NZ617805B2 - Polysiloxane-based fouling release coats including enzymes - Google Patents

Abstract

Disclosed herein are polysiloxane based fouling release coatings comprising a polysiloxane-based binder matrix from a polysiloxane based binder which is a functional organopolysiloxane with terminal and/or pendant functionality, said polysiloxane-based binder matrix constituting 50-90 % by dry weight of the coat, one or more enzymes and one or more hydrophilic-modified polysiloxane oils in an amount of 0.05-10 % by dry weight of the coat. t of the coat, one or more enzymes and one or more hydrophilic-modified polysiloxane oils in an amount of 0.05-10 % by dry weight of the coat.

Description

POLYSILOXANE-BASED FOULING RELEASE COATS INCLUDING ENZYMES FIELD OF THE INVENTION The present invention relates to novel polysiloxane-based fouling release coats having included therein in for marine bio-fouling. In enzymes, particular suppressing particular variants, the coat further comprises one or more hydrophilic-modified polysiloxanes oils; and/or the binder matrix has included as a part thereof hydrophilic oligomer/polymer moieties.

BACKGROUND OF THE INVENTION In McDaniel al. "Formulating with Additives the Performance et Bioengineered Enhancing and Functionality of Paints and Coatings", Coatings World, 15 March 2010, it is mentioned that "Several different have reported on efforts to develop marine anti-fouling paints groups low- containing enzymes. One approach involves incorporation of hydrolytic enzymes into surface polydimethylsiloxane coatings to provide a dual mechanism for reducing energy attachment of marine organisms.

"Siloxane-based Kim et al. 2001 biocatalytic films and paints for use as reactive coatings.

Biotechnology and Bioengineering, Vol. 72, discloses a polysiloxane film containing immobilised proteases. The enzymes are immobilised either by sol-gel entrapment or by covalent linkage to the polydimethylsiloxane matrix. A decreased tendency of protein adsorption on PDMS films are reported when the siloxane films contain the immobilised proteases.

In EP1661955A1 an antifouling coating comprising immobilised enzymes in a siloxane matrix is disclosed. barnacle settlement indicate that the of Laboratory assays performance a silicone-based antifouling coating is improved when enzymes are immobilised in it.

WO 01/072911 discloses a method for releasing antimicrobial compounds incorporating enzymes into antifouling coatings. The method depends on the simultaneous incorporation of an enzyme and its substrate into an antifouling coating.

PC T/DK2012/050226 In US 770, 188 an antifouling paint composition is disclosed. The composition contains a which can selected from list and an that has been resin, be a containing silicone, enzyme modified coating its surface with a lipid to obtain improved stability in organic solvents.

In WO 00/50521 a marine antifouling composition is disclosed. The composition comprises a binder which an or and microorganism. may be silicone, amylolytic proteolytic enzyme a SUMMARY OF THE INVENTION The inventors have now for new present developed paint compositions preparing polysiloxane-based fouling release coatings (i.e. a cured paint coat) which comprise one or more enzymes. In this the advantages of silicone fouling release are combined with way, low-friction those of traditional anti-fouling coatings, thus gaining a foul-free, surface. in a first aspect the present invention relates to a cured fouling release coat comprising a polysiloxane-based binder matrix and one or more of enzymes capable preventing settling by one or more bio-fouling species.

A second of the invention relates to a kit for a fouling release said kit aspect preparing coat, comprising a first container holding a polysiloxane binder base, and a second container holding a siloxane curing agent and optionally a catalyst, wherein the polysiloxane binder of the first container is curable in the of the content of the second container. base presence The one or more enzyme is either a constituent of the first container or a constituent of the second container, or alternatively kept separately in a third container.

In embodiments of the above the further one currently preferred aspects, a) coat comprises or more hydrophilic-modified polysiloxanes oils; and/or the binder matrix has included as thereof moieties. a part hydrophilic oligomer/polymer A third aspect of the invention relates to a method of coating a surface of a substrate, comprising the sequentia I of: steps a. one or more of one or more of applying layers a primer composition and/or applying layers a tie-coat composition onto the surface of said substrate, and b. one or more layers of a coating composition so as to obtain a fouling release coat applying as defined herein on the coated surface of said substrate.

PC T/DK2012/050226 A fourth aspect of the invention relates to a marine structure comprising on at least a part of the outer surface thereof an outermost release defined herein. fouling coat as DETAILED DISCLOSURE OF THE INVENTION The cured coat paint As mentioned above, the present invention provides a cured paint coat comprising a polysiloxane-based binder matrix, constituting at least 40 weight of the preferably by dry and one or more coat, enzymes.

The paint coat is preferably used as the coat in a coating system comprising two or more coat layers at least a primer coat and a tie coat in addition to the paint (e.g. top coat).

The one or more enzymes Inclusion of the one or more enzymes in the fouling release coat improves the resistance towards bio-fouling of said polysiloxane-based fouling release coat. The enzymes contribute to the fouling release properties of the coating preventing settlement before or during, or alternatively reverting settlement. Even though siloxane-based fouling release coatings are very good at hindering settlement of bio-fouling organisms, enzymes can contribute to the overall antifouling ability of a fouling release either selected targeted mechanisms coating, by towards troublesome bio-fouling or of the specifically species, by a general improvement protection mechanism via a broad spectrum antifouling mechanism.

All enzymes capable of preventing settlement of bio-fouling organisms are considered relevant for this invention. However of particular interest are hydrolytic enzymes. Hydrolytic enzymes are those selected from EC class 3. Of particular interest are those selected from the EC classes: following EC 3.1: ester bonds (esterases: nucleases, phosphodiesterases, lipase, phosphatase) EC 3.2: sugars (DNA glycosylases, glycoside hydrolase) EC 3.3: ether bonds EC 3.4: peptide bonds (Proteases/peptidases) EC 3.5: carbon-nitrogen bonds, other than bonds peptide EC 3.6 acid anhydrides (acid anhydride hydrolases, including helicases and GTPase) EC 3.7 carbon-carbon bonds PC T/DK2012/050226 EC 3.8 halide bonds EC 3.9: bonds phosphorus-nitrogen EC 3.10: sulfur-nitrogen bonds EC 3.11: carbon-phosphorus bonds EC 3.12: sulfur-sulfur bonds EC 3.13: carbon-sulfur bonds EC 4.2: includes that cleave carbon-oxygen bonds, such as dehydratases lyases In one embodiment, the one or more enzymes include a hydrolytic enzyme.

In one embodiment, the one or more enzymes are selected from EC classes: EC 3. EC 3. 1, 2, EC 3.4 and EC 4.2.

In another embodiment, the one or more enzymes are selected from serine proteases, cysteine proteases, metalloproteinase, cellulase, hemicellulase, pectinase, glycosidases.

Savinase Commercial examples of enzymes which are believed to be useful are (ex Novozymes Endolase Novozymes Alcalase Novozymes Esperase A/S), (ex A/S), (ex A/S), Subtilisin (ex Novozymes), Papain (ex Sigmaaldrich), Carlsberg (ex Sigmaaldrich), pectinase (ex Sigmaaldrich), and polygalacturonase (ex Sigmaaldrich).

In one embodiment, the one or more enzymes include an enzyme which is capable of degrading the exopolymeric substances (i.e. adhesives) of barnacles. Thus, the enzyme must deter settlement of barnacle larvae, without killing or in other exerting cypris preferably ways the barnacle toxic effects. The of an hinder settlement of to ability enzyme to reversibly "Barnacles test" barnacles can be tested in accordance with the settlement described in the Experimenta Is section herein.

In another the one or more include an which is of embodiment, enzymes enzyme capable degrading the exopolymeric substances (i.e. adhesives) of algae. Thus the enzyme must deter settlement of without or in other the algal zoospores, preferably killing ways exerting algal zoospore to toxic effects. The ability of an enzyme to reversibly hinder settlement of test" can be tested in accordance with the "Algae settlement described in the algae Is section herein.

Experimenta In another embodiment, the one or more enzymes include an enzyme which is selected to exert an effect on specific organisms, be it toxic or not. Hence, in this embodiment, the effect of the enzyme in addition to being settlement lowering, also affect viability and may, mortality of the bio-fouling organism in question.

PC T/DK2012/050226 In some interesting embodiments, the one or more enzymes are pre-formulated before being mixed with other constituents. For the immobilized on or paint example, enzymes may be within filler particles, on binder constituents, or if such constituents are also present be formulated with hydrophilic mono-, oligo-, or polymers or with hydrophilic-modified oils further polysiloxane (see below).

In one interesting embodiment, the one or more enzymes one or some of the one or more are e. either surface treatment or immobilisation. enzymes) formulated, g. by by In one variant, the one or more enzymes may be entrapped in an aerogel, xerogel, or matrix in a manner similar to that described in , in order to kryogel-type obtain in the wet with the cured and controlled release of stability paint, compatibility coat the enzymes when the network of the encapsulation material is degraded hydrolysis by by seawater.

Similarly, the enzymes may be encapsulated in a polymeric material, similar to the material described in US in order for the enzymes to be shielded from but not from 7,377,968, xylene, seawater.

Another way of pre-treating the enzyme is ionic interaction with either a polyanionic or polycationic material. on the of the a the suitable Depending pI enzyme, polymer carrying charge will affiliate strongly to enzymes giving rise to ionic cross-linking and thus stabilisation of the enzymes. onto suitable such or is an alternative Adsorption a material, as clay nitrocellulose, way to obtain increased enzyme stability during the preparation, application and curing of an enzyme-containing fouling release coating.

Establishment of covalent bonds between bifunctional cross-linkers can also enzymes, using potentially improve the enzyme stability. This can be referred to as both cross-linking and Cross-linked are available for polymerisation. enzyme aggregates (CLEA commercially some of the more common enzymes.

Hence in one embodiment, the one or more enzymes are reacted with a bifunctional cross- linker form so as to enzyme aggregates.

Homo and hetero-bifunctional cross-linkers can be used to immobilise enzymes onto another activated material, such as a binder constituent. Hetero-bifunctional cross-linkers have the advantage of being selective in each end of the molecule. This ensures that the cross-linking PC T/DK2012/050226 only occurs between the molecules of interest. However, homo-bifunctional cross-linkers are also immobilise onto material. Immobilisation of frequently used to enzymes a separate enzymes may be performed before and after film curing, either binding the enzyme to a precursor of the film or activating a cured film and binding the enzymes to the activated sites.

Also, modification of the surface of enzymes improve their compatibility with solvents, such oils or solvents. and acids are as hydrophobic Poly(ethylene glycol) fatty commonly applied to render enzymes more compatible with the environments they are intended to be kept in.

Hence in one further the is surface-modified, with embodiment, enzyme preferably Poly(ethylene glycol).

The one or more settlement of bio-fouling on the enzyme applied to prevent organisms foul-release wt'/o, polysiloxane-based coating should preferably comprise at a maximum 5 e. 0.0005-4 wt'/o, such as 0.001-3 wt'/o, or 0.002-2 wt'/o, or 0.003-1.5 wt'/o, or 0.01-0.05 wt'/o, of the total of the foul-release calculated amount of weight paint coat, as pure enzyme compared to the total weight of the cured coating.

Polysi loxane-based bi nder matrix The fouling release coat of the invention has included therein a polysiloxane-based binder matrix. The binder is in the form of a cross-linked matrix which incorporates the one or more well other e. etc. in the enzymes as as constituents, g. biocides, additives, pigments, fillers, fouling release coat. it should understood that the polysiloxane-based binder matrix is made of Hence, be up reactive polysiloxane binder components, e. functional organopolysiloxanes, cross-linkers, silicates ethyl silicate), and the like. Thus, it is believed that the reaction between such (e.g. will result in the binder matrix in the form of three-dimensional components a typically interconnected network. covalently The cured coat be formed in various e. polymerization/cross-linking paint may ways, g. by formation of siloxane bonds through a condensation reaction or the use of their reactive such as for example amine/epoxy, carbinol/isocyanate etc. Condensation reaction is groups preferred.

PC T/DK2012/050226 The polysiloxane-based binder matrix is prepared from a polysiloxane based binder which is a functional with terminal The terminal organopolysiloxane, and/or pendant functionality. functionality is preferred. The functionality can either be hydrolysable groups, such as for example alkoxy ketoxime or the functionality can be silanol groups. A groups, groups minimum of two reactive molecule is If the molecule contains two groups per preferred. only reactive for example silanol it be necessary to use an additional groups, groups, may reactant, a cross-linker, to obtain the desired cross-link density. The cross-linker can for example be an alkoxy silane such as methyltrimethoxysilane, but a wide range of useful silanes are available as will be described further on. The silane can be used as it is or as hydrolysation-condensation products of same. Although condensation cure is much preferred, the functionality of the organopolysiloxane is not limited to a condensation cure. If so desired, other of curing can be utilized, for example either alone or in types amine/epoxy combination with a condensation reaction. In such cases, the organopolysiloxane can have terminal of or amine and pendant hydrolysable for example with groups epoxy groups, a lkoxyfunctiona lity.

In some embodiments, the fouling release coating composition including the polysiloxane- based binder system be a reaction-curable composition or a condensation-curable will evident for the skilled in the art. hereof are two- composition as be person Examples a component condensation curing composition based on a silanol-reactive polydiorganosiloxane and a silane with hydrolysable or a one-component condensation-curable groups, composition based on a polydiorganosiloxane with alkoxy or other hydrolysable reactivity.

Another example is a reaction curable composition based on an epoxyfunctional polysiloxane binder and an amine functional polysiloxane curing agent. Combinations of reaction-curable compositions and condensation-curable compositions are possible, if the binder or the curing includes condensation curable such as alkoxy agent (or both) groups, groups.

In one embodiment, the binder phase comprises a binder and (ii) a cross-linking agent of which the binder should include hydrolysable or other reactive so as to (i) groups groups participate in the formation of the matrix. -90 The binder typically constitutes % dry weight of the coating composition. (i) by 0-10 The cross-linking agent preferably constitutes % weight of the coating (ii) by dry composition and is, e. an organosilicon compound represented the general formula g. , by (2) shown below, a partial hydrolysis-condensation product thereof, or a mixture of the two: PC T/DK2012/050226 wherein, each R represents, independently, an unsubstituted or substituted monovalent of 1 carbon atoms or each X hydrocarbon group to 6 a hydrolysable group, represents, independently, a hydrolysable and a represents an integer from 0 to 2, such as from 0 group, to 1.

