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 Research and Development Funded by the Federal Government This disclosure was made with government support under government contract number NCMS FY2017 Ship Coating 201853. The United States 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 on December 30, 2021, the entire disclosure of which is incorporated herein by reference.

[0003] A coating composition for applying to a substrate and a method of coating a substrate are described herein.

Background Art

[0004] Outdoor structures such as wind turbines, bridges, towers, tanks, pipes, and fleet vehicles such as railway vehicles are constantly exposed to wind and rain and must be designed to withstand extreme temperature changes, wind shear, precipitation, icing, and other environmental hazards without significant damage that can be time - consuming and costly or without the need for regular maintenance. Similarly, marine structures such as ship hulls and offshore oil rigs and wind turbines are exposed to seawater as well as extreme weather and environmental conditions and are thus susceptible to corrosion, marine fouling, wear, and impact. To meet the specification requirements of these industrial structures, more effective treatment and coating systems are continuously being sought.

Summary of the Invention

[0005] This disclosure is directed to a coating composition. The coating composition can include a polyurea component including an isocyanate component, an amine - functional resin, and an aliphatic copolymer, and a polysiloxane component. This disclosure is further directed to a method for coating a substrate. The method can include applying the coating composition described herein to at least a portion of the substrate. [Modes for carrying out the invention]

[0006] This specification provides coating compositions and methods that can be applied to substrates for improving adhesion removal and / or de-icing performance. This disclosure relates to coating compositions that can combine adhesion removal and de-icing performance with flexibility and durability. In some cases, the coatings described herein can be formed quickly, significantly reducing the time required to recoat the substrate, thereby reducing downtime and shortening the time it takes to return the product to service.

[0007] Many conventional de-icing / de-icing coatings are soft and offer little protection from abrasion or impact. Many conventional epoxy coatings may offer some protection from abrasion and impact, but they cannot prevent or minimize marine de-icing and de-icing. The coating compositions described herein may exhibit excellent durability and desirable properties such as high contact angle (water and diiodomethane), low de-icing strength, high marine de-icing, high abrasion resistance, and high Young's modulus.

[0008] This specification describes a coating composition that may contain a polyurea component and 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. The polyurea component may include the isocyanate component, the 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 polyetherdiamine.

[0009] The coating compositions described herein may contain amine-functionalized resins in amounts of 16 to 43% by weight (e.g., 20 to 40% by weight, 18 to 32% by weight, or 30 to 35% by weight). The compositions may contain 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 amine-functionalized resins. All proportions of the amine-functionalized resin are expressed in weight percent based on the total solid weight of the composition. In some cases, the amine-functionalized resin may include difunctional amines, triamines, aliphatic diamine chain extenders, or combinations thereof.

[0010] In some cases, the coating composition may include an isocyanate component and an amine-functionalized resin in an equivalent ratio of 1.01:1 to 1.4:1 (e.g., 1.08:1, 1.13:1, or 1.25:1). The composition may contain an isocyanate component and an amine-functional resin having equivalent ratios 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 contain a difunctional amine in an amount of 8 to 25% by weight (e.g., 10 to 22%, 12 to 18%, or 15 to 20%). The compositions may contain 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or 25% of the difunctional amine. All proportions of the difunctional amine are expressed in weight percent based on the total solid weight of the composition. In some cases, the difunctional amine may include aspartic acid esters.

[0012] The coating compositions described herein may contain triamines in amounts of 5 to 15% by weight (e.g., 5 to 12%, 10 to 15%, or 8 to 14%). The compositions may contain 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% triamines. All proportions of triamines are expressed in weight percent based on the total solid weight of the composition. In some cases, the triamines may include polyetheramines.

[0013] The coating compositions described herein may contain an aliphatic diamine chain extender in an amount of 3.6 to 12% by weight (e.g., 4 to 10%, 6 to 9.5%, or 8.5 to 9%). The compositions may contain 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 the aliphatic diamine chain extender. All proportions of the aliphatic diamine chain extender are expressed in weight percent based on the total solid weight of the composition. In some cases, the aliphatic diamine chain extender may include ethyl cyanide.

[0014] The coating compositions described herein may contain 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 contain 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60% of the polysiloxane component. All proportions of the polysiloxane component are expressed in weight percent based on the total solid weight of the composition. The polysiloxane component may include amine-functional silicones, silicone polyether copolymers, phenyl silicones, or combinations thereof. The amine-functional silicone fluid may include monofunctional, difunctional, or trifunctional amines. Optionally, the polysiloxane component may include polydimethylsiloxane, phenylmethylpolysiloxane, polyphenylmethyldimethylsiloxane, or combinations thereof.

