Antifouling paint composition

Abstract

The antifouling coating composition contains (A) a binder containing a (meth)acrylic copolymer (i) containing a silyl ester group, (B) cuprous oxide in a solid content of 2.0 to 30 vol%, for example 5.0 to 20 vol%, and (C) hollow spheres in a solid content of 2.0 to 65 vol%, for example 10 to 55 vol%,.

Description

[Technical Field]

[0001] The present invention relates to an antifouling coating composition comprising a (meth)acrylic copolymer containing a silyl ester group, cuprous oxide, and hollow spheres. The composition may further comprise an acrylic copolymer and / or a monocarboxylic acid or a metal salt thereof. The present invention further relates to a method of protecting an object from fouling by applying the antifouling coating composition of the present invention to the object, and an object coated with the antifouling composition of the present invention. [Background technology]

[0002] Copper-containing self-polishing paints are the most commonly used antifouling paints. Cuprous oxide is a biocide that is broadly effective against animal fouling. After being released into seawater, cuprous oxide is converted relatively quickly into less toxic compounds, allowing it to be used in antifouling paints at high concentrations. However, reducing the overall amount of biocides used, while maintaining the overall performance of the antifouling paint, is beneficial from an environmental protection standpoint. Cuprous oxide remains a preferred biocide in antifouling paints, but more efficient use of added cuprous oxide can result in more sustainable and economical products.

[0003] Therefore, the inventors sought an antifouling paint that could reduce the level of cuprous oxide. However, reducing the level of cuprous oxide is not easy. When reducing the content of cuprous oxide in a paint, it is necessary to increase the content of other components in order to maintain the same other properties of the paint. [Overview of the project] [Problems that the invention aims to solve]

[0004] For example, cuprous oxide has relatively low oil absorption compared to many typical fillers used in antifouling coatings, so substituting cuprous oxide for fillers in a 1:1 volume ratio is not a practical solution. This is because such a product would have a significantly increased viscosity, requiring more solvent to maintain a viscosity suitable for coating. An increase in solvent means an increase in volatile components, and many countries have strict limits on the amount of volatile components in paints. Simply substituting a small amount with a highly oil-absorbing filler also presents problems. This is because the resulting paint composition would have a lower pigment volume concentration, negatively impacting the coating properties. Therefore, it is difficult to reform antifouling coatings to reduce the cuprous oxide content. [Means for solving the problem]

[0005] The inventors propose the use of hollow spheres, particularly hollow microspheres, as a partial replacement material for cuprous oxide. Surprisingly, the inventors have found that when hollow spheres are used as a partial replacement material for cuprous oxide, they not only function as an antifouling coating but also offer several additional advantages. [Modes for carrying out the invention]

[0006] The density of copper-containing antifouling paint is approximately 2 g / mL, and a 20L paint container supplied to a customer weighs approximately 40 kg. By replacing some of the cuprous oxide (specific gravity 5.8 g / cm³) with lightweight hollow spheres (e.g., specific gravity 0.2-0.5 g / cm³), the weight of the antifouling paint can be significantly reduced. If the weight of a 20L container is reduced from 40 kg to 30 kg, handling during transportation and at shipyards will be easier, and fuel consumption during transportation will be reduced. Furthermore, if the same dry film thickness is applied to a substrate such as a ship, the weight of the antifouling coating on the ship will be significantly reduced, thus reducing the fuel consumption of the ship during navigation. This reduction in fuel consumption due to weight reduction will result in a reduction in greenhouse gas emissions.

[0007] Solvent-based paints require organic solvents such as xylene to maintain a viscosity suitable for application methods such as spray painting. Hollow spheres have a low specific gravity, resulting in low oil absorption and a high volume / weight ratio. The inventors discovered that replacing cuprous oxide (or other conventional fillers) with hollow spheres tends to reduce viscosity. This means that the amount of organic solvent can be reduced while maintaining paint suitable for spray painting. Reducing the volatile organic compound (VOC) content is advantageous from an environmental, health, and safety perspective.

[0008] By combining the reduction of biocide content, VOCs, and product density, an antifouling product with an improved sustainability profile can be realized. In one embodiment, considering the undesirable environmental impact of plastic pollution being released during paint polishing on ships, it is preferable that the hollow spheres are not polymer-based. Therefore, the use of hollow glass spheres or hollow ceramic spheres is preferred.

[0009] Since cuprous oxide is expensive, cost reduction can be achieved by removing some of the cuprous oxide and replacing it with hollow spheres. If these objectives can be achieved without substantially compromising antifouling performance, the product will clearly have an advantage.

[0010] There are documents that describe several paint compositions using hollow spheres. British Patent No. 2099444 describes an antifouling composition comprising a binder resin, a biocide, a solvent, and hollow particles. The objective of British Patent No. 2099444 is to slow the release rate of a biocide in a coating that can be applied to a high film thickness without cracking. The binder used in the examples is not silyl ester copolymer based.

[0011] International Publication No. 2014 / 055418 describes antifouling coating compositions using acrylic resins, fluororesins and / or fumed silica, and copper flakes. Cuprous oxide is preferably avoided. Example 1 illustrates the use of microspheres, but examples of their use in combination with self-polishing silyl ester copolymer binders are not shown.

[0012] The present invention aims to provide a low-density antifouling coating composition that offers good antifouling performance and is more sustainable, environmentally friendly, and economical, in the context of self-polishing antifouling coatings. Surprisingly, the inventors have found that by using hollow spheres, particularly hollow microspheres, as a partial substitution agent for cuprous oxide, the resulting composition is not only a functional antifouling coating but also possesses the advantages highlighted above.

[0013] [Overview of the prefecture] In one aspect, the present invention is (A) A binder comprising a (meth)acrylic copolymer (i) containing a silyl ester group, (B) Cuprous oxide in solid content of 2.0 to 30 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 2.0 to 65% by volume.

[0014] Viewed in another aspect, the present invention is (A) At least one species of bird (C) 1-6 A binder comprising an alkyl)silyl (meth)acrylate monomer, preferably a (meth)acrylic copolymer containing at least one triisopropylsilyl (meth)acrylate monomer, (B) Cuprous oxide in solid content of 2.0 to 30 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 2.0 to 65% by volume.

[0015] Viewed in another aspect, the present invention is (A) Binder, (i) (meth)acrylic copolymers containing silyl ester groups, for example, at least one tri(C) 1-6 A copolymer containing alkyl)silyl (meth)acrylate monomers, preferably at least one triisopropylsilyl (meth)acrylate monomer. (ii) A binder comprising a monocarboxylic acid or a metal salt thereof, (B) Cuprous oxide in solid content of 2.0 to 30 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 2.0 to 65% by volume.

