Additive composition for antifouling coatings

Abstract

The present disclosure is generally directed to an additive composition for antifouling coatings. The additive composition includes a superhydrophobic film modifier and a biocide enhancer including one or both of Compound IA and Compound IB. The additive composition can be used to inhibit marine biofouling. Antifouling paints including the additive composition are also provided.

Description

[Background technology]

[0001] Ships, fish farming nets, underwater structures, and underwater equipment are frequently targets for marine organisms such as barnacles, bryozoans, hydrozoans, mussels, and algae. Such organisms can grow, multiply, and eventually cause significant 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, thus increasing fuel consumption and slowing the ship's speed. To keep the hull clean and smooth for maximum fuel efficiency, the hull needs to be protected from the growth of marine organisms. The transportation of marine organisms from one part of the world to another can also introduce invasive organisms and disturb the local ecosystem. Therefore, proper protection against marine biofouling is advantageous for underwater components.

[0002]

[0002] Antifouling paints are often added to underwater parts to limit marine biofouling. The binder systems used in such antifouling paints generally include an erodible binder. Erosion of the paint film helps prevent fouling by releasing biocides from the coating over time, thus inhibiting the attachment of marine organisms. There are two main types of erodible antifouling coatings: self-polishing and ablative.

[0003]

[0003] The binder system of disintegrating coatings mainly includes rosin, which reacts with seawater to become water-soluble and erode. Alternatively, rosin or rosin derivatives are used in mixtures 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. In self-polishing antifouling coatings, the binder system mainly includes hydrolyzable acrylate polymers. The hydrolyzable functionality is generally imparted to the polymer by either metal carboxylate 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 erosion rate over time for self-polishing coatings. There are also hybrid coatings, whose binder system includes erodible acrylate and rosin, like self-polishing paints. The thickness of the leached layer is less than that in disintegrating coatings, but greater than that in pure self-polishing coatings.

[0004]

[0004] Most commercial antifouling paints contain high metal content due to high concentrations of cuprous oxide (Cu2O) used as a biocide, typically about 40% by weight is required for adequate antifouling protection. Cuprous oxide can be harmful to many organisms, and leaching from antifouling paints can cause elevated copper levels in water, sediments, and the surrounding environment. Artificially high copper levels can have a significant impact on ecosystems. While cuprous oxide is widely used as an antifouling agent in antifouling paints, antifouling paints may also contain additional biocides, since cuprous oxide alone is generally only effective against sessile fouling organisms such as barnacles.

[0005]

[0005] There is therefore a need for ecologically and economically improved antifouling coatings which have a reduced biocide content. A reduced copper content would be particularly useful. Summary of the Invention

[0006]

[0001] In general, the present disclosure is directed to additive compositions, for example, additive compositions for use with antifouling coatings. The additive compositions include a superhydrophobic film modifier and a biocide enhancer. Advantageously, the additive compositions of the present disclosure can increase the efficacy of biocides, such as cuprous oxide (Cu2O), and thus reduce the concentration of biocide required for adequate antifouling protection. The additive compositions can improve the antifouling performance of all types of antifouling coatings, such as disintegrating coatings, self-polishing coatings, and hybrid coatings, and can also be used in simple contact leaching coatings. The improved antifouling performance provided by the additive compositions is particularly surprising because, for example, antifouling coatings including the additive compositions may not be superhydrophobic, despite the presence of a superhydrophobic film modifier in the antifouling coating.

[0007]

[0006] An additive composition for an antifouling coating according to an exemplary implementation of the present disclosure includes a superhydrophobic film modifier and a biocide enhancer. The biocide enhancer includes one or both of Compound IA and Compound IB. Compound IA has the formula:

[0008] [ka]

[0009] Alternatively, compound IB may have the formula:

[0010] [ka]

[0011] But often

[0007] In the formula, Me may be Cu, Zn, Co, Ni, Ca, Mg, or Mn;

[0008] In the formula, R1 is independently hydrogen, halogen, linear or branched C 1~20 Alkyl, C 2~20 Alkenyl, C2~20 Alkynyl, C 3~12 Cycloalkyl, C 6~20 Aryl, and C 7~20 It may be selected from arylalkyl.