[0015] The polyurea component may further contain a tin compound. In some examples, the tin compound may be an organotin compound. In some examples, the tin compound may be present in 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 contain 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 proportions of the tin compound are expressed in weight percent based on the total solid weight of the composition. Optionally, the tin compound may be dibutyltin dilaurate (DBDL) and / or dibutyltin diacetate (DBDA). In some examples, the composition may not contain tin or an organotin compound.

[0016] The coating compositions described herein may further contain 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 contain a silver or copper-containing compound. In some examples, the composition may not contain a biocide.

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

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

[0019] In some examples, the coating composition may comprise an isocyanate component, 16-43% by weight of an amine-functionalized resin, and a polyurea component containing an aliphatic copolymer, and up to 60% by weight of a polysiloxane component, wherein the equivalence ratio of the isocyanate component to the amine-functionalized resin is in the range of 1.01:1-1.2:1, and the amine-functionalized resin comprises 8-25% by weight of a difunctional amine, 5-15% by weight of a triamine, and 3.6-12% by weight of an aliphatic diamine chain extender. Optionally, the coating composition may further comprise less than 1% by weight and / or up to 10% by weight of an organotin compound, the additives including wetting agents, dispersants, UV absorbers, hindered amine light stabilizers (HALS), organic clay derivatives, fumed silica, pigments, biocides, or combinations thereof.

[0020] Methods for coating substrates are also disclosed herein. Suitable examples of substrates include metals, plastics, concrete, asphalt, wood, geotextiles, glass fiber composites, and / or carbon fiber composites. In some examples, metal substrates may include iron, steel, steel alloys, galvanized metals, and / or aluminum. Methods for coating substrates may 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 may include a first coating and / or primer.

[0021] Optionally, the method may further include preparing at least a portion of the substrate before applying the coating composition. In some examples, preparing at least a portion of the substrate may include performing grit blasting, sandblasting, priming, and / or electrodeposition coating on 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 purge spray, mechanical purge 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 include the coating compositions described herein. Suitable substrates for use in the methods described herein include metals, plastics, concrete, asphalt, wood, geotextiles, glass fiber composites, and / or carbon fiber composites. Suitable metal substrates include, for example, ferrous metals, aluminum, aluminum alloys, and other metal and alloy substrates. Ferrous metal substrates used in the practice of this disclosure may include iron, steel, and their alloys. Non-limiting examples of useful steel materials include hot-rolled and cold-rolled steels, galvanized (zinc-coated) steels, electro-galvanized steels, stainless steels, pickled steels, and combinations thereof. Combinations or composites of ferrous and non-ferrous metals may also be used.

[0024] The substrate may constitute vehicles, structures, or industrial protective structures (e.g., electrical box enclosures, transformer housings, motor control enclosures, railway vehicle containers), tunnels, bridges, oil or gas industry components (e.g., platforms, pipes, tanks, containers, and their supports), marine components, vehicle body parts, aerospace components, pipelines, storage tanks, wind turbine components, roof structure components, piles, abutments, seawalls, and general steel specimens. The article may include a substrate containing the coating composition described herein.

[0025] As used herein, “structure” means 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 structures exposed to corrosive environments. “Vehicle” means, in its broadest sense, without limitation, all types of vehicles, including cars, trucks, buses, tractors, harvesters, heavy-duty equipment, vans, golf carts, motorcycles, bicycles, railway vehicles, airplanes, helicopters, and boats of all sizes.

[0026] In some examples, the coated substrate may have desirable adhesion release properties. Biofouling, where marine organisms attach to the hull, can be disadvantageous for marine vessels and ships. The attached marine organisms can increase the roughness of the ship's surface, increase frictional resistance, and impede the movement of the ship. The organisms can damage the hull and increase the corrosion rate of the hull. In some examples, the coated substrate may exhibit a maximum barnacle adhesion force of 0.2 MPa when subjected to the barnacle removal release test as described below. For example, the maximum barnacle adhesion force can be 0.1 MPa, 0.15 MPa, or 0.2 MPa. In the barnacle removal release test, the substrate can be exposed to conditions favorable for barnacle attachment for a specific period, such as 30 days. The force required to remove the barnacles can be recorded as the maximum average load force. The barnacle removal release test can include a barnacle breakage test to confirm that the recorded removal force is not due to the adhesion of the barnacles to the substrate but rather due to defective areas of the barnacles.

