Antifouling composition

Abstract

The present invention provides an antifouling coating composition comprising (i) a silyl (meth) acrylate copolymer comprising at least 15 wt% of silyl ester monomers relative to the total weight of monomers in the silyl (meth) acrylate copolymer, and / or (ii) a (meth) acrylic polymer comprising at least 15 wt% of silyl ester monomers relative to the total weight of monomers in the silyl (meth) acrylate copolymer, a (meth) acrylic polymer comprising 10 wt% or less of a silyl ester monomer and 5.0 wt% or less of a metal ester monomer with respect to the total weight of monomers in the (meth) acrylic polymer; (iii) a monocarboxylic acid or a metal salt thereof; (iv) a biocide comprising: a. A bromopyrrole nitrile; and b. One or more copper compounds having a copper content of at least 40 wt% relative to the formula amount of the copper compound wherein the coating composition comprises, as a whole, 10.0 wt% or less of a biocide; and (v) at least 35 wt%, relative to the total weight of the coating composition as a whole, of a combined pigment, extender and biocide.

Description

Technical Field

[0001] This invention relates to marine antifouling coating compositions, and more specifically to antifouling coating compositions comprising a biocide (insecticide, antimicrobial agent, bioocide) in an amount of 10.0 wt% or less, wherein the biocide includes tralopyril and a copper compound having a copper content of at least 40 wt%. The composition further contains a monocarboxylic acid or its metal salt, a (meth)acrylic silyl ester copolymer and / or a (meth)acrylic polymer, and pigments and / or extenders. The invention further relates to a method for protecting an object from fouling (scaling, buildup), and to an object coated with the antifouling composition of the invention. Background Technology

[0002] Surfaces submerged in seawater are fouled by marine organisms such as green and brown algae, barnacles, mussels, and tube worms. This fouling is undesirable and has economic consequences on marine structures such as ships, oil platforms, and buoys. Fouling can lead to surface biodegradation, increased load, and accelerated corrosion. On ships, fouling increases frictional drag, resulting in reduced speed and / or increased fuel consumption.

[0003] Antifouling paints are used to prevent the settling and growth of marine organisms. These paints typically contain film-forming binders, as well as various components such as pigments, extenders, additives, solvents, and bioactive substances (biocides). Biocides can be broadly classified into those effective against soft fouling such as green and brown algae, grasses, and slime, and those effective against hard fouling such as barnacles, mussels, and tube worms.

[0004] The largest product segment of antifouling coating systems for merchant ships is self-polishing antifouling coatings (SPC). Most products are copper-based, containing relatively high total amounts of biocides, pigments, and extenders. Commercial copper-based products typically contain 20-50% cuprous oxide (I) by weight and an additional 1-10% by weight of organic biocides to broaden the product's antifouling activity range. Cuprous oxide (I) is known to have good activity against hard fouling, while organic biocides are primarily effective against soft fouling. One of the success factors of SPC products is the ability to adjust polishing rates to maximize their effectiveness on ships with varying operating speeds and activities.

[0005] Regulatory bodies have approved a limited number of biocides for use as marine antifouling agents. Approved biocides are considered safe to use and have no adverse environmental impacts. However, optimizing the combination of biocides in coating films to minimize their use remains important. Restrictions on the use of biocides are increasing, and it is likely that the amount of biocides in antifouling coatings will have to be significantly reduced in the future. Maintaining good long-term antifouling performance presents challenges when reducing biocide levels.

[0006] Low-biocide formulations are typically associated with formulations containing low levels of pigments and extenders, often combined with polysiloxane binders or binders with polysiloxane blocks and / or added silicone oils. An example of a commercial product is biocide-fouling release coatings (FRCs). Reducing biocides to low levels in conventional self-polishing antifouling coatings would require the complete or partial replacement of the biocides with other components. This would affect the coating's self-polishing properties, mechanical properties, and antifouling performance unless the formulation is carefully redesigned. Therefore, there remains a need to develop new self-polishing antifouling coating compositions containing reduced levels of biocides.

[0007] Bromopyrrolidone (tralopyril) is a relatively new metal-free organic marine antifouling agent with broad-spectrum activity against hard-shelled and soft-bodied invertebrates such as barnacles, hydroids, mussels, oysters, tube worms, and tunicates. Bromopyrrolidone is sold under the trade name Econea, and supplier datasheets recommend its use in antifouling coating compositions at 4 to 6 wt%. Achieving sufficient antifouling performance is challenging when using smaller amounts of bromopyrrolidone as the sole biocide for effective combat against hard fouling.

[0008] The inventors have unexpectedly discovered that combining bromopyrrolidone with copper compounds as defined herein can produce self-polishing antifouling coating compositions having a total biocide content of 10 wt% or less. These coating compositions exhibit unexpectedly attractive antifouling properties. Summary of the Invention

[0009] In one aspect, the present invention relates to an antifouling coating composition comprising: (i) A silyl methacrylate copolymer comprising at least 15 wt% silyl ester monomers relative to the total weight of the monomers present in the silyl methacrylate copolymer; and / or (ii) (meth)acrylic polymer ((meth)acrylic polymer) comprising 10 wt% or less of silyl ester monomer and 5.0 wt% or less of metal ester monomer relative to the total weight of the monomers present in the (meth)acrylic polymer. (iii) Monocarboxylic acid or its metal salt; (iv) Biocides, including: a. Bromopyrrolidinium (tralopyril); and b. One or more copper compounds having a copper content of at least 40 wt% relative to the formula weight of the copper compound, wherein the coating composition as a whole contains 10.0 wt% or less of a biocide; and (v) At least 35 wt% of the combined pigments, extenders and biocides relative to the total weight of the coating composition as a whole.

[0010] In another aspect, the present invention relates to an antifouling coating composition comprising: (i) a silyl methacrylate copolymer comprising at least 15 wt% silyl ester monomers relative to the total weight of the monomers present in the silyl methacrylate copolymer; and (ii) A (meth)acrylic acid polymer comprising 10 wt% or less of silyl ester monomers and 5.0 wt% or less of metal ester monomers relative to the total weight of the monomers present in the (meth)acrylic acid polymer; (iii) Monocarboxylic acids or their metal salts; (iv) Biocides, including: a. Bromopyrrolidinium; and b. One or more copper compounds having a copper content of at least 40 wt% relative to the formula weight of the copper compound, wherein the coating composition as a whole contains 10.0 wt% or less of a biocide; and (v) At least 35 wt% of the combined pigments, extenders and biocides relative to the total weight of the coating composition as a whole.

[0011] In another aspect, the present invention relates to an antifouling coating composition comprising: (ii) At least one, preferably at least two (meth)acrylic acid polymers, comprising 10 wt% or less of silyl ester monomers and 5.0 wt% or less of metal ester monomers relative to the total weight of the monomers present in the (meth)acrylic acid polymer; (iii) Monocarboxylic acids or their metal salts; (iv) Biocides, including: a. Bromopyrrolidinium; and b. One or more copper compounds having a copper content of at least 40 wt% relative to the formula weight of the copper compound, wherein the coating composition as a whole contains 10.0 wt% or less of a biocide; and (v) At least 35 wt% of the combined pigments, extenders and biocides relative to the total weight of the coating composition as a whole.

[0012] In a further aspect, the present invention relates to a method for protecting an object from contamination, the method comprising coating at least a portion of the contaminated object with an antifouling coating composition as defined above.

[0013] In another aspect, the present invention relates to an object coated with an antifouling coating composition as defined above.

[0014] definition

[0015] As used herein, the terms “marine antifouling coating composition,” “antifouling coating composition,” or simply “coating composition” refer to a composition which, when applied to a surface, prevents or minimizes the growth of marine organisms on the surface.

[0016] The antifouling coating composition of the present invention is a "self-polishing" coating. By "self-polishing" or "polishing," we mean that the coating material at the surface of the coating film is removed over time due to degradation and / or erosion by the surrounding water medium, resulting in a reduction in film thickness.

[0017] As used herein, the term "paint" refers to a composition comprising, as described herein, an antifouling coating composition and an optional solvent, which is ready for use (ready-to-use), for example, for spraying. Thus, the antifouling coating composition may be a paint on its own, or the coating composition may be a concentrate to which a solvent is added to produce a paint.

[0018] As used herein, the terms "(meth)acrylic polymer" and "(meth)acrylate silyl ester copolymer" refer to polymers comprising repeating units derived from (meth)acrylate monomers. Generally, a (meth)acrylic polymer or a (meth)acrylate silyl ester copolymer will comprise at least 50 wt% of repeating units derived from (meth)acrylate monomers, i.e., acrylate and / or methacrylate monomers.

[0019] When a given wt% of a monomer in a polymer is given, wt% is relative to the total (weight) of the monomers present in the copolymer.

[0020] As used herein, the term "hydrocarbon group" refers to any group containing only C and H atoms, and therefore encompasses alkyl, aryl, cycloalkyl, aralkyl, etc.

[0021] As used herein, the term "alkyl" refers to a saturated straight-chain or branched group.

[0022] As used herein, the term "cycloalkyl" refers to a cyclic alkyl group.

[0023] As used herein, the term "alkylene" refers to a divalent alkyl group.

[0024] As used herein, the term "aryl" refers to a group comprising at least one aromatic ring. Aryl groups can be substituted or unsubstituted. An example of an aryl group is the phenyl group, i.e., C6H5. Phenyl groups can be substituted or unsubstituted.

[0025] As used herein, the term "(meth)acrylate" includes both methacrylate and acrylate.

[0026] As used herein, the term “volatile organic compound (VOC)” refers to a compound having a boiling point of 250°C or lower at a standard atmospheric pressure of 1 atm.

[0027] As used herein, "antifouling agent" or "biocide" refers to a bioactive compound or mixture of bioactive compounds that prevent or minimize the settling and / or growth of marine organisms on a surface.

[0028] As used herein, the term "monocarboxylic acid" refers to a compound containing a -COOH group.

[0029] The term “adhesive” is defined as a portion of a composition comprising components (i), (ii) and (iii) as defined herein, as well as any other components, which together form a matrix that imparts strength and / or flexibility to a coating film.

[0030] The term "Tg" refers to the glass transition temperature.

[0031] Unless otherwise specified, the term "wt% based on total weight of composition" means wt% of the components present in the total coating composition.

[0032] As used herein, the term "wt% based on total dry weight of the composition" means wt% of the dry components present in the dry weight of the coating composition, i.e., excluding solvents and other volatiles unless otherwise specified. Detailed Implementation

[0033] This invention relates to a novel antifouling coating composition comprising: (i) a (meth)acrylate silyl ester copolymer and / or (ii) a (meth)acrylate polymer; (iii) a monocarboxylic acid or a metal salt thereof; and (iv) a biocide comprising bromopyrrolidone (tralopyril) and a copper compound in an amount of 10.0 wt% or less; and (v) a combination of pigments, extenders, and biocide in an amount of at least 35 wt% relative to the total weight of the coating composition.

[0034] The adhesives of the present invention comprise components (i) to (iii) that are always present (or have always been present). The coating compositions of the present invention comprise (i) a silyl methacrylate copolymer and / or (ii) a methacrylate copolymer as defined herein.

[0035] In a preferred embodiment, the antifouling coating composition of the present invention comprises (i) a silyl methacrylate copolymer as defined herein.

[0036] In a second preferred embodiment, the antifouling coating composition of the present invention comprises both (meth)acrylate silyl ester copolymer (i) and (meth)acrylate polymer (ii) as defined herein.

[0037] In a third preferred embodiment, the antifouling coating composition of the present invention comprises a (meth)acrylic polymer (ii) as defined herein.

[0038] In a fourth preferred embodiment, the antifouling coating composition of the present invention comprises at least two (meth)acrylic polymers (ii), such as (meth)acrylic polymer (ii-a) and (meth)acrylic polymer (ii-b), wherein polymers (ii-a) and (ii-b) are different.

[0039] (Meth)acrylate silyl ester copolymer (i)

[0040] The use of (meth)acrylate silyl ester copolymers in antifouling coating compositions is well known, and in its most extensive embodiments, the present invention covers any of these well-known copolymers.

