Compositions for antifouling protection

Abstract

To provide ecologically and economically improved marine antifouling paints with reduced copper content or that fully replace cuprous oxide in conventionally used antifouling paints.SOLUTION: The present invention relates to antifouling compositions that are highly effective against marine biofouling of surfaces of ships and marine structures and comprise compounds such as ethyl 4,4,4-trifluoroacetoacetate and / or a zinc complex thereof, and their use for inhibiting marine biofouling, as well as antifouling paints comprising the compositions.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to antifouling compositions comprising compounds of formula IA and / or IB which are highly effective against marine biofouling on the surfaces of ships and marine structures, their use for controlling marine biofouling and antifouling paints comprising the compositions. [Background technology]

[0002] Ships, aquaculture nets, underwater structures and equipment are susceptible to attack by marine organisms such as barnacles, bryozoans, hydroids, mussels and algae. The organisms grow and reproduce, eventually causing serious problems. For example, in the case of a ship's hull, the growth of marine organisms on the hull can increase the frictional resistance between the hull and the water, which can increase fuel consumption and slow the ship's speed. Ship's hull needs to be protected against the growth of marine organisms to keep it clean and smooth for maximum fuel efficiency. There is also concern about transporting marine organisms from one part of the world to another, where invasive organisms can destroy native ecosystems. Therefore, for the underwater parts, adequate protection against marine organism fouling is required, which is typically achieved by anti-fouling paints.

[0003] The binder systems used in such antifouling paints are typically composed of an erodible binder. Erosion of the paint film helps prevent fouling by releasing antifouling agents (biocides) from the coating over time, thus impeding the attachment of fouling organisms. There are two main types of erodible antifouling coatings, described by the industry as "self-polishing" and "disintegrating".

[0004] The binder system of the disintegrating coating consists mostly of rosin, which reacts with seawater to become water soluble and erode away. Alternatively, rosin or rosin derivatives are also used in mixtures with non-eroding binders such as polyester resins, acrylic resins, epoxy resins, polyvinyl 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 by either metal carbonate acrylate monomers or silyl acrylate monomers. Erodible polyester binders are also used, resulting in lower cost antifouling paints. The difference between disintegrating and self-polishing coatings is mainly in the thickness of the leaching layer and the more linear rate of erosion over time for self-polishing coatings.

[0006] There are also "hybrid coatings" where the binder system consists of erodible acrylates and rosin, such as in self-polishing paints. The thickness of the leaching layer is less than in disintegrating coatings, but greater than in true self-polishing coatings.

[0007] Most commercial antifouling paints contain high metal content, typically about 40% by weight, due to the high concentration of copper(I) oxide (Cu2O) used as a biocide therein. Copper(I) oxide is potentially harmful to many organisms. Leaching from antifouling paints can contribute to elevated copper levels in water, sediments and the surrounding environment. Artificially high copper levels can have significant ecological impacts. Cu2O is very widely used in antifouling paints as an antifouling agent, but Cu2O alone is only effective against hard fouling organisms such as barnacles, so antifouling paints may also contain additional biocides.

[0008] As an additional drawback, copper(I) oxide typically imparts a strong reddish-brown color to antifouling paint coatings and can react with carbon dioxide in the atmosphere and chlorides from seawater to form uneven streaks on the surface of the coating, an unattractive appearance that can occur, for example, shortly after a vessel is launched into the sea. Some yacht owners and cruise ship operators prefer the bright colors and uniform appearance that cannot be obtained with paints containing copper(I) oxide.

[0009] Attempts to replace copper(I) oxide in commercial antifouling paints have led to the development of alternatives to copper(I) oxide, such as the white copper thiocyanate and tralopyril, an agricultural pesticide with efficacy against barnacles, but these alternatives are costly and not as effective as copper(I) oxide-based antifouling paints. Summary of the Invention [Problem to be solved by the invention]

[0010] There is therefore a need for ecologically and economically improved marine antifouling paints in which the copper content in conventionally used antifouling paints is reduced or even completely replaces copper(I) oxide. [Means for solving the problem]

[0011] The antifouling compositions of the present invention comprising compounds of formula IA and / or IB meet this need. The inventors have surprisingly found that compounds of formula IA and / or IB are both highly effective and versatile agents for enhancing the antifouling performance of all types of antifouling paints, such as disintegrating or self-polishing paints, and can also be used in simple contact leaching coatings.