[0027] In some examples, the coated substrate may have desirable ice removal properties. When ice accumulates on the surface, such as on a wind turbine blade, it can degrade performance and cause overloading and / or rotor imbalance of the turbine. The shedding of ice, the falling of large flakes of ice from the structure, can pose a danger to the surroundings. In some examples, the coated substrate may exhibit a maximum average load force of 400 N when subjected to the icing test described below. For example, the maximum average load force can be 250 N, 275 N, 300 N, 325 N, 350 N, 375 N, or 400 N.

[0028] The coating on the substrate may be damaged by wear during manufacturing and service. In some examples, the coatings described herein may be durable and the coated substrate may be resistant to wear. The coated substrate may have a loss of less than 60 mg for the coating with respect to abrasion resistance measured by ASTM D4060-14. For example, the coating loss may 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 measured by ASTM D4060-14.

[0029] In some examples, the coated substrate may have desirable marine biofouling removal properties. A biofilm, which is a thin sheet of bacteria, can form on the surface of marine vessels. The biofilm can cause degradation of materials such as corrosion of iron and non-ferrous metals due to the influence of microorganisms, an increase in drag, and a decrease in 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] Where used herein, unless otherwise expressly specified, all numbers, including those representing values, ranges, quantities, or percentages, may be interpreted as being preceded by the word “approximately,” even if the term does not explicitly appear. Any numerical range enumerated herein is intended to include all subranges contained therein. The plural encompasses the singular, and vice versa. For example, this disclosure describes a “certain” amine-functionalized resin, but mixtures of such resins may also be used. Where used herein, the term “polymer” means both prepolymers, oligomers, and homopolymers and copolymers, and the prefix “poly” means two or more. Similarly, where used herein, the terms “on top,” “coated on top,” “formed on top,” “deposited on top,” “layered,” and “provided on top” mean a surface that is coated, formed, deposited, layered, or provided on, but not necessarily in contact with, the surface. For example, a coating layer "formed on top of" a substrate does not preclude the presence of other coating layers of the same or different composition located between the formed coating and the substrate.

[0031] While the numerical ranges and parameters representing the broad scope of this disclosure are approximations, the numerical values ​​shown in specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors that inevitably arise from the standard variability observed in their respective test measurements. Where ranges are given, any endpoint within those ranges and / or any numerical value within those ranges can be combined within the scope of this disclosure.

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

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

[0034] Each of the features and examples described above and below, as well as any combination thereof, can be said to be included in this disclosure.

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

[0036] While the numerical ranges and parameters representing the broad scope of this disclosure are approximations, the numerical values ​​shown in specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors that inevitably arise from the standard variability observed in their respective test measurements.

[0037] Comparative examples and examples of de-icing and deposit-removing coating compositions were prepared and their performance was evaluated. The evaluated compositions are listed in Table 1. Examples 1 and 2 are comparative examples. Examples 3 and 4 are examples of the coating compositions described herein. [Table 1]

[0038] Isocyanate-functionalized prepolymer #1 was synthesized according to the process described in US8,691,929 (Example 1). Isocyanate-functionalized prepolymer #2 was synthesized according to the process described in US8,691,929 (Example 2). Other additives included: Bentone 34 (a clay derivative available from Akzo Nobel Chemicals (Amsterdam, Netherlands)), BYK-9077 (a solvent-free wetting and dispersing additive available from BYK Additives and Instruments (Wesel, Germany)), pigment (e.g., TiO2), hydrophilic fumed silica, and a UV absorber.

[0039] The B-pack (amine) sample was first prepared by combining 50% amine-functionalized resin with, where applicable, BYK-9077 dispersant, UV absorber, and DBDL. Under stirring, the pigment was added to the resin blend, where applicable, and ground with a Cowles blade under high shear for 30 minutes. After the grinding step was complete, the remaining 50% of the amine-functionalized resin, along with the amine-functionalized silicone and polysiloxane components, where applicable, was added under low shear and mixed for 10 minutes to complete the B-pack formulation. The sample was shaken for 10 minutes before all coating operations to ensure homogeneity.