[0016] Viewed in another aspect, the present invention is (A) A binder comprising a (meth)acrylic copolymer (i) containing a silyl ester group, (B) 10-47% by weight of cuprous oxide, (C) Provides an antifouling coating composition containing 0.25 to 15% by weight of hollow spheres.

[0017] In one aspect, the present invention is (A) Binder, (i) (meth)acrylic copolymer containing a silyl ester group, preferably at least one tri(C) 1-6 A copolymer containing alkyl)silyl (meth)acrylate monomers, preferably at least one triisopropylsilyl (meth)acrylate monomer. (ii) A binder comprising a monocarboxylic acid or a metal salt thereof, (B) 10-47% by weight of cuprous oxide, (C) Provides an antifouling coating composition containing 0.25 to 15% by weight of hollow spheres.

[0018] In another embodiment, the present invention provides a process for protecting an object from fouling, comprising the step of coating at least a portion of the object susceptible to fouling with an antifouling coating composition as defined herein. The present invention also relates to an object coated with an antifouling coating composition as defined herein.

[0019] [Definition] The terms “marine antifouling coating composition,” “antifouling coating composition,” “antifouling paint 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. These terms are used interchangeably herein.

[0020] The antifouling coating composition of the present invention should be considered a "self-polishing" coating. "Self-polishing" or "polishing" means that the thickness of the coating 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.

[0021] The term "hydrocarbyl group" refers to any group that contains only carbon and hydrogen atoms, and therefore includes alkyl groups, alkenyl groups, aryl groups, cycloalkyl groups, arylalkyl groups, etc. As used herein, the term "alkyl" refers to a saturated linear group, a saturated branched group, or a saturated cyclic group. As used herein, the term "cycloalkyl" refers to a cyclic alkyl group.

[0022] 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.

[0023] The term (meth)acrylic copolymer containing a silyl ester group defines the properties of the binder component essential in the present invention. This component is also referred to herein as “silyl ester copolymer” and / or “(meth)acrylicsilyl ester copolymer”.

[0024] The terms "(meth)acrylic polymer" and "(meth)acrylic copolymer containing silyl ester groups" refer to polymers containing repeating units derived from (meth)acrylate monomers. Generally, "(meth)acrylic polymer" and "(meth)acrylic copolymer containing silyl ester groups" will contain at least 50% by weight of (meth)acrylate monomers, i.e., repeating units derived from acrylate monomers and / or methacrylate monomers.

[0025] When the weight percentage of a particular monomer is given for a polymer, that weight percentage represents the ratio of each monomer present in the polymer to the total weight of that monomer. The term "(meth)acrylate" encompasses both methacrylate and acrylate. As used herein, the term "monocarboxylic acid" refers to a compound containing one -COOH group.

[0026] The term “binder” defines a portion of a composition comprising a (meth)acrylic copolymer containing a silyl ester group and other components that together form a matrix that imparts strength and / or flexibility to the coating. For example, as used herein, the term “binder” means comprising a (meth)acrylic copolymer containing a silyl ester group together with a monocarboxylic acid and optionally an acrylic copolymer, i.e., comprising components (i), (ii), and (iii) as defined herein.

[0027] The term "Tg" refers to the glass transition temperature. 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 itself may be a paint, or it may be a concentrated liquid produced by adding a solvent to manufacture a paint.

[0028] The term cuprous oxide refers to the chemical compound copper(I) oxide (Cu₂O). The term "weight % based on the total weight of the composition" refers to the weight % of the component present in the final usable composition unless otherwise specified. The term "dry weight % based on the total weight of the composition" refers to the weight percentage of the components present in the final usable composition, ignoring the weight of the solvent, unless otherwise specified.

[0029] Solids volume (SV) is an index that measures the volume of solid film raw materials remaining after the paint has dried. The solids volume % is expressed as follows:

[0030] %SV = (Volume of solid components) / (Total volume of wet paint) × 100

[0031] Solids volume is a parameter commonly used in the paint industry. The term "volatile organic compound (VOC)" refers to compounds with a boiling point of 250°C or lower at standard atmospheric pressure (1 atm).

[0032] The terms "antifouling agent" or "biocide" refer to a bioactive compound or mixture of bioactive compounds that prevents or inhibits the attachment and / or growth of marine organisms on a surface.

[0033] [Detailed description of the invention] The present invention relates to a novel antifouling coating composition. The antifouling coating composition contains a binder (A) comprising a (meth)acrylic copolymer (i) containing a silyl ester group. Preferably, the (meth)acrylic copolymer (i) containing a silyl ester group is a copolymer of at least one (meth)acrylate monomer and at least one silyl ester (meth)acrylate monomer. More preferably, the (meth)acrylic copolymer containing a silyl ester group contains a triisopropylsilyl (meth)acrylate monomer.

[0034] The binder (A) preferably further contains (ii) a monocarboxylic acid or a metal salt thereof, and optionally (iii) a (meth)acrylic polymer (e.g., (meth)acrylic polymer (iii-a) and / or (meth)acrylic polymer (iv) as defined herein).

[0035] These binder components are used in combination with cuprous oxide and hollow spheres in a specific weight / solids volume ratio to form the antifouling coating composition of the present invention.

[0036] The use of hollow spheres in coating compositions reduces the amount of cuprous oxide, resulting in more sustainable and environmentally friendly paints. Furthermore, replacing cuprous oxide with hollow spheres also reduces the VOC content in the paint, making it easier to meet strict government VOC content regulations.

[0037] Furthermore, the paint of the present invention is lighter than paints with a high cuprous oxide content. This lower density reduces both the fuel costs of transporting the product to the application site and the fuel costs of the coated vessel. For container ships, the weight of the applied antifouling coating is critical. Reducing the coating weight allows for a reduction in the vessel's fuel costs.

[0038] Finally, hollow spheres are less expensive than cuprous oxide. If an antifouling coating composition with equivalent effectiveness can be prepared while reducing the amount of cuprous oxide, costs can be significantly reduced.

