WO2022040513A1

WO2022040513A1 - Coating compositions and methods

Info

Publication number: WO2022040513A1
Application number: PCT/US2021/046868
Authority: WO
Inventors: Zhiqiang Cao; Boyi SONG
Original assignee: Wayne State University
Priority date: 2020-08-20
Filing date: 2021-08-20
Publication date: 2022-02-24

Abstract

Surface coating compositions according to aspects of the present disclosure which include a primer layer, wherein the primer layer includes a reaction product of: 1) an epoxy resin and/or a urethane resin and 2) a hardener, wherein at least the epoxy resin, the urethane resin, or the hardener includes reactive moieties which are, or include, polymerizable double bonds. The surface coating compositions further include a top coat layer, wherein the top coat layer includes at least a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer, or a hydrophilic hydrogel. The top coat layer and the primer layer are covalently bonded to each other by a reaction product of 1) polymerizable double bonds of zwitterionic monomers and/or hydrophilic monomers, with 2) the polymerizable double bonds of the primer layer. Methods of coating a substrate, and kits for making the surface coating compositions, are provided according to aspects of the present disclosure.

Description

COATING COMPOSITIONS AND METHODS

REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Patent Application Serial No. 63/068,113, filed August 20, 2020, the entire content of which is incorporated herein by reference.

GOVERNMENT SUPPORT

[0002] This invention was made with government support under Grant No. 1410853, awarded by the National Science Foundation. The Government has certain rights in the invention.

FIELD OF THE INVENTION

[0003] General aspects of the present invention relate to materials for protecting surfaces from fouling and other types of physical, chemical, and biological deterioration. According to specific aspects, hydrogel containing materials are provided for protecting surfaces from fouling and other types of degradation.

BACKGROUND OF THE INVENTION

[0004] There is a continuing need for coating compositions and methods that improve the useful lifetime of surfaces and decrease the need for cleaning and maintenance of such surfaces.

SUMMARY OF THE INVENTION

[0005] Surface coating compositions are provided according to aspects of the present disclosure which include a primer layer, wherein the primer layer includes a reaction product of 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least the epoxy resin, the urethane resin, or the hardener includes reactive moieties, wherein the reactive moieties are, or include, polymerizable double bonds. The surface coating compositions further include a top coat layer, wherein the top coat layer includes at least a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer, or a hydrophilic hydrogel. The top coat layer and the primer layer are covalently bonded to each other by a reaction product of 1) polymerizable double bonds of zwitterionic monomers and/or hydrophilic monomers, with 2) the polymerizable double bonds of the primer layer. According to aspects of the present disclosure, the reactive moieties comprising polymerizable double bonds are selected from the group consisting of: methacrylate, acrylate, vinyl, and allyl. According to aspects, the epoxy resin includes epoxy acrylate.

[0006] According to aspects of the present disclosure, the primer layer includes a reaction product of an epoxy resin and a hardener, wherein at least one of: the epoxy resin and the hardener, comprises reactive moieties comprising polymerizable double bonds. According to aspects of the present disclosure, the reactive moieties comprising polymerizable double bonds are selected from the group consisting of: methacrylate, acrylate, vinyl, and allyl. According to aspects, the epoxy resin includes epoxy acrylate. [0007] According to aspects of the present disclosure, the primer layer includes a reaction product of a urethane resin and a hardener, wherein at least one of: the urethane resin and the hardener, comprises reactive moieties comprising polymerizable double bonds. According to aspects of the present disclosure, the reactive moieties comprising polymerizable double bonds are selected from the group consisting of: methacrylate, acrylate, vinyl, and allyl. According to aspects, the epoxy resin includes epoxy acrylate. [0008] Surface coating compositions are provided according to aspects of the present disclosure which include a primer layer, wherein the primer layer includes a reaction product of: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least the epoxy resin, the urethane resin, or the hardener includes reactive moieties, wherein the reactive moieties are, or include, polymerizable double bonds. The surface coating compositions further include a top coat layer, wherein the top coat layer includes at least a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer, or a hydrophilic hydrogel, wherein the hydrophilic polymer and/or hydrophilic hydrogel consists of, or includes, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative. The top coat layer and the primer layer are covalently bonded to each other by a reaction product of 1) polymerizable double bonds of zwitterionic monomers and/or hydrophilic monomers, with 2) the polymerizable double bonds of the primer layer. According to aspects of the present disclosure, the reactive moieties comprising polymerizable double bonds are selected from the group consisting of: methacrylate, acrylate, vinyl, and allyl. According to aspects, the epoxy resin includes epoxy acrylate. [0009] Surface coating compositions are provided according to aspects of the present disclosure which include a primer layer, wherein the primer layer includes a reaction product of: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least the epoxy resin, the urethane resin, or the hardener includes reactive moieties, wherein the reactive moieties are, or include, polymerizable double bonds. The surface coating compositions further include a top coat layer, , wherein the top coat layer consists of_a zwitterionic polymer and/or a zwitterionic hydrogel. The top coat layer and the primer layer are covalently bonded to each other by a reaction product of 1) polymerizable double bonds of zwitterionic monomers, with 2) the polymerizable double bonds of the primer layer. According to aspects of the present disclosure, the reactive moieties comprising polymerizable double bonds are selected from the group consisting of: methacrylate, acrylate, vinyl, and allyl. According to aspects, the epoxy resin includes epoxy acrylate.

[0010] According to aspects, a surface coating composition of the present disclosure is disposed on a surface of a substrate. According to aspects, the substrate is a surface of a boat or water-exposed structure. According to aspects, the substrate is a surface of a boat vessel or a surface of a water-exposed structure selected from the group consisting of: boat hulls, boat decks, offshore drilling platforms, pipelines, bridges, storage vessels, underwater cables, and underwater equipment.

[0011] According to aspects of the present disclosure, surface coating compositions include a top coat layer, wherein the top coat layer includes a zwitterionic polymer and/or a zwitterionic hydrogel, wherein the zwitterionic polymer or zwitterionic hydrogel includes a zwitterionic polymer having the structural formula: III, IV, or VI:

(III), where each Ri, R2, and R3 is independently a C1-C30 straight chain or branched, optionally substituted, alkyl group, where R2 and R3 taken together with N+ form a cationic center, where M+ is a metal ion, an ammonium ion, or an organic ion, Li is a linker that covalently couples a polymer sidechain to a polymer backbone, A(=O)O- is an anionic group where A is C, S, SO, P, or PO, L2 is a linker that covalently couples the cationic center to the anionic group, X- is a counter ion associated with the cationic center, and n is an integer in the range of 2 to 100,000;

where M is a monomeric repeating unit, L4 is a linker that covalently couples a polymer sidechain to a polymer backbone, n is an integer in the range of 2 to 100,000, X" is a counter ion associated with a cationic center, and Y⁺ is a counter ion associated with an anionic center;

where each Ri, R2, and R3 is independently a C1-C30 straight chain or branched, optionally substituted, alkyl group, where R2 and R3 taken together with N+ form the cationic center, Li is a linker that covalently couples the polymer sidechain to the polymer backbone, and n is an integer in the range of 2 to 100,000.

[0012] According to aspects of the present disclosure, surface coating compositions include a top coat layer, wherein the top coat layer includes a hydrophilic polymer and/or a hydrophilic hydrogel, wherein the hydrophilic polymer or hycrophilic hydrogel includes a polymer having the structural formula: VII or VIII:

where Ri, R2, R3, R4, and Rs are each independently selected from hydrogen, alkyl, and aryl groups; Li is a linker that covalently couples a cationic center to the polymer backbone; L2 is a linker that covalently couples the cationic center to an anionic group;

A(=O)O" is the anionic group; A is C, S, SO, P, or PO; X" is a counter ion associated with the cationic center; M⁺ is a metal ion, an ammonium ion, or an organic ion; L3 is a linker that covalently couples two polymer backbones; n is an integer in the range of 2 to about 100,000; m is a positive non-zero integer; and m/n is in the range of 0.1% - 99.9%.

where Ri, R2, and R3 are each independently selected from hydrogen, alkyl, and aryl groups; Li is a linker that covalently couples the polymer sidechain to the polymer backbone; X" is a counter ion associated with the cationic center; M⁺ is a metal ion, an ammonium ion, or an organic ion; L3 is a linker that covalently couples two polymer backbones; n is an integer in the range of 2 to about 100,000; m is a positive non-zero integer; and m/n is in the range of 0.1% - 99.9%.

[0013] Surface coating compositions are provided according to aspects of the present disclosure which include a) a primer layer, wherein the primer layer includes a reaction product of: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least the epoxy resin, the urethane resin, or the hardener includes reactive moieties, wherein the reactive moieties are, or include, polymerizable double bonds; b) a top coat layer, wherein the top coat layer includes at least a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer, or a hydrophilic hydrogel, wherein the top coat layer and the primer layer are covalently bonded to each other by a reaction product of 1) polymerizable double bonds of zwitterionic monomers and/or hydrophilic monomers, with 2) the polymerizable double bonds of the primer layer; and c) an anti-mud component. According to aspects of the present disclosure, the reactive moieties comprising polymerizable double bonds are selected from the group consisting of: methacrylate, acrylate, vinyl, and allyl. According to aspects, the epoxy resin includes epoxy acrylate.

[0014] Surface coating compositions are provided according to aspects of the present disclosure which include a) a primer layer, wherein the primer layer includes a reaction product of: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least the epoxy resin, the urethane resin, or the hardener includes reactive moieties, wherein the reactive moieties are, or include, polymerizable double bonds; b) a top coat layer, wherein the top coat layer includes at least a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer, or a hydrophilic hydrogel, wherein the top coat layer and the primer layer are covalently bonded to each other by a reaction product of 1) polymerizable double bonds of zwitterionic monomers and/or hydrophilic monomers, with 2) the polymerizable double bonds of the primer layer; and c) an anti-mud component, wherein the top coat includes a reaction product of: 1) one or more of: a zwitterionic monomer and a hydrophilic monomer; with 2) an anti-mud component which includes a negatively charged monomer and/or a negatively-charged crosslinker, wherein the reaction product resists mud accumulation on a substrate coated with the surface coating composition. According to aspects, the epoxy resin includes epoxy acrylate.

[0015] According to aspects of the present disclosure, the anti-mud component is selected from one or more of negatively charged monomers of either acid or salt forms of the following: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2-propene- 1 -sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4-vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, phosphoric acid 2-hydroxyethyl methacrylate ester, and a derivative of one or more of the foregoing. [0016] Methods of coating a substrate are provided according to aspects of the present disclosure which include: applying a curable primer composition to the substrate, the curable primer composition comprising: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds; curing the curable primer composition, forming a primer layer; applying a curable top coat composition onto the primer layer, the curable top coat composition comprising one or more of: zwitterionic monomers and hydrophilic monomers, wherein the zwitterionic monomers and/or hydrophilic monomers comprise polymerizable double bonds, thereby forming a curable bilayer composition on the substrate; and curing the bilayer composition, thereby forming a surface coating composition comprising the primer layer and a top coat layer, wherein the top coat layer and the primer layer are covalently bonded to each other by a reaction product of polymerizable double bonds of the zwitterionic monomers and/or hydrophilic monomers of the top coat layer with the polymerizable double bonds of the primer layer. According to aspects disclosed herein, the curable top coat composition includes: 1) one or more of: a zwitterionic monomer and a hydrophilic monomer; and 2) an anti-mud component which comprises a negatively charged monomer and/or crosslinker, wherein the reaction product resists mud accumulation on a substrate coated with the surface coating composition. According to aspects disclosed herein, the antimud component is a negatively charged monomer of either acid or salt forms of the following: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2-propene-l- sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4-vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, and phosphoric acid 2-hydroxyethyl methacrylate ester; a derivative of one or more thereof, and a combination of two or more thereof. According to aspects disclosed herein, the hydrophilic polymer and/or hydrophilic hydrogel consists of, or includes, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative. According to aspects disclosed herein, the top coat layer consists of a zwitterionic polymer and/or a zwitterionic hydrogel. According to aspects disclosed herein, the epoxy resin comprises epoxy acrylate.

[0017] Kits for coating a substrate are provided according to aspects of the present disclosure which include: a first component of a curable primer composition comprising an epoxy resin or a urethane resin; a second component of a curable primer composition comprising a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds, and wherein the first component and second component of the curable primer composition are separately packaged; and a first component of a curable top coat composition, the first component of the curable top coat composition comprising one or more of: a zwitterionic monomer, a hydrophilic monomer, a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer and a hydrophilic hydrogel, wherein mixing of the first and second components of the curable primer composition produces a curable primer composition, which, applied to a substrate and cured produces a primer layer, and wherein the curable top coat composition, when applied to the primer layer, produces a curable bilayer composition including a primer layer and a top coat layer, and wherein the top coat layer and the primer layer covalently bond to each other by a reaction product of polymerizable double bonds of one or more of: zwitterionic monomers, hydrophilic monomers, or a combination of both thereof, with the polymerizable double bonds of the primer layer. Optionally further included is a crosslinker and/or a thickener. Optionally further included is a second component of a curable top coat composition, the second component of the curable top coat composition comprising an initiator, wherein the first component of the curable top coat composition and second component of the curable top coat composition are packaged separately. Kits for coating a substrate are provided according to aspects of the present disclosure wherein the first component of the curable top coat composition comprises polymerizable double bonds containing monomers and/or crosslinkers. Kits for coating a substrate are provided according to aspects of the present disclosure wherein the hydrophilic polymer and/or hydrophilic hydrogel consists of, or comprises, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative. Kits for coating a substrate are provided according to aspects of the present disclosure wherein the top coat layer consists of a zwitterionic polymer and/or a zwitterionic hydrogel. Kits for coating a substrate are provided according to aspects of the present disclosure wherein the epoxy resin comprises epoxy acrylate.

[0018] Kits for coating a substrate are provided according to aspects of the present disclosure which include: a) a first component of a curable primer composition comprising an epoxy resin or a urethane resin; b) a second component of a curable primer composition comprising a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds, and wherein the first component and second component of the curable primer composition are separately packaged; c) a first component of a curable top coat composition, the first component of the curable top coat composition comprising one or more of: a zwitterionic monomer, a hydrophilic monomer, a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer and a hydrophilic hydrogel; and d) an antimud component, wherein the anti-mud component comprises one or more of: a negatively-charged monomer and a negatively-charged crosslinker, wherein mixing of the first and second components of the curable primer composition produces a curable primer composition, which, applied to a substrate and cured produces a primer layer, and wherein the curable top coat composition, when applied to the primer layer, produces a curable bilayer composition including a primer layer and a top coat layer, and wherein the top coat layer and the primer layer covalently bond to each other by a reaction product of polymerizable double bonds of one or more of: zwitterionic monomers, hydrophilic monomers, or a combination of both thereof, with the polymerizable double bonds of the primer layer. According to aspects of the present disclosure, the anti-mud component is a negatively charged monomer of either acid or salt forms of the following: 3 -sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2-propene-l -sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4-vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, and phosphoric acid 2-hydroxyethyl methacrylate ester; a derivative of one or more thereof, and a combination of two or more thereof. Optionally further included is a crosslinker and/or a thickener. Optionally further included is a second component of a curable top coat composition, the second component of the curable top coat composition comprising an initiator, wherein the first component of the curable top coat composition and second component of the curable top coat composition are packaged separately. Kits for coating a substrate are provided according to aspects of the present disclosure wherein the first component of the curable top coat composition comprises polymerizable double bonds containing monomers and/or crosslinkers. Kits for coating a substrate are provided according to aspects of the present disclosure wherein the hydrophilic polymer and/or hydrophilic hydrogel consists of, or comprises, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative. Kits for coating a substrate are provided according to aspects of the present disclosure wherein the top coat layer consists of a zwitterionic polymer and/or a zwitterionic hydrogel. Kits for coating a substrate are provided according to aspects of the present disclosure wherein the epoxy resin comprises epoxy acrylate.

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 is a schematic diagram of a coating according to aspects of the present disclosure including a top coat 1, and a primer coat 2, the combination disposed on a substrate 3.

[0020] Figures 2A and 2B show SEM images of a cross-section of a coating according to aspects of the present disclosure including a top coat 4, and a primer coat 5, scale bar = 10 pm.