[0040] A-Pack (isocyanate) was prepared by combining isocyanate-functionalized prepolymer #1 with, where applicable, 0-30% of the total composition amount of silicone copolymer. The samples were mixed by stirring with an impeller blade in a nitrogen-rich environment. An alternative A-Pack containing isocyanate-functionalized prepolymer #2, synthesized through the process described in US8,691,929 (Example 2), was also used.

[0041] The substrate was coated via extrusion of the coating. The wet sample was first filled 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 toll). Coating was performed using a 6-inch static mixing tip (Nordson 7701488) and a pneumatic gun (Cox A25 dual-component 50 mL pneumatic cartridge gun) set to a coating pressure of 20-30 psi. The sample was extruded and then quickly withdrawn to approximately 20 mils. The coating thickness was controlled by drawing down using shims. The iron substrate (CRS steel, smooth finish Q-panel stock #QD-412, E-coated CRS-ACT product #26241) was prepared on a magnetic board to hold the sample in place and maintain a flat work surface. Non-ferrous substrates (4-inch x 8-inch pre-primed aluminum: Q-Panel Stock #AQ-48) were 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 cured for seven days before any tests were performed.

[0042] The coatings were evaluated for surface free energy, water and diiodomethane (DM) contact angle, de-icing ability, abrasion resistance, and deposit removal characteristics.

[0043] An icing test was developed to evaluate the effectiveness of formulation changes against icing. The test method used was described in U.S. Army Corps of Engineers Research and Development Center document number ERDC / CRRELTR-06-11 (incorporated herein by reference). The fixture design described therein was modified to connect to existing test equipment and accept a test panel approximately 0.032 inches thick. Generally, the procedure was as follows: A 4-inch wide test panel was coated on both sides with the desired coating(s). After adequate curing time, five 1 x 4 inch strips were cut from the test panel. The test strips were taped in place at the center of the test fixture so that the fixture could be filled with 1 inch of water. The fixture was filled with cold water, ensuring that both sides of the coated panel were in contact with 1 inch of water. The entire test fixture was placed overnight in a -20°C freezer. The test fixture was then transferred to a tensile testing machine (e.g., INSTRON 5567) equipped with an environmental chamber set to -20°C. The test fixture was mounted so that the fixed end of the tensile testing machine was connected to the fixture and the movable jaws were 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 the maximum force required to remove the panel from the ice was recorded using a constant elongation rate. Typically, five samples of each coating variation were tested, and the average maximum load was reported.

[0044] To evaluate the effectiveness of formulation changes in preventing fouling-release, a barnacle removal and detachment test was developed. The test method used was described in Staffslien, 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 formulation changes against microbial detachment, a microbial removal test using a 20 psi water jet was developed. The test method used was described in Staffslien, 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 for 1000 cycles at 60 RPM under vacuum using a Taber 5150 instrument based on ASTM D4060-14 with a CS-17 abrasive disc, at a weight of 1 kg. The abrasive disc was resurfaced for 50 cycles with an S-11 abrasive disc 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 preferred compositions and methods Any reference to a composition, article, or method, as used below, shall be understood separately as a reference to each of those compositions, articles, or methods (for example, “Exemplary Embodiments 1-4 shall be understood as Exemplary Embodiments 1, 2, 3, or 4”).

[0049] An exemplary embodiment 1 is a coating composition comprising a polyurea component containing an isocyanate component, an amine-functionalized resin, and an aliphatic copolymer, and a polysiloxane component.

[0050] Exemplary Embodiment 2 is a coating composition according to any preceding or subsequent exemplary embodiment, wherein the equivalent ratio of the isocyanate component to the amine-functionalized resin is in the range of 1.01:1 to 1.4:1.

[0051] Exemplary Embodiment 3 is a coating composition according to any preceding or subsequent exemplary embodiment, wherein the amine-functionalized resin is in the range of 16 to 43% by weight.

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

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

[0054] Exemplary Embodiment 6 is a coating composition according to any preceding or subsequent exemplary embodiment, wherein the isocyanate component comprises a prepolymer formed from isophorone diisocyanate and polyetherdiamine.

[0055] Exemplary Embodiment 7 is a coating composition according to any preceding or succeeding exemplary embodiment, wherein the amine-functionalized resin comprises a difunctional amine, a triamine, an aliphatic diamine chain extender, or a combination thereof.