[0039] Even at low biocide levels, the antifouling performance of the composition is maintained as shown in the examples. The novel combination of the present invention also holds true in the context of self-polishing coating compositions. The antifouling coating of the present invention is based on a (meth)acrylic copolymer having pendant hydrolyzable silyl groups. In seawater, the copolymer gradually decomposes as the pendant silyl groups on the polymer backbone are hydrolyzed. The remaining (meth)acrylic copolymer acquires pendant carboxylic acid groups, becoming sufficiently hydrophilic to be washed away or eroded from the coating surface. This controlled dissolution, i.e., self-polishing effect, allows for controlled release of biocides in the coating, resulting in excellent antifouling and a smooth surface, and consequently, reduced frictional resistance. The use of hollow spheres in such a self-polishing coating composition is novel.

[0040] [Binder (A)] [(meth)acrylic copolymer (i) containing silyl ester groups] The binder (A) comprises at least one (meth)acrylic copolymer (i) containing a silyl ester group.

[0041] The use of (meth)acrylic copolymers containing silyl ester groups in antifouling coating compositions is well known, and in the broadest embodiment of the present invention, the present invention encompasses any of these well known copolymers.

[0042] A (meth)acrylic copolymer (i) containing a silyl ester group contains repeating units derived from a (meth)acrylate monomer. Preferably, a (meth)acrylic copolymer (i) containing a silyl ester group contains at least 50% by weight of repeating units derived from a (meth)acrylate monomer, i.e., acrylate monomer and / or methacrylate monomer. A (meth)acrylic copolymer (i) containing a silyl ester group is even more preferably containing at least 80% by weight, more preferably at least 85% by weight, and even more preferably at least 90% by weight of repeating units derived from a (meth)acrylate monomer. A preferred silyl ester group-containing (meth)acrylic copolymer present in the composition of the present invention contains 80-100% by weight, more preferably 85-100% by weight, and even more preferably 90-100% by weight of repeating units derived from a (meth)acrylate monomer.

[0043] In a preferred embodiment, the (meth)acrylic copolymer containing a silyl ester group contains 100% by weight of structural units derived from (meth)acrylate monomers, i.e., it does not contain any other types of monomers.

[0044] The coating composition of the present invention may contain a mixture of two or more different (meth)acrylic silyl ester copolymers (i), as described, for example, in British Patent No. 2576431. Alternatively, only one (meth)acrylic silyl ester copolymer binder (i) may be used.

[0045] The silyl ester group-containing (meth)acrylic copolymer (i) 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).

[0046] [(meth)acrylsilyl ester monomer (a1)] Preferably, the (meth)acrylic silyl ester copolymer (i) contains at least one residue of the silyl ester monomer (a1) of formula (I).

[0047]

Chemical formula

[0048] In the formula, R 1 is H or CH3, R 2 each independently represents a C1-C 10 hydrocarbyl group and an -OSi(R 3 )3 group, R 3 each independently represents a straight-chain or branched C1-C 10 alkyl group selected from the group consisting of alkyl groups.

[0049] The term "hydrocarbyl" is intended to include straight-chain or branched alkyl groups such as methyl, isopropyl, propyl, butyl, isobutyl, tert-butyl, 1,1,2-trimethylpropyl, and 2-ethylhexyl groups, cycloalkyl groups such as cyclohexyl and substituted cyclohexyl groups, and aryl groups such as phenyl and substituted phenyl groups. Each R 2 is preferably an independent C 1-8 alkyl group. All R 2 groups are preferably the same.

[0050] Each R 3 is preferably an independent C 1-4 alkyl group. All R 3 groups are preferably the same.

[0051] The monomer (a1) as defined by general formula (I) includes silyl ester monomers such as tri-n-propylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tert-butyldimethylsilyl (meth)acrylate, texyldimethylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, bis(trimethylsiloxy)methylsilyl (methacrylate), and tris(trimethylsiloxy)silyl (meth)acrylate.

[0052] The use of triisopropylsilyl acrylate and / or triisopropylsilyl methacrylate is preferred. Therefore, R 2 Preferably, it is isopropyl.

[0053] The silyl ester monomer of formula (I) can be used alone or in combination of two or more silyl ester monomers of formula (I). Preferably, the (meth)acrylic silyl ester copolymer (i) contains one or two different monomers of formula (I), and in particular contains one monomer.

[0054] Preferably, the (meth)acrylic silyl ester copolymer (i) contains at least 30% by weight of silyl ester monomers (e.g., those of formula (I) as specified herein) based on the total weight of monomers present in the copolymer. Preferably, the (meth)acrylic silyl ester copolymer contains at least 35% by weight, more preferably at least 40% by weight, for example at least 45% by weight, of silyl ester monomers based on the total weight of monomers present in the copolymer.

[0055] Preferably, the (meth)acrylic silyl ester copolymer (i) contains less than 80% by weight of silyl ester monomers (e.g., those of formula (I)) based on the total weight of monomers present in the copolymer. Preferably, the (meth)acrylic silyl ester copolymer contains less than 75% by weight, more preferably less than 70% by weight, for example less than 65% by weight, of silyl ester monomers based on the total weight of monomers present in the copolymer.

[0056] [Ethylene-unsaturated monomer (a2)] Preferably, the (meth)acrylicsilyl ester copolymer (i) of the present invention contains a residue of at least one ethylenically unsaturated monomer (a2) that is polymerizable 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.

[0057] 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.

[0058] 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, isooctyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)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, 4-Glycidyloxybutyl(meth)acrylate, and 2-(trimethylsilyloxy)ethyl( Examples include meth)acrylates, as well as organosiloxane group-containing (meth)acrylates such as 3-tris(trimethylsiloxy)silylpropyl (meth)acrylate, α-(meth)acryloyloxypropyl-ω-butylpolydimethylsiloxane, α-(meth)acryloyloxypropyl-ω-trimethylsilylpolydimethylsiloxane, α-(meth)acryloyloxyethyl-ω-trimethylsilylpolydimethylsiloxane, and α,α'-(methylmethacryloyloxypropyl)-bis(ω-butyl)polydimethylsiloxane.

[0059] Examples of suitable vinyl monomers (a2) include styrene, vinyl 2-ethylhexanoate, and vinyl neodecanoate. Mixtures of different monomers (a2) may also be used.

[0060] Preferably, the ethylenically unsaturated monomer (a2) is represented by formula (II).

[0061] [ka]

[0062] In the formula, R 4 is H or CH3, and R 5 C1~C 20 Hydrocarbyl substituents, preferably C 1-10 alkyl substituents, for example, C 1-8 It is an alkyl group. 5 The group may be linear or branched. Most preferably, R 5 R is a methyl, ethyl, propyl, butyl, hexyl, octyl, or decyl group, which may be linear or branched (if possible). An ideal choice is R 5 These are methyl, ethyl, n-propyl, n-butyl, or isobutyl groups.