[0021] Figure 3 is a graph showing the water contact angle on the top coat surface of a coating according to aspects of the present disclosure (2K-1). The coating surface consistently showed a water contact angle of about 0° at different time points after continuous shearing (1300rpm) in sea water at room temperature.

[0022] Figure 4 is a graph showing anti-fouling properties of coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, assessed by resistance to human fibrinogen (Fg) absorption, compared to epoxy, SPC, and FRC commercial marine coatings. Absorption level on bare epoxy samples was considered as 100%. All data are presented as mean of replicates (n=3). Statistical analysis: one-way ANOVA with Tukey's multiple comparisons. ***: p < 0.0002. ****: p < 0.0001.

[0023] Figure 5A shows representative SEM images of coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, compared to epoxy, SPC, and FRC commercial marine coatings after 24 h and 14 days culture in ULVA, Cyclotella, or Navicula suspension at shaking conditions, scale bar = 10 pm.

[0024] Figures 5B and 5C are graphs showing the calculated density of adhesion for ULVA zoospores after 24 hours and 14 days culture, respectively, for coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, compared to epoxy, SPC, and FRC commercial marine coatings. All data are presented as the mean of random selected region (n=5). Statistical analysis showed that differences between coatings according to aspects of the present disclosure and the commercial marine coatings were statistically significant in all groups (statistical analysis: unpaired One- Way ANOVA with Tukey's multiple comparisons, p<0.03).

[0025] Figures 5D and 5E are graphs showing the calculated density of adhesion for Cyclotella after 24 hours and 14 days culture, respectively, for coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, compared to epoxy, SPC, and FRC commercial marine coatings. All data are presented as the mean of random selected region (n=5). Statistical analysis showed that differences between coatings according to aspects of the present disclosure and the commercial marine coatings were statistically significant in all groups (statistical analysis: unpaired One- Way ANOVA with Tukey's multiple comparisons, p<0.03).

[0026] Figures 5F and 5G are graphs showing the calculated density of adhesion for Navicula after 24 hours and 14 days culture, respectively, for coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, compared to epoxy, SPC, and FRC commercial marine coatings. All data are presented as the mean of random selected region (n=5). Statistical analysis showed that differences between coatings according to aspects of the present disclosure and the commercial marine coatings were statistically significant in all groups (statistical analysis: unpaired One- Way ANOVA with Tukey's multiple comparisons, p<0.03).

[0027] Figure 6 shows images illustrating the ability of mussels to walk on coatings according to aspects of the present disclosure, example designated 2K-0, compared to epoxy, SPC, and FRC commercial marine coatings. For this example, six live Canadian mussels were placed on a sample plate coated with the indicated coating. The positions of the mussels were recorded over three days of observation. This test was performed in sea water, using periodic light conditions, and at room temperature. As shown in these images, mussels initially placed on a coating according to aspects of the present disclosure moved off of the coating, while mussels on other coatings did not move significantly.

[0028] Results of tests of exposure of 2K coating vs. FRC to seawater in natural conditions for up to 3 months are shown in Figure 7A. Results of tests of exposure of 2K coating vs SPC to seawater in natural conditions for up to 1.5 months are shown in Figure 7B. 2K-0 has 0% crosslinking for the top coat. 2K-1 has 1% crosslinking for the top coat. Uncoated area on the panel was epoxy bottom paint. The coating samples were attached to a floating raft and washed with flowing water/wiping gently before visual examination at each time point as indicated. The contamination of the sample and the percentage of the surface coverage by fouling were recorded for scoring according to (ASTM D5479-94 and ASTM D3623-78a). Higher score (100 maximum) indicates higher anti-marine fouling performance. 2K-0 and 2K-1 surfaces were also found free of mud adhesion.

[0029] Figure 8 schematically shows methods and surface coating compositions 100 according to aspects of the present disclosure wherein the resin includes “resin” which is epoxy resin or urethane resin modified to include reactive double bonds (Resin-C=C) and hardener (H) modified to include reactive double bonds (H-C=C), or epoxy resin or urethane resin modified to include reactive double bonds (Resin-C=C) and hardener (H) without reactive double bonds, or “resin” which is epoxy resin or urethane resin without reactive double bonds (Resin) and hardener (H) modified to include reactive double bonds (H-C=C). A curing reaction 6 is performed to produce a cured primer containing reactive double bonds (Primer-C=C). zwitterionic monomer containing reactive double bonds (ZM-C=C) and/or hydrophilic monomer containing reactive double bonds (HM- C=C) are polymerized by a polymerization reaction 7 to produce a topcoat 8 and an interface 9 wherein the polymerization reaction includes reaction of ZM-C=C and/or HM-C=C with the polymerizable double bonds of primer layer 10 (Primer-C=C), thus covalently bonding the topcoat layer 8 to the primer layer 10.

[0030] Figure 9 shows mud adhesion level on coating samples as determined by UV-vis absorbance experiment. 5wt% AA, 10wt% AA, 30wt% AA and 50wt% AA represent coating compositions containing a primer layer of cured epoxy based on Interlux VC performance modified with acrylated epoxy (Allnex Ebecryl 3605) and a top coat layer resulted from a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer, lwt% MBAA crosslinker (relative to CBAA), 5wt%, 10wt%, 30wt% or 50wt% of anti-mud acrylic acid (AA) monomer (relative to CBAA), 3wt% ammonium persulfate (APS as initiator, relative to CBAA)) and lwt% tetramethylethylenediamine (TMEDA as catalyst or accerlator, relative to CBAA) according to aspects of the present disclosure described above. One-way ANOVA was conducted for statistical analysis: ****■. p<0.0001; ns: not statistically significant at p < 0.05.

DETAILED DESCRIPTION OF THE INVENTION [0031] Scientific and technical terms used herein are intended to have the meanings commonly understood by those of ordinary skill in the art.

[0032] The singular terms "a," "an," and "the" are not intended to be limiting and include plural referents unless explicitly stated otherwise or the context clearly indicates otherwise.

[0033] The abbreviation “CBMA” refers to 3-[[2-

(methacryloyloxy )ethyl]dimethylammonio]propionate.

[0034] The abbreviation “PCBMA” refers to poly (3- [[2-

(methacryloyloxy)ethyl]dimethylammonio]propionate).

[0035] The abbreviation “SBMA” refers to [2-(methacryloyloxy)ethyl]dimethyl-(3- sulfopropyl)ammonium hydroxide.

[0036] The abbreviation “PSBMA” refers to poly[2- (methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide.

[0037] The abbreviation “MPC” refers to methacryloyloxyethyl phosphorylcholine.

[0038] The abbreviation “PMPC” refers to poly(methacryloyloxyethyl phosphorylcholine).

[0039] The abbreviation “CBOH” refers to (N-(carboxymethyl)-2-hydroxy-N,N- dimethyl-3-[(2-methyl-l-oxo-2-propen-l-yl)oxy]-l-propanaminium).

[0040] The abbreviation “PCBOH” refers to poly(N-(carboxymethyl)-2-hydroxy-N, N-dimethyl-3 -[(2-methyl- 1 -oxo-2-propen- 1 -yl)oxy]- 1 -propanaminium).

[0041] The abbreviation “CAR” refers to carnitine: ((2R)-3 -carboxy -N,N,N- trimethyl-2-[( 1 -oxo-2-propen- 1 -yl)oxy]- 1 -propanaminium.

[0042] The abbreviation “PCAR” refers to: poly(((2R)-3-carboxy-N,N,N-trimethyl-

2- [( 1 -oxo-2-propen- 1 -yl)oxy ] - 1 -propanaminium) .

[0043] The abbreviation “CBAA” refers to 3 -((3- acrylamidopropyl)dimethylammonio)propanoate. [0044] The abbreviation “PCBAA” refers to poly (3 -((3- acrylamidopropyl)dimethylammonio)propanoate).

[0045] The abbreviation CBAA-1 refers to 2-((3- acrylamidopropyl)dimethylammonio)acetate. [0046] The abbreviation PCBAA- 1 refers to poly(2-((3- acrylamidopropyl)dimethylammonio)acetate). [0047] The abbreviation CBMAA refers to 3 -((3- methacrylamidopropyl)dimethylammonio)propanoate.

[0048] The abbreviation PCBMAA refers to poly(3-((3- methacrylamidopropyl)dimethylammonio)propanoate).

[0049] The abbreviation MBAA refers to N,N' -methylene bis acrylamide.

[0050] Surface coating compositions are provided according to aspects of the present disclosure which include a top coat layer disposed on a primer layer, wherein the top coat layer and the primer layer are covalently bonded to each other.

[0051] A primer layer of a surface coating composition according to aspects of the present disclosure includes a reaction product of: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, includes reactive moieties having polymerizable double bonds

[0052] A top coat layer of a surface coating composition according to aspects of the present disclosure is a hydrophilic top coat layer and includes one or more of: a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer and a hydrophilic hydrogel. A hydrophilic top coat layer has a surface characterized by a static water contact angle < 90° according to aspects of the present disclosure. In certain aspects, a hydrophilic top coat layer has a surface characterized by a static water contact angle < 60°. In certain aspects, a hydrophilic top coat layer has a surface characterized by a static water contact angle < 30°. In certain aspects, a hydrophilic top coat layer has a surface characterized by a static water contact angle < 15°. In certain aspects, a hydrophilic top coat layer has a surface characterized by a static water contact angle < 5°.

[0053] The thickness a primer layer of a surface coating composition according to aspects of the present disclosure should be large enough such that the primer layer functions appropriately, e.g., to protect an underlying surface. According to aspects of the disclosure, the thickness of the primer layer of a surface coating composition is about 1 pm to about 10 cm, about 10 pm to about 5 cm, about 10 pm to about 1 cm, about 50 pm to about 5 mm, about 100 pm to about 1 cm, about 500 pm to about 5 cm, about 10 pm to about 1 mm, about 50 pm to about 5 mm, about 100 pm to about 1 cm, about 500 pm to about 5 cm, about 10 pm to about 100 pm, about 50 pm to about 500 pm, about 100 pm to about 1 mm, about 500 pm to about 5 mm thick, about 1 mm to about 1 cm, or about 5 mm to about 5 cm thick. [0054] The thickness of a hydrophilic top coat layer of a surface coating composition according to aspects of the present disclosure should be large enough such that the hydrophilic top coat layer functions appropriately, e.g., to protect an underlying surface. According to aspects of the disclosure, the thickness of the hydrophilic top coat layer is about 1 pm to about 10 cm, about 10 pm to about 5 cm, about 10 pm to about 1 cm, about 50 pm to about 5 mm, about 100 pm to about 1 cm, about 500 pm to about 5 cm, about 10 pm to about 1 mm, about 50 pm to about 5 mm, about 100 pm to about 1 cm, about 500 pm to about 5 cm, about 10 pm to about 100 pm, about 50 pm to about 500 pm, about 100 pm to about 1 mm, about 500 pm to about 5 mm thick, about 1 mm to about 1 cm, or about 5 mm to about 5 cm thick.

[0055] The thickness of a hydrophilic top coat layer of a surface coating composition according to aspects of the present disclosure may be varied depending on its stiffness and desired use. The stiffness of a PCBAA hydrophilic hydrogel element of a hydrophilic top coat layer can be altered, for example, by changing the MBAA crosslinker density. For example, increasing molar ratios of the MBAA crosslinker can be added to CBAA monomer to produce a PCBAA hydrophilic hydrogel element of a hydrophilic top coat layer with increasing stiffness. Hydrophilic hydrogel generated from other polymers may be altered analogously.

[0056] A top coat layer and a primer layer of a surface coating composition according to aspects of the present disclosure are covalently bonded to each other by a reaction product of polymerizable double bonds of one or more of: zwitterionic monomers, hydrophilic monomers, or a combination of both thereof, with the polymerizable double bonds of the primer layer.

[0057] A top coat layer and a primer layer of a surface coating composition according to aspects of the present disclosure are covalently bonded to each other by a reaction product of polymerizable double bonds of one or more of: zwitterionic monomers, hydrophilic monomers, or a combination of both thereof, with the polymerizable double bonds of a crosslinker in the top coat layer, and with the polymerizable double bonds of the primer layer.

[0058] A primer layer of a surface coating composition according to aspects of the present disclosure includes a reaction product of: an epoxy resin and a hardener, wherein either, or both, the epoxy resin and the hardener include reactive moieties having polymerizable double bonds. Epoxy resin may contain low molecular weight oligomers and/or monomers which include reactive moieties having polymerizable double bonds.

[0059] A primer layer of a surface coating composition according to aspects of the present disclosure includes a reaction product of: a urethane resin and a hardener, wherein either, or both or, the urethane resin and the hardener includes reactive moieties having polymerizable double bonds. Urethane resin may contain low molecular weight oligomers and/or monomers which include reactive moieties having polymerizable double bonds.

[0060] The reactive moieties including polymerizable double bonds can be, without limitation, methacrylate, acrylate, vinyl, or allyl.

[0061] Introduction of polymerizable double bonds such as methacrylate, acrylate, vinyl, or allyl is achieved by reacting an epoxy resin or urethane resin with, or by mixing a hardener with, a reactive moiety including polymerizable double bonds. The resins may contain low molecular weight oligomers and/or monomers which react with a reactive moiety including polymerizable double bonds.

[0062] According to aspects, introduction of polymerizable double bonds is achieved by reacting an epoxy resin with a reactive carboxylic acid moiety which further includes a polymerizable double bond, such as acrylic acid.

[0063] According to aspects, introduction of polymerizable double bonds is achieved by reacting an epoxy resin with, or by mixing a hardener with, a reactive amine moiety which further including a polymerizable double bond, such as 3-butenylamine, 2- aminoethyl methacrylate, methacryloyl-L-lysine, N-(2-aminoethyl) methacrylamide, and 2-(tert-butylamino)ethyl methacrylate.

[0064] According to aspects, introduction of polymerizable double bonds is achieved by mixing an epoxy resin with acrylated epoxy and/or acrylated multi-poxy (> 2 oxirane groups) to the epoxy resin.

[0065] According to aspects, introduction of polymerizable double bonds is achieved by reacting a urethane part of a two-part polyurethane with, or mixing a hardener part with, a reactive alcohol moiety which further includes a polymerizable double bond, such as vinyl alcohol, crotyl alcohol, CBOH, HEMA, or HPMA, and/or a polyol such as castor oil.

[0066] According to aspects, introduction of polymerizable double bonds is achieved by reacting a urethane resin with, or mixing hardener with, a reactive amine moiety which further includes a polymerizable double bond, such as 3-butenylamine, 2- aminoethyl methacrylate, methacryloyl-L-lysine, N-(2-aminoethyl) methacrylamide, and 2-(tert-butylamino)ethyl methacrylate, and/or polyamines.

[0067] A surface coating composition according to aspects of the present disclosure is disposed on a surface of a substrate.

[0068] The term “substrate” as used herein refers to a material that is modified with a surface coating composition according to aspects of the present disclosure or a material to be modified with a surface coating composition according to aspects of the present disclosure.

[0069] In particular aspects of the present disclosure, the surface of the substrate is or includes agarose, alginate, poly-hydroxyethyl-methacrylate (PHEMA), polydimethylsiloxane (PDMS), polyurethane (PU), polystyrene (PS), PVC panel, silicone rubber, silicone hydrogel, epoxy, epoxy-coated steel, PU-coated steel, steel, glass, ceramic, plastic, metal, wood, a derivative of any of the foregoing, or a combination of any two or more of the foregoing.

[0070] In particular aspects of the present disclosure the substrate is a painted or fiberglass boat or ship hull or other marine surface.

[0071] In particular aspects of the present disclosure a preferred substrate is a polyHEMA, polystyrene (PS), PDMS, or PU surface of a medical device.

[0072] In non-limiting examples, the substrate is a surface of a boat or water- exposed structure. In further non-limiting examples, the substrate is surface exposed to water selected from the group consisting of: boat hulls, boat decks, offshore drilling platforms, pipelines, bridges, storage vessels, underwater cables, and underwater equipment. In particular aspects of the present disclosure the substrate is a painted or fiberglass boat or ship hull or other marine surface.

[0073] In particular aspects of the present disclosure a substrate is a surface of a medical device. In particular aspects of the present disclosure a preferred substrate is a polyHEMA, polystyrene (PS), PDMS, or PU surface of a medical device.

