FOULING CONTROL COATING COMPOSITION

FIELD

[01] The present disclosure relates to a fouling control coating composition, to a method of preparing a fouling control coating composition, to a multilayer fouling control coating system and to a multilayer self-adhesive fouling control coating composition. The present disclosure also extends to a substrate coated on at least a portion thereof with a coating layer derived from the aforementioned coating compositions and systems.

BACKGROUND

[02] Coating compositions formulated to prevent (or reduce) the adhesion of fouling organisms (such as micro-organisms, plants and small animals) to surfaces are well known in the art. Areas where such coatings are of particular interest are those where a surface is exposed to water, wherein the water contains fouling organisms that will adhere to the surface, thus fouling the surface. Such areas include marine applications, offshore buoys, pipes or tubes used to convey water and nuclear systems, and offshore structures and bridges. For example, if the surface is the hull of a ship, the adhesion of organisms such as barnacles to the surface causes an increase in frictional resistance, which leads to a drastic reduction in the fuel efficiency of the ship.

[03] Traditionally, there have been three ways that a coating composition can be designed to reduce and/or prevent the adhesion and build-up of fouling organisms on a surface. Firstly, the coating composition can contain a biocide agent (such as an anti-fouling biocide agent, also known as an anti-foulant agent) which serves to physiologically disrupt or kill the fouling organism. This can happen prior to, during or after adhesion of the organism to the surface such that the fouling organism falls away from the surface. This mode of adhesion reduction/prevention is often referred to as “anti-fouling” and such coatings often referred to as anti-fouling coatings.

[04] Secondly, the coating composition may be designed to slowly degrade over time, such that fouling organisms adhered to the surface will gradually fall off the surface with the degradation of the coating. The degradation is often caused by a slow hydrolysation of the coating (usually a binder within the coating). This mode of adhesion reduction/prevention is often referred to as “self-polishing” and such coatings are often referred to as self-polishing coatings or ablative coatings. These coatings often work by having a binder that hydrolyses upon contact with water, which results in the controlled degradation of the coating and causes adhered fouling organisms to fall away from the coated surface. [05] Finally, coatings have been developed which have a very smooth, slippery, low-friction surface onto which fouling organisms have difficulty attaching. Any which do attach often do so only weakly and can usually be easily removed, for example with water washing over the coated surface. Such coatings are often referred to as “fouling release coatings”.

[06] The aforementioned ways of reducing and/or preventing the adhesion and build-up of fouling organisms on a surface can all be considered as providing fouling control.

[07] As well as being effective at reducing and/or preventing the adhesion and build-up of fouling organisms on a surface, a coating composition also needs to possess a range of properties in order to meet the requirements for use. The coating compositions should be stable upon storage prior to use, be easily applied to a substrate (such as by spraying or other means of application), demonstrate good adhesion to the substrate and have excellent durability and properties suitable for their end use.

SUMMARY

[08] According to the present disclosure there is provided a fouling control coating composition comprising a polysiloxane and a thixotropic additive, wherein the thixotropic additive comprises a reaction product of reactants comprising an isocyanate compound, a mono-functional primary fatty amine and a di-functional primary amine.

[09] There is also provided a method of preparing a fouling control coating composition, the method comprising the steps of:

(i) combining an isocyanate compound with a polysiloxane to provide an intermediate composition;

(ii) adding a mono-functional primary fatty amine to the intermediate composition; and

(iii) adding a di-functional primary amine to the intermediate composition.

[10] There is also provided a multilayer fouling control coating system comprising:

(i) an epoxy layer applied over and to at least a portion of a substrate;

(ii) a top coat applied over and to at least a portion of the epoxy layer, wherein the top coat is derived from a fouling control coating composition as defined herein or prepared as defined herein. [11] There is also a multilayer self-adhesive fouling control coating system comprising:

(i) an optional removable underlying layer;

(ii) an adhesive layer, applied over and to the optional underlying layer (i) when present;

(iii) a synthetic material layer applied over and to the adhesive layer (ii);

(iv) a fouling control layer applied over and to the synthetic material layer (iii), wherein the fouling control layer is derived from a fouling control coating composition as defined herein or prepared as defined herein;

(v) an optional removable polymeric film applied over and to the fouling control layer (iv).

[12] There is also provided a substrate at least partially coated with a fouling control layer, wherein the fouling control layer is derived from a fouling control coating composition as defined herein or prepared as defined herein.

[13] There is also provided a method of coating at least a portion of a substrate with a fouling control coating composition as defined herein or prepared as defined herein, the method comprising applying the fouling control coating composition onto at least a portion of the substrate.

[14] There is also provided a use of a fouling control coating composition as defined herein or prepared as defined herein for at least partially coating a substrate to prevent fouling thereon.

DETAILED DESCRIPTION

[15] When describing the compositions of the disclosure, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.

[16] As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word “about”, even if the term does not expressly appear. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. When ranges are given, any endpoints of those ranges and/or numbers within those ranges can be combined within the scope of the present disclosure. Including and like terms means “including but not limited to”. Similarly, as used herein, the terms “on”, “applied on/over”, “formed on/over”, “deposited on/over”, “overlay” and “provided on/over” mean formed, overlay, deposited, or provided on but not necessarily in contact with the surface. For example, a coating layer “formed over” a substrate does not preclude the presence of one or more other coating layers of the same or different composition located between the formed coating layer and the substrate. Including, for example, and like terms means including but not limited to, for example, but not limited to, and the like.

[17] Singular encompasses plural and vice versa. For example, although reference is made herein to "a" polysiloxane, “a” biocide, “an” isocyanate compound, and the like, one or more of each of these and any other components can be used. As used herein, the term "polymer" refers to oligomers and both homopolymers and copolymers, and the prefix "poly" refers to two or more.

[18] The terms "comprising", "comprises" and "comprised of’ as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. Additionally, although the present disclosure has been described in terms of “comprising”, the coating compositions detailed herein may also be described as “consisting essentially of’ or “consisting of’.

[19] As used herein, the term "and/or," when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a list is described as comprising group A, B, and/or C, the list can comprise A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

[20] The term "about" as used herein when referring to a measurable value such as a parameter, an amount, a temporal duration, and the like, indicate that a value includes the standard deviation of error for the device or method being employed to determine the value. The term "about" is meant to encompass variations of +/-10% or less, +/-5% or less, or +/-0.1 % or less of and from the specified value, insofar such variations are appropriate to perform in the disclosure. It is to be understood that the value to which the modifier "about" refers is itself also specifically disclosed.

[21] The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

[22] The term "alkyl", as used herein, relates to saturated hydrocarbon radicals being straight or branched, polycyclic, acyclic, cyclic or part cyclic/acyclic moieties or combinations thereof and containing 1 to 10 carbon atoms, such as 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, or 1 to 4 carbon atoms. The alkyl groups in the present disclosure and as claimed may alternatively be selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl and cyclic or branched variants thereof, n-hexyl and cyclic or branched variants thereof, n-heptyl and cyclic or branched variants thereof and n-octyl and cyclic or branched variants thereof, more typically, from the group consisting of methyl, ethyl, n-propyl isopropyl and most typically, from the group consisting of methyl.

[23] The term “aryl” as used herein, relates to an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic. The aryl group may be selected from such monocyclic and bicyclic rings. Said radical may be optionally substituted with one or more substituents independently selected from alkyl or alkoxy radicals. The aryl groups in the present disclosure and as claimed may alternatively be selected from the group consisting of phenyl, naphthyl, indenyl and alkyl substituted phenyl, more typically, methyl substituted phenyl and phenyl, most typically, phenyl.

[24] As used herein, the term "substantially free" means that the material being discussed is present in the composition, if at all, as an incidental impurity. In other words, the material does not affect the properties of the composition. As used herein, the term "completely free" means that the material being discussed is not present in the composition at all.

[25] As used herein, the terms "at least a portion of the surface of a substrate" and “at least partially coated” mean that the coating composition may be applied to any fraction of the surface. For many applications, the coating composition is at least applied to the part of the substrate (e.g. a vessel) where the surface (e.g. the ship's hull) may come in contact with water.

[26] As used herein, the term “fouling control” means to prevent or reduce the adhesion of fouling organisms to a surface. [27] Unless otherwise defined, all terms used in the disclosure, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. By means of further guidance, definitions for the terms used in the description are included to better appreciate the teaching of the present disclosure. All publications referenced herein are incorporated by reference thereto.

[28] Suitable features of the disclosure are now set forth.

FOULING CONTROL COATING COMPOSITION

[29] The fouling control coating composition comprises a polysiloxane and a thixotropic additive, wherein the thixotropic additive comprises a reaction product of reactants comprising an isocyanate compound, a mono-functional primary fatty amine and a di-functional primary aromatic amine.

[30] The polysiloxane acts to provide a very smooth, slippery, low-friction surface onto which fouling organisms have difficulty attaching once the coating composition has been applied to a substrate to provide a coating thereon. Thus, the polysiloxane provides a fouling release coating effect. Therefore, the fouling control coating composition provides a fouling release effect.