[0012] wherein each R2 may be independently selected from NH, O, S, and Se; R3 may be NH, N(R4), O, S, or Se;

[0010] In the formula, R4 is hydrogen, a linear or branched C 1~20 Alkyl, C 2~20 Alkenyl, C 2~20 Alkynyl, C 3~12 Cycloalkyl, C 6~20 Aryl, or C 7~20 It may be arylalkyl,

[0011] In the formula, R5 and R6 are each independently H, a straight-chain 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, or R5 and R6 together may form a =O, =S, =Se, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4) group.

[0013] In a first exemplary embodiment: Me can be Cu or Zn; R1 can be, independently, H, F, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclo-butyl, cyclo-pentyl, cyclo-hexyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12R2 may be selected from, independently, NH and O; R3 is N(R4) or O; R4 is H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclo-butyl, cyclo-pentyl, cyclo-hexyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12 R5 and R6 may each independently be selected from H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, and benzyl, or R5 and R6 together may 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), or =CH(NHtertC4H9).

[0014] In a second exemplary embodiment, the weight ratio of the superhydrophobic film modifier to the biocide enhancer is 10:1 to 1:10, preferably 5:1 to 1:5, and most preferably 3:1 to 1:3.

[0015] In a third exemplary embodiment, the additive composition further comprises a biocide, which may be selected from the group consisting of 2-pyridinethiol-1-oxide copper salt (copper pyrithione, CuPT), 2-pyridinethiol-1-oxide zinc salt (zinc pyrithione, ZnPT), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), cuprous oxide (CuO), zinc oxide (ZnO), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (tralopyril), ethane-1,2-diylbis(trifluoromethyl)pyridinethiol, and the like. The biocide enhancer may include one or more of zinc 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, fluanides, and 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil). The weight ratio of biocide enhancer to biocide may be 10:1 to 1:10, preferably 5:1 to 1:5, and most preferably 1:1 to 1:3.

[0016] In a fourth exemplary embodiment, the superhydrophobic film modifier can include porous diatomaceous earth particles coated with a hydrophobic layer.

[0017]

[0016] Each of the exemplary aspects mentioned above can be combined with one or more of the other exemplary aspects mentioned above in a certain embodiment. For example, all of the first, second, third, and fourth exemplary aspects mentioned above can be combined with each other in some embodiments. As another example, any combination of two or three of the first, second, third, and fourth exemplary aspects mentioned above can be combined in other embodiments. Thus, the exemplary aspects mentioned above can be utilized in combination with each other in some exemplary embodiments.

[0018] In a fifth exemplary aspect, a method is provided that includes using an additive composition to inhibit marine biofouling on a solid surface. The antifouling composition may be used in combination with a superhydrophobic film modifier, a biocide enhancer, and a polymer, copolymer, or both a polymer and copolymer to enable controlled release of one or more of the biocides.

[0019]

[0018] In a sixth exemplary embodiment, the antifouling paint comprises an additive composition and a superhydrophobic film modifier, a biocide enhancer, and a polymer, copolymer, or both polymer and copolymer for enabling controlled release of one or more of the biocides. The biocide enhancer can be present in the antifouling paint at about 0.2 wt% to about 20 wt%, preferably about 0.5 wt% to about 10 wt%, and more preferably about 1 wt% to about 5 wt%. The biocide can be present in the antifouling paint at less than about 30 wt%. The superhydrophobic film modifier can be present in the antifouling paint at about 0.2 wt% to about 20 wt%, preferably about 0.5 wt% to about 10 wt%, and more preferably about 1 wt% to about 5 wt%. The antifouling paint does not have to be superhydrophobic.

[0020] In a seventh exemplary embodiment, a method for inhibiting marine biofouling on a solid surface includes applying an antifouling paint onto the solid surface.

[0021]

[0002] Other features and aspects of the present disclosure are described in more detail below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022]

[0003] It should be understood by those skilled in the art that this disclosure is a description of exemplary embodiments only and is not intended to limit the broad aspects of the present disclosure.

