Stain-controlling coating composition

Abstract

The present invention relates to a fouling control coating composition comprising an anionic polymer containing one or more metal cations, wherein the anionic polymer has a siloxane moiety covalently bonded via an amide group. The anionic polymer is an acrylate copolymer prepared from at least one acrylate monomer and at least one acrylamide monomer to which a polysiloxane moiety is bonded. The composition is particularly useful as a self-polishing fouling control coating.

Description

[Technical Field]

[0001] The present invention relates to fouling control coating compositions, substrates or articles coated with such fouling control coating compositions, and methods for controlling aquatic fouling on artificial objects using such coatings. [Background technology]

[0002] Fouling of ship hulls and other floating objects by aquatic organisms is an ongoing problem. Fouling can increase the frictional resistance of boats in the water, potentially increasing fuel costs. In stationary structures, such as drilling rigs, fouling can alter the water flow around support legs, leading to unpredictable and potentially increasing stresses. Fouling can also make inspections more difficult by obscuring defects and cracks. Furthermore, fouling can reduce the flow rate of piping, such as the intakes of cooling water or ballast tanks, by narrowing the cross-sectional area.

[0003] Coatings can be used to reduce fouling. Such coatings may contain biocides to control the growth of aquatic organisms on the surface. Coatings are typically classified into two broad categories: “hard” antifouling coatings, from which biocides gradually leach out over time, and “erosive” antifouling coatings (sometimes called self-polishing coatings), from which the coating gradually erodes to release biocides. However, biocides may pose environmental risks, especially in areas with heavy shipping activity. Therefore, biocides are subject to increasingly stringent environmental legislation.

[0004] Biocide-free coatings are available, including so-called "fouling-removing" coatings, which have a "low surface energy" surface that inhibits the adhesion of fouling organisms and also allow fouling organisms to be washed away more easily from the surface. The fouling control effect can be enhanced by including non-biocidal adhesion-reducing fluids in the formulation. Biocide-free self-polishing coatings, so-called surface-active self-polishing coatings, can also be used, in which gradual abrasion or dissolution is designed to prevent the settlement and growth of biological fouling and continuously present a new, clean surface that promotes its release. Examples are described in International Publication Nos. 2004 / 081121 and International Publication Nos. 2009 / 011332.

[0005] Self-polishing coatings are another type of fouling control coating. They gradually wear or dissolve while continuously presenting a new, clean surface, and their activity can be enhanced by containing biocide antifouling agents. Examples are described in European Patent No. 2489710, European Patent No. 2489711, Japanese Patent Application Publication No. 2006077095, U.S. Patent Application Publication No. 2017 / 0022373, International Publication No. 2004 / 081121, International Publication No. 2009 / 011332, and International Publication No. 2019 / 081495.

[0006] However, there is still a need for further types of fouling control coatings with improved properties. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2004 / 081121 [Patent Document 2] International Publication No. 2009 / 011332 [Patent Document 3] European Patent No. 2489710 [Patent Document 4] European Patent No. 2489711 [Patent Document 5] Japanese Patent Application Publication No. 2006077095 [Patent Document 6] U.S. Patent Application Publication No. 2017 / 0022373 [Patent Document 7] International Publication No. 2004 / 081121 [Patent Document 8] International Publication No. 2009 / 011332 [Patent Document 9] International Publication No. 2019 / 081495 [Overview of the Initiative] [Means for solving the problem]

[0008] The present invention relates to a fouling control coating composition comprising an anionic polymer containing one or more metal cations, wherein the anionic polymer has a siloxane moiety covalently bonded via an amide group. The anionic polymer is an acrylate copolymer prepared from at least one acrylate monomer and at least one acrylamide monomer to which a polysiloxane moiety is bonded.

[0009] The present invention also relates to a method for controlling aquatic fouling on an artificial object, comprising applying the coating composition to the surface of the artificial structure. The artificial structure is intended to be permanently or intermittently immersed in water, such as seawater, freshwater, or brackish water.

[0010] The present invention further relates to a substrate or article coated with the above-described fouling control coating composition both before and after drying and / or curing.

[0011] The present invention also relates to the use of such coating compositions for controlling aquatic fouling of artificial structures.

[0012] term In the following discussion, references to the amount of components in the overall coating composition refer to the uncured or undried composition unless otherwise specified. Furthermore, unless otherwise specified, the concentrations given are weight percent of the overall coating composition. If the coating composition is provided in separate parts (e.g., a binder-containing portion and a curing agent-containing portion), the amount of components in the overall coating composition is based on the total amount of components in all combined different parts.

[0013] References to “terminal” groups in resins, polymers, or oligomers refer to groups attached to the oligomer / polymer chain or “backbone” at the end (terminal) position. References to “pendant” groups refer to groups attached to the oligomer / polymer chain at positions other than the terminal position.

[0014] References to "aliphatic hydrocarbyl" groups or substituents include saturated and unsaturated hydrocarbyl groups (e.g., alkyl or alkenyl groups), which may be cyclic, linear, or branched, or may include mixtures of cyclic and acyclic portions. Similarly, references to "alkyl" or "alkenyl" groups or substituents include groups that are cyclic, linear, or branched, or mixtures of cyclic and acyclic portions. Unsaturated groups, such as alkenyl groups, have at least two carbon atoms.

[0015] A reference to "aryl" refers to an aromatic hydrocarbon group that may contain one or more aromatic rings. A reference to "heteroaryl" refers to an aromatic group that contains one or more heteroatoms in its aromatic ring, typically selected from oxygen, nitrogen, and sulfur.

[0016] The monomer (or monomer unit) content of a polymer or oligomer is expressed in either weight percent or mole percent, and can be calculated from the weight fraction or mole fraction of the monomer used to prepare the polymer or oligomer, respectively.

[0017] The term "monomer unit" refers to the constituent monomers of a polymer, that is, the portion derived from the monomers after they have been incorporated into the polymer.

[0018] Atmospheric pressure is defined as 1.013 bar-a, where bar-a represents absolute bar, as opposed to gauge bar.

[0019] The term "saturated carbon atom" refers to a carbon atom that has four single covalent bonds with other atoms and no double or triple covalent bonds with other atoms.

[0020] The abbreviation PDMS refers to polydimethylsiloxane. [Modes for carrying out the invention]

[0021] [Anionic polymer] The coating composition comprises one or more binder resins, at least one of which is an acrylate-based anionic polymer containing one or more metal cations. The anionic polymer can be formed from at least one monomer having anionic functional groups, with one or more metal cations used to balance the negative charge. In embodiments, the anionic polymer is a thermoplastic polymer.