[31] Any suitable polysiloxane may be used. Mixtures of different polysiloxanes may be used.

[32] Polysiloxanes have a structure defined by diorganosiloxane residues and terminal organosiloxane residues, and, optionally, branch organosiloxane residues. Such polysiloxanes include polysiloxanes derived from organo silicon compounds (such as dimethyldichlorosilane) and water and subsequent polymerisation. In addition, organo silicon compounds can be hydrolysed to form a polymer terminated with silanol groups. Such silane precursors with acidforming groups can be used to introduce branching into the silicone polymer chain.

[33] The polyorganosiloxane may comprise predominantly dimethyl siloxane units, such as those prepared by polymerization of a precursor siloxane comprising at least two siloxane units which have a silicon-bonded hydroxyl group in the presence of an acidic condensation catalyst.

[34] The polysiloxane may comprise a polydiorganosiloxane, such as a polydialkylsiloxane, polydiarylsiloxane and/or polyalkylarylsiloxane, such as a polydimethylsiloxane, a polydiethylsiloxane and/or a polydimethylphenylsiloxane. [35] The polysiloxane may include terminal and/or pendant functionality. The functionality may be provided by a hydrolysable group such as alkoxy and/or ketoxime groups, or by a reactive group such as a hydroxyl, amino, epoxy, carboxyl, carbinol, methacryl, mercapto group, vinyl or hydride group. The polysiloxane may comprise at least two reactive groups.

[36] The polysiloxane may comprise a hydroxyl-functional polyorganosiloxane, such as a hydroxyl-terminated polysiloxane. The hydroxyl-functional polyorganosiloxane may comprise a dihydroxyl polydiorganosiloxane, such as a dihydroxyl polydimethylsiloxane, a dihydroxyl polydiethylsiloxane and/or a dihydroxyl polymethylphenylsiloxane (such as dihydroxyl polydimethylsiloxane). The polysiloxane may comprise a linear dihydroxyl polydimethylsiloxane.

[37] The polysiloxane may comprise a commercially available polysiloxane material. A commercially available polysiloxane material may comprise a SF2001 E series, such as SF2001 EDK005 and SF2001 EDK020, commercially available from KCC Silicone; a DMS-S series such as DMS-S27 and DMS-S42, commercially available from Gelest; a Bluesil FLD series such as Bluesil FLD 48V750, Bluesil 48V3500 and Bluesil 48V10000, commercially available from BlueStar Silicones; and/or a OHX Polymer Series such as OHX-0750 polymer, 750 cSt, OHX-4010 polymer, 4000 cSt, OHX-0135 polymer 12500 cSt, commercially available from Xiameter Silicones.

[38] The weight-average molecular weight (Mw) of the polysiloxane may be from 500 to 100,000 Daltons, such as from 1 ,000 to 50,000, such as from 5,000 to 50,000 Daltons, such as from 10,000 to 45,000 Daltons.

[39] The weight-average molecular weight (Mw) may be measured by any suitable method. Techniques to measure the weight-average molecular weight will be well known to those skilled in the art. The Mw values and ranges given herein are as determined by gel permeation chromatography using a polystyrene standard according to ASTM D6579-11 ("Standard Practice for Molecular Weight Averages and Molecular Weight Distribution of Hydrocarbon, Rosin and Terpene Resins by Size Exclusion Chromatography". UV detector: 254 nm, solvent: unstabilised THF, retention time marker: toluene, sample concentration: 2 mg/ml).

[40] A suitable hydroxyl-functional polyorganosiloxane may have any suitable hydroxyl (OH) content. A suitable hydroxyl-functional polyorganosiloxane may have a hydroxyl content from 0.01 to 0.4%, such as from 0.1 to 0.2 %. Methods to measure hydroxyl (OH) content will be well known to a person skilled in the art. The hydroxyl content values and ranges given herein are as determined by the method described in ‘Characterisation of silicone prepolymers and disparity in results; G.B.Shah; eXPRESS Polymer Letters Vol. 2, No.11 (2008) 829-834’.

[41] The polysiloxane may comprise a reactive silicone polymer comprising a reactive functional group, such as a hydroxyl (OH) group, i.e. providing a hydroxyl-functional silicone polymer. The term “reactive silicone polymer” as used herein means a silicone polymer operable to react with a crosslinker (when present).

[42] The fouling control coating composition may comprise a non-reactive silicone polymer. The term "non-reactive silicone polymer" as used herein is meant a silicone polymer that does not react with a crosslinker. The non-reactive silicone polymer is unreactive to the extent that it does not interfere in the reaction between the reactive silicone polymer and the crosslinker (when present).

[43] The fouling control coating composition may comprise a reactive polysiloxane and a non- reactive silicone polymer.

[44] The non-reactive silicone polymer may be produced by any suitable method. The non- reactive silicone polymer may comprise (homo)polymers and/or copolymers derived from combinations of polysiloxanes. Examples of suitable polysiloxanes include polyorganosiloxanes such as polydimethylsiloxane, polydiethylsiloxane and/or polymethylphenylsiloxane. The non- reactive polymer may comprise a copolymer of polyorganosiloxanes, such as poly(dimethylsiloxane-co-methylphenylsiloxane).

[45] The non-reactive silicone polymer may comprise commercially available polysiloxane materials. Examples of suitable polysiloxane materials include DMS T series (polydimethylsiloxane) such as DMS T21 , DMS T22, DMS T23, DMS T25 and DMS T31 , commercially available from Gelest; PMM series (poly(dimethylsiloxane-co- methylphenylsiloxane)) such as PMM1025 and PMM5021 , commercially available from Gelest; SF series (polydimethylsiloxane) such as SF1000N, commercially available from KCC Silicone; SF series (poly(dimethylsiloxane-co-methylphenylsiloxane)) such as SF5000P and SF5400P, commercially available from KCC Silicone; AK series (polydimethylsiloxane) such as AK-100, AK-200, AK-350 and AK-500, commercially available from Wacker Silicones; Belsil DM1000 (polydimethylsiloxane) commercially available from Wacker Silicones; AP series (poly(dimethylsilioxane-co-methylphenylsiloxane)) such as AP-100, AP-200, AP-500 and AP- 1000, commercially available from Wacker Silicones; Silopren W series (polydimethylsiloxane) such as Silopren W1000, commercially available from Momentive Performance Chemicals; Element 14 series (polydimethylsiloxane) such as 14 PDMS-E 500 and 14 PDMS-E 1000, commercially available from Momentive Performance Chemicals; Dow Corning 200 fluid (polydimethylsiloxane), commercially available from Dow Corning; Xiameter PMX-200 silicone fluid (polydimethylsiloxane) commercially available from Dow Corning; Silicon fluid series (poly(dimethylsiloxane-c-methylphenylsiloxane)) such as Silicon 510 Fluid and Silicon 550 Fluid, commercially available from Dow Corning; Bluesil Fluid FLD 47V1000 (polydimethylsiloxane) commercially available from Bluestar Silicones; Mirasil DM1000 (polydimethylsiloxane) commercially available from Bluestar Silicones; Rhodorsil series (poly(dimethylsiloxane-co- methylphenylsiloxane)) such as Rhodorsil oil 510 and Rhodorsil oil 550, commercially available from Bluestar Silicones; PSF series (polydimethylsiloxane) such as PSF 100, PSF 200, PSF 350 and PSF 500, commercially available from Clearco Silicone Fluids and PhenylMethyl Silicone Fluids (poly(dimethylsiloxane-co-methylphenylsiloxane)), such as PM-125, commercially available from Clearco Silicone Fluids.

[46] The fouling control coating composition may comprise a poly(dimethylsiloxane-co- polymethylphenylsiloxane).

[47] The non-reactive silicone polymer may have any suitable weight-average molecular weight (Mw). The non-reactive silicone polymer may have an Mw from 6000 to 28,0000 Daltons (Da = g/mole), such as from 10,000 to 28,000 Da, such as from 15,000 to 25,000 Da.

[48] The coating composition may comprise 20 % by weight or greater, such as 30 % by weight or greater, or 40 % by weight or greater of the polysiloxane based on the total weight of the composition. The coating composition may comprise 90 % by weight or lower, such as 80 % by weight or lower, or 70 % by weight or lower of the polysiloxane based on the total weight of the composition. The polysiloxane may be present in the coating composition in an amount ranging from 20 to 90 % by weight, such as from 30 to 80 % by weight, such as from 40 to 80 % by weight, based on the total weight of the composition. This refers to the total amount of polysiloxane present in the composition.

[49] The reactive silicone polymer may be present in the coating composition in any suitable amount. The coating composition may comprise from 19 to 80 wt%, such as from 37 to 65 wt% of the reactive silicone polymer based on the total solid weight of the coating composition. [50] The non-reactive silicone polymer may be present in the coating composition in any suitable amount. The coating composition may comprise from 1 to 25 wt%, such as from 2 to 15 wt% or even from 3 to 10 wt% of the non-reactive silicone polymer based on the total solid weight of the coating composition.