[0056] Exemplary Embodiment 8 is a coating composition according to any preceding or succeeding exemplary embodiment, wherein the bifunctional amine is in the range of 8 to 25% by weight, based on the total solid weight of the composition.

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

[0058] Exemplary Embodiment 10 is a coating composition according to any preceding or succeeding exemplary embodiment, wherein the triamine is in the range of 5 to 15% by weight, based on the total solid weight of the composition.

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

[0060] Exemplary Embodiment 12 is a coating composition according to any preceding or succeeding exemplary embodiment, wherein the aliphatic diamine chain extender is in the range of 3.6 to 12% by weight, based on the total solid weight of the composition.

[0061] Exemplary Embodiment 13 is a coating composition according to any preceding or subsequent exemplary embodiment, wherein the aliphatic diamine chain extender comprises an ethyl cyanide.

[0062] Exemplary Embodiment 14 is a coating composition according to any preceding or succeeding exemplary embodiment, wherein the polysiloxane component constitutes up to 60% by weight based on the total solid weight of the composition.

[0063] Exemplary Embodiment 15 is a coating composition according to any preceding or subsequent exemplary embodiment, wherein the polysiloxane component comprises an amine-functionalized silicone, a silicone polyether copolymer, a phenyl silicone, or a combination thereof.

[0064] An exemplary embodiment 16 is a coating composition according to any preceding or subsequent exemplary embodiment, wherein the polysiloxane component comprises polydimethylsiloxane, phenylmethylpolysiloxane, polyphenylmethyldimethylsiloxane, or a combination thereof.

[0065] Exemplary Embodiment 17 is a coating composition according to any preceding or subsequent exemplary embodiment, further comprising a tin compound, wherein the tin compound optionally comprises an organosin compound.

[0066] Exemplary embodiment 18 is a coating composition according to any preceding or subsequent exemplary embodiment, wherein the organotin compound comprises less than 1% by weight of the composition based on the total solid weight of the composition.

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

[0068] Exemplary embodiment 20 is a coating composition according to 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 to 43% by weight of an amine-functionalized resin, a polyurethane component containing an aliphatic copolymer, and up to 60% by weight of a polysiloxane component, wherein the equivalent ratio of the isocyanate component to the amine-functionalized resin is in the range of 1.01:1 to 1.4:1.

[0070] Exemplary Embodiment 22 is a coating composition according to any preceding or subsequent exemplary embodiment, wherein the amine-functionalized resin comprises 8 to 25% by weight of a bifunctional amine, 5 to 15% by weight of a triamine, and 3.6 to 12% by weight of an aliphatic diamine chain extender.

[0071] Exemplary embodiment 23 is a coating composition according to any preceding or subsequent exemplary embodiment, further comprising less than 1% by weight of an organotin compound.

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

[0073] An exemplary embodiment 25 is a coating composition comprising a polyurea component containing an isocyanate component, 8 to 25% by weight of a difunctional amine, 5 to 15% by weight of a triamine, 3.6 to 12% by weight of an aliphatic diamine chain extender, and an aliphatic copolymer, and up to 60% by weight of a polysiloxane component, wherein the equivalent ratio of the total amount of the isocyanate component to 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 according to any preceding or subsequent exemplary embodiment, further comprising less than 1% by weight of an organotin compound.

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

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

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

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

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

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

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

[0082] An exemplary embodiment 34 is an article comprising a substrate described in any prior exemplary embodiment.

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

[0084] Exemplary embodiment 36 is the method of any preceding or subsequent exemplary embodiment, wherein the substrate includes metal, plastic, concrete, asphalt, wood, geotextile, glass fiber composite material, and / or carbon fiber composite material.

[0085] Exemplary embodiment 37 is the method of any preceding or subsequent exemplary embodiment, wherein the metal substrate includes iron, steel, steel alloy, galvanized metal, and / or aluminum.

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

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

[0088] Exemplary embodiment 40 is a method of any preceding or subsequent exemplary embodiment, wherein preparing at least a portion of the substrate involves performing grit blasting, sandblasting, priming, and / or electrodeposition coating on at least a portion of the substrate.

[0089] Exemplary embodiment 41 is a method of any preceding or subsequent exemplary embodiment in which 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 of any preceding or subsequent exemplary embodiment in which the coating composition is applied, including 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 purge spray, a mechanical purge 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 exhibits a maximum average load force of 400 N when subjected to an ice-setting test.

