WO2015131032A1

WO2015131032A1 - Tie coat composition and antifouling system

Info

Publication number: WO2015131032A1
Application number: PCT/US2015/017966
Authority: WO
Inventors: Wen LIAO
Original assignee: Momentive Performance Materials Inc.
Priority date: 2014-02-28
Filing date: 2015-02-27
Publication date: 2015-09-03

Abstract

A multi-layer antifouling coating system comprising (a) a base coating for coating a substrate, (b) a tie coat layer, and (c) an antifouling coating composition adapted to be disposed over the base coating. The tie coat layer comprises a multi-functional silicon-containing material. In one embodiment, the multi-functional silicon-containing material comprises an amino functional siloxane and/or reaction products thereof. In one embodiment, the multi-functional silicon-containing material comprises a reaction product of an amino functional siloxane and an epoxy compound.

Description

TIE COAT COMPOSITION AND ANTIFOULING SYSTEM

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to and the benefit of U.S.

Provisional Patent Application No. 61/945,979 entitled "Tie Coat Composition and Antifoulmg System Comprising the Same," filed on February 28, 2014, the entire disclosure of which is incorporated herein by reference.

FIELD

[0002] The present technology provides an antifouling coating composition, a coating system comprising such antifouling compositions, and articles comprising such coating systems. The antifouling compositions and coating systems can be utilized on articles exposed to aquatic or marine environments and can provide antifouling properties to the article.

BACKGROUND

[0003] Biofouling or biological fouling is the undesirable accumulation of microorganisms, algae, plants, and animals on wetted surfaces. It is found in almost all environments where aqueous liquids are in contact with other materials. The specific and non-specific interactions of proteins and cells with artificial surfaces form the basis of many medical, biochemical, and biotechnological applications. In order to prevent unwanted deposition (or biofouling), any non-specific protein and cell adsorption has to be suppressed. Preventing biological deposits of proteins or bacteria plays a key role in the field of hygiene and in keeping clean surfaces permanently. In addition, unwanted biological deposits on large wetted surfaces, such as ship hulls, water tanks, offshore rigs, etc., and in inaccessible places, such as large pipe systems, represent a major economic problem. Biofouling on ship hulls, for example, can reduce the performance of the vessel in the water and increase its fuel consumption, which can significantly increase operating cost for ship owners and operators. As much as $50 billion in annual fuel saving has been realized by the shipping industry due to the use of antifouling coatings on ship hulls.

[0004] Conventional antifoulants are mostly toxic organometallic compounds or metals such as lead, arsenic, mercury, copper, tin, etc. These materials, however, can pose risks to the environment, and efforts have been made to find environmentally benign technologies.

[0005] The current antifouling technologies can be generally classified into four major categories: (1) biocidal antifouling paints containing a marine biocide, (2) non- biocidal electrical coatings, (3) non-biocidal antifouling paints, which almost exclusively function as fouling release, and (4) next generation fouling release products employing amphiphilic polymers or hydrogel materials to deter the settlement of microorganisms on a surface. Recently, hydrogel-forming coatings, in particular polyether-containing hydrogels, have been reported to be especially efficient in preventing marine fouling. Poly(ethyleneglycol) has been known to inhibit adhesion of protein "glue" secreted by the microorganism prior to establishing a thriving colony (see, for example, Merrill E. W., in Poly(ethylene glycol) Chemistry, Ed. J. M. Harris, pp 199-220, Plenum Press, New York: 1992; C.-G. Golander, Jamea N. Herron, Kap Lim, P. Claesson, P. Stenius, J. D. Andrade, in Poly(ethylene glycol) Chemistry, Ed. J. M. Harris, Plenum Press, New York: 1992). U.S. Pub. No. 2005/0031793 and 2009/0029043 describe the syntheses of multifunctional star shaped polymers and their use for the preparation of thin hydrogel containing surface coatings to actively suppress unspecific protein adsorption.

[0006] Silicone antifouling products, i.e., non-biocidal or amphiphilic or hydrogel fouling release technologies, rely on the non-stick feature to discourage the attachment of marine organisms. Because of the non-stick nature, typical silicone fouling release coatings do not adhere well to anticorrosion coatings, typically an epoxy coating, that are used to coat the surface of an article such as a ship's hull. Strong adhesion is important to have sufficient coating durability.