[0022] Examples of anionic polymers include those having anionic moieties selected from phosphonates, sulfonates, carboxylates, and carbonates. At least one anionic moiety is a carboxylate, and in further embodiments, all anionic moieties are carboxylates.

[0023] Anionic polymers contain siloxane moieties covalently bonded via amide bonds. Anionic polymers can be formed by polymerization of unsaturated monomers, at least one of which has an amide-bonded siloxane moiety. In another embodiment, the siloxane moiety can be bonded to the polymer, for example, by forming the polymer from monomers having suitable functional groups to which the siloxane moiety can be bonded.

[0024] Monomers to which at least one siloxane (or all siloxanes) are bonded are acrylamide monomers, which will be described in more detail below. The siloxane moiety will also be described below. Before bonding to the acrylamide monomer, the siloxane moiety may contain a group that is reactive with the amide moiety of the monomer, typically located at the terminal end of the siloxane group. In some embodiments, the siloxane moiety before bonding to the monomer or polymer contains only one group that is reactive with the amide. The siloxane moiety may contain other functional groups at pendant or terminal positions that do not react with the amide moiety, but in embodiments, no other reactive groups are present.

[0025] The amount of metal cation-containing anionic polymer in the coating composition may be in the range of 20 to 80% by weight, for example, 20 to 75% by weight, 25 to 70% by weight, or 25 to 60% by weight.

[0026] [Metal cations] The metal cation can be selected from divalent or trivalent metal ions. In embodiments, the metal ion can be selected from alkaline earth metal ions (e.g., Mg, Ca, Sr), transition metals or "d-block" ions (e.g., first-period transition metals, e.g., Ti, Fe, Co, Ni, Cu, Zn), typical "p-block" metals (e.g., Al, Sn), and lanthanides (e.g., La, Ce, Pr). The metal ion can be selected from Mg, Ca, Zn, and Cu, and is typically selected from Cu and Zn.

[0027] The metal cation can be provided in the form of a salt of anionic monomer, for example, as a metal salt of an acrylate monomer, as will be described in more detail below. In other embodiments, it can be provided in the form of another salt, for example, as a salt of an organic acid, for example, a carboxylic acid, and examples of such salts will also be provided in more detail below.

[0028] The metal content of the metal ion-containing anionic polymer may be in the range of 1 to 20% by weight, for example, 2 to 15% by weight or 2 to 10% by weight. [Siloxane portion]

[0029] The anionic polymer contains siloxane moieties covalently bonded via amide bonds. The siloxane moieties may be linear, branched, or cyclic, or may contain mixtures of cyclic and acyclic moieties or regions. In embodiments, the siloxane moieties contain 4 to 150 silicon atoms. In embodiments, the amide bonds to the siloxane moieties and polymer can be represented by formula (1), where b is in the range of 3 to 150, e.g., 3 to 100 or 8 to 80; c is in the range of 0 to 20, e.g., 0 to 10, 0 to 5 or 0 to 3; and j is in the range of 1 to 6, e.g., 2 to 4. [ka]

[0030] Each A is [OSi(R c )2]

[0031] Each R c This is independently, and in some cases, a substituted C. 1~20 Aliphatic hydrocarbyl groups, and in some cases substituted C 6~12 An aryl group and one or more C 1~6 C having an alkyl group, and possibly substituted C 6~12 Selected from aryl groups. Optional substituents are further defined below.

[0032] T is -O-, -NR t - Either it is - or it does not exist.

[0033] Each R h is independently H and, as further described below, optionally substituted C 1~20 alkyl selected from. In an embodiment, C 1~20 alkyl is C 1~10 or C 1~6 alkyl.

[0034] Each R t is independently selected from H, C 1~6 alkyl, and C 1~6 haloalkyl, where halo can be selected from Cl and Br.

[0035] In an embodiment, the siloxane moiety and its amide bond to the anionic polymer can be represented by formula (2). [Chemical formula]

[0036] In an embodiment, in either formula (1) or (2), there is no halide or halide-containing substituent.

[0037] In an embodiment, in formula (2), each R c is an unsubstituted C 1~6 alkyl group or a phenyl group optionally substituted with one or more C 1~6 alkyl groups. In an embodiment, each R c is unsubstituted methyl or unsubstituted phenyl.

[0038] [Monomer unit of anionic polymer] Anionic polymers are acrylate copolymers. Such polymers or copolymers can be obtained by polymerization of a mixture of monomers containing one or more acrylate and / or acrylamide monomers. Acrylate monomers are monomers having an acrylate moiety in which a C=C double bond is directly bonded to a carboxyl group or carboxylate group. Acrylamide monomers are those in which a C=C double bond is directly bonded to an amide group.

[0039] In the embodiment, the acrylate polymer comprises one or more acrylate monomer units represented by formula (3). [ka]

[0040] Each R f H, C 1~20 Aliphatic hydrocarbyl, C 6~12 Aryl, and C 1~6 Alkyl, C(O)O - and C(O)OR t C having one or more substituents selected from 6~12 Selected from the list.

[0041] Each R g These are, independently, H, and C 1~20 Aliphatic hydrocarbyl (e.g., alkyl), C 6~12 Aryl, and one or more (e.g., 1 to 4) C 1~6 C substituted with an aliphatic hydrocarbyl group 6~12 Selected from the alphabet. f and R g Each aliphatic hydrocarbyl substituent, aliphatic hydrocarbyl group, and aryl group within may be substituted as further described below.

[0042] In the explicit section, C 1~20 Aliphatic hydrocarbils are C 1~10 or C 1~6Aliphatic hydrocarbyl groups, for example, C 1~10 or C 1~6 It can be selected from alkyl groups. In this embodiment, each R g This is selected from hydrogen and methyl.

[0043] In one embodiment, R g The groups are H and unsubstituted C, independently. 1~6 Alkyl, for example, H and C 1~4 Alkyl, for example, selected from H and methyl. In one embodiment, R f H, -C(O)O-, -C(O)OR t , and -C(O)O - and -C(O)OR t C which may be replaced by one or more groups selected from 1~6 Selected from alkyl groups. f In some cases, C is replaced. 1~6 In embodiments where the alkyl group is one optional -C(O)O - or -C(O)OR t Only substituents are present.

[0044] In some embodiments, the acrylate polymer is a copolymer comprising one or more further monomer units. In one embodiment, the one or more further monomer units can be selected from those represented by formula (4). [ka]

[0045] R f and R g This is defined as above. Z is -OR h and -N(R h ) Selected from 2.