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

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

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

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

[0097] While specific embodiments of this disclosure have been described above for illustrative purposes, it will be apparent to those skilled in the art that numerous modifications can be made to the details of the invention without departing from the invention as defined in the appended claims. The following is further disclosed regarding the present invention. [1] A coating composition, A polyurea component comprising an isocyanate component, an amine-functionalized resin, and an aliphatic copolymer, A coating composition comprising a polysiloxane component. [2] The coating composition according to [1], wherein the equivalent ratio of the isocyanate component to the amine-functionalized resin is in the range of 1.01:1 to 1.4:1. [3] The coating composition according to [1] or [2], wherein the amine-functionalized resin is in the range of 16 to 43% by weight. [4] The coating composition according to any one of [1] to [3], wherein the aliphatic copolymer component comprises a silicone copolymer. [5] The coating composition according to any one of [1] to [4], wherein the aliphatic copolymer component comprises a silicone polyether copolymer. [6] The coating composition according to any one of [1] to [5], wherein the isocyanate component comprises a prepolymer formed from isophorone diisocyanate and polyetherdiamine. [7] The coating composition according to any one of [1] to [6], wherein the amine-functionalized resin comprises a bifunctional amine, a triamine, an aliphatic diamine chain extender, or a combination thereof. [8] The coating composition according to [7], wherein the difunctional amine comprises an aspartic acid ester. [9] The coating composition according to [7] or [8], wherein the triamine comprises a polyetheramine.

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

[11] The coating composition according to any one of [1] to

[10] , wherein the polysiloxane component constitutes up to 60% by weight based on the total solid weight of the composition.

[12] The coating composition according to any one of [1] to

[11] , wherein the polysiloxane component comprises an amine-functionalized silicone, a silicone polyether copolymer, a phenyl silicone, or a combination thereof.

[13] The coating composition according to any one of [1] to

[12] , wherein the polysiloxane component comprises polydimethylsiloxane, phenylmethylpolysiloxane, polyphenylmethyldimethylsiloxane, or a combination thereof.

[14] A coating composition according to any one of [1] to

[13] , further comprising a tin compound, wherein the tin compound optionally comprises an organotin compound.

[15] A coating composition according to any one of [1] to

[14] , further comprising a biocide.

[16] A coating composition, It is a polyurea component, Isocyanate components, 16-43% by weight of amine-functional resin, and Polyurea components containing aliphatic copolymers, It contains up to 60% by weight of polysiloxane components, A coating composition in which the equivalent ratio of the isocyanate component to the amine-functionalized resin is in the range of 1.01:1 to 1.4:1.

[17] The amine-functionalized resin is 8-25% by weight of a difunctional amine, 5-15% by weight of triamine, and The coating composition according to

[16] , comprising 3.6 to 12% by weight of an aliphatic diamine chain extender.

[18] The coating composition according to

[16] or

[17] , further comprising up to 30% by weight of an additive, wherein the additive comprises a wetting agent, a dispersant, a UV absorber, a hindered amine light stabilizer (HALS), an organic clay derivative, fumed silica, a pigment, a biocide, or a combination thereof.

[19] A coating composition, It is a polyurea component, Isocyanate components, 8-25% by weight of a difunctional amine, 5-15% by weight of triamine, 3.6-12% by weight of an aliphatic diamine chain extender, and Polyurea components containing aliphatic copolymers, It contains up to 60% by weight of polysiloxane components, A coating composition in which the equivalent ratio of the total amount of the isocyanate component to the difunctional amine, triamine, and aliphatic diamine chain extender is in the range of 1.01:1 to 1.4:1.

[20] A substrate comprising the coating composition described in any of [1] to

[19] .

[21] The coated substrate, as described in

[20] , exhibits a maximum average load force of 400 N when subjected to an ice formation test, a maximum barnacle adhesion force of 0.2 MPa when subjected to a barnacle removal and peeling test, a minimum average removal of at least 30% of C. lytica when subjected to a microbial removal test with a 20 psi water jet, a minimum average removal of at least 50% of 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] An article comprising the base material described in

[20] or

[21] .

[23] A method for coating a substrate, comprising applying a coating composition according to

[21] or

[22] to at least a portion of the substrate.

[24] The method according to

[23] , wherein the substrate is a metal, plastic, concrete, asphalt, wood, geotextile, glass fiber composite material, and / or carbon fiber composite material.

