Antifouling composition

Abstract

The present invention relates to an antifouling coating composition comprising: (i) a (meth)acrylic silyl ester copolymer containing at least 15% by weight of silyl ester monomers relative to the total weight of monomers in the (meth)acrylic silyl ester copolymer; and / or (ii) a (meth)acrylic polymer containing 10% by weight or less of silyl ester monomers and 5.0% by weight or less of metal ester monomers relative to the total weight of monomers in the (meth)acrylic polymer; (iii) a monocarboxylic acid or a metal salt thereof; and (iv) a biocide comprising a. tralopyryl and b. one or more copper compounds having a copper content of at least 40% by weight relative to the formula weight of the copper compound, wherein the biocide content in the entire coating composition is 10.0% by weight or less; and (v) a total of at least 35% by weight of pigments, fillers, and biocides relative to the total weight of the entire coating composition.

Description

[Technical Field]

[0001] The present invention relates to marine antifouling coating compositions, and more specifically to antifouling coating compositions containing a biocide in an amount of 10.0% by weight or less, wherein the biocide comprises tralopyryl and a copper compound having a copper content of at least 40% by weight. These compositions further contain a monocarboxylic acid or its metal salt, a (meth)acrylic silyl ester copolymer and / or a (meth)acrylic polymer, and a pigment and / or an extender. The present invention further relates to a method for protecting an object from fouling and an object coated with the antifouling composition of the present invention. [Background technology]

[0002] Surfaces submerged in seawater are fouled by marine organisms such as green algae, brown algae, barnacles, mussels, and tubifex worms. Such fouling is undesirable and has economic implications for offshore structures such as ships, oil platforms, and buoys. Fouling can lead to biological degradation of the surface, increased load, and accelerated corrosion. In ships, fouling increases frictional resistance, resulting in reduced speed and / or increased fuel consumption.

[0003] Antifouling paints are used to prevent the attachment and growth of marine organisms. These paints generally contain a film-forming binder along with various components such as pigments, fillers, additives, and solvents, as well as bioactive substances (biocidals). Biocides can be broadly classified into those effective against soft fouling caused by soft-attaching organisms such as green algae, brown algae, seagrasses, and slime, and those effective against hard fouling caused by hard-attaching organisms such as barnacles, mussels, and tube parasites.

[0004] The largest product segment in the antifouling coating system for merchant ships is the self-polishing antifouling coating (SPC). Most of these products are copper-based and have a relatively high total content of biocides, pigments, and extenders. Commercially available copper-containing products usually contain 20 - 50 wt% of cuprous oxide, which is known to have good activity against fouling by hard adherent organisms, in order to expand the antifouling activity spectrum of the product, and further contain 1 - 10 wt% of an organic biocide that is mainly effective against fouling by soft adherent organisms. One of the success factors of SPC products is that the polishing rate can be adjusted to maximize the effectiveness of the product in ships with different operating speeds and activity situations.

[0005] There are only a limited number of biocides approved by regulatory authorities for use as marine antifouling agents. The approved biocides are considered to be safe to use and have no harmful effects on the environment. However, it is still important to optimize the effects of the combination of biocides in the coating film and minimize their use. Regulations on the use of biocides are being strengthened, and in the future, it is highly likely that the amount of biocides in antifouling coatings will need to be significantly reduced. When reducing the amount of biocides, there are challenges in maintaining good long-term antifouling performance.

[0006] Low-biocide formulations are generally related to formulations with low pigment and extender contents and are often combined with polysiloxane-based binders or binders having polysiloxane blocks and / or added silicone oils. An example of a commercially available product is a biocidal fouling release coating (FRC). To reduce the biocide content in conventional self-polishing antifouling coatings, the biocide needs to be completely or partially replaced with other components. This will affect the self-polishing properties, mechanical properties, and antifouling performance of the coating unless the formulation is carefully redesigned. Therefore, there is still a need to develop new self-polishing antifouling coating compositions with reduced biocide content. Summary of the Invention

Problems to be Solved by the Invention

[0007] Tralopyril is a relatively new metal-free organic marine antifoulant that exhibits broad activity against hard-shell and soft-bodied invertebrates such as barnacles, hydroids, mussels, oysters, tube worms, and tunicates. Tralopyril is sold under the trade name "Econea" and according to the supplier's product datasheet, its use at 4-6% by weight in antifouling coating compositions is recommended. When reducing the amount of tralopyril used alone as a biocide effective against fouling by hard fouling organisms, there is a problem in achieving sufficient antifouling performance.

Means for Solving the Problems

[0008] The present inventors have surprisingly found that by combining tralopyril with a copper compound as defined herein, a self-polishing antifouling coating composition with a total biocide content of 10% by weight or less can be prepared. Such coating compositions have unexpectedly excellent antifouling properties.

Modes for Carrying Out the Invention

[0009] [Summary of the Invention] In one aspect, the present invention is an antifouling coating composition comprising (i) a (meth)acrylic silyl ester copolymer containing at least 15% by weight of silyl ester monomer based on the total weight of the monomers present in the (meth)acrylic silyl ester copolymer, and / or (ii) a (meth)acrylic polymer containing 10% by weight or less of silyl ester monomer and 5.0% by weight or less of metal ester monomer based on the total weight of the monomers present in the (meth)acrylic polymer, and (iii) a monocarboxylic acid or its metal salt, and (iv) a. tralopyril, and b. A biocide comprising one or more copper compounds having a copper content of at least 40% by weight relative to the formula weight of the copper compound, The biocide content in the entire coating composition is 10.0% by weight or less, and (v) The present invention relates to an antifouling coating composition comprising, in total, at least 35% by weight of pigments, fillers, and biocides based on the total weight of the entire coating composition.

[0010] In another aspect, the present invention relates to an antifouling coating composition, (i)(meth)acrylicsilyl ester copolymers containing at least 15% by weight of silyl ester monomers relative to the total weight of monomers present in the (meth)acrylicsilyl ester copolymer, (ii) A (meth)acrylic polymer containing 10% by weight or less of silyl ester monomers and 5.0% by weight or less of metal ester monomers based on the total weight of monomers present in the (meth)acrylic polymer, (iii) monocarboxylic acid or its metal salt, (iv)a. Tralopiril, b. A biocide comprising one or more copper compounds having a copper content of at least 40% by weight relative to the formula weight of the copper compound, The biocide content in the entire coating composition is 10.0% by weight or less, and (v) The present invention relates to an antifouling coating composition comprising, in total, at least 35% by weight of pigments, fillers, and biocides based on the total weight of the entire coating composition.

[0011] In another aspect, the present invention relates to an antifouling coating composition, (ii) at least one, preferably at least two, (meth)acrylic polymers, each containing 10% by weight or less of silyl ester monomers and 5.0% by weight or less of metal ester monomers relative to the total weight of monomers present in each (meth)acrylic polymer, (iii) monocarboxylic acid or its metal salt, (iv)a. Tralopiril, b. A biocide comprising one or more copper compounds having a copper content of at least 40% by weight relative to the formula weight of the copper compound, The biocide content in the entire coating composition is 10.0% by weight or less, and (v) The present invention relates to an antifouling coating composition comprising, in total, at least 35% by weight of pigments, fillers, and biocides based on the total weight of the entire coating composition.

[0012] In a further aspect, the present invention relates to a process for protecting an object from contamination, comprising the step of coating at least a portion of the object susceptible to contamination with the antifouling coating composition defined above. In another aspect, the present invention relates to an object coated with the antifouling coating composition defined above.

[0013] [Definition] As used herein, the terms “marine antifouling coating composition,” “antifouling coating composition,” or simply “coating composition” refer to compositions that, when applied to a surface, prevent or minimize the growth of marine organisms on that surface. The antifouling coating composition of the present invention is a "self-polishing" coating. "Self-polishing" or "polishing" means that the coating thickness decreases over time as the coating material is removed from the coating surface as a result of deterioration and / or erosion by the surrounding water medium.

[0014] As used herein, the term "paint" refers to a composition comprising the antifouling coating composition described herein and optionally a solvent, in a state suitable for use, for example, spraying. Therefore, the antifouling coating composition may be a paint itself, or it may be a concentrated liquid for which a solvent is added to produce a paint.

[0015] As used herein, the terms “(meth)acrylic polymer” and “(meth)acrylic silyl ester copolymer” refer to polymers containing repeating units derived from (meth)acrylate monomers. Generally, (meth)acrylic polymers or (meth)acrylic silyl ester copolymers contain at least 50% by weight of (meth)acrylate monomers, i.e., repeating units derived from acrylate monomers and / or methacrylate monomers.

[0016] When the weight percentage of a particular monomer is given for a polymer, that weight percentage represents the ratio to the total weight of the monomers present in the copolymer.

[0017] As used herein, the term "hydrocarbyl group" refers to any group containing only a carbon (C) atom and a hydrogen (H) atom, and therefore includes alkyl groups, aryl groups, cycloalkyl groups, arylalkyl groups, and the like.

[0018] As used herein, the term "alkyl" refers to a saturated linear group or a saturated branched group. As used herein, the term "cycloalkyl" refers to a cyclic alkyl group. As used herein, the term "alkylene" refers to a divalent alkyl group. As used herein, the term "aryl" refers to a group containing at least one aromatic ring. The aryl group may or may not have substituents. An example of an aryl group is phenyl, i.e., C6H5. The phenyl group may or may not have substituents.

[0019] As used herein, the term "(meth)acrylate" encompasses both methacrylate and acrylate. As used herein, the term "volatile organic compound (VOC)" refers to a compound having a boiling point of 250°C or less at standard atmospheric pressure (1 atm).

[0020] As used herein, the terms “antifouling agent” or “biocide” refer to a bioactive compound or mixture of bioactive compounds that prevents or minimizes the attachment and / or growth of marine organisms on a surface.

[0021] As used herein, the term "monocarboxylic acid" refers to a compound containing one -COOH group.

[0022] The term “binder” means a portion of a composition comprising components (i), (ii), and (iii) as defined herein, and other components that together form a matrix that imparts strength and / or flexibility to the coating. The term "Tg" refers to the glass transition temperature.

[0023] The term "weight % based on the total weight of the composition" refers to the weight % of the components present in the entire coating composition, unless otherwise specified. As used herein, the term “weight % based on the total dry weight of the composition” refers, unless otherwise specified, to the weight % of the dry components present in the dry weight of the coating composition, excluding solvents and other volatile components.

[0024] [Detailed description of the invention] The present invention relates to a novel antifouling coating composition, the antifouling coating composition containing (i) a (meth)acrylic silyl ester copolymer and / or (ii) a (meth)acrylic polymer, (iii) a monocarboxylic acid or its metal salt, and (iv) 10.0% by weight or less of a biocide comprising tralopyryl and a copper compound, and (v) a total of at least 35% by weight of pigments, fillers, and biocides relative to the total weight of the coating composition.

[0025] The binders of the present invention, if present, all contain components (i) to (iii). The coating compositions of the present invention contain (i) (meth)acrylic silyl ester copolymer and / or (ii) (meth)acrylic copolymer as defined herein.