[0012] Thus, it is now possible to partially or completely replace Cu2O in antifouling paints, and therefore dramatically reduce the metal content therein, while maintaining adequate antifouling performance. Furthermore, the antifouling compositions of the present invention, including compounds of formula IA and / or IB, are essentially colorless, and therefore do not interfere with the bright colors often desired for marine hulls. [Brief description of the drawings]

[0013] [Figure 1] Figure 2 shows a panel coated with the antifouling paint of Example 2, Table 1. The figure shows the appearance of the panel after 6 months in seawater (Himeji, 1.5 m depth). The black square indicates the area for the negative control, i.e. the coating without any antifouling components. [Diagram 2] Figure 2 shows panels coated with the antifouling paint of Example 2, Table 2. The figure shows the appearance of the panels after 4 months in seawater (Himeji, Nagasaki and Onagawa). Panel 6 of the "Nagasaki" and "Himeji" trials respectively shows a panel after 1 month in seawater. Panel 6 of the "Onagawa" trial shows a panel after 4 months in seawater. [Diagram 3] Figure 2 shows a panel coated with the antifouling paint of Example 2, Table 3. The figure shows the appearance of the panel after one month in seawater (Nagasaki, 1.5 m depth). The black square indicates the area for the negative control, i.e. the coating without any antifouling components. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] 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 this invention pertains. The following abbreviations and terms are used herein: AIBN: Azobis(isobutyronitrile) AMBN: Azobis-(2-methylbutyronitrile) A630-20X: Fatty acid amide BA: Butyl acrylate Chlorothalonil: 2,4,5,6-tetrachlorobenzene-1,3-dicarbonitrile Copper Omadine®, CuPT, Copper Pyrithione: 2-Pyridinethiol-1-oxide Copper Cu2O: Copper(I) oxide CuSCN: Copper(I) thiocyanate DCOIT: 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one Diuron: 3-(3,4-dichlorophenyl)-1,1-dimethylurea Disparlon A650-20x: Synthetic polyamide wax dispersion. Acts as an excellent suspending agent for heavy pigments and metallics. Has high shear thinning properties resulting in excellent application properties. ETFAA: Ethyl 4,4,4-trifluoroacetoacetate Laroflex® MP 25: Copolymer of vinyl chloride and vinyl isobutyl ether 2MEA: 2-Methoxyethyl acrylate monomer Medetomidine: 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole MMA: Methyl methacrylate monomer MIBK: Methyl isobutyl ketone MPM: Methoxypropylene monomer PGM: Propylene glycol monomethyl ether TIPX: Triisopropylsilyl acrylate monomer Tralopyril: 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile VAGH: Vinyl chloride / vinyl acetate / vinyl alcohol copolymer (commercially available) Zineb: Ethan-1,2-diylbis(dithiocarbamate) zinc Ziram: Zinc N,N-dimethylcarbamodithioate Zn(ETFAA)2: Di(ethyl 4,4,4-trifluoroacetoacetate)zinc, also referred to herein as ZnETFAA ZnO: Zinc oxide ZnPT: Zinc pyrithione: 2-pyridinethiol-1-oxide zinc The term "(meth)acrylate" is a collective name that refers to both acrylate and methacrylate monomers. The terms "methacrylate" or "meth-acrylate" refer only to methacrylate monomers.

[0015] Bentone SD2 is an organoclay added for anti-settling properties, Bentone #38 is a quaternium 18-hectorite clay, and Minex 4 is a nepheline syenite clay. Disparlon 6900-20x (A630-20X polyamide wax) is a 20% dispersion in xylene of polyamide wax used as a rheology modifier, and Disperbyk 161 is a dispersing additive. Resin refers to any prepolymer or polymer that can serve as a raw material for the binder used in the antifouling paint of the present invention. Rosin or gum rosin refers to colophony (CAS: 8050-09-7, see also https: / / www.megaglori.com / what-is-gum-rosin / ).