[0046] Z is N(R h In the embodiment where R f and R g In all cases, the carbonyl-containing portion is -C(O)O- , -C(O)OR t or -C(O)NR t It does not contain 2.

[0047] Each R h Independently, H, and C which is substituted in some cases, as further described below. 1~20 Selected from alkyl groups. In an embodiment, C 1~20 Alkyl is C 1~10 or C 1~6 It is alkyl.

[0048] In embodiments, the monomer of formula (3) may be based on acrylate, methacrylate, itaconate, maleate, or crotonate. These also apply to the monomer of formula (4), but may include acrylamide and methacrylamide. In embodiments, the monomers of formulas (3) and (4) are based on acrylate or methacrylate.

[0049] In the embodiment, at least one monomer unit of formula (4) is present, where Z is N(R h )2, and the siloxane portion is R h The substituent on the group, and the siloxane portion may be as follows: [ka]

[0050] Typically, the siloxane portion is -NR t One R of two parts t These are substituents on the group, and can be represented, for example, as follows: [ka]

[0051] In such an embodiment, NR t NH is CR t j (CH2) j And j is 1 to 6, for example, 2 to 4.

[0052] In some embodiments, the siloxane moiety can be bonded to a monomer, for example, by a condensation reaction in which a siloxane having a terminal amine moiety is reacted with an acyl halide functional monomer according to the following formula (before or after polymerization, typically before polymerization). [ka]

[0053] Other types of comonomers that can form part of anionic polymers (i.e., non-acrylate or acrylamide monomers) include those having polymerizable unsaturated carbon-carbon bonds, for example, those represented by formula (5). [ka]

[0054] Each R j These are independently H, a halide (e.g., selected from F and Cl), and C 1~6 Selected from alkyl groups. k R j , C 2~6 Alkenil, C 6~12 Aryl, and one or more C 1~6 C substituted with an aliphatic hydrocarbyl group 6~12 It can be selected from the alphabet. In this embodiment, R j and R k Only one of them may be a halide, or it may contain a halide-containing substituent. In the embodiment, R k is C 6~12 Contains an aryl compound. In the embodiment, the comonomer is R h and R g As described above regarding those related to this, they may include one or more optionally selected substituents.

[0055] The average number of monomer units in an acrylate-based anionic polymer can range from 5 to 500, for example, from 10 to 300.

[0056] In the embodiment, the optionally substituted group may include 1 to 4 substituents, for example, 1 or 2 substituents.

[0057] In the embodiment, the viscosity of the siloxane-modified anionic polymer is in the range of 3 to 100 poise, for example, 5 to 50 poise, when measured at 25°C.

[0058] In embodiments, metal cation-containing siloxane-modified anionic polymers are prepared, for example, by using anionic monomers in their acidic form, i.e., protonated form, where the monomer unit is of formula (4) where Z is OH, and then exchanging one or more H ions with metal cations.

[0059] When preparing siloxane-modified anionic polymers, the proportion of anionic monomers (or protonated forms of anionic monomers) in the monomer mixture is typically in the range of 0.5 to 20% by weight, for example, 1 to 12% by weight, or for example, 2 to 10% by weight.

[0060] In some embodiments, the anionic monomer is an acrylate-based anionic monomer containing at least 80% of monomer units according to formulas (3) and (4) on a molar basis. In further embodiments, this amount is at least 90% or at least 95% on a molar basis. In further embodiments, all monomer units are according to formulas (3) and (4).

[0061] In an embodiment, in the anionic polymer, the amount of metal cation with respect to the anionic monomer units in the polymer is at least 80 mol%, for example, at least 90 mol% or at least 95 mol%. In this sense, monomer units containing an acidic group, for example, the monomer unit of formula (4) where Z is -OH, are considered anionic monomer units. Otherwise, the anionic polymer may become overly soluble and decompose too rapidly when contacted with water.

[0062] In an embodiment, anionic monomer units not charge-balanced by metal cations can be charge-balanced by other cations, such as protons or amine cations. In an embodiment, substantially all anionic monomer units are charge-balanced by metal cations.

[0063] [Optional substituent] R c The above optional substituents can be selected from halides (e.g., selected from F and Cl), -OR t and -N(R t )2.

[0064] R g and R h The optional substituents of can be selected from halides, -OR t , -N(R t )2, the siloxane moiety defined above, -OC(O)R t , -C(O)N(R t )2 and -OC(O)N(R t )2. Further optional substituents include polyethers, polyamines, and -([CR t 2] j E-) p R t and -E-([CR t 2] j E-) p R t The polyether / amine groups selected from. Each E is independently selected from O and NR t Selected from. Each Rt As defined above, j can be 1 to 6, for example, 2 to 4, and p can be 1 to 20. f For this, the same optional substituent is applied, and any further optional substituent is -C(O)O - , -C(O)OR t Selected from.

[0065] Any halide substituent or any halide in any substituent is typically selected from F and Cl.

[0066] [Other Organic Anions] The coating composition may contain one or more further organic anions. These can be ionically bonded to the polymer, for example, as counterions having divalent or trivalent metal ions in the anionic polymer.

[0067] In embodiments, the organic anion is a carboxylate anion having at least one carboxylate group. The organic anion typically contains a total of 2 to 50 carbon atoms.

[0068] The organic ion consists of at least one carboxyl group and a halide (typically selected from F and Cl), R t OR as defined above t and N(R t )C having one or more additional substituents of any choice selected from 2 2~50 It may be a hydrocarbyl group. In embodiments, it is unsubstituted except having at least one carboxyl group, for example, one or two carboxyl groups. In embodiments, there is only one carboxyl group.

[0069] The hydrocarbyl group is a C4-C group selected from aliphatic, aromatic, or aliphatic-substituted aromatic groups. 20 A hydrocarbyl group may also be used.

[0070] In the embodiment, the organic ion is a fatty acid, a fatty acid including naphthenic acid and versatic acid, an aliphatic group, for example a saturated aliphatic group, for example C4-C 20 Alkyl alkyl groups or C6-C 20 Selected from carboxyl-containing compounds selected from alkyl groups.

[0071] The organic ions may be part of the carboxyl-containing compounds present in the rosin, selected from, for example, gum rosin, wood rosin, and tall oil rosin. In embodiments, the rosin may be hydrogenated or disproportionated rosin.

[0072] [Optional components] The coating composition may optionally contain one or more other components selected from, for example, curable resins, crosslinking agents, reactive diluents, corrosion inhibitors, pigments, gloss additives, waxes, rosins, fillers and extenders, thixotropic agents, plasticizers, inorganic and organic dehydrating agents (stabilizers), UV stabilizers, defoamers, and any combination thereof. These components are well known to those skilled in the art.