[0023]

[0004] The present disclosure is generally directed to an additive composition for antifouling coatings. The additive composition includes a superhydrophobic film modifier and a biocide enhancer. The additive composition can be included in an antifouling paint that also includes one or more biocides. The antifouling paint can inhibit fouling of the surface of an underwater object, such as a ship's hull or any other marine structure. As a result, it has been demonstrated that the addition of the additive composition can provide an enhancer or adjuvant effect that improves the effectiveness of known biocides while not exhibiting significant biocidal activity alone. Furthermore, the superhydrophobic film modifier in combination with the biocide enhancer can advantageously enhance the efficacy of the biocide in the antifouling paint. In particular, it has been surprisingly found that the superhydrophobic film modifier in combination with the biocide enhancer significantly enhances the antifouling efficacy of the biocide in the antifouling paint against the settlement of marine organisms such as barnacles, bryozoans, hydrozoans, mussels, and algae. This surprising result could enable the formulation of antifouling paints containing lower amounts of biocides, such as cuprous oxide (CuO), which could alleviate at least some of the environmental issues associated with such products.

[0024] The biocide enhancer comprises one or both of a compound of formula IA and a compound of formula IB. Compound IA has the following formula:

[0025] [ka]

[0026] and compound IB has the formula

[0027] [ka]

[0028] having

[0006] In the formula, Me is Cu, Zn, Co, Ni, Ca, Mg, or Mn, and R1 is independently hydrogen, halogen, linear or branched C 1~20 Alkyl, C 2~20Alkenyl, C 2~20 Alkynyl, C 3~12 Cycloalkyl, C 6~20 Aryl, and C 7~20 arylalkyl, where each R2 is independently selected from NH, O, S, and Se, where R3 is NH, N(R4), O, S, or Se, where 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, or C 7~20 arylalkyl, wherein R and R are each independently H, 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, or R5 and R6 taken together form a =O, =S, =Se, =NR4, =C(R4)2, =C(R4)(OR4), =C(R4)(NHR4) group.

[0029] In certain exemplary embodiments: Me may be Cu or Zn; R1 is, independently, H, F, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclo-butyl, cyclo-pentyl, cyclo-hexyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12 R2 may be independently selected from NH and O; R3 is N(R4) or O; R4 is H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclo-butyl, cyclo-pentyl, cyclo-hexyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12R5 and R6 may each independently be selected from H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, and benzyl, or R5 and R6 together may 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), or =CH(NHtertC4H9).

[0030]

[0008] In certain exemplary embodiments, in compound IB, 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.

[0031] Suitable compounds of formula IA and IB, respectively, include, 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 oro-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, [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; and [tert-butyl 4,4,4-trifluoro-3-oxobutanoate]2Cu.

[0032]

[0010] In certain exemplary embodiments, the superhydrophobic film modifier can include a superhydrophobic diatomaceous earth-derived powder. Furthermore, the porous diatomaceous earth particles can have a surface and a continuous hydrophobic layer that conforms and bonds to the surface of the diatomaceous earth particles. The diatomaceous earth particles can have the surface structure of uncalcined diatomaceous earth. The surface structure of the diatomaceous earth can be highly partitioned with ridges and peaks that extend outward from the particle. The hydrophobic layer can be a self-assembled monolayer (SAM) such that the topography of the diatomaceous earth particles is preserved. The hydrophobic layer can include perfluorinated hydrocarbon moieties, such as tridecafluorohexyl units. As another example, the hydrophobic layer can include hexafluoropropene oxide oligomer moieties. Suitable superhydrophobic diatomaceous earth-derived powders are available from Dry Surface Technologies LLC and are described in U.S. Patent No. 8,216,674, which is incorporated by reference in its entirety for all purposes.

[0033]

[0011] In the additive composition according to the exemplary embodiment of the present disclosure, the relative amounts of the superhydrophobic film modifier and the biocide enhancer may vary, for example, depending on the nature of the superhydrophobic film modifier and the nature of the biocide enhancer. However, advantageously, the weight ratio of the superhydrophobic film modifier to the biocide enhancer may be 10:1 to 1:10, preferably 5:1 to 1:5, and most preferably 3:1 to 1:3. Such weight ratios have been found to advantageously enhance the efficacy of biocides such as cuprous oxide when the additive composition is incorporated into an antifouling paint, thereby allowing the amount of biocide to be reduced compared to an antifouling paint without the additive composition.

[0034]

[0012] In certain exemplary embodiments, the additive composition includes a superhydrophobic film modifier and a biocide enhancer, and the additive composition is substantially free of other materials. Thus, in such exemplary embodiments, the additive composition may be a two-component additive composition. The two-component additive composition may be provided as an ingredient in an antifouling coating. Furthermore, as described in more detail below, the two-component additive composition may then be added to other components to form an antifouling coating that includes the additive composition. As discussed above, the additive composition may advantageously enhance the efficacy of a biocide, such as cuprous oxide, in the antifouling coating.

