NZ618053B2

NZ618053B2 - Fouling control coating compositions

Info

Publication number: NZ618053B2
Application number: NZ618053A
Authority: NZ
Inventors: Anders Blom; Peter Christian Weinrich Thorlaksen; Diego Meseguer Yebra
Original assignee: Hempel A/S
Priority date: 2011-06-30
Filing date: 2012-06-29
Publication date: 2015-07-28

Abstract

Disclosed is a fouling control cured paint coating comprising a polysiloxane-based binder matrix and one or more biocides, said binder matrix having included as a part thereof hydrophilic oligomer/polymer moieties, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.02 to :20, and wherein ?50 % of the binder system is polysiloxane parts. The application further discloses a marine structure comprising on at least a part of the outer surface thereof an outermost coating of the cured paint coat. Also disclosed is the use of the combination of one or more polysiloxane components modified with hydrophilic oligomer/polymer moieties and one or more biocides, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.02 to :20, for improving the antifouling properties of a polysiloxane based coating composition. e or more biocides is in the range 1:0.02 to :20, and wherein ?50 % of the binder system is polysiloxane parts. The application further discloses a marine structure comprising on at least a part of the outer surface thereof an outermost coating of the cured paint coat. Also disclosed is the use of the combination of one or more polysiloxane components modified with hydrophilic oligomer/polymer moieties and one or more biocides, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.02 to :20, for improving the antifouling properties of a polysiloxane based coating composition.

Description

/000479 T/DK2012/050228 WO PC COMPOSITIONS FOULING CONTROL COATING FIELD OF THE INVENTION The present invention relates to novel fouling control coating compositions.

BACKGROUND OF THE INVENTION Traditionally, silicone formulations rely on physical means, this being mainly a factor of modulus of and surface tension create low bio-fouling surface. The traditional elasticity to a polydimethylsiloxane (PDMS) coatings have shown difficulty in resisting bio-fouling over time, thus decreasing the advantage of reduction. drag Hence, there is a need for fouling control polysiloxane-based coating compositions combining the benefits of conventional polysiloxane-based fouling-release coating compositions with the benefits of biocide-based antifouling coating compositions. discloses an antifouling material that include one or more of a number of suitable block etc. which provide biocidal copolymers (e.g. copolymers, graft copolymers, and/or fouling release characteristics. The copolymers may include a polysiloxane backbone with one or more polymers grafted onto the polysiloxane backbone. Such grafted polymers biocidal may carry groups. discloses an antifouling coating composition comprising a curable polymer an organosiloxane-containing and an organosilicone (e.g. polymer) polymer. discloses a method to physically deter marine fouling which method involves forming on the substrate a coating composition comprising curable polyorgano- siloxane, block organosilicon cross-linking and/or polyoxyalkylene copolymer, agent catalyst. The polyoxyalkylene is reacted to the silicone binder addition reaction (vinyl/hydride) to form a block copolymer of polyoxyalkylene and polysiloxane. The can be terminated with vinyltrimethoxysilane to form a moisture copolymer subsequently curable binder.

US 2004/006190 discloses a room-temperature curable organopolysiloxane composition, which includes an organopolysiloxane with the terminals blocked with a hydroxyl a (A) group, hydrolysable or both these of and an organosilicon compound group, types groups, (B) PC T/DK2012/050228 containing a hydrolysable a partial hydrolysis-condensation product thereof, or a group, mixture of the and with least one bonded two, a polysiloxane at oxyalkylene group to a C-C-Si silicon atom via, for example, a linkage. discloses a process for coating a siliceous substrate with a silicon- wherein in first biocide is containing layer, a step a layer comprising a applied.

US 2002/0197490 Al discloses a curable antifouling polysiloxane based composition silica in combination with silica. In some comprising hydrophobic possibly hydrophilic embodiments, the composition further comprises a silicone oil, e. oils comprising or moieties. It is further that poly(ethylene glycol) poly(propylene glycol) envisaged, in and antifouling agents may be used, particular copper inorganic copper compounds.

EP 2 103 655 Al discloses a curable antifouling polysiloxane based composition comprising a reaction curable silicone rubber and mixture. In a particularly designed organopolysiloxane some embodiments, the composition further comprises a silicone oil, e. a polyether- modified silicone oil. It is further that antifouling be in envisaged, agents may used, and particular copper inorganic copper compounds.

US 313,193 Bl i.a. discloses a composition comprising a silanol-terminated polydimethyl siloxane, a dimethylethoxy-terminated siloxane, siloxane, and polydimethyl polydiethoxy benzalkonium chloride. The polydiethoxy siloxane reacts with the polydimethyl siloxanes so that the polydiethoxy siloxane becomes an integral part of the binder network. jP 2006 052283 A discloses polyether-modified silicone a coating composition comprising a oil having polyoxyalkylene side chains, an acrylic binder system based on a polysiloxane type macropolymer and an antifoulant. jP 2006 299132 A discloses an which is on antifouling coating composition based a vinyl copolymer binder system which include polysiloxane side chains, and which is modified with certain reactive and which further e. an silanes, comprises, g. poly(oxyalkylene)-modified polysiloxane. The composition may also include an antifouling agent. jP 05-263022 discloses a hydrolysable coating composition based on an acid- typically binder for attachment. anhydride vinyl preventing aquatic organism EP 1 261 318 Al discloses a triphenylboron compound-containing antifouling coating composition stabilised with an amine compound. The composition comprises a non-reactive polysiloxane modified with oxyalkylene groups. (oil) PC T/DK2012/050228 US 2009/0018276 Al discloses a polysiloxane based coating composition having biocide moieties bound the binder matrix. covalently to The silicone based fouling release coatings have demonstrated an advantage over conventional antifouling coatings showing significant lower resistance, hence reduced drag fuel of marine vessels. The difference is obvious the consumption especially as long as silicone coating is free from marine fouling including slime fouling. Many conventional silicone have until now been able maintain slime free surface for shorter coatings only to a a period.

A few biocide containing antifouling coatings have demonstrated a greater resistance towards marine fouling compared to the silicone based fouling release coatings under e. static conditions. The surface characteristics of such will however lead an increased a coating to drag resistance compared to silicone coatings even when the surface is fouling free.

The rationale behind the invention has been the slime free of present to prolong period a silicone based coating combining the biocidal components from the antifouling coatings with a silicone based fouling release coating. This provides a coating with low resistance drag that will remain free for time than conventional silicone release fouling a longer based fouling coatings.

SUMMARY OF THE INVENTION above-mentioned In view of the needs, the present inventors have now developed paint compositions for preparing new fouling control coatings (i.e. a cured paint coat) comprising polysiloxane-based binder matrix included thereof a having as a part hydrophilic oligomer/polymer moieties, and one or more biocides, which matrix facilitates and (ii) controls the leaching of the biocides. In this the advantages of silicone fouling release way, low- are combined with those of traditional anti-fouling coatings, thus gaining a foul-free, friction surface with the use of a relatively small amount of biocide.

The inventors have realised that the of polysiloxane-based binder present use a system having included as a part thereof hydrophilic oligomer/polymer moieties, in particular moieties, (see further below) renders it possible to obtain a media for poly(oxyalkylene) water- and biocidal transport through the cured polysiloxane matrix film. The leach rate of the biocide can be controlled amongst others the amount and the hydrophilicity of the hydrophilic moieties. oligomer/polymer PC T/DK2012/050228 in a first aspect the present invention relates to a cured paint coat comprising a polysiloxane-based binder matrix and one or more said binder matrix biocides, having included as a part thereof hydrophilic oligomer/polymer moieties, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the 1:0.02 and wherein more than of the binder matrix is range to 1:20, 50 % by weight represented polysiloxane parts.

A second of the invention relates marine structure on least of aspect to a comprising at a part the outer surface thereof a paint coat as defined herein.

In a third the present invention relates to a fouling control coating composition aspect polysiloxane-based binder said binder one or more comprising a system, system comprising polysiloxane components modified with hydrophilic oligomer/polymer moieties, and one or more wherein the ratio between the moieties biocides, weight hydrophilic oligomer/polymer and the one or more biocides is in the range 1:0.02 to 1:20, and wherein more than 50 % weight of the binder system is represented polysiloxane parts.

In fourth the invention relates control a aspect, present to a fouling coating composition comprising a polysiloxane-based binder system, said binder system comprising one or more hydrophilic moieties which at one or both ends -Si(R*), oligomer/polymer carry groups, R* R* wherein each independently is selected from C& 4-alkyl and C& 4-alkoxy, or is another condensation curable termination, at least one being 4-alkoxy, or at least one being another condensation curable and one or more wherein the termination, biocides, weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.02 to 1:20, and wherein more than 50 % weight of the binder system is represented by polysiloxane parts.

A fifth aspect of the invention relates to a fouling control coating composition comprising a polysiloxane-based binder said binder cross-linker of formula system, system comprising a (2a) (2~) PC T/DK2012/050228 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 each is independently selected from 4-alkyl group; C, -CH„-CH, CH„-CH, CH, CH„-CH(CH, )„-CH,CH, CH, phenyl (-C, and 4- (e.g. CH, H, C, ), ), and in and alkylcarbonyl (e.g. -C(=O)CH„-C(=O)CH, CH, -C(=O)CH, CH, CH, particular methyl; each is independently selected from C»-alkylene -CH&CH&-, -CH&CH(CHg)-, (e.g.

-CH&CH&CH&-, -CH&CH&CH&CH&-, arylene 4-phenylene) and -CH&CH(CH&CH&)-), (e.g. 1, C, alkylene substituted with aryl (e. 1-phenyl ethylene), in particular from C»-alkylene such as -CH, CH, and -CH, is 0-50; a is 0-2; z is 1-3; CH(CH, )-); and one or more biocides, wherein the weight ratio between the poly(oxyalkylene) and the one or more biocides is in the 1:0.02 to 1:20, and wherein more than 50 % weight range by of the binder system is represented by polysiloxane parts.

A sixth aspect of the invention relates to the use of the combination of one or more polysiloxane components modified with hydrophilic moieties and one or oligomer/polymer more biocides, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.02 to 1:20, for improving the antifouling properties a polysiloxane based coating composition.

DETAILED DISCLOSURE OF THE INVENTION The cured paint coat As mentioned above, the present invention provides a cured paint coat comprising a polysiloxane-based binder matrix and one or more biocides, said binder matrix having included thereof wherein the ratio as a part hydrophilic oligomer/polymer moieties, weight between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the 1:0.02 such 1:0. and wherein more than of the range to 1:20, as 05 to 1:10, 50 % by weight binder system is represented polysiloxane parts.