[0073] The total amount of such further optional components may be in the range of 0 to 65% by weight, typically 50% or less by weight of the coating composition, for example, 35% or less by weight, based on the total content of the coating composition.

[0074] Except for organic solvents, marine biocides, pigments, fillers, and extenders discussed further below, the coating composition contains less than 5% by weight or less than 3% by weight of any further optional components.

[0075] The coating composition may contain small amounts of non-volatile and non-reactive oligomers or polymer fluids (e.g., polysiloxane oil or fluoropolymers, e.g., perfluoropolyethers), or hydrocarbon waxes or oil mixtures (e.g., petrolatum), or it may not contain such non-volatile and non-reactive fluids. For example, their content may be 5% by weight or less, e.g., 3% by weight or less, 1% by weight or less, or 0.1% by weight or less.

[0076] [organic solvent] The composition may contain one or more organic solvents. These organic solvents are typically organic liquids that have a boiling point of 250°C or less at atmospheric pressure (i.e., 101.3 kPa or 1.013 bar-a) and evaporate from the coating composition during the drying and curing process.

[0077] The organic solvent can be selected from hydrocarbon compounds and heteroatom-containing organic compounds, where the heteroatom is selected from O, S, and N, for example, O.

[0078] Examples of organic solvents include alkyl aromatic hydrocarbons (e.g., xylene, toluene, and trimethylbenzene) and aliphatic hydrocarbons (e.g., C 4~20 Cyclic and acyclic hydrocarbons selected from alkanes, or mixtures of any two or more thereof), alcohols (e.g., benzyl alcohol, octylphenol, resorcinol, n-butanol, isobutanol, and isopropanol), ethers (e.g., methoxypropanol), glycol ethers (e.g., phenyl, benzyl, or C of ethylene glycol, diethylene glycol, propylene glycol, or dipropylene glycol). 1~4 Examples include alkyl ethers or diethers, ketones (e.g., methyl ethyl ketone, methyl isobutyl ketone, and methyl isopentyl ketone), and esters (e.g., butyl acetate). In embodiments, the organic solvent contains 2 to 20 carbon atoms, for example, 3 to 15 carbon atoms. A mixture of any two or more organic solvents can be used.

[0079] The total amount of organic solvent can be up to 80% by weight of the total weight of the coating composition, for example, in the range of 10-80% by weight, 20-80% by weight, or 25-65% by weight.

[0080] The organic solvent content is separate from the water content. Coating compositions are typically non-aqueous compositions. Water may be present, but typically at low concentrations. If present, the water concentration is typically 5% by weight or less, for example, 1% by weight or less.

[0081] [Marine biological agents] The coating composition may, in some embodiments, contain one or more marine biocides. Marine biocides are chemical substances known to have chemical or biological bactericidal activity against marine or freshwater organisms.

[0082] The coating compositions described herein do not require any additional marine biocides, but may incorporate them as needed. In embodiments where marine biocides are present, the marine biocides may be present in concentrations of up to 50% by weight, for example, up to 30% by weight or up to 10% by weight. However, in embodiments, the amount of marine biocides is limited, for example, 1% by weight or less of the total coating composition, for example, 0.5% by weight or less or 0.1% by weight or less. In embodiments, the coating composition does not contain marine biocides.

[0083] If used, suitable marine biological agents are well known in this art and include inorganic, organometallic, metal-organic, or organic biocides.

[0084] Examples of inorganic biocides include copper compounds, such as copper oxide, copper thiocyanate, copper bronze, copper carbonate, copper chloride, copper-nickel alloys, and silver salts, such as silver chloride or silver nitrate.

[0085] Examples of organometallic biocides and metal-organic biocides include zinc pyrithione (zinc salt of 2-pyridinethiol-1-oxide), copper pyrithione, bis(N-cyclohexyl-diazenium dioxy)copper, zinc ethylene-bis(dithiocarbamate) (i.e., zineb), zinc dimethyldithiocarbamate (dilam), and manganese ethylene-bis(dithiocarbamate) (i.e., mancozeb) complexed with a zinc salt.

[0086] Organic biocides include formaldehyde, dodecylguanidine monohydrochloride, thiabendazole, medetomidine, N-trihalomethylthiophthalimide, trihalomethylthiosulfamide, N-arylmaleimide, such as N-(2,4,6-trichlorophenyl)maleimide, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diurone), 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, and 2-methylthio-4-butyl Amino-6-cyclopropylamino-s-triazine, 3-benzo[b]thienyl-5,6-dihydro-1,4,2-oxathiazidine-4-oxide, 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone, 2,4,5,6-tetrachloroisophthalonitrile, tolylfluanide, diclofluanide, diiodomethyl-p-tosylsulfone, capsaicin and substituted capsaicin, N-cyclopropyl-N'-(1,1-dimethyl Ethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine, 3-iodo-2-propynylbutylcarbamate, medetomidine, 1,4-dithiaanthraquinone-2,3-dicarbonitrile (dithianone), borane, e.g., pyridinetriphenylborane, 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole derivatives substituted at position 5 and possibly at position 1, e.g., 2-(p-chlorophenyl)-3-cyano-4 Examples include bromo-5-trifluoromethylpyrrole (tralopyryl), furanones, such as 3-butyl-5-(dibromomethylidene)-2(5H)-furanone, macrocyclic lactones, such as avermectin, such as avermectin B1, ivermectin, doramectin, abamectin, amamectin, and selamectin, and quaternary ammonium salts, such as didecyldimethylammonium chloride and alkyldimethylbenzylammonium chloride.

[0087] Biocides may, in embodiments, be encapsulated, adsorbed, captured, supported, or bound. Certain biocides are advantageously difficult or hazardous to handle and are used in encapsulated, captured, absorbed, supported, or bound forms. Encapsulation, capture, absorption, support, or binding of biocides can provide secondary mechanisms for controlling biocide leaching from coating systems to achieve slower release and sustained effects. The methods of encapsulating, capturing, adsorbing, supporting, or binding biocides are not particularly limited. Examples include the use of single-layer and double-layer amino-formaldehyde, or hydrolyzed polyvinyl acetate-phenol resin capsules or microcapsules as described in International Publication No. 2006 / 032019. An example of a suitable encapsulated biocide is encapsulated 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolon, commercially available from Dow Microbial Control as Sea-Nine CR2 Marine Antifouling Agent. Examples of methods by which absorbed, supported, or conjugated biocides may be prepared include the use of host-guest complexes, e.g., clathrate as described in European Patent No. 0709358, phenolic resin as described in European Patent No. 0880892, carbon-based adsorbents, e.g., those described in European Patent No. 1142477, or microporous inorganic carriers, e.g., amorphous silica, amorphous alumina, pseudoboehmite, or zeolite as described in International Publication No. 00 / 11949.

