Composition for antifouling protection

Abstract

The present invention relates to antifouling compositions comprising compounds of formula IA and / or IB which are highly effective in preventing marine biofouling on the surfaces of ships and marine structures, their use for inhibiting marine biofouling, and antifouling coatings comprising said compositions.

Description

Technical Field

[0001] The present invention relates to antifouling compositions comprising compounds of formula IA and / or IB which are highly effective in preventing marine biofouling on the surfaces of ships and marine structures, their use for inhibiting marine biofouling, and antifouling coatings comprising said compositions. Background Art

[0002] Ships, aquaculture nets, underwater structures and equipment are often subject to the attack of marine organisms such as barnacles, bryozoans, hydrozoans, mussels, algae, etc. The organisms can grow and multiply and eventually cause serious problems. For example, in the case of the hull of a ship, the growth of marine organisms on the hull increases the frictional resistance between the hull and the water, which increases fuel consumption and reduces the speed of the ship. The hulls of ships need to be protected from the growth of marine organisms in order to keep them clean and smooth for maximum fuel efficiency. There is also the problem of transporting marine organisms from one part of the world to another, where foreign organisms have the potential to disrupt the local ecology. Therefore, underwater components require adequate protection against marine biofouling, which is usually achieved through antifouling coatings.

[0003] The binder system used for such antifouling coatings is usually composed of an erodible binder. Erosion of the coating film helps prevent fouling by releasing the antifouling agent (biocide) from the coating over time, thereby preventing the attachment of fouling organisms. There are two main types of erodible antifouling coatings, which the industry describes as "self-polishing" and "ablative".

[0004] The binder system of the ablative coating is mainly composed of rosin, which reacts with seawater to become water-soluble and is eroded away. Alternatively, rosin or rosin derivatives are also mixed with non-erodible binders such as polyester resins, acrylic resins, epoxy resins, vinyl chloride resins, chlorinated rubber resins, chlorinated polyethylene resins, chlorinated polypropylene resins, styrene-butadiene resins or polyamide resins.

[0005] In "self-polishing antifouling coatings", the binder system is based on hydrolyzable acrylate polymers. The hydrolyzable functionality is usually provided to the polymer via metal carboxylate acrylate monomers or silyl acrylate monomers. Erosion-resistant polyester binders are also used and make the antifouling coating less expensive. The difference between ablative coatings and self-polishing coatings lies primarily in the thickness of the leached layer and the more linear erosion rate of self-polishing coatings over time.

[0006] There are also "hybrid coatings" whose binder system consists of easily erodible acrylates (such as in self-polishing coatings) and rosin. The thickness of the leached layer is thinner than in ablative coatings, but thicker than in true self-polishing coatings.

[0007] Most commercially available antifouling coatings contain high metal content due to the high concentration of cuprous oxide (Cu2O) used as a biocide, i.e., typically about 40 wt% (which is required for adequate antifouling protection). Cuprous oxide is potentially harmful to many organisms. Leaching in antifouling coatings can lead to elevated copper levels in water, sediments and the surrounding environment. Artificially high copper levels may have significant ecological impacts. Although Cu2O is widely used as an antifouling agent in antifouling coatings, antifouling coatings may also contain additional biocides, since Cu2O alone is only effective against hard fouling organisms such as barnacles.

[0008] As another disadvantage, cuprous oxide generally imparts a heavy reddish-brown color to antifouling coating films and may also react with atmospheric carbon dioxide and chlorides in seawater to form uneven streaks on the surface of the coating. This is an unattractive appearance and may occur, for example, soon after a vessel is put to sea. Some yacht owners and cruise ship operators prefer bright colors and a uniform appearance that cannot be obtained with coatings containing cuprous oxide.

[0009] Attempts to replace cuprous oxide in commercial antifouling paints have led to the development of alternatives to cuprous oxide, such as white copper thiocyanate, and tralopyril, an agricultural insecticide effective against barnacles. But these alternatives cost more, and they are not as effective as cuprous oxide-based antifouling paints.

[0010] Therefore, there is a need for ecologically and economically improved marine antifouling coatings having a reduced copper content, or even completely replacing cuprous oxide in conventionally used antifouling coatings.

[0011] The antifouling compositions of the present invention comprising compounds of formula IA and / or IB meet this need. The inventors surprisingly found that compounds of formula IA and IB are highly effective and versatile agents for enhancing the antifouling properties of all types of antifouling coatings (e.g. ablative coatings or self-polishing coatings) and can also be used with simple contact leaching coatings.

[0012] Thus, it is now possible to partially or completely replace Cu2O in antifouling coatings, thereby substantially reducing the metal content therein while maintaining adequate antifouling performance. Furthermore, the antifouling compositions of the invention comprising compounds of formula IA and / or IB are substantially colorless and thus do not interfere with the bright colors typically desired for ship hulls. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 Depicted is a panel coated with the antifouling coating of Table 1 of Example 2 and shows the appearance of the panel after 6 months in seawater (Himeji, depth: 1.5 m). The black squares represent areas of negative control (i.e. coating without any antifouling component).

