Composition for antifouling protection

Abstract

The present invention relates to antifouling compositions comprising a compound of formula IA and / or IB for efficient prevention of marine biofouling on surfaces of ships and marine structures, their use for inhibiting marine biofouling, and antifouling paints comprising said compositions.

Description

[0001] This application is a divisional application of application No. 202080044338.0, filed on December 4, 2020, entitled "Composition for Antifouling Protection". Technical Field

[0002] This invention relates to antifouling compositions comprising IA and / or IB compounds for effectively preventing marine biofouling on the surfaces of ships and marine structures, their use in inhibiting marine biofouling, and antifouling coatings comprising said compositions. Background Technology

[0003] Ships, aquaculture nets, underwater structures, and equipment are often susceptible to corrosion from marine organisms such as barnacles, bryozoans, hydroids, clams, and algae. These organisms can grow and reproduce, ultimately leading to serious problems. For example, in the case of ship hulls, the growth of marine organisms on the hull increases frictional resistance between the hull and the water, thus increasing fuel consumption and reducing ship speed. Ship hulls need to be protected from the effects of marine organism growth to keep them clean and smooth for maximum fuel efficiency. Another issue is the transportation of marine organisms from one part of the world to another; invasive species can potentially disrupt local ecosystems. Therefore, underwater components require adequate protection against marine biofouling, which is typically achieved through antifouling coatings.

[0004] The adhesive systems used in these antifouling coatings are typically composed of easily eroded adhesives. Erosion of the coating film helps prevent fouling by releasing antifouling agents (biocides) from the coating over time, thus preventing the adhesion of fouling organisms. There are two main types of erosive antifouling coatings, which the industry describes as "self-polishing" and "ablation."

[0005] The adhesive system for ablative coatings is primarily composed of rosin, which reacts with seawater to become water-soluble and is then eroded away. Alternatively, rosin or rosin derivatives can be mixed with non-erosive adhesives 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.

[0006] In self-polishing antifouling coatings, the adhesive system is based on hydrolyzable acrylate polymers. Hydrolyzable functional groups are typically provided to the polymer via metal carboxylate acrylate monomers or silyl acrylate monomers. Easily eroded polyester adhesives are also used, making the antifouling coating less expensive. The main difference between ablative coatings and self-polishing coatings lies in the thickness of the leaching layer and the more linear erosion rate of self-polishing coatings over time.

[0007] There are also “hybrid coatings” whose binder system consists of easily eroded acrylates (such as in self-polishing coatings) and rosin. The leached layer is thinner than that in an ablative coating, but thicker than a true self-polishing coating.

[0008] Most commercially available antifouling coatings contain high levels of cuprous oxide (Cu₂O), which is used as a biocide—typically around 40 wt% (as required for proper antifouling protection). Cuprous oxide is potentially harmful to many organisms. Leaching from antifouling coatings can lead to elevated copper levels in water, sediment, and the surrounding environment. High anthropogenic copper levels can have significant ecological impacts. While Cu₂O is widely used as an antifouling agent in antifouling coatings, these coatings may also contain additional biocides, as Cu₂O alone is only effective against hard-fouling organisms such as barnacles.

[0009] As another drawback, cuprous oxide typically imparts a deep reddish-brown hue to antifouling coatings and can also react with atmospheric carbon dioxide and seawater chlorides to create uneven streaks on the coating surface. This is an unattractive appearance and can occur, for example, shortly after a vessel is launched. Some yacht owners and cruise operators prefer the brighter colors and more uniform appearance that cannot be achieved with coatings containing cuprous oxide.

[0010] Attempts to replace cuprous oxide in commercially available antifouling coatings have led to the development of alternatives, such as white copper thiocyanate and the agricultural insecticide tralopyril, which is effective against barnacles. However, these alternatives are more expensive and less effective than cuprous oxide-based antifouling coatings.

[0011] Therefore, there is a need for marine antifouling coatings that are improved both ecologically and economically, with reduced copper content, or even completely replacing cuprous oxide in conventionally used antifouling coatings.

[0012] The antifouling compositions of the present invention, comprising compounds of formula IA and / or IB, meet this need. The inventors have surprisingly discovered that compounds of formula IA and IB are highly efficient and versatile agents that enhance 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 of the coating.