[0063] Suitable monomers of formula (II) as monomer (a2) in (meth)acrylicsilyl ester polymer (i) 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.

[0064] Suitable options for the monomer of formula (II) include methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, or isooctyl acrylate. A mixture of different monomers of formula (II) may be used.

[0065] The ethylenically unsaturated monomer (a2) may also be represented by formula (III).

[0066] [ka]

[0067] In the formula, R 6 is H or CH3, and R 7 This is a C3-C atom containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom. 40 A substituent, preferably containing at least one oxygen atom, is C 3-20 It is a substituent.

[0068] Preferably, R 7 The base is given by the formula -(CH2CH2O) n -R 8 It is expressed as, in the formula, R 8 C1~C 10 Hydrocarbyl substituents, preferably C1-C 10 alkyl or C6~C 10 The aryl substituent is such that n is an integer in the range of 1 to 5, preferably 1 to 3. Preferably, R 7 The formula is (CH2CH2O) n -R 8 It is expressed as, in the formula, R 8 C1~C 10 The alkyl substituent is preferably CH3 or CH2CH3, and n is an integer in the range of 1 to 3, preferably 1 or 2.

[0069] Examples of such monomers include 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.

[0070] Preferred monomers (a2) in this embodiment are 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, or 2-(2-ethoxyethoxy)ethyl methacrylate.

[0071] 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 expressed as, in the formula, R 9 C1~C 10 Hydrocarbyl substituents, preferably C1-C 10 alkyl or C6~C 10 The aryl substituent is such that p is an integer in the range of 1 to 10, preferably 1 to 4.

[0072] Examples of monomers of formula (III) include 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.

[0073] R 7The 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 in the formula, 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.

[0074] Examples of monomers of formula (III) include furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycerol formal (meth)acrylate, isopropylidene glycerol (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 isopropylidene glycerol methacrylate.

[0075] The monomer of formula (III) is preferably 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, or tetrahydrofurfuryl acrylate. A mixture of different monomers of formula (III) may be used.

[0076] A mixture of different monomers of formula (II) and formula (III) may be used in combination. When the (meth)acrylic silyl ester copolymer (i) of the present invention contains monomer (III), it is preferable that at least one monomer of formula (II) is included.

[0077] The preferred (meth)acrylic silyl ester copolymer (i) of the present invention contains structural units derived from one or more monomers of formula (I), such as triisopropylsilyl acrylate and / or triisopropylsilyl methacrylate; structural units derived from one or more monomers of formula (II), such as methyl methacrylate and / or butyl acrylate; and optionally, structural units derived from one or more monomers of formula (III), such as 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, and 2-(2-ethoxyethoxy)ethyl acrylate.

[0078] Preferably, the content of the silyl ester monomer (a1) in the (meth)acrylic silyl ester copolymer (i) (e.g., monomer of formula (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 the (meth)acrylic silyl ester copolymer.

[0079] Preferably, the (meth)acrylic silyl ester copolymer (i) contains monomer (a2) (for example, of 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 entire (meth)acrylic silyl ester copolymer.

[0080] Preferably, the (meth)acrylic silyl ester copolymer (i) contains at least 15% by weight, particularly 15-65% by weight, of the monomer component of formula (II).

[0081] Preferably, the (meth)acrylsilyl ester copolymer (i) contains less than 40% by weight, more preferably 2.0 to 35% by weight, of the monomer of formula (III).

[0082] The (meth)acrylic silyl ester copolymer (i) has a weight-average molecular weight (Mw) of preferably 5,000 to 70,000, preferably 8,000 to 55,000, and more preferably 20,000 to 45,000. Mw is measured by the method described in the examples.

[0083] The (meth)acrylic silyl ester copolymer (i) preferably has a polydispersity index (PDI) of 1.5 to 8.0, more preferably 2.0 to 5.0.

[0084] The copolymer preferably has a glass transition temperature (Tg) of at least 15°C, preferably at least 20°C, for example, at least 25°C, all of which are measured according to the Tg test described in the Examples section. Values ​​below 80°C, for example below 70°C, for example below 60°C, or for example below 55°C are preferred.

[0085] 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.

[0086] In one preferred embodiment, the antifouling coating composition of the present invention preferably contains 2.0 to 30% by weight, for example 3.0 to 25% by weight, and particularly 5.0 to 20% by weight, of (meth)acrylic silyl ester copolymer (i) based on the entire coating composition.

[0087] In one preferred embodiment, the antifouling coating composition of the present invention preferably contains 5 to 40% by weight, for example 7 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.

[0088] In one preferred embodiment, the antifouling coating composition of the present invention preferably contains 5.0 to 60% by volume, for example 10 to 50% by volume, and particularly 15 to 40% by volume, of (meth)acrylic silyl ester copolymer (i) based on the total weight of the coating composition.

[0089] 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.

[0090] [Monocarboxylic acids or their metal salts (ii)] The antifouling coating composition of the present invention preferably contains a monocarboxylic acid or a metal salt thereof. This component constitutes part of the binder (A).

[0091] The monocarboxylic acid or its metal salt present in the antifouling coating composition of the present invention preferably contains 5 to 50 carbon atoms, more preferably 10 to 40 carbon atoms, and even more preferably 12 to 25 carbon atoms.

[0092] The monocarboxylic acid present in the antifouling coating composition of the present invention is preferably rosin, modified rosin, C6-C 20 Cyclic monocarboxylic acids, C5~C 24 acyclic aliphatic monocarboxylic acids, C7~C 20 Selected from aromatic monocarboxylic acids and mixtures thereof.

[0093] Metal salts of 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.

[0094] The term resin acid refers to a mixture of monocarboxylic acids present in rosin. Resin acid is also called rosin acid.

[0095] 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 usually exists as a mixture of acids.

[0096] Typical examples of rosin sources include gum rosin, wood rosin, and tall oil rosin. Gum rosin, also known as colophony or colophonium, is particularly preferred. Preferred rosins contain more than 85% resin acid, more preferably more than 90% resin acid.

[0097] 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.

[0098] Typical examples of modified resin acids include dihydroabietic acid, dihydropimalic acid, and tetrahydroabietic acid, as well as modified mixtures of naturally derived resin acids such as partially hydrogenated rosin, fully hydrogenated rosin, and disproportionated rosin.

[0099] C6~C 20 Typical examples of cyclic monocarboxylic acids include naphthenic acid and trimethylisobutylenecyclohexenecarboxylic acid.