[0016] "Biocide" means any chemical compound that prevents the establishment and / or growth of marine life on a surface and / or helps repel marine life from a surface.

[0017] The terms "antifouling paint", "antifouling coating" and "antifouling formulation" are used interchangeably herein.

[0018] The present invention provides a new approach to inhibit fouling of the surface of underwater objects such as the hull of a ship or any other marine structure. In particular, the present invention provides a compound represented by the formula IA and / or IB

[0019] [ka] [In the formula, Me represents a metal, preferably Cu, Zn, Co, Ni, Ca, Mg or Mn; R1 may be any functionality that provides, for example, high hydrophobicity, R1 is 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 arylalkyl; Each R2 is independently selected from NH, O, S, and Se; R3 is NH, N(R4), O, S, or Se; R4 is hydrogen, linear or branched C 1~20 Alkyl, C 2~20 Alkenyl, C 2~20 Alkynyl, C 3~12 Cycloalkyl, C 6~20 Aryl, C 7~20 is arylalkyl, R5 and R6 are each H, a straight or branched chain C 1~20 Alkyl, C 2~20 Alkenyl, C 2~20 Alkynyl, C 3~12 Cycloalkyl, C 6~20 Aryl and C 7~20 arylalkyl; or R5 and R6 together form a =O, =S, =Se, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4) group. The present invention provides an antifouling composition comprising a compound of the formula:

[0020] In one embodiment, the present invention provides a compound of formula IA and / or IB as depicted above. [In the formula, Me represents Cu, Zn, Ca, Mg or Mn; R1 is 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 arylalkyl; Each R2 is independently selected from NH, O, and S; R3 is NH, N(R4), O and S; R4 is H, linear 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 is arylalkyl, R5 and R6 are each H, a straight or branched chain C 1~4 Alkyl, C 2~4 Alkenyl, C 2~4 Alkynyl, C 3~6 Cycloalkyl, C 6~12 Aryl and C 7~12 arylalkyl; or R5 and R6 together form a =O, =S, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4) group. The present invention provides an antifouling composition comprising a compound of the formula:

[0021] In one embodiment, the present invention provides a compound of formula IA and / or IB as depicted above. [In the formula, Me represents Cu or Zn; R1 is H, F, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12 independently selected from alkyl and benzyl; Each R2 is independently selected from NH and O; R3 is N(R4) and O; R4 is H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C12 alkyl and benzyl; R5 and R6 are each independently selected from H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl and benzyl; or R5 and R6 together form =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) groups. The present invention provides an antifouling composition comprising a compound of the formula:

[0022] In one embodiment, the present invention provides a compound of formula IA and / or IB as depicted above. [In the formula, Me represents Cu or Zn; Each R1 is independently selected from H and F; Each R2 is independently selected from NH and O; R3 is N(CH3), N(C2H5) and O; R4 is H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12 alkyl and benzyl; R5 and R6 are each H; or R5 and R6 together form =CH(OCH3); =CH(OC2H5), =CH(NHCH3); =CH(NHC2H5) groups. The present invention provides an antifouling composition comprising a compound of the formula:

[0023] In one embodiment, the compound of formula IB is as defined above, except that when Me is Cu, each R1 is F, each R2 is O, R3 is O, R5 and R6 are each H, and R4 is not ethyl.