[0014] Figure 2 Panels coated with the antifouling coating of Table 2 of Example 2 are depicted and show the appearance of the panels after 4 months in seawater (Himeji, Nagasaki and Onagawa). Panel 6 of the "Nagasaki" test and the Himeji test each show the panel after 1 month in seawater. Panel 6 of the "Onagawa" test shows the panel after 4 months in seawater.

[0015] Figure 3 Depicted is a panel coated with the antifouling coating of Table 3 of Example 2 and shows the appearance of the panel after 1 month in seawater (Nagasaki; depth: 1.5 m). The black squares represent areas of negative control (i.e. coating without any antifouling component). DETAILED DESCRIPTION

[0016] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention relates. The following abbreviations and terms are used herein:

[0017] AIBN: Azobis(isobutyronitrile)

[0018] AMBN: Azobis-(2-methylbutyronitrile)

[0019] A630-20X: Fatty acid amide

[0020] BA: Butyl acrylate

[0021] Chlorothalonil: 2,4,5,6-Tetrachlorobenzene-1,3-dicarbonitrile

[0022] Copper Pyrithione CuPT, Copper Pyrithione: Copper 2-pyridinethiol-1-oxide

[0023] Cu2O: Cuprous Oxide

[0024] CuSCN: Copper(I) thiocyanate

[0025] DCOIT: 4,5-dichloro-2-octyl-4-isothiazolin-3-one

[0026] Diuron: 3-(3,4-dichlorophenyl)-1,1-dimethylurea

[0027] Disparlon A650-20x: Synthetic polyamide wax dispersion. Excellent anti-settling agent for heavy pigments and metallic paints. Highly shear-thinning, resulting in excellent application performance.

[0028] ETFAA: Ethyl 4,4,4-trifluoroacetoacetate

[0029] MP 25: Copolymer of vinyl chloride and vinyl isobutyl ether

[0030] 2MEA: 2-methoxyethyl acrylate monomer

[0031] Medetomidine: 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole

[0032] MMA: Methyl methacrylate monomer

[0033] MIBK: Methyl isobutyl ketone

[0034] MPM: Methoxypropylene monomer

[0035] PGM: Propylene glycol monomethyl ether

[0036] TIPX: Triisopropylsilyl acrylate monomer

[0037] Trolopride:4-Bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile

[0038] VAGH: Vinyl chloride / vinyl acetate / vinyl alcohol copolymer (commercial product)

[0039] Zineb: Zinc ethane-1,2-diylbis(dithiocarbamate)

[0040] Ziram: N,N-dimethylaminodithioester zinc

[0041] Zn(ETFAA)2: Zinc di(ethyl 4,4,4-trifluoroacetoacetate), also referred to herein as ZnETFAA

[0042] ZnO: Zinc Oxide

[0043] ZnPT: Zinc pyrithione: 2-pyridinethiol-1-oxide zinc

[0044] The term "(meth)acrylate" is a general term referring to acrylate and methacrylate monomers. The term "methacrylate" or "meth-acrylate" refers only to methacrylate monomers.

[0045] Bentonite SD2 is an organoclay added for anti-settling properties; Bentonite #38 is a quaternary ammonium 18-hectorite clay; Minex 4 is a nepheline syenite clay. Disperbyk 161 is a dispersing additive. Resins refer to all prepolymers or polymers that can be used as raw materials for the binder used in the antifouling coating of the present invention. Rosin or gum rosin refers to gum rosin (CAS: 8050-09-7, see also https: / / www.megaglori.com / what-is-gum-rosin / ).

[0046] "Biocide" means any compound that prevents the settlement of marine organisms on a surface and / or prevents the growth of marine organisms on a surface and / or promotes the migration of marine organisms from a surface.

[0047] The terms "antifouling paint," "antifouling coating" and "antifouling formulation" are used interchangeably herein.

[0048] The present invention provides a new method to inhibit fouling of underwater surfaces such as ship hulls or any other marine structures. Specifically, the present invention provides an antifouling composition comprising a compound of formula IA and / or IB:

[0049]

[0050]

[0051] in

[0052] Me represents a metal, preferably Cu, Zn, Co, Ni, Ca, Mg or Mn;

[0053] R1 can be any functional group that imparts high hydrophobicity, for example,

[0054] R1 is independently selected from hydrogen, halogen, linear or branched C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 3-12 Cycloalkyl, C 6-20 Aryl and C 7-20 Aralkyl;

[0055] R2 are each independently selected from NH, O, S and Se;

[0056] R3 is NH, N(R4), O, S and Se;

[0057] R4 is hydrogen, straight or branched C 1-20 Alkyl, C2-20 Alkenyl, C 2-20 Alkynyl, C 3-12 Cycloalkyl, C 6-20 Aryl, C 7-20 Aralkyl;

[0058] R5 and R6 are each independently selected from H, a linear or branched C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 3-12 Cycloalkyl, C 6-20 Aryl and C 7-20 Aralkyl; or

[0059] R5 and R6 together form a group =O, =S, =Se, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4).