[0074] A zwitterionic polymer included in a top coat layer of surface coating compositions according to aspects of the present disclosure is a polymerization product of zwitterionic monomers.

[0075] Zwitterionic Monomers [0076] According to aspects described herein, the zwitterionic monomer has the structural formula (I):

where Ri, R2, and R3 are each independently selected from hydrogen, alkyl, and aryl groups; Li is a linker that covalently couples a cationic center to a polymer backbone; L2 is a linker that covalently couples the cationic center to an anionic group; A(=O)O" is the anionic group; X" is a counter ion associated with the cationic center; and M⁺ is a metal cation, an ammonium cation, or an organic cation.

[0077] According to aspects of the present disclosure, the zwitterionic monomer has the structural formula (V):

[0078] For each Ri, R2, and R3 in structural formulas shown herein representative alkyl groups include C1-C30 straight chain and branched alkyl groups. According to aspects of the present disclosure, the alkyl group is further substituted with one of more substituents including, for example, an aryl group (e.g., -CH2C6H5, benzyl).

[0079] For each Ri, R2, and R3 in structural formulas shown herein representative aryl groups include C6-C12 aryl groups including, for example, phenyl including substituted phenyl groups (e.g., benzoic acid).

[0080] For each Ri, R2, and R3 in structural formulas shown herein representative alkyl groups include C1-C10 straight chain and branched alkyl groups. [0081] According to aspects of the present disclosure, the alkyl group is further substituted with one of more substituents including, for example, an aryl group (e.g., - CH2C5H6, benzyl).

[0082] According to aspects of the present disclosure, R2 and R3 in structural formulas shown herein are methyl.

[0083] According to aspects of the present disclosure, Ri, R2, and R3 in structural formulas shown herein are methyl.

[0084] According to aspects of the present disclosure, R2 and R3 are taken together with N⁺ form the cationic center in structural formulas shown herein.

[0085] According to aspects of the present disclosure, Li includes a functional group (e.g., ester or amide) that couples the remainder of Li to the C=C double bond for the monomers, or the backbone for the polymers. In addition to the functional group, Li can include a C1-C20 alkylene chain. Representative Li groups include -C(=O)O-(CH2)ni- and -C(=O)NH-(CH2)nl-, where nl is 1-20 (e.g., nl = 2).

[0086] L2 can be a C1-C20 alkylene chain according to aspects of the present disclosure. Representative L2 groups include -(CH2)n2-, where n2 is 1-20 (e.g., 1, 2, or 3).

[0087] A(=O)O is an anionic group in structural formulas shown herein. The group is a carboxylic acid (where A is C), a sulfinic acid (where A is S), a sulfonic acid (where A is SO), a phosphinic acid (where A is P), or a phosphonic acid (where A is PO).

[0088] As noted, X in structural formula shown herein is the counter ion associated with the cationic center. The counter ion can be the counter ion that results from the synthesis of the cationic polymers or the monomers (e.g., Cl', Br', I'). The counter ion that is initially produced from the synthesis of the cationic center can also be exchanged with other suitable counter ions to provide polymers having controllable hydrolysis properties and other biological properties. According to aspects of the present disclosure, representative hydrophobic counterions include carboxylates, such as benzoic acid and fatty acid anions (e.g., CH3(CH2)n3CO2- where n3 can be from 1 to 19); alkyl sulfonates (e.g., CH3(CH2)n3SO3- where n3 can be from 1 to 19); salicylate; lactate; bis(trifluoromethylsulfonyl)amide anion (N'(SO2CF3)2); and derivatives thereof. Other counter ions also can be chosen from chloride, bromide, iodide, sulfate; nitrate; perchlorate (CIO4); tetrafluoroborate (BF4); hexafluorophosphate (PFe); trifluoromethylsulfonate (SO3CF3); and derivatives thereof. Other suitable counter ions include salicylic acid (2-hydroxybenzoic acid), benzoate, and lactate.

[0089] M+ in structural formula (I) is a metal ion, an ammonium ion, or an organic ion.

[0090] In structural formulas shown herein N⁺ is the cationic center. In certain embodiments, the cationic center is a quaternary ammonium (N bonded to Li, R2, R3, and L2). In addition to ammonium, other useful cationic centers (R2 and R3 taken together with N) include imidazolium, triazaolium, pyridinium, morpholinium, oxazolidinium, pyrazinium, pyridazinium, pyrimidinium, piperazinium, and pyrrolidinium.

[0091] According to aspects of the present disclosure, Ri, R2, and R3 in structural formulas shown herein are independently selected from the group consisting of C1-C3 alkyl. In one embodiment, Ri, R2, and R3 in structural formulas shown herein are methyl. In another embodiment Ri in structural formulas shown herein is hydrogen, R2 and R3 are methyl.

[0092] According to aspects of the present disclosure, Li in structural formulas shown herein is selected from the group consisting of -C(=O)O-(CH2)nl- and - C(=O)NH-(CH2)nl-, wherein nl is 1-20. In one embodiment, Li in structural formulas shown herein is -C(=O)O-(CH2)2-. In another embodiment, Li in structural formulas shown herein is -C(=O)NH-(CH2)3-

[0093] According to aspects of the present disclosure, L2 in structural formulas shown herein is -(CH2)n2-, where n2 is an integer from 1-20. In one embodiment, L2 in structural formulas shown herein is -(CH2)-. In another embodiment, L2 in structural formulas shown herein is -(CH2)2-

[0094] According to aspects of the present disclosure, Ri, R2, and R3 in structural formulas shown herein are methyl, Li in structural formulas shown herein is -C(=O)O- (CH2)2-, L2 in structural formulas shown herein is -(CH2)-, A is C.

[0095] According to aspects of the present disclosure, Ri in structural formulas shown herein is hydrogen, R2, and R3 in structural formulas shown herein are methyl, Li in structural formulas shown herein is -C(=O)NH-(CH2)3-, L2 in structural formulas shown herein is -(CH2)2-, A is C.

[0096] According to aspects of the present disclosure, structural formula I represents CBMA, CBAA, CBAA-1, CBMAA, CBOH, SBMA, or MPC. [0097] According to aspects of the present disclosure, the zwitterionic monomer has the structural formula (II):

, where M is a monomeric repeating unit, L4 is a linker, X- is a counter ion associated with a cationic center of structure (II) and Y+ is a counter ion associated with an anionic center of structure (II). According to aspects of the present disclosure, M is a repeating unit of a polymer selected from the group consisting of: polyester, polyamide, poly(amino acid), polyimide, polycarbonate, polysiloxane, polyurethane, polyphosphazene, acrylic polymer, amino resin, epoxy resin, phenolic resin, and alkyd resin. According to aspects of the present disclosure, L4 is -C(=O)O-(CH2)n4- or - C(=O)NH-(CH₂)n4-, where n4 is an integer from 0 to 20, such as where n4 is 0 (i.e. not present), 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0098] According to aspects of the present disclosure, L4 in structural formulas shown herein is -C(=O)O-.

[0099] According to aspects of the present disclosure, L4 in structural formulas shown herein is -C(=O)O-, and structural formula II represents CAR.

[00100] Zwitterionic monomers can be obtained by synthesis and/or are commercially available.

[00101] Zwitterionic monomers containing carboxybetaine and sulfobetaine can be synthesized by using a tertiary amine containing acrylate, acrylamide, or vinyl monomer to react with lactone or sultone, or to react with alkyl halides containing acid groups, or to react with alkyl halides containing acid esters followed by removal acid ester to give acid groups.

[00102] Zwitterionic Polymers

[00103] An included zwitterionic polymer according to aspects of the present disclosure has a plurality of repeating units, where each repeating unit has structural formula (III):

[00104] An included zwitterionic polymer according to aspects of the present disclosure has a plurality of repeating units, where each repeating unit has structural formula (VI):

where, n is an integer from 2 to about 100000.

[00105] For each Ri, R2, and R3 in structural formulas of zwitterionic polymers shown herein, representative alkyl groups include C1-C30 straight chain and branched alkyl groups. According to aspects of the present disclosure, the alkyl group is further substituted with one of more substituents including, for example, an aryl group (e.g., - CH2C6H5, benzyl).

[00106] For each Ri, R2, and R3 in structural formulas of zwitterionic polymers shown herein representative aryl groups include C6-C12 aryl groups including, for example, phenyl including substituted phenyl groups (e.g., benzoic acid).

[00107] For each Ri, R2, and R3 in structural formulas of zwitterionic polymers shown herein representative alkyl groups include C1-C10 straight chain and branched alkyl groups. According to aspects of the present disclosure, the alkyl group is further substituted with one of more substituents including, for example, an aryl group (e.g., - CH2C6H5, benzyl). [00108] According to aspects of the present disclosure, R2 and R3 in structural formula (III) and (VI) shown herein are methyl.

[00109] According to aspects of the present disclosure, Ri, R2, and R3 in structural formula (III) and (VI) shown herein are methyl.

[00110] According to aspects of the present disclosure, Ri in structural formula (III) and (VI) shown herein is hydrogen.

[00111] According to aspects of the present disclosure, R2 and R3 are taken together with N+ form the cationic center in structural formula (III) and (VI) shown herein.

[00112] M+ in structural formula (III) is a metal ion, an ammonium ion, or an organic ion.

[00113] According to aspects of the present disclosure, Li includes a functional group (e.g., ester or amide) that couples the remainder of Li to the C=C double bond for the monomers, or the backbone for the polymers. In addition to the functional group, Li can include a C1-C20 alkylene chain. Representative Li groups include -C(=O)O-(CH2)ni- and -C(=O)NH-(CH2)ni-, where nl is 1-20 (e.g., nl = 2). According to aspects of the present disclosure, LI is -C(=O)O-(CH2)ni- or -C(=O)NH-(CH2)ni-, where nl is an integer from 1 to 20, such as where nl is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[00114] L2 can be a C1-C20 alkylene chain according to aspects of the present disclosure. Representative L2 groups include -(CH2)n2-, where n2 is 1-20 (e.g., 1, 2, or 3). [00115] A(=O)O- is an anionic group in structural formulas shown herein. The group is a carboxylic acid (where A is C), a sulfinic acid (where A is S), a sulfonic acid (where A is SO), a phosphinic acid (where A is P), or a phosphonic acid (where A is PO).

[00116] An included zwitterionic polymer according to aspects of the present disclosure is a carnitine-derived zwitterionic polymer having a plurality of repeating units, where each repeating unit has structural formula (IV):

, where M is a monomeric repeating unit, L4 is a linker, n is an integer from 2 to about 100000, X" is a counter ion associated with the cationic center, and Y⁺ is a counter ion associated with the anionic center. According to aspects of the present disclosure, M is a repeating unit of a polymer selected from the group consisting of: polyester, polyamide, poly(amino acid), polyimide, polycarbonate, polysiloxane, polyurethane, polyphosphazene, acrylic polymer, amino resin, epoxy resin, phenolic resin, and alkyd resin. L4 is -C(=O)O-(CH2)n4- or -C(=O)NH-(CH2)n4-, where n4 is an integer from 0 to 20, such as where n4 is 0 (i.e. not present), 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[00117] As noted, X" in structural formulas shown herein is the counter ion associated with the cationic center. The counter ion can be the counter ion that results from the synthesis of the cationic polymers or the monomers (e.g., Cl", Br", I"). The counter ion that is initially produced from the synthesis of the cationic center can also be exchanged with other suitable counter ions to provide polymers having controllable hydrolysis properties and other biological properties. According to aspects of the present disclosure, representative hydrophobic counter ions include carboxylates, such as benzoic acid and fatty acid anions (e.g., CH3(CH2)n3CO2‘ where n3 = 1-19); alkyl sulfonates (e.g., CH3(CH2)n3SO3‘ where n3 = 1-19); salicylate; lactate; bis(trifluoromethylsulfonyl)amide anion (N'(SO2CF3)2); and derivatives thereof. Other counter ions also can be chosen from chloride, bromide, iodide, sulfate; nitrate; perchlorate (CIO4); tetrafluoroborate (BF4); hexafluorophosphate (PFe); trifluoromethyl sulfonate (SO3CF3); and derivatives thereof. Other suitable counter ions include salicylic acid (2 -hydroxybenzoic acid), benzoate, and lactate.

[00118] According to aspects, Ri, R2, and R3 are each independently selected from hydrogen, alkyl, and aryl groups; Li is a linker that covalently couples a cationic center to a polymer backbone; L2 is a linker that covalently couples the cationic center to an anionic group; A(=O)O- is the anionic group; A is C, S, SO, P, or PO; X" is a counter ion associated with the cationic center; M⁺ is a counter ion associated with the (A=O)O- anionic center; and n is an integer in the range of 2 to about 100,000.

[00119] An included zwitterionic polymer according to aspects of the present disclosure has a plurality of repeating units, where each repeating unit has structural formula (I), where Ri is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, Ci-Ce alkyl, and C6-C12 aryl groups; R2 and R3 are independently selected from the group consisting of alkyl and aryl, or taken together with a nitrogen to which they are attached form a cationic center; Li is a linker that covalently couples the cationic center [N⁺(R2)(R3)] to a monomer double bond or its polymer backbone [-(CH2- CRi)n-]; L2 is a linker that covalently couples an anionic center [A(=O)-O-] to the cationic center; A is C, S, SO, P, or PO; M⁺ is a metal ion, an ammonium ion, or an organic ion; X" is a counter ion associated with the cationic center; and n is an integer in the range of 2 to about 100,000.

[00120] An included zwitterionic polymer according to aspects of the present disclosure according to aspects of the present disclosure has a plurality of repeating units selected from the group consisting of: a sulfobetaine acrylate, a sulfobetaine methacrylate, a sulfobetaine acrylamide, a sulfobetaine methacrylamide, a sulfobetaine vinyl compound, a carboxybetaine acrylate, a carboxybetaine methacrylate, a carboxybetaine acrylamide, a carboxybetaine methacrylamide, a carboxybetaine vinyl compound, a phosphobetaine acrylate, a phosphobetaine methacrylate, a phosphobetaine acrylamide, a phosphobetaine methacrylamide, a phosphobetaine vinyl compound; and a mixture of any two or more thereof.

[00121] An included zwitterionic polymer according to aspects of the present disclosure is selected from the group consisting of: a sulfobetaine acrylate polymer, a sulfobetaine methacrylate polymer, a sulfobetaine acrylamide polymer, a sulfobetaine methacrylamide polymer, a sulfobetaine vinyl polymer, a carboxybetaine acrylate polymer, a carboxybetaine methacrylate polymer, a carboxybetaine acrylamide polymer, a carboxybetaine methacrylamide polymer, a carboxybetaine vinyl polymer, a phosphobetaine acrylate polymer, a phosphobetaine methacrylate polymer, a phosphobetaine acrylamide polymer, a phosphobetaine methacrylamide polymer, a phosphobetaine vinyl polymer; a polymer comprising of two or more zwitterionic repeating units selected from the group consisting of: a sulfobetaine acrylate, a sulfobetaine methacrylate, a sulfobetaine acrylamide, a sulfobetaine methacrylamide, a sulfobetaine vinyl compound, a carboxybetaine acrylate, a carboxybetaine methacrylate, a carboxybetaine acrylamide, a carboxybetaine methacrylamide, a carboxybetaine vinyl compound, a phosphobetaine acrylate, a phosphobetaine methacrylate, a phosphobetaine acrylamide, a phosphobetaine methacrylamide, a phosphobetaine vinyl compound; and a mixture of any two or more zwitterionic polymers thereof. [00122] An included zwitterionic polymer according to aspects of the present disclosure is selected from the group consisting of: PCBAA, PCBAA-1, PCBMA, PCBMAA, PSBMA, PMPC, PCBOH, PCAR, and a mixture of any two or more thereof.

[00123] In structural formulas herein N⁺ is the cationic center. In certain embodiments, the cationic center is a quaternary ammonium (N bonded to Li, R2, R3, and L2). In addition to ammonium, other useful cationic centers (R2 and R3 taken together with N) include imidazolium, triazaolium, pyridinium, morpholinium, oxazolidinium, pyrazinium, pyridazinium, pyrimidinium, piperazinium, and pyrrolidinium.

[00124] A zwitterionic polymer formed from a zwitterionic monomer in structural formulas shown herein can have 2 to about 100,000 monomer unit per polymer chain.