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

Without being bound to particular theory, it is believed that the function of the polysiloxane-based binder matrix rendered hydrophilic means of by oligomer/polymer moieties is to facilitate the transport and accessibility of the biocide at the surface upon contact with sea-water. Potentially, a hydrated formed at the coating-water interphase layer PC T/DK2012/050228 will also aid in retaining the biocide at the surface, hence allowing the coating to exert its deterrent for extended intervals. fouling activity exposure It should be understood that the hydrophilic oligomer/polymer moieties forms a part of the polysiloxane-based binder matrix, i.e. that the moieties are covalently incorporated into the binder matrix. It should also understood that the formed covalent are be bond(s) preferably non-hydrolysa ble.

The polysiloxane-based binder matrix constitutes least 40 such typically at by dry weight, 40-98 '/o 45-95 '/o 50-95 '/o as dry weight, or dry weight, or dry weight, in by by by '/o '/o '/o particular 50-90 or 55-90 or 60-90 or by dry weight, by dry weight, by dry weight, 60-80 of the cured coat. by dry weight, paint 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 '/o '/o than 60 weight, e. more than 70 weight, of the binder matrix is represented by g. by by polysiloxane parts. Preferably, the polysiloxane constitute 50-99.99 e. parts by weight, g. '/o '/o '/o '/o 50-99. in 60-99. or 50-99 or 60-98 9 by weight, particular 5 by weight, by weight, 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 matrix e. the binder components and cross-linkers). The by weight, (i. any remainder of the binder matrix is preferably made of the hydrophilic oligomer/polymer moieties and (non-polysiloxane-type) cross-linkers. This being said, the hydrophilic '/o '/o moieties makes 1-30 such 2-20 oligomer/polymer preferably up by weight, as by 1-10 '/o weight, e. weight, of the binder matrix. g. by It should of course be understood that the hydrophilic moieties which are oligomer/polymer 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 for material an it is moieties, respectively, a given starting (or adduct), typically fairly straightforward to distinguish between the two. However, in order to eliminate any doubt about linkers between the it should be understood that the hydrophilic any two, 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, -[hydrophilic oligomer]-CH, -Si(Me), type CH, CH, CH, CH, polysiloxane], the [polysiloxane-0]-Si(Me)2 parts are accounted for as silicone parts, whereas the CH2CH2CH2-[hydrophilic oligomer]-CH2CH, CH, moiety is accounted for as the hydrophilic oligomer moiety.

PC T/DK2012/050228 Suitable hydrophilic oligomer/polymer moieties are those selected from poly(vinyl pyrrolidone), poly[N-(2-hydroxypropyl)methacrylamide], poly(N, dimethacrylamide), poly(acrylic acid), poly(glycerol), polyHEMA, polysaccharides, poly(vinyl alcohol), polyketones, poly(aldehyde guluronate), polyvinylamine, polycaprolactones, poly(vinyl like acetate), polyoxyalkylenes poly(ethylene glycol), poly(propylene glycol), poly(2-methyl- 2-oxazoline), etc. including copolymers of the foregoing. Preferably the hydrophilicity is obtained modification with moieties like by polyoxyalkylene poly(ethylene glycol).

Incorporation of the above mentioned hydrophilic oligomer/polymer into the polysiloxane polymer backbone is done through a linking The linking is understood typically group. group the of the reaction of two reaction functional one functional as product mutually groups; group on the polysiloxane backbone and one on the hydrophilic oligomer/polymer. E. an amine linking is result of for example but not exclusively the reaction of a group glycidyl ether with a primary or secondary amine. Examples of useful linking groups between the hydrophilic oligomer/polymer and the polysiloxane backbone are: amine ether groups, amide 3-triazole, C-C bonds, C-C double bonds, C-C triple bonds, Si-C groups, groups. 1,2, C-S S-S bonds, bonds, bonds, urethane urea groups. Most preferred linking group is group, Si-C the bond prepared hydrosilylation reaction catalyzed platinum where the by by functional on the backbone is and the functional on the group polysiloxane a hydride group hydrophilic oligomer/polymer is an allyl group.

In some embodiments, it is preferred that the hydrophilic moieties provide oligomer/polymer a permanent hydrophilic contribution to the binder matrix. Hence, in such embodiments, the hydrophilic oligomer/polymer moieties are preferably devoid of bonds which are hydrolysable in sea-water. Hence, the hydrophilic moieties do preferably, oligomer/polymer not include ester bonds or acid anhydride bonds.

In other embodiments, it is also preferred that the hydrophilic moieties oligomer/polymer provide a permanent hydrophilic contribution to the binder matrix. But, in such embodiments, the link between the hydrophilic oligomer/polymer moieties and the silicone is devoid of bonds which are hydrolysable in sea-water. Hence, the hydrophilic preferably, oligomer/polymer moieties are not attached to the polysiloxane through hydrolysable bonds such as for example ester bonds or acid anhydride bonds. However, the hydrophilic moiety in itself include such for an may hydrolysable bonds, as example acetate capped lkylene). poly(oxya In the present context moieties are understood as those encompassing at oligomer/polymer least 3 repeating units, such as at least 5 repeating units. Typically, oligomer/polymer PC T/DK2012/050228 moieties used for modification include 3-1,000 repeating units, such as 3-200, or 5-150, or -100, or 10-80, or 5-20, units. repeating In some preferred embodiments, the hydrophilic oligomer/polymer moieties (i.e. oligomeric or incorporated into the binder matrix) have a number average molecular polymeric groups in the of 100-50, such in the of 100-30, in weight range 000 g/mol, as range 000 g/mol, (M„) particular in the range of 150-20,000 or in the range of 200-10,000 g/mol. g/mol, In the with the terms "hydrophilic moieties", present description claims, oligomer/polymer moieties", "hydrophilic polymer and similar are intended to mean that the oligomeric or moieties, in themselves e. when represented as discrete molecules) have a polymeric (i. of least 1 in demineralized water 25'C. solubility at %(w/w) at Polysi Ioxane-based binder system The cured of the invention is from binder which paint coat typically prepared a system upon cross-linked curing forms a polysiloxane-based binder matrix which incorporates the biocide(s) as well as other constituents such as additives, pigments, fillers, etc. in the cured int coat.

Hence, it should be understood that the polysiloxane-based binder matrix is made of reactive binder e. functional cross-linkers, polysiloxane components, g. organopolysiloxanes, silicates (e. ethyl silicate), and the like. Thus, it is believed that the reaction between such components will result in the binder matrix in the form of a three-dimensional typically interconnected network. covalently The cured paint coat be formed in various e. polymerization/cross-linking may ways, g. by formation of siloxane bonds condensation reaction or the of their reactive through a by use groups such as for example amine/epoxy, carbinol/isocyanate etc. Condensation reaction is preferred.

The binder is functional with terminal polysiloxane based a organopolysiloxane, and/or pendant functionality. The terminal functionality is preferred. The functionality can either be hydrolysable such as for example alkoxy ketoxime or the functionality groups, groups, groups can be silanol groups. A minimum of two reactive groups per molecule is preferred. If the molecule contains only two reactive for example silanol it be necessary groups, groups, may an additional cross-linker, obtain the desired cross-link The to use reactant, a to density. cross-linker can for example be an alkoxy silane such as methyltrimethoxysilane, but a wide PC T/DK2012/050228 range of useful silanes are available as will be described further on. The silane can be used as it is or hydrolysation-condensation of same. condensation cure is much as products Although preferred, the functionality of the organopolysiloxane is not limited to a condensation cure. If so desired, other of curing can be utilized, for example amine/epoxy either alone or in types combination with condensation reaction. In such the can have a cases, organopolysiloxane terminal of or amine and pendant hydrolysable for example with groups epoxy groups, a 1ity. lkoxyf unct i on a The polysiloxane-based binder system discussed above is characterized having included therein, as a part of the binder matrix, one or more polysiloxane components which are modified with moieties. such hydrophilic oligomer/polymer Hence, polysiloxane components cross-linkers will upon reaction with other polysiloxane components and provide hydrophilic to the binder system. Alternatively, hydrophilic moieties properties oligomer/polymer functionalized with reactive silanes which enable them to react with the polysiloxane binder, or the hydrophilic oligomer/polymer moieties, and form a non-hydrolysable bond, also be used. silicon-reactive Si-OH The polysiloxane components must include groups such as groups, Si-OR hydrolysable such as (such as alkoxy, oxime, acetoxy etc. etc. so as groups groups, to facilitate reaction with other constituents of the polysiloxane-based binder system.

In one currently preferred embodiment of the above, the hydrophilic oligomer/polymer is moiety a poly(oxyalkylene) moiety.

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

Another example is a reaction curable composition based on an epoxy-functional polysiloxane binder and an amine functional Combinations of reaction-curable polysiloxane curing agent. compositions and condensation-curable compositions are possible, if the binder or the curing agent both) includes condensation curable such as alkoxy groups. (or groups, In one embodiment, the binder phase comprises a binder and a cross-linking agent of (i) (ii) which the binder should include hydrolysable or other reactive so as to (i) groups groups in the formation of the matrix. participate PC T/DK2012/050228 -90 The binder constitutes % weight of the coating composition, and it (i) typically by dry should that the binder of different e. two or more of the be understood, may be types, g. described above, so that the binder for example, comprise a non-modified types (i) may, curable polysiloxane and a curable polysiloxane which has been modified with hydrophilic moieties.

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' and each and is selected from alkyl, aryl, alkenyl a hydrolysable group; independently 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 -alkylene 1-25, 1-2, and a+b is to a C, linker; a 000, b 500 at least 5.

In one alternative the binder includes curable embodiment, a diorganopolysiloxane represented a general formula shown below: by (1x) PC T/DK2012/050228 A', A', A', A', wherein each of a and b are as above for formula and wherein each is selected from or an of 2-5 carbon atoms. independently oxygen alkyl group In another embodiment, the polysiloxane binder has hydrophilic oligomer/polymer moieties grafted as side chains hydrophilic as depicted below, and can be (pendant groups), prepared reaction between functional and by a hydrosilylation a hydride polysiloxane a hydrophilic component containing an unsaturated (-CH=CH2) such as for example an allyl or vinyl group in of such in accordance with formula group, presence a hydrosilylation catalyst, as platinum, where the example of a hydrophilic compound is an allyl-terminated poly(ethylene (1c), 60-150'C.

The synthesis is carried out at elevated temperatures, such as To render glycol). 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 the hydrophilic compound to the and it is outlined in formula grafting polysiloxane, and the functionalization may be done, but not necessarily, prior to the bonding of a (1b), hydrophilic group.

CH. H CH CHs —— — — — —— H Si 0 Si 0 Si 0 Si H 2 ~Si 0 CI, CH3 CH, CH~ Platinum catalyst 60-l50 C 0 CH, — — — Si Si Si Og Q~ C 0 Si CH- CH, CH s CHs The resulting binder from the reaction is further modified with a hydrophilic (1b) component, for example poly(ethylene glycol) mono allyl ether as outlined in formula (1c) resulting in a curable, polysiloxane modified with hydrophilic oligomer/polymer moieties.