The outlined in formula cross-linker for the binder The compound acts as a (i). composition can be formulated as a one component curable RTV (room-temperature the binder and the cross-linking If the on vulcanizable) by admixing agent (ii). reactivity the terminal Si-group of the binder consist of readily hydrolysable groups, such as dimethoxy or trimethoxy, a separate cross-linker is usually not necessary to cure the film.

The behind the mechanism and of cross-linkers is described in technology curing examples prior art (US 2004/006190).

In one R such In this embodiment, represents a hydrophilic group as a poly(oxyalkylene).

Si-atom case, it is preferred to have a C»-alkyl spacer between the and the polyoxyalkylene Hence, the organopolysiloxane have oxyalkylene domains. group. may Preferred cross-linkers are those selected from tetramethoxysilane, tetraethoxysilane; tetra-n-butoxysila ne; ne; vinyltris(methylethyloximino) sila ne; vinyltris- tetra pro poxysila sila methyltris(methylethyloximino) sila methyltris(acetoxime) sila (acetoxime) ne; ne; ne; vinyltrimethoxysila ne; methyltrimethoxysila ne; vinyltris(iso pro penoxy) sila ne; tetraacetoxy- di-t-butoxy- silane; methyltriacetoxysilane; ethyltriacetoxysilane; vinyltriacetoxysilane; and well diacetoxysilane; methyltris(ethyllactate)silane vinyltris(ethyllactate)silane as as hydrolysis-condensation products of the same.

Other interesting cross-linkers are those selected from vinyltriethoxysilane, methyltriethoxy- silane, ethyltrimethoxysilane, ethyltrimethoxysilane, tetraisopropoxysilane, tetrabutoxysilane as well as hydrolysis-condensation products of the same.

In some the polysiloxane-based binder interesting embodiments, comprises a polydimethyl- siloxane-based binder. lmethylsiloxan).

In other interesting embodiments, the binder include fluoro-modifications, e. may g. modified binders such silanol-terminated fluoroalkyl polysiloxane as poly(trifluoropropy- The polysiloxane-based binder matrix constitutes at least 40 at typically by dry weight, '/D '/D '/D least 50 dry weight, preferably at least 60 dry weight, e. at least 70 by by g. by '/D '/D '/D in particular 50-90 or 50-98 e. 50-96 weight, by dry weight, by dry weight, g. by dry PC T/DK2012/050226 60-95 '/D 50-95 '/D 60-94 '/D weight, in particular weight, or weight, or by dry by dry by dry '/D '/D '/D or 70-96 or even 70-94 or 75-93 weight, by dry weight, by dry weight, by dry 75-92 '/D weight, or dry weight, of the coating composition. li c-modIfi ed loxane oils Hydrophi polysi The fouling release coat may further include hydrophilic-modified polysiloxane oils, i.e. constituents which do not form covalent bonds to the polysiloxane-based binder matrix.

Hydrophilic-modified oils are surfactants and emulsifiers polysiloxane widely used as due to the content of both hydrophilic and lipophilic groups in the same molecule. In contrast to the polysiloxane components discussed above, the hydrophilic-modified polysiloxane oils are selected so that they do not contain groups that can react with the binder (or binder components) or the cross-linker (if hence the hydrophilic-modified polysiloxane oils present), are intended to be non-reactive, in particular with respect to the binder components. In silicon-reactive particular, the hydrophilic-modified polysiloxane oils are devoid of any groups Si-OH Si-OR such as hydrolysable such as (such as alkoxy, oxime, acetoxy groups, groups etc. etc. avoid reaction with constituents of the polysiloxane-based binder groups, so as to system.

The non-reactive hydrophilic-modified polysiloxane oils are modified the addition typically by non-ionic of oligomeric or polymeric groups which can be polar and/or capable of hydrogen bonding, enhancing their interaction with polar solvents, in particular with water, or with other oligomeric or Examples of these include, amides polar polymeric groups. groups (e.g. pyrrolidone), poly[N-(2-hydroxypropyl)methacrylamide]), poly(vinyl poly(N, dimethacrylamide), acids alcohols (e.g. poly(acrylic acid)), (e.g. poly(glycerol), polyHEMA, ketones polysaccharides, poly(vinyl alcohol)), (polyketones), aldehydes (e.g. poly(aldehyde guluronate), amines polyvinylamine), esters polycaprolactones, (e.g. (e.g. poly(vinyl ethers like acetate)), (e.g. polyoxyalkylenes poly(ethylene glycol), poly(propylene glycol)), imides etc. of the (e.g. poly(2-methyloxazoline)), including copolymers foregoing.

Preferably the hydrophilicity is obtained modification with polyoxyalkylene groups.

As it should understood that the moieties with which before, be hydrophilic oligomer/polymer the polysiloxane oils are modified are of non-silicon origin. Preferably, the above-mentioned "oligomers" and "polymers" include at least 3 units, such as at least 5 repeating repeating units. In the or include 3-1, many interesting embodiments, oligomers polymers 000 -100 repeating units, such as 3-200, or 5-150, or repeating units.

PC T/DK2012/050226 In some preferred embodiments, the hydrophilic (i.e. oligomeric or polymeric groups groups) have number molecular in the of 100-50, such in a average weight range 000 g/mol, as (M„) the range of 100-30,000 g/mol, in particular in the range of 200-20, 000 g/mol, or in the range of 200-10,000 g/mol.

In the with the term "hydrophilic-modified" in the context of present description claims, oil" "hydrophilic-modified polysiloxane is intended to mean that the oligomeric or polymeric with which the is in themselves e. discrete groups polysiloxane modified, (i. as molecules) 'C. have a solubility of at least 1 '/D(w/w) in demineralized water at Of particular interest are those hydrophilic-modified polysiloxane oils in which the relative of the moieties is 1'/D or more of the total 1-90'/D), such weight hydrophilic weight (e.g. as '/D 5-80'/D), 10'/D 10-70'/D) or more (e. in particular or more (e. of the total weight of the g. g. hydrophilic-modified oil. polysiloxane In a preferred embodiment, the hydrophilic-modified polysiloxane oil (if present) has a number average molecular weight in the of 100-100,000 such as in the (M„) range g/mol, of 250-75, in in the of 500-50, range 000 g/mol, particular range 000 g/mol.

It is also preferred if the hydrophilic-modified polysiloxane oils (if present) have a viscosity in the of 10-20,000 mPa such as in the of 20-10,000 mPa in particular in the range s, range s, 40-5, range of 000 mPa s.

The hydrophilic-modified polysiloxane oils be utilized to control the accessibility of the one or more control the of well distribute enzymes and/or to leaching any biocides, as as to the enzyme in the wet paint.

In one currently preferred embodiment, the hydrophilic-modified polysiloxane oil is a poly(oxyalkylene)-modified polysiloxane.

In one variant hereof, the poly(oxyalkylene)-modified polysiloxane oil is a polysiloxane thereto chains. An illustrative of the structure of having grafted poly(oxyalkylene) example such hydrophilic-modified polysiloxane oils is formula (A): PC T/DK2012/050226 —— — — R Si 0 Si Si 0 Si R wherein each is independently selected from C»-alkyl (including linear or branched hydrocarbon and (-C, in particular each is groups) aryl (e.g. phenyl H, methyl; -H, -CH„-CH, independently selected from C, 4-alkyl (e.g. CH„-CH, CH, CH„-CH(CH, -CH, CH, CH, phenyl (-C, and 4-alkylcarbonyl -C(=0)CH„-C(=0)CH, CH, H, C, (e.g. CH3 ), ), and -C(=0)CH, in particular and each is independently selected from CH, CH, methyl; C~ q-alkylene (e. -CH~CH~-, -CH~CH(CHq)-, -CH~CH~CH~-, -CH~CH~CH~CH~-, arylene 4-phenylene) and C»- alkylene substituted with -CH&CH(CH&CH&)-), (e.g. 1, aryl (e.g. 1-phenyl in from C»-alkylene such -CH&CH&- and -CH, x is ethylene), particular as CH(CH&)-); 1-100 0-50 1-50. 0-2500, is and x+y is 1-2000; and n is 0-50, m is and m+n is Commercially available hydrophilic-modified polysiloxane oils of this are DC5103 type (Dow Corning), DC Q2-5097 (Dow Corning), and DC193 (Dow Corning).

In another variant hereof, the poly(oxyalkylene)-modified polysiloxane oil is a polysiloxane in the backbone thereof chains. An illustrative having incorporated poly(oxyalkylene) example of the structure of such hydrophilic-modified polysiloxane oils is formula (B): — — —— — — — R 0 R Si 0 Si 0 Si 0 R 0 R PC T/DK2012/050226 wherein each is independently selected from C»-alkyl (including linear or branched and in each is hydrocarbon groups) aryl (e.g. phenyl (-C,H, particular methyl; -H, -CH„-CH, independently selected from 4-alkyl (e. CH„-CH, CH, CH„-CH(CH, C, g. )„ -CH, CH, CH, phenyl (-C, and 4-alkylcarbonyl -C(=O)CH„-C(=O)CH, CH, H, C, (e.g. CH3 ), ), and in and each is selected from -C(=O)CH, CH, CH, particular methyl; independently q-alkylene -CH~CH~-, -CH~CH(CHq)-, -CH~CH~CH~-, -CH~CH~CH~CH~-, C~ (e.g. arylene 4-phenylene) and C»- alkylene substituted with -CH&CH(CH&CH&)-), (e.g. 1, aryl (e.g.

-CH&CH&- -CH, 1-phenyl ethylene), in particular from C»-alkylene such as and CH(CH&)-); x is 0-50 1-50. 0-2500; and n is 0-50, m is and m+n is available hydrophilic-modified oils of this are DC Q4-3669 Commercially polysiloxane type DC2-8692.

(Dow Corning), DC Q4-3667 (Dow Corning) and In still another variant the oil is hereof, poly(oxyalkylene)-modified polysiloxane a polysiloxane having incorporated in the backbone thereof polyoxyalkylene chains and having grafted thereto polyoxyalkylene chains. An illustrative example of the structure of such hydrophilic-modified oils is formula polysiloxane (C): R R R 2 I 3 1 3 s1 2 — — — — Si 0 Si 0 Si R R~O R~O wherein each is independently selected from C»-alkyl (including linear or branched hydrocarbon and aryl phenyl (-C, in particular methyl; each is groups) (e.g. H, independently selected from -H, 4-alkyl -CH&, -CH&CH&, -CH&CH&CH&, C& (e.g. -CH(CH&)p, -CH, CH, CH, CH, phenyl (-C, and 4-alkylcarbonyl (e. -C(=O)CH„-C(=O)CH, CH3 ), H, ), C, g. and -C(=O)CH, CH, in particular and methyl; each is independently selected from PC T/DK2012/050226 q-alkylene -CH~CH~-, -CH~CH(CHq)-, -CH~CH~CH~-, -CH~CH~CH~CH~-, C~ (e.g. and C»- substituted with -CH&CH(CH&CH&)-), arylene (e.g. 1,4-phenylene) alkylene aryl (e.g.

-CH, -CH, 1-phenyl ethylene), in particular from -alkylene such as CH, and CH(CH, )-); x is 0-2500, is 1-100 and x+y is 1-2000; k is 0-50, I is 0-50 and k+I is 1-50; and n is 0-50, m is 0-50 and m+n is 1-50.

In the above structures and the -CH&CH(CH&)-, -CH&CH(CH&CH&)-, etc.

(A), (B) (C), groups in of the two orientations. it should understood may be present any possible Similarly, be that the segments present x and times typically are randomly distributed, or distributed as blocks, within the polysiloxane structure.

In these embodiments and the is selected from variants, poly(oxyalkylene) preferably polyoxyethylene, polyoxypropylene and poly(oxyethylene-co-oxypropylene), which sometimes are referred and to as poly(ethylene glycol), poly(propylene glycol) poly(ethylene glycol-co-propylene glycol). Hence, in the above structures and each linking (A), (B) (C), two atoms is preferably selected from -CH&CH&- and -CH, CH(CH&)-, whereas each oxygen silicon atom and an atom is selected from -alkyl. linking a oxygen preferably C, non-reactive It should be understood that the one or more hydrophilic-modified polysiloxane oils if present be of different e. two or more of the described above. may types, g. types If present, the one or more hydrophilic-modified polysiloxane oils are typically included in the coating composition in an amount of 0.01-20 '/o, e. 0.05-10 '/o, weight. In certain g. by dry the one or more hydrophilic-modified oils constitutes 0.05-7 embodiments, polysiloxane by 1-5 '/o 5-3 '/o dry weight, e. 0. dry weight, in particular 0. dry weight, of the coating g. by by composition. In certain other embodiments, the one or more hydrophilic-modified '/o '/o 2- oils constitutes 1-10 e. 2-9 in polysiloxane by dry weight, g. by dry weight, particular '/o 3-7 '/o 3-5 '/o 4-8 '/o 7 dry weight, or dry weight, or dry weight, or dry weight, by by by by of the coating composition.

Fluorinated oils As an alternative or in addition the hydrophilic-modified polysiloxane oils, the coating to, to, composition (and thereby the paint coat) may have included therein one or more fluorinated "oil" oil(s). the term is inherently meant that the constituent does not form covalent bonds to the polysiloxane-based binder matrix. Hence, the fluorinated do not contain oil(s) groups cross-linker that can react with the binder (or binder components) or the (if present), hence the one or more fluorinated are intended to be non-reactive, in particular with respect oil(s) to the binder components. In particular, the fluorinated oils are devoid of any silicon-reactive groups such as Si-OH groups, hydrolysable groups such as Si-OR (such as alkoxy, oxime, acetoxy etc.) groups, etc., so as to avoid reaction with constituents of the polysiloxane-based binder system.

It is preferred that the one or more fluorinated oil(s) (if present) have a viscosity in the range of 10-20,000 mPa·s, such as in the range of 20-10,000 mPa·s, in particular in the range of 40-5,000 mPa·s.

In a preferred embodiment, the fluorinated oil(s) (if present) has a number average molecular weight (Mn) in the range of 100-100,000 g/mol, such as in the range of 250- 75,000 g/mol, in particular in the range of 500-50,000 g/mol.

The one or more fluorinated oils may be utilized to control the accessibility of the one or more enzymes and/or to control the leaching of any biocides, as well as to distribute the enzyme in the wet paint.

In one embodiment, the one or more fluorinated oils are selected from fluoroalkyl modified oils, e.g. perfluorinated oils, perfluoroalkyl-modified polysiloxane, perfluoro siloxane, perfluoro polyether, perfluorinated alkanes, or perfluoroalkyl modified polyalkylene oxide, perfluoro polyalkylene oxide.