[0024] Suitable compounds of formula IA and IB, respectively, are, for example Ethyl 3-amino-4,4,4-trifluorocrotonate; [Ethyl 3-amino-4,4,4-trifluorocrotonate]2Zn, [Ethyl 3-amino-4,4,4-trifluorocrotonate]2Cu, Ethyl 3-amino-2-methylene-(methylamino)-4,4-difluorocrotonate, [Ethyl 3-amino-2-methylene-(methylamino)-4,4-difluorocrotonate]2Zn, [Ethyl 3-amino-2-methylene-(methylamino)-4,4-difluorocrotonate]2Cu 4,4,4-trifluoro-N,N-dimethyl-3-oxobutanamide; [4,4,4-trifluoro-N,N-dimethyl-3-oxobutanamide]2Cu, [4,4,4-trifluoro-N,N-dimethyl-3-oxobutanamide]2Zn, dodecyl 4,4,4-trifluoro-3-oxobutanoate, [Dodecyl 4,4,4-trifluoro-3-oxobutanoate]2Zn, Dodecyl 4,4,4-trifluoro-3-oxobutanoate]2Cu, benzyl 4,4,4-trifluoroacetoacetate, [Benzyl 4,4,4-trifluoroacetoacetate]2Zn, [benzyl 4,4,4-trifluoroacetoacetate]2Cu, Octyl 4,4,4-trifluoroacetoacetate, [Octyl 4,4,4-trifluoroacetoacetate]2Zn, [Octyl 4,4,4-trifluoroacetoacetate]2Cu, isopropyl 4,4,4-trifluoroacetoacetate, [Isopropyl 4,4,4-trifluoroacetoacetate]2Zn, [Isopropyl 4,4,4-trifluoroacetoacetate]2Cu, Ethyl 4,4,4-trifluoroacetoacetate, [Ethyl 4,4,4-trifluoroacetoacetate]2Zn tert-butyl 4,4,4-trifluoro-3-oxobutanoate, [tert-butyl 4,4,4-trifluoro-3-oxobutanoate]2Zn, [tert-Butyl 4,4,4-trifluoro-3-oxobutanoate]2Cu It is.

[0025] 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.

[0026] Surprisingly, it has been found that compounds of formulae IA and IB significantly enhance the antifouling effectiveness of antifouling compositions against colonization by marine organisms such as barnacles, bryozoans, hydroids, mussels and algae.

[0027] The antifouling compositions of the present invention may further comprise one or more biocides capable of preventing fouling on the surface of an object.

[0028] Such biocides may be inorganic, organometallic or organic biocides.

[0029] Examples of inorganic biocides are copper and copper compounds such as copper oxides, e.g., copper(I) oxide and copper(II) oxide; copper alloys, e.g., copper-nickel alloys; copper salts, e.g., copper thiocyanate (CuSCN), copper sulfide; or barium metaborate.

[0030] Examples of organometallic biocides are zinc 2-pyridinethiol-1-oxide [ZnPT, zinc pyrithione]; organocopper compounds such as copper 2-pyridinethiol-1-oxide [CuPT, copper pyrithione], copper acetate, copper naphthenate, copper 8-uinolinonate [oxine-copper], copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzenesulfonate) and copper bis(pentachlorophenolate); dithiocarbamate compounds such as zinc N,N-dimethylcarbamodithioate [ziram], zinc ethane-1,2-diylbis(dithiocarbamate) [zineb], manganese ethylenebis(dithiocarbamate) [maneb] or manganese ethylenebis(dithiocarbamate) complexed with a zinc salt [mancozeb].

[0031] Examples of organic biocides are heterocyclic compounds such as 2-(tert-butylamino)-4-(cyclopropylamine)-6-(methylthio)-1,3,5-triazine [sibutrin], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 1,2-benzisothiazolin-3-one [BIT], 2-(thiocyanatomethylthio)-1,3-benzothiazole [bentiazole], 3-benzo[b]thien-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide [bethoxadin] and 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; urea derivatives such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea [diuron]; amides and imides of carboxylic, sulfonic and sulfenic acids such as N -(dichlorofluoromethylthio)phthalimide, N-dichlorofluoromethylthio-N',N'-dimethyi-N-phenylsulfamide [dichlfluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide [tolylfluanid] and N-(2,4,6-trichlorophenyl)maleimide; other organic compounds, such as pyridinetriphenylborane, aminetriphenylborane, 3-iodo-2-propynyl-N-butylcarbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile [chlorothalinyl], p-((diiodomethyl)sulfonyl)toluene or 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril].