PC T/DK2012/050228 The binder obtained can be used as is, or in combination with a curable diorganosiloxane the generic presented in formula As previously described, hydrophilic polymers type (1)). other 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 backbone polysiloxane (matrix).

PC T/DK2012/050228 Pendant hydrophilic oligomers/polymer moieties in principle carry functional (non- the free e. biocidal etc. in reactive) groups at end, g. groups exhibiting a effect, However, most embodiments, the hydrophilic oligomers/polymer moieties are not carrying such functional but are in the form of the native oligomer/polymer, possibly end-capped, groups, like with an or with or terminated. alkyl group, possibly a hydroxyl group methoxy A-B-A Another variation of the binder is an copolymer of polysiloxane and a hydrophilic such An of the structure of the is polymer as poly(oxyalkylene). example polymer (B), depicted in formula (1d). In this variation, units of a polymer with hydrophilic character, such as polyoxyalkylene are introduced in the backbone of the polysiloxane to form an alternating block such in the binder copolymer. Introducing hydrophilic groups as oxyalkylene groups may increase the hydrophilicity of the binder as described in reference . The A-B- binders can be used alone or in combination, and the structure of the can be copolymer 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 polymer. groups by H-, c In yet another variant, the hydrophilic component is obtained hydrosilylation of a polyoxyalkylene compound containing at least one, unsaturated (-CH=CH, such as an group 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 methyl, ethyl, C& C& (e.g. propyl, and at least one 4-alkoxy, such as for butyl, methoxy, ethoxy, propoxy, butoxy), being C& or in the of example trimethoxysilane, triethoxysilane methyldimethoxysilane, presence a hydrosilylation catalyst, such as platinum, yielding a curable poly(oxyalkylene). The reaction 60-150'C. is carried out at elevated temperatures, such as The synthesis is outlined in formula (le). The polymer has to be used in combination with, e. component (formula g. , (i) Further examples of useful silanes include, without limited triethoxysilane, (1). being to, tri tert-butyldiethoxysila ne. pro poxysila ne, PC T/DK2012/050228 C CH.

— —— — H Si C C .

Q H, PlBEH&UM CBtBlpSt .C C — — — H, C C Q St H-, —— — Sa Q C .C C The cross-linking agent preferably constitutes 0-10 % weight of the coating (ii) by dry and e. an the formula composition is, g. organosilicon compound represented by general , (2) shown below, a partial hydrolysis-condensation product thereof, or a mixture of the two: Si X4 „. wherein, each R represents, an unsubstituted or substituted monovalent independently, 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. cross-linker The compound outlined in formula acts as a for the binder (i). The 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 embodiment, R represents a hydrophilic such as a In this group poly(oxyalkylene). case, it is preferred to have a C2 5-alkyl spacer between the Si-atom and the polyoxyalkylene Hence, the organopolysiloxane have oxyalkylene domains. group. may PC T/DK2012/050228 In one variant, the hydrophilicity be obtained added to the hydrophilicity which may (or may have been obtained outlined in by incorporating a hydrophilic group to component as previous section), using a hydrophilic silane, such as the generic expressed in by type formula The hydrophilic silane will react with the silanol or the hydrolysable in (2a). groups the binder or and component (formula thereby incorporate a hydrophilic (1) (le)), component. p p c 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; each is selected from -H, 4-alkyl independently, a hydrolysable group; independently C& (e. -CH&, -CH&CH&, -CH&CH&CH&, -CH(CH&)&, -CH&CH&CH&CH&), phenyl (-C6H&), and C& alkylcarbonyl -C(=O)CH&, -C(=O)CH&CH& and -C(=O)CH, in particular and (e.g. CH, CH, each is selected from -alkylene -CH, -, -CH, methyl; independently C, (e.g. CH, CH(CH, )-, -, -, -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&CH&- -CH, 0-2; 1-3. as and CH(CH&)-); is 0-50; a is z is Introducing oxyalkylene units in the organopolysiloxane will increase the of the hydrophilicity when -[CH&CH&-0]- is used. binder, especially ethyleneoxide type A-B-A In a further embodiment, the hydrophilic modification of the binder consists of both modifications described and of pendant hydrophilic moieties. (as above) oligomer/polymer cross-linkers Preferred are those selected from tetramethoxysilane, tetraethoxysilane; tetra-n-butoxysila vinyltris(methylethyloximino) sila vinyltris- ne; ne; ne; tetra pro poxysila sila sila sila (acetoxime) ne; methyltris(methylethyloximino) ne; methyltris(acetoxime) ne; vinyltrimethoxysila ne; methyltrimethoxysila ne; vinyltris(iso sila ne; pro penoxy) di-t- tetraacetoxysilane; methyltriacetoxysilane; ethyltriacetoxysilane; vinyltriacetoxysilane; butoxydiacetoxysila ne; methyltris(ethyllactate) sila ne a nd vinyltris(ethyllactate) sila ne as well as hydrolysis-condensation products of the same.

PC T/DK2012/050228 Other interesting cross-linkers are those selected from vinyltriethoxysilane, tetra methyltriethoxysila ne, ethyltrimethoxysila ne, ethyltrimethoxysila ne, isopropoxysila ne, tetrabutoxysilane as well as hydrolysis-condensation products of the same.

In some interesting embodiments, the polysiloxane-based binder comprises a binder. polydimethylsiloxane-based In other interesting embodiments, the binder include fluoro-modifications, e. may g. modified binders such silanol-terminated fluoroalkyl polysiloxane as poly(trifluoropropy- lmethylsiloxan).

The polysiloxane-based binder constitutes at least 40 such system typically by dry weight, '/D '/D '/D 40-98 or 45-95 or 50-95 in as by dry weight, by dry weight, by dry weight, 50-90 '/D 55-90 '/D 60-90 '/D particular dry weight, or dry weight, or dry weight, of by by by coating composition.

Coating compositions In view of the above, the cured coating be from a of different may prepared range combinations of reactive polysiloxanes and silanes.

Hence, in one embodiment, the invention provides a fouling control coating composition polysiloxane-based binder said binder one or more comprising a system, system comprising polysiloxane components modified with hydrophilic oligomer/polymer moieties, and one or more biocides, wherein the weight ratio between the hydrophilic moieties oligomer/polymer and the one or more biocides is in the 1:0.02 in 1:0. and range to 1:20, particular 05 to 1:10, wherein more than 50 weight of the binder system is represented polysiloxane by by parts.

In another embodiment, the invention provides a fouling control coating composition comprising a polysiloxane-based binder said binder comprising one or more system, system moieties which one or both ends -Si(R*), hydrophilic oligomer/polymer at carry groups, wherein each independently is selected from 4-alkyl and 4-alkoxy (e. methyl, ethyl, C, C, g. and at least one 4-alkoxy, or is propyl, butyl, methoxy, ethoxy, propoxy, butoxy), being C, another condensation curable termination, at least one being C& 4-alkoxy, or at least one being another curable termination, and one or more biocides, wherein the weight ratio between the moieties and the one or more biocides is in the hydrophilic oligomer/polymer PC T/DK2012/050228 range 1:0.02 to 1:20, and wherein more than 50 % weight of the binder system is represented by polysiloxane parts.

In one embodiment, the one or more hydrophilic oligomer/polymer moieties carry at only one end -Si(R*), In this it is possible to construct a binder of a polysiloxane chain groups. way, of the moieties. having grafts hydrophilic oligomer/polymer In another embodiment, the one or more hydrophilic moieties at both oligomer/polymer carry ends -Si(R*), the will in the groups. During curing, hydrophilic component be incorporated crosslinked network and constitute a non-hydrolysable hydrophilic moiety. In this it is way, possible to construct a binder of a polysiloxane chain interrupted segments of the which are connected the sites. hydrophilic oligomer/polymer moieties, through crosslinking In a still further embodiment, the invention provides a fouling control coating composition polysiloxane-based binder said binder cross-linker comprising a system, system comprising a of formula above, wherein R represents a poly(oxyalkylene), and one or more biocides, wherein the weight ratio between the and the one or more biocides is in poly(oxyalkylene)) the 1:0.02 1:20. range to In a still further embodiment, the invention provides a fouling control coating composition comprising a polysiloxane-based binder said binder comprising a cross-linker system, system of formula (2a) each R an unsubstituted or substituted monovalent wherein, represents, independently, hydrocarbon group of 1 to 6 carbon atoms or a hydrolysable each X represents, group; a hydrolysable each is independently selected from -H, 4-alkyl independently, group; C& (e. -CH&, -CH&CH&, -CH&CH&CH&, -CH(CH&)&, -CH&CH&CH&CH&), phenyl (-C6H&), and C& alkylcarbonyl -C(=O)CH&, -C(=O)CH&CH& and -C(=O)CH, CH, CH, in particular and (e.g. each is independently selected from -alkylene -CH, -, -CH, )-, methyl; C, (e.g. CH, CH(CH, -CH, -, -CH, -, -CH, CH, CH, CH, CH, CH, CH(CH, CH, )-), arylene (e. 1,4-phenylene) and g. C, , PC T/DK2012/050228 alkylene substituted with aryl 1-phenyl ethylene), in particular from C»-alkylene such (e.g.

-CH&CH&- and -CH, is 0-50; is 0-2; z is 1-3; as CH(CH&)-); a and one or more biocides, wherein the weight ratio between the poly(oxyalkylene) and the one or more biocides is in the 1:0.02 to 1:20, and wherein more than 50 weight range by of the binder is system represented by polysiloxane parts.

In one variant of the above embodiments, the hydrophilic moieties are oligomer/polymer selected from poly(vinyl pyrrolidone), poly[N-(2-hydroxypropyl)methacrylamide], poly(acrylic acid), poly(glycerol), polyHEMA, polysaccharides, poly(vinyl alcohol), polyketones, poly(aldehyde guluronate), polyvinylamine, polycaprolactones, poly(vinyl acetate), like poly(2-methyl polyoxyalkylenes poly(ethylene glycol), poly(propylene glycol), oxazoline), including copolymers of the foregoing, in particular poly(oxyalkylenes), especially from and polyoxyethylene, polyoxypropylene poly(oxyethylene-co-oxypropylene). "polysiloxane-based system" The term binder is intended to mean that the binder system mainly consists of polysiloxane i.e. that more than 50 more parts, by weight, preferably '/o '/o than e. more than 70 of the binder is 60 by weight, g. by weight, system represented by 50-99. '/o polysiloxane parts. Preferably, the polysiloxane parts constitute 99 weight, e. by g. '/o '/o '/o '/o 50-99.9 in particular 60-99.5 or 50-99 or 60-98 by weight, by weight, by weight, 70-97 '/o 70-99 '/o 80-98 '/o 90- weight, or weight, or even weight, or weight, or by by by by 97 weight, of the binder system (i.e. the binder components and cross-linkers). by any The remainder of the binder is made of the system preferably hydrophilic oligomer/polymer cross-linkers. moieties and any (non-polysiloxane-type) This being said, the hydrophilic 1-30 '/o 2-20 '/o oligomer/polymer moieties preferably makes weight, such as up by by e. 1-10 of the binder weight, g. by weight, system.