[0007] U.S. Patent Nos. 4,978,704 and 4,996,112 describe a one part RTV composition using a mixture of an aminosilane and an epoxysilane. U.S. Pub No. 2011/0250350 describes using aminosilanes mixed with silanol-terminated polydiorganosiloxane as a tie coat to improve adhesion. U.S. Pub. No. 2011/0250350 discloses adhesion improvement using bis(trialkoxysilyalky)amine and Ν,Ν'- bis(trialkoxysilylalkyl)alkylenediames in a silicone tie coat.

[0008] U.S. Patent No. 6,723,376 describes a coating process using a curable silicon- containing functional group that is capable of latent condensation reaction to form an undercoat and followed by coating a curable polymeric fouling inhibiting material. The curing of the fouling inhibiting material bonds the top coat to the undercoat by condensation reaction with the curable silicon-containing functional groups in the undercoat. U.S. Patent No. 5,691,019 discloses coating a fouling release layer onto an adhesion promoting anticorrosive layer, where the bonding of the fouling release layer to the anticorrosive layer is enabled by the incorporation of a curable aminosilicone fluid to the anticorrosive layer. The aminosilicone blooms to the interface between anticorrosive layer and fouling release layer to connect the two layers with respective chemical reactions of amines with epoxide of the epoxy layer and alkoxysilane with the silane or silanol of polydimethylsiloxane in the fouling release silicone layer. The incompatible nature of the aminosilicone in the epoxy formula helps the blooming of the aminosilicone. However, the incompatibility also drives up the requirement of the amount of aminosilicone. The aminosilicone molecules tend to aggregate into large globules sporadically scattering on the epoxy surface. Bonding can only occur at the sparsely area where aminosilicone globules cover. It typically requires a very large amount of aminosilicone to fully cover the epoxy surface in order to create sufficient bonding. As a result, the use of aminosilicone for adhesion is not efficient.

[0009] To overcome the poor adhesion of silicone to epoxy coatings, a tie coat layer is often employed between epoxy and silicone coating layers. While tie coat layers are configured to promote adhesion of the fouling layer to the anti corrosion base layer, many tie coat layers do not provide sufficient adhesion, and the fouling release coating may more readily be removed or prone to chipping.

SUMMARY

[0010] In one aspect, the present technology provides a coating system for coating an article and providing a surface exhibiting an antifouling property. In one aspect, the antifouling coating system comprises (a) a base coating layer, (b) a tie coat layer, and (c) an antifouling coating layer. The tie coat layer comprises a multi- functional silicon- containing material and/or reaction products thereof. The tie coat layer provides and promotes adhesion of the antifouling coating layer and the base coating layer.

[0011] In one aspect, the present technology provides antifouling coating system comprising a base coat layer; a tie coat layer overlying the base coat layer; and a fouling release layer overlying the tie coat layer, wherein the tie coat layer comprises a multi-functional silicon-containing material.

[0012] In one embodiment, the multi-functional silicon containing material comprises an adhesion promoter.

[0013] In one embodiment, the multi-functional silicon containing material comprises an amino functional siloxane, a reaction product thereof, or combinations of two or more thereof.

[0014] In one embodiment, the multi-functional silicon containing material comprises a reaction product of an amino functional siloxane and an epoxy compound.

[0015] In one embodiment, the multi-functional silicon containing material comprises an amino functional material of the formula:

(R¹0)a(R -a-Si-M-(Si(R¹)₂0)_r-(Si(R¹)(Ol/₂)(0))t-(Si(X)(Ol/₂)(0))v-Si(R¹)₂-M-Si(OR¹)a(R -a where each occurrence of R¹ is independently H or an alkyl radical, M is independently R² or oxygen; r is 0 - 1000; t is 1 to 20; v is 0 to 20; X is -R²-(N(R¾b(Y)b- R²)_c-N(R³)2-b(Y)b; a is 1-3; b is 0 - 2; c is 0 - 5; Y is independently R¹ or an organic radical with an epoxide at one terminal; each occurrence of R² is independently a C2- C10 alkylene; and each occurrence of R³ independently H or an alkyl radical.

[0016] In one embodiment, b is 0. In one embodiment, the amino functional material is of the formula:

[0017] In one embodiment, Y is chosen from an organic radical of the formula -CH₂CH(OH)CH₂-0-P; P is:

-(C6HhR⁵(4-h)-CR2⁶-C6HhRVh)-0-CH2CH(OH)CH₂ )i-C6HhR⁵(4-h)-CR2⁶-C6HhR⁵(4-h)-0-Z; where h is 0-4 ; each occurrence of R⁵ is independently chosen from a Ci-Cio alkyl or a substituted or unsubstituted phenyl; each occurrence of R⁶ is independently H or Ci- Cio alkyl; i is 0-100; and Z is

where m is 1-20.