Commercially available examples of such oils are: Lumiflon LF-200: (Fluoroethylene-Alkyl Vinyl Ether) alternating copolymer.

In another embodiment, the one or more fluorinated oils are selected from fluoroalkyl modified polyoxyalkylene polysiloxane oils (e.g. PEG-PDMS). These compounds are polysiloxanes which have been modified with fluoroalkylene and polyoxyalkylene, and can have a linear or branched/pendant conformation, or a combination of a linear and branched/pendant conformation. In the linear form, the polymer will generally have the structure A-B-C where A is a fluoroalkyl group, B is a polysiloxane and C is a polyoxyalkylene.

Therefore, it will only have one fluoroalkyl group and one polyoxyalkylene group per polysiloxane molecule. In a variation, the modification of the polysiloxane molecule is in a branched/pendant conformation, in which the fluoroalkylene group(s) and the PC T/DK2012/050226 polyoxyalkylene are attached to the polysiloxane backbone in non-terminal group(s) This allows more than one of each molecule. of positions. group per polysiloxane Examples possible synthetic routes are disclosed in US 445, 114.

This of fluorinated oils to provide certain advantages. Without bound to type appears being it is believed that the of the oils the surface of the any particular theory, migration to coating during curing be higher due to the fluorination; that the fluorination may (ii) may lower the of the oil adsorb non-fluorinated affinity to to pigments compared to analogues.

PEG- Commercially available examples of such oils are Fluorosil 2110, a perfluoro nonyl ethyl 8 dimethicone and C1910, a fluorinated silicone of the same generic structure as polyether Fluorosil 2110.

It should be understood that the one or more non-reactive fluorinated oil(s), if present, may of different e. two or more of the described above. be types, g. types If present, the one or more fluorinated oils are typically included in the coating composition in an amount of 0.01-20 '/o, e. 0.05-10 '/o, weight. In certain embodiments, the one g. by dry '/o '/o or more fluorinated oils constitutes 0.05-7 e. 0.1-5 in by dry weight, g. by dry weight, -3 '/o particular 0. dry weight, of the coating composition. In certain other embodiments, 1-10 '/o 2-9 '/o the one or more fluorinated oils constitutes e. by dry weight, g. by dry weight, 2-7 '/o 3-7 '/o 3-5 '/o 4-8 '/o in particular dry weight, or dry weight, or dry weight, or by by by weight, of the coating composition. by dry if with one or more hydrophilic-modified the one or Also, present together polysiloxane oils, more fluorinated oils and the one or more hydrophilic-modified polysiloxane oils are typically included in the coating composition in a combined amount of 0.01-20 '/o, e. 0.05-10 '/o, g. by In certain the one or more fluorinated oils constitutes 0.05-7 dry weight. embodiments, by 1-5 '/o 5-5 '/o dry weight, e. 0. dry weight, in particular 0. dry weight, of the coating g. by by In certain other the one or more fluorinated oils constitutes 1-10 composition. embodiments, '/o 2-9 '/o 2-7 '/o 3-7 '/o dry weight, e. dry weight, in particular dry weight, or by g. by by by 2-6 '/o 3-5 '/o 4-8 '/o or or or of the dry weight, by dry weight, by dry weight, by dry weight, coating composition.

Hydrophilic modification of the binder matrix In some the binder matrix has included thereof interesting embodiments, as a part hydrophilic oligomer/polymer moieties.

PC T/DK2012/050226 In one embodiment, the binder includes a curable diorganopolysiloxane represented a formula shown below: general wherein each is independently selected from a hydroxyl a hydrolysable group and group, another functional such as amine or each is independently selected from group, epoxy; A' A' alkenyl and a hydrolysable each and is independently selected from alkyl, aryl, group; alkyl, aryl alkenyl and a hydrophilic such as a polyoxyalkylene wherein, if group, group, A'is and/or a hydrophilic such as a polyoxyalkylene such be group, group, group may attached the silicon atom via C»-alkylene 1-25, 1-2, and a+b is to a linker; a 000, b 500 at least 5.

In one alternative embodiment, the binder includes a curable diorganopolysiloxane represented a general formula shown below: by (1x) A" A" A', A', A', A', wherein each of a and b are as above for formula and wherein each is independently selected from oxygen or an alkyl group of carbon atoms.

In another embodiment, the polysiloxane binder has hydrophilic oligomer/polymer moieties side chains and can grafted as (pendant hydrophilic groups), as depicted below, be prepared a hydrosilylation reaction between a hydride functional polysiloxane and a hydrophilic component containing an unsaturated (-CH=CH, such as for example an allyl or vinyl group in presence of a hydrosilylation catalyst, such as platinum, in accordance with formula group, PC T/DK2012/050226 where the example of a hydrophilic compound is an allyl-terminated poly(ethylene (1c), The is carried elevated such 60-150'C. To render glycol). synthesis out at temperatures, as the polymer curable, it is necessary to functionalise it with a hydrolysable, or other means reactive, such as vinyltrimethoxysilane. The reaction is following same principles as group, when grafting the hydrophilic compound to the polysiloxane, and it is outlined in formula and the functionalization be done, but not necessarily, prior to the bonding of a (1b), may hydrophilic group.

CH. H CH. 0 CH, , —— — — — —— S; Si 0 Si H 2 ~Si 0 H + CHq 0+Si CH3 CH, CHa Platinum catalyst 60-150~ Si 0 0 — — — Si 0 Si 0 Si 0+Si 0 —— S' Hac 0 The binder from the reaction is further modified with resulting (1b) a hydrophilic component, for example poly(ethylene mono allyl ether as outlined in formula resulting in a glycol) (1c) curable, polysiloxane modified with hydrophilic moieties. oligomer/polymer PC T/DK2012/050226 L, B 6 sk c3&. !-'!a:in..:n «sos/yet Scan'-1 0~ 3A-, A — c s! c c&q CH, The binder obtained can be used as is, or in combination with a curable diorganosiloxane the generic presented in formula 1). As previously described, hydrophilic polymers other type than poly(ethylene are also useful for rendering the polysiloxane hydrophilic. glycol) It is the moieties the possible to graft hydrophilic pendant to polysiloxane prior to grafting the hydrolysable silane to the polysiloxane (i.e. in reverse order than the synthesis described in formulae and (1b) (1c). in one the cured polysiloxane-based Hence, interesting embodiment, paint coat comprising a binder matrix has included as a part thereof pendant hydrophilic oligomer/polymer moieties. "pendant" The means that the moieties are attached expression hydrophilic oligomer/polymer non-terminal to the polysiloxane backbone at a position and that such moieties are attached "graft" at the one end so that the pendant hydrophilic forms a to the only oligomer/polymer "branched". backbone This is can also referred polysiloxane (matrix). be to as PC T/DK2012/050226 Pendant hydrophilic oligomers/polymer moieties in principle at the free end carry functional (non-reactive) the free e. biocidal etc. groups at end, g. groups exhibiting a effect, However, in most embodiments, the hydrophilic oligomers/polymer moieties are not carrying such functional but are in the form of the native oligomer/polymer form, possibly groups, like with an or with or end-capped, alkyl group, possibly a hydroxyl group methoxy terminated.

A-B-A Another variation of the binder is an of and copolymer polysiloxane a hydrophilic polymer such as poly(oxyalkylene). An example of the structure of the polymer is (B), depicted in formula In this variation, units of a polymer with hydrophilic character, such (1d). are introduced in the backbone of the form an as polyoxyalkylene polysiloxane to alternating block copolymer. Introducing hydrophilic groups such as oxyalkylene groups in the binder increase the of the binder as described in reference . The may hydrophilicity A-B- binders can be used alone or in combination, and the structure of the copolymer can be B-A-B. B-A-B, A and In case of a pendant curable functionality is required, since the terminal of the silicone portion would be blocked the hydrophilic groups by polymer. (l~) si ct In another variant, the hydrophilic component is obtained hydrosilylation of a yet by least unsaturated (-CH=CH, such an polyoxyalkylene compound containing at one, group as allyl or a vinyl with a silane having a hydride e. HSi(R*), wherein group, group, g. groups, each independently is selected from 4-alkyl and 4-alkoxy C, C, (e.g. methyl, ethyl, propyl, butyl, methoxy, ethoxy, and butoxy), at least one being C& 4-alkoxy, such as for propoxy, example trimethoxysilane, triethoxysilane or methyldimethoxysilane, in the presence of a such curable The reaction hydrosilylation catalyst, as platinum, yielding a poly(oxyalkylene). 60-150'C. is carried out at elevated temperatures, such as The synthesis is outlined in formula The has in combination e. (le). polymer to be used with, g. component (formula , (i) 1). Further examples of useful silanes include, without being limited to, triethoxysilane, tri tert-butyldiethoxysila ne. pro poxysila ne, PC T/DK2012/050226 C CH.

— —— — H Si C C . 9 H, PlBEH&UM CBtBlpSt .C C — — — H, C C G St H-, —— — Sa 9 C .C C In one variant, the hydrophilicity may be obtained (or added to the hydrophilicity which may have been obtained incorporating a hydrophilic to binder as outlined in previous by group (i) such the in formula section), by using a hydrophilic silane, as generic type expressed (2a).

The hydrophilic silane will react with the silanol or the hydrolysable in the binder groups or and component (formulae thereby incorporate a hydrophilic component. (1) (le)), wherein, each R represents, independently, an unsubstituted or substituted monovalent hydrocarbon of 1 to 6 carbon atoms or a hydrolysable each X represents, group group, a hydrolysable each is independently selected from -H, 4-alkyl independently, group, C, -CH&, -CH2CH&, -CH2CH2CH&, -CH(CH&)2, -CH2CH2CH2CH&), phenyl and (e.g. (-C6H5), C& alkylcarbonyl -C(=O)CH&, -C(=O)CH2CH& and -C(=O)CH, in particular and (e.g. CH, CH, each is selected from 5-alkylene -CH2CH2-, methyl; independently C2 (e.g. -CH2CH(CHg)-, -, -, -CH, CH, CH, -CH, CH, CH, CH, -CH, CH(CH, arylene 4-phenylene) and CH, )-), (e.g. 1, C, alkylene substituted with 1-phenyl in particular from -alkylene such aryl (e.g. ethylene), C, -CH, and -CH, is 0-50; is 0-2; z is 1-3. as CH, CH(CH, )-); a PC T/DK2012/050226 Introducing oxyalkylene units in the organopolysiloxane will increase the hydrophilicity of the when -[CH&CH&-0]- is used. binder, especially ethyleneoxide type Without being bound to any particular theory, it is believed that the function of the polysiloxane-based binder matrix rendered hydrophilic means of by oligomer/polymer moieties is facilitate the and of the one or more and to transport accessibility enzymes any biocides at the surface upon contact with sea-water. Potentially, a hydrated layer formed at the coating-water will also aid in the biocide the interphase retaining enzyme and/or at surface, hence allowing the coating to exert its fouling deterrent activity for extended exposure interva Is.

A-B-A In further the modification of the binder consists of both a embodiment, hydrophilic modifications (as described above) and of pendant hydrophilic oligomer/polymer moieties.

It should understood that the moieties forms of the be hydrophilic oligomer/polymer a part polysiloxane-based binder matrix, i.e. that the moieties are covalently incorporated into the binder matrix. It should also be understood that the formed covalent are bond(s) preferably non-hydrolysable.

The polysiloxane-based binder matrix typically constitutes at least 40 % dry weight, at least 50 % at least 60 % e. at least 70 % by dry weight, preferably by dry weight, g. by 50-90 50-98 50-96 weight, in particular % dry weight, or % dry weight, e. % dry by by g. by weight, in particular 60-95 % weight, or 50-95 % weight, or 60-94 % by dry by dry by dry or 70-96 or even 70-94 or 75-93 weight, % by dry weight, % by dry weight, % by dry 75-92 weight, or % dry weight, of the cured paint coat. matrix" The term "polysiloxane-based binder is intended to mean that the binder matrix consists of i.e. that more than more mainly polysiloxane parts, 50 % by weight, preferably than 60 % weight, e. more than 70 % weight, of the binder matrix is represented by g. by by the constitute 50-99. e. polysiloxane parts. Preferably polysiloxane parts 99 % by weight, g. 50-99. 60-99. 50-99 60-98 9 % weight, in particular 5 % weight, or % weight, or % by by by or 70-97 % or even 70-99 % or 80-98 % or by weight, by weight, by weight, by weight, 97 of the binder matrix e. the binder and cross-linkers). The % by weight, (i. components any remainder of the binder matrix is e. made of any hydrophilic oligomer/polymer moieties and (non-polysiloxane-type) cross-linkers. This the hydrophilic any being said, 1-30 2-20 oligomer/polymer moieties preferably makes % weight, such as % up by by 1-10 weight, e. % weight, of the binder matrix. g. by PC T/DK2012/050226 It should of course be understood that the hydrophilic oligomer/polymer moieties which are included in the polysiloxane-based binder matrix are of non-silicon origin.

When calculating the amount of the polysiloxane parts and the hydrophilic oligomer/polymer moieties, for a given starting material an it is fairly respectively, (or adduct), typically between the two. in order eliminate straightforward to distinguish However, to any doubt about linkers between the two, it should be understood that the hydrophilic moieties include all atoms not the silicon atom which oligomer/polymer up to, but including, is adjacent to the hydrophilic oligomer/polymer moiety. As an example, in a structure of the -[O- [polysiloxane-O]-Si(Me), -CH, CH, CH, -[hydrophilic oligomer]-CH, CH, CH, -Si(Me), type the are accounted for silicone whereas polysiloxane], [polysiloxane-O]-Si(Me), parts as parts, the CH, CH, CH, -[hydrophilic oligomer]-CH, CH, CH, moiety is accounted for as the hydrophilic oligomer moiety.

Suitable hydrophilic oligomer/polymer moieties are those selected from poly(vinyl pyrrolidone), poly[N-(2-hydroxypropyl)methacrylamide], N-dimethacrylamide), poly(N, poly(acrylic acid), poly(glycerol), polyHEMA, polysaccharides, poly(vinyl alcohol), polyketones, poly(aldehyde guluronate), polyvinylamine, polycaprolactones, poly(vinyl acetate), polyoxyalkylenes like poly(ethylene poly(2-methyl- glycol), poly(propylene glycol), 2-oxazoline), etc. including copolymers of the foregoing. Preferably the hydrophilicity is obtained modification with polyoxyalkylene moieties. of the above mentioned into the Incorporation hydrophilic oligomer/polymer polysiloxane polymer backbone is typically done through a linking group. The linking group is understood as the product of the reaction of two mutually reaction functional one functional groups; on the backbone and one on the E. an group polysiloxane hydrophilic oligomer/polymer. g. amine linking group is result of for example but not exclusively the reaction of a glycidyl ether with a or secondary amine. Examples of useful linking between the primary groups hydrophilic oligomer/polymer and the polysiloxane backbone are: amine groups, ether C-C C-C C-C Si-C amide groups. 3-triazole, bonds, double bonds, triple bonds, groups, 1,2, bonds, C-S bonds, S-S bonds, urethane urea Most preferred linking is group, groups. group Si-C the bond prepared hydrosilylation reaction catalyzed platinum where the by by functional on the polysiloxane backbone is a hydride and the functional on the group group is an hydrophilic oligomer/polymer allyl group.