[0035]

[0013] The additive composition according to the exemplary embodiment of the present invention may further include one or more biocides capable of preventing fouling on the surface of an object. Such biocides may be inorganic, organometallic, or organic biocides.

[0036] Examples of inorganic biocides are: copper and copper compounds, such as copper oxides, for example cuprous oxide and cupric oxide; copper alloys, for example copper-nickel alloys; copper salts, for example copper thiocyanate (CuSCN), copper sulfide; or barium metaborate.

[0037]

[0015] Examples of organometallic biocides are: zinc salts of 2-pyridinethiol-1-oxide [ZnPT, zinc pyrithione]; organocopper compounds such as copper salts of 2-pyridinethiol-1-oxide [CuPT, copper pyrithione], copper acetate, copper naphthenate, 8-quinolinonate [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].

[0038] 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 isomers of carboxylic, sulfonic and sulfenic acids. imides, such as N-(dichlorofluoromethylthio)phthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide [dichlfluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide [tolylfluanid], and N-(2,4,6-trichlorophenyl)maleimide; and other organic compounds, such as pyridinetriphenylborane, aminetriphenylborane, 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 [tralopyril].

[0039] Other examples of biocides are tetraalkylphosphonium halides, guanidine derivatives, imidazole-containing compounds, for example 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine] and derivatives, avermectins such as ivermectin and its derivatives, or macrocyclic lactones including spinosyns such as spinosad and its derivatives, or enzymes such as oxidases, or proteolytic, hemicellulolytic, cellulolytic, lipolytic, or amylolytic active enzymes.

[0040] In one exemplary embodiment, the additive composition according to an exemplary aspect of the present invention comprises a superhydrophobic film modifier, a biocide enhancer, and a 2-pyridinethiol-1-oxide copper salt (CuPT, copper pyrithione), a 2-pyridinethiol-1-oxide zinc salt (ZnPT, zinc pyrithione), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), cuprous oxide (CuO), zinc oxide (ZnO), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, and ... The biocides include one or more biocides selected from the group consisting of tetracycline (tralopyril), 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, fluanides, and 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil).

[0041]

[0019] In the additive composition according to the exemplary embodiment of the present disclosure, the relative amounts of the superhydrophobic film modifier, the biocide enhancer, and the biocide may vary depending, for example, on the nature of the superhydrophobic film modifier, the nature of the biocide enhancer, and the nature of the biocide. However, advantageously, the weight ratio of the biocide enhancer to the biocide may be 10:1 to 1:10, preferably 5:1 to 1:5, and most preferably 1:1 to 1:3. Furthermore, the weight ratio of the superhydrophobic film modifier to the biocide may be 10:1 to 1:10, preferably 5:1 to 1:5, and most preferably 3:1 to 1:3. Such weight ratios have been found to advantageously enhance the efficacy of the primary biocide, such as cuprous oxide, when the additive composition is incorporated into the antifouling paint, thereby allowing the amount of the primary biocide to be less than that of an antifouling paint without the additive composition.

[0042]

[0020] In certain exemplary embodiments, the additive composition includes a superhydrophobic film modifier, a biocide enhancer, and a biocide (e.g., one that is not cuprous oxide), and the additive composition is substantially free of other materials. Thus, the additive composition may be a three-component additive composition in such exemplary embodiments. The three-component additive composition may serve as an ingredient in an antifouling coating. Furthermore, as described in more detail below, the three-component additive composition may then be added to other components to form an antifouling coating that includes the additive composition. As discussed above, the additive composition may advantageously enhance the efficacy of a biocide, such as cuprous oxide, in the antifouling coating.