[0088] [Pigments, fillers, and corrosion inhibitors] In embodiments, one or more pigments, fillers, and anticorrosive agents may be included in the coating composition.

[0089] Examples of suitable fillers include zinc oxide, barium sulfate, calcium sulfate, calcium carbonate, silica, or silicates (e.g., talc, feldspar, and clay) (such as calcined silica, bentonite, and other clays). Some fillers (e.g., fumed silica) may have a thixotropic effect on the coating composition.

[0090] The proportion of filler may range from 0 to 25% by weight based on the total weight of the coating composition. If clay is present, the amount of clay is up to 1% by weight, e.g., 0.1 to 1% by weight, based on the total weight of the coating composition. If thixotrope is present, the amount of thixotrope is up to 5% by weight, e.g., 0.1 to 5% by weight, based on the total weight of the coating composition.

[0091] Examples of pigments include black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, indanthron blue, aluminum cobalt oxide, carbazole dioxazine, chromium oxide, isoindoline orange, bis-acetoaceto-tolidiole, benzimidazolone, quinafthron yellow, isoindoline yellow, tetrachloroisoindolinone, quinophthalone yellow, and metal flake materials, such as aluminum flakes.

[0092] Examples of corrosion inhibitors include zinc powder and zinc alloys, as well as so-called lubrication pigments, such as graphite, molybdenum disulfide, tungsten disulfide, and boron nitride. If present, the corrosion inhibitor may be present in an amount of up to 25% by weight of the entire coating composition, for example, in the range of 0.1 to 25% by weight.

[0093] In embodiments including any pigments, fillers, or anticorrosive agents, they may together constitute up to 50% by weight, for example up to 40% by weight, of the coating composition based on the total weight of the coating composition. In embodiments, there may be at least 0.1% by weight, for example at least 5% by weight, at least 10% by weight, or at least 20% by weight of these components. Exemplary ranges include 0.1–50% by weight, 0.1–40% by weight, 5–50% by weight, 5–40% by weight, 10–50% by weight, 10–40% by weight, 20–50% by weight, and 20–40% by weight.

[0094] [Properties of the coating composition] In the embodiments, the coating composition has a non-volatile substance content of 35% by weight or more, based on the total weight of the coating composition. In further embodiments, the non-volatile substance content is 50% by weight or more, for example, 70% by weight or more. In embodiments, the non-volatile substance content is 85% by weight or less. The non-volatile substance content can be determined according to ASTM D2697, for example, D2697-03 (2014).

[0095] In the embodiment, the touch-dry time of the coating composition at 23°C and 50% relative humidity is in the range of 0.1 to 4 hours, for example, in the range of 0.2 to 3 hours. The touch-dry time is the time after which the coating is not sticky when lightly pressed with a finger and no marks are left on the coating.

[0096] In the embodiment, the hard-dry time is 1 to 30 hours, for example, 2 to 20 hours, at 23°C and 50% relative humidity. The hard-dry time is the time it takes for no film damage or marks to occur when a thumb is pressed firmly against the surface and twisted 180°.

[0097] [Preparation of coating composition] The coating composition can be prepared by mechanical mixing of components using conventional means and apparatus, such as stirring mixers, including anchor, paddle, propeller, turbine, and helical mixers.

[0098] In embodiments, the composition is prepared and provided in separate parts, for example, in a two-pack or two-component (2K) system. However, typically, the coating composition is a one-pack (1K) composition, i.e., the formulation is provided in a single pack so that mixing of separate curing and binder components is not required at the time of application.

[0099] The coating composition can achieve highly effective fouling control performance without the need for marine biokillers.

[0100] In embodiments, the coating is a so-called self-polishing coating, that is, designed to gradually wear down or erode over time, preventing the adhesion of fouling organisms or at least limiting the duration of fouling organisms on the coating surface.

[0101] [Application of coating composition] The coating composition can be applied to the substrate by known methods, such as conventional air spraying, or by airless spraying or air mix spraying equipment. Alternatively, for example, when used as a stripe coat, or for smaller vessels such as yachts, it can be applied using a brush or roller. The composition can be applied under ambient conditions without preheating. For spray application, conventional pressures, such as 3-6 bara (absolute bar), can be used.

[0102] The coating is typically applied to achieve a total dry film thickness of 100–1000 μm, for example, 100–500 μm or 150–350 μm. The applied film thickness may vary depending on the properties of the substrate to be coated and the environment to which it will be exposed.

[0103] [Coating type] The coating composition can be used alone or as part of a coating system comprising multiple coating compositions. The coating composition can be applied directly to a substrate surface or a pre-coated surface. For example, it can be applied over a primer or intermediate coat, such as a tie coat.

[0104] A particular advantage of the coating composition described above is its ability to combine desirable attributes such as good adhesion to an undercoat or tiecoat while still possessing highly effective fouling control properties.

[0105] In one embodiment, the coating composition is applied directly to the undercoated surface. In a further embodiment, the coating composition is applied to a tie coat layer. The tie coat may be on top of the primer layer or directly on the substrate surface.

[0106] In some embodiments, the coating composition is applied directly to a bare substrate. In other embodiments, the coating composition is applied to a pre-coated substrate so as to include one or more existing pre-cured and / or dried coating layers.

[0107] In the embodiment, the coating composition is applied to a primer layer on a substrate. The origin of the primer layer is not particularly limited, but in the embodiment, the primer is an epoxy resin-based primer.

[0108] In the embodiment, the coating composition is applied to a tie coat layer on a substrate, and the tie coat layer may optionally be on a primer layer on the substrate.

[0109] In one embodiment, the coating composition forms part of a multi-coat system that additionally includes a primer and / or tie coat.

[0110] In some embodiments, a tie coat layer can be applied on top of the primer layer to aid in bonding between the coating composition and the primer layer. However, in some embodiments, a tie coat is not required.

[0111] [Base material] The substrate to which the coating is applied may be intended to be permanently or intermittently immersed in water during use. Examples of substrates include metal, concrete, wood, or polymer surfaces.