[0100] C5~C 24 Representative examples of 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. Acyclic aliphatic monocarboxylic acids are liquid acyclic C 10 ~C 24 Monocarboxylic acids or liquid branched chain C 10 ~C 24 It is preferable to select from the monocarboxylic acids of acyclic C. 10 ~C 24 Many of the monocarboxylic acids may be of natural origin, 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.

[0101] Preferably, the monocarboxylic acid is rosin, modified rosin, or acyclic C 10 ~C 24 Monocarboxylic acids, C6~C 20 The cyclic monocarboxylic acid, or a metal salt thereof. 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, such as rosin, modified rosin, or a metal salt thereof.

[0102] More preferably, the monocarboxylic acid is rosin or a metal salt of rosin. More preferably, the monocarboxylic acid or its metal salt is 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 the most preferred.

[0103] In one embodiment, the antifouling coating composition is a liquid acyclic saturated C 12-24 Monocarboxylic acids or their salts or liquid acyclic branched chains C 12-24 A monocarboxylic acid or its salt in less than 1.0% by weight, for example, a liquid acyclic saturated C 12-24 Monocarboxylic acids or their salts or liquid acyclic branched chains C 12-24 The coating composition contains less than 0.5% by weight, particularly less than 0.1% by weight, of a monocarboxylic acid or a salt thereof. 12-24 Monocarboxylic acids or their salts or liquid acyclic branched chains C 12-24 It does not have to contain monocarboxylic acids or their salts. The term "liquid" refers to the state at 23°C and 1 atmosphere.

[0104] The amount of monocarboxylic acid or its metal salt present in binder (A) is preferably 5.0 to 55% by weight (dry solids), more preferably 10 to 50% by weight (dry solids), and even more preferably 15 to 45% by weight (dry solids), based on the total weight of binder (A).

[0105] The final antifouling coating composition of the present invention preferably contains 1.0 to 30% by weight, for example 2 to 20% by weight (dry solids), and particularly 3.0 to 15% by weight (dry solids), of a monocarboxylic acid or its metal salt, based on the entire coating composition.

[0106] The final antifouling coating composition of the present invention preferably contains 2.0 to 25% by volume, preferably 3.0 to 20% by volume, for example 3.0 to 15% by volume, of a monocarboxylic acid or its metal salt in terms of solid content.

[0107] When a blend of monocarboxylic acids or their metal salts is used, these proportions are relative to the total amount of monocarboxylic acids or their metal salts present.

[0108] Viewed in another aspect, the present invention is an antifouling coating composition, (A) Binder, (i) (meth)acrylic copolymer containing a silyl ester group, (ii) comprising a monocarboxylic acid or a metal salt thereof, The above antifouling coating composition contains a binder comprising 4.0 to 20% by volume of component (ii) and 10 to 60% by volume of component (i), (B) Cuprous oxide in solid content of 2.0 to 30 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 2.0 to 65% by volume.

[0109] [(meth)acrylic polymer (iii)] In some embodiments, the binder used in the antifouling coating composition of the present invention contains (meth)acrylic polymer (iii). This also constitutes part of the binder component (A) of the composition.

[0110] In the context of the present invention, the term "(meth)acrylic polymer" refers to a polymer comprising at least one monomer based on acrylic acid, methacrylic acid, acrylic acid ester, and / or methacrylic acid ester. In a preferred embodiment, binder A of the coating composition of the present invention comprises a (meth)acrylic copolymer (iii) containing 0.5 to 10% by weight of (meth)acrylic acid monomer relative to the total weight of monomers in the copolymer.

[0111] Copolymer (iii) is required to be different from copolymer (i) in binder (A) of the present invention.

[0112] The (meth)acrylic polymer (iii) of the present invention contains 10% by weight or less, preferably less than 5% by weight, for example less than 2% by weight, or less than 1% by weight, of a silyl ester monomer such as the above formula (a1) based on the total weight of monomers present in the (meth)acrylic polymer (iii). The most preferred (meth)acrylic polymer (iii) does not contain any silyl ester groups.

[0113] The (meth)acrylic polymer (iii) of the present invention further contains repeating units derived from (meth)acrylate monomers. Preferably, the (meth)acrylic polymer (iii) contains at least 50% by weight of repeating units derived from (meth)acrylate monomers, i.e., acrylate monomers and / or methacrylate monomers.

[0114] (Meth)acrylic polymer (iii) more preferably contains at least 60% by weight, more preferably at least 75% by weight, and even more preferably at least 90% by weight of repeating units derived from (meth)acrylate monomers.

[0115] In one embodiment, the (meth)acrylic polymer (iii) contains 100% by weight of structural units derived from (meth)acrylate monomers, i.e., it does not contain any other types of monomers.

[0116] The (meth)acrylic polymer (iii) may be a homopolymer or a copolymer, and preferably a copolymer.

[0117] In one embodiment, the binder A of the coating composition of the present invention contains at least one (meth)acrylic polymer (iii) in addition to (meth)acrylic silyl ester copolymer (i) and monocarboxylic acid (ii).

[0118] The (meth)acrylic polymer (iii) has a Tg of less than 10°C, more preferably less than 0°C, even more preferably less than -5°C, and even more preferably less than -10°C, all of which are measured according to the Tg test described in the Examples section. Values ​​above -65°C, for example above -55°C, are preferred.

[0119] In one embodiment, the (meth)acrylic polymer (iii) 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 (iii-a) is preferably in the range of 0.5 to 10% by weight, for example, 0.5 to 5.0% by weight, preferably 1.0 to 4.0% by weight.

[0120] Preferably, the (meth)acrylic polymer (iii) has an acid value of less than 60 mgKOH / g polymer, more preferably less than 40 mgKOH / g polymer, and even more preferably less than 25 mgKOH / g polymer. Preferably, the acid value is greater than 2 mgKOH / g polymer, for example, greater than 5 mgKOH / g polymer. The acid value is measured according to the procedure described in ISO 2114:2000 Method A.

[0121] If (meth)acrylic acid monomer (a3) ​​is present, it is preferable that a second (meth)acrylate monomer (a4), described later, is present to form a copolymer. The (meth)acrylate monomer (a4) preferably constitutes at least 50% by weight, for example at least 75% by weight or at least 80% by weight, and particularly 90 to 99.5% by weight, for example 95.0 to 99.5% by weight, of the (meth)acrylic polymer (iii).

[0122] The (meth)acrylic polymer (iii) may be a homopolymer containing only structural units derived from the (meth)acrylate monomer (a4).