[00125] According to aspects of the present disclosure, Ri, R2, and R3 in structural formulas shown herein are independently selected from the group consisting of C1-C3 alkyl. In one embodiment, Ri, R2, and R3 in structural formulas shown herein are methyl.

[00126] According to aspects of the present disclosure, Li in structural formulas shown herein is selected from the group consisting of -C(=O)O-(CH2)nl- and - C(=O)NH-(CH2)nl-, wherein nl is 1-20. In one embodiment, Li in structural formulas shown herein is -C(=O)O-(CH2)2-.

[00127] According to aspects of the present disclosure, L2 in structural formulas shown herein is -(CH2)n2-, where n2 is an integer from 1-20. In one embodiment, L2 in structural formula (III) shown herein is -(CH2)-.

[00128] According to aspects of the present disclosure, Ri, R2, and R3 in structural formulas shown herein are methyl, Li in structural formulas shown herein is -C(=O)O- (CH2)2-, L2 in structural formulas shown herein is -(CH2)-, A is C.

[00129] According to aspects of the present disclosure, Ri, in structural formulas shown herein is hydrogen, R2 and R3 in structural formulas shown herein are methyl, Li in structural formulas shown herein is -C(=O)NH-(CH2)3-, L2 in structural formulas shown herein is -(CH2)2-, A is C.

[00130] According to aspects, the zwitterionic polymer is selected from the group consisting of: PCBMA, PCBAA, PCBAA-1, PCBMAA, PCBOH, PCAR, PSBMA, or PMPC.

[00131] Methods of polymerizing reaction components having reactive groups to produce a polymerization product include radical polymerization, living polymerization, condensation, ring opening polymerization and click chemistry. Details of polymerization mechanisms are well-known along with appropriate reaction conditions, initiators, catalysts and other standard co-factors as exemplified herein.

[00132] Zwitterionic polymers (linear zwitterionic polymers) are synthesized through free radical polymerization method or living polymerization method. These polymerization methods normally involve initiators, zwitterionic monomers, catalysts (optional), and the polymerization condition is selected from ambient temperature, heating, lighting, etc. The feeding monomer amount relative to initiator amount is varied to obtain polymers with different molecular weight (MW). The obtained polymers are included in a top coat layer of surface coating compositions according to aspects of the present disclosure.

[00133] A zwitterionic polymer formed from a zwitterionic monomer in structural formulas shown herein can have 2 to about 100,000 monomer unit per polymer chain.

[00134] Hydrophilic Monomers

[00135] A hydrophilic polymer included in a top coat layer of surface coating compositions according to aspects of the present disclosure is a polymerization product of hydrophilic monomers.

[00136] The hydrophilic monomer may be, or include, without limitation, one or more of 2-Methyl-2-propene-l -sulfonic acid sodium salt, sodium 4- vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4- vinylbenzoic acid, y -Dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, phosphoric acid 2-hydroxyethyl methacrylate ester, acrylic acid, methacrylic acid, betacarboxyethyl acrylate, vinyl alcohol, vinylpyrrolidone, acrylamide, N-isopropyl- acrylamide, methyl-methacrylate, hydroxyethyl-methacrylate, poly(ethylene glycol) methacrylate (PEGMA), (poly)ethylene glycol diacrylate (PEGDA), (poly)ethylene glycol dimethacrylate, hydroxypolyethoxy allyl ether, N, N-Dimethylacrylamide, sodium 1 -allyloxy -2 hydroxypropyl sulfonate, or a derivative of one or more of the foregoing.

[00137] A hydrophilic polymer included in a top coat layer of surface coating compositions according to aspects of the present disclosure is a polymerization product of one or more of hydrophilic monomers and/or zwitterionic monomers.

[00138] Methods of polymerizing reaction components having reactive groups to produce a polymerization product include radical polymerization, living polymerization, condensation, ring opening polymerization and click chemistry. Details of polymerization mechanisms are well-known along with appropriate reaction conditions, initiators, catalysts and other standard co-factors as exemplified herein.

[00139] Hydrophilic polymers are synthesized through free radical polymerization method or living polymerization method. These polymerization methods normally involve initiators, hydrophilic monomers, catalysts (optional), and the polymerization condition is selected from ambient temperature, heating, lighting, etc. The feeding monomer amount relative to initiator amount is varied to obtain polymers with different molecular weight (MW). The obtained polymers are included in a top coat layer of surface coating compositions according to aspects of the present disclosure.

[00140] A hydrophilic polymer formed can have 2 to about 100,000 monomer unit per polymer chain.

[00141] Hydrophilic Hydrogel

[00142] A hydrophilic top coat layer according to aspects of the present disclosure includes a hydrophilic hydrogel that forms covalent bonds with the molecules present in the primer layer.

[00143] A hydrophilic hydrogel includes a polymer and hydrophilic liquid. According to aspects of the present disclosure the hydrophilic hydrogel includes water.

[00144] A hydrophilic hydrogel according to aspects of the present disclosure is or includes a zwitterionic polymer. The term “zwitterionic” as used herein refers to molecules that carry both positive and negative charges (e.g., negatively-charged carboxylate groups and positively-charged ammonium groups).

[00145] A hydrophilic hydrogel according to aspects of the present disclosure is or includes a polymer comprising repeating subunits, and the repeating subunits of the polymer are zwitterionic. The hydrophilic hydrogel element may be or include a crosslinked or non-crosslinked polymer. The hydrophilic hydrogel element may be or include a natural or synthetic polymer or network.

[00146] The hydrophilic hydrogel may be or include one or more of crosslinked poly(2-Methyl-2-propene-l -sulfonic acid sodium salt), non-crosslinked poly(2-Methyl- 2-propene-l -sulfonic acid sodium salt), crosslinked poly(sodium 4- vinylbenzenesulfonate), non-crosslinked poly(sodium 4-vinylbenzenesulfonate), crosslinked poly(2-propene-l -sulfonic acid), non-crosslinked poly(2-propene-l -sulfonic acid), crosslinked poly(sodium acrylate), non-crosslinked poly(sodium acrylate), crosslinked poly(sodium 4-vinylbenzoic acid), non-crosslinked poly(sodium 4- vinylbenzoic acid), crosslinked poly(y,y-Dimethylallyl phosphate ammonium salt), noncrosslinked poly(y,y-Dimethylallyl phosphate ammonium salt), crosslinked poly(diethyl allyl phosphate), non-crosslinked poly(diethyl allyl phosphate), crosslinked poly(phosphoric acid 2-hydroxyethyl methacrylate ester), non-crosslinked poly(phosphoric acid 2-hydroxyethyl methacrylate ester), crosslinked poly-acrylic acid, non-crosslinked poly-acrylic acid, crosslinked poly(vinyl alcohol), non-crosslinked poly(vinyl alcohol), crosslinked polyvinylpyrrolidone), non-crosslinked poly(vinylpyrrolidone), silicone-containing hydrogel, crosslinked polyacrylamide, non- crosslinked polyacrylamide, crosslinked poly-(N-isopropyl-acrylamide), non-crosslinked poly-(N-isopropyl-acrylamide), crosslinked poly-methyl-methacrylate, non-crosslinked poly-methyl-methacrylate, crosslinked poly-hydroxyethyl-methacrylate (PHEMA), non- crosslinked PHEMA, crosslinked polyethylene glycol (PEG), non-crosslinked PEG, crosslinked poly(ethylene glycol) methacrylate (PEGMA), non-crosslinked PEGMA, crosslinked poly(ethylene glycol) diacrylate (PEGDA), polypropylene glycol, crosslinked zwitterionic poly-(sulfobetaine), non-crosslinked zwitterionic poly- (sulfobetaine), crosslinked zwitterionic poly-(carboxybetaine), non-crosslinked zwitterionic poly-(carboxybetaine), crosslinked zwitterionic poly-(phosphorylcholine), non-crosslinked zwitterionic poly-(phosphorylcholine), crosslinked PSBMA, non- crosslinked PSBMA, crosslinked PMPC, non-crosslinked PMPC, crosslinked PCBMA, non-crosslinked PCBMA, crosslinked PCBAA, non-crosslinked PCBAA, crosslinked PCBAA-1, non-crosslinked PCBAA- 1, crosslinked PCBMAA, non-crosslinked PCBMAA, crosslinked PCBOH, non-crosslinked PCBOH, crosslinked PCAR, non- crosslinked PCAR, crosslinked alginate, crosslinked chitosan, gelatin, collagen, fibrin, agarose, hyaluronic acid, cellulose, polypeptides, or a derivative of one or more of the foregoing.

[00147] The hydrophilic hydrogel may be or include a polymer having a structure of formula VII:

where Ri, R2, R3, R4, and R5 are each independently selected from hydrogen, alkyl, and aryl groups; Li is a linker that covalently couples a cationic center to the polymer backbone; L2 is a linker that covalently couples the cationic center to an anionic group; A(=O)O" is the anionic group; A is C, S, SO, P, or PO; X" is a counter ion associated with the cationic center; M⁺ is a metal ion, an ammonium ion, or an organic ion; L3 is a linker that covalently couples two polymer backbones; n is an integer in the range of 2 to about 100,000; m is a positive non-zero integer; and m/n is in the range of 0.1% - 99.9%. [00148] The hydrophilic hydrogel may be or include a polymer having a structure of formula VII where Ri, R4, and Rs are each independently selected from the group consisting of hydrogen, fluorine, trifluoromethyl, Ci-Ce alkyl, and C6-C12 aryl groups; R2 and R3 are independently selected from the group consisting of alkyl and aryl, or taken together with the nitrogen to which they are attached form a cationic center; Li is a linker that covalently couples the cationic center [N⁺(R2)(R3)] to a polymer backbone [-(CH2- CRi)n-]; and L2 is a linker that covalently couples an anionic center [A(=O)-O‘] to the cationic center.

[00149] The structure of formula VII, in certain embodiments, is a polymerization product of a) zwitterionic carboxybetaine monomers, sulfobetaine monomers, or phosphobetaine monomers, or a combination of two or more thereof with b) crosslinkers. [00150] A zwitterionic monomer according to aspects of the present disclosure is selected from the group consisting of: a sulfobetaine acrylate, a sulfobetaine acrylamide, a sulfobetaine vinyl compound, a carboxybetaine acrylate, a carboxybetaine acrylamide, a carboxybetaine vinyl compound, a phosphobetaine acrylate, a phosphobetaine acrylamide, a phosphobetaine vinyl compound; and a mixture of any two or more thereof. [00151] A zwitterionic monomer according to aspects of the present disclosure is selected from the group consisting of: CBAA, CBAA-1, CBOH, CBMA, CBMAA, SBMA, MPC; and a mixture of any two or more thereof.

[00152] The hydrophilic hydrogel according to aspects of the present disclosure includes a zwitterionic polymer having a plurality of repeating units selected from the group consisting of: a sulfobetaine acrylate, a sulfobetaine methacrylate, a sulfobetaine acrylamide, a sulfobetaine methacrylamide, a sulfobetaine vinyl compound, a carboxybetaine acrylate, a carboxybetaine methacrylate, a carboxybetaine acrylamide, a carboxybetaine methacrylamide, a carboxybetaine vinyl compound, a phosphobetaine acrylate, a phosphobetaine methacrylate, a phosphobetaine acrylamide, a phosphobetaine methacrylamide, a phosphobetaine vinyl compound; and a mixture of any two or more thereof.

[00153] A hydrophilic hydrogel according to aspects of the present disclosure includes a zwitterionic polymer selected from the group consisting of: a sulfobetaine acrylate polymer, a sulfobetaine methacrylate polymer, a sulfobetaine acrylamide polymer, a sulfobetaine methacrylamide polymer, a sulfobetaine vinyl polymer, a carboxybetaine acrylate polymer, a carboxybetaine methacrylate polymer, a carboxybetaine acrylamide polymer, a carboxybetaine methacrylamide polymer, a carboxybetaine vinyl polymer, a phosphobetaine acrylate polymer, a phosphobetaine methacrylate polymer, a phosphobetaine acrylamide polymer, a phosphobetaine methacrylamide polymer, a phosphobetaine vinyl polymer; a polymer comprising of two or more zwitterionic repeating units selected from the group consisting of: a sulfobetaine acrylate, a sulfobetaine methacrylate, a sulfobetaine acrylamide, a sulfobetaine methacrylamide, a sulfobetaine vinyl compound, a carboxybetaine acrylate, a carboxybetaine methacrylate, a carboxybetaine acrylamide, a carboxybetaine methacrylamide, a carboxybetaine vinyl compound, a phosphobetaine acrylate, a phosphobetaine methacrylate, a phosphobetaine acrylamide, a phosphobetaine methacrylamide, a phosphobetaine vinyl compound; and a mixture of any two or more zwitterionic polymers thereof.

[00154] A hydrophilic hydrogel according to aspects of the present disclosure includes a zwitterionic polymer selected from the group consisting of: PCBAA, PCBAA- 1, PCBMA, PCBMAA, PCBOH, PSBMA, PMPC, and a mixture of any two or more thereof. [00155] The hydrophilic hydrogel may be or include a polymer having a structure of formula VIII:

[00156] The hydrophilic hydrogel may be or include a polymer having a structure of formula VIII where Ri, R2, and R3 are each independently selected from the group consisting of hydrogen, fluorine, trifluoromethyl, Ci-Ce alkyl, and C6-C12 aryl groups; Li is -C(=O)O-(CH2)Z- or -C(=O)NH-(CH2)z-; and z is an integer from 0 (i.e. not present) to 20, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[00157] The structure of formula VIII, in certain embodiments, is a polymerization product of zwitterionic carnitine derived monomers with crosslinkers.

[00158] A zwitterionic carnitine derived monomer according to aspects of the present disclosure is selected from the group consisting of: a carnitine derived acrylate, a carnitine derived acrylamide, a carnitine derived vinyl compound; and a mixture of any two or more thereof.

[00159] A zwitterionic carnitine derived monomer according to aspects of the present disclosure is selected from the group consisting of L-carnitine acrylate monomer.

[00160] A zwitterionic carnitine derived monomer according to aspects of the present disclosure is selected from the group consisting of CAR monomer.

[00161] A crosslinker reacted with a monomer to form the structure of formula VII, or VIII, in certain embodiments, according to aspects of the present disclosure is a polyreactive crosslinking agent. According to particular aspects, a crosslinker reacted with a zwitterionic monomer, or a zwitterionic carnitine derived monomer, to produce a hydrophilic hydrogel element according to aspects of the present disclosure is an acryloyl-containing crosslinker. According to particular aspects, a crosslinker reacted with a zwitterionic monomer, or a zwitterionic carnitine derived monomer to produce a hydrophilic hydrogel element according to aspects of the present disclosure is an allyl crosslinker. According to particular aspects, a crosslinker reacted with a zwitterionic monomer, or a zwitterionic carnitine derived monomer to produce a hydrophilic hydrogel element according to aspects of the present disclosure is a vinyl compound.

[00162] A crosslinker reacted with a zwitterionic monomer, or a zwitterionic carnitine derived monomer according to aspects of the present disclosure is one or more of: allyl methacrylate, diallyl itaconate, monoallyl itaconate, dially maleate, diallyl fumarate, diallyl succinate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, diethylene glycol bis-allyl carbonate, divinyl ether of diethylene glycol, triallyl phosphate, triallyl trimellitate, allyl ether, diallylimidazolidone, pentaerythritol triallyl ether (PETE), N,N-diallylmelamine, triallyl-l,3,5-triazine-2,4,6-(lH,3H,5H)trione (TATT), 2,4,6-Triallyloxy-l,3,5-triazine; vinyl compounds, e.g. divinyl benzene, N,N'- methylene bis acrylamide (MBAA), methylenebis(methacrylamide), ethylene glycol dimethacrylate, ethylene glycol diacrylate, neopentylglycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, hexamethylene bis maleimide, divinyl urea, bisphenol A bis methacrylate, divinyl adipate, glycerin trimethacrylate, trimethylolpropane triacrylate, trivinyl trimellitate, 1,5-pentadiene, 1,7-octadiene, 1,9-decadiene, l,3-bis(4-methacryloxybutyl) tetramethyl disiloxane, divinyl ether, divinyl sulfone, N-vinyl-3(E)-ethylidene pyrrolidone (EVP), ethylidene bis(N-vinyl pyrrolidone) (EBVP).