[0112] The polymer surface includes polyvinyl chloride (PVC) or a composite material of fiber-reinforced resin. It also includes a flexible polymer carrier foil, such as a PVC carrier foil, where the uncoated side is or may be bonded to a different surface.

[0113] In the embodiment, the substrate is a surface that may be submerged in water, selected from, for example, one or more of the hull (or at least the waterline portion of the hull), propeller, and rudder. [Examples]

[0114] Next, the present invention will be described with reference to the following non-limiting embodiments.

[0115] [Procedure 1 - Synthesis of metal ion-containing monomer mixture] The monomer mixture was prepared according to the synthesis scheme from Production Example M3 of European Patent No. 2489710.

[0116] 70.1 g xylene, 15.2 g 1-methoxypropanol-2-ol, and 47.6 g zinc oxide were added to a flask equipped with an overhead stirrer and a temperature probe, and heated to 75°C. A mixture of 38.0 g methacrylic acid, 31.6 g acrylic acid, 44.0 g oleic acid, 2.7 g acetic acid, and 6.8 g propionic acid was added over 3 hours using a dropping funnel. The contents were then stirred at 75°C for a further 2 hours, after which 90.0 g xylene and 54.0 g 1-methoxypropanol-2-ol were added as after-feed additions, and the mixture was cooled. A solid monomer mixture containing the zinc salt of the acid was formed, which was filtered and recovered.

[0117] [Step 2 - Synthesis of acrylamide-modified polydimethylsiloxane monomers] A round-bottom flask was equipped with an overhead stirrer, thermocouple, condenser, and dropping funnel. It was also connected to a nitrogen line. 200 g of monoaminopropyl-terminated PDMS (MCR-A12, manufactured by Gelest Chemicals), 10.5 g of triethylamine (TEA), and 100 ml of chloroform were added to the flask, and the temperature was reduced to 2°C using an ice bath.

[0118] A dropping funnel containing 9.4 g of acryloyl chloride and 100 ml of chloroform was used to slowly add the contents to a round-bottom flask over a period of 5 hours.

[0119] The precipitate of TEA:HCl salt was filtered off and washed with 20 ml of chloroform. The washings were then combined with the filtrate. The combined filtrate / washings were washed twice with 200 ml of water, once with an aqueous NaCl solution (75 g NaCl in 200 ml of water), and once with a saturated sodium bicarbonate solution (16 g NaHCO3 in 200 ml of water).

[0120] The organic phase was dried overnight using 30 g of sodium sulfate, and then filtered to remove the sodium sulfate. The solvent was then removed from the filtrate by rotary evaporation, leaving behind acrylamide-modified PDMS.

[0121] [Step 3 - Synthesis of metal ion-containing (meth)acrylate copolymers] Two metal-modified anionic polymers were prepared using the materials and quantities listed in Table 1, following a procedure similar to that of Production Example S4 in European Patent No. 2489710.

[0122] Approximately 75% by weight of the total solvent was added to the reaction vessel and heated to 100°C. Separately, the monomer mixture from step 1, additional monomers, and azo initiator were dissolved in 10% by weight of the total solvent and added dropwise to the reaction vessel, which was heated with constant stirring for 5 hours. Then, using the remaining 15% by weight of the solvent, a solution containing the peroxide initiator was formed and then added to the reaction vessel over 30 minutes. The reaction was continued at 100°C for a further 90 minutes, after which it was cooled to room temperature.

[0123] These experiments were also performed with the copolymer solutions of Example 1 and Comparative Example 1, as well as with a commercially available fouling control coating, Intersleek® 1100SR (International Paints), for comparison.

[0124] [Table 1]

[0125] [Anti-fouling activity] The coating was applied to plywood test panels in a 6x6 "Latin grid" arrangement. The panels were immersed in seawater from Singapore or the northeast coast of the UK for 18 weeks, with an intermediate check performed at week 9. The degree of contamination observed was assigned on a scale from 1 to 100, where 100 represents the contamination observed for the performance of the commercially available Intersleek® 1100SR after 18 weeks, and 0 represents zero contamination.

[0126] The degree of cracking in the coating was also observed at the end of 18 weeks of immersion. A cracking rating of 1 to 5 was given, where 5 indicated no cracking and 1 indicated severe cracking.

[0127] The results are shown in Table 2.

[0128] [Table 2]

[0129] Example 1 not only exhibits the best activity against contamination but also possesses excellent resistance to the degradation of commercially available compositions.

[0130] [Flexibility] Flexibility tests were performed using a conical mandrel according to ASTM D522. The results are shown in Table 3. High mm values ​​indicate low flexibility, while low values ​​indicate good flexibility.

[0131] The samples were coated onto an aluminum panel using a 200 μm drawdown bar and dried at ambient temperature for 7 days before testing.

[0132] [Table 3]

[0133] The experiment demonstrates that compositions containing anionic polymers in which the polysiloxane moiety is bonded via amide groups are more flexible than the corresponding polymers in which the polysiloxane moiety is bonded by a different group, in this case via carboxyl groups.

[0134] [Polishing speed] A layer of epoxy coating (Intergard® 263, manufactured by International Paint) was applied to a polished Perspex disc with a diameter of 23 cm.

[0135] The test coatings were applied to the edges of the disks via a 600 μm drawdown cube. After drying the disks at ambient temperature for two weeks, testing began. Five replication experiments were performed for each test coating.

[0136] The substrate was immersed in seawater and rotated at 700 rpm. The film thickness was measured at periodic intervals using a laser surface shape analyzer, and film loss was calculated. The results are shown in Table 4.

[0137] [Table 4]