[0043] In an exemplary embodiment using a three-part additive composition, the biocide enhancer can be present in the three-part additive composition at about 5 wt% to about 60 wt%, preferably about 10 wt% to about 50 wt%, and more preferably about 15 wt% to about 45 wt%. Additionally, the superhydrophobic film modifier can be present in the three-part additive composition at about 5 wt% to about 60 wt%, preferably about 10 wt% to about 50 wt%, and more preferably about 15 wt% to about 45 wt%. The biocide (e.g., not cuprous oxide) can be present in the three-part additive composition at about 20 wt% to about 70 wt%, preferably about 25 wt% to about 60 wt%, and more preferably about 30 wt% to about 55 wt%. Such concentrations have been found to advantageously enhance the efficacy of a primary biocide, such as cuprous oxide, when the three-component additive composition is included in an antifouling paint, thereby allowing for a lower amount of the primary biocide, such as cuprous oxide, to be used compared to an antifouling paint that does not include the additive composition.

[0044]

[0022] An exemplary embodiment of the present invention further provides the use of the additive composition for inhibiting marine biofouling on a solid surface, which may be any solid surface of an underwater object such as a vessel, aquaculture fish net, underwater structures and equipment, tanks, offshore buildings, pipes, nets, piers, pilings, or poles.

[0045]

[0023] The additive compositions according to exemplary embodiments of the present invention may be further utilized in combination with polymers and / or copolymers that enable the controlled release of one or more of the superhydrophobic film modifiers, biocide enhancers, and biocides by releasing these components from the antifouling coating over time, for example, as in the case of self-polishing or disintegrating coatings.

[0046]

[0024] The superhydrophobic film modifier and biocide enhancer are versatile agents that can be used in all kinds of antifouling coatings, for example, antifouling coatings based on a variety of different polymers and / or copolymers that are typically used as binders in antifouling coating compositions. Thus, the polymers and / or copolymers that allow the controlled release of one or more of the superhydrophobic film modifier, biocide enhancer, and biocide can be any polymers and / or copolymers that are typically used as binders in antifouling coatings. Polymers and / or copolymers suitable for that purpose are known to those skilled in the art. Depending on the amount and type of binder used, one or more of the superhydrophobic film modifier, biocide enhancer, and biocide are released in a controlled manner at a predetermined desired rate, for example, a rate suitable for the navigation pattern of the ship.

[0047]

[0025] For example, the polymers and / or copolymers used as binders in the "self-polishing antifouling coating" that enable the controlled release of one or more of the superhydrophobic film modifier, biocide enhancer, and biocide 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 selected from 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; phenyl (meth)acrylate; benzyl (meth)acrylate; acrylate; 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, and the like; phenoxyethyl (meth)acrylate; 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, and the like;The (meth)acrylate monomer portion in the (meth)acrylate polymers and / or copolymers may further comprise silyl (meth)acrylates, 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 ... myrsilyl (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;

[0048] The polymers and / or copolymers that enable controlled release of one or more of the superhydrophobic film modifier, biocide enhancer, and biocide can also be VAGH copolymers, which can be dissolved in 2:3 xylene:MIBK.

[0049]

[0027] Thus, in one embodiment, the polymer and / or copolymer enabling controlled release of one or more of the superhydrophobic film modifier, biocide enhancer, and biocide 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. Preferably, the (meth)acrylate polymers and / or copolymers are copolymers of monomeric moieties selected from the group consisting of ethyl acrylate, methyl methacrylate, and zinc methacrylate, more preferably, the (meth)acrylate polymers and / or copolymers are copolymers of monomeric moieties selected from the group consisting of ethyl acrylate, methyl methacrylate, 2-methoxyethyl acrylate, and zinc methacrylate, and most preferably, the (meth)acrylate polymers and / or copolymers are copolymers of monomeric moieties selected from the group consisting of methyl methacrylate, butyl acrylate, 2-methoxyethyl acrylate, and tri-isopropylsilyl acrylate.

[0050]

[0028] As a result, an exemplary embodiment of the present invention further provides an antifouling coating comprising an additive composition and a polymer and / or copolymer that enables controlled release of one or more of a superhydrophobic film modifier, a biocide enhancer, and a biocide.