[0041] The (meth)acrylate silyl ester copolymer (i) comprises repeating units derived from (meth)acrylate monomers. Preferably, the (meth)acrylate silyl ester copolymer (i) comprises at least 80 wt% of repeating units derived from (meth)acrylate monomers, i.e., repeating units of acrylate and / or methacrylate monomers. More preferably, the (meth)acrylate silyl ester copolymer (i) comprises at least 85 wt%, more preferably at least 90 wt%, and even more preferably at least 95 wt% of repeating units derived from (meth)acrylate monomers. The preferred (meth)acrylate silyl ester copolymer present in the compositions of the present invention comprises 80-100 wt%, more preferably 85-100 wt%, and even more preferably 90-100 wt% of repeating units derived from (meth)acrylate monomers.

[0042] In a preferred embodiment, the (meth)acrylate silyl ester copolymers comprise 100 wt% structural units derived from (meth)acrylate monomers, i.e., they do not contain any other type of monomers.

[0043] The coating compositions of the present invention may comprise a mixture of two or more different (meth)acrylate silyl ester copolymers (i), such as those described in GB2576431.

[0044] The (meth)acrylate silyl ester copolymer of the present invention preferably comprises structural units derived from (meth)acrylate silyl ester monomers (a1) and structural units derived from polymerizable olefinic unsaturated monomers (a2).

[0045] (Meth)acrylate silyl ester monomer (a1)

[0046] Preferably, the (meth)acrylate silyl ester copolymer (i) comprises residues of at least one silyl ester monomer (a1) of formula (I): (I) in R 1 It is H or CH3; R 2 Each is independently selected from C1-C10 hydrocarbon groups and OSi(R) 3 )3 groups; Among them, R 3 Each is independently selected from the group consisting of straight-chain or branched C1-C10 alkyl groups.

[0047] The term "alkyl group" is intended to encompass straight-chain or branched alkyl groups, such as methyl, isopropyl, propyl, butyl, isobutyl, tert-butyl, 1,1,2-trimethylpropyl, and 2-ethylhexyl; cycloalkyl groups, such as cyclohexyl and substituted cyclohexyl groups; and aryl groups, such as phenyl and substituted phenyl groups. Preferably, each R... 2 Independently C1-8 alkyl. Preferably all R 2 The functional groups are the same.

[0048] Preferred for each R 3 Independently C1-4 alkyl. Preferably all R 3 The functional groups are the same.

[0049] The monomers (a1) defined by general formula (I) include silyl ester monomers such as tri-n-propyl silyl acrylate, tri-isopropyl silyl acrylate, tri-n-butyl silyl acrylate, tri-isobutyl silyl acrylate, tri-2-ethylhexyl silyl acrylate, tert-butyl dimethyl silyl acrylate, thexyldimethylsilyl(meth)acrylate, tert-butyldiphenyl silyl acrylate, bis(trimethylsiloxy)methylsilyl (meth)acrylate, and tris(trimethylsiloxy)silyl (meth)acrylate.

[0050] Triisopropyl silyl acrylate and / or triisopropyl silyl methacrylate are preferred. Therefore, R 2 Isopropyl is preferred.

[0051] The silyl methacrylate monomer of formula (I) can be used alone, or two or more silyl methacrylate monomers of formula (I) can be used in combination. The silyl methacrylate copolymer (i) preferably contains one or two different monomers of formula (I), especially one.

[0052] The (meth)acrylate silyl ester copolymer (i) preferably comprises at least 15 wt% of silyl ester monomers relative to the total weight of the monomers present in the copolymer, for example, those of formula (I). Preferably, the (meth)acrylate silyl ester copolymer comprises at least 30 wt%, more preferably at least 40 wt%, such as at least 45 wt%, of silyl ester monomers relative to the total weight of the monomers present in the copolymer.

[0053] The (meth)acrylate silyl ester copolymer (i) preferably comprises less than 80 wt% silyl ester monomers relative to the total weight of the monomers present in the copolymer. Preferably, the (meth)acrylate silyl ester copolymer comprises less than 75 wt% silyl ester monomers, more preferably less than 70 wt%, such as less than 65 wt%, relative to the total weight of the monomers present in the copolymer.

[0054] Alkenyl unsaturated monomer (a2)

[0055] The (meth)acrylate silyl ester copolymer (i) of the present invention preferably contains residues of at least one olefinically unsaturated monomer (a2) that will polymerize with the (meth)acrylate silyl ester monomer (a1). Monomers (a1) and (a2) are different. Monomer (a2) preferably does not contain silyl ester groups. Monomer (a2) preferably does not contain metal ester groups.

[0056] The olefinically unsaturated monomer (a2) is preferably selected from (meth)acrylate monomers and vinyl monomers. Preferably, the olefinically unsaturated monomer (a2) is a (meth)acrylate monomer.

[0057] Examples of suitable (meth)acrylate monomers (a2) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isodecanyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,5-methyl (meth)acrylate,5-Trimethylcyclohexyl ester, isobornyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, methoxycarbonylmethyl methacrylate (meth)acrylate), ethoxycarbonyl methyl methacrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl acrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl(meth)acrylate, 2-(2-ethoxy-2-oxoethoxy)-2-oxoethyl(meth)acrylate, oligo(oxycarbonylmethyl) methyl acrylate (meth)acrylate), oligo(oxycarbonylmethyl)ethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, glycerolformal(meth)acrylate, isopropylideneglycerol(meth)acrylate, glycerolcarbonate(meth)acrylate, cyclic trimethylolpropane formal(meth)acrylate, glycidyl(meth)acrylate, and 4-glycidyloxybutyl(meth)acrylate; Examples of suitable vinyl monomers (a2) are styrene, vinyl 2-ethylhexanoate, and vinyl neodecanoate.

[0058] A mixture of different monomers (a2) can be used.

[0059] Preferably, the olefinically unsaturated monomer (a2) has formula (II): (II) Among them, R 4 It is H or CH3, and R 5 It is a C1-C20 hydrocarbon substituent, preferably a C1-C10 alkyl substituent, such as a C1-C8 alkyl. R 5 The group can be straight-chain or branched. Most preferably, R 5 It is a methyl, ethyl, propyl, butyl, hexyl, octyl, or decyl group, which can be straight-chain or branched (if possible). R 5 The ideal choices are methyl, ethyl, n-butyl, isobutyl, or isooctyl.

[0060] Examples of suitable monomers of formula (II) for monomer (a2) in (meth)acrylic polymer (ii-a) include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, 2-octyl methacrylate, isooctyl methacrylate, 2-propylheptyl methacrylate, isodecanyl methacrylate, cyclohexyl methacrylate, 3,5,5-trimethylcyclohexyl methacrylate, and isobornyl methacrylate.

[0061] Preferred choices for monomers of formula (II) include methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, or isobutyl methacrylate.

[0062] A mixture of different monomers of formula (II) can be used.

[0063] Alkenyl unsaturated monomers (a2) can also have formula (III): (III) Among them, R 6 It is H or CH3, and R 7 It is a C3-C40 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom, and more preferably a C3-C20 substituent containing at least one oxygen atom.

[0064] Preferably, R7 The group has the formula (CH2CH2O). n -R 8 , where R 8 It is a C1-C10 hydrocarbon substituent, preferably a C1-C10 alkyl or C6-C10 aryl substituent, and n is an integer in the range of 1 to 5, preferably 1 to 3. Preferably, R 7 It has the formula (CH2CH2O) n -R 8 , where R 8 It is a C1-C10 alkyl substituent, preferably CH3 or CH2CH3, and n is an integer in the range of 1 to 3, preferably 1 or 2.

[0065] Such monomers can be 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl methacrylate, or 2-[2-(2-ethoxyethoxy)ethoxy]ethyl methacrylate.

[0066] The preferred monomer (a2) of formula (III) is 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate or 2-(2-ethoxyethoxy)ethyl methacrylate.

[0067] R 7 The group can also have the formula (CH2C(O)O)pR 9 or (CH(CH3)C(O)O)pR 9 , where R 9 It is a C1-C10 hydrocarbon substituent, preferably a C1-C10 alkyl or C6-C10 aryl substituent, and p is an integer in the range of 1 to 10, preferably 1 to 4.

[0068] The monomers of such formula (III) can be methoxycarbonyl methyl methacrylate, ethoxycarbonyl methyl methacrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl methacrylate, 2-(2-ethoxy-2-oxoethoxy)-2-oxoethyl methacrylate, oligomeric (oxycarbonylmethyl)methyl (meth)acrylate, and oligomeric (oxycarbonylmethyl)ethyl (meth)acrylate.

[0069] R 7The group can also be a cyclic group containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom. In this embodiment, R 7 It can be the WR group 10 , where R 10 It is a cyclic ether, such as oxirane, furan, oxolane, oxane, dioxolane, dioxane, optionally substituted with an alkyl group, and W is a C1-C4 alkylene group.

[0070] The monomers of such formula (III) can be furfuryl methacrylate, tetrahydrofurfuryl methacrylate, glycerol formal (meth)acrylate, isopropylideneglycerol (meth)acrylate, glycerol carbonate (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycidyl methacrylate, and 4-glycidyloxybutyl methacrylate. Preferred cyclic ethers should contain at least four atoms in the ring, such as tetrahydrofurfuryl methacrylate and isopropylideneglycerol methacrylate.

[0071] The monomer of formula (III) is preferably 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate or tetrahydrofurfuryl acrylate.

[0072] A mixture of different monomers of formula (III) can be used.

[0073] Mixtures of different monomers of formula (II) and formula (III) can also be used together.

[0074] If the monomer of formula (III) is present in the (meth)acrylate silyl ester copolymer (i) of the present invention, then preferably at least one monomer of formula (II) is also present.

[0075] The preferred (meth)acrylate silyl ester copolymer (i) of the present invention comprises structural units derived from one or more monomers of formula (I), such as triisopropyl silyl acrylate and / or triisopropyl silyl methacrylate, structural units derived from one or more monomers of formula (II), such as methyl methacrylate and / or butyl acrylate, and optionally structural units derived from one or more monomers of formula (III), such as 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, and 2-(2-ethoxyethoxy)ethyl acrylate.

[0076] Preferably, relative to the total weight of the monomers present in the (meth)acrylate copolymer (i) as a whole, the content of one or more (meth)acrylate monomers (a1) (such as monomers of formula (I)) in the (meth)acrylate copolymer (i) is in the range of 30-80 wt%, preferably 35-75 wt%, such as 40-70 wt% and 45-65 wt%.

[0077] Preferably, the (meth)acrylate silyl ester copolymer (i) comprises 20-70 wt%, such as 30-60 wt% and 35-55 wt%, more preferably 35-55 wt% of monomers (a2) (such as those of formula (II) or formula (III)) relative to the total weight of the monomers present in the (meth)acrylate silyl ester copolymer as a whole.

[0078] Preferably, the (meth)acrylate silyl ester copolymer (i) comprises at least 15 wt%, especially 15-65 wt%, of one or more monomers of formula (II).

[0079] Preferably, the (meth)acrylate silyl ester copolymer (i) contains less than 40 wt%, more preferably 2.0 to 35 wt%, of one or more monomers of formula (III).

[0080] When R in equation (III) 7 The functional group is of the formula -(CH2CH2O). n -R 8 When the group is, the (meth)acrylate silyl ester copolymer (i) may contain 2.0 to 40 wt% of one or more monomers of formula (III).

[0081] When R in equation (III) 7 When the group is a cyclic group, the (meth)acrylate silyl ester copolymer (i) may contain 5.0 to 40 wt% of one or more monomers of formula (III).

[0082] The (meth)acrylate silyl ester copolymer (i) preferably has a weight-average molecular weight (Mw) of 5,000-70,000, more preferably 8,000-55,000, and more preferably 20,000-45,000. Mw is determined as described in the Examples section. The (meth)acrylate silyl ester copolymer (i) preferably has a polydispersity index (PDI) of 1.5 to 8.0, more preferably 2.0 to 5.0.