[0018] In one embodiment, the amino functional compound is an epoxy modified compound of the formula:

[0019] In one embodiment, the multi-functional silicon-containing material comprises an adhesion promoter of the formula U-Q-R⁸-SiR⁵ R⁷(3-_g), wherein Q is -CH₂CH(OH)CH₂-0- or -CH₂CH(OH)CH₂-NR⁴-_; U is:

-(C6HhR )-CR2⁶-C6HhR⁵(4-h) -CH2CH(OH)CH2-0)i-C6HhR⁵(4- )-CR2⁶-C₆HhR⁵(4- )-0-Z; where each occurrence of R⁵ is independently chosen from a Ci to Cio alkyl or a substituted or un-substituted phenyl group; each occurrence of R⁷ is independently chosen from an alkoxy, an acetoxy, or a ketoxime radical; R⁸ is a Ci to C4 alkylene g is 0-2; h is 0-4; where R⁴ is H or -CH₂CH(OH)CH₂-U-; each occurrence of R⁶ is independently H or alkyl; i is 0-100; and Z is H, Q-R⁸-SiR⁵hR⁷(3-h), or

where m is 1-20.

[0020] In one embodiment, the adhesion promoter is chosen from a compound of the

or a combination thereof.

[0021] In one embodiment, the tie coat layer further comprises a binder and optionally a cure catalyst.

[0022] In another aspect, the present technology provides tie coat compositions.

[0023] In still another aspect, the present technology provides an article comprising the antifouling system. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is schematic of a fouling release coating system in accordance with an embodiment of the present technology.

DETAILED DESCRIPTION

[0025] The present technology provides an antifouling coating system. In one aspect, the antifouling coating system comprises (a) a base coating composition for coating a target substrate, (b) a tie coat layer, and (c) an antifouling coating composition. The tie coat layer comprises a multi-functional silicon-containing material and reaction products thereof.

[0026] The singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise.

[0027] As used herein, the terms "antifouling coating composition," "antifouling layer," "foul release coating," "fouling release coating," etc., and variants thereof can be used interchangeably and refer to a coating composition that is applicable to a surface and capable of preventing aquatic organisms from depositing (or fouling) and growing on the surface. Fouling release compositions and coatings can be employed as the fouling release coating of a fouling release or antifouling system.

[0028] Figure 1 illustrates an embodiment of a fouling release system 100 in accordance with an embodiment of the present technology. The fouling release system 100 comprises a base coating layer 110, a tie coat layer 120, and a fouling release topcoat layer 130. The fouling release system can be applied to a substrate 200 having a surface intended to be protected biological fouling. The tie coat layer 120 comprises a tie coat composition comprising a multi-functional silicon-containing material.

Tie Coat Composition

[0029] The tie coat layer comprises or is formed from a tie coat composition comprising a multi-functional silicon- containing material. The multi-functional silicon- containing material can comprise a multi-functional siloxane that is reactive with itself, silanes, reactive silicone polymers, epoxy resins, etc. Various multifunctional silicon-containing compounds can be employed, including those that are classified or used as adhesion promoters. The tie coat layer further comprises a binder material and optionally a cure promoting catalyst. [0030] In one embodiment, the multi-functional silicon-containing material employed in the tie-coat composition and layer comprises an amino functional silicon- containing compound, a condensation product, and/or a reaction product thereof. In one embodiment, the tie-coat composition comprises (a) a reaction product of (i) an amino functional silicone-containing compound, and (ii) an epoxy compound, (b) a binder, and (c) optionally a cure promoting catalyst.

[0031] In one embodiment, the tie-coat composition comprises an amino functional adhesion promoter of the Formula (1):

(R¹0)a(R¹)3-a-Si-M-(Si(R¹)₂0)_r-(Si(R¹)(Oi/₂)(0))t-(Si(X)(Oi/₂)(0))v-Si(R¹)₂-M-Si(OR¹)a(R¹)3-a (1) where R¹ is H or an alkyl radical; M is R² or oxygen; r is 0 - 1000; t is 1 to 20; v is 0 to 20; X is -R²-(N(R¹)i-b(Y)b-R²)c-N(R¹)₂-b(Y)b; a is 1 - 3; c is 0 - 5; b is 0 - 2; Y is R¹ or an organic radical with an epoxide at one terminal; R² is a C2-C10 alkylene; and R³ is 4 or an alkyl radical. In one embodiment, each occurance of R¹ and R³ is indepenently chosen from a C1-C10 alkyl radical; a C2- C6 alkyl radical; even a C3-C4 alkyl radical. In one embodiment, Rl is independently chosen from a C1-C4 alkyl radical and R³ is H.