[00163] A crosslinker reacted with a zwitterionic monomer, or a zwitterionic carnitine derived monomer according to aspects of the present disclosure is MBAA.

[00164] A zwitterionic hydrogel included in a top coat layer of surface coating compositions according to aspects of the present disclosure is a polymerization product of one or more of zwitterionic monomers and crosslinkers.

[00165] A hydrophilic hydrogel included in a top coat layer of surface coating compositions according to aspects of the present disclosure is a polymerization product of one or more of hydrophilic monomers and/or zwitterionic monomers and crosslinkers. [00166] Methods of polymerizing reaction components having reactive groups to produce a polymerization product include radical polymerization, living polymerization, condensation, ring opening polymerization and click chemistry. Details of polymerization mechanisms are well-known along with appropriate reaction conditions, initiators, catalysts and other standard co-factors as exemplified herein.

[00167] Hydrophilic hydrogels and zwitterionic hydrogels are synthesized through free radical polymerization methods or living polymerization methods. These polymerization methods normally involve initiators, hydrophilic and/or zwitterionic monomers, crosslinkers, catalysts (optional), and the polymerization condition is selected from ambient temperature, heating, lighting, etc. The feeding monomer amount relative to initiator amount is varied to obtain hydrogels with different curing degrees. The feeding monomer amount relative to crosslinker amount is varied to obtain hydrogels with different crosslinking degrees. Curing and crosslinking may be varied to achieve a range of mechanical properties of the obtained hydrogels. The obtained hydrogels are included in a top coat layer of surface coating compositions according to aspects of the present disclosure.

[00168] Mixed charge monomers

[00169] A hydrophilic polymer included in a top coat layer of surface coating compositions according to aspects of the present disclosure is a polymerization product of one or more of mixed charge monomers, with or without zwitterionic monomers.

[00170] A hydrophilic hydrogel included in a top coat layer of surface coating compositions according to aspects of the present disclosure is a polymerization product of one or more of mixed charge monomers and crosslinkers, with or without zwitterionic monomers.

[00171] Mixed charge monomers according to aspects of the present disclosure include positively charged monomers and negatively charged monomers, the net charge of which is neutral or negative, i.e., the number of negatively charged monomers is equal to or larger than the number of positively charged monomers.

[00172] Negatively charged monomers are anionic molecules containing polymerizable double bonds with the anionic center being a carboxylic acid, a sulfinic acid, a sulfonic acid, a phosphinic acid, or a phosphonic acid.

[00173] Negatively charged monomer can be selected from one or more negatively charged monomers of either acid or salt forms of the following, including but not limited to: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2-propene-l -sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4-vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, phosphoric acid 2-hydroxyethyl methacrylate ester, or a derivative of one or more of the foregoing.

[00174] Positively charged monomers are cationic molecules containing polymerizable double bonds, with the cationic center being a primary, secondary, tertiary, or quaternary amine.

[00175] Positively charged monomers can be selected from one or more positively charged monomers, including but not limited to: methacrylamide propyl trimethyl ammonium chloride, 2-acrylamido-2-methyl propyl sulfonic acid, methacrylamide ethyl trimethylamino methyl sulfate, dimethylaminoethyl (acrylate and) methacrylate dimethyl sulfate, methylaminoethyl methacyrlate methyl chloride. Surface coating compositions are provided according to aspects of the present disclosure wherein the top coat further includes an anti-mud component.

[00176] Surface coating compositions are provided according to aspects of the present disclosure wherein the top coat comprises a reaction product of: 1) one or more of: a zwitterionic monomer and a hydrophilic monomer; and 2) one or more of: a negatively- charged “anti-mud” monomer and a crosslinker; wherein the reaction product resists mud accumulation on a substrate coated with the surface coating composition.

[00177] Anti-mud monomers can be selected from one or more negatively charged monomers of either acid or salt forms of the following, but not limited to: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2-propene-l -sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4- vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, phosphoric acid 2-hydroxyethyl methacrylate ester, or a derivative of one or more of the foregoing. The amount of an anti-mud monomers in the top coat can be selected from 0.1 wt% to 99wt%, as long as the monomers can be fully dissolved in the top coat precursor solution.

[00178] Methods of coating a substrate according to aspects of the present disclosure include: applying a curable primer composition to the substrate for forming a primer layer on the substrate, the curable primer composition comprising: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds; curing the curable primer composition; applying a curable top coat composition onto the cured primer layer, the curable top coat composition comprising one or more of: a zwitterionic monomers, and hydrophilic monomers, thereby forming a bilayer composition on the substrate; and curing the bilayer composition through radical polymerization, thereby forming a surface coating composition, wherein the top coat layer and the primer layer are covalently bonded to each other by a reaction product of polymerizable double bonds of the zwitterionic monomers and/or hydrophilic monomers with the polymerizable double bonds of the primer layer. Optionally, the curable top coat composition includes: 1) one or more of: a zwitterionic monomer and a hydrophilic monomer; and 2) a negatively-charged monomer and/or crosslinker, wherein the reaction or cured product resists mud accumulation on a substrate coated with the surface coating composition. Optionally, the curable top coat composition includes: 1) one or more of: a zwitterionic monomer, a hydrophilic monomer, and a negatively-charged monomer and/or crosslinker, and 2) a crosslinker, wherein the reaction or cured product is a hydrogel. Optionally, the curable top coat composition includes: mixed charge monomers with or without a crosslinker, wherein the reaction or cured product is a hydrophilic polymer or hydrophilic hydrogel.

[00179] Curing of a primer layer is achieved using any of various suitable methods, such as, but not limited to, ambient temperature, heating, and/or exposure to UV light. Curing of a top coat layer is achieved using any of various suitable methods, such as, but not limited to, ambient temperature, heating, and/or exposure to UV light.

[00180] According to aspects of the present disclosure, curing of the top coat layer, the primer layer, or both the top coat layer and the primer layer, is achieved by exposure to temperatures in the range of about 15 °C to 25 °C, 10 °C to 40 °C, or 0 °C to 70 °C.

[00181] According to aspects of the present disclosure, curing of the top coat layer, the primer layer, or both the top coat layer and the primer layer, is achieved by exposure to ambient environmental conditions.

[00182] The primer layer does not have to be fully cured, which might take hours to days, before applying the curable top coat composition. While curing, the primer layer can be visually and/or physically examined, such as by light touching. Once the primer layer shows a physical integrity on the substrate, such as when the primer layer is at least partially cured so that it is no longer a liquid, and has become a semi solid, or gel, for example when the primer layer is dry to the touch, the curable top coat composition can be applied and won’t disrupt the physical integrity of the cured or partially cured primer layer. Thus, when referring to a primer layer herein, the term “cured primer layer” refers to a fully cured primer layer as well as a partially cured primer layer that has been cured sufficiently such that it is no longer a liquid, and has become a semi solid, or gel, and is dry to the touch such that application of the curable top coat composition does not disrupt the physical integrity of the cured primer layer.

[00183] Kits for coating a substrate according to aspects of the present disclosure include: a first component of a curable primer composition including an epoxy resin or a urethane resin; a second component of a curable primer composition including a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, includes reactive moieties comprising polymerizable double bonds, and wherein the first component of the curable primer composition and second component of the curable primer composition are separately packaged to prevent contact prior to mixing to form a curable primer composition; and a curable top coat composition, the curable top coat composition including one or more of: a zwitterionic monomer, a hydrophilic monomer, a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer and a hydrophilic hydrogel.

[00184] Kits for coating a substrate according to aspects of the present disclosure include: a first component of a curable primer composition including an epoxy resin or a urethane resin; a second component of a curable primer composition including a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, includes reactive moieties including polymerizable double bonds, and wherein the first component of the curable primer composition and second component of the curable primer composition are separately packaged to prevent contact prior to mixing to form a curable primer composition; and a curable top coat composition, the curable top coat composition including one or more of: a zwitterionic monomer, a hydrophilic monomer, a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer and a hydrophilic hydrogel, and the curable top coat composition further including a negatively-charged monomer, a negatively-charged crosslinker, or both thereof.

[00185] Kits for coating a substrate according to aspects of the present disclosure include: a first component of a curable primer composition including an epoxy resin or a urethane resin; a second component of a curable primer composition including a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, includes reactive moieties including polymerizable double bonds, and wherein the first component of the curable primer composition and second component of the curable primer composition are separately packaged to prevent contact prior to mixing to form a curable primer composition; and a curable top coat composition, the curable top coat composition including mixed charge monomers with or without a crosslinker.

[00186] Kits for coating a substrate according to aspects of the present disclosure include: a first component of a curable primer composition including an epoxy resin or a urethane resin; a second component of a curable primer composition including a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, includes reactive moieties including polymerizable double bonds, and wherein the first component of the curable primer composition and second component of the curable primer composition are separately packaged to prevent contact prior to mixing to form a curable primer composition; a first component of a curable top coat composition, the first component of the curable top coat composition including one or more of: a zwitterionic monomer, a hydrophilic monomer, a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer, a hydrophilic hydrogel, and optionally further includes one or more of: an anti -mud monomer, a crosslinker, and a thickener; and a second component of a curable top coat composition including an initiator, wherein the first component of the curable top coat composition and second component of the curable top coat composition are separately packaged to prevent contact prior to mixing to form a curable top coat composition. A catalyst is optionally included in the first component of the curable top coat composition. A thickener is optionally included in the first and/or second component of the curable top coat composition. First and second components of the curable top coat composition are present in aqueous solution and may optionally include a second or more solvents. A VOC is optionally included in the first and/or second component of the curable top coat composition.

[00187] Kits for coating a substrate according to aspects of the present disclosure include: a first component of a curable primer composition including an epoxy resin or a urethane resin; a second component of a curable primer composition including a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, includes reactive moieties including polymerizable double bonds, and wherein the first component of the curable primer composition and second component of the curable primer composition are separately packaged to prevent contact prior to mixing to form a curable primer composition; a first component of a curable top coat composition, the first component of the curable top coat composition including mixed charge monomers with or without a crosslinker; and a second component of a curable top coat composition including an initiator, wherein the first component of the curable top coat composition and second component of the curable top coat composition are separately packaged to prevent contact prior to mixing to form a curable top coat composition. A catalyst is optionally included in the first component of the curable top coat composition. A thickener is optionally included in the first and/or second component of the curable top coat composition. First and second components of the curable top coat composition are present in aqueous solution and may optionally include a second or more solvents. A VOC is optionally included in the first and/or second component of the curable top coat composition. A thickener according to aspects of the present disclosure includes, but is not limited to: carboxymethyl/hydroxyethyl cellulose, sodium polyacrylate, waterborne polyurethane starch, gelatin, alginate, agar, and a combination of any two or more thereof.

[00188] A volatile organic compound (VOC) included in a component or composition according to aspects of the present disclosure includes, but is not limited to: alcohols (isopropanol, methanol, ethanol, ethylene glycol, etc.), acids (acetic acid, butyric acid, etc.), amines (diethylenetriamine, methyl diethanolamine, etc.), acetone, acetonitrile, tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, or a combination of any two or more thereof.

[00189] Embodiments of inventive compositions and methods are illustrated in the following examples. These examples are provided for illustrative purposes and are not considered limitations on the scope of inventive compositions and methods.

[00190] Examples

[00191] Preparation of modified epoxy resin as a first primer component

[00192] An epoxy resin of a commercial two-part transparent epoxy (brand: totalboat) was modified to include reactive moieties including polymerizable double bonds by mixing the epoxy resin with acrylic acid (v/v: 2%) in presence of tetrabutylammonium bromide (0.1 wt%) and hydroquinone (0.02wt%). The reaction mixture was protected by nitrogen and heated to 70°C for 4 hours. The obtained modified epoxy resin including polymerizable double bonds was sealed and stored in the dark.

[00193] The epoxy resin can be modified to include more, or fewer, reactive moieties including polymerizable double bonds by changing the amount of acrylic acid mixed with the epoxy resin, such as a volume/volume (v/v) percentage of acrylic acid/epoxy resin of: 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, or more, or less.

[00194] Alternatively, an acrylated epoxy resin and/or acrylated tri-poxy resin, synthesized or commercially provided, can be mixed at room temperature without the need for heating, with an unmodified epoxy resin to achieve a desired degree of reactive polymerizable double bonds in the epoxy resin mixture. For example acrylated epoxy (Allnex Ebecryl 3605) was mixed with an unmodified epoxy (Interlux VC performance, epoxy part) at v/v: 1 :5 to prepare the modified epoxy resin.

[00195] Modified Epoxy Primer layer application

[00196] The hardener part of a commercial two-part transparent epoxy (brand: totalboat) was mixed with the modified epoxy resin including polymerizable double bonds described above(v/v= 2% acrylic acid/epoxy resin) at a ratio of v/v=l :2 hardener/modified epoxy. The resulting mixture of hardener and modified epoxy resin including polymerizable double bonds, a curable primer composition, was de-bubbled, e.g., through centrifugation, and then brushed on a substrate, in this example an epoxycoated plate, producing a curable primer composition on the substrate. The curable primer composition was cured by heating the primer layer-coated plate to 60-70 °C for about one hour such that the primer layer became touch-dry.

[00197] The heating used in this example accelerated the primer layer curing process. For room temperature curing of the primer layer, the curing rate can be accelerated by increasing the amount of hardener, e.g., polyoxypropylenediamine, and/or by adding catalyst, e.g., N-(2-aminoethyl) piperazine, and/or DMP-30. A primer layer curing time is typically in the range of 30 min- 4 hours or longer.

[00198] Alternatively, the hardener part of a commercial two-part epoxy (Interlux VC performance) was mixed with the modified epoxy resin including polymerizable double bonds described above (v/v= 1 :5 acrylated epoxy/epoxy resin) at a ratio of v/v=l : l hardener/modified epoxy. The resulting mixture of hardener and modified epoxy resin including polymerizable double bonds, a curable primer composition, was directly brushed on a substrate, in this example an epoxy-coated plate or a sanded stainless steel substrate, producing a curable primer composition on the substrate. The curable primer composition was cured by at room temperature for about two hours such that the primer layer became touch-dry.

[00199] Top coat application on epoxy primer layer

[00200] A curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer ((poly(3-((3- acrylamidopropyl)dimethylammonio)propanoate)), lwt% MBAA crosslinker (N,N'- methylenebisacrylamide) (relative to CBAA), 0.1 wt% 1-2959 UV initiator, 15wt% antimud acrylic acid monomer, and 5 vol% iso-propanol (VOC) was degassed and applied to the surface of the cured primer layer with a brush. The curable top coat composition was then cured by exposure to UV light 1 hour and a hard top coat (2K-1; lwt% crosslinker relative to CBAA) was formed on the primer layer, producing a surface coating composition (2K-1; 1 wt% crosslinker in the top coat layer relative to CBAA) on the substrate. Similar to this protocol except that 0 wt% MBAA crosslinker was used in the formula, the top coat layer was formed on the primer layer, producing a surface coating composition (2K-0; 0 wt% crosslinker in the top coat layer).

[00201] Alternatively, a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer, lwt% MBAA crosslinker (N,N- methylenebisacrylamide) (relative to CBAA), 15wt% anti-mud sodium acrylate monomer (or SMAP monomer (3 -sulfopropyl methacrylate potassium)), 0.5wt% ammonium persulfate (APS as initiator) and 0.2wt% tetramethylethylenediamine (TMEDA as catalyst or accerlator) was mixed with 500 pL carboxymethylcellulose sodium salt (high viscosity) solution (10wt% aq.) as a thickener. The resulting solution was applied to the surface of the cured primer layer with a brush. The curable top coat layer was observed to cure at room temperature in about 1 h (~0.5 h working time) and was left unattended at least overnight, to allow full curing, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00202] Alternatively, a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer, lwt% MBAA crosslinker (N,N- methylenebisacrylamide) (relative to CBAA), 30wt% anti-mud acrylic acid monomer (relative to CBAA), 3wt% ammonium persulfate (APS as initiator, relative to CBAA)) and lwt% tetramethylethylenediamine (TMEDA as catalyst or accerlator, relative to CBAA) was mixed in water. The resulting solution was applied to the surface of the cured primer layer with a brush. The curable top coat layer was observed to cure at room temperature in about 2 h (~0.5 h working time) and was left unattended for 4 days to allow full curing of the primer layer, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00203] Alternatively, a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBMAA monomer, lwt% MBAA crosslinker (N,N'- methylenebisacrylamide) (relative to CBMAA), 30wt% anti-mud acrylic acid monomer (relative to CBMAA), 3wt% ammonium persulfate (APS as initiator, relative to CBMAA) and lwt% tetramethylethylenediamine (TMEDA as catalyst or accerlator, relative to CBMAA) was mixed in water. The resulting solution was applied to the surface of the cured primer layer with a brush. The curable top coat layer was observed to cure at room temperature in about 2 h (-0.5 h working time) and was left unattended for 4 days to allow full curing of the primer layer, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00204] Alternatively, other types of redox systems can also be used to initiate the polymerization of top coat monomers and/or crosslinkers in the curable top coat composition with the polymerizable double bonds from primer layer. The targeted curing time can be altered from 0.5, 1, 3, to 8 hours or longer.