[0083] The copolymer preferably has a glass transition temperature (Tg) of at least 15°C, preferably at least 20°C, such as at least 25°C, all values ​​measured according to the Tg test described in the Examples section. Values ​​less than 80°C are preferred, such as less than 70°C, for example less than 60°C or less than 55°C.

[0084] (i) methacrylate silyl ester copolymer can be provided in a polymer solution, such as a xylene solution. The polymer solution is ideally adjusted to have a solids content of 30 to 90% by weight, preferably 40 to 85% by weight, and more preferably 45 to 75% by weight.

[0085] In a preferred embodiment, the antifouling coating composition of the present invention preferably comprises 2.0 to 30 wt% of (meth)acrylate silyl ester copolymer (i), such as 5.0 to 25 wt%, particularly 7.0 to 20 wt% or 7.0 to 15 wt%, based on the total coating composition.

[0086] In a preferred embodiment, the antifouling coating composition of the present invention preferably comprises 5.0 to 40 wt% of (meth)acrylate silyl ester copolymer (i), such as 7.0 to 30 wt%, particularly 10 to 25 wt%, based on the total dry weight of the coating composition.

[0087] In a preferred embodiment, the (meth)acrylate silyl ester copolymer (i) in the antifouling coating composition of the present invention is present in an amount of 20-70 wt%, preferably 30-65 wt%, more preferably 40-60 wt%, based on the total dry weight of the binder in the coating composition.

[0088] If the antifouling coating composition contains a mixture of two or more different (meth)acrylate silyl copolymers (i), these percentages apply to the content of all (meth)acrylate silyl copolymers (i) present. Preferably, only one (meth)acrylate silyl copolymer (i) is present.

[0089] (Meth)acrylic polymer (ii)

[0090] The (meth)acrylic polymer (ii) of the present invention comprises structural units derived from (meth)acrylic monomers and / or (meth)acrylic ester monomers containing carboxylic acids. The (meth)acrylic polymer (ii) comprises 10 wt% or less of silyl ester monomers and 5.0 wt% or less of metal ester monomers relative to the total weight of the monomers present in the polymer.

[0091] The (meth)acrylic polymer (ii) of the present invention preferably comprises repeating units derived from (meth)acrylic ester monomers. Preferably, the (meth)acrylic polymer (ii) comprises at least 50 wt% of repeating units derived from (meth)acrylic ester monomers, i.e., acrylate and / or methacrylate monomers.

[0092] Further preferred is that the (meth)acrylic polymer (ii) contains at least 60 wt%, more preferably at least 75 wt%, and even more preferably at least 90 wt% of repeating units derived from (meth)acrylic ester monomers.

[0093] In one embodiment, the (meth)acrylic polymer (ii) comprises 100 wt% structural units derived from (meth)acrylic ester monomers, i.e., they do not contain any other type of monomers.

[0094] The (meth)acrylic polymer (ii) of the present invention comprises 10 wt% or less, preferably less than 5.0 wt%, of silyl ester monomers, such as those of formula (I) above, relative to the total weight of the monomers present in the (meth)acrylic polymer (ii), and 5.0 wt% or less, preferably less than 3.0 wt%, of metal ester monomers, such as those of less than 2.0 wt% or less than 1.0 wt%. Most preferably, the (meth)acrylic polymer (ii) does not contain any silyl ester groups.

[0095] It is also preferred that the (meth)acrylic polymer (ii) of the present invention does not contain any metal ester groups.

[0096] (ii) The (meth)acrylic acid polymer can be a homopolymer or a copolymer, preferably a copolymer.

[0097] (ii)Meth)acrylic acid polymers can be provided in polymer solutions, such as solutions in solvents. The polymer solution is ideally adjusted to have a solids content of 30 to 90% by weight, preferably 40 to 85% by weight, and more preferably 45 to 75% by weight.

[0098] In one embodiment, the coating composition of the present invention comprises at least one (meth)acrylic polymer (ii), such as (meth)acrylic polymer (ii-a). However, it is possible to use two (meth)acrylic polymers (ii), such as (meth)acrylic polymer (ii-a) and (meth)acrylic polymer (ii-b).

[0099] In one embodiment, the coating composition of the present invention does not contain the (meth)acrylate silyl ester copolymer component (i), but includes two (meth)acrylate polymers (ii), such as (meth)acrylate polymer (ii-a) and (meth)acrylate polymer (ii-b).

[0100] (Meth)acrylic acid polymer (ii-a)

[0101] In one embodiment, (meth)acrylic polymer (ii) is (meth)acrylic polymer (ii-a).

[0102] The (meth)acrylic acid polymer (ii-a) has a Tg below 10.0°C, preferably below 0°C, more preferably below -5°C, and even more preferably below -10°C, all values ​​measured according to the Tg test described in the Examples section. Values ​​greater than -65°C are preferred, for example, greater than -55°C or greater than -45°C.

[0103] In one embodiment, the (meth)acrylic acid polymer (ii-a) comprises a (meth)acrylic acid monomer (a3). A suitable (meth)acrylic acid monomer (a3) ​​is methacrylic acid or acrylic acid. The content of (meth)acrylic acid (a3) ​​in the (meth)acrylic acid polymer (ii-a) is preferably in the range of 0.5 to 10.0 wt%, such as 1.0 to 5.0 wt%.

[0104] Preferably, the (meth)acrylic acid polymer (ii-a) has an acid value of less than 60 mg KOH / g polymer, more preferably less than 40 mg KOH / g polymer, and even more preferably less than 25 mg KOH / g polymer. Preferably, the acid value is greater than 2 mg KOH / g polymer, such as greater than 5 mg KOH / g polymer. The acid value is determined according to the steps described in Method A of ISO 2114:2000.

[0105] When a (meth)acrylic acid monomer (a3) ​​is present, a second (meth)acrylic acid ester monomer (a4) as described below is preferably present to form a copolymer therefrom.

[0106] In another embodiment, the (meth)acrylate polymer (ii-a) comprises at least one (meth)acrylate monomer (a4). The (meth)acrylate monomer (a4) preferably forms at least 50 wt% of the (meth)acrylate polymer (ii-a), such as at least 75 wt% or at least 80 wt%, especially 95.0-99.5 wt%.

[0107] (Meth)acrylic acid polymers (ii-a) can be homopolymers containing only structural units derived from (meth)acrylic acid monomers (a4).

[0108] Examples of suitable (meth)acrylate monomers (a4) have the following formula (II) as defined above: (II) Among them, R 4 It is H or CH3, and R 5 It is a C1-C20 hydrocarbon substituent, preferably a C1-10 alkyl substituent, such as a C1-8 alkyl. R 5 The group can be straight-chain or branched. Most preferably, R 5 These are methyl, ethyl, propyl, butyl, hexyl, octyl, or decyl groups, which may be straight-chain or branched (if possible). The preference for formula (II) described above in relation to (meth)acrylate silyl ester copolymers (i) also applies to (meth)acrylate polymers (ii-a).

[0109] Examples of suitable monomers of formula (II) that serve as monomers (a4) in (meth)acrylic polymers (ii-a) include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, 2-octyl methacrylate, isooctyl methacrylate, 2-propylheptyl methacrylate, isodecanyl methacrylate, cyclohexyl methacrylate, 3,5,5-trimethylcyclohexyl methacrylate, and isobornyl methacrylate.

[0110] Preferred choices of monomers of formula (II) that serve as monomers (a4) in (meth)acrylic polymers (ii-a) include methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-octyl acrylate, isooctyl acrylate, or isodecanyl acrylate.

[0111] Mixtures of different monomers of formula (II) can also be used in (meth)acrylic polymers (ii-a).

[0112] Preferably, the (meth)acrylic polymer (ii-a) comprises structural units derived from (meth)acrylic monomer (a3) ​​and (meth)acrylate monomer (a4).

[0113] In a preferred embodiment, the (meth)acrylic polymer (ii-a) comprises structural units derived from acrylic acid and / or methacrylic acid and methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-octyl acrylate, isooctyl acrylate and / or isodecanyl acrylate.

[0114] (Meth)acrylic acid polymers (ii-a) may also contain structural units derived from the following: other olefinic unsaturated monomers, such as vinyl monomers, for example, styrene, vinyl 2-ethylhexanoate and vinyl neodecanoate.

[0115] The (meth)acrylic acid polymer (ii-a) preferably has a weight-average molecular weight of 5,000-100,000, more preferably 10,000-80,000, and especially 15,000-50,000. Mw is determined as described in the Examples section. The (meth)acrylic acid polymer (ii-a) preferably has a polydispersity index (PDI) of 1.5 to 5.0.

[0116] When using (meth)acrylate silyl ester copolymer (i), the (meth)acrylate polymer (ii-a) is typically present in an amount of 0.5 to 10 wt%, preferably 1.0 to 5.0 wt%, relative to the total weight of the coating composition as a whole.

[0117] When using (meth)acrylate silyl ester copolymer (i), the (meth)acrylate polymer (ii-a) is typically present in an amount of 1.0 to 12 wt%, preferably 2.0 to 7.0 wt%, relative to the total dry weight of the coating composition as a whole.

[0118] When using (meth)acrylate silyl ester copolymer (i), the (meth)acrylate copolymer (ii-a) is typically present in an amount of 2.0 to 25 wt%, preferably 5.0 to 20 wt%, based on the total dry weight of the binder in the coating composition of the present invention.

[0119] When the (meth)acrylic polymer (ii-a) is used in the absence of the (meth)acrylic silyl ester copolymer (i), it may be present in an amount of 1.0 to 12 wt%, preferably 2.0 to 7.0 wt%, relative to the total weight of the coating composition as a whole.

[0120] When the (meth)acrylic polymer (ii-a) is used in the absence of the (meth)acrylic silyl ester copolymer (i), it may be present in an amount of 1.5 to 15 wt%, preferably 2.5 to 10 wt%, relative to the total dry weight of the coating composition.

[0121] When (meth)acrylic acid copolymer (ii-a) is used in the absence of (meth)acrylic acid silyl ester copolymer (i), it can be present in an amount of 5 to 30 wt%, preferably 10 to 25 wt%, based on the total dry weight of the binder in the coating composition.

[0122] (Meth)acrylic polymer (ii-b)

[0123] In one embodiment, the coating composition of the present invention may further comprise (meth)acrylic polymer (ii-b).

[0124] If both (meth)acrylic polymer (ii-a) and (meth)acrylic polymer (ii-b) are present, it is preferable that (meth)acrylic silyl ester copolymer (i) is absent.

[0125] The (meth)acrylic acid polymer (ii-b) has a glass transition temperature (Tg) of at least 10°C, preferably at least 15°C, such as at least 17°C, or at least 20°C, all values ​​measured according to the Tg test described in the Examples section. Values ​​less than 80°C are preferred, such as less than 70°C, for example, less than 55°C. Therefore, the Tg of the (meth)acrylic acid polymer (ii-b) is at least 10°C, while the Tg of the (meth)acrylic acid polymer (ii-a) is less than 10°C. Preferably, the Tg of the (meth)acrylic acid polymer (ii-b) is at least 10°C, while the Tg of the (meth)acrylic acid polymer (ii-a) is 0°C or lower.

[0126] In one embodiment, the (meth)acrylic polymer (ii-b) does not contain the (meth)acrylic monomer (a3).

[0127] (Meth)acrylic polymer (ii-b) includes at least one (meth)acrylic ester monomer (a5).

[0128] Examples of suitable (meth)acrylate monomers (a5) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isodecanyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,5-methyl (meth)acrylate,5-Trimethylcyclohexyl ester, isobornyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, oligo(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, oligo(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate (meth)acrylate), methoxycarbonyl methyl methacrylate, ethoxycarbonyl methyl methacrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl methacrylate, 2-(2-ethoxy-2-oxoethoxy)-2-oxoethyl methacrylate, oligomeric (oxycarbonylmethyl)meth(meth)acrylate, oligomeric (oxycarbonylmethyl)ethyl(meth)acrylate, tetrahydrofurfuryl methacrylate, glycerolformal (glycerolformal (meth)acrylate), isopropylideneglycerol (isopropylideneglycerol (meth)acrylate), glycerolcarbonate (glycerolcarbonate) (meth)acrylate), cyclic trimethylolpropane formal (meth)acrylate, glycidyl acrylate, and 4-glycidyloxybutyl acrylate; More preferred examples of (meth)acrylate monomers (a5) have formula (II) as defined above for (meth)acrylate polymers (ii-a).