[0032] In one embodiment, the Y group is an organic radical having at least one epoxy functional group. The organic radical may be an organic radical comprising at least one carbon atom. The organic radical may include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen or may be composed exclusively of carbon and hydrogen. The organic radical may include a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, halo alkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example, carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, etc. In one embodiment, Y is of the formula -CH₂CH(OH)CH₂-0-P; P is:

-(C6HhR⁵(4-h)- CR2⁶-C6HhR⁵(4-h)-0-CH2CH(OH)CH2-0)i-C6HhR⁵(4-h)-CR₂ ⁶-C6HhR⁵(4-h)-0-Z; where h is 0-4; each occurrence of R⁵ is independently chosen from a C1-C10 alkyl or a substituted phenyl; each occurrence of R⁶ is independently chosen from H or a C1-C10 alkyl; h is 0-4; i is 0-100; and Z is:

where m is 1-20.

[0033] In one embodiment, the amino functional silicon-containing material of

Formula (1) does not contain any Y groups, i.e., b is 0 the material represents an amino functional siloxane. A non-limiting example of a suitable amino functional siloxane is a compound of the Formula (2):

[0034] In one embodiment, the amino functional compound of Formula (1) is an epoxy modified compound comprising at least one Y group that is an organic radical with an epoxide at one terminal. The Y group can comprise, for example, a radical of partially ring opened bisphenol A diglycidoxy ether, bisphenol F diglycidoxy ether, epoxy cresol novolac, bis-(3,4-epoxycyclohexyl)adipate (e.g., Cyracure® UVR8128), 3,4- poxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (e.g., Cyracure® UVR6110).

[0035] In one embodiment, the epoxy modified adhesion promoter is of the

Formula (3):

[0036] In one embodiment, the antifouling coating composition comprises an adhesion promoter of the Formula (4):

U-Q-R⁸-SiR⁵ _gR⁷(3-g) (4)

wherein Q is -CH₂CH(OH)CH₂-0- or -CH₂CH(OH)CH₂-NR⁴-; U is:

-0-(C6HhRV )-CR2⁶-C6HhR⁵(4- )-0-CH2CH(OH)CH2-0)i-C6HhR⁵(4-h)-CR2⁶-C₆HhR⁵(4-h)-0-Z; where each occurrence of R⁵ is independently chosen from a Ci to Cio alkyl or a substituted or un- substituted phenyl group; R⁷ is independently chosen from an alkoxy, an acetoxy, or a ketoxime radical; R⁸ is a Ci to C₄ alkylene; g is 0-2; h is 0-4, R⁴ is H or -CH₂CH(OH)CH₂-U-; each occurrence of R⁶ is H or an alkyl; i is 0-100; and Z is

where m is 1-20.

[0037] In one embodiment, the adhesion promoter of the Formula 4 is an amino functional material that is the reaction product of Epon 828 from Momentive Specialty Chemicals and Silquest A- 1100 from Momentive Performance Materials having the Formula (4a) or (4b):

or

[0038] The tie coat composition further comprises a binder. The binder is not particularly limited and can be chosen from any material suitable as a binder. In one embodiment, the binder can be chosen from an epoxy compound, a curable silicon- containing compound, or a combination of two or more thereof. Examples of suitable silicon-containing compounds for the binder include, but are not limited to, curable polysiloxanes. Examples of curable poly siloxanes include, but are not limited to, condensation curable siloxanes or siloxanes curable via hydrosilylation. Non-limiting examples of suitable siloxanes include, hydrogen polydimethylsiloxane, hydroxyl functional polydimethylsiloxane, etc. Other suitable siloxanes include amino- or epoxy- functional siloxanes, e.g., amino- or epoxy-functional polydimethylsiloxanes.