Bi oci des The coating composition used for forming a cured fouling control coat also includes one or more biocides. "biocide" In the present context, the term is intended to mean an active substance intended to destroy, deter, render harmless, prevent the action of, or otherwise exert a controlling effect on harmful organism chemical or biological means. any by Illustrative of biocides are those selected from metallo-dithiocarbamates such examples as bis(dimethyldithiocarba mato) zinc, ethylene-bis(dithioca rba mato) zinc, ethylene-bis(dithio- PC T/DK2012/050228 carbamato)manganese, and complexes between these; bis(1-hydroxy-2(1H)-pyridine- thionato-O, bis(l-hydroxy-2(1H)-pyridinethionato-O, S)-zinc; S)-copper; copper acrylate; phenyl(bispyridyl)-bismuth dichloride; metal biocides such as copper(I)oxide, cuprous oxide, metallic metal alloys such as copper-nickel alloys; metal salts such as cuprous copper, copper basic barium and thiocyanate, copper carbonate, copper hydroxide, metaborate, copper sulphide; heterocyclic nitrogen compounds such as 7a-tetrahydro((trichloro- 3a,4,7, -thio) -1H-iso indole-1, -dion 1-(2, 6-trichloro- methyl) 3(2H) e, pyridine-triphenylbo 4, rane, 2-methylthio- phenyl)-1H-pyrrole-2, 5-dione, 2, 6-tetrachloro(methylsulfonyl)-pyridine, 3,5, 4-tert-butyla minocyclo mine-s-triazin, a nd quino line derivatives; heterocyclic sulfur pro pyla compounds such as 2-(4-thiazolyl)benzimidazole, 5-dichloron-octylisothiazolinone, -dichlorooctyl-3(2H)-isothiazoline (Sea-Nine-211N), 2-benzisothiazolinone, 4, 1, and 2-(thiocyanatomethylthio)-benzothiazole; urea derivatives such as N-(1, -2, 5-dioxo -N, bis(hydroxymethyl) imidazolidinyl) N'-bis(hydroxymethyl) urea, and N-(3, dichlorophenyl)-N, N-dimethylurea, N-dimethylchlorophenylurea; amides or imides of carboxylic acids; sulfonic acids and of sulfenic acids such as 6-trichlorophenyl maleimide, 2,4, sulfonyl)fluoro-N-(4-methyl 1,1-dichloro-N-((dimethylamino) phenyl)-metha nesulfenamide, 2-dibromonitrilo-propionamide, N-(fluorodichloromethylthio)-phthalimide, N-dimethyl- 2, N, N'-phenyl-N'-(fluorodichloromethylthio)-sulfamide, and N-methylol salts or esters formamide; of carboxylic acids such as 2-((3-iodopropynyl)oxy)-ethanol phenylcarbamate and N, didecyl-N-methyl-poly(oxyethyl)ammonium amines such as dehydroabiethyl- propionate; amines and substituted methane such cocodimethylamine; as di(2-hydroxy-ethoxy)methane, '-dich loro-2, 2'-dihydroxydi phenylmetha ne, a nd methylene- bisthiocya nate; substituted benzene such as 6-tetrachloro-1, 3-benzenedicarbonitrile, 1-dichloro-N-((dimethyl- 2,4, 5, 1, -sulfonyl) fluoro-N-phenylmetha nd 1-((diiodo a mino) nesulfen amide, a methyl) sulfonyl) methyl-benzene; tetraalkyl phosphonium halogenides such as tri-n-butyltetradecyl derivatives such n-dodecylguanidine phosphonium chloride; guanidine as hydrochloride; disulfides such as bis-(dimethylthiocarbamoyl)-disulfide, tetramethylthiuram disulfide; imidazole containing such as medetomidine; 2-(p-chlorophenyl)cyano compound, bromotrifluoromethyl and mixtures thereof. pyrrole Presently, it is preferred that the biocide does not comprise tin. biocides are those selected from the of 6-tetra- Currently preferred group consisting 2,4, 5, N-dichloro- chloroisophtalonitrile (Chlorothalonil), copper thiocyanate (cuprous sulfocyanate), fluoromethylthio-N', N'-dimethyl-N-phenylsulfamide (Dichlofluanid), 3-(3,4-dichlorophenyl)- 1-dimethylurea N'-tert-butyl-N -cyclopropylmethylthio-1, 5-triazine-2, 1, (Diuron), 3, diamine 4-bromo(4-chlorophenyl)(trifluoromethyl)-1H-pyrrole (Cybutryne), carbonitrile, (2-(p-chlorophenyl)cyanobromotrifluoromethyl pyrrole; Tralopyril), tert-butyl-N'-cyclo 5-tria 4-dia [1- pro pylmethylthio-1, zine-2, mine (Cybutryne), 3, (RS) PC T/DK2012/050228 -dichloron-octyl 3-dimethylphenyl)ethyl]-3H-imidazole (Medetomidine), (2, 4, isothiazolinone Sea-Nine dichlor-N-((dimethylamino)sulfonyl)fluor-N-(p- (DCOIT, 211N), 3-benzothiazole tolyl)methansulfenamid (Tolylfluanid), 2-(thiocyanomethylthio)-1, ((2- benzothiazolylthio)methyl thiocyanate; TCMTB), triphenylborane pyridine bis(1- (TPBP); S)-(T-4) zinc zinc bis(1- hydroxy-2(1H)-pyridinethionato-O, (zinc pyridinethione; pyrithione), hydroxy-2(1H)-pyridinethionato-O, S)-T-4) pyridinethione; pyrithione; copper (copper copper zinc ethylene-1, 2-bis-dithiocarbamate (zinc-ethylene-N-N'- Copper Omadine), dithiocarbamate; Zineb), copper(i) oxide, metallic copper, 3-(3,4-dichlorophenyl)-1, dimethylurea (Diuron) and diiodomethyl-p-tolylsulfone; Arnica l 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 against soft fouling such as slime and algae. Examples of such biocides N'-tert-butyl-N'-cyclopropylmethylthio-1, 5-triazine-2, 4-diamine are (Cybutryne), 4, dichloron-octylisothiazolinone Sea-Nine (DCOIT, 211N), bis(1-hydroxy-2(1H)- pyridinethionato-O, S)-(T-4) zinc (zinc pyridinethione; zinc bis(1-hydroxy-2(1H)- pyrithione), S)-T-4) pyridinethionato-O, copper (copper pyridinethione; copper pyrithione) and zinc ethylene-1, 2-bis-dithiocarbamate (zinc-ethylene-N-N'-dithiocarbamate; Zineb), copper(I) metallic bis(1-hydroxy-2(1H)- oxide, copper, copper thiocyanate, (cuprous sulfocyanate), pyridinethionato-O, S)-T-4) pyridinethione; pyrithione; copper (copper copper Copper Omadine).

In a further particularly preferred embodiment, the biocide is an organic biocide, such as a pyrithione complex, such as zinc pyrithione, or such as pyrithione. Organic biocides copper are those either fully or in of organic origin. part being As detailed in US 7,377,968, in those instances in which the biocide is depleted rapidly from the film due to e. a water solubility or a level of immiscibility with the matrix g. high 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 dosage and extending the effective lifetime in the film. Encapsulated biocides can also be added if the free biocide alters the of the properties polysiloxane matrix in a way that is detrimental for its use as antifouling coatings (e. mechanical integrity, drying times, etc. -dichloron-octyl In a particularly preferred embodiment, the biocide is encapsulated 4, isothiazolinone (Sea-Nine CR2).

The biocide has in the of 0-20 such 0.00001-20 preferably a solubility range mg/L, as mg/L, in water at 25 PC T/DK2012/050228 1-15 5-8 The biocide constitutes 0. % weight, e. 0. % weight, in typically by dry g. by dry 1-6 of the particular % by dry weight, coating composition.

The relative weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the of 1:0.02 to 1:20, or 1:0.05 to 1:20, or 1:0.06 to typically range or 1:008 or 1:005 or 1:0.1 even 1:0.15 or 1:005 1:16, to 1:12, to 1:10, to 1:10, to 1:6, to 1:5, or 1:0.1 to 1:5, or 1:0.2 to 1:4. In other embodiments, the relative weight ratio between the moieties and the one or more biocides is hydrophilic oligomer/polymer typically in the range of 1:0.02 to 1:20, or 1:0.05 to 1:20, or 1:0.06 to 1:16,or 1:0.08 to 1:14,or 1:0. 1 to 1:12, or 1:0 05 to 1:10, even 1:0.15 to 1:10, or 1:0 05 to 1: or 1:0. 1 to 1: or 9, 8, 1:0.2 1:7.

Catalyst The for cured control further coating composition used forming a fouling coat may comprise a condensation catalyst to accelerate the cross-linking. Examples of suitable 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 dilaurate, dioctyl tin diacetate, dioctyl tin dioctoate, dioctyl tin 2-ethylhexanoate, dioctyltin di neodecanoate, tin naphthenate, tin tin oleate, tin bismuth 2-ethylhexanoate, bismuth butyrate, caprylate, cobalt octanoate, bismuth neodecanoate, iron 2-ethylhexanoate, lead 2-ethyloctoate, ethylhexanoate, 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 titanate, tetra(isopropenyloxy)-titanate, titanium tetrabutanolate, titanium tatrapropanolate; titanium zirconium zirconium chelated tetraisopropanolate, tetrapropanolate, tetrabutanolate; titanates such as diisopropyl bis(acetylacetonyl)titanate. Further catalysts include tertiary amines, such as triethylamine, tetrametylethylenediamine, pentamethyldiethylenetriamine and 4-ethylenepiperazine. Further include Even 1, examples guanidine based catalysts. 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 catalyst to be used is on the reactivity of the catalyst and the cross-linker(s) and depending desired time. In embodiment the concentration is between 0.01- drying a preferred catalyst 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 (i) agent (ii).