[0026] In one preferred embodiment, the antifouling coating composition of the present invention contains (meth)acrylic silyl ester copolymer (i) as defined herein.

[0027] In a second preferred embodiment, the antifouling coating composition of the present invention contains both (meth)acrylicsilyl ester copolymer (i) and (meth)acrylic polymer (ii) as defined herein.

[0028] In a third preferred embodiment, the antifouling coating composition of the present invention contains a (meth)acrylic polymer (ii) as defined herein.

[0029] In a fourth preferred embodiment, the antifouling coating composition of the present invention contains at least two (meth)acrylic polymers (ii) (for example, (meth)acrylic polymer (ii-a) and (meth)acrylic polymer (ii-b), wherein these polymers (ii-a) and (ii-b) are different).

[0030] [(meth)acryl silyl ester copolymer (i)] The use of (meth)acrylic silyl ester copolymers in antifouling coating compositions is well known, and in its broadest embodiment, the present invention encompasses any of these well known copolymers.

[0031] (meth)acrylicsilyl ester copolymer (i) contains repeating units derived from (meth)acrylate monomers. Preferably, (meth)acrylicsilyl ester copolymer (i) contains at least 80% by weight of repeating units derived from (meth)acrylate monomers, i.e., acrylate monomers and / or methacrylate monomers. More preferably, (meth)acrylicsilyl ester copolymer (i) contains at least 85% by weight, more preferably at least 90% by weight, and even more preferably at least 95% by weight of repeating units derived from (meth)acrylate monomers. Preferred (meth)acrylicsilyl ester copolymers present in the composition of the present invention contain 80 to 100% by weight, more preferably 85 to 100% by weight, and even more preferably 90 to 100% by weight of repeating units derived from (meth)acrylate monomers.

[0032] In a preferred embodiment, the (meth)acrylic silyl ester copolymer contains 100% by weight of structural units derived from (meth)acrylate monomers, i.e., it does not contain any other types of monomers.

[0033] The coating composition of the present invention may contain a mixture of two or more different (meth)acrylsilyl ester copolymers (i), as described, for example, in British Patent No. 2576431.

[0034] The (meth)acrylicsilyl ester copolymer of the present invention preferably contains structural units derived from a (meth)acrylicsilyl ester monomer (a1) and structural units derived from a polymerizable ethylenically unsaturated monomer (a2).

[0035] [(meth)acrylsilyl ester monomer (a1)] Preferably, the (meth)acrylicsilyl ester copolymer (i) contains a residue of at least one silyl ester monomer (a1) represented by formula (I).

[0036] [ka]

[0037] In the formula, R 1 is H or CH3, R 2 These are, independently of each other, C1-C10 hydrocarbyl groups and OSi(R 3 ) Selected from 3 units, R 3 These are independently selected from the group consisting of linear or branched C1-C10 alkyl groups.

[0038] The term "hydrocarbyl" encompasses linear 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, and aryl groups such as phenyl and substituted phenyl. 2 It is preferable that each of the R groups is independently a C1-C8 alkyl group. 2 It is preferable that the groups are the same.

[0039] Each R 3 It is preferable that each of the R groups is independently a C1-C4 alkyl group. 3 It is preferable that the groups are the same.

[0040] Examples of monomers (a1) defined by general formula (I) include tri-n-propylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, tert-butyldimethylsilyl (meth)acrylate, texyldiethyldimethylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, bis(trimethylsiloxy)methylsilyl (meth)acrylate, and tris(trimethylsiloxy)silyl (meth)acrylate.

[0041] The use of triisopropylsilyl acrylate and / or triisopropylsilyl methacrylate is preferred. Thus, R 2 is preferably isopropyl.

[0042] The (meth)acrylic silyl ester monomer represented by formula (I) can be used alone or in combination of two or more silyl ester monomers represented by formula (I). The (meth)acrylic silyl ester copolymer (i) preferably contains one or two different monomers represented by formula (I), and particularly preferably contains one kind.

[0043] The (meth)acrylic silyl ester copolymer (i) preferably contains at least 15% by weight of the silyl ester monomer (for example, those represented by formula (I) in the present specification) based on the total weight of the monomers present in the copolymer. Preferably, the (meth)acrylic silyl ester copolymer contains at least 30% by weight of the silyl ester monomer based on the total weight of the monomers present in the copolymer, more preferably at least 40% by weight, for example at least 45% by weight.

[0044] The (meth)acrylic silyl ester copolymer (i) preferably contains less than 80% by weight of the silyl ester monomer based on the total weight of the monomers present in the copolymer. Preferably, the (meth)acrylic silyl ester copolymer contains less than 75% by weight of the silyl ester monomer based on the total weight of the monomers present in the copolymer, more preferably less than 70% by weight, for example less than 65% by weight.

[0045] [Ethylenically unsaturated monomer (a2)] The (meth)acrylicsilyl ester copolymer (i) of the present invention preferably contains a residue of at least one ethylenically unsaturated monomer (a2) that can polymerize with the (meth)acrylicsilyl ester monomer (a1). Monomer (a1) and monomer (a2) are different. Monomer (a2) preferably does not contain a silyl ester group. Monomer (a2) preferably does not contain a metal ester group.

[0046] The ethylenically unsaturated monomer (a2) is preferably selected from (meth)acrylate monomers and vinyl monomers. Preferably, the ethylenically unsaturated monomer (a2) is a (meth)acrylate monomer.

[0047] 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, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and 2-(2-ethoxyethoxy)ethyl (meth)acrylate. Examples include ethyl (meth)acrylate, methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, 2-(2-ethoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, oligo(oxycarbonylmethyl)methyl (meth)acrylate, oligo(oxycarbonylmethyl)ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycerol formal (meth)acrylate, isopropylideneglycerol (meth)acrylate, glycerol carbonate (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycidyl (meth)acrylate, and 4-glycidyloxybutyl (meth)acrylate.

[0048] Examples of suitable vinyl monomers (a2) include styrene, vinyl 2-ethylhexanoate, and vinyl neodecanoate. A mixture of different monomers (a2) may be used. Preferably, the ethylenically unsaturated monomer (a2) is represented by formula (II).

[0049] [ka]

[0050] In the formula, R 4 is H or CH3, and R 5 R is a C1-C20 hydrocarbyl substituent, preferably a C1-C10 alkyl substituent, for example, a C1-C8 alkyl substituent. 5 The group may be linear or branched. Most preferably, R 5 R is a methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, or decyl group, and may be linear or branched (where possible). 5 The ideal choices are methyl, ethyl, n-butyl, isobutyl, or isooctyl.

[0051] Examples of monomers represented by formula (II) that are suitable as monomer (a2) in (meth)acrylic polymer (ii-a) 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, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0052] Preferred options for the monomer represented by formula (II) include methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, or isobutyl methacrylate. A mixture of different monomers represented by formula (II) may be used.

[0053] The ethylenically unsaturated monomer (a2) may be represented by formula (III).

[0054] [ka]

[0055] In the formula, R 6 is H or CH3, and R 7 This is a C3-C40 substituent containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom, and more preferably a C3-C20 substituent containing at least one oxygen atom.

[0056] Preferably, R 7 The base is (CH2CH2O) n -R 8 This is represented by R 8 is a C1-C10 hydrocarbyl substituent, preferably a C1-C10 alkyl substituent or a C6-C10 aryl substituent, and n is an integer in the range of 1-5, preferably 1-3. Preferably, R 7 The formula is (CH2CH2O) n -R 8 This is represented by R 8 n is a C1-C10 alkyl substituent, preferably CH3 or CH2CH3, and n is an integer in the range of 1-3, preferably 1 or 2.

[0057] Such monomers may be 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-(2-butoxyethoxy)ethyl (meth)acrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl (meth)acrylate, or 2-[2-(2-ethoxyethoxy)ethoxy]ethyl (meth)acrylate.

[0058] The preferred monomer (a2) represented by formula (III) is 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, or 2-(2-ethoxyethoxy)ethyl methacrylate.

[0059] R 7 The base is the formula (CH2C(O)O) p -R 9 Or (CH(CH3)C(O)O) p -R 9 It may also be represented by R 9 p is a C1-C10 hydrocarbyl substituent, preferably a C1-C10 alkyl substituent or a C6-C10 aryl substituent, and p is an integer in the range of 1-10, preferably 1-4.

[0060] Such monomers represented by formula (III) may be methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, 2-(2-ethoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, oligo(oxycarbonylmethyl)methyl (meth)acrylate, and oligo(oxycarbonylmethyl)ethyl (meth)acrylate.

[0061] R 7 The group may be a cyclic group containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom. In this embodiment, R 7 is the base WR 10 It may be so, and here, R 10 is a cyclic ether such as oxirane, furan, oxolane, oxane, dioxolane, or dioxane, and may optionally be alkyl-substituted, while W is a C1-C4 alkylene.

[0062] Such monomers represented by formula (III) may be furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycerol formal (meth)acrylate, isopropylideneglycerol (meth)acrylate, glycerol carbonate (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycidyl (meth)acrylate, and 4-glycidyloxybutyl (meth)acrylate. Preferred cyclic ethers contain at least four atoms in the ring, such as tetrahydrofurfuryl acrylate and isopropylideneglycerol methacrylate.

[0063] The monomer represented by 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.

[0064] A mixture of different monomers represented by formula (III) may be used. Furthermore, mixtures of different monomers represented by formulas (II) and (III) may be used in combination.

[0065] If the monomer represented by formula (III) is present in the (meth)acrylicsilyl ester copolymer (i) of the present invention, it is preferable that at least one monomer represented by formula (II) is also present.

[0066] The preferred (meth)acrylic silyl ester copolymer (i) of the present invention contains structural units derived from one or more monomers represented by formula (I), such as triisopropylsilyl acrylate and / or triisopropylsilyl methacrylate, and structural units derived from one or more monomers represented by formula (II), such as methyl methacrylate and / or butyl acrylate, and optionally contains structural units derived from one or more monomers represented by formula (III), such as 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, and 2-(2-ethoxyethoxy)ethyl acrylate.

[0067] Preferably, the content of (meth)acrylicsilyl ester monomer (a1) (for example, a monomer represented by formula (I)) in the (meth)acrylicsilyl ester copolymer (i) is in the range of 30 to 80% by weight, preferably 35 to 75% by weight, for example, 40 to 70% or 45 to 65% by weight, based on the total weight of monomers present in the entire (meth)acrylicsilyl ester copolymer.

[0068] Preferably, the (meth)acrylic silyl ester copolymer (i) contains monomer (a2) (for example, one represented by formula (II) or formula (III)) in an amount of 20 to 70% by weight, for example, 30 to 60% by weight or 35 to 55% by weight, more preferably 35 to 55% by weight, relative to the total weight of monomers present in the (meth)acrylic silyl ester copolymer.