[0129] Preferred choices of monomers of formula (II) as monomer (a5) include methyl methacrylate, n-butyl acrylate, n-butyl methacrylate and isobutyl methacrylate.

[0130] A mixture of different (a5) monomers can also be used.

[0131] (Meth)acrylate monomers (a5) may also contain hydrophilic groups. Examples of suitable monomers are shown in the following formula (VI): (VI) Where R 11 It is H or CH3, and R 12 It is a C3-C40 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom, such as a C3-C20 substituent, or R 12 It represents the poly(alkylene glycol) group.

[0132] (Meth)acrylic acid copolymer (ii-b) may include at least one monomer of formula (VI), wherein R 12 The group has the formula (CH2CH2O). n -R 13 , where R 13 It is a C1-C10 hydrocarbon substituent, preferably a C1-C10 alkyl or C6-C10 aryl substituent, and n is an integer in the range of 1 to 5, preferably 1 to 3. Preferably, R 12 It has the formula (CH2CH2O) n -R 13 , where R 13 It is a C1-C10 alkyl substituent, preferably CH3 or CH2CH3, and n is an integer in the range of 1 to 3, preferably 1 or 2.

[0133] Such monomers can be 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl methacrylate, or 2-[2-(2-ethoxyethoxy)ethoxy]ethyl methacrylate.

[0134] Preferably, the (meth)acrylic polymer (ii-b) includes one or more of 2-methoxyethyl acrylate or 2-(2-ethoxyethoxy)ethyl acrylate.

[0135] (Meth)acrylic acid polymers (ii-b) may include at least one monomer of formula (VI), wherein R 12 The group is a poly(alkylene glycol) group, such as a poly(ethylene glycol) group. Such a group can have the formula (CH₂CH₂O). m -R 13 Or (CH2CH(CH3)O) m -R 14 , where R 14 It is a C1-C10 hydrocarbon substituent, preferably a C1-C10 alkyl or C6-C10 aryl substituent, and m is an integer in the range of 5 to 25, preferably 5 to 15.

[0136] Such monomers can be poly(ethylene glycol) methyl ether acrylate, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) methyl ether methacrylate, or poly(ethylene glycol) ethyl ether methacrylate. Preferably, such monomers have a number average molecular weight (Mn) of 300-1000, more preferably 300-550.

[0137] (Meth)acrylic acid polymer (ii-b) may also contain at least one monomer of formula (VI), wherein R 12 The group has the formula (CH2C(O)O). p -R 15 Or (CH(CH3)C(O)O) p -R 15 , where R 15 It is a C1-C10 hydrocarbon substituent, preferably a C1-C10 alkyl or C6-C10 aryl substituent, and p is an integer in the range of 1 to 10, preferably 1 to 4.

[0138] Such monomers can be methoxycarbonyl methyl methacrylate, ethoxycarbonyl methyl methacrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl methacrylate, 2-(2-ethoxy-2-oxoethoxy)-2-oxoethyl methacrylate, oligomeric (oxycarbonylmethyl)methacrylate, and oligomeric (oxycarbonylmethyl)ethyl (meth)acrylate.

[0139] (Meth)acrylic acid polymers (ii-b) may include at least one monomer of formula (VI), wherein R 12 The group is a cyclic group containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom. More preferably, R 12 It is a group with up to 20 carbon atoms, WR 16 , where R 16It is a cyclic ether, such as ethylene oxide, furan, oxolane, oxane, dioxolane, dioxane, optionally substituted with an alkyl group, and W is a C1-C4 alkylene group.

[0140] Such monomers can be furfuryl methacrylate, tetrahydrofurfuryl methacrylate, glycerol formal (meth)acrylate, isopropylideneglycerol (meth)acrylate, glycerol carbonate (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycidyl methacrylate, and 4-glycidyloxybutyl methacrylate. Preferred cyclic ethers should contain at least four atoms in the ring. Tetrahydrofurfuryl methacrylate and isopropylideneglycerol methacrylate are more preferred.

[0141] The monomer of formula (VI) is preferably 2-methoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate or poly(ethylene glycol) methyl ether methacrylate.

[0142] The monomer of formula (VI) preferably forms at least 10 wt% of the (meth)acrylic acid polymer (ii-b). A particularly preferred amount of the monomer of formula (VI) in the copolymer (ii-b) is 10 to 65 wt%, preferably 15 to 55 wt%, such as 18 to 50 wt%. When a mixture of monomers of formula (VI) is present, these amounts relate to the weight fraction of the combination of monomers of formula (VI) in the copolymer.

[0143] In a preferred embodiment, the (meth)acrylic acid polymer (ii-b) comprises at least one monomer of formula (II) and at least one monomer of formula (VI).

[0144] In a preferred embodiment, the (meth)acrylic acid polymer component (ii-b) consists only of monomers of formulas (II) and (VI). The (meth)acrylic acid polymer (ii-b) preferably does not contain the (meth)acrylic acid monomer (a3).

[0145] (Meth)acrylic acid polymers (ii-b) may also contain structural units derived from: other olefinically unsaturated monomers, such as vinyl monomers, for example, styrene, vinyl 2-ethylhexanoate, vinyl neodecanoate, and N -Vinylpyrrolidone.

[0146] The (meth)acrylic acid polymer (ii-b) preferably has a weight-average molecular weight (Mw) of 10,000-100,000, more preferably 15,000-70,000, and especially 20,000-50,000. Mw is determined as described in the Examples section. The (meth)acrylic acid polymer (ii-b) preferably has a polydispersity index (PDI) of 1.5 to 5.0.

[0147] When using (meth)acrylic polymer (ii-b), it can be present in an amount of 1.0 to 15 wt%, preferably 2.0 to 12 wt%, relative to the total weight of the coating composition as a whole.

[0148] When using (meth)acrylic polymer (ii-b), it can be present in an amount of 1.5 to 20 wt%, preferably 2.5 to 15 wt%, relative to the total dry weight of the coating composition.

[0149] When the (meth)acrylic acid copolymer (ii-b) is used in the antifouling coating composition of the present invention, it can be present in an amount of 5.0 to 40 wt%, preferably 10 to 35 wt%, based on the total dry weight of the binder in the coating composition.

[0150] Preparation of (meth)acrylate silyl ester copolymer (i) and (meth)acrylate polymer (ii)

[0151] (Meth)acrylate silyl ester copolymers (i) and (meth)acrylate polymers (ii) can be prepared using polymerization reactions known in the art. The polymers can be obtained by means of a mixture of polymeric monomers in the presence of a polymerization initiator, methods such as solution polymerization, bulk polymerization, emulsion polymerization, dispersion polymerization, and suspension polymerization carried out in a conventional manner such as free radical polymerization, or by controlled polymerization techniques. In the case of copolymers, the final polymer can be a random copolymer, alternating copolymer, gradient copolymer, or block copolymer.

[0152] When preparing coating compositions using any polymer, it is preferable to dilute the polymer with an organic solvent to obtain a polymer solution with a suitable viscosity. From this perspective, solution polymerization is desirable.

[0153] Examples of suitable initiators for free radical polymerization in solvents include azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), and 1,1'-azobis(cyanocyclohexane); and peroxides such as tert-amyl peroxyneoplastate, tert-butyl peroxyneoplastate, and tert-amyl peroxy-2-ethylhexanoate. tert -amyl peroxy-2-ethylhexanoate), tert-butyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethyl butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetic acid, tert-butyl peroxyisobutyrate, tert-butyl peroxybenzoate, 1,1-di(tert-amyl peroxy)cyclohexane (1,1-di( tert -amyl peroxy)cyclohexane), tert-amyl peroxy-2-ethylhexyl carbonate ( tert -amylperoxy 2-ethylhexyl carbonate), tert-butylperoxyisopropyl carbonate ( tert- butylperoxy isopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate ( tert 2-butylperoxy-2-ethylhexyl carbonate), polyether polytert-butylperoxycarbonate (polyether poly- tert- (butylperoxy carbonate), di-tert-butyl peroxide, and dibenzoyl peroxide. These compounds are used alone or as a mixture of two or more of them.

[0154] Examples of organic solvents include aromatic hydrocarbons such as xylene, toluene, and mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isopentyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone; esters such as butyl acetate, tert-butyl acetate, amyl acetate, propyl propionate, n-butyl propionate, isobutyl isobutyrate, and ethylene glycol methyl ether acetate; ethers such as dimethyl glycol ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, and tetrahydrofuran; alcohols such as n-butanol, isobutanol, methyl isobutyl methanol, and benzyl alcohol; ether alcohols such as butoxyethanol and 1-methoxy-2-propanol; and aliphatic hydrocarbons such as white solvent oils (petroleum solvent oils, spirits, turpentine), and limonene. These solvents are used alone or as mixtures of two or more of them.

[0155] Monocarboxylic acids (iii)

[0156] The antifouling coating composition of the present invention comprises a monocarboxylic acid or its metal salt.

[0157] The monocarboxylic acid present in the antifouling coating composition of the present invention is preferably selected from rosin, modified rosin, C6-C20 cyclic monocarboxylic acids, C5-C24 acyclic aliphatic monocarboxylic acids, C7-C20 aromatic monocarboxylic acids, and their metal salts. The metal salts of the monocarboxylic acids include alkali metal carboxylates, alkaline earth metal carboxylates (e.g., calcium carboxylate, magnesium carboxylate), and transition metal carboxylates (e.g., zinc carboxylate, copper carboxylate). Preferably, the metal carboxylate is a transition metal carboxylate, and particularly preferably, zinc carboxylate or copper carboxylate. The metal carboxylate can be generated in situ in the antifouling coating composition.

[0158] Preferably, the monocarboxylic acid is a cyclic monocarboxylic acid. Rosin is a mixture of monocarboxylic acids called resin acids. Resin acids are also known as rosin acids. Representative examples of resin acids include rosin acid, neorosin acid, dehydrorosin acid, longleaf rosin acid, L-piperidine, piperidine, isopiratic acid, sandaracopidrilic acid, communiic acid, and meric acid, as well as secodehydroabietic acid. It should be understood that rosin is derived from natural sources, and therefore they typically contain mixtures of acids.

[0159] Representative examples of rosin include gum rosin, wood rosin, and tall oil rosin. Gum rosin, also known as colophony or colophonium, is particularly preferred. Preferred rosins are those containing more than 85% resin acids, and even more preferably more than 90% resin acids.

[0160] Commercial-grade rosin typically has an acid value of 155 to 180 mg KOH / g, as specified in ASTM D465. Preferred rosin for use in the compositions of the present invention has an acid value of 155 to 180 mg KOH / g, more preferably 160 to 175 mg KOH / g, and even more preferably 160 to 170 mg KOH / g. Commercial-grade rosin typically has a softening point of 70°C to 80°C (Ring & Ball method), as specified in ASTM E28. Preferred rosin for use in the compositions of the present invention has a softening point of 70°C to 80°C, more preferably 75°C to 80°C.

[0161] Representative examples of modified resin acids include dihydrorosinic acid, dihydropiperic acid, and tetrahydrorosinic acid; and modified rosins, such as partially hydrogenated rosin, fully hydrogenated rosin, and disproportionated rosin.

[0162] Representative examples of C6-C20 cyclic monocarboxylic acids include cycloalkanoic acids and trimethylisobutylenecyclohexenecarboxylic acid.