PC T/DK2012/050228 In some embodiments, a catalyst is not included. li c-modIfi loxane oils Hydrophi ed polysi The composition further include hydrophilic-modified polysiloxane oils, i.e. constituents which do not form covalent bonds to the polysiloxane-based binder matrix. Hydrophilic- modified polysiloxane oils are widely used as surfactants and emulsifiers due to the content of both hydrophilic and lipophilic in the same molecule. In contrast to the polysiloxane groups discussed the hydrophilic-modified oils are selected that components above, polysiloxane so they do not contain groups that can react with the binder (or binder components) or the cross-linker hence the hydrophilic-modified polysiloxane oils are intended to be (if present), non-reactive, in particular with respect to the binder components. In particular, the Si-OH hydrophilic-modified polysiloxane oils are devoid of silicon-reactive such as any groups hydrolysable such as Si-OR as oxime, acetoxy etc. groups, groups (such alkoxy, groups, etc. so as to avoid reaction with constituents of the polysiloxane-based binder 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. poly(vinyl pyrrolidone), poly[N-(2-hydroxypropyl)methacrylamide]), poly(N, dimethacrylamide), acids alcohols polyHEMA, (e.g. poly(acrylic acid)), (e.g. poly(glycerol), polysaccharides, ketones aldehydes poly(vinyl alcohol)), (polyketones), (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 before, it should be understood that the hydrophilic moieties with which oligomer/polymer non-silicon above-mentioned the polysiloxane oils are modified are of origin. Preferably, the "oligomers" "polymers" and include at least 3 repeating units, such as at least 5 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.

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

PC T/DK2012/050228 "hydrophilic-modified" In the present description with claims, the term in the context of oil" "hydrophilic-modified is intended mean that the or polysiloxane to oligomeric polymeric groups with which the polysiloxane is modified, in themselves (i.e. as discrete molecules) 'C. have a solubility of at least 1 '/D(w/w) in demineralized water at Of interest are those hydrophilic-modified oils in which the relative particular polysiloxane 1'/D weight of the hydrophilic moieties is or more of the total weight 1-90'/D), such as (e.g.

'/D or more 5-80'/D), in 10'/D or more 10-70'/D) of the total of the (e.g. particular (e.g. weight hydrophilic-modified polysiloxane oil.

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

It is also if the hydrophilic-modified oils have in preferred polysiloxane (if present) a viscosity -20, 20-10, the range of 000 mPa such as in the range of 000 mPa in particular in the s, s, of 40-5, 000 mPa s. range In addition the utilization of the modified with to polysiloxane components hydrophilic oligomer/polymer moieties, the hydrophilic-modified polysiloxane oils may be utilized to control the leaching of the biocide.

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

In one variant the oil is hereof, poly(oxyalkylene)-modified polysiloxane a polysiloxane having grafted thereto chains. An illustrative example of the structure of poly(oxyalkylene) such hydrophilic-modified polysiloxane oils is formula (A): PC T/DK2012/050228 —— — — 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 groups) aryl (e.g. phenyl H, methyl; each is independently selected from C& 4-alkyl (e. -CH&, -CH&CH3, -CH, CH, CH„-CH(CH, )„-CH,CH, CH, phenyl (-C, and 4-alkylcarbonyl CH, H, C, (e.g.

), ), -C(=O)CH„-C(=O)CH, and -C(=O)CH, in particular and each is CH, CH, CH, methyl; -CH, -, -CH, -CH, -, independently selected from -alkylene (e. CH, CH(CH, )-, CH, CH, C, g.

-CH&CH&CH&CH&-, arylene 4-phenylene) and C»-alkylene -CH&CH(CH&CH&)-), (e.g. 1, substituted with aryl (e.g. 1-phenyl ethylene), in particular from C»-alkylene such as 1-100 -CH&CH&- and -CH, CH(CH, x is 0-2500, is and x+y is 1-2000; and n is 0-50, m is )-); 0-50 and m+n is 1-50.

Commercially available hydrophilic-modified polysiloxane oils of this are DC5103 (Dow type Corning), DC Q2-5097 (Dow Corning), and DC193 (Dow Corning).

In another variant hereof, the poly(oxyalkylene)-modified polysiloxane oil is a polysiloxane having incorporated in the backbone thereof chains. An illustrative poly(oxyalkylene) example of the structure of such hydrophilic-modified polysiloxane oils is formula (B): PC T/DK2012/050228 — — — — —— — 0 R 0 R 0 R R R Si 0 Si 0 Si 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, C, (e.g. CH, CH3, -CH(CH, )„-CH,CH, CH, CH, phenyl (-C, and 4-alkylcarbonyl (e. -C(=O)CH3, ), H, ), C, g.

-C(=O)CH&CH& and -C(=O)CH, in particular and each is independently CH, CH, methyl; selected from C»-alkylene -CH&CH&-, -CH&CH&CH&-, (e.g. -CH&CH(CH&)-, -CH&CH&CH&CH&-, -CH&CH(CH&CH&)-), arylene 4-phenylene) and C»- alkylene (e.g. 1, substituted with 1-phenyl in particular from -alkylene such as aryl (e.g. ethylene), C, -CH, and -CH, x is 0-2500; and n is 0-50, m is 0-50 and m+n is 1-50.

CH, CH(CH, )-); Commercially available hydrophilic-modified polysiloxane oils of this are DC Q4-3669 type DC Q4-3667 and DC2-8692.

(Dow Corning), (Dow Corning) In still another variant hereof, the poly(oxyalkylene)-modified polysiloxane oil is a polysiloxane having incorporated in the backbone thereof chains and having polyoxyalkylene grafted thereto polyoxyalkylene chains. An illustrative example of the structure of such hydrophilic-modified polysiloxane oils is formula (C): R R R 2 I 1 3 — — — — Si 0 Si 0 Si R 0 R 0 R PC T/DK2012/050228 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, C, g. CH3, -CH(CH, )„-CH,CH, CH, phenyl (-C, and 4-alkylcarbonyl -C(=O)CH3, CH, H, C, (e.g. ), ), and in and each is -C(=O)CH, CH, -C(=O)CH, CH, CH, particular methyl; independently selected from C»-alkylene -CH&CH&-, -CH&CH(CH&)-, -CH&CH&CH&-, -CH&CH&CH&CH&-, (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 1-100 0-50 0-2500, is and x+y is 1-2000; k is 0-50, I is and k+I is 1-50; and n is 0-50, m is 0-50 and m+n is 1-50.

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

(A), (B) (C), be present in of the two possible orientations. Similarly, it should be understood may any 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 to as poly(ethylene and poly(ethylene glycol), poly(propylene glycol) 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 linking a silicon atom and an atom is selected from C»-alkyl. oxygen preferably 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 The one or more hydrophilic-modified oils are included in the polysiloxane coating 01-20 '/o, 05-10 '/o, composition in an amount of 0. e. 0. dry weight. In certain g. by 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.

When the one or more hydrophilic-modified polysiloxane oil are included, the ratio between on the one hand the combined amount of the hydrophilic oligomer/polymer moieties of the binder matrix and the one or more hydrophilic-modified and on the other polysiloxane oil(s) hand the one or more biocides is typically in the range of 1:0.02 to 1:20, or 1:0.05 to 1:20, PC T/DK2012/050228 or 1:0.06 to 1:16, or 1:0.08 to 1:12, or 1:0. 1 to 10, even 1:0.15 to 1: or 1:0. 1 to 1: or 6, 5, 1:0.2 1:4. In other the ratio between on the one hand the combined to embodiments, amount of the hydrophilic oligomer/polymer moieties of the binder matrix and the one or more hydrophilic-modified polysiloxane and on the other hand the one or more biocides oil(s) is in the ra of 1:0.02 1: or 1:0. 1: or 1:0. 1: or 1:0. typica lly nge to 20, 05 to 20, 06 to 16, 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.

In should that in some the the be understood, embodiments, paint coat (and coating composition) is completely devoid of any hydrophilic-modified polysiloxane oils. In some other embodiment, the paint composition (and the coating composition) is also devoid of "additives" of the non-reactive fluids mentioned under and fluorinated oils any (cf. "oil free". immediately below). Such compositions may be referred to as Fluorinated oils As an alternative to, or in addition to, the hydrophilic-modified polysiloxane oils, the coating composition (and thereby the paint coat) have included therein one or more fluorinated "oil" oil(s). By 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 that can react with the binder binder or the cross-linker hence (or components) (if present), the one or more fluorinated oil(s) are intended to be non-reactive, in particular with respect to the binder components. In particular, the fluorinated oils are devoid of silicon-reactive such as Si-OH hydrolysable such as Si-OR as oxime, groups groups, groups (such alkoxy, acetoxy etc. etc. so as to avoid reaction with constituents of the polysiloxane-based groups, , 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 such as in the range of 20-10,000 mPa in particular in the range of s, s, 40-5, 000 mPa s.

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

The one or more fluorinated oils be utilized to control the accessibility of the one or more enzymes and/or to control the leaching of 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 a fluoroalkyl group 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 fluoroalkyl group(s) and the polyoxyalkylene group(s) are attached to the polysiloxane backbone in non-terminal positions. This allows more than one of each group per polysiloxane molecule. Examples of possible synthetic routes are disclosed in US 5,445,114.

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

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

It should be understood that the one or more non-reactive fluorinated oil(s), if present, may be of different types, e.g. two or more of the types described above.

PC T/DK2012/050228 If present, the one or more fluorinated oils are included in the coating composition typically in an amount of 0.01-20 e. 0.05-10 In certain the one %, g. %, by dry weight. embodiments, 05-7 1-5 or more fluorinated oils constitutes 0. % dry weight, e. 0. % dry weight, in by g. by particular 0. % weight, of the coating composition. In certain other embodiments, by dry the one or more fluorinated oils constitutes 1-10 e. 2-9 % by dry weight, g. % by dry weight, 2-7 3-7 3-5 4-8 in particular % weight, or % weight, or % weight, or % by dry by dry by dry of the coating composition. by dry weight, Also, if present together with one or more hydrophilic-modified polysiloxane oils, the one or more fluorinated oils and the one or more hydrophilic-modified polysiloxane oils are typically included in the in combined amount of 0.01-20 e. 0.05-10 coating composition a %, g. %, by 05-7 dry weight. In certain embodiments, the one or more fluorinated oils constitutes 0. % e. 0.1-5 % in particular 0.5-5 % of the coating dry weight, g. by dry weight, by dry weight, 1-10 composition. In certain other embodiments, the one or more fluorinated oils constitutes 2-9 2-7 3-7 % weight, e. % weight, in particular % weight, or % by dry g. by dry by dry by or 2-6 % or 3-5 % or 4-8 % of the dry weight, by dry weight, by dry weight, by dry weight, coating composition.

Solvents, additives, and fillers pigments The coating composition used for forming a cured fouling control coat may further comprise solvents and additives. of solvents are and aromatic such white Examples aliphatic, cycloaliphatic hydrocarbons as spirit, cyclohexane, toluene, xylene and naphtha solvent, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; octamethyltrisiloxane, and mixtures water-based thereof. Alternatively, the solvent system may include water or be (&50% water in the solvent system).