[0051]

[0029] In the antifouling paint according to the exemplary embodiment of the present disclosure, the relative amounts of the superhydrophobic film modifier, the biocide enhancer, and the biocide may vary depending on, for example, the nature of the superhydrophobic film modifier, the nature of the biocide enhancer, and the nature of the biocide. However, advantageously, the biocide enhancer can be present in the antifouling paint at about 0.1 wt% to about 25 wt%, preferably about 0.5 wt% to about 10 wt%, and more preferably about 1 wt% to about 5 wt%. Furthermore, the superhydrophobic film modifier can be present in the antifouling paint at about 0.2 wt% to about 20 wt%, preferably about 0.5 wt% to about 10 wt%, and more preferably about 1 wt% to about 5 wt%. The biocide can be present in the antifouling paint at less than about 30 wt%. Such concentrations have been found to advantageously increase the effectiveness of the primary biocide, such as cuprous oxide, in the antifouling paint, thereby allowing the amount of the primary biocide to be reduced as compared to antifouling paints without the additive composition. The total cuprous oxide content in the antifouling paint according to exemplary embodiments of the present invention may be less than about 50 wt%, more preferably less than about 40 wt%, and most preferably less than about 30 wt%. Thus, the copper content of the antifouling paint can be kept at a relatively low level.

[0052] 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 additive composition, the solid surface being any solid surface of an underwater object such as a vessel, aquaculture fish net, underwater structures and equipment, tanks, offshore buildings, pipes, nets, piers, pilings or poles, etc.

[0053]

[0031] The foregoing description is exemplary in nature and is not intended to limit in any way the scope, applicability, or configuration of the present disclosure. Various changes to the described embodiments may be made in the function and arrangement of the elements described herein without departing from the scope of the present disclosure.

[0054]

[0032] 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.

[0055]

[0033] As used in this application and the claims, the singular forms "a," "an," and "the" include the plural forms unless the context clearly dictates otherwise. Furthermore, the term "includes" means "comprises." The methods and compositions of the present disclosure can include, consist of, or consist essentially of the essential elements and limitations of the embodiments described herein, including their components, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful in biocidal compositions.

[0056]

[0034] Unless otherwise indicated, all numerical values ​​expressing properties such as amounts of ingredients, molecular weights, percentages, and the like, when used in the specification or claims, should be understood to be modified by the term "about". Thus, unless otherwise indicated, either implicitly or explicitly, the numerical parameters recited are approximations that may depend on the desired properties sought and / or the detection limits in standard test conditions / methods. In cases where the embodiments are directly and explicitly distinguished from the prior art discussed, the numerical values ​​of the embodiments are not approximations unless the word "about" is explicitly stated.

[0057]

[0035] As used herein, "optional" or "optionally" means that the subsequently described material, event, or circumstance may or may not be present or occur, and that the description includes examples in which the material, event, or circumstance is present or occurs and examples in which it does not occur. As used herein, "w / w%" and "wt%" mean weight percentage of the total weight or weight percentage relative to another component in a composition.

[0058]

[0036] The term "about" is intended to mean approximately, within a region, roughly, or around. When the term "about" is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the stated numerical values. Unless otherwise indicated, the numerical parameters set forth in the following specification and attached claims should be understood to be approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, the numerical parameters should be read in light of the number of reported significant digits and the application of ordinary rounding techniques.

[0059]

[0037] When used to describe the amount of a substance in a material, the term "substantially free" is not limited to complete or total absence, but can also correspond to the absence of any appreciable or detectable amount of the described substance in the material. Thus, for example, a material is "substantially free" of a substance if the amount of the substance in the material is less than the precision of an industry-accepted instrument or test for measuring the amount of the substance in the material. In certain exemplary embodiments, a material may be "substantially free" of a substance if the amount of the substance in the material is less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.5%, or less than 0.1% by weight of the material.

[0060]

[0038] The phrase "effective amount" refers to an amount of a compound that enhances, ameliorates, stimulates, or promotes a response to a particular condition or disorder, or a particular symptom of a condition or disorder.

[0061]

[0039] The term "enhancer," as used herein, refers to an additive that may affect the performance of an active compound when used in combination with the active compound, but that does not itself exhibit any biocidal activity and / or does not itself exhibit significant biocidal activity in the compositions of the present invention.

[0062]

[0040] The term "biocide," as used herein, refers to any chemical compound that prevents the settlement of marine life on a surface and / or prevents the growth of marine life on a surface and / or promotes the removal of marine life from a surface.

[0063]

[0041] The terms "antifouling paint" and "antifouling coating" are used interchangeably herein.

[0064]

[0042] As used herein, references to chemical formulas use standard element symbols according to the periodic table (e.g., C represents carbon, N represents nitrogen, etc.) Furthermore, references to chemical formulas are based on standard bonding, such that carbon can make up to four bonds and nitrogen can make up to three bonds, unless otherwise specified.