[51] The fouling control coating composition may comprise a biocide. The biocide (also known as an anti-fouling biocide agent or anti-foulant agent) acts to physiologically disrupt or kill a marine organism. Thus, the biocide provides an anti-fouling coating effect. Therefore, the fouling control coating composition may provide an anti-fouling effect.

[52] Any suitable biocide agent may be used.

[53] The biocide may comprise an inorganic compound, a metal-containing organic compound and/or a metal-free organic compound.

[54] The inorganic compound may comprise a copper compound (such as copper sulfate, copper powder, cuprous thiocyanate, copper carbonate, copper chloride, and/or cuprous oxide), zinc sulfate, zinc oxide, and/or a copper nickel alloy.

[55] The metal-containing organic compound may comprise an organo-copper compound and/or an organo-zinc compound. The metal-containing organic compound may comprise manganese ethylene bis dithiocarbamate (maneb) and/or propineb. Examples of organo-copper compounds include copper nonylphenol-sulfonate, copper bis(ethylenediamine) bis(dodecylbenzene sulfonate), copper acetate, copper naphthenate, copper pyrithione (also known as copper omadine) and copper bis(pentachlorophenolate). Examples of the organo- zinc compounds include zinc acetate, zinc carbamate, bis(dimethylcarbamoyl) zinc ethylene- bis(dithiocarbamate), zinc dimethyl dithiocarbamate, zinc pyrithione, and zinc ethylene- bis(dithiocarbamate). The metal-containing organic compound may comprise (polymeric) manganese ethylene bis dithiocarbamate complexed with zinc salt (mancozeb).

[56] The metal-free organic compound may comprise a N-trihalomethylthiophthalimide, a trihalomethylthiosulphamide, a dithiocarbamic acid, a N-arylmaleimide, a 3-(substituted amino)- 1 ,3 th iazolidine-2, 4-dione, a dithiocyano compound, a triazine compound and/or an oxathiazine.

[57] Examples of a N-trihalomethylthiophthalimide include N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide. [58] Examples of a dithiocarbamic acid include bis(dimethylth iocarbamoyl) disulphide, ammonium N-methyldithiocarbamate and ammonium ethylene-bis(dithiocarbamate).

[59] Examples of a trihalomethylthiosulphamide include N-(dichlorofluoromethylthio)-N’,N’- dimethyl-N-phenylsulphamide and N-(dichlorofluoromethylthio)-N’,N’-dimethyl-N-(4- methylphenyl)sulphamide.

[60] Examples of a N-arylmaleimide include N-(2,4,6-trichlorophenyl)maleimide, N-4 tolylmaleimide, N-3 chlorophenylmaleimide, N-(4-n-butylphenyl)maleimide, N- (anilinophenyl)maleimide, and N-(2,3-xylyl)maleimide.

[61] Examples of a 3-(substituted amino)-1 ,3-thiazolidine-2, 4-diones include 2- (thiocyanomethylthio)-benzothiazole, 3-benzylideneamino-1 , 3-thiazolidine-2, 4-dione, 3-(4- methylbenzylideneamino)-1 ,3-thiazolid ine-2, 4-dione, 3-(2-hydroxybenzylideneamino)-1 ,3- thiazolidine-2, 4-dione, 3-(4-dimethylaminobenzylideamino)-1 ,3-th iazolidine-2, 4-dione, and 3- (2,4-dichlorobenzylideneamino)-1 ,3-thiazolid ine-2, 4-dione.

[62] Examples of a dithiocyano compound include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene.

[63] Examples of a triazine compound include 2-methylthio-4-butylamino-6-cyclopropylamino- s-triazine.

[64] Examples of an oxathiazine include 1 ,4,2-oxathiazines and their mono- and di-oxides such as disclosed in WO 98/05719: mono- and di-oxides of 1 ,4,2-oxathiazines with a substituent in the 3 position representing (a) phenyl; phenyl substituted with 1 to 3 substituents which are independently hydroxyl, halo, C1-C12 alkyl, C5-C6 cycloalkyl, trihalomethyl, phenyl, C1-C5 alkoxy, C1-C5 alkylthio, tetrahydropyranyloxy, phenoxy, C1-C4 alkyl carbonyl, phenyl carbonyl, C1-C4 alkylsulfinyl, carboxy or its alkali metal salt, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, phenylaminocarbonyl, tolylaminocarbonyl, morpholinocarbonyl, amino, nitro, cyano, dioxolanyl or C1-C4 alkyloxyiminomethyl; naphthyl; pyridinyl; thienyl; furanyl; orthienyl orfuranyl substituted with one to three substituents which are independently C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, halo, cyano, formyl, acetyl, benzoyl, nitro, C1-C4 alkoxycarbonyl, phenyl, phenylaminocarbonyl or C1-C4 alkyloxyiminomethyl; or (b) a substituent of generic formula :

[65] wherein X is oxygen or sulphur; Y is nitrogen, CH or C(Ci-C4 alkoxy); and the C6 ring may have one C1-C4 alkyl substituent; a second substituent which is C1-C4 alkyl or benzyl being optionally present in position 5 or 6.

[66] The metal-free organic compound may comprise 2,4,5,6-tetrachloroisophthalonitrile, N,N- dimethyl-dichlorophenylurea, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, N,N-dimethyl-N’- phenyl-(N-fluorodichloromethylthio)-sulfamide, tetramethylthiuramdisulphide, 3-iodo-2- propinylbutyl carbamate, 2-(methoxycarbonylamino)benzimidazole, 2,3,5,6-tetrachloro-4- (methylsulphonyl)pyridine, diiodomethyl-p-tolyl sulphone, phenyl(bispyridine)bismuth dichloride, 2-(4-thiazolyl)benzimidazole, dihydroabietyl amine, N-methylol formamide and pyridine triphenylborane.

[67] The biocide may comprise a specific barnaclecide, such as cuprous oxide or thiocyanate. Another suitable barnaclecide is ECONEA (2-(p-chlorophenyl)-3-cyano-4-bromo-5- trifluoromethyl pyrrole), commercially available from Janssen Pharmaceuticals. Another suitable barnaclecide is SELEKTOPE (also known as medetomidine or 4-[1-(2,3-dimethylphenyl)ethyl]- 1 /-/-imidazole), commercially available from l-Tech AB.

[68] The fouling control coating composition may comprise 1 % by weight or greater, such as 2 % by weight or greater or 4 % by weight or greater of the biocide based on the total weight of the composition. The fouling control coating composition may comprise 15 % by weight or lower, such as 10 % by weight or lower, or 8 % by weight or lower of the biocide based on the total weight of the composition. The biocide may be present in the fouling control coating composition in an amount ranging from 1 to 15 % by weight, such as from 2 to 10 % by weight, such as from 4 to 8 % by weight, based on the total weight of the composition.

[69] The fouling control coating composition comprises a thixotropic agent. The thixotropic additive comprises a reaction product of reactants comprising an isocyanate compound, a mono-functional primary fatty amine and a di-functional primary amine. The thixotropic additive is formed in situ during formation of the fouling control coating composition. [70] Without being bound by theory, the reaction product of reactants comprising an isocyanate compound, a mono-functional primary fatty amine and a di-functional primary amine is believed to form a thixotropic agent that comprises a three-dimensional network containing urea linkages.

[71] The isocyanate compound, mono-functional primary fatty amine and di-functional primary amine reactants are reacted in suitable amounts so as to form the thixotropic agent in situ. The reactants may comprise a molar excess of isocyanate groups compared to amine groups (i.e. of the mono-functional primary fatty amine and the di-functional primary amine together). The reactants may comprise from 0.1 % to 50 % molar excess of isocyanate groups, such as from 5 % to 20 % molar excess of isocyanate groups, such as from 10 % to 20 % molar excess of isocyanate groups, compared to amine groups (i.e. of the mono-functional primary fatty amine and the di-functional primary amine together). This is believed to ensure that substantially all amine groups are reacted and converted into urea groups by reaction with the isocyanate groups, which has a beneficial effect on the physical and fouling release properties of the fouling control coating composition comprising the thixotropic agent. The thixotropic agent formed in situ may comprise excess, unreacted isocyanate groups, which may react with moisture in use.

[72] All (i.e. 100 %) of the amine groups in the reactants that are reacted so as to form the thixotropic agent may be present in the mono-functional primary fatty amine and di-functional primary amine reactants.

[73] The molar % of amine groups of the mono-functional primary fatty amine may be from 0.1 % to 99.9 %, such as from 50 to 90 %, such as from 60 to 80 %, wherein the total molar % of amine groups of both mono- and di-functional primary amines represents 100 %.

[74] Any suitable isocyanate compound may be used.

[75] By the term “isocyanate compound” we mean a chemical compound comprising at least one isocyanate group. The isocyanate compound may comprise two or more (such as two or three) isocyanate groups. The isocyanate compound may be a polyisocyanate.

[76] The isocyanate compound may be di- or tri-functional (such as tri-fu notional). The isocyanate compound may be a diisocyanate. The isocyanate compound may be a tri isocyanate. [77] The isocyanate compound may be an aliphatic, cycloaliphatic, araliphatic and/or aromatic compound. The isocyanate compound may be an aliphatic polyisocyanate.