[0069] Preferably, the (meth)acrylic silyl ester copolymer (i) contains at least 15% by weight of the monomer component represented by formula (II), and more preferably 15 to 65% by weight.

[0070] Preferably, the (meth)acrylic silyl ester copolymer (i) contains less than 40% by weight of the monomer represented by formula (III), and more preferably 2.0 to 35% by weight.

[0071] R in equation (III) 7 The base is formula -(CH2CH2O)n -R 8 When the group is represented by , the (meth)acrylic silyl ester copolymer (i) may contain 2.0 to 40% by weight of the monomer represented by formula (III).

[0072] R in equation (III) 7 When the group is a cyclic group, the (meth)acrylicsilyl ester copolymer (i) may contain 5.0 to 40% by weight of the monomer represented by formula (III).

[0073] The (meth)acrylic silyl ester copolymer (i) preferably has a weight-average molecular weight (Mw) of 5,000 to 70,000, preferably 8,000 to 55,000, and more preferably 20,000 to 45,000. Mw is measured according to the description in the examples. The (meth)acrylic silyl ester copolymer (i) preferably has a polydispersity index (PDI) of 1.5 to 8.0, and more preferably 2.0 to 5.0.

[0074] The above copolymer preferably has a glass transition temperature (Tg) of at least 15°C, preferably at least 20°C, for example at least 25°C, and all values ​​are measured according to the Tg test described in the examples. Preferably, a value of less than 80°C is preferred, for example less than 70°C, for example less than 60°C or less than 55°C. The (meth)acrylsilyl ester copolymer (i) may be provided as a polymer solution such as a xylene solution. The polymer solution is preferably prepared to have a solid content of 30-90% by weight, preferably 40-85% by weight, and more preferably 45-75% by weight.

[0075] In a preferred embodiment, the antifouling coating composition of the present invention preferably contains, based on the entire coating composition, 2.0 to 30% by weight, for example 5.0 to 25% by weight, and particularly 7.0 to 20% by weight or 7.0 to 15% by weight of (meth)acrylic silyl ester copolymer (i).

[0076] In one preferred embodiment, the antifouling coating composition of the present invention preferably contains 5.0 to 40% by weight, for example 7.0 to 30% by weight, and particularly 10 to 25% by weight, of (meth)acrylic silyl ester copolymer (i) based on the total dry weight of the coating composition.

[0077] In one preferred embodiment, the amount of (meth)acrylic silyl ester copolymer (i) present in the antifouling coating composition of the present invention is 20 to 70% by weight, preferably 30 to 65% by weight, and more preferably 40 to 60% by weight, based on the total dry weight of the binder in the coating composition.

[0078] If the antifouling coating composition contains a mixture of two or more different (meth)acrylic silyl ester copolymers (i), these proportions apply to the total content of all (meth)acrylic silyl ester copolymers (i) present. It is preferable that only one type of (meth)acrylic silyl ester copolymer (i) is present.

[0079] [(meth)acrylic polymer (ii)] The (meth)acrylic polymer (ii) of the present invention contains structural units derived from a carboxylic acid containing a (meth)acrylic monomer and / or a (meth)acrylate monomer. The (meth)acrylic polymer (ii) contains 10% by weight or less of silyl ester monomer and 5.0% by weight or less of metal ester monomer based on the total weight of monomers present in the polymer.

[0080] The (meth)acrylic polymer (ii) of the present invention preferably contains repeating units derived from (meth)acrylate monomers. Preferably, the (meth)acrylic polymer (ii) contains at least 50% by weight of repeating units derived from (meth)acrylate monomers, i.e., acrylate monomers and / or methacrylate monomers.

[0081] The (meth)acrylic polymer (ii) contains, more preferably, at least 60% by weight, more preferably at least 75% by weight, and even more preferably at least 90% by weight, repeating units derived from (meth)acrylate monomers.

[0082] In one embodiment, the (meth)acrylic polymer (ii) contains 100% by weight of structural units derived from (meth)acrylate monomers, i.e., it does not contain any other types of monomers.

[0083] The (meth)acrylic polymer (ii) of the present invention contains 10% by weight or less, preferably less than 5.0% by weight, for example less than 2.0% by weight or less than 1.0% by weight, of silyl ester monomers (for example, those represented by formula (I) above) based on the total weight of monomers present in the (meth)acrylic polymer (ii), and contains 5.0% by weight or less, preferably less than 3.0% by weight, for example less than 2.0% by weight or less than 1.0% by weight, of metal ester monomers. Most preferably, the (meth)acrylic polymer (ii) does not contain silyl ester groups.

[0084] The (meth)acrylic polymer (ii) of the present invention may also preferably contain no metal ester groups.

[0085] The (meth)acrylic polymer (ii) may be a homopolymer or a copolymer, and is preferably a copolymer.

[0086] The (meth)acrylic polymer (ii) may be provided as a polymer solution, such as a solution in a solvent. The polymer solution is preferably prepared to have a solids content of 30-90% by weight, preferably 40-85% by weight, and more preferably 45-75% by weight.

[0087] In one embodiment, the coating composition of the present invention contains at least one (meth)acrylic polymer (ii), for example, (meth)acrylic polymer (ii-a). However, it is also possible to use two types of (meth)acrylic polymer (ii), for example, (meth)acrylic polymer (ii-a) and (meth)acrylic polymer (ii-b).

[0088] In one embodiment, the coating composition of the present invention does not contain (meth)acrylic silyl ester copolymer component (i), but contains two types of (meth)acrylic polymers (ii), for example, (meth)acrylic polymer (ii-a) and (meth)acrylic polymer (ii-b).

[0089] [(meth)acrylic polymer (ii-a)] In one embodiment, (meth)acrylic polymer (ii) is (meth)acrylic polymer (ii-a).

[0090] The Tg of (meth)acrylic polymer (ii-a) is less than 10.0°C, preferably less than 0°C, more preferably less than -5°C, and even more preferably less than -10°C, and all values ​​are measured according to the Tg test described in the examples. Values ​​higher than -65°C are preferred, for example, higher than -55°C or higher than -45°C.

[0091] In one embodiment, the (meth)acrylic polymer (ii-a) contains a (meth)acrylic acid monomer (a3). A suitable (meth)acrylic acid monomer (a3) ​​is methacrylic acid or acrylic acid. The (meth)acrylic acid (a3) ​​content in the (meth)acrylic polymer (ii-a) is preferably in the range of 0.5 to 10.0% by weight, for example, 1.0 to 5.0% by weight.

[0092] The (meth)acrylic polymer (ii-a) has an acid value preferably less than 60 mgKOH / g polymer, more preferably less than 40 mgKOH / g polymer, and even more preferably less than 25 mgKOH / g polymer. The acid value is preferably higher than 2 mgKOH / g polymer, for example, higher than 5 mgKOH / g polymer. The acid value is measured according to the procedure described in ISO 2114:2000 Method A.

[0093] If (meth)acrylic acid monomer (a3) ​​is present, it is preferable that the following second (meth)acrylate monomer (a4) be present in order to form a copolymer.

[0094] In another embodiment, the (meth)acrylic polymer (ii-a) contains at least one (meth)acrylate monomer (a4). Preferably, the (meth)acrylate monomer (a4) constitutes at least 50% by weight, for example, at least 75% by weight or at least 80% by weight, and particularly preferably 95.0 to 99.5% by weight of the (meth)acrylic polymer (ii-a).

[0095] The (meth)acrylic polymer (ii-a) may be a homopolymer containing only structural units derived from the (meth)acrylate monomer (a4). An example of a suitable (meth)acrylate monomer (a4) is the one represented by formula (II) as defined above.

[0096] [ka]

[0097] In the formula, R 4 is H or CH3, and R 5 R is a C1-C20 hydrocarbyl substituent, preferably a C1-C10 alkyl substituent, for example, a C1-C8 alkyl substituent. 5 The group may be linear or branched. Most preferably, R 5The group is a methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, or decyl group, and may be linear or branched (where possible). The preferred features of formula (II) described above in relation to (meth)acrylic silyl ester copolymer (i) also apply to (meth)acrylic polymer (ii-a).

[0098] Examples of monomers represented by formula (II) that are suitable as monomer (a4) in (meth)acrylic polymer (ii-a) 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, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0099] Preferred options for the monomer represented by formula (II) as monomer (a4) in (meth)acrylic polymer (ii-a) include methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-octyl acrylate, isooctyl acrylate, or isodecyl acrylate.

[0100] A mixture of different monomers represented by formula (II) may be used in the (meth)acrylic polymer (ii-a).

[0101] Preferably, the (meth)acrylic polymer (ii-a) contains structural units derived from (meth)acrylic acid monomer (a3) ​​and (meth)acrylate monomer (a4).

[0102] In a preferred embodiment, the (meth)acrylic polymer (ii-a) contains 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 isodecyl acrylate.

[0103] The (meth)acrylic polymer (ii-a) may contain structural units derived from other ethylenically unsaturated monomers such as vinyl monomers (e.g., styrene, vinyl 2-ethylhexanoate, and vinyl neodecanoate).

[0104] The (meth)acrylic polymer (ii-a) preferably has a weight-average molecular weight of 5,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 15,000 to 50,000. Mw is measured according to the description in the examples. The (meth)acrylic polymer (ii-a) preferably has a polydispersity index (PDI) of 1.5 to 5.0.

[0105] When (meth)acrylic polymer (ii-a) is used, the (meth)acrylic silyl ester copolymer (i) is typically present in an amount of 0.5 to 10% by weight, preferably 1.0 to 5.0% by weight, relative to the total weight of the entire coating composition.

[0106] When (meth)acrylic polymer (ii-a) is used, the (meth)acrylic silyl ester copolymer (i) is typically present in an amount of 1.0 to 12% by weight, preferably 2.0 to 7.0% by weight, based on the total dry weight of the entire coating composition.

[0107] When (meth)acrylic copolymer (ii-a) is used, the (meth)acrylic silyl ester copolymer (i) is typically present in an amount of 2.0 to 25% by weight, preferably 5.0 to 20% by weight, based on the total dry weight of the binder in the coating composition of the present invention.

[0108] When used in the absence of (meth)acrylic polymer (ii-a), the (meth)acrylic silyl ester copolymer (i) may be present in an amount of 1.0 to 12% by weight, preferably 2.0 to 7.0% by weight, relative to the total weight of the entire coating composition.

[0109] When used in the absence of (meth)acrylic polymer (ii-a), the (meth)acrylic silyl ester copolymer (i) may be present in an amount of 1.5 to 15% by weight, preferably 2.5 to 10% by weight, relative to the total dry weight of the coating composition.

[0110] When used in the absence of (meth)acrylic polymer (ii-a), it may be present in the coating composition in an amount of 5 to 30% by weight, preferably 10 to 25% by weight, based on the total dry weight of the binder.

[0111] [(meth)acrylic polymer (ii-b)] In one embodiment, the coating composition of the present invention may further contain (meth)acrylic polymer (ii-b).