[00205] Alternatively, a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer, lwt% MBAA crosslinker (N,N- methylenebisacrylamide) (relative to CBAA), 15wt% anti-mud sodium acrylate monomer, 0.5wt% ammonium persulfate (APS as initiator) and 0.2wt% tetramethylethylenediamine (TMEDA as catalyst or accerlator) was mixed with 500 L sodium decanoate (surfactant) solution (10wt% aq.). The resulting solution was applied to the surface of the cured primer layer with a sprayer. The curable top coat composition was observed to cure at room temperature in about 1 h (-0.5 h working time) and was left unattended at least overnight, to allow full curing, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA. [00206] Alternatively, a curable top coat composition, a solution in water, containing mixed charge monomers (45wt% methacrylamide propyl trimethyl ammonium chloride monomer, 30wt% sodium acrylate monomer), 1.5wt% ammonium persulfate (APS as initiator) and 0.5wt% tetramethyl ethylenedi amine (TMEDA as catalyst or accerlator) can be mixed in water. The resulting solution can be applied to the surface of the cured primer layer with a brush or sprayer. The curable top coat composition can be observed to cure at room temperature in about 2 h (~0.5 h working time) and left unattended at least overnight, to allow full curing, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00207] Alternatively, a curable top coat composition, a solution in water, containing mixed charge monomers (45wt% methacrylamide propyl trimethyl ammonium chloride monomer, 30wt% sodium acrylate monomer), lwt% MBAA crosslinker (N,N'- methylenebisacrylamide) (relative to mixed charge monomers), 1.5wt% ammonium persulfate (APS as initiator) and 0.5wt% tetramethylethylenediamine (TMEDA as catalyst or accerlator) can be mixed in water. The resulting solution can be applied to the surface of the cured primer layer with a brush or sprayer. The curable top coat composition can be observed to cure at room temperature in about 2 h (-0.5 h working time) and left unattended at least overnight, to allow full curing, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00208] Modifying either part of a two-part urethane as a first primer component

[00209] An urethane resin of a commercial two-part urethane (POR-15 2K Urethane) can be modified to include reactive moieties including polymerizable double bonds by mixing the urethane resin with vinyl alcohol (v/v: 2%) in presence of 1,3-dinitrobenzene (0.02wt%). The reaction mixture should be protected from moisture and react for 4 hours. The obtained modified urethane resin including polymerizable double bonds should be sealed and stored in the dark.

[00210] The urethane resin can be modified to include more, or fewer, reactive moieties including polymerizable double bonds by changing the amount of vinyl alcohol mixed with the urethane resin, such as a volume/volume (v/v) percentage of vinyl alcohol/urethane resin of: 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, or more, or less. [00211] Alternatively, molecules containing alcohol moiety and a polymerizable double bond, such as vinyl alcohol, crotyl alcohol, CBOH, HEMA, or HPMA, and/or a polyol such as castor oil, either synthesized or commercially provided, can be mixed at ambient temperature with a hardener part of a two-part urethane to achieve a desired degree of reactive polymerizable double bonds in the hardener part. For example vinyl alcohol can be mixed with the hardener part of a commercial two-part urethane (POR-15 2K Urethane) at v/v: 4: 100 to prepare the modified hardener.

[00212] Alternatively, an urethane resin of a commercial two-part urethane (POR-15 2K Urethane) can be modified to include reactive moieties including polymerizable double bonds by mixing the urethane resin with N-(2-aminoethyl) methacrylamide (wt/v: 2%) in presence of 1,3-dinitrobenzene (0.02wt%). The reaction mixture should be protected from moisture and react for 4 hours. The obtained modified urethane resin including polymerizable double bonds should be sealed and stored in the dark.

[00213] The urethane resin can be modified to include more, or fewer, reactive moieties including polymerizable double bonds by changing the amount of N-(2- aminoethyl) methacrylamide mixed with the urethane resin, such as a weight/volume (wt/v) percentage of N-(2-aminoethyl) methacrylamide/urethane resin of: 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, or more, or less.

[00214] Alternatively, molecules containing amine moiety and a polymerizable double bond, including but not limited to 3-butenylamine, 2-aminoethyl methacrylate, methacryloyl-L-lysine, N-(2-aminoethyl) methacrylamide, and 2-(tert-butylamino)ethyl methacrylate, and/or polyamines, either synthesized or commercially provided, can be mixed at ambient temperature with a hardener part of a two-part urethane to achieve a desired degree of reactive polymerizable double bonds in the hardener part. For example N-(2-aminoethyl) methacrylamide can be mixed with the hardener part of a commercial two-part urethane (POR-15 2K Urethane) at wt/v: 4: 100 to prepare the modified hardener.

[00215] Modified Urethane Primer layer application

[00216] The hardener part of a commercial two-part urethane (POR-15 2K Urethane) can be mixed with the modified urethane resin including polymerizable double bonds described above(v/v= 2% vinyl alcohol/urethane resin) at a ratio of v/v=l :3 hardener/modified urethane. The resulting mixture of hardener and modified urethane resin including polymerizable double bonds, a curable primer composition, can be directly brushed on a substrate, in this example an epoxy-coated plate or a sanded stainless steel, producing a curable primer composition on the substrate. The curable primer composition can be cured at ambient temperature for about 1 hour such that the primer layer becomes touch-dry.

[00217] Alternatively, the urethane part of a commercial two-part urethane (POR-15 2K Urethane) can be mixed with the modified hardener including polymerizable double bonds described above (v/v= 4: 100 vinyl alcohol/hardener) at a ratio of v/v=3:l urethane/modified hardener. The resulting mixture of urethane resin and modified hardener including polymerizable double bonds, a curable primer composition, can be directly brushed on a substrate, in this example an epoxy-coated plate or a sanded stainless steel substrate, producing a curable primer composition on the substrate. The curable primer composition can be cured at ambient temperature for about two hours such that the primer layer becomes touch-dry.

[00218] Alternatively, the hardener part of a commercial two-part urethane (POR-15 2K Urethane) can be mixed with the modified urethane resin including polymerizable double bonds described above (wt/v= 2% N-(2-aminoethyl) methacrylamide/urethane resin) at a ratio of v/v=l:3 hardener/modified urethane. The resulting mixture of hardener and modified urethane resin including polymerizable double bonds, a curable primer composition, can be directly brushed on a substrate, in this example an epoxy-coated plate or a sanded stainless steel, producing a curable primer composition on the substrate. The curable primer composition can be cured at ambient temperature for about 1 hour such that the primer layer becomes touch-dry.

[00219] Alternatively, the urethane part of a commercial two-part urethane (POR-15 2K Urethane) can be mixed with the modified hardener including polymerizable double bonds described above (wt/v= 4: 100 N-(2-aminoethyl) methacryl ami de/hardener) at a ratio of v/v=3: l urethane/modified hardener. The resulting mixture of urethane resine and modified hardener including polymerizable double bonds, a curable primer composition, can be directly brushed on a substrate, in this example an epoxy-coated plate or a sanded stainless steel substrate, producing a curable primer composition on the substrate. The curable primer composition can be cured at ambient temperature for about two hours such that the primer layer becomes touch-dry.

[00220] Top coat application on urethane primer layer [00221] A curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer ((poly(3-((3- acrylamidopropyl)dimethylammonio)propanoate)), lwt% MBAA crosslinker (N,N'- methylenebisacrylamide) (relative to CBAA), 0.1 wt% 1-2959 UV initiator, 15wt% antimud acrylic acid monomer, and 5 vol% iso-propanol (VOC) can be degassed and applied to the surface of the cured modified urethane primer layer with a brush. The curable top coat composition was then cured by exposure to UV light 0.5 hour and a top coat can be formed on the primer layer, producing a polymer surface coating composition on the substrate. Similar to this protocol except that 0 wt% MBAA crosslinker was used in the formula, the top coat layer can be formed on the primer layer, producing a hydrogel surface coating composition.

[00222] Alternatively, a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer, lwt% MBAA crosslinker (N,N- methylenebisacrylamide) (relative to CBAA), 15wt% anti-mud sodium acrylate monomer (or SMAP monomer (3 -sulfopropyl methacrylate potassium)), 0.5wt% ammonium persulfate (APS as initiator) and 0.2wt% tetramethylethylenediamine (TMEDA as catalyst or accerlator) can be mixed with 500 pL carboxymethylcellulose sodium salt (high viscosity) solution (10wt% aq.) as a thickener. The resulting solution can be applied to the surface of the cured modified urethane primer layer with a brush. The curable top coat layer can be cured at room temperature in about 1 h (~0.5 h working time) and can be left unattended at least for 12 h, to allow full curing of the modified urethane primer layer (e.g., POR-15 2K Urethane requires at least 12 h for a full cure), before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00223] Alternatively, a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer, lwt% MBAA crosslinker (N,N- methylenebisacrylamide) (relative to CBAA), 30wt% anti-mud acrylic acid monomer (relative to CBAA), 3wt% ammonium persulfate (APS as initiator, relative to CBAA)) and lwt% tetramethylethylenediamine (TMEDA as catalyst or accerlator, relative to CBAA) can be mixed in water. The resulting solution can be applied to the surface of the cured modified urethane primer layer with a brush. The curable top coat layer can cure at room temperature in about 2 h (-0.5 h working time) and be left unattended for at least 12 h to allow full curing of the primer layer, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00224] Alternatively, a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBMAA monomer, lwt% MBAA crosslinker (N,N'- methylenebisacrylamide) (relative to CBMAA), 30wt% anti-mud acrylic acid monomer (relative to CBMAA), 3wt% ammonium persulfate (APS as initiator, relative to CBMAA) and lwt% tetramethylethylenediamine (TMEDA as catalyst or accerlator, relative to CBMAA) can be mixed in water. The resulting solution can be applied to the surface of the cured modified urethane primer layer with a brush. The curable top coat layer can cure at room temperature in about 2 h (~0.5 h working time) and be left unattended for 12 h to allow full curing of the primer layer, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00225] Alternatively, other types of redox systems can also be used to initiate the polymerization of top coat monomers and/or crosslinkers in the curable top coat composition with the polymerizable double bonds from primer layer. The targeted curing time can be altered from 0.5, 1, 3, to 8 h or longer if needed.

[00226] Alternatively, a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer, lwt% MBAA crosslinker (N,N- methylenebisacrylamide) (relative to CBAA), 15wt% anti-mud sodium acrylate monomer, 0.5wt% ammonium persulfate (APS as initiator) and 0.2wt% tetramethylethylenediamine (TMEDA as catalyst or accerlator) can be mixed with 500 L sodium decanoate (surfactant) solution (10wt% aq.). The resulting solution can be applied to the surface of the cured modified urethane primer layer with a sprayer. The curable top coat composition can cure at room temperature in about 2 h (-0.5 h working time) and be left unattended at least 12 h, to allow full curing, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00227] Alternatively, a curable top coat composition, a solution in water, containing mixed charge monomers (45wt% methacrylamide propyl trimethyl ammonium chloride monomer, 30wt% sodium acrylate monomer), 1.5wt% ammonium persulfate (APS as initiator) and 0.5wt% tetramethyl ethylenedi amine (TMEDA as catalyst or accerlator) can be mixed in water. The resulting solution can be applied to the surface of the cured modified urethane primer layer with a brush or sprayer. The curable top coat composition can be observed to cure at room temperature in about 2 h (~0.5 h working time) and left unattended for at least 12 h, to allow full curing, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00228] Alternatively, a curable top coat composition, a solution in water, containing mixed charge monomers (45wt% methacrylamide propyl trimethyl ammonium chloride monomer, 30wt% sodium acrylate monomer), lwt% MBAA crosslinker (N,N'- methylenebisacrylamide) (relative to mixed charge monomers), 1.5wt% ammonium persulfate (APS as initiator) and 0.5wt% tetramethylethylenediamine (TMEDA as catalyst or accerlator) can be mixed in water. The resulting solution can be applied to the surface of the cured modified urethane primer layer with a brush or sprayer. The curable top coat composition can be observed to cure at room temperature in about 2 h (-0.5 h working time) and left unattended for at least 12 h, to allow full curing, before contacting the formed top coat with water. If needed, the curing time can be further controlled by changing the composition of APS and TMEDA.

[00229] Coating characterization

[00230] A surface coating composition according to aspects of the present disclosure containing both a primer layer and a top coat layer was further investigated to characterize the coating composition structure. For sectional imaging, surface coating composition according to aspects of the present disclosure were vertically cut into half to expose the cross-section. Samples were dehydrated in a gradient ethanol series, dried in vacuum, and then coated with nano-gold using an SEEVac Conductive IV sputter coater before imaged by a JSM - 6510LV scanning electron microscope (SEM).

[00231] The surface of the surface coating composition, i.e. the exposed surface of the top coat layer, showed super-hydrophilic properties. Water contact angle on the exposed surface of the top coat layer, e.g., 2K-1, showed a water contact angle of approximately 0° indicating water fully spread on this super-hydrophilic coating surface.

[00232] To examine the durability of a coating according to aspects of the present disclosure under sea water shearing conditions, a shearing force was created using a 5- cm stirring bar at 1300 rpm in a beaker (D = 10 cm) on a magnetic stirring plate. Samples of the surface coating composition were firmly clamped and positioned at the inner wall of the beaker. The coating was found to be super-durable in sea water under shearing conditions for over four months, at room temperature as indicated by the approximately 0° water contact angle measured at different time points, up to at least 4 months, during the continuous shearing. It should be noted that a negative result in this test, would result in exposure of hydrophobic substrate and therefore would show an increase of contact angle, which was not the case in these examples, see Figure 3.

[00233] Inventive coating resists protein absorption

[00234] Human fibrinogen (obtained from Sigma-Aldrich) was used as an example protein for adsorption testing. Protein adsorption was tested on a variety of stainless steel substrates coated with various materials and was measured using an enzyme-linked immunosorbent assay (ELISA). The tested coatings included: 1) bare epoxy coating, 2) SPC coating (SPC: copper-based self-polished coating) (Interlux Y5584; coated on top of epoxy bottom paint), 3) FRC coating (PropGlide fouling release coating; coated without bottom paint according to the manufacturer’s protocol), and 4 and 5) surface coating compositions according to aspects of the present disclosure “2K-0” and “2K-1” as detailed above, coated on top of epoxy bottom paint which was itself in direct contact with the stainless steel.

[00235] All samples of coated substrates were incubated with Img/ml human fibrinogen (Fg) for 10 minutes at room temperature, followed by 5 washes with phosphate-buffered saline (PBS) buffer. They were then incubated with 1 mg/ml bovine serum albumin solution for 10 minutes at room temperature with 5 washes with PBS buffer. The samples were removed from the fifth PBS wash and transferred to new wells. They were next incubated with a l :200-dilution of horseradish peroxidase (HRP)- conjugated anti-fibrinogen (US Biological, Life Sciences) in PBS for 10 minutes, followed by another 5 washes with PBS buffer. After the fifth wash, the samples were transferred to new wells and SIGMAFAST OPD (Sigma-Aldrich) was added to each well to produce a detectable signal indicative of presence of fibrinogen. The samples were incubated in the OPD solution for 30 minutes in the dark. The supernatant was removed from each test well, transferred to a 96-well plate, and its absorbance at 490 nm was measured using a UV-VIS spectrometer (Thermo Scientific Multiscan Go). All samples were measured in triplicate.