[78] The isocyanate may be liquid at the conditions at which the fouling control coating composition is prepared, stored and put to use. The isocyanate may be liquid at ambient temperature.

[79] The isocyanate compound may comprise 1 ,6-hexamethylene diisocyanate, 1 ,10- decamethylene diisocyanate, lysine alkyl ester diisocyanate, tetramethylxylylene diiso-cyanate, 1 ,5-tetrahydronaphthalene diisocyanate, diisocyanatotoluene, isophorone diisocyanate, methylene-bis(cyclohexyl) 2,4'-diisocyanate, 4-methylcyclohexane 1 ,3-diisocyanate and/or hexamethylene diisocyanate isocyanurate trimer, which has three reactive isocyanate groups.

[80] The isocyanate compound may comprise hexamethylene diisocyanate and/or hexamethylene diisocyanate isocyanurate trimer.

[81] Any suitable mono-functional primary fatty amine may be used.

[82] As will be known by the skilled person, primary fatty amines commonly have more than 8 carbon atoms in the hydrocarbon chain, such as up to 24 carbon atoms.

[83] By the term “mono-functional primary fatty amine” we mean a chemical compound of the formula R-NH2 wherein the R group represents a hydrocarbon group of eight or more carbon atoms.

[84] The mono-functional primary fatty amine may be aliphatic or aromatic. The monofunctional primary fatty amine may be optionally substituted.

[85] The mono-functional primary fatty amine may be derived from a natural fatty acid. Methods of producing the mono-functional primary fatty amine are well known to the skilled person.

[86] The mono-functional primary fatty amine may comprise a Ca to C24, such as a Ca to Cia, aliphatic amine. The mono-functional primary fatty amines may comprise octyl amine, lauryl amine, myristyl amine, stearyl amine, coco alkylamine, tallow alkylamine, hydrogenated tallow alkylamine, oleylamine and/or soya amine. The mono-functional primary fatty amine may comprise coco alkylamine.

[87] Commercially available mono-functional primary fatty amines include Armenn 8D, Armeen 12D, Armeen C, Armeen CD, Rofamine K, Armeen O and Armeen OD (where D represents the distilled form of the amine).

[88] The mono-functional primary fatty amine may be liquid at the conditions at which the fouling control coating composition is prepared, stored and put to use. The mono-functional primary fatty amine may be liquid at ambient temperature

[89] Any suitable di-functional primary amine may be used.

[90] By the term “di-functional primary amine” we mean a chemical compound comprising two primary amine (i.e. -NH2) groups (i.e. linked by a hydrocarbon group).

[91] The di-functional primary amine may be a di-functional cyclo-aliphatic primary amine or a di-functional primary araliphatic primary amine.

[92] The di-functional primary cycloaliphatic amine may comprise bicyclo[2.2.1]heptane bis(methylamine), meta-xylylene diamine and/or ortho-xylylene diamine.

[93] The di-functional primary cycloaliphatic amine may comprise bicyclo[2.2.1]heptane bis(methylamine).

[94] The di-functional primary cycloaliphatic amine may comprise meta-xylylene diamine and/or ortho-xylylene diamine. The di-functional primary amine may comprise meta-xylylene diamine.

[95] The di-functional primary amine may be liquid at the conditions at which the fouling control coating composition is prepared, stored and put to use. The di-functional primary amine may be liquid at ambient temperature.

[96] The fouling control coating composition may comprise 0.1 % by weight or greater, such as 0.5 % by weight or greater, or 1 % by weight or greater of the thixotropic additive (i.e. once formed) based on the total weight of the composition. The fouling control coating composition may comprise 10 % by weight or lower, such as 5 % by weight or lower, or 3 % by weight or lower of the thixotropic additive (i.e. once formed) based on the total weight of the composition. The thixotropic additive may be present in the fouling control coating composition in an amount ranging from 0.1 to 10 % by weight, such as from 0.5 to 5 % by weight, such as from 1 to 3 % by weight, based on the total weight of the composition.

[97] The thixotropic additive comprising the reactant product of reactants comprising an isocyanate compound, a mono-functional primary fatty amine and a di-functional primary amine provides appropriate sag resistance at lower viscosity, with retention of a homogeneous and smooth micro-surface, and short processing times.

[98] The fouling control coating composition may further comprise a cross-linker. The crosslinker may be provided to cross-link the polysiloxane, such as via functional groups, such as pendant or terminal (such as terminal) functional groups, on the polysiloxane.

[99] Any suitable cross-linker may be used.

[100] The cross-linker may comprise an acetoxy or ketoxime silane. Such cross-linkers may enable the provision of a stable 1 K composition, and provide good adhesion to substrates having an epoxy coating thereon.

[101] The cross-linker may comprise vinyltris(methylethyloximino)silane; vinyltris- (acetoxime)silane; methyltris(methylethyloximino)silane; methyltris(acetoxime)silane; tetraacetoxy-silane; methyltriacetoxysilane; ethyltriacetoxysilane; vinyltriacetoxysilane; and/or di-t-butoxy-diacetoxysilane; as well as reactive hydrolysis-condensation products of the same.

[102] The cross-linker may comprise an acetoxysilane, such as ethyltriacetoxysilane, and/or a reactive hydrolysis-condensation product of the same.

[103] The fouling control coating composition may comprise 1 % by weight or greater, such as 2 % by weight or greater or 4 % by weight or greater of the cross-linker based on the total weight of the composition. The fouling control coating composition may comprise 15 % by weight or lower, such as 10 % by weight or lower, or 8 % by weight or lower, of the cross-linker based on the total weight of the composition. The cross-linker may be present in the fouling control coating composition in an amount ranging from 1 to 15 % by weight, such as from 2 to 10 % by weight, such as from 4 to 10 % by weight, based on the total weight of the composition, or any other range combination using these endpoints.

[104] The fouling control coating composition may further comprise a catalyst. The catalyst may be provided to catalyse the reaction of the polysiloxane and the cross-linker.

[105] Any suitable catalyst may be used.

[106] A suitable catalyst may comprise an organometallic catalyst. The organometallic catalyst may comprise suitable metal ions, such as zinc, tin, bismuth, aluminium or titanium ions.

[107] A commercially available organometallic catalyst may comprise TibKat 422, TibKat 223, TibKat 233, TibKat 318, TibKat 320, tetramethylguanidine, Kosmos Pro-1 , TibKat 226, TibKat 716, TibKat 717, TibKat 718, TibKat 720, TibKat 216, TibKat 348, K-Kat XK-651 , K-Kat XC- B221 , K-Kat 670, K-Kat XK-648, K-Kat XK-675, K-Kat 678, Borchikat 24, Borchikat 0244, Neostann U-100, Neostann U-130, Neostann U-200, Neostann U-220H, Neostann U-303, Neostann U-600, Neostann U-700, Neostann U-810, Neostan U-820, Neostann U-830, Neostan S-1 , Coscat 83, catalyst TD-18, ES CAT-180b, and/or ES CAT 320-25d (available from TIB Chemicals)

[108] A suitable catalyst may comprise an organic catalyst, such as a tertiary amine compound.

A suitable tertiary amine compound catalyst may comprise a guanidine derivative, such as tetramethylguanidine, diisopropyldimethylbutylguanidine and/or dicyclohexyldimethylbutylguanidine. Other suitable tertiary amine compound catalysts include /V,/V,/V,/V-Tetraethylethylenediamine and 1 ,4-diazabicyclo[2.2.2]octane (dabco).

[109] The fouling control coating composition may comprise 0.01 % by weight or greater, such as 0.02 % by weight or greater, of the catalyst based on the total weight of the composition. The fouling control coating composition may comprise 2 % by weight or lower, such as 1 % by weight or lower, or 0.5 % by weight or lower, of the catalyst based on the total weight of the composition. The catalyst may be present in the fouling control coating composition in an amount ranging from 0.01 to 2 % by weight, such as from 0.01 to 1 % by weight, such as from 0.02 to 0.5 % by weight, based on the total weight of the composition, or any other range combination using these endpoints. [1 10] The fouling control coating composition may further comprise other optional materials well known in the art of formulating coatings, such as plasticizers (such as tricresyl phosphate, phthalic diesters or chloroparaffins); defoamers; pigments (such as colour pigments, bright pigments, and extender pigments); fragrances; fillers (such as hydrophobic silica); adhesion agents; buffers; dispersing agents; surfactants; deaerators; surface control additives; surface active components (such as pine oil); hydrophobing agents; wetting additives; rheological agents; anti-cratering additives; radiation curing additives; anti-corrosion additives; pH regulators; levelling agents; thickeners; stabilizers (such as substituted phenols or organ functional silanes); and/or anti-graffiti additives..

[1 11] Suitable pigments will be well known to those skilled in the art. The pigment may comprise organic or inorganic pigments in pure form or incorporated into silicone colour pastes. The pigment may be used in the coating composition in any suitable amount. The pigment may be used in the fouling control coating composition in an amount of from 3 to 7 wt% based on the total weight of the composition.