In some embodiments, it is preferred that the hydrophilic oligomer/polymer moieties provide a permanent hydrophilic contribution to the binder matrix. Hence, in such embodiments, the hydrophilic oligomer/polymer moieties are preferably devoid of any bonds which are PC T/DK2012/050226 hydrolysable in sea-water. Hence, preferably, the hydrophilic oligomer/polymer moieties do not include ester bonds or acid bonds. anhydride In the present context oligomer/polymer moieties are understood as those encompassing at least 3 units, such as at least 5 units. repeating repeating Typically, oligomer/polymer moieties for modification include 3-1, such 3-200, or 5-150, or used 000 repeating units, as -100, or 10-80, or 5-20, repeating units.

In some the moieties e. preferred embodiments, hydrophilic oligomer/polymer (i. oligomeric or polymeric groups incorporated into the binder matrix) have a number average molecular weight in the of 100-50,000 such as in the of 100-30,000 in (M„) range g/mol, range g/mol, in the of 150-20, or in the of 200-10, particular range 000 g/mol, range 000 g/mol.

In the present description with claims, the terms "hydrophilic oligomer/polymer moieties", "hydrophilic moieties", and similar are intended mean that the or polymer to oligomeric polymeric moieties, in themselves (i.e. when represented as discrete molecules) have a 'C. solubility of at least 1 in demineralized water at %(w/w) When the polysiloxane-based binder discussed above is characterized system by having included therein, as a part of the binder matrix, one or more polysiloxane components which are modified with hydrophilic moieties, such polysiloxane components will oligomer/polymer cross-linkers upon reaction with other polysiloxane components and provide hydrophilic properties to the binder system. Alternatively, hydrophilic oligomer/polymer moieties functionalized with reactive silanes which enable them react with the to polysiloxane binder, or the hydrophilic oligomer/polymer moieties, and form a non-hydrolysable bond, may also be used.

The must include silicon-reactive such Si-OH polysiloxane components groups as groups, Si-OR hydrolysable groups such as (such as alkoxy, oxime, acetoxy etc. groups, etc. so as facilitate reaction with other constituents of the polysiloxane-based binder to system.

In one currently preferred embodiment of the above, the hydrophilic oligomer/polymer moiety is a moiety. poly(oxyalkylene) The coating composition The present invention also provides a fouling release coating composition comprising a polysiloxane-based binder said binder one or more system, system comprising polysiloxane PC T/DK2012/050226 components modified with hydrophilic oligomer/polymer moieties, and one or more enzymes.

Such rise the cured release a coating composition gives to fouling coat upon drying/curing.

The polysiloxane-based binder system typically constitutes at least 40 dry weight, at '/o '/o '/o least 50 at least 60 e. at least 70 by dry weight, preferably by dry weight, g. by '/o '/o '/o in 50-90 or 50-98 e. 50-96 weight, particular by dry weight, by dry weight, g. by dry 60-95 '/o 50-95 '/o 60-94 '/o weight, in particular weight, or weight, or by dry by dry by dry '/o '/o '/o or 70-96 or even 70-94 or 75-93 weight, by dry weight, by dry weight, by dry 75-92 '/o weight, or dry weight of the coating composition.

The term "polysiloxane-based binder system" is intended to mean that the binder system consists of i.e. that more than more mainly polysiloxane parts, 50 by weight, preferably '/o '/o than 60 weight, e. more than 70 weight, of the binder system is represented by g. by by the constitute 50-99. e. polysiloxane parts. Preferably, polysiloxane parts 99 by weight, g. 50-99. '/o 60-99. '/o 50-99 '/o 60-98 '/o 9 weight, in particular 5 weight, or weight, or by by by 70-97 '/o 70-99 '/o 80-98 '/o 90- weight, or weight, or even weight, or weight, or by by by by 97 of the binder e. the binder and cross-linkers). by weight, system (i. components any The remainder of the binder system is preferably made of the hydrophilic oligomer/polymer moieties and (non-polysiloxane-type) cross-linkers. This being said, the hydrophilic 1-30 '/o 2-20 '/o oligomer/polymer moieties preferably makes weight, such as up by by 1-10 '/o weight, e. weight, of the binder system. g. by The invention further release present provides a fouling coating composition comprising a 01-20 '/o polysiloxane-based binder system, 0. dry weight of one or more hydrophilic- modified polysiloxanes, and one or more enzymes.

The invention further polysiloxane-based binder present provides a system comprising a silanol-functional binder and a curing agent of the formula or and one or more (le) (2a), enzymes.

The description and embodiments, etc. above with respect to the polysiloxane-based binder the the hydrophilic moieties, the hydrophilic modified system, enzymes, oligomer/polymer etc. also for the two of polysiloxane oils, applies types coating compositions.

Bi oci des The for the cured release include one or coating composition used forming fouling coat may more biocides.

PC T/DK2012/050226 "biocide" In the present context, the term is intended to mean an active substance intended render the action or otherwise exert to destroy, deter, harmless, prevent of, a controlling effect on any harmful organism chemical or biological means. It should be understood, that the biocide(s) if present is used in addition to the one or more enzymes.

Illustrative of biocides are those selected from metallo-dithiocarbamates such examples as bis(dimethyldithiocarbamato)zinc, ethylene-bis(dithiocarbamato)zinc, ethylene-bis(dithio- and between bis(1-hydroxy-2(1H)-pyridine- carbamato)manganese, complexes these; thionato-O, S)-copper; copper acrylate; bis(l-hydroxy-2(1H)-pyridinethionato-O, S)-zinc; phenyl(bispyridyl)-bismuth dichloride; metal biocides such as cuprous oxide, copper(I)oxide, metallic metal such copper-nickel metal salts such copper, copper alloys as alloys; as cuprous thiocyanate, basic copper carbonate, copper hydroxide, barium metaborate, and copper heterocyclic nitrogen compounds such as 7a-tetrahydro((trichloro- sulphide; 3a,4,7, -1H-iso -dion 6-trichloro- methyl) -thio) indole-1, 3(2H) 1-(2,4, e, pyridine-triphenylbo rane, phenyl)-1H-pyrrole-2, 5-dione, 6-tetrachloro(methylsulfonyl)-pyridine, 2-methylthio- 2,3,5, 4-tert-butyla minocyclo mine-s-triazin, a nd line derivatives; heterocyclic sulfur pro pyla quino -dichloron-octylisothiazolinone, compounds such as 2-(4-thiazolyl)benzimidazole, 4, -dichlorooctyl-3(2H)-isothiazoline (Sea-Nine-211N), 2-benzisothiazolinone, and 4, 1, 2-(thiocyanatomethylthio)-benzothiazole; urea derivatives such 3-bis(hydroxyl- as N-(1, 4-dichloro- methyl)-2, 5-dioxoimidazolidinyl)-N, N'-bis(hydroxymethyl)urea, and N-(3, N-dimethylurea, N-dimethylchlorophenylurea; amides or imides of carboxylic phenyl)-N, N, acids; sulfonic acids and of sulfenic acids such as 2,4,6-trichlorophenyl maleimide, 1, dichloro-N-((dimethylamino)sulfonyl)-l-fluoro-N-(4-methylphenyl)-methanesulfenamide, N-dimethyl-N'- dibromonitrilo-propionamide, N-(fluorodichloromethylthio)-phthalimide, phenyl-N'-(fluorodichloromethylthio)-sulfamide, and N-methylol formamide; salts or esters of carboxylic acids such as 2-((3-iodopropynyl)oxy)-ethanol phenylcarbamate and amines such dehydroabiethyl- didecyl-N-methyl-poly(oxyethyl)ammonium propionate; as amines and cocodimethylamine; substituted methane such as di(2-hydroxy-ethoxy)methane, '-dich loro-2, 2'-dihydroxydi phenylmetha a nd methylene- bisthiocya substituted , ne, nate; benzene such 6-tetrachloro-1, 3-benzenedicarbonitrile, 1-dichloro-N-((dimethyl- as 2,4, 5, 1, a mino) -sulfonyl) fluoro-N-phenylmetha nesulfen amide, a nd 1-((diiodo methyl) sulfonyl) methyl-benzene; such tri-n-butyltetradecyl tetraalkyl phosphonium halogenides as phosphonium chloride; guanidine derivatives such as n-dodecylguanidine hydrochloride; disulfides such as bis-(dimethylthiocarbamoyl)-disulfide, tetramethylthiuram disulfide; imidazole such 2-(p-chlorophenyl)cyano containing compound, as medetomidine; bromotrifluoromethyl pyrrole and mixtures thereof.

Presently, it is preferred that the biocide does not comprise tin. (if present) PC T/DK2012/050226 6-tetra- Currently preferred biocides are those selected from the consisting of group 2,4, 5, chloroisophtalonitrile N-dichloro- (Chlorothalonil), copper thiocyanate (cuprous sulfocyanate), fluoromethylthio-N', N'-dimethyl-N-phenylsulfamide (Dichlofluanid), 3-(3,4-dichlorophenyl)- N'-tert-butyl-N 4- 1-dimethylurea (Diuron), -cyclopropylmethylthio-1, 5-triazine-2, 1, 3, diamine 4-bromo(4-chlorophenyl)(trifluoromethyl)-1H-pyrrole (Cybutryne), carbonitrile, (2-(p-chlorophenyl)cyanobromotrifluoromethyl Tralopyril), pyrrole; tert-butyl-N'-cyclo pylmethylthio-1, 5-tria zine-2, 4-dia mine [1- pro 3, (Cybutryne), (RS) -dichloron-octyl 3-dimethylphenyl)ethyl]-3H-imidazole (Medetomidine), 4, Sea-Nine isothiazolinone (DCOIT, 211N), dichlor-N-((dimethylamino)sulfonyl)fluor-N-(p- tolyl)methansulfenamid 2-(thiocyanomethylthio)-1, 3-benzothiazole ((2- (Tolylfluanid), benzothiazolylthio)methyl thiocyanate; TCMTB), triphenylborane pyridine (TPBP); bis(1- hydroxy-2(1H) -(T-4) zinc (zinc pyridinethione; zinc bis(1- nato-O, S) pyrithione), -pyridinethio S)-T-4) hydroxy-2(1H)-pyridinethionato-O, copper (copper pyridinethione; copper pyrithione), 2- (zinc-ethylene-N-N'-dithioca zinc ethylene-1, bis-dithioca rba mate rba mate; Zine b), copper(i) oxide, metallic 3-(3,4-dichlorophenyl)-1, 1-dimethylurea and diiodomethyl- copper, (Diuron) p-tolylsulfone; Amical 48. Preferably at least one biocide is selected from the above list.

In a particularly preferred embodiment, the biocides are preferably selected among biocides which are effective soft such slime and of such biocides against fouling as algae. Examples are N'-tert-butyl-N'-cyclopropylmethylthio-1, 5-triazine-2, 4-diamine 3, (Cybutryne), 4, Sea-Nine dichloron-octylisothiazolinone bis(1-hydroxy-2(1H)- (DCOIT, 211N), pyridinethionato-O, S)-(T-4) zinc (zinc pyridinethione; zinc pyrithione), bis(1-hydroxy-2(1H)- pyridinethionato-O, S)-T-4) pyridinethione; pyrithione; copper (copper copper Copper Omadine) and zinc ethylene-1, 2-bis-dithiocarbamate (zinc-ethylene-N-N'-dithiocarbamate; Zineb), copper(I) oxide, metallic copper, copper thiocyanate, (cuprous sulfocyanate), bis(1- hydroxy-2(1H)-pyridinethionato-O, S)-T-4) pyridinethione; copper (copper copper pyrithione; Copper Omadine).

In a further particularly preferred embodiment, the biocide is an organic biocide, such as a pyrithione such as zinc or such as pyrithione. Organic biocides complex, pyrithione, copper are those either fully or in part being of organic origin.

As detailed in US 377,968, in those instances in which the biocide is depleted rapidly from the film e. water or level of immiscibility with the matrix due to g. a high solubility a high composition, it can be advantageous to add one or more of the biocide(s) in encapsulated form as a means of controlling the biocide and extending the effective lifetime in the dosage film. Encapsulated biocides can also be added if the free biocide alters the properties of the polysiloxane matrix in a that is detrimental for its use as antifouling coatings way (e.g. mechanical times, etc. integrity, drying ).

PC T/DK2012/050226 -dichloron-octyl In a particularly preferred embodiment, the biocide is encapsulated isothiazolinone (Sea-Nine CR2). 0-20 00001-20 The biocide preferably has a solubility in the range of such as 0. mg/L, mg/L, in water at 25 '/o '/o If the biocide constitutes 0.1-15 e. 0.5-8 present, typically by dry weight, g. by dry 1-6 '/o in particular of the coating composition. weight, by dry weight, '/o '/o The biocide constitutes 0.1-15 solids e. 0.5-8 solids typically by volume, g. by volume, 1-6 '/o in particular solids volume, of the coating composition.

If one or more biocides are included, the ratio between on the one hand the combined amount of the moieties of the binder matrix hydrophilic oligomer/polymer (if present; see below) and the one or more hydrophilic-modified polysiloxane and on the other hand oil(s) the one or more biocides is in the of 1:0.02 or 1:0. or typically range to 1:20, 05 to 1:20, 1:006to 1:16,or 1:008to 1:12,or 1:0.1 to 10, even 1:0.15 to 1:6, or 1:0.1 to 1:5, or 1:0.2 to 1:4. In other embodiments, the ratio between on the one hand the combined amount of the moieties of the binder matrix hydrophilic oligomer/polymer (if present; see below) and the one or more hydrophilic-modified polysiloxane oil(s) and on the other hand the one or more biocides is in the of 1:0.02 to 1:20, or 1:0.05 to 1:20, or typically range 1:0.06 to 1:16, or 1:0.08 to 1:14,or 1:0.1 to 12, even 1:0.15 to 1:10,or 1:0.05 to 1:9,or 1:0.1 to 1:8, or 1:0.2 to 1:7.