[0039] Examples of suitable epoxy compounds for the binder include, but are not limited to, Bisphenol A/bisphenol F epoxides; bisphenol A epoxides; epoxy novolac resins; aliphatic epoxy resins; epoxy functional acrylic polymers; epoxy esters; reactive epoxy diluents; combinations of two or more thereof, etc. [0040] The tie coat composition can optionally comprise a cure promoting catalyst. The catalyst can be a catalyst suitable for promoting the curing of siloxanes. Advantageously, condensation catalysts can be employed. Suitable condensation catalysts include, but are not limited to, dialkyltin dicarboxylates such as dibutyltin dilaurate and dioctyltin dilaurate, tertiary amines, the stannous salts of carboxylic acids, such as stannous octoate and stannous acetate, and the like. Other useful catalysts include zirconium-containing, aluminum-containing, and bismuth-containing complexes such as KAT XC6212, K-KAT 5218 and K-KAT 348, supplied by King Industries, Inc., titanium chelates such as the TYZOR®. types, available from DuPont company, and the KR types, available from Kenrich Petrochemical, Inc., and other organometallic catalysts, e.g., those containing a metal such as Al, Zn, Co, Ni, Fe, etc.

[0041] The tie coat composition can comprise from about 0.1 weight percent to about 20 weight percent of the multi-functional silicon-containing material; from about 0.3 weight percent to about 5 weight percent of the multi-functional silicon- containing material; even from about 0.5 weight percent to about 2 weight percent of the multi-functional silicon- containing material. In one embodiment, the multifunctional silicon- containing material is a reaction product of an amino functional silicon compound and an epoxy compound, and the tie coat composition can comprise from about 0.1 weight percent to about 20 weight percent of the reaction product of the amino functional silicon compound and the epoxy compound; from about 0.3 weight percent to about 5 weight percent of the reaction product of the amino functional silicon compound and the epoxy compound; even from about 0.5 weight percent to about 2 weight percent of the reaction product of the amino functional silicon compound and the epoxy compound. The balance of the tie coat can comprise the binder, the catalyst, and/or other desirable materials. In one embodiment, the tie coat composition can comprise from about 80 weight percent to about 99.9 weight percent of the binder; from about 95 weight percent to about 99.7 weight percent of the binder; even from about 98 weight percent to about 99.5 weight percent of the binder. The tie coat composition can comprise from 0 weight percent to about 5 weight percent of the catalyst; from about 0.1 weight percent to about 2 weight percent of the catalyst; even from about 0.2 weight percent to about 1 weight percent of the catalyst. Here as elsewhere in the specification and claims, numerical values can be combined to form new and non-disclosed ranges. Base Coating Layer

[0042] The base coating is not particularly limited and can be chosen as desired for a particular purpose or intended application. The base coating layer may be any material suitable for forming an anticorrosion coating layer in an antifouling coating. Non-limiting examples include epoxy coatings, room-temperature curable silicone coatings, epoxy- silicone coatings, etc.

[0043] In one embodiment, the base coating layer is formed from an epoxy resin composition. The epoxy coating is generally formed by curing an epoxy resin composition that comprises an epoxy resin and an amine-based curing agent for curing the epoxy resin.

[0044] The epoxy resin can be chosen from any suitable epoxy resin including, but not limited to, bisphenol epoxy resin, glycidylester epoxy resin, glycidylamine epoxy resin, phenol novolac epoxy resin, cresol epoxy resin, dimer acid modified epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, epoxidized oil epoxy resin, etc., and combinations of two or more thereof. Non-limiting examples of suitable bisphenol epoxy resins include bisphenol A-type and F-type resins.

[0045] In one embodiment, the epoxy resin comprises from about 10 to about

60% by weight of the base coat composition; even from about 20 to about 50% by weight of the base coat composition.

[0046] Examples of commercially- available products that can be used as the epoxy resin include, but are not limited to, bisphenol epoxy resins such as Epikote and Epikure resins available from Momentive Specialty Chemicals, including, for example, Epikote 828, Epikote 834, Epikote 1001, Epikote 1004, Epikote 807, Epikote 4004P, Epikote 4007P, etc.

[0047] The base coat composition can, in one embodiment, also include an amine-based curing agent for curing the epoxy resin. Examples of suitable amine- based curing agents include, for example, modified Mannich amines formed by Mannich condensation reaction of phenols, formalin, and amine compounds, aliphatic polyamine, etc. In one embodiment, the amine-based curing agent may be present in an amount such that the number of amino groups of the amine-based curing agent is chemically equivalent to the number of epoxy groups of the epoxy resin. In another embodiment, the curing agent can be present in an amount providing an amino group to epoxy group ratio of 0.35:1 to 0.9:1; even 0.4:1 to 0.8:1. In still another embodiment, the amine-based curing agent can be present in an amount of about 10 to about 80 parts by weight with respect to 100 parts by weight of the epoxy resin. Here as elsewhere in the specification and claims, numerical values can be combined to form new and non-disclosed ranges.