[0060] In one embodiment, the present invention provides an antifouling composition comprising a compound of formula IA and / or IB as shown above, wherein

[0061] Me represents Cu, Zn, Ca, Mg or Mn;

[0062] R1 is independently selected from H, F, Cl, Br, I, linear or branched C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl, C 6-12 Aryl and C 7-12 Aralkyl;

[0063] R2 are each independently selected from NH, O and S;

[0064] R3 is NH, N(R4), O and S;

[0065] R4 is H, straight or branched C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl, C 3-8 Cycloalkyl, C 6-12 Aryl, C 7-12 Aralkyl;

[0066] R5 and R6 are each independently selected from H, a linear or branched C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 6-12 Aryl and C 7-12 Aralkyl; or

[0067] R5 and R6 together form a group =O, =S, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4).

[0068] In one embodiment, the present invention provides an antifouling composition comprising a compound of formula IA and / or IB as shown above, wherein

[0069] Me represents Cu or Zn;

[0070] R1 is independently selected from H, F, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12 Alkyl and benzyl groups;

[0071] R2 are each independently selected from NH and O;

[0072] R3 is N(R4) and O;

[0073] R4 is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12 Alkyl and benzyl groups;

[0074] R5 and R6 are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and benzyl; or

[0075] R5 and R6 together form a group =CH(OCH3); =CH(OC2H5); =CH(OnC3H7);

[0076] =CH(OiC3H7); =CH(OnC4H9); =CH(OiC4H9); =CH(Ounc.C4H9),

[0077] =CH(NHCH3); =CH(NHC2H5); =CH(NHnC3H7); =CH(NHiC3H7);

[0078] =CH(NHnC4H9); =CH(NHiC4H9); =CH(NHt.C4H9).

[0079] In one embodiment, the present invention provides an antifouling composition comprising a compound of formula IA and / or IB as shown above, wherein

[0080] Me represents Cu or Zn;

[0081] R1 are each independently selected from H and F;

[0082] R2 are each independently selected from NH and O;

[0083] R3 is N(CH3), N(C2H5) and O;

[0084] R4 is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12 Alkyl and benzyl groups;

[0085] R5 and R6 are each H; or

[0086] R5 and R6 together form a group =CH(OCH3); =CH(OC2H5), =CH(NHCH3);

[0087] =CH(NHC2H5);

[0088] In one embodiment, the compound of formula IB is as defined above, with the proviso that if Me is Cu, then each R1 is F, each R2 is O, R3 is O, and R5 and R6 are each H, then R4 is not ethyl.

[0089] Suitable compounds of the formulae IA and IB are, respectively, for example

[0090] Ethyl 3-amino-4,4,4-trifluorocrotonate;

[0091] [Ethyl 3-amino-4,4,4-trifluorocrotonate]2Zn,

[0092] [Ethyl 3-amino-4,4,4-trifluorocrotonate]2Cu,

[0093] Ethyl 3-amino-2-methylene-(methylamino)-4,4-difluorocrotonate,

[0094] [Ethyl 3-amino-2-methylene-(methylamino)-4,4-difluorocrotonate] 2Zn,

[0095] [Ethyl 3-amino-2-methylene-(methylamino)-4,4-difluorocrotonate] 2Cu

[0096] 4,4,4-Trifluoro-N,N-dimethyl-3-oxobutanamide;