[0112] When both (meth)acrylic polymer (ii-a) and (meth)acrylic polymer (ii-b) are present, it is preferable that (meth)acrylicsilyl ester copolymer (i) is not present.

[0113] The glass transition temperature (Tg) of (meth)acrylic polymer (ii-b) is at least 10°C, preferably at least 15°C, for example at least 17°C or at least 20°C, and all values ​​are measured according to the Tg test described in the examples. Values ​​below 80°C, for example below 70°C, for example below 55°C are preferred. Thus, the Tg of (meth)acrylic polymer (ii-b) is at least 10°C, while the Tg of (meth)acrylic polymer (ii-a) is below 10°C. Preferably, the Tg of (meth)acrylic polymer (ii-b) is at least 10°C, while the Tg of (meth)acrylic polymer (ii-a) is 0°C or less.

[0114] In one embodiment, the (meth)acrylic polymer (ii-b) does not contain the (meth)acrylic acid monomer (a3).

[0115] The (meth)acrylic polymer (ii-b) contains at least one (meth)acrylate monomer (a5).

[0116] 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, isodecyl (meth)acrylate, and cyclohexyl (meth)acrylate. 3,5,5-Trimethylcyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, Benzyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, Oligo(ethylene glycol)(meth)acrylate, Poly(ethylene glycol)(meth)acrylate, 2-Methoxyethyl (meth)acrylate, 2-Ethoxyethyl (meth)acrylate, 2-Butoxyethyl (meth)acrylate, 2-(2-Ethoxyethoxy)ethyl (meth)acrylate )Acrylate, Oligo(ethylene glycol) methyl ether (meth)acrylate, Poly(ethylene glycol) methyl ether (meth)acrylate, Methoxycarbonylmethyl (meth)acrylate, Ethoxycarbonylmethyl (meth)acrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, 2-(2-ethoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, Oligo(oxycarbonylmethyl) Examples include methyl (meth)acrylate, oligo(oxycarbonylmethyl)ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycerol formal (meth)acrylate, isopropylideneglycerol (meth)acrylate, glycerol carbonate (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycidyl (meth)acrylate, and 4-glycidyloxybutyl (meth)acrylate.

[0117] A more preferred example of the (meth)acrylate monomer (a5) is the one represented by formula (II) as defined above for the (meth)acrylic ester polymer (ii-a).

[0118] Preferred options for monomer (a5) represented by formula (II) include methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, and isobutyl methacrylate.

[0119] A mixture of different monomers (a5) may be used.

[0120] The (meth)acrylate monomer (a5) may contain a hydrophilic group. Examples of suitable monomers include those shown in formula (VI) below.

[0121] [ka]

[0122] In the formula, R 11 is H or CH3, and R 12 is a C3-C40 substituent containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom, for example, a C3-C20 substituent, or R 12 This represents a poly(alkylene glycol) group.

[0123] (Meth)acrylic copolymer (ii-b) is represented by the above formula (VI), R 12 The base is (CH2CH2O) n -R 13 (Here, R 13 The group may contain at least one monomer that is a C1-C10 hydrocarbyl substituent, preferably a C1-C10 alkyl substituent or a C6-C10 aryl substituent, where n is an integer in the range of 1-5, preferably 1-3. Preferably, R 12 The formula is (CH2CH2O) n -R 13 (Here, R 13 The group is represented by a C1-C10 alkyl substituent, preferably CH3 or CH2CH3, and n is an integer in the range of 1-3, preferably 1 or 2.

[0124] Such monomers may be 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-(2-butoxyethoxy)ethyl (meth)acrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl (meth)acrylate, or 2-[2-(2-ethoxyethoxy)ethoxy]ethyl (meth)acrylate.

[0125] Preferably, the (meth)acrylic polymer (ii-b) contains one or more of 2-methoxyethyl acrylate and 2-(2-ethoxyethoxy)ethyl acrylate.

[0126] (Meth)acrylic polymer (ii-b) is represented by the above formula (VI), R 12 It may contain at least one monomer whose group is a poly(alkylene glycol) group, such as a poly(ethylene glycol) group. Such a group is of the formula ((CH2CH2O) m -R 13 or (CH2CH(CH3)O) m -R 14 And here, R 14 m is a C1-C10 hydrocarbyl substituent, preferably a C1-C10 alkyl substituent or a C6-C10 aryl substituent, and m is an integer in the range of 5-25, preferably 5-15.

[0127] Such monomers may 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. Preferred monomers of this type have a number-average molecular weight (Mn) of 300 to 1000, more preferably 300 to 550.

[0128] (Meth)acrylic polymer (ii-b) is also represented by formula (VI) above, R12 The base is the formula (CH2C(O)O) p -R 15 Or (CH(CH3)C(O)O) p -R 15 (Here, R 15 The compound may contain at least one monomer that is a group represented by a C1-C10 hydrocarbyl substituent, preferably a C1-C10 alkyl substituent or a C6-C10 aryl substituent, where p is an integer in the range of 1-10, preferably 1-4.

[0129] Such monomers may be methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, 2-(2-ethoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, oligo(oxycarbonylmethyl)methyl (meth)acrylate, and oligo(oxycarbonylmethyl)ethyl (meth)acrylate.

[0130] (Meth)acrylic polymer (ii-b) is represented by the above formula (VI), R 12 It may contain at least one monomer whose group is a cyclic group containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom. More preferably, R 12 This is a group WR having up to 20 carbon atoms. 16 And here, R 16 is a cyclic ether such as oxirane, furan, oxolane, oxane, dioxolane, or dioxane, and may optionally be alkyl-substituted, while W is a C1-C4 alkylene.

[0131] Such monomers may be furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycerol formal (meth)acrylate, isopropylideneglycerol (meth)acrylate, glycerol carbonate (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycidyl (meth)acrylate, and 4-glycidyloxybutyl (meth)acrylate. Preferred cyclic ethers contain at least four atoms in the ring. More preferably, tetrahydrofurfuryl acrylate and isopropylideneglycerol methacrylate.

[0132] The monomer represented by formula (VI) is preferably 2-methoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, or poly(ethylene glycol)methyl ether methacrylate.

[0133] The monomer represented by formula (VI) preferably constitutes at least 10% by weight of the (meth)acrylic polymer (ii-b). A particularly preferred amount of the monomer represented by formula (VI) in copolymer (ii-b) is 10 to 65% by weight, preferably 15 to 55% by weight, for example, 18 to 50% by weight. If a mixture of monomers represented by formula (VI) is present, these amounts relate to the total weight fraction of the monomers represented by formula (VI) in the copolymer.

[0134] In a preferred embodiment, the (meth)acrylic polymer (ii-b) contains at least one monomer represented by formula (II) and at least one monomer represented by formula (VI).

[0135] In a preferred embodiment, the (meth)acrylic polymer component (ii-b) consists only of monomers represented by formulas (II) and (VI). Preferably, the (meth)acrylic polymer (ii-b) does not contain the (meth)acrylic acid monomer (a3).

[0136] The (meth)acrylic polymer (ii-b) may contain structural units derived from other ethylenically unsaturated monomers such as vinyl monomers (e.g., styrene, vinyl 2-ethylhexanoate, vinyl neodecanoate, and N-vinylpyrrolidone).

[0137] The (meth)acrylic polymer (ii-b) preferably has a weight-average molecular weight (Mw) of 10,000 to 100,000, more preferably 15,000 to 70,000, and particularly preferably 20,000 to 50,000. Mw is measured according to the description in the examples. The (meth)acrylic polymer (ii-b) preferably has a polydispersity index (PDI) of 1.5 to 5.0.

[0138] If used, the (meth)acrylic polymer (ii-b) may be present in an amount of 1.0 to 15% by weight, preferably 2.0 to 12% by weight, relative to the total weight of the entire coating composition.

[0139] If used, the (meth)acrylic polymer (ii-b) may be present in an amount of 1.5 to 20% by weight, preferably 2.5 to 15% by weight, relative to the total dry weight of the coating composition.

[0140] When used in the antifouling coating composition of the present invention, the (meth)acrylic copolymer (ii-b) may be present in an amount of 5.0 to 40% by weight, preferably 10 to 35% by weight, based on the total dry weight of the binder in the coating composition.

[0141] Preparation of (meth)acrylicsilyl ester copolymer (i) and (meth)acrylic polymer (ii) (meth)acrylic silyl ester copolymers (i) and (meth)acrylic polymers (ii) can be prepared using polymerization reactions known in the art. These polymers can be obtained by polymerizing monomer mixtures in the presence of polymerization initiators, using any of the following methods: solution polymerization, bulk polymerization, emulsion polymerization, dispersion polymerization, suspension polymerization, conventional methods such as free radical polymerization, or controlled polymerization techniques. In the case of copolymers, the final polymer may be a random copolymer, an alternating copolymer, a gradient copolymer, or a block copolymer.

[0142] Regardless of which polymer is used to prepare the coating composition, it is preferable to dilute the polymer with an organic solvent to obtain a polymer solution with appropriate viscosity. From this viewpoint, solution polymerization is desirable.

[0143] Examples of initiators suitable for free radical polymerization in solvents include azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), and 1,1'-azobis(cyanocyclohexane); as well as tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, and 1,1,3,3-tetramethylbutyl peroxy-2-ethyl Examples of peroxides include hexanoates, tert-butylperoxydiethyl acetate, tert-butylperoxyisobutyrate, tert-butylperoxybenzoate, 1,1-di(tert-amylperoxy)cyclohexane, tert-amylperoxy 2-ethylhexyl carbonate, tert-butylperoxyisopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, polyether poly-tert-butylperoxycarbonate, di-tert-butyl peroxide, and dibenzoyl peroxide. These compounds are used individually or in combination of two or more.

[0144] 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 isoamyl 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 ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, and tetrahydrofuran; alcohols such as n-butanol, isobutanol, methyl isobutylcarbinol, and benzyl alcohol; ether alcohols such as butoxyethanol and 1-methoxy-2-propanol; and aliphatic hydrocarbons such as white spirit and limonene. These solvents can be used alone or in mixtures of two or more.

[0145] [Monocarboxylic acid (iii)] The antifouling coating composition of the present invention contains a monocarboxylic acid or a metal salt thereof.

[0146] 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, the metal carboxylate is zinc carboxylate or copper carboxylate. The metal carboxylate may be formed in situ in the antifouling coating composition.

[0147] The monocarboxylic acid is preferably a cyclic monocarboxylic acid. Rosin is a mixture of monocarboxylic acids called resin acids. Resin acids are also called rosin acids. Typical examples of resin acids include abietic acid, neoabietic acid, dehydroabietic acid, pulsed phosphoric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimalic acid, comnic acid, merxic acid, and secodehydroabietic acid. Rosin is of natural origin and therefore is understood to usually contain a mixture of acids.

[0148] Typical examples of rosin include gum rosin, wood rosin, and tall oil rosin. Gum rosin (also called colohony or colohonium) is particularly preferred. Preferred rosin contains more than 85% resin acid, and more preferably more than 90% resin acid.