[0163] Representative examples of C5-C24 acyclic aliphatic monocarboxylic acids include Versatic TM Acids, neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, 2,2-diethylhexanoic acid, pivalic acid, 2,2-dimethylpropionic acid, trimethylacetic acid, neoopentanoic acid, 2-ethylhexanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, isopalmitic acid, isostearic acid, 16-methylheptadecanoic acid, and 12,15-dimethylhexadecanoic acid. Acyclic aliphatic monocarboxylic acids are preferably selected from liquid, acyclic C10-C24 monocarboxylic acids, or liquid, branched C10-C24 monocarboxylic acids. It should be understood that many acyclic C10-C24 monocarboxylic acids can be derived from natural sources, in which case, in isolated form, they typically exist as mixtures of acids with different chain lengths and different degrees of branching.

[0164] Preferably, the monocarboxylic acid is selected from rosin, modified rosin, acyclic C10-C24 monocarboxylic acids, C6-C20 cyclic monocarboxylic acids, or their metal salts.

[0165] Preferably, the metal salt of the monocarboxylic acid is a copper or zinc salt of rosin or a copper or zinc salt of modified rosin.

[0166] More preferably, the monocarboxylic acid is rosin or modified rosin or its metal salt.

[0167] Further preferred monocarboxylic acids or their metal salts are rosin, hydrogenated rosin, copper salts of rosin, zinc salts of rosin, copper salts of hydrogenated rosin, zinc salts of hydrogenated rosin, and mixtures thereof. Rosin is the most preferred.

[0168] The final antifouling coating composition of the present invention preferably comprises 5.0 to 30 wt% of a monocarboxylic acid and / or its metal salt, such as 5.0 to 25 wt% or 10 to 25 wt%, based on the total coating composition.

[0169] The final coating composition of the present invention preferably comprises 7.0 to 40 wt%, preferably 12 to 32 wt%, of a monocarboxylic acid or its metal salt based on the total dry weight of the coating composition.

[0170] The antifouling coating composition of the present invention preferably contains 25 to 65 wt%, preferably 35 to 60 wt%, more preferably 40 to 60 wt%, of rosin and / or modified rosin and their metal salts present in the antifouling coating composition of the present invention, based on the total dry weight of the binder in the coating composition (iii).

[0171] Components (i) to (iii) constitute the binder in the final coating composition of the present invention. The wt% of the binder in the final coating composition, particularly the combined weight percentage of components (i) to (iii), is 15 to 50 wt% of the total coating composition.

[0172] The binder in the final coating composition, especially the combination of components (i) to (iii), is 20 to 65 wt% of the total dry weight of the coating composition, preferably 25 to 45 wt%.

[0173] Other adhesive components

[0174] In addition to components (i), (ii), and (iii) described above, other binders can be used to adjust the properties of the antifouling coating composition. Examples of binders that can be used include: Hydrophilic copolymers, such as poly( N -Vinylpyrrolidone) copolymers and poly(ethylene glycol) copolymers; vinyl ether polymers and copolymers, such as poly(methyl vinyl ether), poly(ethyl vinyl ether), poly(isobutyl vinyl ether), poly(vinyl chloride-co-isobutyl vinyl ether); Metal-containing (meth)acrylate copolymers, such as zinc (meth)acrylate copolymers and copper (meth)acrylate copolymers; Saturated aliphatic polyesters, such as poly(lactic acid), poly(glycolic acid), poly(2-hydroxybutyric acid), poly(3-hydroxybutyric acid), poly(4-hydroxyvalerate), polycaprolactone, and aliphatic polyester copolymers containing two or more units selected from the above units. Alkyd resins and modified alkyd resins; Hydrocarbon resins, such as hydrocarbon resins formed solely by polymerization of at least one monomer selected from C5 aliphatic monomers, C9 aromatic monomers, indanone monomers, or terpenes or mixtures thereof; Plasticizers, such as polymeric plasticizers, non-reactive silicone oils, mineral oils, chlorinated paraffins, phthalates, phosphate esters, sulfonamides, adipates, epoxidized vegetable oils, methyl esters of rosin, methyl esters of branched-chain fatty acids, and sucrose acetate isobutyrate.

[0175] In a particularly preferred embodiment of the invention, the coating composition does not contain a plasticizer that is paraffin, especially not paraffin containing aromatic groups.

[0176] Preferably, other binders are present in the composition of the present invention in an amount of 0 to 10 wt%, more preferably 0.5 to 7.0 wt%, and even more preferably 1.0 to 5.0 wt%, based on the total weight of the coating composition.

[0177] Biocides (iv)

[0178] The antifouling coating composition further comprises a biocide, i.e., a compound capable of reducing or preventing the deposition and / or growth of marine fouling (fouling) on ​​a surface. The terms antifouling agent, anti-fouling agent, biocide, and toxic agent are used in industry to describe known compounds that work to prevent marine fouling on surfaces. The antifouling agent of the present invention is a marine antifouling agent. These compounds are present in a total amount of 10.0 wt% or less relative to the total weight of the coating composition as a whole. Preferably, the coating composition contains 8.0 wt% or less, even more preferably 5.0 wt% or less of a biocide. Example ranges for the amount of biocide include 0.2 to 10.0 wt%, 0.5 to 8.0 wt%, and 1.0 to 5.0 wt% relative to the total weight of the coating composition as a whole.

[0179] Alternatively, these compounds are present in a total amount of 13.5 wt% or less relative to the total weight of the dry coating composition. Preferably, the coating composition contains 10.0 wt% or less, and even more preferably 7.0 wt% or less of a biocide. Example ranges for the amount of biocide include 0.2 to 13.5 wt%, 0.5 to 10.0 wt%, and 1.0 to 7.0 wt% relative to the total dry weight of the coating composition.

[0180] Biocides must contain bromopyrrolidone (iv-a) and one or more copper compounds (iv-b) as defined below.

[0181] Bromopyrrolidone (iv-a)

[0182] As discussed above, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [bromopyrrole nitrile (tralopyril)] having the following structure must be present in the compositions of the present invention:

[0183] Examples of commercially available brominated pyrrolidones include Econea from Janssen PMP. ® .

[0184] In all embodiments, it is preferred that the bromopyrrolidone is present in an amount of 0.1 to 5.0 wt%, preferably 0.2 to 3.0 wt%, more preferably 0.3 to 2.0 wt%, even more preferably 0.4 to 1.5 wt%, such as 0.4 to 1.0 wt%, relative to the total weight of the composition.

[0185] In all embodiments, it is preferred that the brominated pyrrolidone is present in an amount of 0.2 to 6.5 wt%, preferably 0.3 to 4.0 wt%, more preferably 0.4 to 2.5 wt%, and even more preferably 0.5 to 1.5 wt% relative to the total dry weight of the coating composition.

[0186] Typically, bromopyrrolidone is present in an amount of 5.0 to 60.0 wt%, preferably 7.0 to 60.0 wt%, more preferably 8.0 to 60.0 wt%, even more preferably 9.0 to 60.0 wt%, and even more preferably 10.0 to 60.0 wt%, relative to the total weight of the biocide (iv).

[0187] Copper compounds (iv-b)

[0188] The copper compound can be any suitable copper antifouling compound having a copper content of at least 40 wt% relative to the total weight of the copper compound. Preferably, the copper compound has a copper content of at least 45 wt%, at least 50 wt%, at least 55 wt%, or at least 60 wt%, such as at least 70 wt% or at least 75 wt% relative to the total weight of the copper compound. It should be understood that the copper content is calculated as the mass of copper atoms present in the chemical formula of the copper compound, excluding the carrier material.

[0189] The table below lists commonly used copper compounds and their calculated copper content:

[0190] A single copper compound may be used, or alternatively, a mixture of two or more copper compounds may be used.

[0191] Copper compounds can exist alongside carrier materials, such as encapsulated copper compounds, copper glass, copper-coated particles, and porous particles containing copper compounds. The required wt% of copper refers to the amount of copper in the chemical copper compound and therefore ignores the weight of any carrier.

[0192] Particularly preferred copper compounds are metallic copper, such as copper powder and copper sheets, cuprous oxide (I), copper sulfide (II), and cuprous thiocyanate (I). Cuprous oxide (I) is also known as cuprous oxide.

[0193] Preferably, the copper compound is an inorganic copper compound such as metallic copper, cuprous oxide (I), and copper sulfide (II), more preferably metallic copper powder and cuprous oxide (I).

[0194] In a particularly preferred embodiment, the copper compound is cuprous oxide (I).

[0195] Cuprous oxide (I) materials preferably have a typical particle size distribution of 0.1-70 µm and an average particle size (d50) of 1-25 µm. Cuprous oxide (I) materials may contain stabilizers to prevent surface oxidation and agglomeration. Commercially available examples of cuprous oxide (I) include Nordox Cuprous Oxide Red PaintGrade, Nordox Cuprotech, and Nordox XLT from Nordox AS; cuprous oxide from Furukawa Chemicals Co., Ltd.; Red Copp 97N, Purple Copp, Lolo Tint 97N, Chemet CDC, and Chemet LD from American Chemet Corporation; Cuprous Oxide Red from Spiess-Urania; and roasted cuprous oxide and electrolytic cuprous oxide from Taixing Smelting Plant Co., Ltd.

[0196] In all embodiments, one or more copper compounds are preferably present in an amount of 0.1 to 8.0 wt%, preferably 0.2 to 5.0 wt%, more preferably 0.3 to 3.0 wt%, even more preferably 0.3 to 2.0 wt%, and even more preferably 0.3 to 1.0 wt% relative to the total weight of the composition.

[0197] If a blend of copper compounds is present, each copper compound may be present in an amount of 0.1 to 6.0 wt%, preferably 0.2 to 5.0 wt%, more preferably 0.3 to 3.0 wt%, even more preferably 0.3 to 2.0 wt%, and even more preferably 0.3 to 1.0 wt%, relative to the total weight of the composition.

[0198] It should be understood that the total amount of biocide in the coating composition of the present invention shall not exceed 10.0 wt%. Appropriate amounts and quantities of copper compounds may be selected accordingly.

[0199] More preferably, the coating composition of the present invention contains 8.0 wt% or less, preferably 5.0 wt% or less of a biocide relative to the total weight of the coating composition as a whole.

[0200] In all embodiments, the copper compound is preferably present in an amount of 0.1 to 9.9 wt%, preferably 0.2 to 7.0 wt%, more preferably 0.3 to 4.0 wt%, even more preferably 0.3 to 2.5 wt%, and even more preferably 0.3 to 1.5 wt% relative to the total dry weight of the coating composition. It is also preferred that the total amount of biocide in the coating composition of the present invention does not exceed 13.0 wt%.

[0201] Typically, one or more copper compounds are present in an amount of 5.0 to 90.0 wt%, preferably 6.0 to 87.0 wt%, more preferably 7.0 to 85.0 wt%, even more preferably 8.0 to 82.0 wt%, and even more preferably 9.0 to 80.0 wt%, relative to the total weight of the biocide (iv). In some embodiments, one or more copper compounds are present in an amount of 5.0 to 85.0 wt%, more preferably 6.0 to 82.0 wt%, relative to the total weight of the biocide (iv).

[0202] In those embodiments in which more than one copper compound of the present invention is present, it should be understood that these wt% ranges apply to the total amount of all copper compounds present. Note that if a copper compound does not have 40 wt% copper, it is not a copper compound of the present invention.

[0203] Other biocides

[0204] Besides these biocides, other antifouling compounds may be present. Antifouling agents can be inorganic, organometallic, or organic. Suitable antifouling agents are commercially available.

[0205] Examples of organometallic marine antifouling agents include zinc pyrithione, copper pyrithione, copper di(ethyl 4,4,4-trifluoroacetoacetate), zinc bis(dimethyldithiocarbamate) [zinc thiram], and zinc ethylene bis(dithiocarbamate) [zinc mancozeb], as well as copper and zinc compounds as described in WO2021113564A1. It should be noted that copper pyrithione and copper di(ethyl 4,4,4-trifluoroacetoacetate) have copper contents based on a formula weight of less than 40 wt%, and are therefore not included in the definition of copper compounds in this invention.