[0013] Therefore, Cu2O in antifouling coatings can now be partially or completely replaced, thus significantly reducing the metal content while maintaining adequate antifouling performance. Furthermore, the antifouling compositions of the present invention, comprising compounds of formula IA and / or IB, are substantially colorless and therefore do not interfere with the bright colors typically required for ship hulls. Attached Figure Description

[0014] Figure 1Panels coated with the antifouling coating of Example 2 (Table 1) are depicted, and the appearance of the panels after 6 months in seawater (Himeji, depth: 1.5m) is shown. Black squares represent areas of negative control (i.e., coatings without any antifouling components).

[0015] Figure 2 Panels coated with the antifouling coating of Example 2 (Table 2) are depicted, and their appearance after 4 months in seawater (Himeji, Nagasaki, and Onagawa) is shown. Panels 6 from the Nagasaki and Himeji tests are shown after 1 month in seawater. Panel 6 from the Onagawa test is shown after 4 months in seawater.

[0016] Figure 3 A panel coated with the antifouling coating described in Table 3 of Example 2 is depicted, and the appearance of the panel after one month in seawater (Nagasaki; depth: 1.5m) is shown. Black squares represent areas of negative control (i.e., coatings without any antifouling components). Detailed Implementation

[0017] 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 related to this invention. The following abbreviations and terms are used herein:

[0018] AIBN: Azobis(isobutyronitrile)

[0019] AMBN: Azobis(2-methylbutyronitrile)

[0020] A630-20X: Fatty acid amide

[0021] BA: Butyl acrylate

[0022] Chlorothalonil: 2,4,5,6-Tetrachlorobenzene-1,3-dicarboxynitrile (Copper ), CupT, Copper pyrithione: 2-pyridinethiol-1-copper oxide

[0023] Cu2O: Cuprous oxide

[0024] CuSCN: Copper thiocyanate (I)

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

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

[0027] Disparlon A650-20x: A synthetic polyamide wax dispersion. An excellent anti-settling agent for heavy pigments and metallic paints. It exhibits high shear thinning properties, resulting in superior application performance. ETFAA: Ethyl 4,4,4-trifluoroacetoacetate. MP 25: A copolymer of vinyl chloride and vinyl isobutyl ether

[0028] 2MEA: Ethyl 2-methoxyacrylate monomer

[0029] Metomididine: 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole

[0030] MMA: Methyl methacrylate monomer

[0031] MIBK: Methyl isobutyl ketone

[0032] MPM: Methoxypropylene monomer

[0033] PGM: Propylene Glycol Monomethyl Ether

[0034] TIPX: Triisopropylsilane acrylate monomer trolopiri: 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-onitrile VAGH: Vinyl chloride / vinyl acetate / vinyl alcohol copolymer (commercial)

[0035] Zinc mancozeb: ethane-1,2-dimethylbis(dithiocarbamate) zinc

[0036] Ziram: Zinc N,N-dimethylaminodithioester

[0037] Zn(ETFAA)2: Zinc di(ethyl 4,4,4-trifluoroacetoacetate), also referred to herein as ZnETFAA

[0038] ZnO: Zinc oxide

[0039] ZnPT: Zinc Pyridinethione: 2-Pyridinethiol-1-Zinc Oxide

[0040] The term "(meth)acrylate" is a collective term for acrylates and methacrylate monomers. The terms "methacrylate" or "meth-acrylate" refer only to methacrylate monomers.

[0041] Bentonite SD2 is an organic clay added for anti-settling properties; Bentonite #38 is quaternary ammonium salt 18-lithium montmorillonite clay; Minex 4 is nepheline syenite clay. Disparon 6900-20x (A630-20X polyamide wax) is a 20% dispersion of polyamide wax in xylene, used as a rheology modifier; Disperbyk 161 is a dispersing additive. Resin refers to all prepolymers or polymers that can be used as raw materials for binders in the antifouling coatings of this invention. Rosin or gum rosin refers to rosin resin (CAS: 8050-09-7, see also https: / / www.megaglori.com / what-is-gum-rosin / ).