[0149] Commercially available gum rosin typically has an acid value of 155-180 mgKOH / g as defined in ASTM D465. Rosin suitable for the composition of the present invention has an acid value of 155-180 mgKOH / g, more preferably 160-175 mgKOH / g, and even more preferably 160-170 mgKOH / g. Commercially available gum rosin typically has a softening point (ring-and-ball method) of 70°C-80°C as defined in ASTM E28. Rosin suitable for the composition of the present invention has a softening point of 70°C-80°C, more preferably 75°C-80°C.

[0150] Typical examples of modified resin acids include dihydroabietic acid, dihydropimaric acid, and tetrahydroabietic acid, as well as modified rosins such as partially hydrogenated rosin, fully hydrogenated rosin, and disproportionated rosin. Typical examples of C6-C20 cyclic monocarboxylic acids include naphthenic acid and trimethylisobutylenecyclohexenecarboxylic acid.

[0151] Typical examples of C5-C24 acyclic aliphatic monocarboxylic acids include Versatic® acid, 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, neopentanoic acid, 2-ethylhexanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, isopalmitic acid, isostearic acid, 16-methylheptadecanoic acid, and 12,15-dimethylhexadecanoic acid. The acyclic aliphatic monocarboxylic acid is preferably selected from liquid acyclic C10-C24 monocarboxylic acids or liquid branched-chain C10-C24 monocarboxylic acids. Many acyclic C10-C24 monocarboxylic acids may be naturally occurring, in which case it will be understood that in isolated forms they usually exist as mixtures of acids of different chain lengths with varying degrees of branching.

[0152] Preferably, the monocarboxylic acid is selected from rosin, modified rosin, acyclic C10-C24 monocarboxylic acids, C6-C20 cyclic monocarboxylic acids, or metal salts thereof.

[0153] 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. More preferably, the monocarboxylic acid is rosin, modified rosin, or a metal salt thereof.

[0154] More preferably, the monocarboxylic acid or its metal salt includes gum rosin, hydrogenated gum rosin, copper salt of gum rosin, zinc salt of gum rosin, copper salt of hydrogenated gum rosin, zinc salt of hydrogenated gum rosin, and mixtures thereof. Gum rosin is most preferred.

[0155] The final antifouling coating composition of the present invention preferably contains a monocarboxylic acid and / or its metal salt in an amount of 5.0 to 30% by weight, for example, 5.0 to 25% by weight or 10 to 25% by weight, based on the entire coating composition.

[0156] The final coating composition of the present invention contains a monocarboxylic acid or a metal salt thereof, preferably in an amount of 7.0 to 40% by weight, and preferably 12 to 32% by weight, based on the total dry weight of the coating composition.

[0157] The antifouling coating composition of the present invention contains (iii) rosin and / or modified rosin and their metal salts present in the antifouling coating composition of the present invention, preferably in an amount of 25 to 65% by weight, preferably 35 to 60% by weight, and more preferably 40 to 60% by weight, based on the total dry weight of the binder in the coating composition.

[0158] Components (i) to (iii) constitute the binder in the final coating composition of the present invention. The weight percentage of the binder in the final coating composition, in particular the combined weight percentage of components (i) to (iii), is 15 to 50% by weight of the entire coating composition.

[0159] The weight percentage of the binder in the final coating composition, in particular the combined weight percentage of components (i) to (iii), is 20 to 65% by weight, preferably 25 to 45% by weight, of the total dry weight of the coating composition.

[0160] [Other binder ingredients] In addition to the components (i), (ii), and (iii) described above, additional binders can be used to adjust the properties of the antifouling coating composition. Examples of usable binders include:

[0161] Hydrophilic copolymers, such as poly(N-vinylpyrrolidone) copolymer and poly(ethylene glycol) copolymer; vinyl ether polymers and copolymers, such as poly(methyl vinyl ether), poly(ethyl vinyl ether), poly(isobutyl vinyl ether), and poly(vinyl chloride-co-isobutyl vinyl ether); Metal-containing (meth)acrylate copolymers, such as zinc (meth)acrylate copolymer and copper (meth)acrylate copolymer; Saturated aliphatic polyesters, such as poly(lactic acid), poly(glycolic acid), poly(2-hydroxybutyric acid), poly(3-hydroxybutyric acid), poly(4-hydroxyvaleric acid), polycaprolactone, and aliphatic polyester copolymers comprising two or more units selected from the aforementioned units; Alkyd resins and modified alkyd resins; Hydrocarbon resins, for example, hydrocarbon resins formed solely by the polymerization of at least one monomer selected from C5 aliphatic monomers, C9 aromatic monomers, indencoumarone monomers, or terpenes, or mixtures thereof; Plasticizers, such as polymeric plasticizers, non-reactive silicone oils, mineral oils, chlorinated paraffins, phthalates, phosphate esters, sulfonamides, adipic esters, epoxidized vegetable oils, methyl esters of rosin, methyl esters of branched fatty acids, and sucrose acetate isobutyrate.

[0162] In one particularly preferred embodiment of the present invention, the coating composition does not contain a paraffin as a plasticizer. In particular, it does not contain paraffin containing aromatic groups.

[0163] The composition of the invention contains, based on the total weight of the coating composition, preferably 0 to 10% by weight, more preferably 0.5 to 7.0% by weight, and even more preferably 1.0 to 5.0% by weight, an additional binder.

[0164] [Biocide (iv)] The antifouling coating composition additionally contains a biocide, i.e., a compound capable of inhibiting or preventing the adhesion and / or growth of marine fouling organisms on the surface. The terms “antifouling agent,” “antifoulant,” “biocide,” and “toxic substance” are used in the industry to describe known compounds that act 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% by weight or less relative to the total weight of the entire coating composition. Preferably, the coating composition contains 8.0% by weight or less of the biocide, more preferably 5.0% by weight or less. Examples of ranges for the amount of biocide include 0.2–10.0% by weight, 0.5–8.0% by weight, and 1.0–5.0% by weight relative to the total weight of the entire coating composition.

[0165] From another perspective, these compounds are present in a total amount of 13.5% by weight or less relative to the total weight of the dry coating composition. The coating composition preferably contains 10.0% by weight or less, more preferably 7.0% by weight or less, of the biocide. Examples of ranges for the amount of biocide include 0.2 to 13.5% by weight, 0.5 to 10.0% by weight, and 1.0 to 7.0% by weight relative to the total dry weight of the coating composition.

[0166] The biocides described above must contain tralopiril (iv-a) and one or more copper compounds (iv-b) as defined below.

[0167] [Tralopiril (iv-a)] As described above, the composition of the present invention must contain 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril] having the following structure. [ka]

[0168] An example of a commercially available tralopiril is Econea® from Janssen PMP.

[0169] In all embodiments, it is preferable that tralopiril is present in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 3.0% by weight, more preferably 0.3 to 2.0% by weight, and even more preferably 0.4 to 1.5% by weight, for example, 0.4 to 1.0% by weight, based on the total weight of the composition.

[0170] In all embodiments, it is preferable that tralopyril is present in an amount of preferably 0.2 to 6.5% by weight, preferably 0.3 to 4.0% by weight, more preferably 0.4 to 2.5% by weight, and even more preferably 0.5 to 1.5% by weight, based on the total dry weight of the coating composition.

[0171] Tralopiril is typically present in an amount of 5.0 to 60.0% by weight, preferably 7.0 to 60.0% by weight, more preferably 8.0 to 60.0% by weight, even more preferably 9.0 to 60.0% by weight, and even more preferably 10.0 to 60.0% by weight, relative to the total weight of the biocide (iv).

[0172] [Copper compound (iv-b)] The copper compound may be any suitable copper-based antifouling compound having a copper content of at least 40% by weight relative to the total weight of the copper compound. Preferably, the copper compound has a copper content of at least 45% by weight, at least 50% by weight, at least 55% by weight, or at least 60% by weight, for example, at least 70% by weight or at least 75% by weight relative to the total weight of the copper compound. It will 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. The table below lists commonly used copper compounds and their calculated copper content.

[0173] [Table 1]

[0174] A single copper compound may be used, or a mixture of two or more copper compounds may be used. Copper compounds can be present with carrier materials, such as encapsulated copper compounds, copper glass, copper compound-coated particles, and porous particles containing copper compounds. The weight percentage requirement for copper refers to the amount of copper in the chemical copper compound, and therefore the weight of the carrier is negligible.

[0175] Particularly preferred copper compounds are metallic copper such as copper powder and copper flakes, copper(I) oxide, copper(II) sulfide, and copper(I) thiocyanate. Copper(I) oxide is also known as cuprous oxide. Preferably, the copper compound is an inorganic copper compound such as metallic copper, copper(I) oxide, and copper(II) sulfide, and more preferably metallic copper powder and copper(I) oxide. In one particularly preferred embodiment, the copper compound is copper(I) oxide.

[0176] The copper(I) oxide material preferably has a typical particle size distribution of 0.1 to 70 μm and an average particle size (d50) of 1 to 25 μm. The copper(I) oxide material may contain stabilizers to prevent surface oxidation and caking. Examples of commercially available copper(I) oxides include Nordox Cuprous Oxide Red Paint Grade, Nordox Cuprotech, and Nordox XLT from Nordox AS; Cuprous oxide from Furukawa Chemicals Corporation; Red Copp 97N, Purple Copp, Lolo Tint 97N, Chemet CDC, and Chemet LD from American Chemet Corporation; Cuprous Oxide Red from Spiess-Urania; and Cuprous oxide Roast and Cuprous oxide Electrolytic from Taixing Smelting Plant.

[0177] In all embodiments, it is preferable that the copper compound (one or more) is present in an amount of preferably 0.1 to 8.0% by weight, preferably 0.2 to 5.0% by weight, more preferably 0.3 to 3.0% by weight, even more preferably 0.3 to 2.0% by weight, and even more preferably 0.3 to 1.0% by weight, based on the total weight of the composition.

[0178] If a mixture of copper compounds is present, it is preferable that each copper compound is present in an amount of preferably 0.1 to 6.0% by weight, preferably 0.2 to 5.0% by weight, more preferably 0.3 to 3.0% by weight, even more preferably 0.3 to 2.0% by weight, and even more preferably 0.3 to 1.0% by weight, relative to the total weight of the composition.

[0179] It should be understood that the total amount of biocides in the coating composition of the present invention shall not exceed 10.0% by weight. The appropriate amount and number of copper compounds can be selected accordingly.

[0180] More preferably, the coating composition of the present invention contains 8.0% by weight or less, preferably 5.0% by weight or less, of the biocide based on the total weight of the entire coating composition.

[0181] In all embodiments, it is preferable that the copper compound is present in an amount of preferably 0.1 to 9.9% by weight, preferably 0.2 to 7.0% by weight, more preferably 0.3 to 4.0% by weight, even more preferably 0.3 to 2.5% by weight, and even more preferably 0.3 to 1.5% by weight, based on the total dry weight of the coating composition. Furthermore, it is preferable that the total amount of biocides in the total dry weight of the coating composition of the present invention does not exceed 13.0% by weight.