In one embodiment, the solvents are selected from aliphatic, cycloaliphatic and aromatic 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 or more.

The solvents, if constitute 5-50 % volume of the coating composition. any, typically by PC T/DK2012/050228 Examples of additives are: non-reactive fluids such for as organopolysiloxanes; example polydimethylsiloxane, 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 unsaturated fatty acids such as ethoxylated monoethanolamides of linoleic acid; sodium dodecyl sulfate; and lecithin; soya "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 (e. thixotropic agents) such as colloidal silica, (iv) g. hydrated aluminium silicate aluminium tristearate, aluminium monostearate, (bentonite), xanthan gum, chrysotile, pyrogenic silica, hydrogenated castor oil, organo-modified clays, 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) hydroquinone, 6-bis(tert-butyl) phenol, resorcinol, (vi) 2, 4-tert-butyl 4-di-tert-butylphenyl) catechol, tris(2, phosphite, pentaerythritol Tetrakis(3-(3, di-tert-butylhydroxyphenyl) propionate), bis(2, 2, -tetramethylpiperidyl)sebacate, 6,6, etc. 0-30 '/o, 0-15 '/o, Any additives typically constitute such as by 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 (e. thixotropic agents), preferably in an amount of 0. such as 0. e. g. g. 0. '/o, weight of the coating composition. by dry Furthermore, the coating composition used for forming a cured fouling control 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" properties. are normally characterised in that they render the final 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 coating.

PC T/DK2012/050228 Examples of pigments are grades of titanium dioxide, red iron oxide, zinc oxide, carbon iron red zinc black, graphite, yellow oxide, molybdate, yellow molybdate, sulfide, antimony 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. of fillers are calcium carbonate such Examples as calcite, dolomite, talc, mica, feldspar, barium sulfate, kaolin, nephelin, silica, perlite, magnesium oxide, and quartz flour, etc. Fillers (and also be added in the form of nanotubes or fibres, thus, apart from the pigments) may before-mentioned of the also e. examples fillers, coating composition may comprise fibres, g. those generally and specifically described in WO 00/77102 which is hereby incorporated reference. 0-60 0-50 5-45 Any pigments and/or fillers typically constitute such as preferably %, %, %, -40 5-35 5-25 1-20 such as or or 0. or weight of the coating %, %, %, %, by dry into account the of such constituents composition. Taking density any pigments and/or fillers, 2-20 5-15 typically constitute 0. such as 0. % solids volume of the coating composition %, by With the aim of facilitating application of the coating composition brush easy (e.g. by spray, or roller application techniques), the coating composition typically has a viscosity in the range of 25-25, 000 mPa such as in the range of 150-15,000 mPa in particular in the range of s, s, 200-4, mPa s.

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

The coating composition to be used in the method of the invention is typically prepared mixing two or more components e. two pre-mixtures, one pre-mixture comprising the one PC T/DK2012/050228 or more reactive polysiloxane binders and one pre-mixture comprising the one or more cross- It should understood that when reference is made the linking agents. be to coating composition, it is the mixed coating composition ready to be applied. Furthermore, all '/o '/o amounts stated as weight of the coating composition should be understood as by dry by of the mixed i.e. the from the dry weight paint composition ready to be applied, weight apart solvents (if any).

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 silanol-terminated one or more reactive polydiorganosiloxanes (e. polysiloxanes), one or more reactive polysiloxanes modified with hydrophilic oligomer/polymer moieties selected from and cross-linker; and poly(oxyalkylene)s a 1-15 '/o 5-8 '/o 0. dry weight, or 0. dry weight, of the total paint coat composition of (ii) by by one or more organic biocides, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.1 to 1:10.

In another the binder in the embodiment above preferred embodiment, preferred mentioned, has been pre-reacted in a moisture free environment to form a single component formulation admixing 100 weight of silanol terminated polydiorganosiloxane with 0.5-30 by parts by parts of cross-linker, such or vinyloximosilane. by weight hydrolysable as vinyltrimethoxysilane a In the above embodiments, the remainder of the coat to 100 is paint (up by dry weight) made of one or more constituents selected from preferably up additives, catalysts, pigments, fillers, and hydrophilic-modified polysiloxane oils (preferably those selected from the poly(oxyalkylene)-modified polysiloxane oils). the the above embodiments include Preferably, paint coats according to additives, pigments and fillers in the amounts specified further above.

PC T/DK2012/050228 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/DK2012/050228 "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 control 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.

It should understood that the "fouling release" well "fouling control" be expression (as as relates to all types of bio-fouling of a surface (i.e. settlement of organisms on a surface), in particular surfaces exposed to an aqueous environment or to aqueous liquids within (e.g. etc. It is believed that the defined herein are tanks, pipes, ). however, coatings particularly relevant for avoiding or reducing marine bio-fouling, i.e. bio-fouling arising in connection with the exposure of a surface to a marine environment, in particular to sea-water.

A Marine Structure The present invention also provides a marine structure comprising on at least a part of the outer surface thereof an outermost control from fouling coating prepared a coating composition as defined hereinabove. In particular, at least as part of the outer surface the outermost coating is a submerged of said structure. carrying part The coating composition, the method of establishing the coating on the substrate surface, and the characteristics of the coating follow the directions given hereinabove.

In one the control of the marine structure consist of embodiment, fouling coating system may tie-coat an anticorrosive layer, a and the fouling control coating as described herein.

In an alternative embodiment, the fouling control coating composition is on of a applied top used fouling control coating system, e. on top of a used polysiloxane-based fouling control coat.

PC T/DK2012/050228 In one particular embodiment of the above marine structure, the anticorrosive layer has a 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 control 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 150-400 a total dry film thickness of 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 total film thickness of 20-400 of the control established a dry pm fouling coating by application of layers.

In another embodiment of the above marine structure, the fouling control 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 modified with hydrophilic oligomer/polymer moieties and one or more biocides, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the 1:0.02 for the of range to 1:20, improving antifouling properties a polysiloxane based coating composition. The combination is particularly relevant for improving the antifouling against slime and algae. properties It should be understood that the types of the polysiloxanes modified with hydrophilic oligomer/polymer moieties, the biocides, and the of suitable polysiloxane based binder types are defined further the amounts and relative of the systems as above, just at proportions various ingredients are as defined further above.

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 PC T/DK2012/050228 more of the individual constituents. In such embodiments, the total amount of the types constituent should the amount defined above for the individual respective correspond to constituent. "(s)" The in the expressions: etc. indicates that compound(s), polysiloxane(s), agent(s), one, two or more of the individual constituents types may be present. "one" On the other hand, when the expression is one of the respective used, only (1) constituent is present.

EXAMPLES Materi als Shin-Etsu silanol-terminated RF-5000, ex. japan, polydimethylsiloxane Xylene from local supplier Toluene from local supplier Bayferrox 130M, ex. Lanxess Germany, Iron oxide Aerosil R8200, ex. Evonik Industries Hexamethyldisilazane treated fumed silica Germany, non-reactive DC550, ex. Dow Corning USA, methylphenyl polysiloxane DC190, ex. Dow Corning USA, non-reactive polyether modified polysiloxane Omadine, ex. Arch Chemicals Inc. Ireland, Pyrithione Copper Copper SEA-NINE™ CR2 Marine Antifouling Agent, ex. Dow Microbial Control USA, encapsulated DCOIT Sea-Nine™ ex. Dow Microbial Control DCOIT 211N, China, Silikat TES 40 WN, ex. Wacker Chemic Germany, Ethyl silicate Neostann U-12, ex. Nitto Kasai Dibutyltin Dilaurate japan, ex. Wacker Chemic 4-pentanedione Acetylaceton, Germany, 2, Dynasylan VTMO, ex. Evonik Industries Germany, vinyltrimethoxysilane Platinum in 2.1-2.4% divinyltetramethyldisiloxane complex xylene platinum 684782 concentration, CAS No.

Polydimethylsiloxane, hydride terminated MW„=1100, weight 550 eq. g/eq dimethylsiloxane terminated MWn Methylhydrosiloxane copolymer, hydride 2300, eq. weight 200 g/eq Polyethylene di allyl ether MW„= weight =150 glycol 300g/mol, Eq. g/eq MW„= Polyethylene glycol mono allyl ether (hydroxyl terminated) 350 g/mol, eq. weight g/eq PC T/DK2012/050228 Polyethylene mono allyl ether (hydroxyl terminated) MW„= 500 weight glycol g/mol, eq. g/eq Viscosity In the present application with claims, viscosity is measured at 25 in accordance with ISO 2555: 1989.

Preparation method for the model paints Pendant h dro hilic modified ol siloxane HMP1 A pendant, curable poly(ethylene modified polysiloxane is prepared mixing 25.0 glycol) by dissolved in 50. water (polydimethylsiloxane-methylhydrosiloxane, hydride terminated) 0 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 dry gas keep 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 completion of the reaction, 54. 5 polyethylene glycol mono allyl ether is 80'C. added and allowed to react for 4h at The solvent was hereafter dropwise, partially removed under reduced until the solvent content reached pressure using a rotary evaporator 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 Linear h dro hilic modified ol siloxane HMP2 A linear, curable poly(ethylene modified polysiloxane is prepared mixing 5.00 glycol) 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 keep the reaction atmosphere dry gas moisture free. A magnetic stirrer is used in the reaction flask to keep the solution agitated 65'C. during the synthesis. The solution is heated to To this solution, 65.0 is and allowed react for 1 h polydimethylsiloxane (hydride terminated) added dropwise, to at 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 PC T/DK2012/050228 under reduced pressure using a rotary evaporator until the solvent content reached 10% to obtain the final HMP2. The content of PEG-modified PDMS binder in HMP2 is product 90 % w/w. The amount of PEG in the HMP2 binder is 4.8% w/w calculated on dry weight.

Pendant h dro hilic modified olsiloxane HMP3 A pendant, curable poly(ethylene glycol) modified polysiloxane is prepared mixing 25.0 polydimethylsiloxane-methylhydrosiloxane, hydride terminated dissolved in 50.0 water free with 0.14 divinyltetramethyldisiloxane in solution. The toluene, platinum complex xylene 80'C. solution is heated to To this solution, 4.0 of vinyltrimethoxysilane is added dropwise '/~h 80'C. and allowed to react for at After the completion of the reaction, 68.5 polyethylene glycol mono allyl ether [A350] is added drop wise, and allowed to react for 3h 80'C. at The content of PEG-modified PDMS binder in HMP3 is 66. 1 % w/w. The amount of PEG in the HMP3 binder is 70.3% calculated on weight. w/w dry Linear h dro hilic modified ol siloxane HMP4 A linear, curable poly(ethylene modified polysiloxane is prepared mixing 100.0 of glycol) by hydride terminated polydimethylsiloxane dissolved in 75.0 water free toluene, with 0.17 of platinum divinyltetramethyldisiloxane complex in xylene solution. The solution is heated to 80'C under stirring. To this solution 1.7 di allyl ether is polyethylene glycol [AA300] 80'C. added dropwise, and allowed to react for 2h at After the completion of the reaction 5.4 80'C 80'C. of vinyltrimethoxysilane is added dropwise at and allowed to react for 1h at The content of PEG-modified PDMS binder in HMP4 is 58. The amount of PEG in the 8 % w/w.