[0042] "Biocides" are any compounds that prevent marine organisms from settling on a surface and / or from growing on a surface and / or cause marine organisms to move off the surface.

[0043] The terms “antifouling coating”, “antifouling coating”, and “antifouling agent” are used interchangeably in this document.

[0044] This invention provides a novel method for inhibiting fouling on the surfaces of underwater objects, such as ship hulls or any other marine structures. Specifically, this invention provides an antifouling composition comprising compounds of formula IA and / or IB:

[0045]

[0046] in

[0047] Me represents a metal, preferably Cu, Zn, Co, Ni, Ca, Mg, or Mn;

[0048] R1 can be any functional group that imparts high hydrophobicity, for example...

[0049] R1 is independently selected from hydrogen, halogen, straight-chain or branched C. 1-20 Alkyl, C 2-20 alkenyl, C 2-20 alkynyl group, C 3-12 cycloalkyl, C 6-20 Aryl and C 7-20 Aryl groups;

[0050] R2 is independently selected from NH, O, S and Se;

[0051] R3 is NH, N(R4), O, S, and Se;

[0052] R4 is hydrogen, a straight-chain or branched C4. 1-20 Alkyl, C 2-20 alkenyl, C 2-20 alkynyl group, C3-12 cycloalkyl, C 6-20 Aryl, C 7-20 Aryl groups;

[0053] R5 and R6 are each independently selected from H, linear or branched C. 1-20 Alkyl, C 2-20 alkenyl, C 2-20 alkynyl group, C 3-12 cycloalkyl, C 6-20 Aryl and C 7-20 Aryl groups; or

[0054] R5 and R6 together form groups =O, =S, =Se, =NR4, =C(R4)2, =C(R4)(OR4).

[0055] =C(R4)(NHR4).

[0056] In one embodiment, the present invention provides an antifouling composition comprising compounds of formula IA and / or IB as shown above, wherein

[0057] Me represents Cu, Zn, Ca, Mg, or Mn;

[0058] R1 is independently selected from H, F, Cl, Br, I, and straight-chain or branched C. 1-12 Alkyl, C 2-12 alkenyl, C 2-12 alkynyl group, C 6-12 Aryl and C 7-12 Aryl groups;

[0059] R2 is independently selected from NH, O and S;

[0060] R3 is NH, N(R4), O, and S;

[0061] R4 is H, and C is either straight or branched. 1-12 Alkyl, C 2-12 alkenyl, C 2-12 alkynyl group, C 3-8 cycloalkyl, C 6-12 Aryl, C 7-12 Aryl groups;

[0062] R5 and R6 are each independently selected from H, linear or branched C. 1-4 Alkyl, C 2-4 alkenyl, C 2-4 alkynyl group, C 3-6 cycloalkyl, C 6-12 Aryl and C 7-12 Aryl groups; or

[0063] R5 and R6 together form the groups =O, =S, =NR4, =C(R4)2, =C(R4)(OR4).

[0064] =C(R4)(NHR4).

[0065] In one embodiment, the present invention provides an antifouling composition comprising compounds of formula IA and / or IB as shown above, wherein

[0066] Me represents Cu or Zn;

[0067] 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;

[0068] R2 is independently selected from NH and O;

[0069] R3 is N(R4) and O;

[0070] R4 represents 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;

[0071] R5 and R6 are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and benzyl; or

[0072] R5 and R6 together form the following groups: =CH(OCH3); =CH(OC2H5); =CH(OnC3H7);

[0073] =CH(OiC3H7); =CH(OnC4H9); =CH(OiC4H9); =CH(Ounc.C4H9),

[0074] =CH(NHCH3); =CH(NHC2H5); =CH(NHnC3H7); =CH(NHiC3H7);

[0075] =CH(NHnC4H9); =CH(NHiC4H9); =CH(NHt.C4H9).