[0182] One or more copper compounds are typically present in an amount of 5.0 to 90.0% by weight, preferably 6.0 to 87.0% by weight, more preferably 7.0 to 85.0% by weight, even more preferably 8.0 to 82.0% by weight, and even more preferably 9.0 to 80.0% by weight, 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% by weight, more preferably 6.0 to 82.0% by weight, relative to the total weight of the biocide (iv).

[0183] In embodiments where two or more copper compounds of the present invention exist, it will be understood that these weight percent ranges apply to the total amount of all copper compounds present. Furthermore, if any copper compound has a copper content of less than 40% by weight, that copper compound is not considered a copper compound of the present invention.

[0184] [Other biocides] In addition to these biocides, other antifouling compounds may be present. These antifouling agents may be inorganic, organometallic, or organic. Suitable antifouling agents are commercially available.

[0185] Examples of organometallic marine antifouling agents include zinc pyrithione, copper pyrithione, di(ethyl 4,4,4-trifluoroacetoacetate)copper, bis(dimethyldithiocarbamate)zinc [dilam], and ethylenebis(dithiocarbamate)zinc [zineb], as well as copper and zinc compounds described in International Publication No. 2021 / 113564A1. However, copper pyrithione and di(ethyl 4,4,4-trifluoroacetoacetate)copper have a copper content of less than 40% by weight based on their formula weight, and therefore are not included in the definition of copper compounds in this invention.

[0186] Examples of organic marine antifouling agents include 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine [sibutrin], 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-phenylsulfamide [diclofluanide], and N-dichlorofluoromethylthio-N Examples include ',N'-dimethyl-Np-tolylsulfamide [tolylfluanide], N-(2,4,6-trichlorophenyl)maleimide, triphenylboranepyridine [TPBP], 3-iodo-2-propynyl N-butylcarbamate [IPBC], 2,4,5,6-tetrachloroisophthalonitrile [chlorothalonyl], p-((diiodomethyl)sulfonyl)toluene, and 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine].

[0187] Other examples of marine antifouling agents include macrocyclic lactones, such as tetraalkylphosphonium halides, avermectins and their derivatives (e.g., ivermectin); furanone and lactam compounds (e.g., 4-(4-chlorophenyl)-5-hydroxy-5-methyl-2(5H)-furanone and 4-(4-chlorophenyl)-5-methylene-1H-pyrrole-2(5H)-one); spinosins and their derivatives (e.g., spinosad); capsaicin and its derivatives (e.g., phenylcapsaicin); and enzymes (e.g., oxidase, protease, hemicellulase, cellulase, lipase, amylase).

[0188] Preferred biocides are zinc pyrithione, copper pyrithione, ethylenebis(dithiocarbamate)zinc [zineb], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide [dichlorofluanide], 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine], di(ethyl 4,4,4-trifluoroacetoacetate)copper, and phenylcapsaicin.

[0189] Since different biocides affect different marine fouling organisms, mixtures of biocides can be used, as is well known in the art. Mixtures of antifouling agents are generally preferred.

[0190] Even if biocides other than those specified in (iv-a) and (iv-b) are used, those biocides are included in the total biocide content and are therefore included in the 10.0% by weight limit.

[0191] Some biocides may be encapsulated or adsorbed onto inert carriers, or bound to other materials, for release control purposes. The weight of such carriers is not considered when determining the 10.0% by weight limit.

[0192] [Pigments and fillers (v)] The coating composition of the present invention further contains a pigment and / or an extender. Preferably, the total amount of the extender and / or pigment and biocide present in the composition of the present invention is at least 35% by weight of the total weight of the entire coating composition. It is important that the total amount of the extender and / or pigment and biocide is 35% by weight or more in order to achieve appropriate self-polishing properties, coating film properties, and sufficient antifouling performance.

[0193] The preferred total amount of fillers and / or pigments and biocides is 35-65% by weight, more preferably 40-60% by weight, and even more preferably 45-60% by weight, based on the total weight of the composition.

[0194] The preferred total amount of fillers and / or pigments and biocides is 40-80% by weight, more preferably 45-75% by weight, and even more preferably 50-75% by weight, based on the total dry weight of the coating composition.

[0195] Those skilled in the art will understand that the content of fillers and pigments varies depending on the particle size distribution, particle shape, surface morphology, affinity between the particle surface and the resin, other present components, and the end use of the coating composition.

[0196] Pigments are materials that impart color to coating compositions. They generally exist in the form of insoluble fine particles in the coating. Pigments may be inorganic pigments, organic pigments, or mixtures thereof. Inorganic pigments are preferred. Examples of inorganic pigments include titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, zinc sulfide, lithopone, and graphite. Examples of organic pigments include carbon black, phthalocyanine blue, phthalocyanine green, naphthol red, and diketopyrrolopyrrole red. Pigments may be surface-treated. Various inorganic or organic surface treatments are used to improve storage stability and pigment performance, such as rheological properties and dispersibility in coating compositions. For example, titanium dioxide may be surface-treated with silicon compounds, zirconium compounds, aluminum compounds, and / or zinc compounds.

[0197] Fillers are materials added to paints to adjust or improve their properties. These materials typically have low coloring power and are therefore distinguished from pigments. Fillers are usually granular or powdery and insoluble in paints. Fillers may be inorganic or organic materials. Inorganic fillers are preferred. Inorganic fillers may be natural minerals or synthetic materials.

[0198] Examples of inorganic fillers include dolomite, plastrite, 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 fillers mentioned above, the coating composition may also contain reinforcing agents such as flakes or fibers, as described in, for example, International Publication No. 00 / 77102. Preferably, the antifouling coating composition of the present invention contains zinc oxide as a bulking agent.

[0199] [Other ingredients] In addition to the above components and optional components, the antifouling coating composition according to the present invention may optionally further contain one or more components selected from other additives, solvents, and diluents.

[0200] Examples of additives that can be added to antifouling coating compositions include rheological modifiers, wetting and dispersing agents, and dehydrating agents.

[0201] Examples of rheological modifiers include thixotropic agents, thickeners, and anti-settling agents. Typical examples of rheological modifiers include silica such as fumed silica, organically modified clay, amide wax, polyamide wax, amide derivatives, polyethylene wax, oxidized polyethylene wax, cured castor oil wax, ethylcellulose, aluminum stearate, and mixtures thereof. Rheological modifiers that require activation may be added directly to the coating composition and activated during the paint manufacturing process, or they may be added to the coating composition in a pre-activated form, such as a solvent paste. Each rheological modifier is present in the composition of the present invention in an amount of preferably 0 to 5.0% by weight, more preferably 0.2 to 3.0% by weight, and even more preferably 0.5 to 2.0% by weight, based on the total weight of the coating composition.

[0202] The dehydrating agent improves the storage stability of the antifouling coating composition containing (meth)acrylic silyl ester copolymer (i). The dehydrating agent is preferably a compound that removes moisture and water from the coating composition. This compound is also referred to as a water scavenger, drying agent, or desiccant. The dehydrating agent may be a hygroscopic material that absorbs water or binds water as crystal water, 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; orthoborates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, and tri-tert-butyl borate; alkoxysilanes such as trimethoxymethylsilane, triethoxymethylsilane, tetraethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and ethyl polysilicate; and isocyanates such as p-toluenesulfonyl isocyanate.

[0203] Preferred dehydrating agents include alkoxysilanes such as tetraethoxysilane, as well as inorganic dehumidifying agents such as anhydrous calcium sulfate, calcium sulfate hemihydrate, and zeolite powder. The use of alkoxysilanes is particularly preferred.

[0204] The dehydrating agent is added to the composition of the present invention in an amount preferably 0 to 5.0% by weight, more preferably 0.5 to 2.5% by weight, and even more preferably 1.0 to 2.0% by weight, based on the total weight of the composition.

[0205] The dehydrating agent is added to the composition of the present invention in an amount preferably 0 to 7.0% by weight, more preferably 0.5 to 4.0% by weight, and even more preferably 1.0 to 3.0% by weight, based on the total dry weight of the coating composition.

[0206] It is highly preferable that the antifouling composition contains a solvent. This solvent is preferably volatile and preferably an organic solvent. Examples of organic solvents and diluents include aromatic hydrocarbons such as xylene, toluene, and mesitylene; ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone; esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl 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 isobutylcarbinol, and benzyl alcohol; ether alcohols such as butoxyethanol and 1-methoxy-2-propanol; terpenes such as limonene; aliphatic hydrocarbons such as white spirits; and optionally, mixtures of two or more solvents and diluents.

[0207] Preferred solvents are aromatic hydrocarbon solvents, ketones, alcohols, and mixtures thereof, in particular xylene and mixtures of aromatic hydrocarbons.

[0208] The amount of solvent is preferably as small as possible. The solvent content may be up to 45% by weight of the composition, preferably up to 35% by weight, and may be as low as 30% by weight, for example, but may be as low as 20% by weight or less, for example, 15% by weight or less. Furthermore, those skilled in the art will understand that some raw materials contain solvents and contribute to the above total solvent content, and that the solvent content will vary depending on other components present and the final use of the coating composition.

[0209] Those skilled in the art will understand that the solvent used depends on the recommended application method of the final product. Alternatively, the coating can be dispersed in an organic non-solvent or an aqueous dispersion of the film-forming components in the coating composition.

[0210] [Coating composition] The compositions described herein can be prepared at concentrations suitable for use (e.g., in spray application). In this case, the composition is a paint itself. Alternatively, the composition may be a concentrated liquid for paint preparation. In this case, a solvent and optionally other components are added to the compositions described herein to form a paint. Preferred solvents are as described above with respect to the compositions.

[0211] The coating composition may be supplied as a one-component, two-component, or three-component type. If a curing agent is included, it is naturally kept separate from the curable components until application to the substrate. Biocides can be kept as a separate component from the binder, but it is preferable that they be present together in the supplied formulation.

[0212] When supplied as a one-component type, the composition is preferably supplied in a pre-mixed form, i.e., a ready-to-use form. Optionally, the one-component product may be diluted with a solvent before application.

[0213] The antifouling coating composition of the present invention preferably has a solid content of more than 60% by weight, for example more than 65% by weight, and preferably more than 70% by weight. The antifouling coating composition of the present invention preferably has a solid content of more than 40% by volume, for example more than 45% by volume, and preferably more than 50% by volume.

[0214] More preferably, the antifouling coating composition has 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, or 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.

[0215] The viscosity of the coating composition, when measured using a cone-plate viscometer in accordance with ISO 2884-1:2006, may be in the range of less than 2000 cP, for example, less than 1000 cP, for example, less than 800 cP, or less than 500 cP. A viscosity of 200 cP or higher can be used.

[0216] In one embodiment, the antifouling coating composition is The coating composition comprises 2.0 to 40% by weight, preferably 5.0 to 30% by weight, of component (i) relative to the total weight of the entire composition, The coating composition comprises 0.5 to 10% by weight, preferably 1.0 to 5% by weight of component (ii), The coating composition contains 5.0 to 25% by weight of component (iii) based on the total weight of the entire composition.