[0097] [4,4,4-Trifluoro-N,N-dimethyl-3-oxobutyramide]2Cu,

[0098] [4,4,4-trifluoro-N,N-dimethyl-3-oxobutyramide]2Zn,

[0099] Dodecyl 4,4,4-trifluoro-3-oxobutyrate,

[0100] [Dodecyl 4,4,4-trifluoro-3-oxobutyrate]2Zn,

[0101] Dodecyl 4,4,4-trifluoro-3-oxobutyrate]2Cu,

[0102] Benzyl 4,4,4-trifluoroacetoacetate,

[0103] [Benzyl 4,4,4-trifluoroacetoacetate]2Zn,

[0104] [Benzyl 4,4,4-trifluoroacetoacetate]2Cu,

[0105] Octyl 4,4,4-trifluoroacetoacetate,

[0106] [Octyl 4,4,4-trifluoroacetoacetate]2Zn,

[0107] [Octyl 4,4,4-trifluoroacetoacetate]2Cu,

[0108] Isopropyl 4,4,4-trifluoroacetoacetate,

[0109] [Isopropyl 4,4,4-trifluoroacetoacetate]2Zn,

[0110] [Isopropyl 4,4,4-trifluoroacetoacetate]2Cu,

[0111] Ethyl 4,4,4-trifluoroacetoacetate,

[0112] [Ethyl 4,4,4-trifluoroacetoacetate]2Zn

[0113] Tert-butyl 4,4,4-trifluoro-3-oxobutyrate,

[0114] [tert-Butyl 4,4,4-trifluoro-3-oxobutyrate]2Zn,

[0115] [tert-Butyl 4,4,4-trifluoro-3-oxobutyrate]2Cu

[0116] In some embodiments, the antifouling composition comprises a compound of formula IA or IB as defined above. In some embodiments, the antifouling composition comprises a compound of formula IA and IB as defined above.

[0117] Surprisingly, it has been found that compounds of formulae IA and IB significantly enhance the antifouling efficacy of antifouling compositions against the settlement of marine organisms such as barnacles, bryozoans, hydrozoans, mussels, algae, etc.

[0118] The antifouling composition of the present invention may further comprise one or more biocides capable of preventing the surface of an object from being fouled.

[0119] The biocide may be an inorganic biocide, an organometallic biocide or an organic biocide.

[0120] Examples of inorganic biocides are copper and copper compounds, such as copper oxides, for example cuprous oxide and cupric oxide; copper alloys, for example cupronickel; copper salts, for example copper thiocyanate (CuSCN), copper sulfide; or barium metaborate.

[0121] Examples of organometallic biocides are zinc 2-pyridinethiol-1-oxide [ZnPT, zinc pyrithione]; organic copper compounds, such as copper 2-pyridinethiol-1-oxide [CuPT, copper pyrithione], copper acetate, copper naphthenate, copper 8-aminourate [oxine-copper], copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzenesulfonate) and copper bis(pentachlorophenol); dithiocarbamate compounds, such as zinc N,N-dimethylaminodithioester [ziram], zinc ethane-1,2-diylbis(dithiocarbamate) [mancob], ethylenebis(dithiocarbamate)manganese [maneb] or ethylenebis(dithiocarbamate)manganese complexed with a zinc salt [mancozeb].

[0122] Examples of organic biocides are heterocyclic compounds such as 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine [cyclobutanenitrile], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 1,2-benzisothiazolin-3-one [BIT], 2-(thiocyanatomethylthio)-1,3-benzothiazole [benzothiazole], 3-benzo[b]thiophen-2-yl-5,6-dihydro-1,4,2-thiazine-4-oxide [benzothiazolin] and 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; urea derivatives such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea [diuron]; carboxylic acids, sulfonic acids and sulfenic acids amides and imides of, for example, N-(dichlorofluoromethylthio)phthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfonamide [difluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-toluenesulfonamide [tolyfluanid] and N-(2,4,6-trichlorophenyl)maleimide; other organic compounds, for example, pyridine triphenylborane, amine triphenylborane, 3-iodo-2-propynyl-n-butylcarbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile [chlorothalonil], p-((diiodomethyl)sulfonyl)toluene or 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [trolopride].

[0123] Other examples of biocides are tetra-alkylphosphonium halogenides; guanidine derivatives; imidazole-containing compounds, such as 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine] and derivatives; macrolides, including avermectins and their derivatives, such as ivermectin, or spinosad and their derivatives, such as spinosad, or enzymes, such as oxidases, or enzymes having proteolytic, hemicellulolytic, cellulolytic, lipolytic or amylolytic activity.

[0124] In one embodiment, the antifouling composition of the present invention comprises a compound of formula IA and / or IB as defined above and one or more additional biocides selected from the group consisting of: 2-pyridinethiol-1-oxide copper (CuPT, copper pyrithione), 2-pyridinethiol-1-oxide zinc (ZnPT, zinc pyrithione), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), cuprous oxide (Cu2O), zinc oxide (ZnO), 4-bromo-2-(4-chlorophenyl)- -5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (trolopride), ethane-1,2-diylbis(dithiocarbamate) zinc (mancozeb), N,N-dimethylaminodithiocarbamate zinc (ziram), 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), copper(I) thiocyanate (CuSCN), 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (medetomidine), triazine, halofuran and 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil).

[0125] In a preferred embodiment, the antifouling composition of the present invention comprises a compound of formula IA and / or IB as defined above and one or more biocides selected from the group consisting of CuPT, ZnPT, DCOIT, Cu2O and trolopride.