[1 12] The fouling control coating composition may further comprise a solvent and/or diluent, such as an organic solvent and/or diluent. Suitable organic solvents and diluents include aromatic hydrocarbons such as benzene; toluene; xylene; solvent naphtha 100, 150, 200; isoparaffinic fluids (such as Isopar H and/or Isopar V); those available from Exxon-Mobil Chemical Company under the SOLVESSO trade name; ketones such as methyl isobutyl or combinations thereof. The solvent may comprise xylene. The solvent and/or diluent may be used in the fouling control coating composition in an amount from 0 to 25 wt% based on the total weight of the composition. The solvent and/or diluent may be selected so as to provide the desired viscosity and/or biocide loading in the composition.

[1 13] The fouling control coating composition may have any suitable viscosity. The viscosity of the fouling control coating composition will be dependent on factors such as the end use of coating composition. The fouling control coating composition may have a viscosity of froml OOO to 10000 mPa.s at 20 °C and shear rate 1.5 s ^-1 , which may be measured according to ASTM D2196-10. The fouling control coating composition may have viscosity of froml OOO to 5000 mPa.s at 20 °C and shear rate 1 .5 s ^-1 , such as from 1000 to 3000 mPa.s, such as from 1000 to 2000 mPa s or from 1000 to 1500 mPa.s at 20 °C and shear rate 1 .5 s ^-1 .

[1 14] Methods to measure viscosity will be well known to those skilled in the art. The viscosity values and ranges given herein are measured according to ASTM D2196-10 ("Standard Test Methods for Rheological Properties of Non-Newtonian Materials by Rotational (Brookfield type) Viscometer). The viscosity values and ranges given herein are measured with a Brookfield RV with different spindles and at different spindle speeds. The viscosity at high shear rate (e.g. 100 rpm) corresponds to the conditions during application of the coating composition, e.g. brush or spray application. The viscosity at low shear rate (e.g. 10 rpm) represents the conditions directly after application of the coating composition. The shear thinning behaviour (thixotropy) of the coating composition is represented by the ratio between the viscosity at high shear (e.g. 100 rpm) and the viscosity at low shear (e.g. 10 rpm).

[1 15] The fouling control coating composition may be cured at ambient temperature for a suitable period of time, such as from 2 to 12 hours. The curing time will be dependent on a number of factors including the dry film thickness coating composition, the temperature and the relative humidity of the curing environment.

[1 16] The fouling control coating composition may be cured by a heat curing process. The fouling control coating composition may be cured at a temperature from 60 to 130°C, such as from 90 to 120°C. The fouling control coating composition may be heat cured for a period of time from 5 to 15 minutes. Other methods of curing include using an IR (Infra-Red) application technique at a temperature of from 50 to 80°C, such as from 55 to 65°C.

[1 17] The fouling control coating composition may be a 1 K (i.e. one component) coating composition. It is believed that the thixotropic agent provides a stable composition that can be stored as a one component composition prior to use. Without being bound by theory, it is believed that the excess of isocyanate groups in the thixotropic additive also function as a moisture scavenger. The isocyanate groups are believed to react with moisture from the composition and/or the environment to form urea linkages, which improves the toughness of the formed coating layer.

[1 18] The use of a 1 K coating composition provides advantages in use, such as in terms of storage and ease of application. The use of a 1 K coating composition minimises handling of the reactive reagents by the user and avoids possible mixing failures (which often occur with 2K coating compositions). Moreover, the 1 K coating composition is beneficial for the environment as it only makes use of one container, saving packaging material. The use of only one container also saves space during transport and storage. METHOD OF PREPARING THE FOULING CONTROL COATING COMPOSITION

[1 19] The fouling control coating composition as described herein may be prepared by any suitable method, including for example a method comprising the steps of:

(i) combining an isocyanate compound with a polysiloxane to provide an intermediate composition;

(ii) adding a mono-functional primary fatty amine to the intermediate composition; and

(iii) adding a di-functional primary amine to the intermediate composition.

[120] The intermediate composition comprises the isocyanate compound and the polysiloxane, and may further comprise additional components.

[121] Step (ii) may be followed by step (iii), such that a mono-functional primary fatty amine is added to the intermediate composition first, followed by addition of a di-functional primary amine; or steps (ii) and (iii) may be performed concurrently, such that the mono-functional primary fatty amine and di-functional primary amine are added to the intermediate composition together.

[122] Step (ii) may be followed by step (iii), such that a mono-functional primary fatty amine is added to the intermediate composition first, followed by addition of a di-functional primary amine. Adding the components in this order facilitates formation of a coating composition with the required gelation.

[123] Preparing the fouling control coating composition may further comprise the step of adding a biocide. The biocide may be added at any stage of the preparation process. The biocide may be added to the polysiloxane prior to step (i) in which the intermediate composition is provided. For example, the biocide may be combined with a polysiloxane prior to addition of an isocycanate compound and formation of the intermediate composition. In this case, the method includes the step of combining a biocide with a polysiloxane, followed by the addition of an isocyanate compound to provide an intermediate composition.

[124] The biocide may be added to the intermediate composition obtained in step (i). The biocide may be added following step (ii) or following step (iii).

[125] After and/or during each of steps (i), (ii) and (iii), the mixture may be stirred. Each mixture may be stirred for approximately 10 minutes in order to obtain a homogenous mixture. [126] The isocyanate compound and polysiloxane may be added in amounts as discussed above in relation to the fouling control coating composition.

[127] The isocyanate compound may be added in an amount of 0.1 % by weight or greater, such as 0.2 % by weight or greater or 0.5 % by weight or greater based on the total weight of the coating composition. The isocyanate compound may be added in an amount of 10 % by weight or lower, such as 5 % by weight or lower, or 2 % by weight or lower based on the total weight of the coating composition. The isocyanate compound may be added in an amount ranging from 0.1 to 10 % by weight, such as from 0.2 to 5 % by weight, such as from 0.5 to 2 % by weight, based on the total weight of the coating composition, or any other range combination using these endpoints.

[128] The mono-functional primary fatty amine may be added in an amount of 0.1 % by weight or greater, such as 0.2 % by weight or greater or 0.3 % by weight or greater based on the total weight of the coating composition. The mono-functional primary fatty amine may be added in an amount of 5 % by weight or lower, such as 2 % by weight or lower, or 1 % by weight or lower based on the total weight of the coating composition. The mono-functional primary fatty amine may be added in an amount of from 0.1 to 5 % by weight, such as from 0.2 to 2 % by weight, such as from 0.3 to 1 % by weight, based on the total weight of the coating composition, or any other range combination using these endpoints.

[129] The di-functional primary aromatic amine may be added in an amount of 0.01 % by weight or greater, such as 0.03 % by weight or greater, or 0.05 % by weight or greater based on the total weight of the coating composition. The di-functional primary aromatic amine may be added in an amount of 0.3 % by weight or lower, such as 0.2 % by weight or lower, or 0.15 % by weight or lower based on the total weight of the coating composition. The di-functional primary aromatic amine may be added in an amount of from 0.01 to 0.3 % by weight, such as from 0.03 to 0.2 % by weight, such as from 0.05 to 0.15 % by weight, based on the total weight of the coating composition, or any other range combination using these endpoints.

MULTILAYER FOULING CONTROL COATING SYSTEM

[130] There is also provided a multilayer fouling control coating system comprising:

(i) an epoxy layer applied over and to at least a portion of a substrate; (ii) a top coat applied over and to at least a portion of the epoxy layer, wherein the top coat is derived from a fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein.

[131] Suitable substrates are those that are in contact with water, such as sea water. The substrate may comprise an underwater structure. The substrate may comprise a structure that is partially submerged in water, such as an offshore structure or bridge. The substrate may comprise an offshore buoy, a pipe or tube used to convey water or a nuclear system. The substrate may be at least a portion of the outermost surface of a marine structure, such as the hull of a ship.

[132] Examples of suitable substrates include metal substrates such as steel, iron or aluminium, and non-metal substrates, such as glass-fibre reinforced polyester.

[133] The substrate may comprise an epoxy (coating) layer applied over and to at least a portion of the substrate. The substrate may comprise a metal substrate (such as a steel substrate) at least partially coated with an anticorrosive coating such as a cured epoxy-based coating. The substrate may comprise a glass-fibre reinforced polyester substrate at least partially coated with an epoxy primer coating.

[134] Suitable epoxy coatings are reactive two-component epoxy I amine systems which may contain no or a low amount of non-reactive binder. The epoxy coating may have a medium solids content (moderate volatile organic compound, VOC), or a high solids content (low VOC) or can be solvent free (very low VOC). Suitable epoxy coatings inclue Sigmashield 610, Sigmashield 620, Sigmaprime 700, Novaguard 840 and Sigmashield 1200.

[135] By “top coat” we mean that the coat is the outermost coating applied to the substrate. Thus, the top coat may be the coat that is exposed to the environment, such as an aquatic environment.