[0217] In one embodiment, the antifouling coating composition is The coating composition comprises 2.0 to 40% by weight, preferably 5.0 to 30% by weight, of component (i) relative to the total weight of the entire composition, The coating composition comprises 0.5 to 10% by weight, preferably 1.0 to 5.0% by weight of component (ii), Based on the total weight of the entire coating composition, component (iii) is present in an amount of 5.0 to 25% by weight, The composition contains 0.1 to 5.0% by weight, preferably 0.2 to 3.0% by weight, more preferably 0.3 to 2.0% by weight, and even more preferably 0.4 to 1.0% by weight of tralopyril, based on the total weight of the composition. The composition contains one or more copper compounds present in an amount of 0.1 to 8.0% by weight, preferably 0.2 to 5.0% by weight, more preferably 0.3 to 3.0% by weight, even more preferably 0.3 to 2.0% by weight, and even more preferably 0.3 to 1.0% by weight, based on the total weight of the composition.

[0218] In one embodiment, the antifouling coating composition is The coating composition comprises 0.5 to 10% by weight, preferably 1.0 to 6.0% by weight of component (ii-a), The coating composition comprises 0.5 to 10% by weight, preferably 1.0 to 6.0% by weight of component (ii-b), Based on the total weight of the entire coating composition, component (iii) is present in an amount of 5.0 to 25% by weight, The composition contains 0.1 to 5.0% by weight, preferably 0.2 to 3.0% by weight, more preferably 0.3 to 2.0% by weight, and even more preferably 0.4 to 1.0% by weight of tralopyril, based on the total weight of the composition. The composition contains one or more copper compounds present in an amount of 0.1 to 8.0% by weight, preferably 0.2 to 5.0% by weight, more preferably 0.3 to 3.0% by weight, even more preferably 0.3 to 2.0% by weight, and even more preferably 0.3 to 1.0% by weight, based on the total weight of the composition.

[0219] In all embodiments, the biocide content in the entire coating composition is 10.0% by weight or less.

[0220] [Method for producing an antifouling coating composition] The antifouling coating composition can be prepared using any process known in the art. The order of adding and mixing the raw materials is preferably carried out according to the recommendations of the supplier of the raw materials and mixing equipment.

[0221] Biocides may be pre-mixed into solutions or pastes containing binder components and / or solvents and / or pigments (e.g., zinc oxide) for the purpose of safer and easier handling in the paint manufacturing process, improved storage stability of coating compositions, and / or improved antifouling performance of applied coatings.

[0222] [apply] The antifouling coating composition of the present invention can be applied to all or part of any surface of an object susceptible to fouling. The surface may be permanently submerged in water or intermittently submerged (e.g., due to tidal movements, loading of different cargoes, or swells). Typical examples of such surface objects include ship hulls or the surfaces of fixed marine objects such as oil platforms or buoys. The coating composition can be applied by any convenient means, for example, by painting the coating onto the object (e.g., with a brush or roller) or by spraying (e.g., by an airless spray). Typically, the surface needs to be isolated from seawater to allow for coating. The coating can be applied in accordance with methods conventionally known in the art.

[0223] When applying an antifouling coating to an object (e.g., a ship's hull), the object's surface is not protected by a single coat of antifouling material. Depending on the properties of the surface, the antifouling coating can be applied directly to an existing coating system. Such a coating system may consist of several layers of different common types of paints (e.g., epoxy, polyester, vinyl, or acrylic, or mixtures thereof). Starting with an uncoated surface (e.g., steel, aluminum, composite materials), the entire coating system typically includes one or two layers of primer or anticorrosion coating (e.g., curable epoxy coating or curable modified epoxy coating), one layer of tie coat (e.g., curable modified epoxy coating or physically drying vinyl coating), and one or two layers of antifouling paint. In exceptional cases, additional layers of antifouling paint may be applied. If the surface has a previously applied, undamaged antifouling coating, the new antifouling paint can be applied directly, usually in one or two coats, and exceptionally, more coats. When applying an antifouling coating composition in two or more coats, the different coats may consist of antifouling coatings of different compositions, resulting in the formation of a coating system having different antifouling coating layers.

[0224] The antifouling coating layer may differ in terms of the type and / or amount of biocide and binder, the binder composition, and / or the polishing rate. In certain cases, for example in outfitting applications, it is preferable to use antifouling coating compositions with different polishing speeds for different coating layers. In that case, it is preferable that the polishing speed of the outermost layer is higher than that of the lower layers.

[0225] A coating film formed from the coating composition of the present invention can also be cleaned, for example, by a robot, a remotely operated vehicle (ROV), or a manual device. Cleaning can be performed retrospectively or preventively. Underwater cleaning can be carried out using, for example, mechanical means (brushes, squeegees, etc.), high-pressure water, ultraviolet light, lasers, or ultrasound. Robots used for underwater cleaning are described, for example, in International Publication Nos. 2019 / 170888, 2020 / 207791, and 2020 / 207792. Cleaning settings applicable when using brushes are described, for example, in International Publication No. 2021 / 180588. The present invention is defined below with reference to non-limiting embodiments.

[0226] [Examples] <Materials and Methods> <Measurement of polymer solution viscosity> The viscosity of the polymer was measured according to ASTM D2196 Test Method A, using a Brookfield DV-I Prime digital viscometer equipped with an LV-2(62) spindle at a rotation speed of 12 rpm. The polymer solution was adjusted to 23.0°C ± 0.5°C before measurement.

[0227] <Measurement of non-volatile substance content in polymer solutions> The non-volatile substance (NVM) content in the polymer solution was measured according to ISO 3251:2019. A 0.5 g ± 0.1 g test sample was taken and dried in a ventilated oven at 105°C for 3 hours. The weight of the residue was considered as the NVM content. The NVM content is expressed as a weight fraction (%). The values ​​shown are the average of three parallel measurements.

[0228] <Measurement of polymer molecular weight distribution> The properties of the polymer were identified by gel permeation chromatography (GPC) measurement. The molecular weight distribution (MWD) was measured by connecting two PLgel 5μm Mixed-D columns (manufactured by Agilent) in series to an Omnisec Resolve and Reveal system (manufactured by Malvern). The calibration of the column was performed by conventional calibration using a narrow-distribution polystyrene standard. The analysis conditions were as follows.

[0229]

Table 2

[0230] A sample was prepared by dissolving a polymer solution corresponding to 25 mg of the dry polymer in 5 ml of tetrahydrofuran (THF). The sample was held at room temperature for at least 3 hours before sampling for GPC measurement. Before analysis, the sample was filtered through a 0.45 μm nylon filter. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are reported. The polydispersity index (PDI) is expressed as Mw / Mn.

[0231] <Measurement of glass transition temperature> The glass transition temperature (Tg) was determined by differential scanning calorimetry (DSC). The DSC measurement was carried out using a DSC Q200 from TA Instruments, with an empty pan used as a reference, and heating-cooling-heating was performed at a heating rate of 10 °C / min and a cooling rate of 10 °C / min within the temperature range of -80 °C to 150 °C. The data was processed using the Universal Analysis software from TA Instruments. The inflection point within the glass transition range specified in ISO 11357-2:2020 during the second heating is reported as the Tg of the polymer.

[0232] Samples were prepared by dropping and spreading each polymer solution onto individual glass panels using an applicator with a gap size of 100 μm. After drying the glass panels at room temperature overnight, they were dried at 50 °C for 24 hours in a ventilated heating cabinet. The dried polymer material was scraped off the glass panels, and approximately 10 mg of the dried polymer material was transferred to an aluminum pan. Before measurement, the pan was sealed with a non-airtight lid.

[0233] <Preparation Procedure of Copolymer Solution S1> 60.0 parts of xylene was charged into a temperature-controlled reaction vessel equipped with a stirrer, a condenser, a nitrogen inlet, and a supply port. 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. This premix was charged into the reaction vessel at a constant rate over 2 hours using a metering pump under a nitrogen atmosphere. After reacting for an additional 30 minutes, a boost initiator solution of 0.25 parts of 2,2’-azobis(2-methylbutyronitrile) and 7.6 parts of xylene was supplied to the reaction vessel at a constant rate over 20 minutes. The reaction vessel was maintained at the reaction temperature for an additional 1.5 hours. Then, the reactor was heated to 105 °C and held at that temperature for 1 hour. Finally, the reactor was cooled to room temperature. All “parts” shown above are “parts by weight”.

[0234] Copolymer solution S1 had the following properties. NVM 60.1 wt%; Viscosity 1089 cP; Mw 23,936; PDI 2.43; Tg 47 °C

[0235] Copolymer solutions S2 to S11 were prepared in the same manner as above. The details of the monomer composition and procedure are shown in Table 1.

[0236] <Preparation Procedure of Copolymer Solution A1> 40.0 parts xylene and 10.0 parts 1-methoxy-2-propanol were added to a temperature-controlled reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet, and feed port. The reaction vessel was heated and maintained at a reaction temperature of 100°C. A premix was prepared consisting of 75.0 parts n-butyl acrylate, 22.0 parts methyl methacrylate, 3.0 parts methacrylic acid, and 1.60 parts tert-amylperoxy-2-ethylhexanoate. This premix was added to the reaction vessel at a constant rate over 3 hours using a metering pump under a nitrogen atmosphere. After reacting for a further 30 minutes, a boost initiator solution of 0.40 parts tert-amylperoxy-2-ethylhexanoate and 5.0 parts xylene was supplied to the reaction vessel at a constant rate over 20 minutes. The reaction vessel was maintained at the reaction temperature for a further 1.5 hours, and then cooled to room temperature. All "parts" mentioned above are "parts by weight".

[0237] Copolymer solution A1 had the following properties. NVM65.4wt%; Viscosity 1095cP; Mw 26,530; PDI 2.93; Tg -20℃

[0238] Copolymer solutions A2 to A4 were prepared in the same manner as described above. Tert-butylperoxy-2-ethylhexanoate was used as an initiator in the preparation of A3 and A4. The monomer compositions and detailed procedures are shown in Table 2.

[0239] <Preparation procedure for zinc rosinate solution Z1> 88 parts of rosin solution (containing 60% by weight of gum rosin in xylene), 7 parts of zinc oxide, and 5 parts of xylene were placed in a temperature-controlled reaction vessel equipped with a stirrer and a reflux condenser. The mixture was slowly heated to 70°C and held at that temperature for 2 hours. Heating was stopped, and the solution was cooled to room temperature while stirring. The zinc rosinate solution Z1 had an NVM of 62.1% by weight.

[0240] [Table 3]

[0241] [Table 4]

[0242] [Table 5] JPEG2026522944000012.jpg248162JPEG2026522944000013.jpg24887

[0243] <Calculation of volatile organic compound (VOC) content in antifouling coating compositions> The volatile organic compound (VOC) content of the antifouling coating composition was calculated in accordance with ASTM D5201-01.