[0126] In a more preferred embodiment, the antifouling composition of the present invention comprises a compound of formula IA and / or IB as defined above and one or more biocides selected from CuPT and Cu O. The ratio of the compound of formula IA and / or IB (wt%) to CuPT (wt%) and / or the ratio of the compound of formula IA and / or IB (wt%) to Cu O (wt%) is advantageously from 100:1 to 1:100, preferably from 15:1 to 1:15, most preferably from 5:1 to 1:5.

[0127] In a specific embodiment, the antifouling composition of the present invention comprises the compound of formula IA and / or IB and CuPT. The ratio of the compound of formula IA and / or IB (wt%) to CuPT (wt%) is advantageously 100:1 to 1:100, preferably 10:1 to 1:10, most preferably 5:1 to 1:5.

[0128] In another specific embodiment, the antifouling composition of the present invention comprises the compound of formula IA and / or IB and Cu2O. The ratio of the compound of formula IA and / or IB (wt%) to Cu2O (wt%) is advantageously 100:1 to 1:100, preferably 10:1 to 1:10, most preferably 5:1 to 1:5.

[0129] In a more specific embodiment, the antifouling composition of the present invention comprises the compound of formula IA and / or IB, CuPT and Cu2O, wherein the ratio of the compound of formula IA and / or IB (wt%) to CuPT (wt%) is 5:1 to 5:1, and wherein the ratio of the compound of formula IA and / or IB (wt%) to Cu2O (wt%) is 5:1 to 1:5.

[0130] In another specific embodiment, the antifouling composition of the present invention comprises the compound of formula IA and / or IB and CuPT and does not contain Cu2O, wherein the ratio of the compound of formula IA and / or IB (wt%) to CuPT (wt%) is 5:1 to 5:1.

[0131] The antifouling compositions of the present invention comprising compounds of formula IA and / or IB as defined above not only provide excellent antifouling properties but are also substantially colourless and therefore do not interfere with the bright colours typically desired for marine hulls.

[0132] The present invention further provides the use of the antifouling composition of the present invention for inhibiting marine biofouling on a solid surface. The solid surface can be any solid surface of an underwater object (e.g., a ship, aquaculture net, underwater structure and equipment, tank, offshore structure, pipeline, net, pier, pile or column, etc.).

[0133] The antifouling compositions of the present invention may further be used in combination with polymers and / or copolymers allowing the controlled release of the compounds of formula IA and / or IB and, if present, also of the one or more biocides contained therein, for example by releasing these agents from the antifouling coating over time (as in the case of self-polishing or ablative coatings).

[0134] The inventors have surprisingly found that the compounds of formula IA and / or IB are universal agents that can be used in all types of antifouling coatings, i.e. antifouling coatings based on various different polymers and / or copolymers commonly used as binders in antifouling coating compositions. Thus, the polymer and / or copolymer that allows the controlled release of the compound of formula IA and / or IB and, if present, the one or more biocides contained therein can be any polymer and / or copolymer that is commonly used as a binder in antifouling coatings. Suitable polymers and / or copolymers for this purpose are known to those skilled in the art. Depending on the amount and type of binder used, the compound of formula IA and / or IB and the one or more biocides will be released in a controlled manner at a predetermined desired rate, for example suitable for the navigation mode of the vessel.

[0135] For example, the polymer and / or copolymer used as a binder in a "self-polishing antifouling coating" allowing controlled release of the compound of formula IA and / or IB and the one or more biocides may be a hydrolyzable acrylate polymer, such as a (meth)acrylate-based polymer and / or copolymer. The (meth)acrylate monomer portion of the (meth)acrylate polymer and / or copolymer may be an alkyl (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate and stearyl (meth)acrylate; and phenyl (meth)acrylate; benzyl (meth)acrylate; or alkoxyalkyl (meth) acrylates, such as methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxybutyl diglycol (meth) acrylate; also phenoxyethyl (meth) acrylate; or hydroxyalkyl (meth) acrylates, such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate or 2-hydroxy-3-phenoxypropyl (meth) acrylate;

[0136] The (meth)acrylate monomer portion in the (meth)acrylate polymer and / or copolymer may further be a silyl (meth)acrylate, such as tribenzylsilyl (meth)acrylate, trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-tert-butylsilyl (meth)acrylate, tri-n-pentylsilyl (meth)acrylate, tri-n-dodecylsilyl (meth)acrylate, tri-n-hexylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate or triphenylsilyl (meth)acrylate;

[0137] The (meth)acrylate polymers and / or copolymers may also contain a metal salt moiety of acrylic acid or methacrylic acid, referred to herein as a "metal (meth)acrylate". The metal may be any suitable metal known to the skilled person, such as zinc, calcium, magnesium, lithium, iron, zirconium, aluminum, cobalt, zirconium, barium and bismuth.

[0138] The polymer and / or copolymer allowing controlled release of the compound of formula IA and / or IB and, if present, the one or more biocides may also be a VAGH copolymer. VAGH copolymers may be dissolved in 2:3 xylene:MIBK.