[0065]

[0043] Throughout this specification and the claims, range limitations are combinable and interchangeable, and such ranges are specified and include all subranges contained therein, unless the context or language indicates otherwise. For example, all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other.

[0066]

[0044] Hereinafter, the present invention will be further described with reference to examples, but it should be understood that the present invention is in no way limited to these examples. EXAMPLES

[0067] It will be understood that the antifouling coatings described in the examples may be substantially free of any material not expressly described.

[0068]

[0046] To confirm the effectiveness of the additive composition, which allows for a significant reduction in the amount of cuprous oxide required for antifouling purposes, the effectiveness of a set of disintegrating antifouling paints was evaluated by immersing experimental painted panels in seawater on a test raft.

[0069]

[0047] For this purpose, various disintegrating antifouling paints were prepared: those containing no biocide and no additive composition ("negative control paint"); those containing only cuprous oxide as the biocide and no additive composition ("positive control paint"); those containing only cuprous oxide and a secondary biocide as the biocide; those containing only cuprous oxide and a biocide enhancer as the biocide; those containing only cuprous oxide and a superhydrophobic film modifier as the biocide; and those containing cuprous oxide with various combinations of superhydrophobic film modifier, biocide enhancer, and secondary biocide.

[0070] The antifouling components in the antifouling paints utilized in this example are shown in Table 1 below. The paints were applied to rectangular fiberglass panels as follows: Each panel was coated on both sides with each paint, using different concentrations of cuprous oxide. The coated panels were immersed in salt water and supported on a floating rack. The panels were inspected after 2 months (Table 2), 4 months (Table 3), 6 months (Table 4), and 18 months (Table 5). The test was based on a modified ASTM standard rating (D6990-05). Each side of the panel was assigned a fouling rating of 1 to 10, with a rating of 10 corresponding to no fouling or 0%, a rating of 0 corresponding to complete or 100% fouling, and ratings in between corresponding to different percentages of fouling. The panels were rinsed and kept wet with water from the test station during the test. The edges of the panels and the mounting holes were not considered in the fouling rating.

[0071]

[0049]

[0072] [Table 1]

[0073] It will be understood that the components listed in Table 1 correspond to the antifouling components in the antifouling paint, namely the primary biocide (cuprous oxide), the superhydrophobic film modifier (modified silicate and aluminosilicate particles), the biocide enhancer (copper di(ethyl 4,4,4-trifluoroacetoacetate)), and the secondary biocide (4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT)). Without being bound to any particular theory, it is believed that the antifouling components in the antifouling paint correspond to components that prevent the settlement of marine organisms on the surface and / or prevent the growth of marine organisms on the surface and / or promote the detachment of marine organisms from the substrate surface. The inactive components make up the remainder of the antifouling paint. Inactive components include gum rosin, Laroflex® MP25 (copolymer of vinyl chloride and vinyl isobutyl ether), chlorinated paraffin / Disperbyk 161 (dispersing additive), talc, red iron oxide, zinc oxide, Disparlon A650-20x (synthetic polyamide wax dispersant), Bentone 38 (organoclay added for anti-settle properties), and xylene.

[0074]

[0051]

[0075] [Table 2]

[0076]

[0052]

[0077] [Table 3]

[0078]

[0053]

[0079] [Table 4]

[0080]

[0054]

[0081] [Table 5]

[0082]

[0055] Each panel containing the additive composition exhibits desirable antifouling performance. A general trend is observed in which all additive compositions evaluated improve the performance of antifouling paints. In particular, coated panels containing the additive composition can exhibit desirable antifouling performance on both the front side (containing 40% cuprous oxide) and the back side (containing 25% cuprous oxide). Thus, it is confirmed that the additive composition can significantly reduce the amount of cuprous oxide required for antifouling purposes.

[0083]

[0056] These and other modifications and variations to the present disclosure may be implemented by those skilled in the art without departing from the spirit and scope of the present invention, as specifically defined by the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged in whole or in part. Furthermore, those skilled in the art will appreciate that the foregoing description is illustrative only and is not intended to limit the invention as further described in such appended claims.