[136] As the top coat is applied as the outermost coat, the top coat may not be coated with any further coats.

[137] The top coat may provide anti-fouling and fouling release properties. [138] The multilayer fouling control coating system may be substantially free of hydrophilic polysiloxanes. Hydrophilic-polysiloxanes are polysiloxanes comprising a hydrophilic group such as a poly(oxyalkylene). Thus, the multilayer fouling control coating system may be substantially free of polysiloxanes comprising a poly(oxyalkylene) group. By “substantially free” we mean that the multilayer fouling control coating system contains less than 5 wt% of hydrophilic polysiloxanes, such as less than 2 wt% of hydrophilic polysiloxanes, such as less than 0.05 wt of hydrophilic polysiloxanes. The multilayer fouling control coating system may contain 0 wt% of hydrophilic polysiloxanes.

MULTILAYER SELF-ADHESIVE FOULING CONTROL COATING COMPOSITION

[139] There is provided a multilayer self-adhesive fouling control coating composition comprising:

(i) an optional removable underlying layer;

(ii) an adhesive layer, applied over and to the optional underlying layer (i) when present;

(iii) a synthetic material layer applied over and to the adhesive layer (ii);

(iv) a fouling control layer applied over and to the synthetic material layer (iii), wherein the fouling control layer is derived from a fouling control coating composition of the disclosure as described herein or is prepared according to the disclosure as described herein;

(v) an optional removable polymeric film applied over and to the fouling control layer (iv).

[140] The multilayer self-adhesive fouling control coating composition may be directly applied on a surface of a substrate in one single step, by simply pasting the self-adhesive composition on the surface to be coated.

[141] The multilayer self-adhesive fouling control coating composition may optionally comprise a removable underlying layer (i) applied on the adhesive layer (ii). The removable underlying layer (when present) is removed prior to application of the composition on the surface of a substrate. The removable underlying layer (i) may be a siliconized paper or siliconized synthetic layer. The removable underlying layer (i) may be a clay coated backing paper coated by an addition-type siliconized system. The clay coated paper may contain a humidity rate of 3% and more, such as from 6% to 10%, by weight of water. [142] The adhesive layer (ii) may be capable of securing the multilayer self-adhesive fouling control coating composition to a desired substrate. Examples of suitable adhesives include pressure sensitive adhesives (PSA). A suitable PSA may be capable of creating lasting adhesion to the substrate to be coated and the synthetic material layer (iii) for at least five years. The PSA may also be resistant to the conditions in which the multilayer self-adhesive fouling control coating composition is used, such as marine conditions.

[143] Examples of suitable PSA materials include acrylic PSA resin, epoxy PSA resin, amino based PSA resin, vinyl based PSA and/or silicone based PSA resin. The PSA may be a solvent based acrylic adhesive. The PSA may be a solvent based acrylic adhesive resistant to water. The PSA may allow application at low temperatures from -10°C to 60°C. PSA based on acrylic acid polymers, such as comprising an acrylic polymer and a cross-linking agent are also suitable.

[144] The adhesive layer (ii) may have a thickness of from 5 pm to 250 pm, such as of from 60 pm to 150 pm, depending on the type of adhesive used and the application envisaged.

[145] The multilayer self-adhesive fouling control coating composition further comprises a layer (iii) of synthetic material. Suitable synthetic materials include polyurethane resins, polyurethane acrylic resins, vinyl chloride resins, rubber- based resins, polyester resins, silicone resins, elastomer resins, fluoro resins, polyamide resins and/or polyolefin resins, such as polypropylene and polyethylene. Such materials for the synthetic material layer (iii) may be present in one sublayer or may be present in two sub-layers or more.

[146] When the synthetic material layer (iii) comprises an elastomer, the elastomer may be an olefin-based elastomer. The olefin-based elastomer may be a polypropylene-based elastomer. The polypropylene-based elastomer may be selected from no-oriented polypropylene, bioriented polypropylene and blow polypropylene, or any combination thereof.

[147] The synthetic material layer (iii) may be treated on one or both of its sides. The synthetic material layer (iii) may be treated on both of its sides.

[148] The synthetic material layer (iii) may be treated using a corona treatment or a plasma treatment, resulting in epoxy functional groups, acrylic functional groups, carboxylic functional groups, amino functional groups, urethane functional groups, and/or silicone functional groups on the surface of the synthetic material layer (iii). [149] The synthetic material layer (iii) may be treated using a primer treatment. The synthetic material layer (iii) may comprise a polypropylene-based elastomer and may be treated with a plasma treatment using a N2 gas, providing amide, amine and imide functional groups on one or both of the sides, such as on both sides, of said layer (iii).

[150] The thickness of synthetic material layer (iii) depends on the nature of the synthetic material. The thickness of the synthetic material layer (iii) may be from 10 pm to 3000 pm, such as from 30 pm to 1000 pm, such as from 50 pm to 300 pm.

[151] The multilayer self-adhesive fouling control coating composition comprises an fouling control layer (iv) applied over and to the synthetic material layer (iii), wherein the fouling control layer is derived from a fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein. The thickness of fouling control layer (iv) may be from 100 pm to 300 pm. This thickness may alternatively be referred to as the dry film thickness.

[152] The multilayer self-adhesive fouling control coating composition may comprise a removable polymeric film (v) applied over and to the fouling control layer (iv) in order to protect the latter, and which is to be removed notably once the adhesive layer of the composition has been applied over the substrate to be coated.

[153] The removable polymeric film (v) may comprise a polyester or a polypropylene film. The removable polymeric film may comprise polyvinylidene fluoride, polyurethane or polyvinylchloride.

COATED ITEM

[154] The fouling control coating composition may be coated onto at least a portion of a substrate so as to provide a coating layer thereon. The coating layer may comprise a single coat of the fouling control coating composition, or may comprise two or more coats of the fouling control coating composition. The coating layer may comprise two or three coats of the fouling control coating composition.

[155] The fouling control coating compositions of the present disclosure can be applied to various substrates including wood, paper, foam, and synthetic materials (such as plastics including elastomeric substrates), leather, textiles, glass, ceramic, metals (such as iron, steel and aluminium), concrete, cement, brick, and the like.

[156] Thus, the present disclosure is also directed to substrates at least partially (i.e. partially or fully) coated with a fouling control layer derived from the coating composition of the present disclosure. The substrates may be pre-treated before application of the fouling control layer. The substrates may be post-treated after application of the fouling control layer, with any other compositions. The substrates may not be post-treated with any other compositions after application of the fouling control coating composition. The fouling control layer derived from the coating composition of the present disclosure may be applied to an edge of a pressure sensitive adhesive foil comprising a fouling release coating, for example to act as an edge sealant fouling release layer.

[157] Any known method can be used to apply the fouling control coating compositions of the disclosure to a substrate. Non-limiting examples of such application methods are spreading (e.g. with paint pad or doctor blade, or by brushing or rolling), spraying (e.g. air-fed spray, airless spray, hot spray, and electrostatic spray), flow coating (e.g. dipping, curtain coating, roller coating, and reverse roller coating), and electrodeposition (see generally, R. Lambourne, Editor, Paint and Surface Coating: Theory and Practice, Eilis Horwood, 1987, page 39 et seq.).

[158] The fouling control coating compositions of the present disclosure can be applied and fully cured at ambient temperature conditions in the range of from -10°C to 50°C. Curing of said composition according to the disclosure may proceed very rapidly, and in general can take place at a temperature within the range of from -10°C to 50°C, such as from 0°C to 40°C, or such as from 3 to 25°C. However, compositions of the present disclosure may be cured by additional heating.

[159] There is provided a substrate at least partially coated with a fouling control layer derived from a fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein. The substrate may be a primer coated and/or intermediate coated substrate, such as a primer coated and/or intermediate coated metal substrate. The substrate may be coated with a pressure sensitive adhesive foil comprising a fouling release coating and the fouling control layer derived from the coating composition of the present disclosure may be applied to an edge of the foil, for example to act as an edge sealant fouling release layer. The substrate may be in contact with water, such as an underwater structure, such as a surface of a ship’s hull. [160] There is provided a method of coating at least a portion of a substrate with a fouling control layer, wherein the fouling control layer is derived from a fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein, the method comprising applying the fouling control coating composition onto at least a portion of the substrate. The method may comprise applying the coating composition of the present disclosure to an edge of a pressure sensitive adhesive foil comprising a fouling release coating.

[161] There is provided the use of a fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein for at least partially coating a substrate to control and/or prevent fouling thereon.

[162] There is provided the use of a fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein for at least partially coating a substrate to prevent fouling thereon.

[163] There is provided a method of at least partially coating a substrate to control and/or prevent fouling thereon, the method comprising applying a fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein onto at least a portion of the substrate. The method may further include the step of curing the fouling control coating composition.

[164] There is provided a method of at least partially coating a substrate to prevent fouling thereon, the method comprising applying a fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein onto at least a portion of the substrate.