[00236] Results indicated that compared to epoxy bottom paint (bare epoxy coating), SPC coating did not significantly reduce Fg absorption at all, see Figure 4. 2K-0 surface coating composition according to aspects of the present disclosure reduced the protein absorption further, while the highest absorption reduction was achieved by 2K-1 surface coating composition according to aspects of the present disclosure, see Figure 4.

[00237] Inventive coating resists marine fouling in lab tests

[00238] Surface coating composition according to aspects of the present disclosure were further compared with commercial coating controls in a lab-based anti-marine fouling test to determine resistance to ULVA zoospore and diatom adhesion.

[00239] The ULVA algae were purchased from Carolina Biology Supply and shipped directly from the Atlantic Ocean in Maine. Soon upon arrival, the algae were washed thoroughly with sterile seawater to remove the unwanted marine organisms. The algae were then transferred to a conical flask with Algae Gro culture media on a shaker at 12 h light/12 h dark cycle. After two days of culture, the culture media containing ULVA zoospores was collected and directly used. Zoospore concentration was adjusted to be 1.3xl0⁴ cell/mL by cell counting under a microscope.

[00240] Both freshwater diatoms Navicula and sea diatoms Cyclotella were purchased from Carolina Biology Supply. The diatom cells were cultured in Algae Gro media in a conical flask. The suspension of cells was diluted with the medium to give a diatom suspension with an appropriate concentration (2>< 10⁴/ml for Navicula and 1 * 10⁵/ml for Cyclotella).

[00241] The coating samples to be tested were co-cultured with zoospore and diatom suspensions for 1 and 14 days, respectively. After the culturing, the coating samples were gently washed to remove loosely bound zoospore or diatom cells. The coating samples were then immersed in a fixative solution of 2.5% glutaraldehyde, 2% paraformaldehyde in 0.1 M sodium phosphate buffer, dehydrated in a gradient ethanol series, dried in vacuum, and visualized under a SEM. Adhered cell density was counted by averaging 5 randomly selected areas (400 pm² each).

[00242] Results indicated that compared to bare epoxy, SPC, and FRC coatings, both 2K-0 and 2K-1 surface coating composition according to aspects of the present disclosure showed nearly full resistance against ULVA zoospore, Cyclotella, and Navicula diatom adhesions, significantly outperforming the commercial antifouling coating controls, see Figure 5.

[00243] Surface coating composition according to aspects of the present disclosure were further compared with commercial coating controls in a lab-based mussel walking assay. Mussels play a major role in marine macro-organisms. These creatures attach indiscriminately to all solid surfaces via adhesive elastomeric protein-based filaments (byssal threads), which enable mussels to adhere to virtually any surface, including metals, minerals, plastics, cement, and even low-surface-energy fluoropolymers.

[00244] Live Canadian mussels were obtained commercially. They were randomly placed on the testing plates containing four evenly coated areas with epoxy coating, SPC, FRC and a “2K-0” surface coating composition according to aspects of the present disclosure. The movements of the mussels were tracked every few hours for up to 3 days. [00245] Figure 6 shows results obtained and indicate that, over time, mussels escaped only the “2K-0” coating area while all the rest of them stayed on the epoxy, SPC, and FRC coating areas.

[00246] Surface coating compositions resist marine fouling

[00247] Surface coating composition according to aspects of the present disclosure, designated 2K-0 and 2K-1, were further compared with commercial coating controls under sea conditions with severe marine fouling issues: i.e. in the presence of algae, seaweed, barnacles, etc., as well as fish eggs, crabs and tiny shrimps.

[00248] A group of epoxy-coated steel plates were evenly coated with 2K coatings, commercial SPC, commercial FRC, or without further coating (bare epoxy paint control) and were immersed ~ 0.5 meters deep into seawater (attached to a floating raft). During each time point evaluation, the plate surface was gently washed with flowing water or wiped by gloves.

[00249] The fouling situations were graded according to the ASTM D5479 - 94 and ASTM D3623 - 78a. In particular, for counting and calculating purposes, fouling presented on the substrate or on the epoxy bottom undercoats, or 1 cm from all edges of the coating area because of the edge effect was ignored. A test surface free of fouling was awarded a rating of 100, the highest achievable score. The presence of algal spores and other biological slimes was disregarded. The rating was reduced to 95 if only incipient fouling is present. When matured forms of fouling were present, the rating was calculated by subtracting from 95 the sum of the number of individuals presented and percent surface covered by colonial forms.

[00250] Results shown in Figures 7A and 7B show that surface coating compositions according to aspects of the present disclosure outperformed FRC in resisting marine fouling after 3 months of static immersion, and performed equally to copper SPC after 1.5 months of immersion. [00251] Negatively charged component in the coating formulation for reduction of mud adhesion

[00252] Mud adhesion is tested as described in this example. A mud and/or sand containing suspension is typically negatively charged, as indicated by Table 1 where zeta potentials for sea water, sea mud, sand, and their combinations are shown.

[00253] Inclusion of a negatively charged monomer in a surface coating composition according to aspects of the present disclosure reduces mud adhesion on the coating. A mud suspension (lOg/L, obtained locally in Detroit) was prepared with sea water and incubated with coatings according to aspects of the present disclosure described above, and control surfaces (SPC as a positive control, epoxy as a negative control) for 6 hours under a stirring condition (200 rpm). Each coating sample was then taken out carefully, gentally washed, and sonicated for 10 min to release the adhered mud into 2 ml sea water. The obtained media were further analyzed with an UV-vis spectrometer for their absorbance at 600nm as a measurement for the level of mud adhesion (higher absorbance values represent higher level of mud adhesion on the sample surface). Results indicate that the epoxy coating had extremely low level of mud adhesion (Absorbance value of 0.005±0.0006 (mean±sandard deviation)) compared to SPC coating having a drastically high level of mud adhesion (Absorbance of 0.277±0.08). Surface coating compositions according to aspects of the present disclosure containing acrylic acid (AA) as an antimud component in general showed a great anti-mud performance (Figure 9). When 5 or 10 wt% of acrylic acid was used in the curable top coat composition, the resulted coating showed a slightly higher mud adhesion relatively to epoxy (Absorbance of 0.03±0.002 and 0.05±0.003 for 5wt% AA and 10wt% AA samples, respectively), which was statistically significant in a One-way ANOVA test, but the mud adhesion level was far below SPC. Further increasing the wt% of acrylic acid in the curable top coat composition such as to 30 wt% and 50 wt% resulted a reduction of mud adhesion to a level not statistically significant from the epoxy coating, the negative control.

[00254] Figure Descriptions

[00255] Figure 1 is a schematic diagram of a coating according to aspects of the present disclosure including a top coat 1, and a primer coat 2, the combination disposed on a substrate 3.

[00256] Figures 2A and 2B show SEM images of a cross-section of a coating according to aspects of the present disclosure including a top coat 4, and a primer coat 5, scale bar = 10 pm.

[00257] Figure 3 is a graph showing the water contact angle on the top coat surface of a coating according to aspects of the present disclosure (2K-1). The coating surface consistently showed a water contact angle of about 0° at different time points after continuous shearing (1300rpm) in sea water at room temperature.

[00258] Figure 4 is a graph showing anti-fouling properties of coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, assessed by resistance to human fibrinogen (Fg) absorption, compared to epoxy, SPC, and FRC commercial marine coatings. Absorption level on bare epoxy samples was considered as 100%. All data are presented as mean of replicates (n=3). Statistical analysis: one-way ANOVA with Tukey's multiple comparisons. ***: p < 0.0002. ****: p < 0.0001.

[00259] Figure 5A shows representative SEM images of coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, compared to epoxy, SPC, and FRC commercial marine coatings after 24 h and 14 days culture in ULVA, Cyclotella, or Navicula suspension at shaking conditions, scale bar = 10 pm.

[00260] Figures 5B and 5C are graphs showing the calculated density of adhesion for ULVA zoospores after 24 hours and 14 days culture, respectively, for coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, compared to epoxy, SPC, and FRC commercial marine coatings. All data are presented as the mean of random selected region (n=5). Statistical analysis showed that differences between coatings according to aspects of the present disclosure and the commercial marine coatings were statistically significant in all groups (statistical analysis: unpaired One- Way ANOVA with Tukey's multiple comparisons, p<0.03).

[00261] Figures 5D and 5E are graphs showing the calculated density of adhesion for Cyclotella after 24 hours and 14 days culture, respectively, for coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, compared to epoxy, SPC, and FRC commercial marine coatings. All data are presented as the mean of random selected region (n=5). Statistical analysis showed that differences between coatings according to aspects of the present disclosure and the commercial marine coatings were statistically significant in all groups (statistical analysis: unpaired One- Way ANOVA with Tukey's multiple comparisons, p<0.03).

[00262] Figures 5F and 5G are graphs showing the calculated density of adhesion for Navicula after 24 hours and 14 days culture, respectively, for coatings according to aspects of the present disclosure, examples designated 2K-0 and 2K-1, compared to epoxy, SPC, and FRC commercial marine coatings. All data are presented as the mean of random selected region (n=5). Statistical analysis showed that differences between coatings according to aspects of the present disclosure and the commercial marine coatings were statistically significant in all groups (statistical analysis: unpaired One- Way ANOVA with Tukey's multiple comparisons, p<0.03).

[00263] Figure 6 shows images illustrating the ability of mussels to walk on coatings according to aspects of the present disclosure, example designated 2K-0, compared to epoxy, SPC, and FRC commercial marine coatings. For this example, six live Canadian mussels were placed on a sample plate coated with the indicated coating. The positions of the mussels were recorded over three days of observation. This test was performed in sea water, using periodic light conditions, and at room temperature. As shown in these images, mussels initially placed on a coating according to aspects of the present disclosure moved off of the coating, while mussels on other coatings did not move significantly.

[00264] Figures 7A and 7B

[00265] Results of tests of exposure of 2K coating vs. FRC to seawater in natural conditions for up to 3 months are shown in Figure 7A. Results of tests of exposure of 2K coating vs SPC to seawater in natural conditions for up to 1.5 months are shown in Figure 7B. 2K-0 has 0% crosslinking for the top coat. 2K-1 has 1% crosslinking for the top coat. Uncoated area on the panel was epoxy bottom paint. The coating samples were attached to a floating raft and washed with flowing water/wiping gently before visual examination at each time point as indicated. The contamination of the sample and the percentage of the surface coverage by fouling were recorded for scoring according to (ASTM D5479-94 and ASTM D3623-78a). Higher score (100 maximum) indicates higher anti-marine fouling performance. 2K-0 and 2K-1 surfaces were also found free of mud adhesion.

[00266] Figure 8 schematically shows methods and surface coating compositions 100 according to aspects of the present disclosure wherein the resin includes “resin” which is epoxy resin or urethane resin modified to include reactive double bonds (Resin-C=C) and hardener (H) modified to include reactive double bonds (H-C=C), or epoxy resin or urethane resin modified to include reactive double bonds (Resin-C=C) and hardener (H) without reactive double bonds, or “resin” which is epoxy resin or urethane resin without reactive double bonds (Resin) and hardener (H) modified to include reactive double bonds (H-C=C). A curing reaction 6 is performed to produce a cured primer containing reactive double bonds (Primer-C=C). zwitterionic monomer containing reactive double bonds (ZM-C=C) and/or hydrophilic monomer containing reactive double bonds (HM- C=C) are polymerized by a polymerization reaction 7 to produce a topcoat 8 and an interface 9 wherein the polymerization reaction includes reaction of ZM-C=C and/or HM-C=C with the polymerizable double bonds of primer layer 10 (Primer-C=C), thus covalently bonding the topcoat layer 8 to the primer layer 10.

[00267] Figure 9 shows mud adhesion level on coating samples as determined by UV-vis absorbance experiment. 5wt% AA, 10wt% AA, 30wt% AA and 50wt% AA represent coating compositions containing a primer layer of cured epoxy based on Interlux VC performance modified with acrylated epoxy (Allnex Ebecryl 3605) and a top coat layer resulted from a curable top coat composition, a solution in water, containing 50wt% zwitterionic CBAA monomer, lwt% MBAA crosslinker (relative to CBAA), 5wt%, 10wt%, 30wt% or 50wt% of anti-mud acrylic acid (AA) monomer (relative to CBAA), 3wt% ammonium persulfate (APS as initiator, relative to CBAA)) and lwt% tetramethylethylenediamine (TMEDA as catalyst or accerlator, relative to CBAA) according to aspects of the present disclosure described above. One-way ANOVA was conducted for statistical analysis: ****■. p<0.0001; ns: not statistically significant at p < 0.05.

[00268] Items

[00269] Item 1. A surface coating composition, comprising: a primer layer, the primer layer comprising a reaction product of: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds; and a top coat layer, the top coat layer comprising one or more of: a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer and a hydrophilic hydrogel, wherein the top coat layer and the primer layer are covalently bonded to each other by a reaction product comprising a reaction product of polymerizable double bonds of one or more of: zwitterionic monomers, hydrophilic monomers, or a combination of both thereof, with the polymerizable double bonds of the primer layer.

[00270] Item 2. The surface coating composition of item 1, wherein the primer layer comprises a reaction product of an epoxy resin and a hardener, wherein at least one of: the epoxy resin and the hardener, comprises reactive moieties comprising polymerizable double bonds.

[00271] Item 3. The surface coating composition of item 1, wherein the primer layer comprises a reaction product of a urethane resin and a hardener, wherein at least one of: the urethane resin and the hardener, comprises reactive moieties comprising polymerizable double bonds.

[00272] Item 4. The surface coating composition of any of items 1 to 3, wherein the reactive moieties comprising polymerizable double bonds are selected from the group consisting of: methacrylate, acrylate, vinyl, and allyl.

[00273] Item 5. The surface coating composition of any of items 1 to 4, disposed on a surface of a substrate.

[00274] Item 6. The surface coating composition of item 5, wherein the substrate is a surface of a boat or water-exposed structure.

[00275] Item 7. The surface coating composition of item 6, wherein the substrate is a surface of a boat vessel or a surface of a water-exposed structure selected from the group consisting of: boat hulls, boat decks, offshore drilling platforms, pipelines, bridges, storage vessels, underwater cables, and underwater equipment. [00276] Item 8. The surface coating composition of any of items 1 to 7, wherein the zwitterionic polymer or zwitterionic hydrogel comprises a zwitterionic polymer having the structural formula: III, IV, or VI:

[00277] Item 9. The surface coating composition of any of items 1 to 8, wherein the hydrophilic hydrogel comprises a polymer having the structural formula: VII or VIII:

where Ri, R2, R3, R4, and Rs are each independently selected from hydrogen, alkyl, and aryl groups; Li is a linker that covalently couples a cationic center to the polymer backbone; L2 is a linker that covalently couples the cationic center to an anionic group; A(=O)O" is the anionic group; A is C, S, SO, P, or PO; X" is a counter ion associated with the cationic center; M⁺ is a metal ion, an ammonium ion, or an organic ion; L3 is a linker that covalently couples two polymer backbones; n is an integer in the range of 2 to about 100,000; m is a positive non-zero integer; and m/n is in the range of 0.1% - 99.9%;

where Ri, R2, and R3 are each independently selected from hydrogen, alkyl, and aryl groups; Li is a linker that covalently couples the polymer sidechain to the polymer backbone; X’ is a counter ion associated with the cationic center; M⁺ is a metal ion, an ammonium ion, or an organic ion; L3 is a linker that covalently couples two polymer backbones; n is an integer in the range of 2 to about 100,000; m is a positive non-zero integer; and m/n is in the range of 0.1% - 99.9%.

[00278] Item 10. The surface coating composition of any of items 1 to 9, wherein the top coat further comprises an anti-mud component.

[00279] Item 11. The surface coating composition of any of items 1 to 10, wherein the top coat comprises a reaction product of: 1) one or more of: a zwitterionic monomer and a hydrophilic monomer; and 2) an anti-mud component which comprises a negatively charged monomer and/or a negatively-charged crosslinker, wherein the reaction product resists mud accumulation on a substrate coated with the surface coating composition.

[00280] Item 12. The surface coating composition of any of items 1 to 11, wherein the anti-mud component is selected from the group consisting of: one or more of negatively charged monomers of either acid or salt forms of the following: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2-propene-l -sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4- vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, phosphoric acid 2-hydroxyethyl methacrylate ester, and a derivative of one or more of the foregoing.