[0048] Non-limiting examples of commercially-available products that can be used as the amine-based curing agent for the epoxy resin include Epikure 3292-FX60 (Momentive Specialty Chemicals), Raccamide TD966 (Dainippon Ink and Chemicals, Incorporated), Sunmide 307D-60 (Sanwa Chemical Co., Ltd.), etc.

[0049] Other suitable base coating materials include, but are not limited to, room-temperature curable silicone coatings, epoxy-silicone coatings, and silicone epoxy hybrid. These materials are not particularly limited and any compositions suitable for use in anti-fouling applications may be used to form the coating. Non-limiting examples of suitable room-temperature curable silicone compositions include those described in U.S. Patent Nos. 5,449,553; 6,165,620; and 7,666,514. Non-limiting examples of suitable epoxy-siloxane copolymers for the coating include those described in U.S. Patent No. 6,391,464.

[0050] The base coating composition can comprise other additives to the base coating with particular properties or characteristics as desired for a particular purpose or intended use. Suitable additives can include, for example, an antimicrobial agent, a pigment, an anti-sagging agent, etc.

[0051] The antimicrobial agent is not particularly limited and can generally be any antimicrobial agent that is compatible with the base coating compositions or the resulting hydrogels. Suitable antimicrobial agents include, but are not limited to, chlorhexidine salts such as chlorhexidine gluconate (CHG), parachlorometaxylenol (PCMX), triclosan, hexachlorophene, fatty acid monoesters and monoethers of glycerin and propylene glycol such as glycerol monolaurate, glycerol monocaprylate, glycerol monocaprate, propylene glycol monolaurate, propylene glycol monocaprylate, propylene glycol moncaprate, phenols, surfactants and polymers that include a (C12- C22) hydrophobe and a quaternary ammonium group or a protonated tertiary amino group, quaternary amino-containing compounds such as quaternary silanes and polyquaternary amines such as polyhexamethylene biguanide, silver containing compounds such as silver metal, silver salts such as silver chloride, silver oxide and silver sulfadiazine, methyl parabens, ethyl parabens, propyl parabens, butyl parabens, octenidene, 2-bromo-2-nitropropane-l,3 diol, or mixtures of two or more thereof.

[0052] Non-limiting examples of suitable quaternary ammonium compounds and phenolic antimicrobial agents include benzalkonium chlorides and/or substituted benzalkonium chlorides, di(C6- Ci4)alkyl di short chain (C1-4 alkyl and/or hydroxyalkyl) quaternaryammonium salts, N-(3-chloroallyl) hexaminium chlorides, benzethonium chloride, methylbenzethonium chloride, and cetylpyridinium chloride. Other suitable quaternary compounds include alkyl dimethylbenzylammonium chlorides, dialkylmethylbenzylammonium chlorides, and mixtures of two or more thereof. An example of a suitable quaternary amine containing silane is octadecyldimethyl(3- trimethoxysilyl propyl) ammonium chloride from Gelest, Inc.

[0053] Examples of suitable pigments include, but are not limited to, talc, silica, mica, clay, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, titanium dioxide, carbon black, etc., and combinations of two or more thereof. In one embodiment, the body pigment may be present in the composition in an amount, for example, of about 5 to about 80% by weight with respect to 100% by weight of the solid content of the base coat composition.

[0054] Examples of suitable anti-sagging agents include, but are not limited to, organic clay wax such as amine salt, stearate, lecithinate, alkylsulfonate of Al, Ca and Zn, polyethylene wax, amide wax, hydrogenated castor oil wax, polyamide wax, a mixture of hydrogenated castor oil wax and polyamide wax, synthetic particulate silica, polyethylene oxide wax, etc., and combinations of two or more thereof. The anti- sagging agent may be present in an amount of about 0.1 to about 5% by weight with respect to 100% by weight of the base coat composition.

[0055] Each of the above components can be combined with the epoxy resin composition according to any suitable method at the desired ratios during preparation of the composition, by using, for example, commercially-available materials. Further, in addition to the above components, optional components such as a solvent, a liquid hydrocarbon resin, a surfactant, an anticorrosive pigment, and the like, that are used in an epoxy resin anticorrosive coating film may be added in appropriate quantities if necessary. In one embodiment, the epoxy resin base coat composition may be provided as a two-part composition comprising a main agent component containing the epoxy resin and a curing agent component containing the amine-based curing agent.