[0032] Other examples of biocides are tetraalkylphosphonium halides, guanidine derivatives, imidazole-containing compounds such as 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine] and derivatives, avermectins and their derivatives, such as ivermectin, or macrocyclic lactones including spinosyns and their derivatives, such as spinosad, or enzymes, such as oxidases or enzymes which are proteolytically, hemicellulolytically, cellulolytically, lipolytically or amylolytically active.

[0033] In one embodiment, the antifouling composition of the present invention comprises a compound of formula IA and / or IB as defined above, as well as copper 2-pyridinethiol-1-oxide (CuPT, copper pyrithione), zinc 2-pyridinethiol-1-oxide (ZnPT, zinc pyrithione), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), copper(I) oxide (CuO), zinc oxide (ZnO), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (tralopyri), and one or more additional biocides selected from the group consisting of zinc ethane-1,2-diylbis(dithiocarbamate) (zineb), zinc N,N-dimethylcarbamodithioate (ziram), 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), copper(I) thiocyanate (CuSCN), 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (medetomidine), triazines, fluanids, and 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil).

[0034] 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 tralopyril.

[0035] In a more preferred embodiment, the antifouling composition of the invention comprises compounds of formulae IA and / or IB as defined above and one or more biocides selected from the group consisting of CuPT and Cu2O. The ratio of compounds of formulae IA and / or IB (wt%) to CuPT (wt%) and / or the ratio of compounds of formulae IA and / or IB (wt%) to Cu2O (wt%) is advantageously between 100:1 and 1:100, preferably between 15:1 and 1:15 and most preferably between 5:1 and 1:5.

[0036] In a particular embodiment, the antifouling composition of the invention comprises a compound of formula IA and / or IB and CuPT. The ratio of compound of formula IA and / or IB (wt%) to CuPT (wt%) is advantageously between 100:1 and 1:100, preferably between 10:1 and 1:10, and most preferably between 5:1 and 1:5.

[0037] In another detailed embodiment, the antifouling composition of the invention comprises a compound of formula IA and / or IB and Cu2O. The ratio of compound of formula IA and / or IB (wt%) to Cu2O (wt%) is advantageously between 100:1 and 1:100, preferably between 10:1 and 1:10, and most preferably between 5:1 and 1:5.

[0038] In a more particular embodiment, the antifouling composition of the present invention comprises a compound of formula IA and / or IB, CuPT and CuO, wherein the ratio of the compound of formula IA and / or IB (wt%) to CuPT (wt%) is from 5:1 to 1:5 and the ratio of the compound of formula IA and / or IB (wt%) to CuO (wt%) is from 5:1 to 1:5.

[0039] In another detailed embodiment, the antifouling composition of the present invention comprises a compound of formula IA and / or IB and CuPT and is free of CuO, and the ratio of compound of formula IA and / or IB (wt%) to CuPT (wt%) is from 5:1 to 1:5.

[0040] 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 essentially colorless and therefore do not interfere with the bright colors often desired for marine hulls.

[0041] The present invention further provides the use of the antifouling composition of the present invention for the inhibition of marine biological fouling on a solid surface, which may be any solid surface such as an underwater object, for example a ship, an aquaculture fishing net, a submerged structure and rigging, a tank, an offshore structure, a pipe, a net, a pier or a piling or pole.

[0042] The antifouling compositions of the present invention may further be used in combination with polymers and / or copolymers that allow for the controlled release of the compounds of formula IA and / or IB contained therein, as well as self-polishing or disintegrating coatings, and, if present, also allow for the controlled release of one or more biocides (e.g., by releasing these agents over time from the antifouling coating).

[0043] The inventors have surprisingly found that the compounds of formula IA and / or IB are versatile agents that can be used in all types of antifouling coatings, i.e., antifouling coatings based on a variety of different polymers and / or copolymers that are typically used as binders for antifouling coating compositions. Thus, the polymers and / or copolymers that allow the controlled release of the compounds of formula IA and / or IB contained therein, and also the controlled release of one or more biocides, if present, can be any polymers and / or copolymers that are typically used as binders in antifouling coatings. Polymers and / or copolymers suitable for this purpose are known to those skilled in the art. Depending on the amount and type of binder used, the compounds of formula IA and / or IB and one or more biocides are released in a controlled manner at a predetermined desired rate, for example, suitable for the sailing pattern of a ship.