Catalyst The coating composition used for forming the cured fouling release coat further condensation accelerate the cross-linking. of suitable comprise a catalyst to Examples catalysts include organometal- and metal salts of organic carboxylic acids, such as dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctoate, dibutyl tin 2-ethylhexanoate, dioctyl tin tin tin tin 2-ethylhexanoate, di dilaurate, dioctyl diacetate, dioctyl dioctoate, dioctyl dioctyltin neodecanoate, tin naphthenate, tin butyrate, tin oleate, tin caprylate, bismuth ethylhexanoate, bismuth octanoate, bismuth neodecanoate, iron 2-ethylhexanoate, lead ethyloctoate, cobaltethylhexanoate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, zinc naphthenate, zinc stearate, cobalt naphthenate and titanium naphtenate; titanate- and zirconate esters such as tetrabutyl titanate, tetrakis(2-ethylhexyl)titanate, triethanolamine tita nate, tita nate, tita nium tetra buta no late, tita nium tatra pro no late; tetra(iso pa pro penoxy) titanium tetraisopropanolate, zirconium tetrapropanolate, zirconium tetrabutanolate; chelated PC T/DK2012/050226 titanates such as diisopropyl bis(acetylacetonyl)titanate. Further catalysts include tertiary such amines, as triethylamine, tetrametylethylenediamine, pentamethyldiethylenetriamine and 1,4-ethylenepiperazine. Further examples include guanidine based catalysts. Even further examples of condensation catalysts are described in and US 2004/006190.

The catalyst be used alone or as combination of two or more catalysts. The amount of is on the of the and the cross-linker(s) and catalyst to be used depending reactivity catalyst desired drying time. In a preferred embodiment the catalyst concentration is between 0. 01-3. 0-10 1-4. 0-6. e. 0. 0 or 5. or 0. 0 or 1. 0 weight of the total %, g. %, %, %, %, by combined amount of the binder and cross-linking agent (ii).

In some embodiments, a catalyst is not included. and fillers Solvents, additives, pigments The coating composition used for forming the cured fouling release coat may further comprise solvents and additives.

Examples of solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent, esters such as methoxypropyl n-butyl and 2-ethoxyethyl and mixtures acetate, acetate acetate; octamethyltrisiloxane, water-based thereof. Alternatively, the solvent system may include water or be (&50% water in the solvent system).

In one the solvents are selected from and aromatic embodiment, aliphatic, cycloaliphatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent, esters such n-butyl and 2-ethoxyethyl as methoxypropyl acetate, acetate acetate; octamethyltrisiloxane, and mixtures thereof, preferably those solvents having a boiling point of 110 or more.

The if constitute 5-50 volume of the solvents, any, typically % by coating composition.

Examples of additives are: non-reactive fluids such as for example polydimethylsiloxane, (i) organopolysiloxanes; methylphenyl polysiloxane; petroleum oils and combinations thereof; surfactants such as derivatives of oxide or ethylene oxide such as alkylphenol- (ii) propylene oxide condensates monoethanolamides of ethylene (alkylphenol ethoxylates); ethoxylated PC T/DK2012/050226 unsaturated fatty acids such as ethoxylated monoethanolamides of linoleic acid; sodium dodecyl sulfate; soya lecithin; "Handbook (iii) wetting agents and dispersants such as those described in M. Ash and I. Ash, 1", 821- of Paint and Coating Raw Materials, Voh 1996, Gower Publ. Ltd. Great Britain, , pp 823 and 849-851; thickeners and anti-settling agents thixotropic agents) such as colloidal silica, (iv) (e.g. hydrated aluminium silicate aluminium tristearate, aluminium monostearate, (bentonite), xanthan chrysotile, pyrogenic silica, hydrogenated castor oil, organo-modified clays, gum, polyamide waxes and polyethylene waxes; such as 4-bis(butylamino)anthraquinone and other anthraquinone derivatives; (v) dyes 1, toluidine dyes, etc. and antioxidants such as bis(tert-butyl) 6-bis(tert-butyl) resorcinol, (vi) hydroquinone, 2, phenol, 4-tert-butyl catechol, tris(2, 4-di-tert-butylphenyl) phosphite, pentaerythritol Tetrakis(3-(3, di-tert-butylhydroxyphenyl) bis(2, -tetramethylpiperidyl)sebacate, propionate), 2,6,6, etc. 0-30 '/o, 0-15 '/o, Any additives typically constitute such as dry weight of the coating composition.

Preferably, the coating composition comprises one or more thickeners and/or anti-settling 2-10 '/o, 5-5 '/o, agents thixotropic preferably in an amount of 0. such as 0. e. (e.g. agents), g. 0.6-4 '/o, weight of the coating composition. by dry Furthermore, the coating composition used for forming the cured fouling release coat may comprise pigments and fillers. and fillers are in the context viewed in constituents that Pigments present conjunction as may be added to the coating composition with only limited implications on the adhesion "Pigments" are characterised in that render the final properties. normally they paint coating "fillers" non-transparent and non-translucent, whereas normally are characterised in that they do not render the paint non-translucent and therefore do not contribute significantly to hide material below the any coating.

Examples of pigments are grades of titanium dioxide, red iron oxide, zinc oxide, carbon black, yellow iron oxide, red yellow zinc sulfide, antimony graphite, molybdate, molybdate, oxide, sodium aluminium sulfosilicates, quinacridones, phthalocyanine blue, phthalocyanine green, black iron oxide, indanthrone blue, cobalt aluminium oxide, carbazole dioxazine, chromium isoindoline bis-acetoacet-o-tolidiole, benzimidazolon, oxide, orange, quinaphtalone yellow, isoindoline yellow, tetrachloroisoindolinone, quinophthalone yellow.

PC T/DK2012/050226 Examples of fillers are calcium carbonate such as calcite, dolomite, talc, mica, feldspar, barium and etc. Fillers sulfate, kaolin, nephelin, silica, perlite, magnesium oxide, quartz flour, (and pigments) may also be added in the form of nanotubes or fibres, thus, apart from the before-mentioned examples of fillers, the coating composition also comprise fibres, e. may g. those and described in WO which is generally specifically 00/77102 hereby incorporated by reference. fillers constitute 0-60 '/o, such 0-50 '/o, 5-45 '/o, Any pigments and/or typically as preferably -40 '/o, 5-35 '/o, 5-25 '/o, 1-20 '/o, such as or or 0. or dry weight of the coating composition. Taking into account the density of pigments and/or fillers, such constituents constitute 0.2-20 '/o, such 0.5-15 solids volume of the typically as by coating composition With the aim of facilitating easy application of the coating composition (e. brush g. by spray, or roller the has in the application techniques), coating composition typically a viscosity range -25, of 000 mPa such as in the range of 150-15,000 mPa in particular in the range of s, s, 200-4, 000 mPa s.

Preparation of the coating composition The coating composition be prepared suitable technique that is commonly used may by any within the field of production. Thus, the various constituents be mixed together paint may three-roll utilizing a mixer, a high speed disperser, a ball mill, a pearl mill, a grinder, a mill two- etc. The coating compositions are prepared and shipped as or three-component typically that should combined and mixed use. The systems be thoroughly immediately prior to paints according to the invention be filtrated using filters, patron filters, wire filters, may bag gap wire filters, metal filters, EGLM turnoclean filters DELTA strain filters wedge edge (ex. Cuno), (ex. Cuno), and jenag Strainer filters (ex. jenag), or by vibration filtration. An example of a suitable preparation method is described in the Examples.

Preferably the enzymes are mixed with other constituents at a late of the paint very stage formulation process, such as after grinding and activation of thixotropic agents. Caution must be taken to keep temperatures relatively low, the lower the better, and if at all necessary- only subject the formulation to elevated temperatures for as short time as possible. In one embodiment, the enzymes are added shortly before application.

The coating composition to be used in the method of the invention is typically prepared by mixing two or more components e. two pre-mixtures, one pre-mixture comprising the one or more reactive polysiloxane binders and one pre-mixture comprising the one or more cross- PC T/DK2012/050226 linking agents. It should be understood that when reference is made to the coating it is the mixed all composition, coating composition ready to be applied. Furthermore, '/o '/o amounts stated as dry weight of the coating composition should be understood as by by weight of the mixed paint composition ready to be i.e. the weight apart from the dry applied, solvents (if any).

Hence, the invention also provides a kit for preparing a fouling release coat as defined herein, said kit first container binder and second comprising a holding a polysiloxane base, a container holding a siloxane curing agent and optionally a catalyst, wherein the polysiloxane binder base of the first container is curable in the presence of the content of the second container. The and in two containers obtain an catalyst curing agent may be separated to extended storage stability. The kit further comprises one or more enzyme either as a constituent of the first container or a constituent of the second container, or alternatively in a third container.

When present in a third container, the one or more enzymes be formulated together with additives obtain and with the content of necessary to stability during storage, miscibility the first and the second container.

Specific embodiments of the coat paint In one preferred embodiment the paint coat (preferably a top coat) comprises: '/o '/o 60-98 or 70-93 of the total coat composition of (i) by dry weight, by dry weight, paint one or more reactive silanol-terminated one or polydiorganosiloxanes (e.g. polysiloxanes), more reactive polysiloxanes modified with hydrophilic oligomer/polymer moieties selected from and a cross-linker; poly(oxyalkylene)s 00001-10 '/o, 002-5 '/o, 0. such as 0. dry weight of the total paint coat composition of (ii) by one or more enzymes, preferably selected from the of hydrolytic enzymes. group In the above embodiment, the remainder of the paint coat to 100 by dry weight) is preferably made of one or more constituents selected from additives, catalysts, pigments, fillers, hydrophilic-modified polysiloxane oils those selected from the (preferably poly(oxyalkylene)-modified polysiloxane oils), and biocides.

In another preferred embodiment the paint coat comprises: PC T/DK2012/050226 60-98 70-93 % weight, or % weight of the total paint coat composition of (i) by dry by dry one or more reactive silanol-terminated and polydiorganosiloxanes (e.g. polysiloxanes) a cross-linker; 0.00001-10 % such as 0.002-5 weight of the total coat composition of (ii) %, by dry paint one or more selected from the of enzymes, preferably group hydrolytic enzymes. 0. weight of the total coat composition of one or more hydrophilic- (iii) %, by dry paint modified oils selected from the polysiloxane poly(oxyalkylene)-modified polysiloxane oils, In the above embodiment, the remainder of the paint coat to 100 % dry weight) is (up by made of one or more constituents selected from additives, preferably up catalysts, pigments, and biocides. fillers, In another preferred embodiment the paint coat comprises: 60-98 or 70-93 of the total of % by dry weight, % by dry weight paint coat composition one or more reactive polysiloxanes silanol-terminated polysiloxanes) and a cross-linker, (e.g. where at least one reactive polysiloxane is modified with a hydrophilic oligomer/polymer in one or several the siloxane moiety places along chain; 0.00001-10 % % weight of the total paint coat composition of one or more (ii) by dry selected from the of enzymes. enzymes, preferably group hydrolytic In the above embodiment, the remainder of the paint coat to 100 % weight) is (up by dry made of one or more constituents selected from additives, preferably up catalysts, pigments, fillers, hydrophilic-modified polysiloxane oils (preferably those selected from the poly(oxyalkylene)-modified polysiloxane oils), and biocides. the the above embodiments include Preferably, paint coats according to additives, pigments and fillers in the amounts specified further above.

The enzymes have been modified or immobilised to improve the stability of the enzymes sea-water. in the wet paint as well as in PC T/DK2012/050226 Application of the coating composition The of the invention is least of the surface coating composition typically applied to at a part of a substrate.

The term "applying" is used in its normal meaning within the industry. Thus, "applying" paint is conducted means of conventional e. by any means, g. by brush, by roller, by spraying, by etc. The commercially most interesting of "applying" the coating composition is dipping, way the is is effected by spraying. Hence, coating composition preferably sprayable. Spraying by means of conventional spraying equipment known to the person skilled in the art. The coating is in a film thickness of 50-600 such as 50-500 e. typically applied dry pm, pm, g. 400 or 20-100 Moreover, the coating composition is preferably such with respect to sag resistance cf. ASTM D 4400-99 e. its in suitable film thickness vertical (i. relating to ability to be applied a to a surface without that it exhibits sag resistance for a wet film thickness to at least sagging) up 70 such as to at least 200 to at least 400 and in particular pm, up pm, preferably up pm, up least to at 600 pm. substrate" The term least a part of the surface of a refers to the fact that the coating composition be to fraction of the surface. For the coating may applied any many applications, composition is at least applied to the part of the substrate (e. a vessel) where the surface the ship's hull) come in contact with water, e. sea-water. (e.g. may g.

The term "substrate" is intended mean solid material onto which the to a coating composition is applied. The substrate typically comprises a metal such as steel, iron, aluminium, or glass- fibre reinforced In the most interesting embodiments, the substrate is a metal polyester. in steel substrate. In an alternative the substrate is substrate, particular a embodiment, a glass-fibre reinforced polyester substrate. In some embodiments, the substrate is at least a of the outermost surface of marine structure. part a "surface" The term is used in its normal sense, and refers to the exterior boundary of an object. Particular examples of such surfaces are the surface of marine structures, such as vessels not limited motor ocean (including but to boats, yachts, motorboats, launches, liners, tugboats, tankers, container ships and other cargo ships, submarines, and naval vessels of all shore and off-shore machinery, constructions and objects of all such as types), pipes, types piers, pilings, bridge substructures, water-power installations and structures, underwater oil well structures, nets and other aquatic culture installations, and etc. buoys, PC T/DK2012/050226 "native" The surface of the substrate either be the surface the steel surface). may (e.g. the substrate is e. with an anticorrosive tie However, typically coated, g. coating and/or a coat, so that the surface of the substrate is constituted such a coating. When present, the (anticorrosive and/or tie) coating is typically applied in a total film thickness of 100-600 such 150-450 e. 200-400 the substrate as g. pm. Alternatively, may carry a paint pm, pm, coat, e. a worn-out fouling release paint coat, or similar.

In one the substrate is metal substrate steel important embodiment, a (e.g. a substrate) coated with an anticorrosive coating such as an anticorrosive epoxy-based coating, e. cured epoxy-based coating, or a shop-primer, e. a zinc-rich shop-primer. In another relevant the substrate is glass-fiber reinforced substrate with an embodiment, a polyester coated epoxy primer coating.