[00281] Item 13. The surface coating composition of any of items 1 to 12, wherein the hydrophilic polymer and/or hydrophilic hydrogel consists of, or comprises, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative. [00282] Item 14. The surface coating composition of any of items 1 to 13, wherein the top coat layer consists of a zwitterionic polymer and/or a zwitterionic hydrogel.

[00283] Item 15. The surface coating composition of any of items 1 to 14, wherein the epoxy resin comprises epoxy acrylate.

[00284] Item 16. A method of coating a substrate, comprising: applying a curable primer composition to the substrate, the curable primer composition comprising: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds; curing the curable primer composition, forming a primer layer; applying a curable top coat composition onto the primer layer, the curable top coat composition comprising one or more of: zwitterionic monomers and hydrophilic monomers, wherein the zwitterionic monomers and/or hydrophilic monomers comprise polymerizable double bonds, thereby forming a curable bilayer composition on the substrate; and curing the bilayer composition, thereby forming a surface coating composition comprising the primer layer and a top coat layer, wherein the top coat layer and the primer layer are covalently bonded to each other by a reaction product of polymerizable double bonds of the zwitterionic monomers and/or hydrophilic monomers of the top coat layer with the polymerizable double bonds of the primer layer.

[00285] Item 17. The method of coating a substrate according to item 16, wherein the primer layer is a primer layer according to any of items 1 to 15.

[00286] Item 18. The method of coating a substrate according to item 16 or 17, wherein the top coat layer is a top coat layer according to any of items 1 to 15.

[00287] Item 19. The method of coating a substrate of any of items 16 to 18, wherein the curable top coat composition further comprises an anti-mud component.

[00288] Item 20. The method of coating a substrate of any of items 16 to 19, wherein the curable top coat composition comprises: 1) one or more of: a zwitterionic monomer and a hydrophilic monomer; and 2) an anti-mud component which comprises a negatively charged monomer and/or crosslinker, wherein the reaction product resists mud accumulation on a substrate coated with the surface coating composition.

[00289] Item 21. The method of coating a substrate of any of items 16 to 20, wherein the anti-mud component is a negatively charged monomer of either acid or salt forms of the following: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2-propene- 1 -sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4-vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, and phosphoric acid 2-hydroxyethyl methacrylate ester; a derivative of one or more thereof, and a combination of two or more thereof.

[00290] Item 22. The method of coating a substrate of any of items 16 to 21, wherein the hydrophilic polymer and/or hydrophilic hydrogel consists of, or comprises, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative.

[00291] Item 23. The method of coating a substrate of any of items 16 to 22, wherein the top coat layer consists of a zwitterionic polymer and/or a zwitterionic hydrogel.

[00292] Item 24. The method of coating a substrate of any of items 16 to 23, wherein the epoxy resin comprises epoxy acrylate.

[00293] Item 25. A kit for coating a substrate, comprising: a first component of a curable primer composition comprising an epoxy resin or a urethane resin; a second component of a curable primer composition comprising a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds, and wherein the first component and second component of the curable primer composition are separately packaged; and a first component of a curable top coat composition, the first component of the curable top coat composition comprising one or more of: a zwitterionic monomer, a hydrophilic monomer, a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer and a hydrophilic hydrogel, wherein mixing of the first and second components of the curable primer composition produces a curable primer composition, which, applied to a substrate and cured produces a primer layer, and wherein the curable top coat composition, when applied to the primer layer, produces a curable bilayer composition including a primer layer and a top coat layer, and wherein the top coat layer and the primer layer covalently bond to each other by a reaction product of polymerizable double bonds of one or more of: zwitterionic monomers, hydrophilic monomers, or a combination of both thereof, with the polymerizable double bonds of the primer layer.

[00294] Item 26. The kit for coating a substrate according to item 25, further comprising an anti-mud component, wherein the anti-mud component comprises one or more of: a negatively-charged monomer and a negatively-charged crosslinker,

[00295] Item 27. The kit for coating a substrate according to item 25 or item 26, further comprising: a crosslinker and/or a thickener. [00296] Item 28. The kit for coating a substrate according to any of items 25 to 27, wherein the anti-mud component is a negatively charged monomer of either acid or salt forms of the following: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2- propene-1 -sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l- sulfonic acid, sodium acrylate, sodium 4-vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, and phosphoric acid 2-hydroxyethyl methacrylate ester; a derivative of one or more thereof, and a combination of two or more thereof.

[00297] Item 29. The kit for coating a substrate according to any one of items 25 to

28, further comprising a second component of a curable top coat composition, the second component of the curable top coat composition comprising an initiator, wherein the first component of the curable top coat composition and second component of the curable top coat composition are packaged separately.

[00298] Item 30. The kit for coating a substrate according to any one of items 25 to

29, wherein the first component of the curable top coat composition comprises polymerizable double bonds containing monomers and/or crosslinkers.

[00299] Item 31. The kit for coating a substrate according to any one of items 25 to

30, wherein the hydrophilic polymer and/or hydrophilic hydrogel consists of, or comprises, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative.

[00300] Item 32. The kit for coating a substrate according to any one of items 25 to

31, wherein the top coat layer consists of a zwitterionic polymer and/or a zwitterionic hydrogel.

[00301] Item 33. The kit for coating a substrate according to any one of items 25 to

32, wherein the epoxy resin comprises epoxy acrylate.

[00302] Item 34. A surface coating composition substantially as shown or described herein.

[00303] Item 35. A method of coating a substrate substantially as shown or described herein.

[00304] Item 36. A kit for coating a substrate substantially as shown or described herein. [00305] Any patents or publications mentioned in this specification are incorporated herein by reference to the same extent as if each individual publication is specifically and individually indicated to be incorporated by reference.

[00306] The compositions and methods described herein are presently representative of preferred embodiments, exemplary, and not intended as limitations on the scope of the invention. Changes therein and other uses will occur to those skilled in the art. Such changes and other uses can be made without departing from the scope of the invention as set forth in the claims.

Claims

- 64 - CLAIMS

1. A surface coating composition, comprising: a primer layer, the primer layer comprising a reaction product of: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds; and a top coat layer, the top coat layer comprising one or more of: a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer and a hydrophilic hydrogel, wherein the top coat layer and the primer layer are covalently bonded to each other by a reaction product comprising a reaction product of polymerizable double bonds of one or more of: zwitterionic monomers, hydrophilic monomers, or a combination of both thereof, with the polymerizable double bonds of the primer layer.

2. The surface coating composition of claim 1, wherein the primer layer comprises a reaction product of an epoxy resin and a hardener, wherein at least one of: the epoxy resin and the hardener, comprises reactive moieties comprising polymerizable double bonds.

3. The surface coating composition of claim 1, wherein the primer layer comprises a reaction product of a urethane resin and a hardener, wherein at least one of: the urethane resin and the hardener, comprises reactive moieties comprising polymerizable double bonds.

4. The surface coating composition of any of claims 1 to 3, wherein the reactive moieties comprising polymerizable double bonds are selected from the group consisting of: methacrylate, acrylate, vinyl, and allyl.

5. The surface coating composition of any of claims 1 to 4, disposed on a surface of a substrate.

6. The surface coating composition of claim 5, wherein the substrate is a surface of a boat or water-exposed structure. - 65 -

7. The surface coating composition of claim 6, wherein the substrate is a surface of a boat vessel or a surface of a water-exposed structure selected from the group consisting of: boat hulls, boat decks, offshore drilling platforms, pipelines, bridges, storage vessels, underwater cables, and underwater equipment.

8. The surface coating composition of any of claims 1 to 7, wherein the zwitterionic polymer or zwitterionic hydrogel comprises a zwitterionic polymer having the structural formula: III, IV, or VI:

(ill), where each Ri, R2, and R3 is independently a C1-C30 straight chain or branched, optionally substituted, alkyl group, where R2 and R3 taken together with N+ form a cationic center, where M+ is a metal ion, an ammonium ion, or an organic ion, Li is a linker that covalently couples a polymer sidechain to a polymer backbone, A(=O)O- is an anionic group where A is C, S, SO, P, or PO, L2 is a linker that covalently couples the cationic center to the anionic group, X- is a counter ion associated with the cationic center, and n is an integer in the range of 2 to 100,000;

- 66 - where M is a monomeric repeating unit, L4 is a linker that covalently couples a polymer sidechain to a polymer backbone, n is an integer in the range of 2 to 100,000, X" is a counter ion associated with a cationic center, and Y⁺ is a counter ion associated with an anionic center;

9. The surface coating composition of any of claims 1 to 8, wherein the hydrophilic hydrogel comprises a polymer having the structural formula: VII or VIII:

where Ri, R2, R3, R4, and R5 are each independently selected from hydrogen, alkyl, and aryl groups; Li is a linker that covalently couples a cationic center to the polymer backbone; L2 is a linker that covalently couples the cationic center to an anionic group; A(=O)O" is the anionic group; A is C, S, SO, P, or PO; X" is a counter ion associated with the cationic center; M⁺ is a metal ion, an ammonium ion, or an organic ion; L3 is a linker that covalently couples two polymer backbones; n is an integer in the range of 2 to about 100,000; m is a positive non-zero integer; and m/n is in the range of 0.1% - 99.9%; - 67 -

where Ri, R2, and R3 are each independently selected from hydrogen, alkyl, and aryl groups; Li is a linker that covalently couples the polymer sidechain to the polymer backbone; X' is a counter ion associated with the cationic center; M⁺ is a metal ion, an ammonium ion, or an organic ion; L3 is a linker that covalently couples two polymer backbones; n is an integer in the range of 2 to about 100,000; m is a positive non-zero integer; and m/n is in the range of 0.1% - 99.9%.

10. The surface coating composition of any of claims 1 to 9, wherein the top coat further comprises an anti-mud component.

11. The surface coating composition of any of claims 1 to 10, wherein the top coat comprises a reaction product of: 1) one or more of: a zwitterionic monomer and a hydrophilic monomer; and 2) an anti-mud component which comprises a negatively charged monomer and/or a negatively-charged crosslinker, wherein the reaction product resists mud accumulation on a substrate coated with the surface coating composition.

12. The surface coating composition of any of claims 1 to 11, wherein the anti-mud component is selected from the group consisting of: one or more of negatively charged monomers of either acid or salt forms of the following: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2-propene-l -sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4- vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, phosphoric acid 2-hydroxyethyl methacrylate ester, and a derivative of one or more of the foregoing. - 68 -

13. The surface coating composition of any of claims 1 to 12, wherein the hydrophilic polymer and/or hydrophilic hydrogel consists of, or comprises, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative.

14. The surface coating composition of any of claims 1 to 13, wherein the top coat layer consists of a zwitterionic polymer and/or a zwitterionic hydrogel.

15. The surface coating composition of any of claims 1 to 14, wherein the epoxy resin comprises epoxy acrylate.

16. A method of coating a substrate, comprising: applying a curable primer composition to the substrate, the curable primer composition comprising: 1) an epoxy resin or a urethane resin and 2) a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds; curing the curable primer composition, forming a primer layer; applying a curable top coat composition onto the primer layer, the curable top coat composition comprising one or more of: zwitterionic monomers and hydrophilic monomers, wherein the zwitterionic monomers and/or hydrophilic monomers comprise polymerizable double bonds, thereby forming a curable bilayer composition on the substrate; and curing the bilayer composition, thereby forming a surface coating composition comprising the primer layer and a top coat layer, wherein the top coat layer and the primer layer are covalently bonded to each other by a reaction product of polymerizable double bonds of the zwitterionic monomers and/or hydrophilic monomers of the top coat layer with the polymerizable double bonds of the primer layer.

17. The method of coating a substrate according to claim 16, wherein the primer layer is a primer layer according to any of claims 1 to 15.

18. The method of coating a substrate according to claim 16 or 17, wherein the top coat layer is a top coat layer according to any of claims 1 to 15.

19. The method of coating a substrate of any of claims 16 to 18, wherein the curable top coat composition further comprises an anti-mud component.

20. The method of coating a substrate of any of claims 16 to 19, wherein the curable top coat composition comprises: 1) one or more of: a zwitterionic monomer and a hydrophilic monomer; and 2) an anti-mud component which comprises a negatively charged monomer and/or crosslinker, wherein the reaction product resists mud accumulation on a substrate coated with the surface coating composition.

21. The method of coating a substrate of any of claims 16 to 20, wherein the anti-mud component is a negatively charged monomer of either acid or salt forms of the following: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2-propene-l- sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l -sulfonic acid, sodium acrylate, sodium 4-vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, and phosphoric acid 2-hydroxyethyl methacrylate ester; a derivative of one or more thereof, and a combination of two or more thereof.

22. The method of coating a substrate of any of claims 16 to 21, wherein the hydrophilic polymer and/or hydrophilic hydrogel consists of, or comprises, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative.

23. The method of coating a substrate of any of claims 16 to 22, wherein the top coat layer consists of a zwitterionic polymer and/or a zwitterionic hydrogel.

24. The method of coating a substrate of any of claims 16 to 23, wherein the epoxy resin comprises epoxy acrylate.

25. A kit for coating a substrate, comprising: a first component of a curable primer composition comprising an epoxy resin or a urethane resin; a second component of a curable primer composition comprising a hardener, wherein at least one of: the epoxy resin, urethane resin, and the hardener, comprises reactive moieties comprising polymerizable double bonds, and wherein the first component and second component of the curable primer composition are separately packaged; and a first component of a curable top coat composition, the first component of the curable top coat composition comprising one or more of: a zwitterionic monomer, a hydrophilic monomer, a zwitterionic polymer, a zwitterionic hydrogel, a hydrophilic polymer and a hydrophilic hydrogel, wherein mixing of the first and second components of the curable primer composition produces a curable primer composition, which, applied to a substrate and cured produces a primer layer, and wherein the curable top coat composition, when applied to the primer layer, produces a curable bilayer composition including a primer layer and a top coat layer, and wherein the top coat layer and the primer layer covalently bond to each other by a reaction product of polymerizable double bonds of one or more of: zwitterionic monomers, hydrophilic monomers, or a combination of both thereof, with the polymerizable double bonds of the primer layer.

26. The kit for coating a substrate according to claim 25, further comprising an anti-mud component, wherein the anti-mud component comprises one or more of: a negatively-charged monomer and a negatively-charged crosslinker,

27. The kit for coating a substrate according to claim 25 or claim 26, further comprising: a crosslinker and/or a thickener.

28. The kit for coating a substrate according to any of claims 25 to 27, wherein the anti-mud component is a negatively charged monomer of either acid or salt forms of the following: 3-sulfopropyl methacrylate potassium, acrylic acid, 2-methyl-2- propene-1 -sulfonic acid sodium salt, sodium 4-vinylbenzenesulfonate, 2-propene-l- sulfonic acid, sodium acrylate, sodium 4-vinylbenzoic acid, y,y-dimethylallyl phosphate ammonium salt, diethyl allyl phosphate, and phosphoric acid 2-hydroxyethyl methacrylate ester; a derivative of one or more thereof, and a combination of two or more thereof.

29. The kit for coating a substrate according to any one of claims 25 to 28, further comprising a second component of a curable top coat composition, the second component of the curable top coat composition comprising an initiator, wherein the first component of the curable top coat composition and second component of the curable top coat composition are packaged separately.

30. The kit for coating a substrate according to any one of claims 25 to 29, wherein the first component of the curable top coat composition comprises polymerizable double bonds containing monomers and/or crosslinkers.

31. The kit for coating a substrate according to any one of claims 25 to 30, wherein the hydrophilic polymer and/or hydrophilic hydrogel consists of, or comprises, a polymeric reaction product of mixed charge monomers, wherein the net charge of the polymeric reaction product is neutral or negative.

32. The kit for coating a substrate according to any one of claims 25 to 31, wherein the top coat layer consists of a zwitterionic polymer and/or a zwitterionic hydrogel.

33. The kit for coating a substrate according to any one of claims 25 to 32, wherein the epoxy resin comprises epoxy acrylate.

34. A surface coating composition substantially as shown or described herein.

35. A method of coating a substrate substantially as shown or described herein.

36. A kit for coating a substrate substantially as shown or described herein.