[0044] For example, the polymers and / or copolymers enabling the controlled release of the compounds of formula IA and / or IB and one or more biocides used as binders in the "self-polishing antifouling coating" may be hydrolyzable acrylate polymers, such as (meth)acrylate-based polymers and / or copolymers. The (meth)acrylate monomer portion in the (meth)acrylate polymers and / or copolymers can be alkyl (meth)acrylates, such as methyl (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, iso-octyl (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; or may be an alkoxyalkyl (meth)acrylate, 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; as well as phenoxyethyl (meth)acrylate; or a hydroxyalkyl (meth)acrylate, such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate or 2-hydroxy-3-phenoxypropyl (meth)acrylate; The (meth)acrylate monomer moiety in the (meth)acrylate polymers and / or copolymers may further be a silyl (meth)acrylate, such as tribenzylsilyl (meth)acrylate, trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-isopropylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, tri-isobutylsilyl (meth)acrylate, tri-t-butylsilyl (meth)acrylate, tri-n-amylsilyl (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; The (meth)acrylate polymers and / or copolymers may also include a metal salt moiety of acrylic acid or methacrylic acid, referred to herein as a “metal salt (meth)acrylate.” 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.

[0045] The polymers and / or copolymers that allow for the controlled release of the compounds of formula IA and / or IB, and, if present, also for the controlled release of one or more biocides, may be VAGH copolymers. The VAGH copolymers may be dissolved in 2:3 xylene:MIBK.

[0046] Thus, in one embodiment, the polymer and / or copolymer allowing for the controlled release of the compounds of formula IA and / or IB and, if present, also for the controlled release of 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)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, zinc (meth)acrylate and silyl (meth)acrylate; 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 methacrylate and tri-isopropylsilyl acrylate, preferably (meth)acrylate. The (meth)acrylate polymer and / or copolymer may be a copolymer of a monomer portion selected from the group consisting of ethyl acrylate, methyl methacrylate, and zinc methacrylate, more preferably the (meth)acrylate polymer and / or copolymer may be a copolymer of a monomer portion selected from the group consisting of ethyl acrylate, methyl methacrylate, 2-methoxyethyl acrylate, and zinc methacrylate, and most preferably the (meth)acrylate polymer and / or copolymer may be a copolymer of a monomer portion selected from the group consisting of methyl methacrylate, butyl acrylate, 2-methoxyethyl acrylate, and tri-isopropylsilyl acrylate.

[0047] The present invention therefore further provides an antifouling paint comprising the antifouling composition of the present invention and a polymer and / or copolymer allowing the controlled release of the compounds of formula IA and / or IB and, if present, also of one or more biocides.

[0048] The content of the compound of formula IA and / or IB in the antifouling coating material of the present invention is about 1 to about 25% by weight, preferably about 3 to about 20% by weight, more preferably about 4 to about 18% by weight, and most preferably about 5 to about 15% by weight.

[0049] Due to the excellent reinforcing properties of the compounds of formula IA and / or IB, only small amounts of one or more biocides are required in the antifouling paint of the present invention. The total content of one or more biocides in the antifouling paint of the present invention is less than about 30% by weight, preferably less than about 25% by weight, more preferably less than about 20% by weight, and most preferably less than about 18% by weight.

[0050] The total CuPT content in the antifouling coating of the present invention is less than about 10% by weight, more preferably less than about 8% by weight, and most preferably less than about 7% by weight.

[0051] The total content of Cu2O in the antifouling coating of the present invention is less than about 20% by weight, more preferably less than about 15% by weight, and most preferably less than about 12% by weight.

[0052] Therefore, the content of toxic metal compounds, especially Cu2O, is kept at very low levels and may even be avoided.