[0123] An example of a suitable (meth)acrylate monomer (a4) is that of formula (II), as defined above.

[0124] [ka]

[0125] In the formula, R 4is H or CH3, and R 5 C1~C 20 Hydrocarbyl substituents, preferably C 1-10 alkyl substituents, for example, C 1-8 It is an alkyl group.

[0126] R 5 The group may be linear or branched. Most preferably, R 5 R is a methyl, ethyl, propyl, butyl, hexyl, octyl, or decyl group, which may be linear or branched (if possible). An ideal choice is R 5 These are methyl, ethyl, n-propyl, n-butyl, isobutyl, or isooctyl groups.

[0127] The preferred selection of formula (II) described above in relation to silyl ester copolymer (i) also applies to (meth)acrylic polymer (iii).

[0128] Suitable monomers of formula (II) as monomers (a4) in (meth)acrylic polymer (iii) 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.

[0129] Suitable monomers of formula (II) as monomer (a4) in (meth)acrylic polymer (iii) include methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-octyl acrylate, or isooctyl acrylate.

[0130] A mixture of different monomers of formula (II) may be used in the (meth)acrylic polymer (iii). The use of two different monomers of formula (II) is particularly preferred. The use of two different monomers of formula (II) is particularly preferred when used in combination with (meth)acrylic acid.

[0131] Preferably, the (meth)acrylic polymer (iii) contains structural units derived from (meth)acrylic acid monomer (a3) ​​and (meth)acrylate monomer (a4).

[0132] In a preferred embodiment, the (meth)acrylic polymer (iii) contains acrylic acid and / or methacrylic acid and structural units derived from methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-octyl acrylate and / or isooctyl acrylate.

[0133] The (meth)acrylic polymer (iii) may further contain structural units derived from vinyl monomers, such as styrene, vinyl 2-ethylhexanoate, and other ethylenically unsaturated monomers such as vinyl neodecanoate.

[0134] The (meth)acrylic polymer (iii) 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 by the method described in the examples. The (meth)acrylic polymer (iii) preferably has a polydispersity index (PDI) of 1.5 to 5.0.

[0135] The (meth)acrylic polymer (iii) 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.

[0136] The (meth)acrylic polymer (iii) is typically present in an amount of 1.0 to 12% by weight, preferably 2.0 to 7.0% by weight, relative to the total dry weight of the entire coating composition.

[0137] (Meth)acrylic polymer (iii) is typically present in the coating composition in an amount of 2.0 to 15% by volume, preferably 3.0 to 10% by volume, in terms of solid content.

[0138] [(meth)acrylic copolymer (iv)] In one embodiment, the binder A of the coating composition of the present invention may contain (meth)acrylic polymer (iv), which is different from (meth)acrylic silyl ester copolymer (i) or (meth)acrylic polymer (iii).

[0139] In one preferred embodiment, the binder A of the coating composition of the present invention comprises a combination of (meth)acrylic silyl ester copolymer (i), a monocarboxylic acid or its metal salt (ii), a (meth)acrylic polymer (iii-a), and a (meth)acrylic copolymer (iv) as defined herein.

[0140] The (meth)acrylic polymer (iv) has a glass transition temperature (Tg) of at least 10°C, preferably at least 15°C, for example at least 17°C or at least 20°C, all of which are measured according to the Tg test described in the Examples section. Values ​​below 80°C, for example below 70°C, for example below 55°C are preferred.

[0141] The (meth)acrylic polymer (iv) of the present invention contains 10% by weight or less, preferably less than 5% by weight, for example less than 2% by weight, or less than 1% by weight, of a silyl ester monomer such as the above formula (a1) based on the total weight of monomers present in the (meth)acrylic polymer (iv). The most preferred (meth)acrylic polymer (iv) does not contain any silyl ester groups.

[0142] The (meth)acrylic polymer (iv) preferably does not contain the acid monomer (a3).

[0143] The (meth)acrylic polymer (iv) of the present invention contains repeating units derived from (meth)acrylate monomers. Preferably, the (meth)acrylic polymer (iv) contains at least 50% by weight of repeating units derived from (meth)acrylate monomers, i.e., acrylate monomers and / or methacrylate monomers.

[0144] The (meth)acrylic polymer (iv) contains repeating units derived from (meth)acrylate monomers, more preferably at least 60% by weight, more preferably at least 75% by weight, and even more preferably at least 90% by weight.

[0145] In one embodiment, the (meth)acrylic polymer (iv) contains 100% by weight of structural units derived from (meth)acrylate monomers, i.e., it does not contain any other types of monomers.

[0146] The (meth)acrylic polymer (iv) preferably contains at least one (meth)acrylate monomer (a5).

[0147] 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, isooctyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,5,5-trimethicyl (meth)acrylate. Lucyclohexyl (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, 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)methyl ( Examples include 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.

[0148] A more preferred example of the (meth)acrylate monomer (a5) is the one of formula (II) defined above for the (meth)acrylsilyl ester copolymer (i).

[0149] As options for the monomer (a5) suitable as the monomer of formula (II), methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, and isobutyl methacrylate can be mentioned.

[0150] Mixtures of different monomers (a5) may also be used. The (meth)acrylate polymer (iv) particularly preferably contains two monomers of formula (II).

[0151] The (meth)acrylate monomer (a5) may further contain a hydrophilic group. Examples of suitable monomers include those represented by the following formula (IV).

[0152]

Chemical formula

[0153] In the formula, R 8 is H or CH3, and R 9 is a C 3-40 substituent containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom, for example a substituent of C3-C 20 , or R 9 represents a poly(alkylene glycol) group.

[0154] The (meth)acrylic copolymer (iv) may contain at least one monomer of the above formula (IV). The R 9 group is represented by the formula (CH2CH2O) n -R 10 In the formula, R 10 is a C1-C 10 hydrocarbyl substituent, preferably a C1-C 10 alkyl or a C6-C 10 aryl substituent, and n is an integer in the range of 1-5, preferably 1-3. Preferably, R 9 is represented by the formula (CH2CH2O) n -R 10 In the formula, R 10 is a C1-C 10The alkyl substituent is preferably CH3 or CH2CH3, and n is an integer in the range of 1 to 3, preferably 1 or 2.

[0155] Examples of such monomers include 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.

[0156] Preferably, the (meth)acrylic polymer (iv) contains one or more of 2-methoxyethyl acrylate or 2-(2-ethoxyethoxy)ethyl acrylate.