[0076] In one embodiment, the present invention provides an antifouling composition comprising compounds of formula IA and / or IB as shown above, wherein

[0077] Me represents Cu or Zn;

[0078] R1 is independently selected from H and F;

[0079] R2 is independently selected from NH and O;

[0080] R3 is N(CH3), N(C2H5) and O;

[0081] R4 represents 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;

[0082] R5 and R6 are both H; or

[0083] R5 and R6 together form the groups =CH(OCH3); =CH(OC2H5); =CH(NHCH3);

[0084] =CH(NHC2H5);

[0085] In one embodiment, the compound of formula IB is defined as above, provided 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.

[0086] Suitable compounds of formulas IA and IB are, for example, ethyl 3-amino-4,4,4-trifluorocrotonate;

[0087] [Ethyl 3-amino-4,4,4-trifluorocrotonate]2Zn,

[0088] [Ethyl 3-amino-4,4,4-trifluorocrotonate]2Cu,

[0089] Ethyl 3-amino-2-methylene-(methylamino)-4,4-difluorocrotonate,

[0090] [Ethyl 3-amino-2-methylene-(methylamino)-4,4-difluorocrotonate]2Zn,[Ethyl 3-amino-2-methylene-(methylamino)-4,4-difluorocrotonate]2Cu4,4,4-trifluoro-N,N-dimethyl-3-oxobutyramide;

[0091] [4,4,4-trifluoro-N,N-dimethyl-3-oxobutyramide]2Cu,

[0092] [4,4,4-trifluoro-N,N-dimethyl-3-oxobutyramide]2Zn, dodecyl 4,4,4-trifluoro-3-oxobutyrate,

[0093] [dodecyl 4,4,4-trifluoro-3-oxobutyrate]2Zn,

[0094] [Dodecyl 4,4,4-trifluoro-3-oxobutyrate]2Cu,

[0095] Benzyl 4,4,4-trifluoroacetoacetate

[0096] [Benzyl 4,4,4-trifluoroacetoacetate]2Zn,

[0097] [Benzyl 4,4,4-trifluoroacetoacetate]2Cu,

[0098] Octyl 4,4,4-trifluoroacetoacetate

[0099] [Ocyl-4,4,4-trifluoroacetoacetate]2Zn,

[0100] [Ocyl-4,4,4-trifluoroacetoacetate]2Cu,

[0101] Isopropyl 4,4,4-trifluoroacetoacetate

[0102] [Isopropyl 4,4,4-trifluoroacetoacetate]2Zn,

[0103] [Isopropyl 4,4,4-trifluoroacetoacetate]2Cu,

[0104] Ethyl 4,4,4-trifluoroacetoacetate,

[0105] [Ethyl 4,4,4-trifluoroacetoacetate]2Zn

[0106] tert-butyl 4,4,4-trifluoro-3-oxobutyrate,

[0107] [tert-butyl 4,4,4-trifluoro-3-oxobutyrate]2Zn,

[0108] [tert-butyl 4,4,4-trifluoro-3-oxobutyrate]2Cu

[0109] In some embodiments, the antifouling composition comprises a compound of formula IA or IB as defined above. In some embodiments, the antifouling composition comprises compounds of formulas IA and IB as defined above.

[0110] Surprisingly, compounds of formulas IA and IB significantly enhanced the antifouling efficacy of the antifouling composition against the settling of marine organisms such as barnacles, bryozoans, hydroids, clams, and algae.

[0111] The antifouling composition of the present invention may further comprise one or more biocides capable of preventing contamination of object surfaces.

[0112] This biocide can be an inorganic biocide, an organometallic biocide, or an organic biocide.

[0113] Examples of inorganic biocides are copper and copper compounds, such as copper oxide, cuprous oxide and copper oxide; copper alloys, such as copper-nickel alloys; copper salts, such as copper thiocyanate (CuSCN), copper sulfide; or barium metaborate.

[0114] Examples of organometallic biocides are zinc 2-pyridinethiol-1-oxide [ZnPT, zinc pyridinethione]; organocopper compounds, such as copper 2-pyridinethiol-1-oxide [CuPT, copper pyridinethione], copper acetate, copper naphthenate, copper 8-aminourea [Oxycin-copper], copper nonylphenol sulfonate, copper bis(ethylenediamine)bis(dodecylbenzenesulfonic acid) and copper bis(pentachlorophenol); dithiocarbamate compounds, such as zinc N,N-dimethylaminodithioester [zinc thiram], zinc ethane-1,2-diylbis(dithiocarbamate) [zinc mancozeb], manganese ethylene bis(dithiocarbamate) [manganese mancozeb], or manganese ethylene bis(dithiocarbamate) [manganese mancozeb] in combination with zinc salts.