HMP4 binder is 1.6% w/w calculated on weight.

Pendant h dro hilic modified ol siloxane HMP5 A pendant, curable poly(ethylene glycol) modified polysiloxane is prepared mixing 25.0 polydimethylsiloxane-methylhydrosiloxane, hydride terminated dissolved in 50.0 water free with 0.14 in solution. The toluene, platinum divinyltetramethyldisiloxane complex xylene 80'C. solution is heated to To this solution, 4.0 of vinyltrimethoxysilane is added dropwise '/~h 80'C. and allowed to react for at After the completion of the reaction, 90.0 polyethylene glycol mono allyl ether [A500] is added dropwise, and allowed to react for 3h at 80'C.

The content of PEG-modified PDMS binder in HMP5 is 70.4 % w/w. The amount of PEG in the HMP5 binder is 75.6% calculated on weight. w/w dry PC T/DK2012/050228 Com ositions A to Z: Part silanol-terminated red iron polydimethylsiloxane, xylene, silica, polyamide wax, oxide, (biocide) are mixed on a Diaf dissolver equipped with an impeller disc (70 mm in diameter) in a 1 L can for 15 minutes at 2000 rpm.

Part 4-pentanedione, (non-reactive (ii) ethyl silicate, (xylene), catalyst, 2, hydrophilic modified polysiloxane methyl are mixed on a Diaf dissolver oil), (phenyl polysiloxane)) with an disc mm in in 1 L can for 2 minutes equipped impeller (70 diameter) a at 500 rpm.

Part (iii) (Reactive hydrophilic modified polysiloxane) the container is closed under dry nitrogen to avoid moisture.

Before the and are mixed mixture. application, part part (ii) part (iii) to a homogenous (i), Test Methods Blister Box Test The Blister Box test is used to determine the influence of polysiloxanes modified with moieties on the of the PDMS which are hydrophilic oligomer/polymer stability coating to they added to.

Preparation of panels Steel are with 100 film of panels (150x75x15 mm) coated pm (dry thickness, DFT) a commercial primer (HEMPADUR Quattro 17634) airless After epoxy applied by spraying. 48 hrs of room silicone tie Nexus is drying at temperature a coat (HEMPASIL 27302) applied 16-30 doctor blade of 300 clearance. After hrs of drying the top coat paint by pm compositions are doctor blade of 400 clearance. The panels are dried for 24 applied by pm hrs before in the blister box. testing Testing The surface with the coating is exposed to 40 saturated water at an panel system vapour, '/60' angle of to the horizontal. The reverse side of the panel is exposed to room PC T/DK2012/050228 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 top coat is based on the below ranking: Adhesion Ranking Value FAIL/POOR No adhesion/poor adhesion GOOD Acceptable adhesion Panels are for two months and checked week. exposed typically every Raft Test Preparation 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 by doctor 16-30 blade of 300 clearance. After hrs of drying the coat paint compositions are pm top doctor blade of 400 clearance. The panels are dried for at least 72 hrs before applied by pm immersion on the raft.

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

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

Test site in Singapore At this test site the panels are immersed into sea water with salinity in the of 29-31 range thousand in the of 29-31 Panels are ever 4-12 parts per at a temperature range inspected weeks and evaluated according to the following scale: PC T/DK2012/050228 Level Description Excellent slime Only Good + Animals & 10% Algae Fair 10 % & + Animals & 25 % Algae Poor + Animals & 25 % Algae Examples The following model paints were 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 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.

PC T/DK2012/050228 Top coat Top coat Model paints composition A composition B Part Silanol-terminated 59.1 27.1 polydimethylsiloxane Xylene 17.4 17.4 Thixotropic agent 2.2 2.2 4. 1 4. 1 Pigments Biocide: pyrithione 4.8 4.8 Copper DCOIT Encapsulated DCOIT Total 87. 55. part (i) 6 6 Part (ii) Ethyl silicate 2.3 2.3 Xylene 3.6 3.6 Dibutyltin dilaurate 0.4 0.4 4-pentanedione Total 7.4 7.4 part (ii) Part (iii) Pendant hydrophilic modified polysiloxane (HMP Linear hydrophilic modified polysiloxane 37 (HMP 2) Total part (iii) 37 Total part (i), (»), 100 100 (iii) Hydrophilic 2.71 1. oligomer/polymer Hydrophilic oligomer/polymer 1.77 3.03 biocide (1:x) HMP binder in % of 6.8 53 binder phase Polysiloxane content of the binder matrix 95.8 97.2 (wt%) Performance on raft Good Good in S ain 8w Adhesion Good Good Comments: The examples B illustrate the performance of the biocide containing paint when the have been in the matrix. compositions hydrophilic polymers incorporated paint PC T/DK2012/050228 Top coat Top coat Top coat composition Model paints composition composition (reference) Part Silanol-terminated 57.1 25. 1 64.1 polydimethylsiloxane Xylene 17.4 17.4 17.4 Thixotropic agent 2.2 2.2 2.2 Pigments 4. 1 4. 1 4. 1 Biocide: 4. 4. 4.

Copper pyrithione 8 8 8 Total 85.6 53.6 92.6 part (i) Part (ii) Ethyl silicate 2.3 2.3 2.3 Non-reactive hydrophilic modified polysiloxane Xylene 3.6 3.6 3.6 Dibutyltin dilaurate 0.4 0.4 0.4 4-pentanedione Total 9.4 9.4 7.4 part (ii) Part (iii) Pendant hydrophilic modified polysiloxane HMP 1 Linear hydrophilic modified polysiloxane HMP 2 Total part (iii) 37 Total part (i), (»), 100 100 100 (iii) Hydrophilic 2.71 1.59 oligomer/polymer Hydrophilic oligomer/polymer 1.77 3.03 biocide (1:x) HMP binder in % of 0 55 binder phase Polysiloxane content of the binder matrix 95.7 97.1 100 (wt%) Performance on raft Excellent Excellent Fair in Singapore (8w) Adhesion Good Good Good PC T/DK2012/050228 Comments: The examples D illustrate the influence of the addition of a hydrophilic modified oil in with moieties reacted polysiloxane a composition hydrophilic oligomer/polymer to the binder. Reference example E shows a biocide containing paint formulation without hydrophilic moieties reacted to the binder.

In the the are in terms of the following examples, coating compositions provided dry weight of the cured film. coat Top coat Model paints composition composition F G (reference) Part Silanol-terminated 63.0 63.0 ol dimeth Isiloxane Thixotropic agent 2.9 2.9 .4 11.

Pigments 6 Biocide: pyrithione 6.2 0.0 Copper Total part 77.5 77.5 Part (ii) Ethyl silicate 0.9 0.9 Non-reactive hydrophilic modified 0.0 0.0 polysiloxane dilaurate 0. 0.

Dibutyltin 5 5 Total part (ii) 1.4 1.4 Part (iii) Pendant hydrophilic modified 21. 21. polysiloxane (HMP3) Total part (iii) 21.0 21.0 Total part (i), (ii), 99. 99. (iii) Hydrophilic 14. 14. oligomer/polymer Hydrophilic oligomer/polymer 0.42 biocide (1:x) PC T/DK2012/050228 HMP binder in %t of 25 binder phase Polysiloxane content of the binder matrix 82.4 82.4 (wt%) Performance on raft Excellent Good in Spain (7w) Comments: The example F and reference example G show the improvement of performance when adding biocide to a hydrophilic modified polysiloxane-based fouling release coating.

Top coat Top coat Top coat Top coat Top coat Model paints composition H composition K composition composition composition j (reference) (reference) Part Silanol-terminated 83.7 75.5 63.0 42. 1 83.7 ol dimeth Isiloxane Thixotropic 2. 2. 2. 2. 2. agent 9 9 9 9 9 Pigments 5.4 5.4 5.4 5.4 11.6 Biocide: Copper pyrithione 6.2 6.2 6.2 6.2 Total 98.2 90.0 77.5 56.5 98.2 part (i) Part (ii) Ethyl silicate 1.2 0.9 0.6 1.2 Non-reactive hydrophilic modified 0.0 0.0 0.0 0.0 0.0 polysiloxane dilaurate 0. 0. 0. 0. 0.

Dibutyltin 5 5 5 5 5 Total part (ii) 1.7 1.6 1.4 1.2 1.7 Part (iii) Pendant hydrophilic modified 8.4 21.0 42. 1 polysiloxane (HMP3) Total part (iii) 8.4 21.0 42. 1 Total part (ii), (i), 99. 100.1 99. 99. 99. 9 9 8 9 (iii) PC T/DK2012/050228 Hydrophilic .9 14.8 29.6 oligomer/polymer Hydrophilic oligomer/polymer 0.42 0.21 biocide (1:x) HMP binder in %t of 25 binder phase Polysiloxane content of the binder matrix 100 93. 82.4 64. 100 (wt%) Performance on raft Poor Excellent Excellent Excellent Poor in Singapore (8w) Comments: The F and shows the of the examples I, j improved performance hydrophilic modified binder with biocide compared to biocides in a polysiloxane binder without hydrophilic moieties (reference example and biocide-free polysiloxane without hydrophilic moieties (reference example K).

Top coat coat coat coat coat Top Top Top Top Model H paints composition composition L composition M composition N composition 0 (reference) Part Silanol-terminated 63.0 75.5 74.5 76.5 83.7 polydimethylsiloxane Thixotropic agent 2.9 2.9 2.9 2.9 2.9 Pigments 5.4 5.4 11.5 11.8 5.4 Biocide: 6.2 6.2 4. 1. 6.2 Copper pyrithione 0 5 Total part 77.5 90.0 92.9 92.7 98.2 Part (ii) Ethyl silicate 0.9 1.2 Non-reactive hydrophilic modified 0.0 0.0 0.0 0.0 0.0 polysiloxane Dibutyltin dilaurate 0.5 0.5 0.5 0.5 0.5 Total part (ii) 1.4 1.6 1.6 1.6 1.7 Part (iii) PC T/DK2012/050228 Pendant hydrophilic modified 21.0 8.4 5.5 5.6 polysiloxane HMP5 Total part (iii) 21.0 8.4 5.5 5.6 Total part (ii), (i), 99. 100. 100. 99. 99. 9 0 0 9 9 (iii) Hydrophilic .9 6.4 4.2 4.2 oligomer/polymer Hydrophilic oligomer/polymer: 0.39 0.98 0.96 0.35 biocide (1:x) HMP binder in %t of .0 10.0 6.8 6.8 binder phase Polysiloxane content of the binder 81.1 92.5 94.8 94.9 100 matrix(wt%) Performance on raft Excellent Excellent Fair Poor Good in Singapore (8w) Comments: Compositions L to 0 are further examples of the performance of a hydrophilic modified polysiloxane binder. Also shown in the examples L to 0 are the different ratios between biocide and that rise an hydrophilic oligomer/polymer gives to improved performance over the biocide-free reference shown as composition H.