[0139] Thus, in one embodiment, the polymer and / or copolymer allowing controlled release of the compound of formula IA and / or IB and, if present, also the one or more biocides, comprises a (meth)acrylate polymer and / or copolymer, or a VAGH copolymer. The (meth)acrylate polymer and / or copolymer may be a polymer or copolymer of monomeric moieties selected from the group consisting of alkyl (meth)acrylates, phenyl (meth)acrylates, benzyl (meth)acrylates, alkoxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, zinc (meth)acrylates and silyl-(meth)acrylates; or the (meth)acrylate polymer and / or copolymer may be a polymer or copolymer of monomeric moieties selected from the group consisting of ethyl acrylate, methyl methacrylate, butyl acrylate, 2-methoxyethyl acrylate, zinc methyl acrylate and triisopropylsilyl acrylate. , preferably, the (meth)acrylate polymer and / or copolymer is a copolymer of monomeric moieties selected from the group consisting of ethyl acrylate, methyl methacrylate and zinc methyl acrylate, more preferably, the (meth)acrylate polymer and / or copolymer is a copolymer of monomeric moieties selected from the group consisting of ethyl acrylate, methyl methacrylate, 2-methoxyethyl acrylate and zinc methyl acrylate, and most preferably, the (meth)acrylate polymer and / or copolymer is a copolymer of monomeric moieties selected from the group consisting of methyl methacrylate, butyl acrylate, 2-methoxyethyl acrylate and triisopropylsilyl acrylate.

[0140] The invention therefore further provides an antifouling coating comprising an antifouling composition according to the invention and a polymer and / or copolymer allowing the controlled release of the compound of formula IA and / or IB and, if present, also the one or more biocides.

[0141] The content of the compound of formula IA and / or IB in the antifouling coating of the present invention is about 1 to about 25 wt%, preferably about 3 to about 20 wt%, more preferably about 4 to about 18 wt%, most preferably about 5 to about 15 wt%.

[0142] Due to the excellent reinforcing properties of the compounds of formula IA and / or IB, only a small amount of the one or more biocides is required in the antifouling coating of the present invention. The total content of the one or more biocides in the antifouling coating of the present invention is less than about 30 wt%, preferably less than about 25 wt%, more preferably less than about 20 wt%, and most preferably less than about 18 wt%.

[0143] The total content of CuPT in the antifouling coating of the present invention is less than about 10 wt%, more preferably less than about 8 wt%, and most preferably less than about 7 wt%.

[0144] The total content of Cu2O in the antifouling coating of the present invention is less than about 20 wt%, more preferably less than about 15 wt%, and most preferably less than about 12 wt%.

[0145] As a result, the content of toxic metal compounds (especially Cu2O) is kept very low or even avoided.

[0146] The present invention further provides a method for inhibiting marine biofouling on a solid surface, characterized in that an antifouling coating comprising the antifouling composition of the present invention is applied to the surface. The solid surface may be any solid surface of an underwater object (e.g., a ship, aquaculture net, underwater structure and equipment, tank, offshore structure, pipeline, net, pier, pile or column, etc.).

[0147] The present invention will be further described below in conjunction with examples, but it should be understood that the present invention is not subject to any limitation of these examples.

[0148] Example

[0149] Example 1 : Preparation of exemplary polymer-based binders for antifouling coatings

[0150] Different exemplary polymer-based binders useful in self-polishing antifouling coatings or hybrid coatings have been prepared as outlined below.

[0151] Example 1A: Synthesis of Acrylate Polymer "Acidic Acrylate Low Acid Value" (referred to herein as "Ac(AV=100-)")

[0152]

[0153] Example 1B: Synthesis of Acrylate Polymer "Acidic Acrylate 100 Acid Value" (referred to herein as "Ac(AV=100)")

[0154]

[0155] Example 1C: Synthesis of an adhesive component using an acrylate polymer "Ac(AV=100-)" to obtain a zinc acrylate polymer (referred to herein as "Zn-Ac(AV=100-)")

[0156]

[0157] Example 1D: Synthesis of an adhesive component using an acrylate polymer "Ac(AV=100)" to obtain a zinc acrylate polymer (referred to herein as "Zn-Ac(AV=100)")

[0158]

[0159] Example IE: Synthesis of Silyl Acrylate Polymer Standard TIPX Adhesive Component (referred to herein as "Si-Ac")

[0160]

[0161] Example 1F: Synthesis of Silyl Acrylate Polymer Low-Level TIPX Adhesive Component (Herein Referred to as "Si-Ac(TIPX-L)")

[0162]

[0163] Example 2 : Efficacy of Cu2O and compounds of the invention in antifouling coatings

[0164] In order to confirm that the amount of Cu2O can be significantly reduced if the compounds of formula IA or IB of the present invention are present in the antifouling coating, the efficacy of a panel of ablative antifouling coatings was evaluated by immersing the coated test panels in seawater on a test raft.