[0157] The (meth)acrylic polymer (iv) may contain at least one monomer of the above formula (IV), where R 9 The group is a poly(alkylene glycol) group, such as a poly(ethylene glycol) group. Such a group is represented by the formula (CH2CH2O). m -R 10 or (CH2CH(CH3)O) m -R 11 It may have R 11 C1~C 10 Hydrocarbyl substituents, preferably C1-C 10 alkyl or C6~C 10The monomer is an aryl substituent, where m is an integer in the range of 5 to 25, preferably 5 to 15. Examples of such monomers include poly(ethylene glycol) methyl ether acrylate, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) methyl ether methacrylate, and poly(ethylene glycol) ethyl ether methacrylate. Such preferred monomers have a number-average molecular weight (Mn) of 300 to 1000, more preferably 300 to 550.

[0158] The (meth)acrylic polymer (iv) may further contain at least one monomer of formula (IV) above. 9 The base is the formula (CH2C(O)O) p -R 12 Or (CH(CH3)C(O)O) p -R 12 It is expressed as, in the formula, R 12 C1~C 10 Hydrocarbyl substituents, preferably C1-C 10 alkyl or C6~C 10 The aryl substituent is such that p is an integer in the range of 1 to 10, preferably 1 to 4.

[0159] Examples of such monomers include 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.

[0160] The (meth)acrylic polymer (iv) may contain at least one monomer of the above formula (IV), where R 9 The group is a cyclic group containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom. More preferably, R 9 WR is a group containing up to 40 carbon atoms. 13And in the formula, R 13 The monomer is a cyclic ether such as oxirane, furan, oxolane, oxane, dioxolane, or dioxane, which is optionally alkyl-substituted, and W is a C1-C4 alkylene. Examples of such monomers include furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycerol formal (meth)acrylate, isopropylidene glycerol (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.

[0161] The monomer of formula (IV) is preferably 2-methoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, or poly(ethylene glycol)methyl ether methacrylate.

[0162] The monomer of formula (IV) preferably constitutes at least 15% by weight of the (meth)acrylic polymer (iv). A particularly preferred amount of the monomer of formula (IV) in the copolymer (iv) is 10 to 65% by weight, preferably 15 to 60% by weight, for example, 18 to 50% by weight. If a mixture of monomers of formula (IV) is present, their content is related to the total weight fraction of the monomer of formula (IV) in the copolymer.

[0163] The monomer of formula (II) preferably constitutes at least 15% by weight of the (meth)acrylic polymer (iv). A particularly preferred amount of the monomer of formula (II) in the copolymer (iv) is 20 to 90% by weight, preferably 50 to 90% by weight, for example, 60 to 80% by weight. If a mixture of monomers of formula (II) is present, their content is related to the total weight fraction of the monomer of formula (II) in the copolymer.

[0164] In a preferred embodiment, the (meth)acrylic polymer (iv) contains at least one monomer of formula (II) and at least one monomer of formula (IV).

[0165] In a preferred embodiment, the (meth)acrylic polymer component (iv) consists only of monomers of formula (II) and formula (IV).

[0166] The (meth)acrylic polymer (iv) may further contain structural units derived from vinyl monomers, such as vinyl monomers, for example, styrene, vinyl 2-ethylhexanoate, vinyl neodecanoate, and other ethylenically unsaturated monomers such as N-vinylpyrrolidone.

[0167] The (meth)acrylic polymer (iv) preferably has a weight-average molecular weight (Mw) of 10,000 to 100,000, more preferably 15,000 to 70,000, and more preferably 20,000 to 50,000. Mw is measured by the method described in the examples.

[0168] The (meth)acrylic polymer (iv) preferably has a polydispersity index (PDI) of 1.5 to 5.0.

[0169] The (meth)acrylic polymer (iv) 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 coating composition. The (meth)acrylic polymer (iv) may be present in an amount of 5.0 to 30% by volume, preferably 7.0 to 25% by volume, based on the solid content. The (meth)acrylic polymer (iv) 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.

[0170] [Preparation of (meth)acrylic silyl ester copolymer (i), and (meth)acrylic polymers (iii) and (iv)] (meth)acrylic silyl ester copolymers (i), (meth)acrylic polymers (iii), and (meth)acrylic polymers (iv) can be prepared using polymerization reactions known in the art. The polymers can be obtained by polymerizing a monomer mixture in the presence of a polymerization initiator, using any of the following methods, such as 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. In the preparation of a coating composition using any of these polymers, it is preferable to dilute the polymer with an organic solvent to obtain a polymer solution with appropriate viscosity. From this viewpoint, it is desirable to employ solution polymerization.

[0171] 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 can be used individually or in combination of two or more.

[0172] 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 monomethyl 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.

[0173] [Other binder ingredients] In addition to the above components (i), (ii), (iii), and (iv), additional binders can be used to adjust the properties of the antifouling coating. Examples of usable binders include:

[0174] 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 (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 these units; Alkyd resins and modified alkyd resins; Rosin and hydrogenated rosin esters, such as methyl esters, glycerol esters, poly(ethylene glycol) esters, pentaerythritol esters, preferably gum rosin and hydrogenated gum rosin esters; Hydrocarbon resins, for example, hydrocarbon resins obtained by polymerization of at least one monomer selected from C5 aliphatic monomers, C9 aromatic monomers, indene coumarone monomers, or terpenes, or mixtures thereof; Plasticizers, such as polymeric plasticizers, non-reactive silicone oils, mineral oils, chlorinated paraffins, phthalates, phosphate esters, sulfonamides, adipates, epoxidized vegetable oils, and sucrose acetate isobutyrate.

[0175] If other binder components are present in addition to components (i), (ii), (iii), and (iv), the weight of these components is preferably less than 20% by weight, for example less than 10% by weight, of the weight of binder (A).

[0176] It is preferable that the binder (A) consists of component (i), optionally component (ii), optionally component (iii), and optionally component (iv), and does not contain any other binder components.

[0177] [Hollow sphere] The antifouling coating composition of the present invention must further contain hollow spheres, in particular hollow microspheres. The term "hollow" means that there is a cavity in the center of a particle that is generally spherical. Hollow spheres are usually less than 1.0 mm in diameter and may be referred to herein as microspheres.

[0178] It is preferable that the hollow sphere is made of an inorganic material, i.e., a hollow sphere made of ceramic or glass.

[0179] Preferably, the hollow sphere is a glass sphere or a ceramic sphere. Hollow glass spheres can be manufactured from glass materials such as fused silica glass, vitreous glass, soda-lime borosilicate glass, sodium borosilicate glass, lead oxide glass, aluminosilicate glass, calcium sodium silicate glass, and oxide glass.