[0138] The results show that Example 1 exhibits a faster polishing rate compared to the comparative coating, which often correlates with improved fouling performance. The degradation rate is also consistent throughout the test period, indicating the absence of significant loss of film integrity, such as cracking, which would cause a rapid and increasing rate of film loss. The present specification includes the following embodiments. Section 1: A fouling control coating composition comprising an anionic polymer containing one or more metal cations, wherein the anionic polymer is an acrylate copolymer prepared from at least one acrylate monomer and at least one acrylamide monomer having a siloxane moiety covalently bonded via an amide group. Section 2: The fouling control coating composition according to claim 1, wherein at least one acrylate monomer unit of the anionic polymer contains an anionic carboxylate ion whose charge equilibrates with one or more metal cations. Section 3: The acrylate monomer is represented by the following formula: [ka] Each R f H, C 1~20 Aliphatic hydrocarbyl, C 6~12 Aryl, one or more C 1~6 C having an alkyl group 6~12 Aryl, C(O)O - , and C(O)OR t Selected from, Each R gH and C are independent of each other. 1~20 Aliphatic hydrocarbyl (e.g., alkyl), C 6~12 Aryl, and one or more (e.g., 1 to 4) C 1~6 C substituted with an aliphatic hydrocarbyl group 6~12 Selected from the alphabet, Each R t H and C are independent of each other. 1~6 Alkyl and C 1~6 Selected from haloalkyl groups, R a , R b and R c The optional substituents above are halides, -OR t and -N(R t ) Selected from 2, R g The optional substituents are halides, -OR t , -N(R t )2, -Si(R b ) 3-d (OR a ) d -OC(O)R t ,-C(O)N(R t )2, and -OC(O)N(R t )2, -([CR t 2] j E-) p R t , and -E-([CR t 2] j E-) p R t Selected from, R f The optional substituents are halides, -OR t , -N(R t )2, -Si(R b ) 3-d (OR a ) d ,-C(O)O - , -C(O)OR t -OC(O)R t ,-C(O)N(R t )2, and -OC(O)N(R t )2, -([CR t 2] j E-)p R t , and -E-([CR t 2] j E-) p R t Selected from, Each R a H and C are independent of each other. 1~12 Alkyl, phenyl, and one or more (e.g., 1-4) C 1~6 Selected from alkyl-substituted phenyls, Each R b H and R are independent of each other. c Selected from, Each R c C is independently and, in some cases, is being substituted. 1~20 Aliphatic hydrocarbyl groups, and in some cases substituted C 6~12 Aryl group, and One or more C 1~6 C having an alkyl group (in some cases substituted) 6~12 Selected from aryl groups, Each E is independent of O and NR t Selected from, Each d is independent and within the range of 0 to 3. Each j is independent and within the range of 1 to 6. The fouling control coating composition according to item 2, wherein each p is independently in the range of 1 to 20. Section 4: The acrylate monomer has the following characteristics: (i) Each R g However, H and unsubstituted C 1~6 To be selected from alkyl groups, (ii)R f However, H, and -C(O)O - and C(O)OR t C potentially substituted with one substituent selected from 1~6 A fouling control composition according to item 3, having one or more of the following characteristics: being selected from alkyl groups. Section 5: The acrylamide monomer having a siloxane moiety covalently bonded via an amide group is represented by the following formula: [ka] Each R a H and C are independent of each other. 1~12 Alkyl, phenyl, and one or more (e.g., 1-4) C 1~6 Selected from alkyl-substituted phenyls, Each R b H and R c Selected independently from, Each R c C is independently and, in some cases, is being substituted. 1~20 Aliphatic hydrocarbyl groups, and in some cases substituted C 6~12 An aryl group and one or more C 1~6 C having an alkyl group (in some cases substituted) 6~12 Selected from aryl groups, Each R f H, C 1~20 Aliphatic hydrocarbyl, C 6~12 Aryl, one or more C 1~6 Alkyl, C(O)O - , and C(O)OR t C has 6~12 Selected from the alphabet, Each R g H and C are independent of each other. 1~20 Aliphatic hydrocarbyl (e.g., alkyl), C 6~12 Aryl, one or more (e.g., 1-4) C 1~6 C substituted with an aliphatic hydrocarbyl group 6~12 Selected from the alphabet, Each R t H and C are independent of each other. 1~6 Alkyl and C 1~6 Selected from haloalkyl groups, R a , R b and R c The optional substituents above are halides, -OR t and -N(R t ) Selected from 2, R g The optional substituents are halides, -ORt , -N(R t )2, -Si(R b ) 3-d (OR a ) d -OC(O)R t ,-C(O)N(R t )2, and -OC(O)N(R t )2, -([CR t 2] j E-) p R t , and -E-([CR t 2] j E-) p R t Selected from, R f The optional substituents are halides, -OR t , -N(R t )2, -Si(R b ) 3-d (OR a ) d ,-C(O)O - , -C(O)OR t -OC(O)R t ,-C(O)N(R t )2, and -OC(O)N(R t )2, -([CR t 2] j E-) p R t , and -E-([CR t 2] j E-) p R t Selected from, Each E is independent of O and NR t Selected from, T is -O-, -NR t - is either or does not exist, b is in the range of 4 to 150. Each d is independent and within the range of 0 to 3. Each j is independent and within the range of 1 to 6. A fouling control composition according to any one of claims 1 to 4, wherein each p is independently in the range of 1 to 20. Section 6: below (i) Each Rg and R f H and unsubstituted C are independent of each other. 1~6 To be selected from alkyl groups, (ii)R a , R b And L, independently, non-substituted C 1~6 Selected from alkyl and phenyl which may be substituted with one or more unsubstituted alkyl groups. (iii) Each R t H and C are independent of each other. 1~6 To be selected from alkyl groups, (iv) No halogen group is present in the monomer. (v) T does not exist, (vi) The fouling control composition according to item 5, wherein one or more of the following applies: j is in the range of 2 to 4. Section 7: The contamination control composition according to any one of claims 1 to 6, wherein the siloxane substituent is a polydimethylsiloxane substituent. Section 8: The contamination control composition according to any one of claims 1 to 7, wherein the siloxane-modified anionic polymer is a thermoplastic polymer. Section 9: The fouling control coating composition according to any one of claims 1 to 8, wherein the metal cation is selected from Mg, Ca, Zn, and Cu. Section 10: A self-polishing, fouling-controlling coating composition according to any one of claims 1 to 9. Section 11: A method for controlling aquatic fouling on an artificial object, comprising the step of applying a fouling control coating composition according to any one of items 1 to 10 to the surface of the artificial object, wherein the artificial object is a structure intended to be permanently or intermittently immersed in water. Section 12: A substrate or article coated with a fouling control coating composition as described in any one of items 1 to 10. Section 13: Use of a coating composition according to any one of items 1 to 10 for controlling aquatic fouling on artificial structures.

Claims

1. A fouling control coating composition comprising an anionic polymer containing one or more metal cations, wherein the anionic polymer is an acrylate copolymer prepared from at least one acrylate monomer and at least one acrylamide monomer having a siloxane moiety covalently bonded via an amide group.

2. The fouling control coating composition according to claim 1, wherein at least one acrylate monomer unit of the anionic polymer contains an anionic carboxylate ion whose charge equilibrium is balanced by one or more metal cations.