[165] There is provided a substrate at least partially coated with a multilayer self-adhesive fouling control coating composition of the disclosure as described herein. The substrate may be a primer coated and/or intermediate coated substrate, such as a primer coated and/or intermediate coated metal substrate. The substrate may be in contact with water, such as an underwater structure, such as a surface of a ship’s hull.

[166] There is provided a method of coating at least a portion of a substrate with a multilayer self-adhesive fouling control coating composition of the disclosure as described herein, the method comprising applying the multilayer self-adhesive fouling control coating composition onto at least a portion of the substrate.

[167] There is provided the use of a multilayer self-adhesive fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein for at least partially coating a substrate to control and/or prevent fouling thereon.

[168] There is provided the use of a multilayer self-adhesive fouling control coating composition of the disclosure as described herein or prepared according to the disclosure as described herein for at least partially coating a substrate to prevent fouling thereon.

[169] There is provided a method of at least partially coating a substrate to control and/or prevent fouling thereon, the method comprising applying a multilayer self-adhesive fouling control coating composition of the disclosure as described herein onto at least a portion of the substrate.

[170] All of the features contained herein may be combined with any of the above aspects and in any combination.

[171] The disclosure will be further discussed with reference to the following non-limiting examples.

EXAMPLES

Example 1A

[172] 535 g of di-hydroxy silicone polymer (3500 cSt) was charged in a 2 litre container. 72 g of silicone colour paste, 38 g of non-reactive polydimethylsilicone (1000 cSt) and 52 g of a hydrocarbon solvent were added to the silicone polymer.

[173] Under stirring, 2 g of hydrophobic nano silica and 68 g of a biocide were added. This mixture was dispersed at high speed for 10 minutes until a fineness of 20 pm was obtained. 159 g of an aromatic solvent was then added and stirred until homogeneous.

[174] During dispersing at medium speed, 12 g of hexamethylene diisocyanate isocyanurate, 7 g of coco-alkyl amine and 1 g of meta-xylylene diamine were added sequentially. After addition of the hexamethylene diisocyanate isocyanurate no rise in temperature was observed, though a temperature rise of about 5°C was observed following addition of both amines, indicating the fast reaction of the amines with the isocyanate, resulting in the in-situ formation of the poly-urea polymers. Approximately 950 g of a silicone composition with fineness < 20 pm was formed.

[175] Under stirring, 53 g of ethyl tri-acetoxy silane and 2 g of dibutyl-tin-diacetoxy catalyst were slowly added and mixed until homogeneous to obtain approximately 1 kg of 1-K coating composition. The coating composition had a high shear viscosity of 9.0 dPas and a low shear viscosity of 20 dPas, with thixotropic index (T.l.) 2.2. With a sag tester (gaps 100 - 300 pm) sag resistance was determined at gap 200 pm, which corresponded to a dry film thickness [dft] of 100 pm. A drawdown on glass showed a tackfree time of < 15 minutes.

[176] The viscosity was measured according to ASTM D2196-10 using a Brookfield RV at 100 rpm and 10 rpm. The thixotropic index is the ratio of values at 10 rpm Z100 rpm. The sag resistance was measured according to ASTM D4400 and the dry film thickness was measured according to ASTM D1640.

[177] To ascertain the storage stability of the 1 K composition, the mixture was stored at ambient conditions for 12 months. After this period, the above properties were checked and found to be unchanged. High shear and low shear viscosity was respectively 9.4 dPas and 24 dPas (T.l. 2,5), fineness was < 20 pm and sag was still at gap 200 pm.

Comparative Example 1B

[178] 546 g of di-hydroxy silicone polymer (3500 cSt) was charged in a 2 litre container. 73 g of silicone colour paste and 39 g of non-reactive polydimethylsilicone (1000 cSt) and 53 g of a hydrocarbon solvent were added. Under stirring, 2 g of hydrophobic nano silica and 69 g of a biocide were added. This mixture was dispersed at high speed for 10 minutes until a fineness of 20 pm was obtained. Then, 162 g of an aromatic solvent was added and stirred till homogeneous.

[179] The resulting base composition had a high shear viscosity of 4.96 dPas and a low shear viscosity could not be measured.

[180] To determine the curing and sag resistance, the base composition was mixed with the cross-linker and the catalyst used in Example 1 A . A drawdown on glass showed a tackfree time of 15-20 minutes. Sag resistance was found to be insufficient. The base composition and hardener composition were separately stored at ambient conditions for 12 months. After storage, wet paint properties and curing were unchanged. However, when stored as mixed 1-K composition, the mixture had a very low viscosity and curing was delayed.

Example 2A

[181] 517 g of di-hydroxy silicone polymer (3500 cSt) was charged in a 2 litre container. 71 g of silicone colour paste, 37 g of non-reactive polydimethylsilicone (1000 cSt) and 51 g of a hydrocarbon solvent were added. Under stirring, 20 g of hydrophobic nano silica and 77 g of a barnaclecide were added. This mixture was dispersed at high speed for 10 minutes until a fineness of < 25 pm was obtained. Then, 154 g of an aromatic solvent was added and stirred till homogeneous. During dispersing at medium speed, 12 g of hexamethylene diisocyanate isocyanurate, 7 g of coco-alkyl amine and 1 g meta-xylylene diamine were sequentially added. After addition of the isocyanate no rise in temperature was observed, however the temperature was found to rise about 5°C when both amines were added, indicating the fast reaction of the amines with the isocyanate, resulting in the in-situ formation of the poly-urea polymers. Approximately 950 g of a silicone composition with fineness < 25 pm was obtained.

[182] Under stirring, 52 g of ethyl tri-acetoxy silane and 2 g of dibutyl-tin-diacetoxy catalyst were slowly added and mixed until homogeneous. The obtained 1 kg of 1-K coating composition had a high shear viscosity of 11 .7 dPas and a low shear viscosity 25 dPas, with thixotropic index (T.l.) 2.2. With a sag tester (gaps 100 - 300 pm) sag resistance was determined at gap 250 pm, which corresponded to a dry film thickness [dft] of 125 pm. A drawdown on glass showed a tackfree time of < 15 minutes.

[183] To ascertain the storage stability of the 1-K composition, the mixture was stored at ambient conditions for 12 months. After this period, the properties were checked and found to be comparable. High shear and low shear viscosity was respectively 13.1 dPas and 33 dPas (T.l. 2,5), fineness was < 25 pm and sag was still at gap 250 pm.

Comparative Example 2B

[184] 517 g of di-hydroxy silicone polymer (3500 cSt) was charged in a 2 litre container. 71 g of silicone colour paste, 37 g of non-reactive polydimethylsilicone (1000 cSt) and 51 g of a hydrocarbon solvent were added. Under stirring, 20 g of hydrophobic nano silica and 77 g of a barnaclecide were added. This mixture was dispersed at high speed for 10 minutes until a fineness of < 25 pm was obtained. Then, 154 g of an aromatic solvent was added and stirred until homogeneous. The resultant base composition had a high shear viscosity of 9.6 dPas while a low shear viscosity could not be measured.

[185] To determine the curing and sag resistance the base composition was mixed with the cross-linker and the catalyst as described for Example 2. A drawdown on glass showed a tackfree time of 15-20 minutes. Sag resistance was insufficient. The base and hardener compositions were separately stored at ambient conditions for 12 months. After storage, wet paint properties and curing were unchanged. However, when stored as mixed 1-K set composition, the mixture had a very low viscosity and curing was delayed.

Example 3A

[186] 1515 g of linear di-hydroxy functional dimethyl silicone polymer (3500 cSt) was charged in a 2.5 litre container. 118 g of silicone colour paste was added together with 156 g of low molecular weight polydimethylphenyl silicone additive (100 cSt) and 9 g of an aromatic solvent. During dispersing at medium speed, 19 g of hexamethylene diisocyanate isocyanurate, 11 g of coco-alkyl amine and 2 g of meta-xylylene diamine were sequentially added. After addition of the isocyanate, no rise in temperature was observed, however the temperature did rise about 5 °C when both amines were added, indicating the quick reaction of the amines with the isocyanate, resulting in the in-situ formation of the poly-urea polymers. The result was approximately 1830 g of a viscous silicone composition with fineness < 25 pm.

[187] Under stirring, 170 g of ethyl tri-acetoxy silane and 0.4 g dibutyl-tin-di-laurate catalyst were slowly added and mixed until homogeneous. The obtained 1-K composition had a high shear viscosity 52,0 dPas and a low shear viscosity 72 dPas, with thixotropic index (T.l.) 1 .4. With a sag tester (gaps 100 - 1100 pm) sag resistance was determined at gap 400 pm, which corresponded to a dry film thickness [dft] of 176 pm.

[188] To examine the storage stability of the 1-K composition, the mixture was stored at 60 °C for 50 days. After this period, the properties were reviewed and found to be unchanged. High shear and low shear viscosity were respectively 49.3 dPas and 82 dPas (T.l. 1 ,7), fineness was < 25 pm and sag was still at gap 400 pm.