[0165] A number of ablative antifouling coatings have been prepared for this purpose which a) comprised only the IA or IB compounds of the present invention (i.e., without a biocide), b) comprised the IA or IB compounds of the present invention together with a biocide (i.e., CuO), c) comprised only a biocide (i.e., CuO, or CuO together with CuPT, respectively, as "positive control coatings"), and d) contained no biocide and no IA or IB compounds ("negative control coatings").

[0166] The compounds of the present invention employed in this example are depicted in Table 1 below. The detailed formulations of the coatings are depicted in Tables 2 to 4 below. The coatings have been applied to PVC panels as follows.

[0167] Each panel was divided into three parts and coated with the corresponding coating (i.e., containing a biocide, or a compound of the present invention, or a biocide together with a compound of the present invention) at three different concentrations (i.e., 25% v / v, 15% v / v, and 5% v / v). The concentrations of these ingredients are as follows Figures 1 to 3 shown.

[0168] Results: The results after immersion in seawater for a predetermined period of time (1, 4 or 6 months, as shown below) are shown in Figure 1 , Figure 2 and Figure 3 .

[0169] Figure 1 :

[0170] Panel 1 depicts a panel coated with an antifouling coating formulation containing only Cu2O as shown in Table 2 below. The three sections represent three areas on a panel that have been treated with coatings containing different concentrations of Cu2O. The coating applied to Section 1 contained 15% v / v Cu2O and the coating applied to Section 2 of the panel contained 5% v / v Cu2O. The last section of Panel 1 (emphasized by a square) is a negative control of the panel to which the coating was applied, wherein the coating did not contain any antifouling active ingredient, i.e., neither a biocide nor a compound of Formula IA or IB. Figure 1 Panels 6 and 12 in are negative controls for untreated PVC panels. Figure 1 Panels 2 to 5 and 7 to 10 are similar to those of Figure 1 Shown are coatings containing different concentrations of a compound of formula IA or IB.

[0171] Figure 2 :

[0172] In each trial (i.e. in Nagasaki, Himeji, and Onagawa), Figure 2 Panel 1 in the figure is a panel coated with an antifouling coating formulation containing only Cu2O as shown in Table 3 below. The concentrations of the components contained in the coating applied to the three parts of the panel are as follows: Figure 2 The concentrations are 25, 15, and 5% by volume. Figure 2 Panel 6 in each trial was a negative control of an untreated PVC panel. Panel 4 in each trial was similar to the coating with 25% v / v CuPt in Part 1; similar to the coating with 5% v / v Cu2O and 25% CuPt in Part 2, and similar to the coating with 5% v / v Cu2O and 15% v / v CuPt in Part 3. Panel 5 in each trial was similar to the coating with 25% v / v ZnETFAA in Part 1, similar to the coating with 5% v / v Cu2O and 25% ZnETFAA in Part 2, and similar to the coating with 5% v / v Cu2O and 15% v / v ZnETFAA in Part 3.

[0173] Figure 3 :

[0174] Figure 3 Panels 7 and 10 in the figure were coated with only Cu2O and Cu2O / CuPT antifouling coating formulations as shown in Table 3. The concentrations were 25, 15, and 5 volume %. Figure 3Panel 12 in the figure is a negative control of an untreated PVC panel. Panels 1 to 6 are similar to the coatings with 25% v / v of the compounds of the invention in Part 1 (i.e., Panel 1: Der-2-Cu; Panel 2: Der-3-Cu; Panel 3: Der-4-Cu; Panel 4: Der-5-Cu; Panel 5: Der-6-Cu; Panel 6: Der-7-Cu, as Figure 3 and as shown in Table 1 below); in Part 2 similar to the coating with 5% v / v Cu2O and 25% of the compound of the invention, and in Part 3 similar to the coating with 5% v / v Cu2O and 15% v / v of the compound of the invention.

[0175] All portions of the panels similar to the paints with different concentrations of the compounds of the invention showed improved antifouling performance compared to the untreated panel control and the solid color paint control.

[0176] A general trend of improving the performance of antifouling coatings was observed for all evaluated derivatives.

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

Claims

1. Use of an antifouling composition comprising a compound of formula IA and / or IB for inhibiting marine biofouling on a solid surface, in Me stands for metal; Each R1 is F, or among three R1, two are F and one is H; R2 are each independently selected from NH, O, S and Se; R3 is NH, N(R4), O, S and Se; R4 is hydrogen, a linear or branched C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-12 cycloalkyl, C6-20 aryl, or C7-20 aralkyl; R5 and R6 are each independently selected from H, a linear or branched C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-12 cycloalkyl, C6-20 aryl and C7-20 aralkyl; or R5 and R6 together form a group =0, =S, =Se, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4), wherein the antifouling composition does not contain Cu(ETFAA)2.