[0206] Examples of organic marine antifouling agents include 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine [cybutryne], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 3-(3,4-dichlorophenyl)-1,1-dimethylurea [diuron], N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfonamide [antibacterial agent], and N-dichlorofluoromethylthio-N′,N′-dimethyl-N-p-toluenesulfonamide [p-toluenesulfonamide]. [Tolylfluanid], N-(2,4,6-trichlorophenyl)maleimide, triphenylboranepyridine [TPBP], 3-iodo-2-propynyl N-butylcarbamate [IPBC], 2,4,5,6-tetrachloroisophthalonitrile [chlorothalonil], p-((diiodomethyl)sulfonyl)toluene and 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [metopril].

[0207] Other examples of marine antifouling agents may include tetraalkylphosphonium halogenides, macrolides including avermectins and their derivatives such as ivermectine; furanones and lactam compounds such as 4-(4-chlorophenyl)-5-hydroxy-5-methyl-2(5H)-furanone and 4-(4-chlorophenyl)-5-methylene-1H-pyrrole-2(5H)-one; spinosad and its derivatives such as spinosad; capsaicin and its derivatives such as phenylcapsaicin; and enzymes such as oxidases, proteolytic enzymes, hemicellulose-degrading enzymes, cellulose-degrading enzymes, lipolytic enzymes, and starch-degrading enzymes.

[0208] Preferred biocides include zinc pyrithione, copper pyrithione, zinc bis(dithiocarbamate) [zinc thiocyanate], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfonamide [antibacterial agent], 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [metopril], copper di(ethyl 4,4,4-trifluoroacetoacetate) and phenyl capsaicin.

[0209] As is known in the art, mixtures of biocides can be used because different biocides act on different marine fouling organisms. Mixtures of antifouling agents are generally preferred.

[0210] If biocides other than (iv-a) and (iv-b) are used, these will still be included in the total biocide content and thus reach the maximum value of 10.0 wt%.

[0211] Some biocides can be encapsulated, adsorbed onto inert carriers, or bound to other materials for controlled release. The weight of any such carrier is disregarded when determining the maximum value of 10.0 wt%.

[0212] Pigments and extenders (v)

[0213] The coating compositions of the present invention further comprise pigments and / or extenders. The total amount of extenders and / or pigments and biocides present in the compositions of the present invention is preferably at least 35 wt% relative to the total weight of the coating composition as a whole. It is important that the total amount of extenders and / or pigments and biocides is 35 wt% or higher in order to obtain suitable self-polishing properties, coating film properties, and sufficient antifouling properties.

[0214] Based on the total weight of the composition, the preferred total amount of the extender and / or pigment and biocide is 35 to 65 wt%, more preferably 40 to 60 wt%, and even more preferably 45 to 60 wt%.

[0215] Based on the total dry weight of the coating composition, the preferred total amount of extender and / or pigment and biocide is 40 to 80 wt%, more preferably 45 to 75 wt%, and even more preferably 50 to 75 wt%.

[0216] Technicians will understand that the content of extenders and pigments will vary depending on particle size distribution, particle shape, surface morphology, particle surface-resin affinity, other components present, and the end use of the coating composition.

[0217] Pigments are materials that provide color to coating compositions. They are typically in the form of fine particles that are insoluble in paint. Pigments can be inorganic, organic, or mixtures thereof. Inorganic pigments are preferred. Examples of inorganic pigments include titanium dioxide, iron oxide red, iron oxide yellow, iron oxide black, zinc sulfide, zinc barium white, and graphite. Examples of organic pigments include carbon black, phthalocyanine blue, phthalocyanine green, naphthol red, and diketopyrrolopyrrole red. Pigments can be surface-treated. Various inorganic or organic surface treatments are used, for example, to improve storage stability and enhance pigment properties, such as rheological properties and dispersibility in coating compositions. As an example, titanium dioxide can be surface-treated with silicon compounds, zirconium compounds, aluminum compounds, and / or zinc compounds.

[0218] Incremental agents are materials added to paints to adjust or improve their properties. These materials typically have low color strength and are therefore distinct from pigments. Incremental agents are usually in granular or powder form and are insoluble in paint. Incremental agents can be inorganic or organic materials. Inorganic incremental agents are preferred. Inorganic incremental agents can be natural minerals or synthetic materials.

[0219] Examples of inorganic extenders include dolomite, plastorite, calcite, quartz, barite, magnesite, silica, nepheline syenite, wollastonite, talc, chlorite, mica, kaolin, pyrophyllite, feldspar, calcium carbonate, magnesium carbonate, barium sulfate, zinc oxide, zinc phosphate, calcium silicate, and silica. In addition to the extenders mentioned above, coating compositions may also contain reinforcing agents, such as flakes and fibers, as described in WO 00 / 77102.

[0220] Preferably, the antifouling coating composition of the present invention contains zinc oxide as a modifier.

[0221] Other components

[0222] In addition to the components and optional components described above, the antifouling coating compositions according to the invention may optionally further comprise one or more components selected from other additives, solvents and diluents.

[0223] Examples of additives that can be added to antifouling coating compositions include rheology modifiers, wetting agents, dispersants, and dehydrating agents.

[0224] Examples of rheology modifiers include thixotropic agents, thickeners, and antisettling agents. Representative examples of rheology modifiers are silica such as pyrolytic silica (fumed silica), organic modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil waxes, ethyl cellulose, aluminum stearate, and mixtures thereof. Rheology modifiers requiring activation can be added to the coating composition as is and activated during paint production, or they can be added to the coating composition in a pre-activated form, such as a solvent paste. Preferably, each rheology modifier is present in the compositions of the present invention in an amount of 0 to 5.0 wt%, more preferably 0.2 to 3.0 wt%, and even more preferably 0.5 to 2.0 wt%, based on the total weight of the coating composition.

[0225] Dehydrating agents improve the storage stability of antifouling coating compositions containing (meth)acrylate silyl ester copolymers (i). The dehydrating agent is preferably a compound that removes moisture and water from the coating composition. It is also referred to as a water remover, desiccant, or dehumidifier. The dehydrating agent can be a hygroscopic material that absorbs or binds water as water of crystallization, or a compound that chemically reacts with water. Examples of dehydrating agents include materials such as anhydrous calcium sulfate, calcium sulfate hemihydrate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves, and zeolites; orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate, and triethyl orthopropionate; ketals; acetals; enol ethers; orthoboronates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, and tritert-butyl borate; alkoxysilanes such as trimethoxymethylsilane, triethoxymethylsilane, tetraethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and polyethyl silicate; and isocyanates such as p-toluenesulfonyl isocyanate.

[0226] Preferred dehydrating agents are alkoxysilanes, such as tetraethoxysilane, and inorganic drying agents, such as anhydrous calcium sulfate, calcium sulfate hemihydrate, and zeolite powder. The use of alkoxysilanes is particularly preferred.

[0227] Preferably, the dehydrating agent is added to the composition of the present invention in an amount of 0 to 5.0 wt%, more preferably 0.5 to 2.5 wt%, and even more preferably 1.0 to 2.0 wt%, based on the total weight of the composition.

[0228] Preferably, the dehydrating agent is added to the composition of the present invention in an amount of 0 to 7.0 wt%, more preferably 0.5 to 4.0 wt%, and even more preferably 1.0 to 3.0 wt%, based on the total dry weight of the coating composition.

[0229] If the antifouling composition contains a solvent, it is highly preferred. The solvent is preferably volatile and, more preferably, organic. Examples of organic solvents and diluents are aromatic hydrocarbons, such as xylene, toluene, and mesitylene; ketones, such as methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, methyl isopentyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone; esters, such as butyl acetate, tert-butyl acetate, amyl acetate, isopentyl acetate, propyl propionate, n-butyl propionate, and isobutyl isobutyrate; ether esters, such as ethylene glycol methyl ether acetate and ethyl 3-ethoxypropionate; ethers, such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, and tetrahydrofuran; alcohols, such as n-butanol, isobutanol, methyl isobutyl methanol, and benzyl alcohol; ether alcohols, such as butoxyethanol and 1-methoxy-2-propanol; terpenes, such as limonene; aliphatic hydrocarbons, such as white solvent oils (petroleum solvent oils, spirits, turpentine); and optionally mixtures of two or more solvents and diluents.

[0230] Preferred solvents are aromatic hydrocarbon solvents, ketones and alcohols and mixtures thereof, especially mixtures of xylene and aromatic hydrocarbons.

[0231] The amount of solvent is preferably as low as possible. The solvent content can be up to 45 wt% of the composition, preferably up to 35 wt% of the composition, such as up to 30 wt%, but can be as low as 20 wt% or less, for example 15 wt% or less. In addition, those skilled in the art will understand that some raw materials contain solvents and contribute to the total solvent content as specified above, and the solvent content will vary depending on the other components present and the end use of the coating composition.

[0232] Technicians will understand that the solvent used will depend on the recommended application method for the final product.

[0233] Alternatively, the coating can be dispersed in an organic non-solvent or an aqueous dispersion of the film-forming component in the coating composition.

[0234] Coating composition

[0235] The compositions described herein can be prepared at a suitable concentration for use, for example, for spray application. In this case, the composition itself is a paint. Alternatively, the composition can be a concentrate for preparing paint. In this case, additional solvents and optional other components are added to the compositions described herein to form a paint. Preferred solvents are as described above with respect to the compositions.

[0236] The coating composition can be supplied as a one-pack, two-pack, or three-pack. If a curing agent is present, it will remain distinctly separate from the curable components until applied to the substrate. While biocides can remain in components separate from the adhesive, it is preferred that these biocides be present together in the supplied formulation.

[0237] When supplied as a single package, the composition is preferably supplied in a ready-mixed or ready-to-use form. Optionally, the single-packaged product may be diluted with a solvent prior to application.

[0238] The antifouling coating composition of the present invention preferably has a solid content of more than 60 wt%, for example more than 65 wt%, and more preferably more than 70 wt%.

[0239] The antifouling coating composition of the present invention should preferably have a solid content of more than 40 vol%, for example more than 45 vol%, preferably more than 50 vol%.

[0240] More preferably, the antifouling coating composition should have a volatile organic compound (VOC) content of less than 500 g / L, preferably less than 420 g / L, more preferably less than 400 g / L, for example less than 380 g / L, less than 350 g / L, and less than 300 g / L. The VOC content can be calculated, for example, as described in ASTM D5201-01 or IED 2010 / 75 / EU, or measured, for example, as described in US EPA Method 24 or ISO 11890-2.

[0241] When measured using a cone-plate viscometer according to ISO 2884-1:2006, the viscosity of the coating composition can be in the range of less than 2000 cP, such as less than 1000 cP, for example less than 800 cP and less than 500 cP. Viscosities of 200 cP or higher can be used.

[0242] In one embodiment, the antifouling coating composition comprises: Component (i) is present in an amount of 2.0 to 40 wt%, preferably 5.0 to 30 wt%, relative to the total weight of the coating composition as a whole. Component (ii) is present in an amount of 0.5 to 10 wt%, preferably 1.0 to 5 wt%, relative to the total weight of the coating composition as a whole. And components (iii) in amounts of 5.0 to 25 wt% based on the total weight of the coating composition as a whole.

[0243] In one embodiment, the antifouling coating composition comprises: Component (i) is present in an amount of 2.0 to 40 wt%, preferably 5.0 to 30 wt%, relative to the total weight of the coating composition as a whole. Component (ii) is present in an amount of 0.5 to 10 wt%, preferably 1.0 to 5.0 wt%, relative to the total weight of the coating composition as a whole. Based on the total weight of the coating composition as a whole, the component (iii) is present in an amount of 5.0 to 25 wt%. The amount of bromopyrrolidone is 0.1 to 5.0 wt%, preferably 0.2 to 3.0 wt%, more preferably 0.3 to 2.0 wt%, and even more preferably 0.4 to 1.0 wt%, relative to the total weight of the composition; and One or more copper compounds are present in an amount of 0.1 to 8.0 wt%, preferably 0.2 to 5.0 wt%, more preferably 0.3 to 3.0 wt%, even more preferably 0.3 to 2.0 wt%, and even more preferably 0.3 to 1.0 wt% relative to the total weight of the composition.