Comparative Example 3B [189] 1005 g of linear di-hydroxy functional dimethyl silicone polymer (3500 cSt) was charged in a 2.5 litre container. 118 g of silicone colour paste was added together with 156 g of low molecular weight polydimethylphenyl silicone additive (100 cSt). 32 g of quaternary ammonium salt of a nano-clay and 9 g of an aromatic solvent were added and the mixture was dispersed at high speed for 30 minutes until a fineness of 25-30 pm was obtained. To finish the preparation, the residual 600 g di-hydroxy silicone polymer (3500 cSt) was added.

[190] After cooling to ambient temperature, 170 g of ethyl tri-acetoxy silane and 0.4 g of dibutyl- tin-di-laurate catalyst were slowly added and mixed until homogeneous. The obtained 1-K composition had high shear viscosity 43,7 dPas and low shear viscosity 78 dPas, with thixotropic index (T.l.) 1 ,8.

[191] With a sag tester (gaps 100 - 1100 pm) sag resistance was determined at gap 300 pm, which corresponded to a dry film thickness [dft] of 135 pm. To ascertain the storage stability of the 1-K composition, the mixture was stored at 60 °C for 50 days. After this period, the properties were analysed and found to be different from the initial properties. High shear and low shear viscosity was respectively 5,9 dPas and 19 dPas (T.l. 3,2), fineness was 30 pm and sag was reduced to gap 100 pm, corresponding to dft 50 pm. This illustrates that the treated nano-clay (thixotropic agent) is not suitable for preparation of a storage stable 1-K composition.

Comparative Example 4

[192] 546 g of linear di-hydroxy functional dimethyl silicone polymer (3500 cSt) was charged in a 2.5 litre container. 73 g of silicone colour paste and 39 g non-reactive polydimethylsilicone (1000 cSt) and 53 g hydrocarbon solvent were added. Under stirring, 71 g of hydrophobic nano silica was added. This mixture was dispersed at high speed for 10 minutes until a fineness of < 25 pm was obtained. Then, 162 g of an aromatic solvent was added and stirred until homogeneous. The resulting base composition had high shear viscosity of 15 dPas and low shear viscosity of 90 dPas, thixotropic index 6.

[193] To determine the curing and sag resistance the base composition, 56 g of ethyl tri-acetoxy silane and 2 g of dibutyl-tin-di-acetate catalyst were added (to provide a hardener composition).

[194] A drawdown on glass showed a tack free time of 15-20 minutes. With a sag tester (gaps 100 - 1100 pm) sag resistance was determined at gap 400 pm, which corresponded to a dry film thickness [dft] of 180 pm. The base and hardener compositions were separately stored at ambient conditions for 12 months. After storage, wet paint properties and curing were unchanged. However, when stored as mixed 1-K set composition, the set mixture had low viscosity, delayed curing and insufficient sag resista nee. The properties of coating compositions 1 A to 4 were tested via the following methods. Results are shown in Table 1 .

Test Methods

Preparation of test structures:

[195] Rectangular stainless steel panels (14 x 20 cm) were cleaned and degreased. The cleaned panels were coated with PPG’s SigmaShield 610® to a dry film thickness of 150 pm and cured for at least 1 day at ambient conditions.

[196] For testing of compositions of Examples 1A and 2A and Comparative Examples 1 B, 2B and 4:

The coating compositions of Examples 1A and 1 B and of Comparative Examples 2A, 2B and 4 were sprayed directly onto the SigmaShield 610® coated panels and cured for at least 1 day at ambient conditions.

[197] For testing of compositions of Example 3A and Comparative Example 3B:

Pressure sensitive adhesive foils (PPG SigmaGlide Foil) were attached to the SigmaShield 610® coated panels. A spacing of 2 cm was kept between the foils, creating artificial seams (gaps) between the foils. The coating compositions of Example 3A and Comparative Example 3B were applied with a brush to the edges of the foils with small overlaps of 1 cm onto the fouling release coating on the outer surface of the foils.

[198] The applied coating compositions were tested for adhesion (dry and wet) and fouling control performance (soft and hard fouling protection) according to the procedures below.

Adhesion (dry):

[199] Cross cut adhesion of the coating composition was measured using a sharp knife to cut a cross-cut into the surface of the coating composition on the test panels. The surface was aggravated with nail scratching and rubbing of a spatula over the surface and the extent of adhesion was evaluated. The adhesion (dry) was evaluated quantitatively using a rating of 0 (total delamination of the coating composition) to 5 (coating composition cannot be removed), with 5 being the best. Fouling Control Performance (soft fouling protection):

[200] The test panels were submerged in seawater in Kats (The Netherlands) and placed on a static raft at depths of 20 cm (centimetres), 50 cm, 110 cm and 140 cm below the water line. Soft fouling includes the adhesion of fouling organisms such as slime and algae. After removal of the panels from the seawater, the fouled surfaces of the test panels were wiped with a soft wet brush and immediately inspected. The test panels were first evaluated after 4 months from initial submersion and then several times up to 12 months from the initial submersion. The fouling control performance (soft fouling protection) was evaluated at each inspection to obtain an average value for the panels at each depth and these values were averaged to obtain the overall performance (soft fouling removal). The overall performance (soft fouling protection) was evaluated using a rating of 0 to 4, with 0 being the best as detailed below.

0: no soft fouling organisms remain on the surface of the test panel.

1 : less than 10% of the surface of the test panel has soft fouling organisms attached thereto. 2: from 10 to 20% of the surface of the test panel has soft fouling organisms attached thereto. 3: from 20 to 50% of the surface of the test panel has soft fouling organisms attached thereto. 4: greater than 50% of the surface of the test panel has soft fouling organisms attached thereto.

Fouling Control Performance (hard fouling removal):

[201] The test panels were submerged in seawater in Kats (The Netherlands) and placed on a static raft at depths of 20cm, 50cm, 110cm and 140 cm below the water line. Hard fouling includes the adhesion of fouling organisms such as barnacles, tubeworms and mussels. After removal of the panels from the seawater, the fouled surfaces of the test panels were wiped with a soft wet brush and immediately inspected. The test panels were evaluated several times during a 4 to 10 month period and the fouling control performance (hard fouling removal) was evaluated at each inspection to obtain an average value for the panels at each depth and these values were averaged to obtain the overall performance (hard fouling removal). The overall performance (hard fouling removal) was evaluated using a rating of 0 to 4, with 0 being the best.

0: no hard fouling organisms remain on the surface of the test panel.

1 : less than 3% of the surface of the test panel has hard fouling organisms attached thereto. 2: from 3 to 10% of the surface of the test panel has hard fouling organisms attached thereto. 3: from 10 to 20% of the surface of the test panel has hard fouling organisms attached thereto. 4: greater than 20% of the surface of the test panel has hard fouling organisms attached thereto. [202] The results are shown in Table 1 below.

Table 1

[203] The first three rows in Table 1 show the viscosity of the composition. The first row provides the initial viscosity. When the viscosity does not change after certain storage periods (as provided in rows 2 and 3 of Table 1), the composition is regarded as stable. From the viscosity data it is clear that only the examples according to the present disclosure are stable as 1-K formulations, while the comparative examples are not. The compositions of the present disclosure also show acceptable fouling control.

Example 5

[204] A fouling control coating composition was prepared according to the components listed in Table 2, below:

Table 2

Component Amount (g)

Siloxane binder 51.0

Silicone oils 8.0

Aliphatic polyisocyanate 1 .8

Mono-functional primary fatty amine 1 .0

Di-functional primary amine 0.2

Silica 18

Silica crosslinker 8.0

PEG 3.5

Potlife extender 4.5

Solvent 4.0

Total 100.0

[205] A performance assessment of the fouling control coating composition described in Example 5 was conducted according to the industrial standard ASTM D3623 (Standard Test Method for Testing Antifouling Panels in Shallow Submergence), wherein a non-fouled surface gives a score of 100 and a completely fouled surface gives a score of 0.

[206] The assessment criterion is defined as follows: Table 3

[207] For the assessment, a test panel (an epoxy panel) coated with the fouling control coating composition described in Example 5 was submerged in seawater and placed on a static raft below the water line. Soft fouling includes the adhesion of fouling organisms such as slime and algae, while hard fouling fouling includes the adhesion of fouling organisms such as barnacles, tubeworms and mussels. After removal of the panel from the seawater, the fouled surface of the test panel was wiped with a soft wet brush and immediately inspected. The test panel was evaluated after 14 months from the initial submersion. The fouling control performance was evaluated using a rating as detailed below:

Table 4

[208] The test panel with the fouling control coating composition of Example 5 was given a score of 85, providing a rating of “excellent”. For reference, a panel coated with a standard fouling release coating (i.e. not containing the thixotropic additive of the present disclosure) was assessed using the same method as described in paragraph 208 and was given a score of 79, providing a rating of “good”, while an epoxy panel with no fouling release coating or thixotropic additive was assessed using the same method as described in paragraph 208 and was given a score of “0”, which provides a rating of “very bad”. [209] Whereas particular examples of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims

[210] Attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[211] All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.

[212] Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

[213] The disclosure is not restricted to the details of the foregoing embodiment(s). The disclosure extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.