This the invention also relates method of surface of being said, to a coating a a substrate, comprising the sequentia I steps of: one or more layers of a primer composition and/or one or more layers of a) applying applying tie-coat onto the surface of said and a composition substrate, one or more layers of a coating composition so as to obtain a fouling release coat b) applying as defined herein on the coated surface of said substrate. "fouling release" bio- It should be understood that the expression relates to all types of fouling of a surface e. settlement of organisms on a in particular surfaces exposed (i. surface), an environment or within etc. It is to aqueous to aqueous liquids (e.g. tanks, pipes, ). however, believed that the coatings defined herein are particularly relevant for avoiding or reducing marine bio-fouling, i.e. bio-fouling arising in connection with the exposure of a surface marine environment, in seawater. to a particular to A Marine Structure The invention also marine structure on least of the present provides a comprising at a part outer surface thereof an outermost fouling release coat as defined hereinabove. In particular, at least as of the outer surface the outermost coating is a submerged of part carrying part said structure.

The coating composition, the method of establishing the coating on the substrate surface, and the characteristics of the follow the directions hereinabove. coating given PC T/DK2012/050226 In one embodiment, the fouling release coating system of the marine structure consist of an anticorrosive tie-coat and the release described herein. layer, a fouling coating as In an alternative embodiment, the fouling release coating composition is applied on top of a used fouling release coating e. on of a used polysiloxane-based fouling release system, g. top coat.

In one particular embodiment of the above marine structure, the anticorrosive has a layer total film thickness of 100-600 such 150-450 e. 200-400 the tie-coat dry as g. pm, pm, pm; 50-500 50-400 75-350 75-300 has a total dry film thickness of such as e. or pm, pm, g. pm or 75-250 and the fouling release coating has a total film thickness of 20-500 pm pm; dry such 20-400 e. 50-300 as g. pm. pm, pm, A further embodiment of the marine structure is that where at least a part of the outermost surface of said structure is with coated a paint system comprising a total dry film thickness of 150-400 of an anticorrosive layer of an epoxy-based coating established application of 1-4, such as 2-4, by layers; total film thickness of 20-400 of the tie-coat established of a dry pm by application layers; and a total film thickness of 20-400 of the fouling release coating established dry pm by application of layers.

In another embodiment of the above marine structure, the fouling release coating is applied on the anticorrosive without the of tie-coat. directly layer use Use forimproving the antifouling properties of a polysiloxane based coating composition The invention further relates the of the combination of one or more to use polysiloxane components (e. those being modified with hydrophilic oligomer/polymer moieties, or in combination with one or more hydrophilic-modified polysiloxane and one or more oils) for the of enzymes improving antifouling properties a polysiloxane based coating composition. The combination is particularly relevant for improving the antifouling properties against slime and algae. In one variant, the coating composition also includes a biocide as described in detail further above.

It should be understood that the of the polysiloxanes modified with hydrophilic types the and the of suitable binder oligomer/polymer moieties, enzymes, types polysiloxane based PC T/DK2012/050226 systems are as defined further above, just at the amounts and relative proportions of the various are defined further above. ingredients as Alternative aspects of the invention An alternative embodiment of the invention relates to a fouling release coating composition comprising a polysiloxane-based binder system, preferably constituting at least 40 % dry weight of the coating composition, and one or more fluorinated oils (cf. the description further above).

It should be understood that all statements above, except of the mandatory presence of one or more i.e. the statements and preference with respect to the polysiloxane-based enzymes, binder system/matrix, the hydrophilic-modified polysiloxane oils, fluorinated oils, pigments, fillers, additives, catalyst, solvents, biocides, etc. also applies for this alternative embodiment.

In one embodiment, the fouling release coating composition comprises a polysiloxane-based binder system, preferably constituting at least 40 % weight of the coating by dry 01-20 composition, and 0. % dry weight of one or more fluorinated oils.

In a variant hereof, the composition further comprises one or more biocides, wherein the ratio between the one or more fluorinated oils and the one or more biocides is in the weight range 1:0.2 to 1:6.Typically, the relative weight ratio between the one or more fluorinated oils and the one or more biocides is in the range of 1:0.05 to 1:1000,e. 1:0.1 to typically g. such 1:0.1 or 1:0.15 in 1:0.2 or 1:0.2 or 1:120, as to 1:10, to 1:8, particular to 1:6, to 1:5, 1:0.25 to 1:4, especially 1:0.3 to 1:3.

In one the fluorinated oils constitute 0.05-10 of the embodiment, % by dry weight coating composition.

In a further embodiment (which can be with the at least one biocide is applicable foregoing), an biocide. organic In a further embodiment (which can be applicable with the foregoing), the one or more 1-10 biocides constitutes 0. % weight of the coating composition. by dry PC T/DK2012/050226 In a further embodiment (which can be applicable with the the coating foregoing), has in the of 25-25, mPa such in the of 150- composition a viscosity range 000 s, as range 200-4, ,000 mPa in particular in the range of 000 mPa s.

Within this alternative is also provided a marine structure comprising on at least a aspect of the outer surface thereof an outermost from the part coating prepared coating composition as defined above. In particular, at least as part of the outer surface carrying the outermost is of said structure. coating a submerged part Within this alternative aspect is also provided the combination of one or more fluorinated oils and one or more biocides, wherein the weight ratio between the one or more fluorinated oils and the one or more biocides is in the 1:0.2 for the range to 1:6, improving antifouling properties of a polysiloxane based coating composition.

General Remarks Although the present description and claims occasionally refer to a polysiloxane, etc. it should be understood that the coating compositions defined herein comprise one, two or more types of the individual constituents. In such embodiments, the total amount of the respective constituent should correspond to the amount defined above for the individual constituent. "(s)" The in the expressions: compound(s), polysiloxane(s), agent(s), etc. indicates that one, two or more of the individual constituents be present. types may "one" On the other when the is one of the hand, expression used, only respective constituent is present.

EXAMPLES Materi als RF-5000, ex. Shin-Etsu silanol-terminated polydimethylsiloxane japan, Xylene from local supplier DC550, ex. Dow Corning USA, non-reactive methylphenyl polysiloxane oil Silikat TES 40 ex. Wacker Chemic Ethyl silicate WN, Germany, Neostann U-12, ex. Nitto Kasai Dibutyltin Dilaurate japan, PC T/DK2012/050226 Acetylaceton, ex. Wacker Chemic Germany, 4-pentanedione Xiameter PMX-200 Sil Fluid ex. Dow Linear oil 1000cs, Corning UK, dimethylpolysiloxane PMX-200 Xiameter Sil Fluid 5000cs, ex. Dow Corning UK, Linear dimethylpolysiloxane oil BYK331, ex. BYK Germany, non-reactive polyether modified polydimethylsiloxane oil Fomblin ex. Solexis Y, Solvay Italy, perfluorinated polyether Lumif Ion LF-200, ex. Lumif Ion Fluorinated polymer japan, Fluorosil 2110, ex. Siltech Corporation Canada, perfluoro nononyl PEG-8 dimethicone ethyl Siltech C-1910, ex. Siltech Corporation Canada, Fluorinated silicone polyetherBayferrox 130M, ex. Lanxess Germany, Iron oxide Aerosil R8200, ex. Evonik Industries Hexamethyldisilazane treated fumed silica Germany, non-reactive Tego glide 435, ex. Evonik Industries Germany, polyether modified polydimethylsiloxane oil Micronised wax Crayvallac super, ex. Cray Valley Aerosil R972, ex. Evonik industries.

Demineralized water Dynasylan VTMO, ex. Evonik Industries Germany, vinyltrimethoxysilane 1-2.4'/o Platinum divinyltetra methyldisiloxa ne in xylene 2. platinum complex CAS No. 684782 concentration, Polydimethylsiloxane, hydride terminated MW„=1100, eq. weight 550 g/eq Methylhydrosiloxane dimethylsiloxane hydride terminated MWn copolymer, 2300, eq. weight g/eq =150 Polyethylene di allyl ether MW„= 300g/mol, Eq. weight glycol g/eq Polyethylene mono allyl ether terminated) MW„= 350 weight glycol (hydroxyl g/mol, eq. g/eq Subtilisin A ex. Sigma-aldrich 90141) , (Cas: from bovine ex. Sigma-aldrich 90027) Trypsin pancreas, (Cas: Savinase 16L EX), ex. Novozymes (type Esperase ex. Novozymes Alcalase, Novozymes 90014) Papain, ex Sigma-aldrich (Cas: Pronase ex. Sigma-aldrich 90360) E, (Cas: Cellusoft L, ex. Novozymes Endolase 5000L, ex. Novozymes Beta-glucoronidase, ex. Sigma-aldrich 90010) (Cas: 90253) Hemicellulase, ex. Sigma-aldrich (Cas: Pectin methyl esterase, ex. Sigma-aldrich (Cas: 90321) 90127) Acylase I, ex. Sigma-aldrich (Cas: Savinase CLEA, ex. Clea technologies BV. Cross-linked enzyme agglomerates of Savinase (Activity: 500AGEU/g) PC T/DK2012/050226 mPEG-NHS Ester, ex. Nanocs PEG1-0001, Mw 000 Da. , 5, ex. nr: 991264 Methoxypolyethyleneglycol maleimide, Sigmaaldrich, Cas Silane-PEG-NHS, ex. Nanocs: Mw(PEG)= 000 Da Viscosity In the present application with claims, viscosity is measured at 25 in accordance with ISO 2555:1989.

Pendant h dro hilic modified ol siloxane HMP1 A pendant, curable poly(ethylene modified polysiloxane is prepared mixing 25.0 glycol) by (polydimethylsiloxane-methylhydrosiloxane, hydride terminated) dissolved in 50.0 water free toluene, with 0.013 of a solution of platinum-divinyltetramethyldisiloxane complex in xylene in a three necked flask with reflux and a continuous flow of nitrogen to keep dry gas the reaction moisture free. A stirrer is in the reaction flask atmosphere magnetic used to 80'C. keep the solution agitated during the synthesis. The solution is heated to To this solution, 11.0 of (vinyltrimethoxysilane) is added dropwise and allowed to react for 1 h at 80'C. After the of the 54. mono ether is completion reaction, 5 polyethylene glycol allyl 80'C. added dropwise, and allowed to react for 4h at The solvent was hereafter partially removed under reduced pressure a rotary evaporator until the solvent content reached using PEG-modified % to obtain the final product HMP1. The content of PDMS binder in HMP1 is 90 % w/w. The amount of PEG in the HMP1 binder is 60.2% calculated on weight. w/w dry of linear modified Preparation hydrophilic polysiloxane (HMP2): A linear, curable modified polysiloxane is mixing 5.00 poly(ethylene glycol) prepared by dissolved in 50. water free with 0.013 of (polyethylene glycol diallyl ether) 0 toluene, a solution of platinum-divinyltetramethyldisiloxane complex in xylene in a three necked flask with reflux and a continuous flow of nitrogen to the reaction atmosphere dry gas keep moisture free. A stirrer is in the reaction flask the solution magnetic used to keep agitated 65'C. during the synthesis. The solution is heated to To this solution, 65.0 polydimethylsiloxane terminated) is added and allowed to react for 1 h at (hydride dropwise, 80'C.

After the completion of the reaction, 35.0 of vinyltrimethoxysilane is added dropwise 80'C 80'C. at and allowed to react for 1 h at The solvent was hereafter partially removed under reduced until the solvent content reached 10% pressure using a rotary evaporator to PC T/DK2012/050226 obtain the final product HMP2. The content of PEG-modified PDMS binder in HMP2 is 90 The amount of PEG in the HMP2 binder is 4.8'/o calculated on w/w. w/w dry weight.

Preparation method for the model paints Part (silanol-terminated silica, (i) polydimethylsiloxane), xylene, (polydimethylsiloxane), (polyamide wax), red iron oxide, (polyether modified polysiloxane), were mixed on a Diaf dissolver with an impeller disc mm in diameter) in a 1 L can for 15 minutes at equipped (70 2000 rpm.

Part ethyl silicate, (xylene), catalyst, 2,4-pentanedione, (methylphenyl polysiloxane)) (ii) were mixed on a Diaf dissolver with an impeller disc mm in diameter) in a 1 L equipped (70 can for 2 minutes at 500 rpm.

Before the application, part and part are mixed and enzymes are added in a (i) (ii) in water the mix is then stirred obtain solution/suspension to homogeneity.

Test Methods Blister Box Test The Blister Box test is used to determine the influence of polysiloxanes modified with hydrophilic moieties on the stability of the PDMS coating to which are oligomer/polymer they added Preparation of panels Steel are with 100 film of panels (150x75x15 mm) coated pm (dry thickness, DFT) a commercial epoxy primer (HEMPADUR Quattro 17634) applied airless spraying. After 48 hrs of at room temperature a silicone tie coat (HEMPASIL Nexus 27302) is drying applied 16-30 doctor blade of 300 clearance. After hrs of drying the top coat paint by pm compositions are applied doctor blade of 400 clearance. The panels are dried for 24 by pm hrs before testing in the blister box.

PC T/DK2012/050226 Testing The surface with the is 40 'C, saturated water an panel coating system exposed to vapour, at '/60' angle of to the horizontal. The reverse side of the panel is exposed to room temperature. At the selected inspection intervals during and after completion of exposure, adhesion between tie and condition of the are evaluated. coat/top coat general top coat Evaluation of adhesion between tie coat and coat is based on the below ranking: Adhesion Value Ranking FAIL/POOR No adhesion/poor adhesion GOOD Acceptable adhesion Panels are exposed for two months and typically checked every week.

Raft Test Preparation of panels An acrylic panel (150x200 sandblasted on one side to facilitate adhesion of the coating, mm), is coated with 100 of a commercial (HEMPEL Light Primer 45551) pm (DFT) epoxy applied by air spraying. After 6 24 hrs of drying at room temperature a tie coat is applied doctor blade of 300 clearance. After 16-30 hrs of the coat compositions are pm drying top paint doctor blade of 400 clearance. The are dried for least 72 hrs before applied by pm panels at immersion on the raft.

Testing Panels are tested at two different locations; Spain and Singapore.

Test site in Spain north-eastern Located in Vilanova in Spain. At this test site the panels are immersed into sea water with salinity in the range of 37-38 parts thousand at an average temperature of 17-18 C.

Test site in Singapore PC T/DK2012/050226 29-31 At this test site the panels are immersed into sea water with salinity in the range of thousand in the of 29-31 parts per at a temperature range 4-12 Panels are inspected ever weeks and evaluated according to the following scale: Level Description Excellent Only slime Good Algae Animals 10% Fair 10 & + Animals & 25 % Algae % Poor + Animals & 25 % Algae Bacterial biofilm retension High through-put screening of fouling-release coatings can be performed at the Center for Nanoscale Science and Engineering at the North Dakota State University, USA.