[0244] In one embodiment, the antifouling coating composition comprises: The component (ii-a) is present in an amount of 0.5 to 10 wt%, preferably 1.0 to 6.0 wt%, relative to the total weight of the coating composition as a whole. The component (ii-b) is present in an amount of 0.5 to 10 wt%, preferably 1.0 to 6.0 wt%, relative to the total weight of the coating composition as a whole. Based on the total weight of the coating composition as a whole, the component (iii) is present in an amount of 5.0 to 25 wt%. The amount of bromopyrrolidone is 0.1 to 5.0 wt%, preferably 0.2 to 3.0 wt%, more preferably 0.3 to 2.0 wt%, and even more preferably 0.4 to 1.0 wt%, relative to the total weight of the composition; and One or more copper compounds are present in an amount of 0.1 to 8.0 wt%, preferably 0.2 to 5.0 wt%, more preferably 0.3 to 3.0 wt%, even more preferably 0.3 to 2.0 wt%, and even more preferably 0.3 to 1.0 wt% relative to the total weight of the composition.

[0245] In all embodiments, the coating composition as a whole contains 10.0 wt% or less of a biocide.

[0246] Method for preparing antifouling coating compositions

[0247] Antifouling coating compositions can be prepared using any method known in the art. The order of adding and mixing the ingredients is preferably as recommended by the supplier of the ingredients and mixing equipment.

[0248] Biocides can be premixed in solutions or pastes containing binder components and / or solvents and / or pigments such as zinc oxide for safer and easier handling during paint (coating) production, for improving the storage stability of paint compositions and / or for improving the antifouling properties of applied paints.

[0249] Apply

[0250] The antifouling coating composition of the present invention can be applied (applied, coated) to the entirety or part of any object surface subjected to fouling. The surface may be permanently or intermittently submerged underwater (e.g., by tidal movements, different cargo loadings, or swells). The object surface will typically be the hull of a vessel or the surface of a fixed marine object such as an oil platform or buoy. The application of the coating composition can be accomplished by any convenient means, such as by smearing (e.g., using a brush or roller) or spraying (e.g., airless spraying) the coating onto the object. Typically, the surface needs to be separated from seawater to allow for coating. The application of the coating can be achieved as conventionally known in the art.

[0251] When antifouling coatings are applied to an object (such as a ship's hull), the surface is not protected by a single antifouling coating. Depending on the nature of the surface, the antifouling coating can be applied directly to an existing coating system. This coating system can include multiple different types of paint layers (coating layers) (e.g., epoxy, polyester, vinyl, or acrylic resins, or mixtures thereof). Starting with an uncoated surface (e.g., steel, aluminum, composite materials), a complete coating system typically consists of: one or two primer or anti-corrosion coatings (e.g., curable epoxy or curable modified epoxy coatings), one bonding coating (e.g., curable modified epoxy or physically dry vinyl coatings), and one or two antifouling paint layers. In exceptional cases, additional antifouling paint layers may be applied. If the surface is from a previously applied clean and complete antifouling coating, new antifouling paint can be applied directly, typically as one or two coats, and more in exceptional cases. When two or more coats of an antifouling coating composition are applied, the different coats can be antifouling coatings of different compositions, resulting in coating systems with different antifouling coatings.

[0252] Antifouling coatings can vary in terms of the type and / or amount of biocides and adhesives, adhesive composition, and / or polishing rate.

[0253] In certain situations, such as for outfitting applications, it is preferable to use antifouling coating compositions with different polishing rates in different coating layers. The outermost layer is then preferably polished at a higher rate than the subsequent layers.

[0254] The coating formed by the coating composition of the present invention can also be cleaned by, for example, robots, remotely operated vehicles (ROVs), or manually operated equipment. Cleaning can be reactive or proactive. Underwater cleaning can be performed, for example, using mechanical devices (such as brushes, scrapers), high-pressure water, ultraviolet light, lasers, or ultrasound. Robots for underwater cleaning are described, for example, in WO2019 / 170888, WO2020 / 207791, and WO2020 / 207792. Cleaning setups that can be used when using brushes are described, for example, in WO2021180588.

[0255] The present invention will now be defined with reference to the following non-limiting embodiments.

[0256] Example

[0257] Materials and methods

[0258] Determination of polymer solution viscosity

[0259] The viscosity of the polymer was determined using a Brookfield DV-I Prime digital viscometer with an LV-2 (62) rotor at 12 rpm, according to ASTM D2196 Test Method A. The polymer solution was conditioned to 23.0°C ± 0.5°C prior to measurement.

[0260] Determination of nonvolatile substance content in polymer solutions

[0261] As described in ISO 3251:2019, the content of nonvolatile substances in a polymer solution is determined. A test sample of 0.5 g ± 0.1 g is taken and dried in a ventilated oven at 105°C for 3 hours. The weight of the remaining material is considered the nonvolatile matter (NVM). The NVM content is expressed as a weight fraction as a percentage. The given value is the average of three parallel measurements.

[0262] Determination of polymer molecular weight distribution

[0263] Polymers were characterized by gel permeation chromatography (GPC). Molecular weight distribution (MWD) was determined using a Malvern Omnisec Resolve and Reveal system and two tandem PLgel 5 μm Mixed-D columns from Agilent. Columns were calibrated using narrow polystyrene standards via routine calibration. Analytical conditions are described below.

[0264]

[0265] Samples were prepared by dissolving a polymer solution corresponding to 25 mg of dry polymer in 5 mL of tetrahydrofuran (THF). Samples were kept at room temperature for at least 3 hours before sampling for GPC measurements. Samples were filtered through a 0.45 µm nylon filter before analysis. Weight-average molecular weight (Mw) and number-average molecular weight (Mn) are reported. The polydispersity index (PDI) is given as Mw / Mn.

[0266] Determination of glass transition temperature

[0267] The glass transition temperature (Tg) was obtained by differential scanning calorimetry (DSC). On a TA Instruments DSC Q200, DSC measurements were performed by running a heat-cool-heat cycle over a temperature range from -80°C to 150°C at a heating rate of 10°C / min and a cooling rate of 10°C / min, using an empty disk as a reference. Data were processed using general-purpose analysis software from TA Instruments. The inflection point of the glass transition range as defined in ISO 11357-2:2020 after the second heating was reported as the Tg of the polymer.

[0268] Samples were prepared by making drawdown of a polymer solution onto a separate glass plate using an applicator with a 100 µm gap. The glass plate was dried overnight at room temperature and then dried in a ventilated heating cabinet at 50°C for 24 hours. The dried polymer material was scraped off the glass plate, and approximately 10 mg of the dried polymer material was transferred to an aluminum dish. The dish was sealed with a non-airtight cap for measurement.

[0269] Steps for preparing copolymer solution S1

[0270] 60.0 parts of xylene were charged into a temperature-controlled reaction vessel equipped with a stirrer, condenser, nitrogen inlet, and feed inlet. The reaction vessel was heated and maintained at a reaction temperature of 95°C. A premix of 55.0 parts of triisopropylsilyl methacrylate, 5.0 parts of 2-(2-ethoxyethoxy)ethyl acrylate, 10.0 parts of n-butyl acrylate, 30.0 parts of methyl methacrylate, and 1.10 parts of 2,2'-azobis(2-methylbutyronitrile) was prepared. The premix was charged into the reaction vessel at a constant rate over 2 hours using a metering pump under a nitrogen atmosphere. After another 30 minutes of reaction, a reinforcing initiator solution of 0.25 parts of 2,2'-azobis(2-methylbutyronitrile) and 7.6 parts of xylene was fed into the reaction vessel at a constant rate over 20 minutes. The reaction vessel was maintained at the reaction temperature for another 1.5 hours. The reactor was then heated to 105°C and maintained at that temperature for 1 hour. Finally, the reactor was cooled to room temperature. All parts given above are by weight.

[0271] Copolymer solution S1 has the following properties: NVM: 60.1 wt%; Viscosity 1089 cP; Mw 23 936; PDI 2.43; Tg 47°C Copolymer solutions S2 to S11 were prepared in a similar manner to those described above. The monomer composition and procedural details are given in Table 1.

[0272] Steps for preparing copolymer solution A1

[0273] 40.0 parts xylene and 10.0 parts 1-methoxy-2-propanol were charged into a temperature-controlled reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet, and feed inlet. The reaction vessel was heated and maintained at a reaction temperature of 100°C. 75.0 parts n-butyl acrylate, 22.0 parts methyl methacrylate, 3.0 parts methacrylic acid, and 1.60 parts tert-amyl peroxy-2-ethylhexanoate were then prepared. tert A premix of 2-amyl peroxy-2-ethylhexanoate was administered. The premix was added to the reaction vessel at a constant rate over 3 hours using a metering pump under a nitrogen atmosphere. After an additional 30 minutes of reaction, a solution of 0.40 parts of tert-amyl peroxy-2-ethylhexanoate and 5.0 parts of xylene as an initiator was fed into the reaction vessel at a constant rate over 20 minutes. The reaction vessel was maintained at the reaction temperature for another 1.5 hours, and then cooled to room temperature. All parts given are by weight.

[0274] Copolymer solution A1 has the following properties: NVM: 65.4 wt%; Viscosity 1095 cP; Mw 26,530; PDI 2.93; Tg -20°C Copolymer solutions A2 to A4 were prepared in a similar manner to those described above. In the preparation of A3 and A4, tert-butyl peroxy-2-ethylhexanoate was used as the initiator. The monomer composition and procedural details are given in Table 2.

[0275] Steps for preparing zinc rosinate solution Z1

[0276] 88 parts of a rosin solution (60 wt% rosin in xylene, 7 parts zinc oxide, and 5 parts xylene) were loaded into a temperature-controlled reaction vessel equipped with a stirrer and a reflux condenser. The mixture was slowly heated to 70°C and maintained at that temperature for 2 hours. The temperature was then turned off, and the solution was stirred while cooling to room temperature.

[0277] Zinc rosinate solution Z1 has 62.1 wt% NVM.

[0278] Table 1: Overview of the (meth)acrylate silyl ester copolymer (i) examples.

[0279]

[0280] Table 2: Overview of the (meth)acrylic acid polymer (ii-a) and (ii-b) examples.

[0281]

[0282] Table 3: Ingredients used in the examples.

[0283]

[0284] 1 As described in WO2020115323 A1

[0285] Calculation of volatile organic compound (VOC) content in antifouling coating compositions

[0286] Calculate the volatile organic compound (VOC) content of the antifouling coating composition according to ASTM D5201-01.

[0287] The viscosity of paint (coating) was determined using a cone-plate viscometer.

[0288] According to ISO 2884-1:2006, the temperature is set at 23°C for 10,000 s. -1A digital cone and plate viscometer, operating at shear rates of 0-10 P and providing a viscosity measurement range, is used to determine the viscosity of antifouling paint compositions. Results are given as the average of three measurements.

[0289] Testing of antifouling performance

[0290] A 20 cm x 30 cm polyvinyl chloride (PVC) sheet was used for testing. The sheet was coated using airless spraying with a first coating of a commercial bonding coating (Safeguard Plus, manufactured by Chokwang Jotun Ltd., South Korea) and a second coating of a commercial antifouling paint (SeaQuantum Ultra III, manufactured by Jotun Paints (Europe) Ltd., UK). The curing / drying times and film thicknesses of both coatings were within the recommended ranges specified in the product's technical data sheet.

[0291] The antifouling coating composition of the examples was applied directly as a final coating onto a pre-coated PVC board using a film applicator with a 400 µm gap size. The test area of ​​the applied coating film was approximately 6.5 cm x 25 cm. The edges of the board were sealed with a commercial antifouling product. The antifouling coating composition of the examples was applied 3–10 days after the paint (coating) was prepared.

[0292] The boards were exposed on rafts in Singapore, with the boards submerged 0.5 m to 1.5 m below sea level. The boards were evaluated visually and graded according to the following criteria: The grading included large algae such as seaweed and animal fouling (dirt) such as barnacles, tube worms, mussels, sponges, and hydras. Microfouling organisms that could be easily removed by hand, such as biofilms or slime, were not included in the grading. Edge effects were excluded from the evaluation.