[0053] The present invention further provides a method for inhibiting marine biofouling on a solid surface, comprising applying to said surface an antifouling coating comprising the antifouling composition of the present invention. The solid surface may be any solid surface such as underwater objects, e.g., ships, aquaculture fishing nets, underwater structures and rigging, tanks, offshore structures, pipes, nets, piers, and pilings or poles.

[0054] In the following, the present invention will be further described with reference to examples, but it should be construed that the present invention is in no way limited to these examples. EXAMPLES

[0055] Example 1: Preparation of an exemplary polymeric binder for antifouling paints Different exemplary polymeric binders that can be used in self-polishing antifouling paints or hybrid coatings were prepared as outlined below.

[0056] Example 1A: Synthesis of acrylate polymer "acid acrylate low acid value", referred to herein as "Ac(AV=100-)"

[0057] [Table 1]

[0058] Example 1B: Synthesis of Acrylate Polymer "Acid Acrylate 100 Acid Value", referred to herein as "Ac(AV=100)"

[0059] [Table 2]

[0060] Example 1C: Synthesis of a binder component using acrylate polymer "Ac(AV=100-)" to give a zinc acrylate polymer referred to herein as "Zn-Ac(AV=100-)".

[0061] [Table 3]

[0062] Example 1D: Synthesis of a binder component using acrylate polymer "Ac(AV=100)" to give a zinc acrylate polymer referred to herein as "Zn-Ac(AV=100)".

[0063] [Table 4]

[0064] Example 1E: Synthesis of a silyl acrylate polymer standard TIPX binder component, referred to herein as "Si-Ac"

[0065] [Table 5]

[0066] Example 1F: Synthesis of a silyl acrylate polymer low-TIPX binder component, referred to herein as "Si-Ac(TIPX-L)"

[0067] [Table 6]

[0068] Example 2: Efficacy of CuO and the compound of the present invention in antifouling paints To confirm that the amount of Cu2O can be significantly reduced when the compounds of formula IA or IB of the present invention are present in antifouling paints, the effectiveness of a series of disintegrating antifouling paints was evaluated by immersing experimental painted panels in seawater on a test raft.

[0069] For this purpose, various disintegrating antifouling paints were prepared: a) containing only the inventive compound IA or IB (i.e. without biocide), b) containing the inventive compound IA or IB together with a biocide (i.e. CuO), c) containing only a biocide (i.e. CuO or CuPT together with CuO, respectively, as "positive control paints"), and d) without a biocide and without the compound IA or IB ("negative control paints").

[0070] The compounds of the present invention used in this example are shown below in Table 1. Detailed formulations of the paints are shown below in Tables 2-4. The paints were applied to PVC panels as follows:

[0071] Each panel was divided into three sections and coated with the respective paint (i.e., containing either a biocide or a compound of the present invention, or containing a compound of the present invention together with a biocide) at three different concentrations, i.e., 25% v / v, 15% v / v, and 5% v / v, respectively. The concentrations of these components are shown in Figures 1-3.

[0072] Results: After immersion in seawater for the indicated times (1, 4 or 6 months as indicated below), the results are shown in Figures 1, 2 and 3.

[0073] Figure 1: Panel 1 illustrates a panel painted with an antifouling paint containing only Cu2O, as shown in Table 2 below. The three sections show three areas of the panel treated with paint containing Cu2O at different concentrations. The paint applied to section 1 contained 15% vol / vol Cu2O, and the paint applied to section 2 of the panel contained 5% vol / vol Cu2O. The last section of panel 1 (highlighted by a rectangle) is a negative control painted panel in which the paint does not contain any antifouling active ingredient, i.e., no biocide or compound of formula IA or IB. Panels 6 and 12 in Figure 1 are negative control untreated PVC panels. Panels 2-5 and 7-10 in Figure 1 are similar to the paint containing the compound of formula IA or IB at different concentrations, as shown in Figure 1.