[0244] <Measurement of paint viscosity using a cone-plate viscometer> The viscosity of the antifouling coating composition is determined according to ISO 2884-1:2006, at a shear rate of 10,000 s⁻¹. -1 A digital cone-plate viscometer with a viscosity measurement range of 0-10P was used for the measurement, set to a temperature of 23°C. The results are shown as the average of three measurements.

[0245] <Stain-resistant performance test> This test used polyvinyl chloride (PVC) panels (20cm x 30cm). Each panel was primed with commercially available Tiecoat (Safeguard Plus, manufactured by Chokwang Jotun Ltd. (South Korea)) using an airless spray, and then intermediate coated with commercially available antifouling paint (SeaQuantum Ultra III, manufactured by Jotun Paints (Europe) Ltd. (UK)). The curing / drying times and film thickness of the primer and intermediate coats were within the recommended ranges specified in the technical data sheets for each product.

[0246] For the pre-coated PVC panels described above, each example of the antifouling coating composition was directly applied as a topcoat using a film applicator with a gap size of 400 μm. The test area of the applied coating film was approximately 6.5 cm × 25 cm. The edges of each panel were sealed with a commercially available antifouling product. Each example of the antifouling coating composition was applied within 3 to 10 days after the paint was prepared.

[0247] The panels were exposed on a raft installed in Singapore. The panels were submerged 0.5 to 1.5 m below the sea surface. Each panel was evaluated by visual inspection and rated according to the following scale. Macroalgae such as seaweed and animal fouling such as barnacles, tube worms, mussels, sponges, and hydroids were included in the rating. Microfouling organisms such as biofilms and slime, which can be easily removed by hand, were not included in the rating. The edge effect was excluded from the evaluation.

[0248]

Table 6

[0249] <General preparation procedure of antifouling coating composition> The components were mixed at the ratios shown in Tables 5 to 15. The mixing order of the raw materials and the preparation of the selected raw material premixes followed the guidelines of the raw material suppliers. The raw materials were dispersed and pulverized using a vibratory shaker in a 250 ml paint can with glass beads (diameter approximately 3 to 4 mm) present.

[0250]

Table 7

[0251]

Table 8

[0252]

Table 9

[0253] [Table 10] JPEG2026522944000022.jpg206117

[0254] [Table 11] JPEG2026522944000024.jpg206110

[0255] <Comments on Tables 5-9> Examples 1 to 28 demonstrate that it is possible to produce antifouling coating compositions with excellent antifouling properties and a biocide content of less than 10.0% by weight. This is achieved by using a combination of a copper compound with a copper content of more than 40% by weight and tralopyryl together with (meth)acrylic silyl copolymer (i) and (meth)acrylic polymer (ii-a) and monocarboxylic acid (iii), and by making the total amount of pigment, filler and biocide more than 35% by weight.

[0256] In Examples 1-9 of Table 5, different copper compounds and tralopyril were tested. Good antifouling performance was obtained for all formulations in Examples 1-9.

[0257] Examples 10-28 in Tables 6 and 7 tested different types of copper compounds, different amounts of copper compounds, tralopyril, and combinations thereof. All formulations in Examples 10-28 showed good antifouling performance.

[0258] Comparative Example C1 in Table 8 is directly comparable to Example 1 in Table 5. Comparative Example C1 does not contain a copper compound. As a result, its antifouling performance after 6 months was inferior. Comparative Example C1 demonstrates that the use of tralopiril alone is insufficient to obtain good long-term antifouling performance.

[0259] Comparative Example C2 is directly comparable to Example 1. Comparative Example 2 does not contain tralopyril. As a result, the antifouling performance after 6 months is inferior, indicating that the combination of copper compounds and tralopyril is essential to obtain good long-term antifouling performance in coating compositions with a total biocide content of less than 10.0% by weight.

[0260] Comparative Example C3 shows that, when tralopyril is not included, increasing the amount of copper(I) oxide from 1% by weight in Comparative Example C2 to 5% by weight in Comparative Example C3 does not improve the antifouling performance.

[0261] Comparative Examples C4, C5, and C6 demonstrate that even when other copper compounds are used, the antifouling performance is reduced in the absence of tralopyril. The comparative examples in Table 9 represent copper compounds outside the scope of the present invention. Comparative examples C7 to C12 contain copper compounds with a copper content of less than 40% by weight. All formulations of comparative examples C7 to C12 exhibit poor long-term antifouling performance.

[0262] [Table 12] JPEG2026522944000026.jpg248108

[0263] [Table 13] JPEG2026522944000028.jpg248147

[0264] [Table 14] JPEG2026522944000030.jpg206110

[0265] <Comments on Tables 10-12> Examples 29-38 in Table 10 tested different (meth)acrylic silyl ester copolymers (i) and (meth)acrylic polymers (ii-a). Different combinations of these polymers were also tested. Good antifouling performance was obtained for all formulations in Examples 29-47.

[0266] Examples 39-48 in Table 11 show examples of different (meth)acrylic silyl ester copolymers (i) and copper compounds. All examples demonstrate good antifouling performance.

[0267] Comparative Example C13 in Table 12 shows that when the total amount of pigment, filler, and biocide was less than 35% by weight based on the total weight of the coating composition, the antifouling performance was already poor after one month.

[0268] Comparative Examples C14, C15, and C16 demonstrate that the antifouling performance is inferior when monocarboxylic acid is not present in the coating composition.

[0269] [Table 15] JPEG2026522944000032.jpg248147

[0270] [Table 16] JPEG2026522944000034.jpg206132

[0271] [Table 17] JPEG2026522944000036.jpg248102

[0272] <Comments on Tables 13-15> Examples 49-75 in Tables 12-15 tested different combinations of binder, biocide, and pigment. Examples 50 and 51 in Table 13 show that zinc salt of rosin (zinc rosinate Z1) can also be used. Examples 67-75 in Table 15 show examples of using a combination of (meth)acrylic polymer (ii-a) and a second (meth)acrylic polymer (ii-b) in the absence of (meth)acrylic silyl ester copolymer (i). Good antifouling performance was obtained in all examples.

[0273] [Table 18] JPEG2026522944000038.jpg248147

[0274] [Table 19] JPEG2026522944000040.jpg248108

[0275] [Table 20] JPEG2026522944000042.jpg248116

[0276] [Table 21] JPEG2026522944000044.jpg206136

[0277] [Table 22] JPEG2026522944000046.jpg206129

[0278] <Comments on Table 16> In these examples, different biocide content and different biocide combinations were used with (meth)acrylic silyl polymer (i), (meth)acrylic polymer (ii), and rosin. All examples showed good antifouling performance.

[0279] <Comments on Table 17> These examples utilized a variety of binder combinations, including a broad range of (meth)acrylic silyl polymers (i), (meth)acrylic polymers (ii), and monocarboxylic acids (iii). All examples demonstrated good antifouling performance.

[0280] <Comments on Tables 18 and 19> These examples demonstrate the use of a wide range of fillers and different rosins, along with combinations of (meth)acrylic polymer (ii-a) and a second (meth)acrylic polymer (ii-b), in the absence of (meth)acrylicsilyl ester copolymer (i). All examples exhibit good antifouling performance.

[0281] <Comments on Table 20> These comparative examples demonstrate that in compositions combining (meth)acrylic polymer (ii-a), a second (meth)acrylic polymer (ii-b), and a carboxylic acid (iii), the antifouling performance is inferior if neither tralopyril (iv-a) nor a copper compound (iv-b) (containing at least 40% by weight of copper) is included.

Claims

1. Antifouling coating composition, (i) (meth)acrylicsilyl ester copolymers containing at least 15% by weight of silyl ester monomers relative to the total weight of monomers in the (meth)acrylicsilyl ester copolymer, and / or (ii) A (meth)acrylic polymer containing 10% by weight or less of a silyl ester monomer and 5.0% by weight or less of a metal ester monomer based on the total weight of monomers in the (meth)acrylic polymer, (iii) Monocarboxylic acid or its metal salt, (iv) a. Tralopiril, and b. A biocide comprising one or more copper compounds having a copper content of at least 40% by weight relative to the formula weight of the copper compound, The coating composition, in whole, contains 10.0% by weight or less of the biocide, and (v) an antifouling coating composition comprising, in total, at least 35% by weight of pigments, fillers, and biocides based on the total weight of the entire coating composition.

2. The antifouling coating composition according to claim 1, which contains (meth)acrylicsilyl ester copolymer (i) or contains both (meth)acrylicsilyl ester copolymer (i) and (meth)acrylic polymer (ii).

3. The antifouling coating composition according to any one of the preceding claims, wherein the coating composition comprises 8.0% by weight or less, preferably 5.0% by weight or less, of the biocide based on the total weight of the entire composition.

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% by weight, preferably at least 50% by weight, and is particularly metallic copper or copper(I) oxide.

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

6. The (meth)acrylic silyl ester copolymer (i) is (a) Equation (I) 【Transformation 7】 [In the formula, R 1 is H or CH 3 And, R 2 These are independently selected from C1 to C10 hydrocarbyl groups, preferably isopropyl. The silyl ester monomer and (b) Formula (II) 【Transformation 8】 [In the formula, R 4 is H or CH 3 And R 5 These are C1-C20 hydrocarbyl substituents, preferably C1-C10 alkyl substituents. One or more monomers, Contains structural units derived from An antifouling coating composition according to any one of the prior claims.

7. The antifouling coating composition according to any one of the preceding claims, wherein the coating composition contains (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 (iii-a) with a Tg of less than 10°C, more preferably less than 0°C, for example less than -10°C.

9. The (meth)acrylic copolymer (ii-a) is (a) (meth)acrylic acid and (b) Formula (II) 【Chemistry 9】 [In the formula, R 4 is H or CH 3 , R 5 is a C1-C20 hydrocarbyl substituent, preferably a C1-C10 alkyl substituent, and most preferably methyl, ethyl, n-propyl, n-butyl, or 2-ethylhexyl.] One or more monomers, The antifouling coating composition according to claim 8, comprising the above.

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

11. The (meth)acrylic ester polymer (ii-b) is (a) Equation (II) 【Chemistry 10】 [In the formula, R 4 is H or CH 3 And R 5 These are C1-C20 hydrocarbyl substituents, preferably C1-C10 alkyl substituents, most preferably methyl, ethyl, n-propyl, n-butyl, or 2-ethylhexyl. One or more monomers, (b) Equation (VI) 【Chemistry 11】 [In the formula, R 11 is H or CH 3 And R 12 is a C3-C40 substituent having at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom, for example, a C3-C20 substituent, or R 12 This represents a poly(alkylene glycol) group. One or more monomers, The antifouling coating composition according to claim 10, comprising the above.

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

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 metal salts thereof, in particular gum rosin, hydrogenated gum rosin, copper salt of gum rosin, zinc salt of gum rosin, copper salt of hydrogenated gum rosin, zinc salt of hydrogenated gum rosin, and mixtures thereof.

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

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

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

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

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