Fouling Release Coating Layer

[0056] The system further comprises a fouling release coting layer. The fouling release coating layer is not particularly limited and can be chosen as desired for a particular purpose or intended application. Any material suitable as a fouling release coating can be employed in the present fouling release system. Non-limiting examples of materials used as fouling release coatings include silicone resin coatings, polytetrafluoroethylene coatings, silicone rubbers such as those disclosed, for example, in GB Patent 1,307,001 and U.S. Patent No. 3,702,778. In one embodiment, the antifouling coating comprises (a) a curable polyether-containing silane, and (b) a functionalized polymer. In one embodiment, the antifouling coating further comprises (c) an adhesion promoter. The antifouling coating composition can also comprise other optional components including, but not limited to an inorganic filler, a crosslinker, a condensation catalyst, etc., or combinations of two or more thereof. In one embodiment, the fouling release coating can comprise a curable polyether-containing silane and the topcoat formulations described in Patent Application Nos. PCT/US2013/042449 and PCT/US2013/075046, which are incorporated herein by reference in their entireties.

[0057] The antifouling coating composition can optionally comprise other additives such as, for example, a filler material, a cross linker, a catalyst, combinations of two or more thereof, etc. In one embodiment, the filler is an inorganic filler. Fillers can be particulates, fibers, pellets, aggregates, agglomerates and granulates. Examples of suitable fillers include, but are not limited to, clays, alumina- silicates, talc, wollastonite, mica, fumed silica, precipitated silica, calcium carbonates, etc. and combinations of two or more thereof. Treated calcium carbonates are available under several trade names Ultra Pflex, Super Pflex, Hi Pflex from Specialty Minerals; Winnofil SPM, SPT from Solvay; Hubercarb lat, Hubercarb 3Qt and Hubercarb W from Huber; Kotomite from ECC; and Omyacarb FT and BLP-3 from Omya. Particulate materials such as any of the foregoing can be present in the antifouling coating composition comprising in an amount of from 0 to 70, even from 35 to 60, weight parts per 100 weight parts of the total composition based on cured coating. Applications

[0058] The antifouling systems (either as a multi-layer or single layer system) can be used in a variety of applications where antifouling and/or antimicrobial properties are desired. The antifouling system can be used to prevent the adsorption of proteins and cells on a surface.

[0059] The base coat can be applied to and adhere to a variety of surfaces including, but not limited to metal (e.g., steel, iron, aluminum, etc.), fiberglass, wood, FRP, concrete etc.

[0060] The coating system can be applied to a target substrate by applying the base coating layer to the target substrate, applying the tie coat layer to the base coat layer, applying the antifouling composition to the tie coat layer prior to the base coating being fully cured, and curing the coating compositions. The respective coating compositions can be applied by any suitable methods including, but not limited to, by brush, by roller, by spraying, by dipping, etc. Curing can be accomplished by any suitable curing mechanism including, for example, moisture condensation.

[0061] The base coating, tie coat layer, and the antifouling coating can be applied to provide coating layers of a desired thickness. In one embodiment, for either the multi-layer or single coating layer systems, the base coating has a thickness of from 50 micrometers to about 500 micrometers; from about 100 micrometers to about 300 micrometers; even from about 150 micrometers to about 200 micrometers. In one embodiment, the antifouling coating can have a thickness of from 50 micrometers to about 400 micrometers; from about 100 micrometers to about 300 micrometers; even from about 150 micrometers to about 250 micrometers.

[0062] The coating systems can be employed in a variety of applications including on the surface of vessels (including but not limited to boats, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines, and naval vessels of all types), pipes, shore and off-shore machinery, constructions and objects of all types such as piers, pilings, bridge substructures, water-power installations and structures, underwater oil well structures, nets and other aquatic culture installations, and buoys, etc.

[0063] While the invention has been described with reference to various exemplary embodiments, it will be appreciated that modifications may occur to those killed in the art, and the present application is intended to cover such modifications and inventions as fall within the spirit of the invention.

Claims

CLAIMS What is claimed is:

1. An antifouling coating system comprising:

a base coat layer;

a tie coat layer overlying the base coat layer; and

a fouling release layer overlying the tie coat layer, wherein the tie coat layer comprises a multi-functional silicon-containing material.

2. The antifouling coating system of claim 1, wherein the multi-functional silicon containing material comprises an adhesion promoter.

3. The antifouling coating system of claim 1, wherein the multi-functional silicon containing material comprises an amino functional siloxane, a reaction product thereof, or combinations of two or more thereof.