[0074] Figure 2: In FIG. 2, Panel 1 in each of the trials, Nagasaki, Himeji, and Onagawa, is a painted panel with an antifouling paint formulated with Cu2O only, as shown in Table 3 below. The concentrations of the components in the paint applied to the three sections of the panel are shown in FIG. 2. The concentrations are 25%, 15%, and 5% by volume. Panel 6 in each trial in FIG. 2 is an untreated PVC panel that serves as a negative control. Panel 4 in each trial is similar in that it has a paint with 25% vol / vol CuPT in section 1, a paint with 5% vol / vol Cu2O and 25% CuPT in section 2, and a paint with 5% vol / vol Cu2O and 15% vol / vol CuPT in section 3. Panel 5 in each trial is similar in that it has a paint with 25% vol / vol ZnETFAA in section 1, a paint with 5% vol / vol Cu2O and 25% ZnETFAA in section 2, and a paint with 5% vol / vol Cu2O and 15% vol / vol ZnETFAA in section 3.

[0075] Figure 3: Panels 7 and 10 in FIG. 3 are painted with antifouling paints containing only Cu2O and Cu2O / CuPT, as shown in Table 3 below. The concentrations are 25%, 15%, and 5% by volume. Panel 12 in FIG. 3 is an untreated PVC panel as a negative control. Panels 1-6 are similar in that the paints have 25% volume / volume of the inventive compound in section 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 shown in FIG. 3 and Table 1 below), the paints have 5% volume / volume Cu2O and 25% volume / volume of the inventive compound in section 2, and the paints have 5% volume / volume Cu2O and 15% volume / volume of the inventive compound in section 3.

[0076] All sections of the panels similar to the paints with different concentrations of the compounds of the present invention show improved antifouling performance compared to the untreated panel control and the plain paint control. A general trend was observed in which all derivatives evaluated improved the performance of the antifouling paint.

[0077] [Table 7]

[0078] [Table 8] TIFF0007667208000010.tif254165

[0079] [Table 9]

[0080] [Table 10] TIFF0007667208000013.tif234167

Claims

1. Formula IA and / or IB 【Chemistry 1】 [In the formula, Me represents Cu, Zn, Ca, Mg or Mn; Each R1 is F, or two of the three R1 are F and one is H; each R2 is independently selected from NH, O, and S; R3 is NH, N(R4), O and S; R4 is H, linear 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 is arylalkyl, R5 and R6 are each H, 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 arylalkyl; or R5 and R6 together form =C(R4) ２ , ═C(R4)(OR4), ═C(R4)(NHR4) groups. and one or more biocides, The biocide is CuPT, ZnPT, DCOIT, Cu ２ An antifouling composition selected from the group consisting of O and tralopyril. (However, the compounds of formula IA and / or IB may be represented by the following formula IA and / or IB [In the formula, Me represents Cu or Zn; Each R1 is F, or two of the three R1 are F and one is H; Each R2 is independently selected from NH and O; R3 is N(R4) and O; R4 is H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, C 8 alkyl, C 9 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, i-propyl, n-butyl, i-butyl, tert-butyl and benzyl; or R5 and R6 together form the 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). It is not a compound of.

2. The biocide is CuPT and Cu ２ The antifouling composition of claim 1 , wherein the antifouling composition is selected from the group consisting of O.

3. 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 ２ 3. The antifouling composition according to claim 2, wherein the ratio of O (wt%) is from 100:1 to 1:

100.

4. Use of the antifouling composition according to any one of claims 1 to 3 for the inhibition of marine biological fouling on solid surfaces.

5. 5. Use according to claim 4, wherein the antifouling composition is used in combination with a polymer and / or copolymer allowing the controlled release of the compounds of formula IA and / or IB.

6. An antifouling paint comprising an antifouling composition according to any one of claims 1 to 3 and a polymer and / or copolymer allowing the controlled release of the compounds of formula IA and / or IB.

7. 7. The antifouling paint according to claim 6, wherein the content of the compounds of formula IA and / or IB is 1 to 25% by weight.

8. 8. An antifouling paint according to claim 6 or 7, wherein the total content of the one or more biocides is less than 30% by weight.

9. The antifouling coating material according to any one of claims 6 to 8, wherein the total content of CuPT is less than 10% by weight.

10. A method for inhibiting marine biological fouling on a solid surface, comprising applying to the surface an antifouling coating according to any one of claims 6 to 9.

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