[0115] Examples of organic biocides are heterocyclic compounds, such as 2-(tert-butylamino)-4-(cyclopropylamine)-6-(methylthio)-1,3,5-triazine [cyclobutyronitrile], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 1,2-benzisothiazolin-3-one [BIT], 2-(thiocyanate methylthio)-1,3-benzothiazole [benzisazole], 3-benzo[b]thiophene-2-yl-5,6-dihydro-1,4,2-thiazine-4-oxide [benzisazine], 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 hyposulfonic acids. Amides and imides, such as N-(dichlorofluoromethylthio)phthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfonamide [antibacterial agent], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-toluenesulfonamide [para-methyl sulfonamide] and N-(2,4,6-trichlorophenyl)maleimide; other organic compounds, such as 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-onitrile [trelopipride].

[0116] Other examples of biocides are tetra-alkylphosphonium halogenides; guanidine derivatives; imidazole-containing compounds, such as 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazolium [metopril] and its derivatives; macrolides, including avermectin and its derivatives, such as ivermectin, or spinosad and its derivatives, such as spinosad; or enzymes, such as oxidases, or enzymes having proteolytic, hemicellulose-degrading, cellulose-degrading, lipolytic, or starch-degrading activities.

[0117] 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 other biocides selected from the group consisting of: 2-pyridinethiol-1-copper oxide (CuPT, copper pyridinethione), 2-pyridinethiol-1-zinc oxide (ZnPT, zinc pyridinethione), 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-pyrrolo-3-onitrile (tralopiol), ethane-1,2-dimethylbis(dithiocarbamate) zinc (zineb), N,N-dimethylmethylaminodithioester zinc (zinc thiram), 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), copper thiocyanate (I)(CuSCN), 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazolium (metopril), triazine, halothane and 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil).

[0118] 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 CuPT, ZnPT, DCOIT, Cu2O and troopipride.

[0119] 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 Cu2O. 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 Cu2O (wt%) is advantageously 100:1 to 1:100, preferably 15:1 to 1:15, and most preferably 5:1 to 1:5.

[0120] In a specific embodiment, the antifouling composition of the present invention comprises a 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, and most preferably 5:1 to 1:5.

[0121] In another specific embodiment, the antifouling composition of the present invention comprises a 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, and most preferably 5:1 to 1:5.

[0122] 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.

[0123] In another specific embodiment, the antifouling composition of the present invention comprises the compound of formula IA and / or IB and CuPT and is free of Cu2O, wherein the ratio of the compound of formula IA and / or IB (wt%) to CuPT (wt%) is 5:1 to 5:1.

[0124] The antifouling compositions of the present invention, which contain compounds of formula IA and / or IB as defined above, not only provide excellent antifouling properties, but are also substantially colorless, thus not interfering with the bright colors typically required for ship hulls.

[0125] The present invention further provides the use of the antifouling composition of the present invention for inhibiting marine biofouling on solid surfaces. The solid surface can be any solid surface of an underwater object (e.g., a ship, aquaculture nets, underwater structures and equipment, tanks, offshore buildings, pipelines, nets, docks, piles or columns, etc.).

[0126] The antifouling compositions of the present invention can be further used in combination with polymers and / or copolymers, thereby allowing controlled release of the compounds of formula IA and / or IB, and, if present, also allowing controlled release of the one or more biocides contained therein, for example by releasing these agents from the antifouling coating over time (as is the case with self-polishing or ablative coatings).

[0127] The inventors have surprisingly discovered that 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 adhesives in antifouling coating compositions). Therefore, the polymers and / or copolymers that allow controlled release of the compounds of formula IA and / or IB, and if present, also allow controlled release of the one or more biocides contained therein, can be any polymers and / or copolymers commonly used as adhesives 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 adhesive used, the compounds of formula IA and / or IB and one or more biocides will be released in a controlled manner at a predetermined desired rate, for example, suitable for the ship's navigation mode.