Claims

1. A superhydrophobic film modifier; and Biocide enhancers comprising one or both of Compound IA and Compound IB 1. An additive composition for an antifouling coating comprising: The compound IA has the following formula: 【Chemical 1】 and The compound IB has the following formula: 【Chemistry 2】 and wherein Me is Cu, Zn, Co, Ni, Ca, Mg, or Mn; In the formula, each R1 is independently 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; wherein each R2 is independently selected from NH, O, S, and Se; wherein R3 is NH, N(R4), O, S, or Se; In the formula, R4 is hydrogen, a linear or branched C １～２０ Alkyl, C ２～２０ Alkenyl, C ２～２０ Alkynyl, C ３～１２ Cycloalkyl, C ６～２０ aryl, or C ７～２０ is arylalkyl, In the formula, R5 and R6 are each independently 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 arylalkyl, or R5 and R6 together are selected from =O, =S, =Se, =NR4, =C(R4) ２ , forming =C(R4)(OR4), =C(R4)(NHR4) groups; Additive composition.

2. 10. The additive composition of claim 1, During the ceremony: Me is Cu or Zn; R1 is independently H, F, 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; Each R2 is independently selected from NH and O; R3 is N(R4) or 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, or benzyl; and 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 represent ═CH(OCH ３ ), =CH(OC ２ H ５ ), =CH(OnC ３ H ７ ), =CH(OiC ３ H ７ ), =CH(OnC ４ H ９ ), =CH(OiC ４ H ９ ), =CH(OtertC ４ H ９ ), =CH(NHCH ３ ), =CH(NHC ２ H ５ ), =CH(NHnC ３ H ７ ), =CH(NHiC ３ H ７ ), =CH(NHnC ４ H ９ ), =CH(NHiC ４ H ９ ), or =CH(NHtertC ４ H ９ ) to form Additive composition.

3. 3. The additive composition of claim 1 or 2, wherein the weight ratio of the superhydrophobic film modifier to the biocide enhancer is from 10:1 to 1:10, preferably from 5:1 to 1:5, and most preferably from 3:1 to 1:

3.

4. 10. The additive composition of claim 1 further comprising a biocide.

5. 2. The additive composition of claim 1, wherein the biocide is selected from the group consisting of 2-pyridinethiol-1-oxide copper salt (copper pyrithione, CuPT), 2-pyridinethiol-1-oxide zinc salt (zinc pyrithione, ZnPT), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), cuprous oxide (Cu ２ 1. An additive composition comprising one or more of: zinc oxide (ZnO), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (tralopyril), ethane-1,2-diylbis(dithiocarbamate) zinc (zineb), N,N-dimethylcarbamodithioate zinc (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).

6. 2. The additive composition of claim 1, wherein the weight ratio of the biocide enhancer to the biocide is from 10:1 to 1:10, preferably from 5:1 to 1:5, and most preferably from 1:1 to 1:

3.

7. 10. The additive composition of claim 1, wherein the superhydrophobic film modifier comprises porous diatomaceous earth particles coated with a hydrophobic layer.

8. 10. A method comprising using the additive composition of claim 1 to control marine biofouling on a solid surface.

9. 10. The method of claim 8, wherein the antifouling composition is used in combination with a polymer, copolymer, or both the polymer and the copolymer to enable controlled release of one or both of the superhydrophobic film modifier and the biocide enhancer.

10. 10. An antifouling paint comprising the additive composition of claim 1; and one or more of the superhydrophobic film modifier, the biocide enhancer, and the biocide. An antifouling paint comprising a polymer, a copolymer, or both said polymer and said copolymer to enable multiple controlled release.

11. 11. The antifouling paint of claim 10, wherein the biocide augmenter is present in the antifouling paint at about 0.2 wt % to about 20 wt %, preferably about 0.5 wt % to about 10 wt %, and more preferably about 1 wt % to about 5 wt %.

12. 12. The antifouling paint of claim 10 or 11, wherein the biocide is present in the antifouling paint at less than about 30 wt%.

13. 11. The antifouling paint of claim 10, wherein the superhydrophobic film modifier is present in the antifouling paint in an amount of from about 0.2 wt % to about 20 wt %, preferably from about 0.5 wt % to about 10 wt %, and more preferably from about 1 wt % to about 5 wt %.

14. The antifouling coating of claim 10, wherein the antifouling coating is not superhydrophobic.

15. 11. A method for inhibiting marine biofouling on a solid surface, comprising applying the antifouling coating of claim 10 onto said solid surface.

Images