[25] The method according to

[24] , wherein the metal substrate comprises iron, steel, steel alloy, galvanized metal, and / or aluminum.

[26] The method according to any one of

[23] to

[25] , wherein at least a portion of the substrate comprises a first coating and / or primer.

[27] The method according to any one of

[23] to

[26] , further comprising preparing at least the portion of the substrate before applying the coating composition.

[28] The method according to

[27] , wherein preparing at least a portion of the substrate involves performing grit blasting, sandblasting, priming, electrodeposition coating, and / or application of a release agent to at least a portion of the substrate.

[29] The method according to any one of

[23] to

[28] , wherein the application of the coating composition comprises extrusion and / or spraying, wherein optionally the spray comprises an air purge spray, a mechanical purge spray, an atomized air spray, a non-atomized air spray, an atomized airless spray, or a non-atomized airless spray.

[30] The method according to any one of

[23] to

[29] , wherein the coated substrate exhibits a maximum average load force of 400 N when subjected to an ice test, a maximum barnacle adhesion force of 0.2 MPa when subjected to a barnacle removal and peeling test, a minimum average removal of at least 30% of C. lytica when subjected to a microbial removal test with a 20 psi water jet, a minimum average removal of at least 50% of 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.

Claims

1. A coating composition, Isocyanate components, Amine-functional resin comprising 8-25% by weight of a bifunctional amine, 5-15% by weight of a triamine, and 3.6-12% by weight of an aliphatic diamine chain extender, and Aliphatic copolymers containing silicone copolymers, Polyurea components including, It contains up to 60% by weight of a polysiloxane component containing an amine-functionalized silicone, A coating composition in which the equivalent ratio of the isocyanate component to the amine-functionalized resin is in the range of 1.01:1 to 1.4:

1.

2. The coating composition according to claim 1, further comprising up to 30% by weight of an additive, wherein the additive comprises a wetting agent, a dispersant, a UV absorber, a hindered amine light stabilizer (HALS), an organic clay derivative, fumed silica, a pigment, a biocide, or a combination thereof.

3. A substrate comprising the coating composition according to any one of claims 1 to 2.

4. The substrate according to claim 3, wherein the coated substrate exhibits a maximum average load force of 400 N when subjected to an ice formation test, a maximum barnacle adhesion force of 0.2 MPa when subjected to a barnacle removal and peeling test, a minimum average removal of at least 30% of C. lytica when subjected to a microbial removal test with a 20 psi water jet, a minimum average removal of at least 50% of N. inserta when subjected to a microbial removal test with a 20 psi water jet, and / or exhibits a maximum loss of 60 mg for abrasion resistance as measured by ASTM D4060-14.

5. An article comprising the base material described in claim 3 or 4.

6. A method for coating a substrate, comprising applying the coating composition according to claim 3 or 4 to at least a portion of the substrate.

7. The method according to claim 6, wherein the substrate includes metal, plastic, concrete, asphalt, wood, geotextile, glass fiber composite material, and / or carbon fiber composite material.

8. The method according to claim 7, wherein the metal substrate includes iron, steel, steel alloy, galvanized metal, and / or aluminum.

9. The method according to any one of claims 6 to 8, wherein at least a portion of the substrate comprises a first coating and / or primer.

10. The method according to any one of claims 6 to 9, further comprising preparing at least the portion of the substrate before applying the coating composition.

11. The method according to claim 10, wherein preparing at least a portion of the substrate includes performing grit blasting, sandblasting, priming, electrodeposition coating, and / or application of a mold release agent to at least a portion of the substrate.

12. The method according to any one of claims 6 to 11, wherein the application of the coating composition comprises extrusion and / or spraying, and optionally the spray comprises an air purge spray, a mechanical purge spray, an atomized air spray, a non-atomized air spray, an atomized airless spray, or a non-atomized airless spray.

13. The method according to any one of claims 6 to 12, wherein the coated substrate exhibits a maximum average load force of 400 N when subjected to an ice test, a maximum barnacle adhesion force of 0.2 MPa when subjected to a barnacle removal and peeling test, a minimum average removal of at least 30% of C. lytica when subjected to a microbial removal test with a 20 psi water jet, a minimum average removal of at least 50% of N. inserta when subjected to a microbial removal test with a 20 psi water jet, and / or exhibits a maximum loss of 60 mg for abrasion resistance as measured by ASTM D4060-14.

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