4. The antifouling coating system of claim 3, wherein the multi-functional silicon containing material comprises a reaction product of two or more amino functional siloxanes.

5. The antifouling coating system of claim 3, wherein the multi-functional silicon containing material comprises a reaction product of an amino functional siloxane and an epoxy compound.

6. The antifouling coating system of claim 1, wherein the multi-functional silicon containing material comprises an amino functional material of the formula:

(R¹0)a(R¹)3-a-Si-M-(Si(R¹)₂0)_r-(Si(R¹)(Ol/₂)(0))t-(Si(X)(Ol/₂)(0))v-Si(R¹)₂-M-Si(OR¹)a(R¹)3-a where each occurrence of R¹ is independently H or an alkyl radical, M is independently R² or oxygen; r is 0 - 1000; t is 1 to 20; v is 0 to 20; X is -R²-(N(R¾_b(Y)b- R²)_c-N(R³)2-b(Y)b; a is 1-3; b is 0 - 2; c is 0 - 5; Y is independently R¹ or an organic radical with an epoxide at one terminal; each occurrence of R² is independently a C2- C10 alkylene; and each occurrence of R³ independently H or an alkyl radical.

7. The antifouling system of claim 6, wherein b is 0.

8. The antifouling system of claim 6, wherein the amino functional material is of the formula:

9. The antifouling system of claim 6, wherein Y is chosen from an organic radical of the formula - -CH₂CH(OH)CH₂-0-P ; P is:

-(C6HhR⁵(4-h)-CR2⁶-C6HhR⁵(4-h)-0-CH2CH(OH)CH₂-0)i-C6HhR⁵(4-h)-CR2⁶-C6HhR⁵(4-h)-0-Z; where h is 0-4; each occurrence of R⁵ is independently chosen from a C1-C10 alkyl or a substituted or unsubstituted phenyl; each occurrence of R⁶ is independently H or Ci- C10 alkyl; i is 0-100; and Z is

where m is 1-20.

10. The antifouling system of claim 6, wherein the amino functional compound is an epoxy modified compound of the formula:

11. The antifouling system of claim 1, wherein the multi-functional silicon- containing material comprises an adhesion promoter of the formula U-Q-R⁸-SiR⁵ R⁷(3- _g), wherein Q is -CH₂CH(OH)CH₂-0- or -CH₂CH(OH)CH₂-NR⁴-; U is:

-(C6HhRV )-CR2⁶-C6HhR⁵(4-h)-0-CH2CH(OH)CH2-0)i-C6HhR⁵(4- )-CR2⁶-C₆HhR⁵(4- )-0-Z; where each occurrence of R⁵ is independently chosen from a Ci to C10 alkyl or a substituted or un-substituted phenyl group; each occurrence of R⁷ is independently chosen from an alkoxy, an acetoxy, or a ketoxime radical; R⁸ is a Ci to C₄ alkylene g is 0-2; h is 0-4; where R⁴ is H or -CH₂CH(OH)CH₂-U-; each occurrence of R⁶ is independently H or alkyl; i is 0-100 and Z is H, Q-R⁸-SiR⁵hR⁷(3-h), or

where m is 1-20.

12. The antifouling coating system of claim 11, wherein the adhesion promoter is chosen from a compound of the formulas:

or a combination thereof.

13. The antifouling system of any of claims 1-12, wherein the tie coat layer comprises the multi-functional silicon-containing material in an amount of from about 0.1 weight percent to about 20 weight percent of the tie coat layer.

14. The antifouling system of any of claims 1-13, wherein the tie coat layer further comprises a binder and optionally a cure catalyst.

15. The antifouling system of any of claims 1-14, wherein the base coating layer comprises an epoxy resin composition.

16. The antifouling system of any of claims 1-15 wherein the antifouling coating layer optionally comprises an inorganic filler; a silane cross linker, a condensation catalyst, or a combination of two or more thereof.

17. An article comprising the antifouling system of any of claims 1-16 applied to at least a portion of a surface of the article.

18. The article of claim 17, wherein the tie coat layer has a thickness from about 5 micrometers to about 400 micrometers.17.

19. The article of any of claims 17 or 18, wherein the base coat layer has a thickness of from about 50 micrometers to about 500 micrometers.

20. The article of any of claims 17-19, wherein the antifouling coating layer has a thickness of from about 50 micrometers to about 400 micrometers.

21. The article of any of claims 17-20, wherein the articles is chosen from a water vessel, a pipe, a piling, a beam, a well structure, a net, or a buoy.