[0128] For example, the polymer and / or copolymer of the compound of formula IA and / or IB and the one or more biocides used as an adhesive in a "self-polishing antifouling coating" that allows controlled release of the compound can be a hydrolyzable acrylate polymer, such as a (meth)acrylate-based polymer and / or copolymer. The (meth)acrylate monomer portion in (meth)acrylate polymers and / or copolymers may be alkyl (meth)acrylates, such as meth (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (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; as well as phenyl (meth)acrylate; benzyl (meth)acrylate... Acrylates; 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 diethylene glycol (meth)acrylate; and phenoxyethyl (meth)acrylates; 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;

[0129] The (meth)acrylate monomer portion in (meth)acrylate polymers and / or copolymers may further be silyl (meth)acrylates, 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.

[0130] (Meth)acrylate polymers and / or copolymers may also contain a metal salt portion of acrylic acid or methacrylic acid, referred to herein as "(meth)acrylate metal salt". The metal may be any suitable metal known to those skilled in the art, such as zinc, calcium, magnesium, lithium, iron, zirconium, aluminum, cobalt, zirconium, barium, and bismuth.

[0131] Polymers and / or copolymers that allow controlled release of compounds of formula IA and / or IB, and if present, also allow controlled release of one or more biocides, may also be VAGH copolymers. VAGH copolymers can be dissolved in 2:3 xylene:MIBK.

[0132] Therefore, in one embodiment, the polymer and / or copolymer that allows controlled release of the compounds of formula IA and / or IB, and if present, also allows controlled release of 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 monomer portions 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 monomer portions selected from the group consisting of ethyl acrylates, methyl methacrylates, butyl acrylates, 2-methoxyethyl acrylates, zinc methyl acrylates, and triisopropylsilyl acrylates. Preferably, the (meth)acrylate polymer and / or copolymer is a copolymer of monomer portions 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 monomer portions 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 monomer portions selected from the group consisting of methyl methacrylate, butyl acrylate, 2-methoxyethyl acrylate, and triisopropylsilyl acrylate.

[0133] Therefore, the present invention further provides an antifouling coating comprising the antifouling composition of the present invention and polymers and / or copolymers, said polymers and / or copolymers allowing controlled release of said formula IA and / or IB compounds and, if present, also allowing controlled release of said one or more biocides.

[0134] The content of the compound of formula IA and / or IB in the antifouling coating of the present invention is from about 1 to about 25 wt%, preferably from about 3 to about 20 wt%, more preferably from about 4 to about 18 wt%, and most preferably from about 5 to about 15 wt%.

[0135] 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 coatings of the present invention. The total content of one or more biocides in the antifouling coatings 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%.

[0136] The total CuPT content 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%.

[0137] The total Cu2O content 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%.

[0138] Therefore, the levels of toxic metal compounds (especially Cu2O) are kept very low, or even avoided altogether.

[0139] The present invention further provides a method for suppressing marine biofouling on a solid surface, characterized by applying an antifouling coating comprising the antifouling composition of the present invention to the surface. The solid surface can be any solid surface of an underwater object (e.g., a ship, aquaculture nets, underwater structures and equipment, tanks, offshore buildings, pipelines, nets, docks, piles or columns, etc.).

[0140] The present invention will be further described below with reference to the embodiments, but it should be understood that the present invention is not limited to these embodiments in any way.

[0141] Example

[0142] Example 1: Preparation of an exemplary polymer-based adhesive for antifouling coatings

[0143] Various exemplary polymer-based adhesives that can be used in self-polishing antifouling coatings or hybrid coatings have been prepared as outlined below.