[0293] Table 4: Rating Criteria for Degree of Soil Damage

[0294] General steps for preparing antifouling coating compositions

[0295] Mix the components according to the proportions given in Tables 5 to 15. Follow the instructions of the raw material supplier to prepare the premix of the components in the correct order. Disperse and grind the components in a 250 ml paint can in the presence of glass beads (approximately 3-4 mm in diameter) using a vibratory shaker.

[0296] Table 5: Examples Values ​​include carrier materials Table 6: Examples

[0297] Table 7: Examples

[0298] Table 8: Comparative Examples

[0299] Table 9: Comparative Examples

[0300] Comments on Tables 5 to 9: Examples 1-28 demonstrate that antifouling coating compositions containing less than 10.0 wt% of a biocide can be prepared to exhibit excellent antifouling properties. This is achieved by using a copper compound containing more than 40 wt% copper and brominated pyrrolidone, along with a combination of a silyl methacrylate copolymer (i) and a methacrylic acid polymer (ii-a), a monocarboxylic acid (iii), and by having a total amount of pigment, extender, and biocide greater than 35 wt%.

[0301] In Examples 1-9 of Table 5, different copper compounds and brominated pyrrolidones were tested. All formulations in Examples 1-9 showed good antifouling properties.

[0302] In Examples 10-28 in Tables 6 and 7, different types of copper compounds and different amounts of copper compounds and brominated pyrrolidones, as well as combinations thereof, were tested. All formulations in Examples 10-28 showed good antifouling properties.

[0303] Comparative Example C1 in Table 8 is directly comparable to Example 1 in Table 5. In Comparative Example C1, a copper compound is lacking. Its antifouling performance after 6 months is poor. Comparative Example C1 demonstrates that the use of bromopyrrolidone alone is insufficient to achieve good long-term antifouling performance.

[0304] Comparative Example C2 can also be directly compared with Example 1. In Comparative Example 2, bromopyrrolidone was missing. The antifouling performance after 6 months was poor, indicating that the combination of copper compounds and bromopyrrolidone is essential for achieving good long-term antifouling performance in coating compositions containing less than 10.0 wt% of a biocide.

[0305] Comparative Example C3 shows that increasing the amount of cuprous oxide (I) from 1 wt% in Comparative Example C2 to 5 wt% in Comparative Example C3 when bromopyrrolidone is absent does not improve the antifouling performance.

[0306] Comparative examples C4, C5, and C6 show that when other copper compounds are used, the antifouling performance is reduced if bromopyrrolidone is also not present.

[0307] The comparative examples in Table 9 show copper compounds other than those described in this invention. Comparative Examples C7 to C12 comprise copper compounds having a copper content of less than 40 wt%. All formulations in Comparative Examples C7 to C12 exhibited poor long-term antifouling properties.

[0308] Table 10: Examples

[0309] Table 11: Examples Values ​​include carrier materials Table 12: Comparative Examples

[0310] Comments on Tables 10 to 12: In Examples 29-38 of Table 10, different (meth)acrylate silyl ester copolymers (i) and (meth)acrylate polymers (ii-a) were tested. Different combinations of these polymers were also tested. All formulations in Examples 29-47 exhibited good antifouling properties.

[0311] Examples 39-48 in Table 11 illustrate examples of different (meth)acrylate silyl ester copolymers (i) and copper compounds. All examples demonstrate good antifouling properties.

[0312] Comparative example C13 in Table 12 shows that if the total amount of pigments, extenders, and biocides is less than 35 wt% based on the total weight of the coating composition, the antifouling performance is already very poor after 1 month.

[0313] Comparative examples C14, C15, and C16 show that the antifouling performance is poor if a monocarboxylic acid is absent in the coating composition.

[0314] Table 13: Examples

[0315] Table 14: Examples

[0316] Table 15: Examples

[0317] Commentary on Tables 13 to 15 : In Examples 49-75 of Tables 12 to 15, different combinations of adhesives, biocides, and pigments were tested. Examples 50 and 51 of Table 13 show that zinc salts of rosin (zinc rosinate Z1) can also be used. Examples 67-75 of Table 15 illustrate the use of combinations of (meth)acrylic polymers (ii-a) and second (meth)acrylic polymers (ii-b) in the absence of (meth)acrylic silyl ester copolymer (i). All examples demonstrate good antifouling properties.

[0318] Table 16: Examples

[0319] Table 17: Examples

[0320] Table 18: Examples

[0321] Table 19: Examples

[0322] Table 20: Comparative Examples

[0323] Comments on Table 16

[0324] These embodiments used different amounts and combinations of biocide, as well as silyl methacrylate polymer (i), methacrylate polymer (ii), and rosin. All embodiments demonstrated good antifouling properties.

[0325] Comments on Table 17

[0326] These embodiments utilize a variety of adhesive combinations, including a broad range of (meth)acrylate silyl polymers (i), (meth)acrylate polymers (ii), and monocarboxylic acids (iii). All embodiments demonstrate good antifouling properties.

[0327] Commentary on Tables 18-19

[0328] These examples demonstrate the use of a wide range of extenders and different rosins, as well as combinations of (meth)acrylic polymers (ii-a) and second (meth)acrylic polymers (ii-b), wherein the (meth)acrylic silyl ester copolymer (i) is absent. All examples exhibit good antifouling properties.

[0329] Comments on Table 20

[0330] Comparative examples show that when bromopyrrolidone (iv-a) or Cu compound (iv-b) (containing at least 40 wt% Cu) is missing in a composition having a combination of (meth)acrylic acid polymer (ii-a), second (meth)acrylic acid polymer (ii-b) and carboxylic acid (iii), the antifouling performance is poor.

Claims

1. An antifouling coating composition comprising: (i) A (meth)acrylate silyl ester copolymer comprising at least 15 wt% silyl ester monomers relative to the total weight of the monomers in the (meth)acrylate silyl ester copolymer, and / or (ii) A (meth)acrylic acid polymer comprising 10 wt% or less of silyl ester monomers and 5.0 wt% or less of metal ester monomers relative to the total weight of the monomers in the (meth)acrylic acid polymer; (iii) Monocarboxylic acids or their metal salts; (iv) Biocides, including: a. Bromopyrrolidinium; and b. One or more copper compounds having a copper content of at least 40 wt% relative to the formula weight of the copper compound, wherein the coating composition as a whole contains 10.0 wt% or less of a biocide; and (v) At least 35 wt% of the combined pigments, extenders and biocides relative to the total weight of the coating composition as a whole.

2. The antifouling coating composition according to claim 1, wherein the composition comprises (meth)acrylate silyl ester copolymer (i) or both (meth)acrylate silyl ester copolymer (i) and (meth)acrylate polymer (ii).

3. The antifouling coating composition according to any one of the preceding claims, wherein the composition comprises 8.0 wt% or less, preferably 5.0 wt% or less, of a biocide relative to the total weight of the coating composition as a whole.

4. The antifouling coating composition according to any one of the preceding claims, wherein the copper compound has a copper content of at least 45 wt%, preferably at least 50 wt%, particularly metallic copper or cuprous oxide (I).

5. The antifouling coating composition according to any one of the preceding claims, wherein brominated pyrrolidone is present in an amount of 0.1 to 5.0 wt%, preferably 0.2 to 3.0 wt%, more preferably 0.3 to 2.0 wt%, and even more preferably 0.4 to 1.0 wt%, relative to the total weight of the composition, and / or in, The one or more copper compounds are present in an amount of 0.1 to 8.0 wt%, preferably 0.2 to 5.0 wt%, more preferably 0.3 to 3.0 wt%, even more preferably 0.3 to 2.0 wt%, and even more preferably 0.3 to 1.0 wt%, relative to the total weight of the composition.

6. The antifouling coating composition according to any one of the preceding claims, wherein the (meth)acrylate silyl copolymer (i) comprises structural units derived from the following monomers: (a) Silicate ester monomers of formula (I), （I） in, R 1 It is H or CH3; R 2 Each is independently selected from C1-C10 hydrocarbon groups. Isopropyl is preferred; (b) One or more monomers of formula (II) (II) Among them, R 4 It is H or CH3, and R 5 It is a C1-C20 hydrocarbon substituent. C1-10 alkyl substituents are preferred.

7. The antifouling coating composition according to any one of the preceding claims, wherein the coating composition comprises a (meth)acrylic polymer (ii).

8. The antifouling coating composition according to any one of the preceding claims, wherein the (meth)acrylic polymer (ii) is a (meth)acrylic polymer (ii-a) having a Tg below 10°C, more preferably below 0°C, such as below -10°C.

9. The antifouling coating composition according to claim 8, wherein the (meth)acrylic acid copolymer (ii-a) comprises (a) (meth)acrylic acid, and (b) One or more monomers of formula (II) (II) Where R 4 It is H or CH3, and R 5 It is a C1-C20 hydrocarbon substituent. C1-10 alkyl substituents are preferred, with methyl, ethyl, n-propyl, n-butyl, or 2-ethylhexyl being the most preferred.

10. The antifouling coating composition according to any one of the preceding claims, wherein the (meth)acrylic polymer (ii) is a (meth)acrylic polymer (ii-b) and has a glass transition temperature (Tg) of at least 10°C.

11. The antifouling coating composition according to claim 10, wherein the (meth)acrylate polymer (ii-b) comprises: (a) One or more monomers of formula (II) (II) Where R 4 It is H or CH3, and R 5 It is a C1-C20 hydrocarbon substituent. Preferably, C1-10 alkyl substituents are used, with methyl, ethyl, n-propyl, n-butyl, or 2-ethylhexyl being the most preferred. (b) One or more monomers of formula (VI) (WE) Where R 11 It is H or CH3, and R 12 It is a C3-40 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom, such as a C3-C20 substituent, or R 12 It indicates a poly(alkylene glycol) group.

12. The antifouling coating composition according to any one of the preceding claims, wherein component (i) is present in an amount of 2.0 to 30 wt%, preferably 5.0 to 25 wt%, relative to the total weight of the coating composition as a whole; and / or Component (ii-a) is present in an amount of 0.5 to 12 wt%, preferably 1.0 to 7.0 wt%, relative to the total weight of the coating composition as a whole; and / or component (ii-b) is present in an amount of 1.0 to 15 wt%, preferably 2.0 to 12 wt%, relative to the total weight of the coating composition as a whole; and The monocarboxylic acid or its metal salt (iii) is present in an amount of 5.0 to 30 wt%, preferably 5.0 to 25 wt%, based on the total weight of the coating composition as a whole.

13. The antifouling coating composition according to any one of the preceding claims, wherein the monocarboxylic acid or its metal salt (iii) is rosin, modified rosin or its metal salt, especially rosin resin, hydrogenated rosin resin, copper salt of rosin resin, zinc salt of rosin resin, copper salt of hydrogenated rosin resin, zinc salt of hydrogenated rosin resin, and mixtures thereof.

14. The antifouling coating composition according to any one of the preceding claims further comprises one or more biocides selected from zinc pyrithione, copper pyrithione, zineb, and 4,5-dichloro-2-octyl-4-isothiazolin-3-one.

15. The antifouling coating composition according to any one of the preceding claims, wherein bromoxypyrrolidone is present in an amount of 5.0 to 60.0 wt%, preferably 7.0 to 60.0 wt%, more preferably 8.0 to 60.0 wt%, even more preferably 9.0 to 60.0 wt%, and even more preferably 10.0 to 60.0 wt%, relative to the total weight of the biocide (iv), and / or The one or more copper compounds are present in an amount of 5.0 to 90.0 wt%, preferably 6.0 to 87.0 wt%, more preferably 7.0 to 85.0 wt%, even more preferably 8.0 to 82.0 wt%, and even more preferably 9.0 to 80.0 wt% of the total weight of the biocide (iv).

16. A method for protecting an object from contamination, the method comprising coating at least a portion of the contaminated object with an antifouling coating composition according to any one of claims 1 to 15.

17. An object coated with an antifouling coating composition according to any one of claims 1 to 15.

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