3. The acrylate monomer is represented by the following formula: 【Chemistry 1】 Each R ｆ H, C １～２０ Aliphatic hydrocarbyl, C ６～１２ Aryl, one or more C １～６ C containing alkyl ６～１２ Ariel, C(O)O － , and C(O)OR ｔ Selected from, Each R ｇ is independently selected from H and C1-20 aliphatic hydrocarbyl, C ６～１２ aryl, and C １～６ aryl substituted with one or more C ６～１２ aliphatic hydrocarbyl groups, Each R ｔ These are H and C, independently. １～６ Alkyl and C １～６ Selected from haloalkyl groups, R ａ , R ｂ and R ｃ The optional substituents above are halides, -OR ｔ and -N(R ｔ ) ２ Selected from, R ｇ The optional substituents are halides, -OR ｔ , -N(R ｔ ) ２ , -Si(R ｂ ) ３－ｄ (OR ａ ) ｄ , -OC(O)R ｔ , -C(O)N(R ｔ ) ２ , and -OC(O)N(R ｔ ) ２ ,-([CR ｔ ２ ] ｊ E-) ｐ R ｔ , and -E-([CR ｔ ２ ] ｊ E-) ｐ R ｔ Selected from, R ｆ The optional substituents are halides, -OR ｔ , -N(R ｔ ) ２ , -Si(R ｂ ) ３－ｄ (OR ａ ) ｄ , -C(O)O － , -C(O)OR ｔ , -OC(O)R ｔ , -C(O)N(R ｔ ) ２ , and -OC(O)N(R ｔ ) ２ ,-([CR ｔ ２ ] ｊ E-) ｐ R ｔ , and -E-([CR ｔ ２ ] ｊ E-) ｐ R ｔ Selected from, Each R ａ H and C are independent of each other. １～１２ Alkyl, phenyl, and one or more C １～６ Selected from alkyl-substituted phenyls, Each R ｂ H and R are independent of each other. ｃ Selected from, Each R ｃ C is independently and, in some cases, is being substituted. １～２０ Aliphatic hydrocarbyl groups, and in some cases substituted C ６～１２ Aryl group, and One or more C １～６ C having an alkyl group, possibly substituted ６～１２ Selected from aryl groups, Each E is independent of O and NR ｔ Selected from, Each d is independently within the range of 0 to 3. Each j is independent and within the range of 1 to 6. The fouling control coating composition according to claim 2, wherein each p is independently in the range of 1 to 20.

4. The acrylate monomer has the following characteristics: (i) Each R ｇ However, H and unsubstituted C １～６ To be selected from alkyl groups, (ii) R ｆ However, H, and -C(O)O － and C(O)OR ｔ A C which may be substituted with one substituent selected from １～６ The fouling control coating composition according to claim 3, having one or more of the following characteristics: being selected from alkyl groups.

5. The acrylamide monomer having a siloxane moiety covalently bonded via an amide group is represented by the following formula: 【Chemistry 2】 Each R ａ These are H and C, independently. １～１２ Alkyl, phenyl, and one or more C １～６ Selected from alkyl-substituted phenyls, Each R ｂ is independently selected from H and R ｃ and Each R ｃ C is independently and, in some cases, is being substituted. １～２０ Aliphatic hydrocarbyl groups, and in some cases substituted C ６～１２ An aryl group and one or more carbon atoms. １～６ C having an alkyl group, possibly substituted ６～１２ Selected from aryl groups, Each R ｆ is selected from H, C １～２０ aliphatic hydrocarbyl, C ６～１２ aryl, one or more C １～６ alkyl, C(O)O － , and C(O)OR ｔ and is selected from C ６～１２ aryl having the same, Each R ｇ These are independently H and C1-20 aliphatic hydrocarbyl, C ６～１２ Aryl, one or more C １～６ C substituted with an aliphatic hydrocarbyl group ６～１２ Selected from the alphabet, Each R ｔ H and C are independent of each other. １～６ Alkyl and C １～６ Selected from haloalkyl groups, R ａ , R ｂ and R ｃ The optional substituents above are halides, -OR ｔ and -N(R ｔ ) ２ Selected from, R ｇ The optional substituents are halides, -OR ｔ , -N(R ｔ ) ２ , -Si(R ｂ ) ３－ｄ (OR ａ ) ｄ , -OC(O)R ｔ , -C(O)N(R ｔ ) ２ , and -OC(O)N(R ｔ ) ２ ,-([CR ｔ ２ ] ｊ E-) ｐ R ｔ , and -E-([CR ｔ ２ ] ｊ E-) ｐ R ｔ Selected from, R ｆ The optional substituents are halides, -OR ｔ , -N(R ｔ ) ２ , -Si(R ｂ ) ３－ｄ (OR ａ ) ｄ , -C(O)O － , -C(O)OR ｔ , -OC(O)R ｔ , -C(O)N(R ｔ ) ２ , and -OC(O)N(R ｔ ) ２ ,-([CR ｔ ２ ] ｊ E-) ｐ R ｔ , and -E-([CR ｔ ２ ] ｊ E-) ｐ R ｔ Selected from, Each E is independent of O and NR ｔ Selected from, T does not exist. b is in the range of 4 to 150. Each d is independently within the range of 0 to 3. Each j is independent and within the range of 1 to 6. The fouling control coating composition according to claim 1, wherein each p is independently in the range of 1 to 20.

6. below (i) Each R ｇ and R ｆ H and unsubstituted C independently １～６ To be selected from alkyl groups, (ii) R ａ , R ｂ And each of L independently, non-substituted C １～６ Selected from alkyl and phenyl which may be substituted with one or more unsubstituted alkyl groups. (iii) Each R ｔ H and C are independent of each other. １～６ To be selected from alkyl groups, (iv) No halogen group is present in the monomer. The fouling control coating composition according to claim 5, wherein one or more of (vi)j is in the range of 2 to 4.

7. The stain-controlling coating composition according to claim 1, wherein the siloxane substituent is a polydimethylsiloxane substituent.

8. The fouling control coating composition according to claim 1, wherein the siloxane-modified anionic polymer is a thermoplastic polymer.

9. The contamination control coating composition according to claim 1, wherein the metal cation is selected from Mg, Ca, Zn, and Cu.

10. The fouling control coating composition according to claim 1, which is a self-polishing fouling control coating composition.

11. A method for controlling aquatic fouling on an artificial object, comprising the step of applying a fouling control coating composition according to any one of claims 1 to 10 to the surface of the artificial structure, wherein the artificial structure is a structure intended to be permanently or intermittently immersed in water.

12. A substrate or article coated with the fouling control coating composition according to any one of claims 1 to 10.

13. Use of the fouling control coating composition according to any one of claims 1 to 10 for controlling aquatic fouling on artificial structures.

Images