[0144] Example 1A: Synthesis of acrylate polymer “acidic acrylate with low acid value” (referred to herein as “Ac(AV=100-)”)

[0145]

[0146] Example 1B: Synthesis of acrylate polymer “Acid Acrylate 100 Acid Value” (referred to herein as “Ac(AV=100)”)

[0147]

[0148] Example 1C: Synthesis of adhesive components using acrylate polymer "Ac(AV=100-)" to obtain zinc acrylate polymer (referred to herein as "Zn-Ac(AV=100-)")

[0149]

[0150] Example 1D: Synthesis of adhesive components using acrylate polymer "Ac(AV=100)" to obtain zinc acrylate polymer (referred to herein as "Zn-Ac(AV=100)")

[0151]

[0152] Example 1E: Synthesis of a standard TIPX adhesive component of a silyl acrylate polymer (referred to herein as "Si-Ac")

[0153]

[0154] Example 1F: Synthesis of a low-grade TIPX adhesive component of silyl acrylate polymer (referred to herein as "Si-Ac(TIPX-L)")

[0155]

[0156]

[0157] Example 2: Efficacy of Cu2O and the compounds of the present invention in antifouling coatings

[0158] To confirm that the presence of the compound of formula IA or IB of the present invention in the antifouling coating can significantly reduce the amount of Cu2O, the efficacy of a group of ablative antifouling coatings was evaluated by immersing the experimental panels with the coating applied into the seawater of the test raft.

[0159] Various ablation antifouling coatings have been prepared for this purpose, which a) contain only the IA or IB compound of the present invention (i.e., without a biocide), b) contain the IA or IB compound of the present invention together with a biocide (i.e., Cu2O), c) contain only a biocide (i.e., Cu2O, or Cu2O together with CuPT as “positive control coatings”), and d) contain neither a biocide nor the IA or IB compound (“negative control coatings”).

[0160] The compounds of the present invention used in this embodiment are described in Table 1 below. Detailed formulations of the coatings are described in Tables 2 to 4 below. The coatings have been applied to the PVC panel as follows.

[0161] Each panel is divided into three sections and coated with three different concentrations (i.e., 25% v / v, 15% v / v, and 5% v / v) of corresponding coatings (i.e., containing a biocide, or the compounds of the present invention, or a biocide together with the compounds of the present invention). The concentrations of these components are as follows: Figures 1 to 3 As shown.

[0162] Results: Results after immersion in seawater for predetermined periods (1, 4, or 6 months, as shown below) are presented. Figure 1 , Figure 2 and Figure 3 .

[0163] Figure 1 :

[0164] Panel 1 depicts a panel coated with an antifouling paint formulation containing only Cu2O, as shown in Table 2 below. These three sections represent three areas on a panel treated with paints containing different concentrations of Cu2O. The paint applied to section 1 contains 15% v / v Cu2O, and the paint applied to section 2 of the panel contains 5% v / v Cu2O. The last section of Panel 1 (emphasized by a square) is a negative control of the panel with the paint applied, where the paint contains no antifouling components, i.e., neither biocides nor compounds of formula IA or IB. Figure 1 Panels 6 and 12 in the diagram are negative controls for untreated PVC panels. Figure 1 Panels 2 to 5 and 7 to 10 are similar to... Figure 1 The coatings shown contain compounds of formula IA or IB at different concentrations.

[0165] Figure 2 :

[0166] In each trial (i.e., in Nagasaki, Himeji, and Onagawa), Figure 2 Panel 1 is a panel coated with a Cu2O-only antifouling paint formulation as shown in Table 3 below. The concentrations of the components in the paint applied to the three parts of the panel are as follows: Figure 2 As shown. Concentrations are 25%, 15%, and 5% by volume. Figure 2 Panel 6 in each test served as a negative control for untreated PVC panels. Panel 4 in each test resembled a coating with 25% v / v CuPt in Part 1; a coating with 5% v / v Cu2O and 25% CuPt in Part 2; and a coating with 5% v / v Cu2O and 15% v / v CuPt in Part 3. Panel 5 in each test resembled a coating with 25% v / v ZnETFAA in Part 1; a coating with 5% v / v Cu2O and 25% ZnETFAA in Part 2; and a coating with 5% v / v Cu2O and 15% v / v ZnETFAA in Part 3.

[0167] Figure 3 :

[0168] Figure 3 Panels 7 and 10 are coated only with the Cu2O and Cu2O / CuPT antifouling coating formulations shown in Table 3 below. The concentrations are 25%, 15%, and 5% by volume, respectively. Figure 3Panel 12 is a negative control for an untreated PVC panel. Panels 1 through 6 in Part 1 are similar to coatings having 25% v / v of the compounds of the present invention (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 shown). Figure 3 (and as shown in Table 1 below); in Part 2, it is similar to a coating having 5% v / v Cu2O and 25% of the compound of the present invention, and in Part 3, it is similar to a coating having 5% v / v Cu2O and 15% v / v of the compound of the present invention.