Assays are performed on 24 wells micro plates, where 12 wells are coated with each release formulation. The are pre-conditioned in deionised water experimental fouling coatings until no toxicity of the water is observed. The coatings are then subjected to static suspensions of marine bacteria (Celluphaga /ytica) or marine algae (Naviculaincerta). The bacterial biofilms are stained and and the are quantified spectroscopically, algae quantified using fluorescence spectroscopy on chlorophyll extracts. The output of the measurements is directly proportional to the amount of biofilm on the coating. For the evaluation of the test- results, it is needed that a suitable commercial standard is included as reference in the test set-up, in the experiments reported here the commercial reference used was Intersleek 700 International The tests were done including a commercial fouling release (ex. paints). silicone-based reference in the form of the Intersleek 700, a hydrophobic fouling release coating.

Barnacles settlement test Ten three-days-old larvae cultured from the adult Balanus amphitrite are added to two cypris millilitres of a solution of the enzyme in artificial sea water 3% salinity and 8. 'Tropic (3. pH 0, Marin' from Aquarintechnik GmbH). 24 well polystyrene plates are used for the incubation, which is done in the dark at 28 After 24 and 48 the settlement and mortality is PC T/DK2012/050226 evaluated counting, cf. Pettitt et al. "Activity of Commercial Enzymes on Settlement and Adhesion of Larvae of the Barnacle Balanus of the Green Ulva Cypris amphitrite, Spores Alga perminuta", 299-311. linza, and the Diatom Navicula Biofouling, Vol. 20, 2004, For an enzyme to be effectively hindering barnacle settlement degradation of its exopolymeric the settlement level in the must lower &0. substances, enzyme sample be significantly 1) than the settlement level in a heat denatured control (i.e. a control containing the corresponding inactive enzyme obtained heating a solution of the enzyme to 100 for five minutes) while mortality levels are similar. Since the concentration of enzyme is not necessarily directly proportional to the activity, a range of concentrations to 0.1 (typically up wt'/o are tested to determine the of enzymes to degrade pure enzyme) capability exopolymeric substances.

Al ae settlement test millilitres of a suspension containing 3 ml zoospores released from the green alga Ulva linza in artificial seawater (see above) is mixed with 15 millilitres of a solution of the in artificial seawater Ten millilitres of this is then transferred enzyme (see above). dispersion into three wells of a Quadriderm dish, containing an acid-washed glass microscope slide.

Incubation occurs in the dark at room temperature 'C) for 60 minutes. After which is and settlement is determined motility assessed by phototaxis, spore density by visualisation using auto fluorescence of chlorophyll, cf. Pettitt et al. Activity of Commercial Enzymes on Settlement and Adhesion of Larvae of the Barnacle Balanus amphitrite, Cypris Spores of the Green Alga Ulva linza and the Diatom Navicula perminuta. Biofouling, Vol 20, 2004. For an enzyme to be effectively hindering settlement degradation of its algal by the settlement level in the must exopolymeric substances, enzyme sample be significantly lower than the settlement level in a heat denatured control (see above) while motility must be similar. Since the concentration of enzyme is not necessarily directly the of concentrations 0. 1 wt'/o proportional to activity, a range (typically up to pure enzyme) are tested to determine the capability of enzymes to degrade exopolymeric substances.

Examples The following model paints can be prepared for testing for antifouling performance.

All entries in model paints table are in weight unless otherwise stated. In the calculation of the final polysiloxane matrix, all the hydrolysable groups are presumed completely hydrolysed and reacted into a matrix through a condensation reaction with the polysiloxane binder. the silicate contributes with 41 of its the calculations of Therefore, ethyl weight to the final polysiloxane matrix and vinyltrimethoxysilane contributes with 54 of its weight PC T/DK2012/050226 correspondingly. When calculating the polysiloxane content of the binder matrix, the constituents included in the calculations the however with the above- as starting materials, mentioned corrections for ethyl silicate and vinyltrimethoxysilane.

Example 1: Enzymes in a polysiloxane matrix.

Part i Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 67.7 X lene 25.4 Aerosil R972 1.16 Micronised wax 1.

Pi ments 4.65 Part Wt% (ii) Eth I silicate 41.1 X lene 31.7 Dibutyltin dilaurate 7.05 entanedione 20. 1 EC1A PDMS-based commercial reference (Intersleek Wt% Wt% wet dr Total 90.9 97.85 part (i) Total 6.1 2.1 part (ii) Demineralized water 3.0 0.00 0. 0.07 Papain 05 Weight % 90.5 oxa ne- po lysil based binder matrix in the dr cured coat Bacterial biofilm 0.58 0.11 0.77 0.06 retention Algal retention 009+ 832 127+ 861 21, 24, PC T/DK2012/050226 Example 2 Polysiloxane-based coatings with different enzymes Part I Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 70.5 X lene 21.2 Hexa meth Idisilazane treated fumed silica 3.7 Pi ments 4.

Part II Wt% Eth I silicate 31.

X lene 49.3 Dibut Itin dilaurate 5.4 2, entanedione 13.6 EC1 EC2 EC3 EC4 Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% wet dr wet dr wet dr wet dr 80.64 94.92 81.46 94.94 86.72 94.68 86.72 94.68 Part 7.37 2.03 7.44 2.03 7.92 2.02 7.92 2.02 Part (ii) 1.99 2.97 2.01 2.97 2.14 2.97 2.14 2.97 Tego Glide 435 9.96 0.00 9.05 0.00 Water 0.05 0.07 Subtilisin A 0.04 0.06 Trypsin 3.21 0.33 Savinase 3.21 0.33 Esperase 8L 86. 86. 86. 86.

Weight % 5 5 3 3 lysil oxa based binder matrix in the dr cured coat Performance in Spain Excellent Excellent Excellent Excellent after 23 weeks Performance in Good Excellent N/A Excellent Singapore after 24 weeks The panel had fallen off the raft within the first eight weeks of immersion.

EC5 EC6 EC7 EC8 Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% wet dr wet dr wet dr wet dr 86.72 94.68 83.98 94.93 83.85 94.71 86.72 94.68 Part 7.92 2.02 7.67 2.03 7.66 2.02 7.92 2.02 Part (ii) 2.14 2.97 2.07 2.97 2.07 2.97 2.14 2.97 Tego Glide 435 6.22 0.00 6.21 0.00 Water 3.21 0.33 Alca lase 0.05 0.07 Papain 0.21 0.30 Pronase 3.21 0.33 Cellusoft PC T/DK2012/050226 Weight % 86.3 86.5 86.3 86.3 lysil oxa based binder matrix in the dr cured coat Performance in Excellent Excellent Excellent Excellent Spain after 23 weeks Performance in Excellent Excellent Good Good Singapore after 24 weeks EC9 EC10 EC11 Wt% Wt% Wt% Wt% Wt% Wt% wet dr wet dr wet dr 86.72 94.68 84.01 94.99 81.08 94.29 Part 7.92 2.02 7.68 2.03 7.41 2.01 Part (ii) 2.14 2.97 2.07 2.97 2.00 2.95 Tego Glide 435 6.22 0.00 9.01 0.00 Water 3.21 0.33 Endo lase 0.01 0.01 beta-glucoronidase 0.50 0.74 Hemicellulase Weight % 86.3 86.6 85.9 lysil oxa based binder matrix in the dr cured coat Performance in Excellent Excellent Excellent S ain after 23 weeks Performance in Excellent Excellent Good Singapore after 24 weeks EC12 EC13 EC14 reference Wt% Wt% Wt% Wt% Wt% Wt% wet wet dr wet dr Part 83.45 94.07 75.99 94.70 89.60 95.00 Part 7.62 2.01 6.94 2.02 8.19 2.

Te o Glide 435 2.06 2.95 1.88 2.97 2.21 2.97 Water 6.18 0. 15.01 0. 00 00 Pectin methyl 0.68 0.97 este rase Ac lase I 0.19 0.

Weight % 85.7 86.3 86.6 polysiloxane-based binder matrix in the dr cured coat Performance in Spain Excellent Excellent Good after 23 weeks Performance in Good Excellent Fair after 24 Singapore weeks PC T/DK2012/050226 Example 3 Polysiloxane-based coatings with an enzyme and silicone oils Part I Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 67.7 X lene 25.4 Aerosil R972 1.16 Micronised wax 1.

Pi ments 4.65 Part II Wt% Eth I silicate 41.1 X lene 31.7 Dibut Itin dilaurate 7.05 entanedione 20. 1 EC15 EC16 EC17 Wt% Wt% Wt% Wt% Wt% Wt% wet dr wet dr wet dr Part 90.15 97.86 88.17 94.87 88.17 94.92 Part 5.96 2.07 5.83 2.00 5.83 2.00 (ii) Glide 435 2.12 3.06 Tego DC550 2. 3. 08 00 Water 3.84 0.00 3.87 0.00 3.87 0.00 0.048 0.07 0.048 0.07 0.048 0.07 Papain 90. 87.7 87.7 Weight % 5 oxa ne- po lysil based binder matrix in the dr cured coat Performance in Poor Poor Excellent ain after 10 weeks EC18 EC19 Wt% Wt% Wt% Wt% wet dr wet dr 88.17 94.91 88.13 94.87 Part .83 2.00 5.83 2.00 Part (ii) 2.12 3.06 Byk 331 PMX-200 Xiameter Sil 0.4 0.58 Fluid 1000cs PMX-200 Xiameter Sil 1.68 2.42 Fluid 5000cs 3.87 0.00 3.87 0.00 Water 0.048 0.07 0.048 0.07 Papain Weight % polysiloxane- 87.7 87.7 based binder matrix in the dr cured coat Performance in Spain Poor Fair after 10 weeks PC T/DK2012/050226 Example 4 Adjusting enzyme amounts Part i Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 67.7 X lene 25.4 Aerosil R972 1.16 Micronised wax 1.

Pi ments 4.65 Part ii Wt% Eth I silicate 41.1 X lene 31.7 Dibut Itin dilaurate 7.05 entanedione 20. 1 EC20 EC21 EC22 Wt% Wt% Wt% Wt% Wt% Wt% wet wet dr wet dr 88.13 94.87 84.8 94.80 85.64 94.57 Part .83 2.00 5.61 2.00 5.67 2.00 Part (ii) 2.12 3.06 2.04 3.06 2.06 3.05 3.87 0. 7.453 0. 3.76 0. 00 00 00 Water 0.048 0.07 0.093 0.14 0.047 0.07 Papain 2.82 0.31 Endo lase 87.7 87. 87.4 Weight % 6 oxa ne- po lysil based binder matrix in the dr cured coat Performance in Fair Good Good ain after 10 weeks Effect of the amount of oil Example 5 Part i Wt% Sila nol-terminated polydimethylsiloxa ne (5000 cSt) 67.7 X lene 25.4 Aerosil R972 1.16 Micronised wax 1.

Pi ments 4.65 Part ii Wt% Eth I silicate 41.1 X lene 31.7 Dibut Itin dilaurate 7.05 4-penta nedione 20. 1 PC T/DK2012/050226 EC23 EC24 EC25 Wt% Wt% dry Wt% Wt% Wt% Wt% wet wet dr wet dr 89.41 96.87 88.17 94.87 89.62 93.25 Part .91 2.04 5.83 2.00 5.75 1.91 Part (ii) 0.7 1.02 2.12 3. 3.42 4.77 Tego Glide 435 3.93 0.00 3.87 0.00 3.84 0.00 Water 0.049 0.07 0.048 0.07 0.048 0.07 Papain Weight % 89.5 87.7 86.2 lysil oxa based binder matrix in the dr cured coat Performance in Poor Excellent Excellent Spain after 10 weeks EC26 EC27 Wt% Wt% Wt% Wt% wet dr wet dr 89.93 94.96 84.84 94.86 Part .95 2.01 5.61 2.00 Part (ii) 2.12 3.00 2.00 3.00 Glide 435 Tego 1.98 0.00 7.46 0.00 Water 0.025 0.04 0. 0.14 Papain Weight % 87.8 87.7 oxa ne- po lysil based binder matrix in the dr cured coat Performance in Excellent Excellent Spain after 10 weeks Example 6 Polysiloxane-based coatings with enzymes and hydrophilic-modified PDMS EC28 EC29 EC30 EC31 reference reference Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% wet dr wet dr wet dr wet dr Sila nol-terminated 20.06 28.41 19.28 28.38 28.47 39.83 27.64 39.70 polydimethylsiloxa ne (5000 cSt) Xylene 18.28 0.00 17.57 0.00 18.28 0.00 17.74 0.00 Micronised wax 2.31 3.27 2.22 3.27 2.31 3.23 2.24 3.22 Pigments 4.31 6.10 4.14 6.09 4.31 6.03 4.18 6.01 PC T/DK2012/050226 Total part 44.96 37.77 43.21 37.75 53.36 49.09 51.81 48.93 silicate 2.42 1.40 2.32 1.40 2.42 1. 2. 1.

Ethyl 38 35 38 Xylene 3.78 0.00 3.63 0.00 3.78 0.00 3.67 0.00 Dibutyltin dilaurate 0.42 0.59 0.40 0.59 0.42 0.59 0.41 0.59 2,4-penta nedione 1.16 0.00 1.11 0.00 1.16 0.00 1.12 0.00 Linear hydrophilic 47.27 60.23 45.43 60.19 38.87 48.94 37.73 48.79 modified polysiloxane (HMP2) Total part 55.04 62.23 52.90 62.18 46.64 50.91 45.28 50.75 (ll) Demineralized water 0.00 0.00 3.85 0.00 0.00 0.00 0.00 0.00 Papain 0.00 0.00 0.05 0.07 0.00 0.00 0.00 0.00 Endo lase 0.00 0.00 0.00 0.00 0.00 0.00 2.92 0.31 Weight % 89.5 89.4 89.6 89.6 lysil oxa based binder matrix in the dr cured coat + + + + Bacterial biofilm 0.77 0.15 0.39 0.06 0.64 0.03 0.50 0.06 retention Example 7 Polysiloxane-based coatings with enzymes and hydrophilic-modified PDMS EC32 EC33 reference Wt% Wt% Wt% Wt% wet dI wet dI nol-terminated Sila 62.08 82.98 60.27 82.73 polydimethylsiloxa ne 5000 cSt Xylene 18.28 0.00 17.74 0.00 Micronised wax 2.31 3.09 2.24 3.08 Pigments 4.31 5.76 4.18 5.74 Total part 86.97 91.83 84.44 91.55 Ethyl silicate 2.42 1.29 2.35 1.29 Xylene 3.78 0.00 3.67 0.00 Dibutyltin dilaurate 0.42 0.56 0.41 0.56 4-penta nedione 1.16 0.00 1.12 0.00 PC T/DK2012/050226 Pendant hydrophilic 5.25 6.32 5.10 6.30 modified polysiloxane (HMP1) Total 13.03 8.17 12.65 8.15 part (ii) Endo lase 2.86 0.30 Weight % 90.1 90.1 lysil oxa based binder matrix in the dry cured coat Performance in Poor Fair Singapore after 8 weeks Example 8: Cross-linking of enzymes (enzyme agglomerates) Part i Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 67.7 X lene 25.4 1.16 Aerosil R972 Micronised wax 05 Pi ments 4.