Top coat Top coat Top coat Top coat Top coat Model H K paints composition composition composition composition composition (reference) (reference) Part Silanol-terminated 83.7 71.6 71.6 75.5 83.7 polydimethylsiloxane Thixotropic agent 2.9 2.9 2.9 2.9 2.9 Pigments 5.4 5.4 5.4 5.4 11.6 Biocide: Copper pyrithione 6.2 6.2 6.2 DCOIT 6.2 Total 98.2 86.1 86.1 90. 98.2 part (i) 0 Part (ii) Ethyl silicate 1.2 1.2 Non-reactive hydrophilic modified 0.0 0.0 3.9 0.0 polysiloxane Non-reactive phenyl modified 0.0 3.9 0.0 0.0 polysiloxane dilaurate 0. 0. 0. 0. 0.

Dibutyltin 5 5 5 5 5 PC T/DK2012/050228 Total part 1.7 5.5 5.5 1.6 1.7 (ii) Part (iii) Pendant hydrophilic modified 8.4 8.4 8.4 polysiloxane HMP3 Total 8.4 8.4 8.4 part (iii) Total part (i), (»), 99.9 100.0 100.0 100.0 99.9 (iii) Hydrophilic .9 5.9 5.9 oligomer/polymer Hydrophilic oligomer/polymer: 1.05 1.05 1.05 biocide (1:x) HMP binder in of .4 10.4 9.88 binder phase Polysiloxane content of the binder matrix 100 92.7 92.7 93.0 100 (wt%) Performance on raft Poor Excellent Excellent Fair Poor in Singapore (8w) Comments: The R shows the effect of different biocide in modified example a a hydrophilic non-reactive polysiloxane binder matrix. Examples P and shows the effect of addition of polysiloxane oils in a biocide containing, hydrophilic modified polysiloxane binder.

Top coat Top coat Top coat Top coat Top coat Model paints composition H composition S composition T composition U composition V (reference) Part Silanol-terminated 83.7 42. 1 41. 42. 63 8 5 polydimethylsiloxane Thixotropic 2. 2. 2. 2. 2. agent 9 9 9 9 9 Pigments 5.4 5.4 5.4 11.6 11.8 Biocide: Copper pyrithione 6.2 6.2 6.2 1.5 Total part 98.2 56.6 77.5 60.3 58.7 Part (ii) Ethyl silicate 1.2 0.6 0.9 Non-reactive modified 0. 0. 0. 0. 0. hydrophilic 0 0 0 0 0 polysiloxane dilaurate 0. 0. 0. 0. 0.

Dibutyltin 5 5 5 5 5 Total 1.7 1.4 1.6 1.6 part (ii) Part (iii) PC T/DK2012/050228 Linear hydrophilic modified 42. 1 21.0 38.1 39.6 polysiloxane HMP4 Total part (iii) 42. 1 21.0 38.1 39.6 Total part (i), (»), 99. 99. 99. 100. 100. 9 9 9 0 0 (iii) Hydrophilic 0.67 0.33 0.60 0.63 oligomer/polymer Hydrophilic oligomer/polymer: 9.28 18.6 6.61 2.39 biocide (1:x) HMP binder in %t of 50.0 25.0 47.0 47.6 binder phase Polysiloxane content of the binder matrix 100 99.2 99.6 99.2 99.2 (wt%) Performance on raft Poor Fair Fair Fair Good in Singapore (6w) Top coat Top coat Top coat Model X Z paints composition composition composition (reference) Y (reference) (reference) Part Silanol-terminated 83.7 42. 1 63.1 polydimethylsiloxane Thixotropic agent 2.9 2.9 2.9 Pigments 11.6 11.6 11.6 Biocide: Copper pyrithione Total 98.2 56.7 77. part (i) 6 Part (ii) Ethyl silicate 1.2 0.6 0.9 Non-reactive hydrophilic modified 0.0 0.0 0.0 polysiloxane Dibutyltin dilaurate 0.5 0.5 0.5 Total part 1.7 1.4 (ii) Part (iii) Linear hydrophilic modified 42. 1 21.0 polysiloxane HMP4 Total 42. 1 21. part (iii) 0 PC T/DK2012/050228 Total part (i), (»), 99.9 100.0 100.0 (iii) Hydrophilic 0.67 0. oligomer/polymer Hydrophilic oligomer/polymer: biocide (1:x) HMP binder in %t of 50.0 25.0 binder phase Polysiloxane content of the binder matrix 100 99.2 99.6 (wt%) Performance on raft Poor Poor Poor Singapore (8w) Comments: The examples U and V show the performance improvement of adding S, T, biocides to an ABA hydrophilic modified polysiloxane binder. Reference examples H and type X is an unmodified binder with and without polysiloxane composition biocide, respectively.

Reference examples Y and Z illustrate the performance of a linear hydrophilic modified without biocides. polysiloxane

Claims

1. A cured paint coat comprising a polysiloxane-based binder matrix and one or more biocides, said binder matrix having included as a part thereof hydrophilic oligomer/polymer moieties, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and 5 the one or more biocides is in the range 1:0.02 to 1:20, and wherein more than 50 % by weight of the binder matrix is represented by polysiloxane parts.

2. The paint coat according to claim 1, wherein the hydrophilic oligomer/polymer moieties are selected from poly(vinyl pyrrolidone), poly[N-(2-hydroxypropyl)methacryl- amide], poly(acrylic acid), poly(glycerol), polyHEMA, polysaccharides, poly(vinyl alcohol), 10 polyketones, poly(aldehyde guluronate), polyvinylamine, polycaprolactones, poly(vinyl acetate), polyoxyalkylenes like poly(ethylene glycol), poly(propylene glycol), poly(2-methyl- 2-oxazoline), including copolymers of the foregoing, in particular poly(oxyalkylenes).

3. The paint coat according to claim 2, wherein the poly(oxyalkylene) is selected from polyoxyethylene, polyoxypropylene and poly(oxyethylene-co-oxypropylene). 15

4. The paint coat according to any one of the preceding claims, wherein at least one biocide is an organic biocide.

5. The paint coat according to any one of the preceding claims, wherein the one or more biocides constitutes 0.1-10 % by dry weight of the paint coat.

6. The paint coat according to any one of the preceding claims, wherein the weight ratio 20 between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.05 to 1:5.

7. A marine structure comprising on at least a part of the outer surface thereof a paint coat as defined in any one of the preceding claims.

8. The structure according to claim 7, wherein at least as part of the outer surface 25 carrying the outermost coating is a submerged part of said structure.

9. A fouling control coating composition comprising a polysiloxane-based binder system, said binder system comprising one or more polysiloxane components modified with hydrophilic oligomer/polymer moieties, and one or more biocides, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.02 to 1:20, and wherein more than 50 % by weight of the binder system is represented by polysiloxane parts.

10. A fouling control coating composition comprising a polysiloxane-based binder system, said binder system comprising one or more hydrophilic oligomer/polymer moieties which at 5 groups, wherein each R* independently is selected from C - one or both ends carry –Si(R*)3 1-4 alkyl and C -alkoxy, at least one being C -alkoxy, and one or more biocides, wherein the 1-4 1-4 weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.02 to 1:20, and wherein more than 50 % by weight of the binder system is represented by polysiloxane parts. 10

11. A fouling control coating composition comprising a polysiloxane-based binder system, said binder system comprising a cross-linker of formula (2a) wherein, each R represents, independently, an unsubstituted or substituted monovalent hydrocarbon group of 1 to 6 carbon atoms or a hydrolysable group; each X represents, 15 independently, a hydrolysable group; each R is independently selected from -H, C -alkyl (e.g. -CH , -CH CH , -CH CH CH , -CH(CH ) , -CH CH CH CH ), phenyl (-C H ), and C - 3 2 3 2 2 3 3 2 2 2 2 3 6 5 1-4 alkylcarbonyl (e.g. –C(=O)CH , -C(=O)CH CH and -C(=O)CH CH CH ), in particular -H and 3 2 3 2 2 3 methyl; each R is independently selected from C -alkylene (e.g. -CH CH -, -CH CH(CH )-, 2-5 2 2 2 3 -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), arylene (e.g. 1,4-phenylene) and C2 20 alkylene substituted with aryl (e.g. 1-phenyl ethylene), in particular from C -alkylene such as -CH CH - and -CH CH(CH )-); p is 0-50; a is 0-2; z is 1-3; 2 2 2 3 and one or more biocides, wherein the weight ratio between the poly(oxyalkylene) and the one or more biocides is in the range 1:0.02 to 1:20, and wherein more than 50 % by weight 25 of the binder system is represented by polysiloxane parts.

12. The coating composition according to any one of the claims 9 and 10, wherein the hydrophilic oligomer/polymer moieties are selected from poly(vinyl pyrrolidone), poly[N-(2- hydroxypropyl)methacrylamide], poly(acrylic acid), poly(glycerol), polyHEMA, polysaccharides, poly(vinyl alcohol), polyketones, poly(aldehyde guluronate), polyvinylamine, polycaprolactones, poly(vinyl acetate), polyoxyalkylenes like poly(ethylene glycol), poly(propylene glycol), poly(2-methyloxazoline), including copolymers of the foregoing, in particular poly(oxyalkylenes).

13. The coating composition according to claim 12, wherein the poly(oxyalkylene) is 5 selected from polyoxyethylene, polyoxypropylene and poly(oxyethylene-co-oxypropylene).

14. The coating composition according to any one of the claims 9-13, wherein at least one biocide is an organic biocide.

15. The coating composition according to any one of the claims 9-14, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in 10 the range 1:0.05 to 1:5.

16. Use of the combination of one or more polysiloxane components modified with hydrophilic oligomer/polymer moieties and one or more biocides, wherein the weight ratio between the hydrophilic oligomer/polymer moieties and the one or more biocides is in the range 1:0.02 to 1:20, for improving the antifouling properties of a polysiloxane based coating 15 composition.