[0169] Compared to untreated panels and solid color paints, all portions of panels coated with different concentrations of the compounds of the present invention showed improved stain resistance.

[0170] All evaluated derivatives showed an overall trend of improving the performance of antifouling coatings.

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

Claims

1. Antifouling compositions containing IA and / or IB compounds in Me stands for metal; R1 is F in each case, or in the three R1s, two are F and one is H; R2 is independently selected from NH, O, S and Se; R3 is NH, N(R4), O, S, and Se; R4 is hydrogen, or a straight-chain 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, linear or branched C. 1-20 Alkyl, C 2-20 alkenyl, C 2-20 alkynyl group, C 3-12 cycloalkyl, C 6-20 Aryl and C 7-20 Aryl groups; or R5 and R6 together form the groups =O, =S, =Se, =NR4, =C(R4)2, =C(R4)(OR4), and =C(R4)(NHR4). The antifouling composition therein does not contain Cu(ETFAA)2, and The antifouling composition further comprises CuPT, and The weight ratio of the IA and / or IB compounds to CuPT is 10:1 to 1:

10.

2. The antifouling composition of claim 1, wherein Me represents Cu, Zn, Ca, Mg or Mn.

3. The antifouling composition of claim 1, wherein in the compound of formula IA and / or IB Me represents Cu, Zn, Ca, Mg, or Mn; R2 is independently selected from NH, O and S; R3 is NH, N(R4), O, and S; R4 is H, straight-chain or branched C. 1-12 Alkyl, C 2-12 alkenyl, C 2-12 alkynyl group, C 3-8 cycloalkyl, C 6-12 Aryl, C 7-12 Aryl groups; R5 and R6 are each independently selected from H, linear or branched C. 1-4 Alkyl, C 2-4 alkenyl, C 2-4 alkynyl group, C 3-6 cycloalkyl, C 6-12 Aryl and C 7-12 Aryl alkyl; or R5 and R6 together form the groups =O, =S, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4).

4. The antifouling composition according to any one of claims 1-3, wherein in the compound of formula IA and / or IB Me represents Cu or Zn; R2 is independently selected from NH and O; R3 is N(R4) and O; R4 represents 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; 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 following groups: =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).

5. The antifouling composition according to any one of claims 1-3, further comprising one or more biocides, wherein the one or more biocides are selected from the group consisting of: 2-pyridinethiol-1-copper oxide, 2-pyridinethiol-1-zinc oxide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, Cu2O, zinc oxide, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-onitrile, ethane-1,2-dimethylbis(dithiocarbamate) zinc, N,N-dimethylaminodithioester zinc, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, copper thiocyanate (I), 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazolium, triazine, halothane, and 2,4,5,6-tetrachloroisophthalonitrile.

6. The antifouling composition according to claim 5, wherein the one or more biocides are selected from 2-pyridinethiol-1-zinc oxide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, Cu2O and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-onitrile.

7. The antifouling composition of claim 6, wherein the one or more biocides are selected from Cu2O.

8. Use of the antifouling composition as described in any of the preceding claims for inhibiting marine biofouling on solid surfaces.

9. The use as claimed in claim 8, wherein the antifouling composition is used in combination with polymers and / or copolymers that allow controlled release of IA and / or IB compounds.

10. An antifouling coating comprising an antifouling composition as described in any one of claims 1 to 7 and a polymer and / or copolymer that allows controlled release of IA and / or IB compounds.

11. The antifouling coating of claim 10, wherein the content of the compound of formula IA and / or IB is 1 to 25 wt%.

12. The antifouling coating as described in any one of claims 10 or 11, wherein when it contains one or more biocides, the total content of the one or more biocides is less than 30 wt%.

13. A method for suppressing marine biofouling on a solid surface, comprising applying an antifouling coating as described in any one of claims 10 to 12 to said surface.

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