Part ii Wt% Eth I silicate 41.1 X lene 31.7 Dibut Itin dilaurate 7. 4-penta 2, nedione 20. 1 EC34 EC35 Wt% Wt% Wt% Wt% wet dr wet dr 91.4 94.5 80.5 94.5 Part 6.0 2.0 5.3 2.0 Part (ii) 2.1 2.9 1.8 2.9 Tego Glide 435 8.8 0.70 Savinase 0.50 0.70 Savinase CLEA Weight % 87.4 87.4 lysil oxa based binder matrix in the dr cured coat Performance in Excellent Fair Spain after 8 weeks PC T/DK2012/050226 Example 9: Modification of enzyme-surfaces Surface modification of was done render the more stable in the enzymes to enzymes paint matrix. The surfaces were modified using mono activated (NHS or maleimide) PEG, that reacts with the nucleophilic amino-acid said chain functionalities.

PEG-papain: 2 of solution of 0.787 wt% in PBS buffered water was mixed with a papain 0.05 mPEG-NHS Ester Nanocs) and left to react for 30 minutes at 25 on a stirring (ex. table.

PEG-Savinase: 0.2 of Methoxypolyethyleneglycol maleimide was added to 10 of the Savinase solution and left to react for 30 minutes at 25 on a stirring table.

Part I Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 67.7 X lene 25.4 Aerosil R972 1.16 Micronised wax 1.05 Pi ments 4.65 Part II Wt% Eth I silicate 41.1 X lene 31.7 Dibut Itin dilaurate 7.05 2, entanedione 20. 1 EC36 EC37 EC38 EC39 Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% wet dr wet dr wet dr wet dr 80. 94. 83.4 94. 88.2 94. 88.2 94. 5 5 9 9 Part .3 2.0 5.5 2.0 5.83 2.0 5.83 2.0 Part (ii) 1.8 2.9 1.9 2.9 2.1 3.0 2. 1 3.0 Tego Glide 435 8.8 0.70 Savinase 9.2 0.70 PEG-Savinase 0.048 0.070 Papain 2.05 0.066 PEG-Papain 3.88 Water Weight % 87.4 87.4 87.7 87.7 lysil oxa based binder matrix in the dr cured coat Performance in Fair Good good Excellent Spain after 8 weeks PC T/DK2012/050226 Example 10: Immobilisation of enzymes in the binder matrix: were modifed with heterobifunctional that in one end reacts with the Enzymes PEG, amino-acid nucleophilic group on the surface of the enzyme, and where the other end is silane functional, rendering the enzyme curable in the matrix: paint Silane-PEG-papain:2 of solution of 0.787 wt% in PBS buffered water was mixed a papain with 0.05 Silane PEG NHS and allowed to react for 30 minutes at 25 Silane-PEG-Savinase: 0.1 of Sil-PEG-NHS was 10 of the savinase solution and added to allowed to react for 30 minutes at 25 Part I Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 67.7 Xylene 25.4 Aerosil R972 1.16 Micronised wax 1.05 Pigments 65 Part II Wt% Eth I silicate 41.1 Xylene 31.7 Dibut Itin dilaurate 7. entanedione 20. 1 EC40 EC41 EC42 EC43 Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% wet dr wet dr wet dr wet dr 80.5 94.5 83.4 94.5 88.2 94.9 88.2 94.9 Part .3 2.0 5.5 2.0 5.83 2.0 5.83 2.0 Part (ii) 1.8 2.9 1.9 2.9 2.1 3.0 2. 1 3.0 Glide 435 Tego 8.8 0.70 Savinase Silane PEG 9.2 0.70 Savinase 0.048 0.070 Papain 2.05 0.066 Silane PEG Papain 3.88 Water 87.4 87.4 87.7 87.7 Weight % lysil oxa based binder matrix in the dr cured coat Performance in Fair Good Excellent good Spain after 8 weeks PC T/DK2012/050226 Example 11: Combining different enzymes: Part i Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 67.7 X lene 25.4 Aerosil R972 1.16 Micronised wax 1.

Pi ments 4.65 Part ii Wt% Eth I silicate 41.1 X lene 31.7 Dibut Itin dilaurate 7.05 entanedione 20. 1 EC44 EC45 Wt% Wt% Wt% Wt% wet dr wet dr 85.7 94.7 89.1 94.8 Part .7 2.0 5.9 2.0 Part (ii) 2.0 3.0 2.1 3.0 Glide 435 Tego 2. 0.21 2. 0.21 Endo lase 5000L 0.047 0.070 Papain Hemicellulase Acylase 3.77 Water Weight % 87.5 87.6. oxa ne- po lysil based binder matrix in the dr cured coat Performance in Fair Good after 16 Spain weeks Example 12: Native vs. heat denatured enzymes: Part i Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 67.7 X lene 25.4 Aerosil R972 1.16 Micronised wax 1.05 Pi ments 4.65 Part ii Wt% Eth I silicate 41.1 X lene 31.7 Dibut Itin dilaurate 7.05 entanedione 20. 1 Two were with identical One of them was immersed in water panels prepared paints. boiling for five minutes to inactivate the enzymes.

PC T/DK2012/050226 EC46 EC47 (Heat treated; reference Wt% Wt% Wt% Wt% wet dr wet dr 89.1 94. 89.1 94.

Part . 2. 5. 2. 9 0 9 0 Part (ii) 2.1 3. 2. 1 3.

Glide 435 Tego 2. 0.21 2. 0.21 Endo lase 5000L Weight % 87.6 87.6 oxa ne- po lysil based binder matrix in the dr cured coat Performance in Poor Fair after 16 Spain weeks Example 13: Fluorinated oils and enzymes Part I Wt% Silanol-terminated ol dimeth Isiloxane 5000 cSt 67.7 X lene 25.4 Aerosil R972 1.16 Micronised wax 1.05 Pi ments 4.65 Part II Wt% Eth I silicate 41.1 X lene 31.7 Dibut Itin dilaurate 7.05 entanedione 20. 1 EC48 EC49 EC50 EC51) Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% wet dr wet dr wet dr wet dr 88.2 94. 91. 95. 88.2 91. 9 8 0 95 8 95 Part .8 2.0 6.1 2.0 5.8 2.0 6.1 2.0 Part (ii) 2.1 3. 2.1 3.

Fluorosil 2110 2.1 3.0 2.2 3.0 C-1910 Fluorosil 0.048 0.070 0.048 0.070 Papain 3.875 3.874 Water Weight % 87.7 87.8 87.8 87.8 lysil oxa based binder matrix in the dr cured coat Performance in Good Fair Good Poor Spain after 21 weeks PC T/DK2012/050226 Example 14 Polysiloxane-based coatings fluorinated oils Model paints EC52 EC53 EC54 EC55 EC56 EC57 Part Silanol-terminated 60.1 60.1 60.1 60.1 64.1 64.1 polydimethylsiloxane 17.4 17.4 17.4 17.4 17.4 17.4 Xylene Thixotropic agent 2.2 2.2 2.2 2.2 2.2 2.2 Pigments 8.9 8.9 3.9 3.9 3.9 8.9 Biocide: Copper pyrithione Total 88.6 88.6 88.6 88.6 92.6 92.6 part (i) Part (ii) silicate 2. 2. 2. 2. 2. 2.

Ethyl 3 3 3 3 3 3 LF-200 FOMBLIN Y-25 Xylene 3.6 3.6 3.6 3.6 3.6 3.6 dilaurate 0.4 0.4 0.4 0.4 0.4 0.4 Dibutyltin 2,4-pentanedione Total part (ii) 11.4 11.4 11.4 11.4 7.4 7.4 Total part (i), (ii), 100 100 100 100 100 100 I I I Weight % polysiloxa 79.9 79.9 79.9 79.9 85.1 85.1 based binder matrix in the cured coat Performance on raft in Singapore Poor Poor Fair Fair Poor Poor weeks Adhesion Good Good Good Good Good Good Model paints EC58 EC59 EC60 EC61 EC62 EC63 Part (i) Silanol-terminated 62.1 62. 1 62. 1 62.1 64.1 64. 1 polydimethylsiloxane Xylene 17.4 17.4 17.4 17.4 17.4 17.4 PC T/DK2012/050226 Thixotropic agent 2.2 2.2 2.2 2.2 2.2 2.2 8. 8. 3. 3. 3. 8.

Pigments 9 9 9 9 9 9 Biocide: Copper pyrithione Total part 90.6 90.6 90.6 90.6 92.6 92.6 Part (ii) Ethyl silicate 2.3 2.3 2.3 2.3 2.3 2.3 FLUOROSIL 2110 C1910 Xylene 3.6 3.6 3.6 3.6 3.6 3.6 Dibutyltin dilaurate 0.4 0.4 0.4 0.4 0.4 0.4 4-pentanedione Total part 9.4 9.4 9.4 9.4 7.4 7.4 (ii) Total part (i), (ii), 100 100 100 100 100 100 I I I Weight % polysiloxa based binder 82.5 82.5 82.5 82.5 85.1 85.1 matrix in the dry cured coat Performance on raft in Poor Excellent Excellent Poor Poor Singapore (24 Fair/Good weeks) Adhesion Good Good Good Good Good Good

Claims (20)

1. A cured fouling release coat comprising a polysiloxane-based binder matrix from a polysiloxane based binder which is a functional organopolysiloxane with terminal and/or pendant functionality, said polysiloxane-based binder matrix constituting 50- 5 90 % by dry weight of the coat, one or more enzymes and one or more hydrophilic- modified polysiloxane oils in an amount of 0.05-10 % by dry weight of the coat.

2. The fouling release coat according to claim 1, wherein the one or more enzymes include hydrolytic enzymes, e.g. those selected from EC classes: EC 3.1, EC 3.2, EC

3.4, and EC 4.2. 10 3. The fouling release coat according to any one of the preceding claims, wherein the one or more enzymes are selected from serine proteases, cysteine proteases, metalloproteinase, cellulase, hemicellulase, pectinase, and glycosidases.

4. The fouling release coat according to any one of the preceding claims, wherein the one or more enzymes include an enzyme which is capable of degrading the 15 exopolymeric substances of marine-based bio-fouling organisms as determined in the Barnacle settlement test described herein.

5. The fouling release coat according to any one of the preceding claims, wherein the one or more enzymes include an enzyme which is capable of degrading the exopolymeric substances of marine-based bio-fouling organisms as determined in the 20 Algae settlement test described herein.

6. The fouling release coat according to any one of the preceding claims, wherein the one or more enzymes are formulated.

7. The fouling release coat according to any one of the preceding claims, wherein the binder matrix has included as a part thereof hydrophilic oligomer/polymer moieties wherein more than 50 % by weight of the binder matrix is represented by polysiloxane parts.

8. The fouling release coat according to any one of the preceding claims, wherein the one or more hydrophilic-modified polysiloxane oils constitute 0.05-7 % by dry weight 5 of the coating composition.

9. The fouling release coat according to any one of the preceding claims, which further comprises one or more thickeners and/or anti-settling agents (e.g. thixotropic agents).

10. The fouling release coat according to any one of the preceding claims, which further comprises one or more solvents selected from aliphatic, cycloaliphatic and aromatic 10 hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; octamethyltrisiloxane, and mixtures thereof, preferably those solvents having a boiling point of 110 °C or more.

11. The fouling release coat according to any one of the preceding claims, wherein the 15 coat further comprises one or more fluorinated oils.

12. The fouling release coat according to any one of the preceding claims, which is prepared from a coating composition having a viscosity in the range of 200-4,000 mPa·s measured at 25 °C in accordance with ISO 2555:1989.

13. The fouling release coat according to any one of the preceding claims, which is 20 prepared from a coating composition that it exhibits sag resistance for a wet film thickness up to at least 300 μm as determined in accordance with ASTM D 4400-99.

14. The fouling release coat according to any one of the preceding claims, which further comprises one or more biocides.

15. A kit for preparing the fouling release coat comprising one or more enzymes and one 25 or more hydrophilic-modified polysiloxane oils according to any one of the claims 1- 14, said kit comprising a first container holding a polysiloxane binder base, and a second container holding a siloxane curing agent and optionally a catalyst, wherein polysiloxane binder base of the first container is curable in the presence of the content of the second container, the kit further comprises one or more enzyme either as a 5 constituent of the first container or a constituent of the second container, or alternatively in a third container.

16. A method of coating a surface of a substrate, comprising the sequential steps of a. applying one or more layers of a primer composition and/or applying one or more layers of a tie-coat composition onto the surface of said substrate, and 10 b. applying one or more layers of a coating composition so as to obtain the fouling release coat comprising one or more enzymes as defined in any one of the claims 1-14 on the coated surface of said substrate.

17. A marine structure comprising on at least a part of the outer surface thereof an outermost fouling release coat as defined in any one of the claims 1-14. 15

18. The structure according to claim 17, wherein at least as part of the outer surface carrying the outermost coating is a submerged part of said structure.

19. A fouling release coating composition comprising a polysiloxane-based binder system including a polysiloxane-based binder which is a functional organopolysiloxane with terminal and/or pendant functionality, said polysiloxane-based binder system 20 constituting 50-90 % by dry weight of the coating composition, said binder system comprising one or more polysiloxane components modified with hydrophilic oligomer/polymer moieties, and one or more enzymes and one or more hydrophilic- modified polysiloxane oils in an amount of 0.05-10 % by dry weight of the coating composition. 25

20. A fouling release coating composition comprising a polysiloxane-based binder system including a polysiloxane-based binder which is a functional organopolysiloxane with terminal and/or pendant functionality, said polysiloxane-based binder system constituting 50-90 % by dry weight of the coating composition, 0.01-20 % by dry weight of one or more hydrophilic-modified polysiloxane oils, and one or more enzymes.