2. The method according to claim 1, wherein Me represents Cu, Zn, Co, Ni, Ca, Mg or Mn.

3. The method according to claim 1, wherein Me represents Cu, Zn, Co, Ni, Ca or Mn.

4. The use as claimed in claim 1, wherein in the compound of formula IA and / or IB Me represents Cu, Zn, Ca, Mg or Mn; R2 are each independently selected from NH, O and S; R3 is NH, N(R4), O and S; R4 is H, linear or branched C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-8 cycloalkyl, C6-12 aryl, C7-12 aralkyl; R5 and R6 are each independently selected from H, a linear or branched C1-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, C3-6 cycloalkyl, C6-12 aryl and C7-12 aralkyl; or R5 and R6 together form a group =O, =S, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4).

5. The use as claimed in claim 1 or 4, wherein in the compound of formula IA and / or IB Me represents Cu or Zn; R2 are each independently selected from NH and O; R3 is N(R4) and O; R4 is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl and benzyl; R5 and R6 are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and benzyl; or R5 and R6 together form the group =CH(OCH3); =CH(OC2H5); =CH(OnC3H7); =CH(OiC3H7); =CH(OnC4H9); =CH(OiC4H9); =CH(OtertC4H9), =CH(NHCH3); =CH(NHC2H5); =CH(NHnC3H7);=CH(NHiC3H7); =CH(NHnC4H9); =CH(NHiC4H9); =CH(NHtertC4H9).

6. The method of claim 1 or 4, wherein each R1 is F.

7. The use according to claim 1 or 4, further comprising one or more biocides, wherein the one or more biocides are selected from the group consisting of 2-pyridinethiol-1-oxide copper, 2-pyridinethiol-1-oxide zinc, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, cuprous oxide, zinc oxide, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, ethane-1,2-diylbis(dithiocarbamate) zinc, N,N-dimethylaminodithioester zinc, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, copper(I) thiocyanate, 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole, triazine, fluorocarbon and 2,4,5,6-tetrachloroisophthalonitrile.

8. The use according to claim 7, wherein the one or more biocides are selected from 2-pyridinethiol-1-oxide copper, 2-pyridinethiol-1-oxide zinc, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, cuprous oxide and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile.

9. The use according to claim 8, wherein the one or more biocides are selected from 2-pyridinethiol-1-oxide copper and cuprous oxide.

10. The use according to claim 8, wherein the ratio of the weight percentage of the compound of formula IA and / or IB to the weight percentage of 2-pyridinethiol-1-copper oxide, and / or the ratio of the weight percentage of the compound of formula IA and / or IB to the weight percentage of cuprous oxide is 100:1 to 1:

100.

11. Use of an antifouling coating for inhibiting marine biofouling on a solid surface, the antifouling coating comprising: an antifouling composition comprising a compound of formula IA and / or IB and a polymer and / or copolymer allowing controlled release of the compound of formula IA and / or IB, in Me stands for metal; Each R1 is F, or among three R1, two are F and one is H; R2 are each independently selected from NH, O, S and Se; R3 is NH, N(R4), O, S and Se; R4 is hydrogen, a linear or branched C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-12 cycloalkyl, C6-20 aryl, or C7-20 aralkyl; R5 and R6 are each independently selected from H, a linear or branched C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-12 cycloalkyl, C6-20 aryl and C7-20 aralkyl; or R5 and R6 together form a group =0, =S, =Se, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4), wherein the antifouling composition does not contain Cu(ETFAA)2.

12. The use according to claim 11, wherein the content of the compound of formula IA and / or IB is 1 to 25 wt%.

13. The use according to claim 11 or 12, comprising one or more biocides, wherein the total content of the one or more biocides is less than 30 wt%.

14. The use according to claim 11 or 12, wherein the total content of 2-pyridinethiol-1-copper oxide is less than 10 wt%.

15. A method for inhibiting marine biofouling on a solid surface comprising applying an antifouling coating to said surface, wherein said antifouling coating comprises: an antifouling composition comprising a compound of formula IA and / or IB and a polymer and / or copolymer allowing controlled release of the compound of formula IA and / or IB, in Me stands for metal; Each R1 is F, or among three R1, two are F and one is H; R2 are each independently selected from NH, O, S and Se; R3 is NH, N(R4), O, S and Se; R4 is hydrogen, a linear or branched C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-12 cycloalkyl, C6-20 aryl, or C7-20 aralkyl; R5 and R6 are each independently selected from H, a linear or branched C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-12 cycloalkyl, C6-20 aryl and C7-20 aralkyl; or R5 and R6 together form a group =0, =S, =Se, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4), wherein the antifouling composition does not contain Cu(ETFAA)2.

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