating composition of claim 16 or 17, further comprising additives in an amount up to 30 wt%, said additives comprising wetting agents, dispersants, UV absorbers, hindered amine light stabilizers (HALS), organoclay derivatives, fumed silica, pigments, biocides, or combinations thereof.

19. 1. A coating composition comprising: A polyurea component comprising: Isocyanate component, 8 to 25% by weight of a difunctional amine, 5 to 15% by weight of a triamine, 3.6 to 12 weight percent of an aliphatic diamine chain extender, and a polyurea component comprising an aliphatic copolymer; up to 60% by weight of a polysiloxane component; A coating composition, wherein the equivalent ratio of the isocyanate component to the total amount of difunctional amine, triamine, and aliphatic diamine chain extenders ranges from 1.01:1 to 1.4:

1.

20. A substrate comprising the coating composition of any one of claims 1 to 19.

21. 21. The substrate of claim 20, wherein the coated substrate exhibits a maximum average load force of 400 N when subjected to an ice accretion test, a maximum barnacle adhesion force of 0.2 MPa when subjected to a barnacle removal peel test, a minimum average removal of at least 30% C. lytica when subjected to a microbial removal test with a 20 psi water jet, a minimum average removal of at least 50% N. incerta when subjected to a microbial removal test with a 20 psi water jet, and / or a maximum loss of 60 mg for abrasion resistance as measured by ASTM D4060-14.

22. 22. An article comprising the substrate of claim 20 or 21.

23. 23. A method for coating a substrate comprising applying to at least a portion of the substrate a coating composition according to claim 21 or 22.

24. 24. The method of claim 23, wherein the substrate comprises metal, plastic, concrete, asphalt, wood, geotextile, fiberglass composite, and / or carbon fiber composite.

25. 25. The method of claim 24, wherein the metal substrate comprises iron, steel, a steel alloy, galvanized metal, and / or aluminum.

26. The method of any one of claims 23 to 25, wherein at least a portion of the substrate comprises a first coating and / or a primer.

27. The method of any one of claims 23 to 26, further comprising preparing at least the portion of the substrate prior to applying the coating composition.

28. 30. The method of claim 27, wherein preparing at least the portion of the substrate comprises grit blasting, sand blasting, priming, electrocoating, and / or applying a release agent to at least the portion of the substrate.

29. 29. The method of any one of claims 23 to 28, wherein applying the coating composition comprises extrusion and / or spraying, optionally wherein spraying comprises air purged spray, mechanical purged spray, atomized air spray, non-atomized air spray, atomized airless spray, or non-atomized airless spray.

30. 30. The method of any one of claims 23 to 29, wherein the coated substrate exhibits a maximum average load force of 400 N when subjected to an ice accretion test, a maximum barnacle adhesion force of 0.2 MPa when subjected to a barnacle removal peel test, a minimum average removal of at least 30% C. lytica when subjected to a microbial removal test with a 20 psi water jet, a minimum average removal of at least 50% N. incerta when subjected to a microbial removal test with a 20 psi water jet, and / or a maximum loss of 60 mg in abrasion resistance as measured by ASTM D4060-14.

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