[0180] Preferably, the hollow glass spheres are produced from sodium borosilicate or soda-lime borosilicate.

[0181] A suitable example of a ceramic hollow sphere is an aluminosilicate-based sphere.

[0182] Hollow spheres may or may not be coated. Hollow spheres may or may not be treated. When treated, hollow spheres are often treated with silanes such as vinylsilane.

[0183] Preferably, the hollow glass spheres are neutral or alkaline. The pH of the hollow spheres may be in the range of 7 to 12, preferably 7 to 10. The pH of the glass spheres can be determined by mixing the glass spheres with water at a load of 5 volume percent and measuring the pH of the slurry.

[0184] The antifouling paint composition contains at least 2.0 volume%, preferably at least 5.0 volume%, and more preferably at least 10 volume%, of hollow spheres in terms of solid content. In some embodiments, for example, when lightweight hollow glass spheres are used, it is even more preferable to contain at least 15 volume%, or at least 20 volume%, of hollow spheres in terms of solid content. The antifouling paint composition contains less than 65 volume%, preferably less than 55 volume%, preferably 50 volume%, or less, for example, less than 40 volume%, of hollow spheres in terms of solid content.

[0185] To significantly reduce the cuprous oxide content, it is preferable to include hollow spheres in a minimum of 2.5 volume percent of the solid content.

[0186] Expressed in weight percent, the content of hollow spheres is preferably in the range of 0.1% to 12.0% by weight, more preferably 0.4% to 10.0% by weight, and even more preferably 0.7% to 7.0% by weight.

[0187] The ratio of hollow spheres to cuprous oxide (solid content volume % / solid content volume %) is preferably in the range of 0.1 to 15, preferably 0.1 to 10, and particularly 0.5 to 5.0.

[0188] The combined solid content volume % (vol) of the hollow sphere and cuprous oxide is preferably 15 to 70 vol%, particularly 15 to 60 vol%, and more preferably 20 to 50 vol% in terms of solid content. Having the volume of the hollow sphere within this range is sufficient to reduce the amount of cuprous oxide, reduce VOCs, and obtain a lighter product while maintaining good antifouling and mechanical properties. In one embodiment, the solid content volume % of the hollow sphere is higher than the solid content volume of cuprous oxide, for example, at least 1% higher.

[0189] In the following examples, the ratio of the solid content volume of the hollow sphere to the solid content volume of cuprous oxide in the present invention is given as an example of 0.1:1 to 10:1. However, the ratio of the solid content volume of the hollow sphere to the solid content volume of cuprous oxide is preferably about 1, for example, 0.5:1 to 3:1.

[0190] The hollow spheres of the present invention are generally microspheres. The size of the spheres should not be too large. If they are too large, the surface roughness of the coating will increase, which may affect application by airless spray. The size of the hollow microspheres is provided by the supplier and is generally indicated as d50 or a size range.

[0191] (d50) may be in the range of 10 to 100 μm, more preferably 10 to 90 μm, even more preferably 15 to 70 μm, and most preferably 15 to 55 μm. The top cut (d90) may be 200 μm or less, more preferably 150 μm or less, and even more preferably 120 μm or less.

[0192] While there is no absolute lower limit to particle size, the benefits of density reduction will be diminished if very fine particles are used. It is preferable that the D50 size is 1 μm or larger.

[0193] The particle size of the hollow spheres can be measured, for example, by sieving or laser diffraction analysis. The density of the hollow spheres varies depending on the properties of the hollow spheres. In the case of slightly denser ceramic or glass hollow spheres, the limit value in volume percent is somewhat lower. The density of the hollow spheres of the present invention is 0.1 to 1.0 g / cm³. 3 It may also be within that range.

[0194] The compressive strength of the hollow spheres is preferably at least 1500 psi, for example, at least 3000 psi, in order to withstand the shear forces during spray painting and paint preparation (crushing). If hollow spheres with low compressive strength are used, they cannot be included in the crushing process and may not withstand spray painting of the paint, so application should be done by brush or roller.

[0195] Suitable hollow glass spheres are commercially available. Examples include 3M's glass bubble K, S, iM, and XLD series, Potters' Q-cel and Sphericel®, Sinosteel Maanshan and SMC Minerals and Chemicals' hollow glass microspheres, Poraver's poraSpheres, Trelleborg's Ecospheres, and Cenostar's hollow glass. Cenospheres are available, for example, from Cenostar or Omya as Fillite.

[0196] [Biocide] The terms antifouling agents, antifouling agents, biocides, and toxic substances are used in the industry to describe known compounds that act to prevent marine surface fouling. The antifouling agent of the present invention is a marine antifouling agent.

[0197] The coating composition contains cuprous oxide. The cuprous oxide material typically has a particle size distribution of 0.1 to 70 μm and an average particle size (d50) of 1 to 25 μm. The cuprous oxide material may contain stabilizers to prevent surface oxidation and aggregation. Examples of commercially available cuprous oxides include Nordox AS's Nordox Cuprous Oxide Red Paint Grade and Nordox XLT; Furukawa Chemicals Corporation's Cuprous Oxide; American Chemet Corporation's Red Copp 97N, Purple Copp, Lolo Tint 97N, Chemet CDC, and Chemet LD; Spiess-Urania's Cuprous Oxide Red; and Taixing Smelting Plant's Cuprous Oxide Roast and Cuprous Oxide Electrolytic.

[0198] The antifouling coating composition of the present invention may contain cuprous oxide in a solid content of 2.0 to 30% by volume, preferably 5.0 to 25% by volume, and more preferably 5.0 to 20% by volume.

[0199] The antifouling coating composition of the present invention may contain 10 to 47% by weight, for example 12 to 40% by weight, of cuprous oxide based on the total weight of the coating composition. The coating composition may also contain 10 to 30.0% by weight, for example 10 to 27% by weight, of cuprous oxide.

[0200] The coating composition of the present invention may contain additional antifouling agents. The antifouling agent may be inorganic, organometallic, or organic. Suitable antifouling agents are commercially available.

[0201] Examples of inorganic antifouling agents include copper thiocyanate, copper sulfide, and metallic copper such as copper powder and copper flakes.

[0202] Examples of organometallic marine antifouling agents include zinc pyrithione, copper pyrithione, bis(dimethyldithiocarbamate)zinc [dilam], ethylenebis(dithiocarbamate)zinc [zineb], di(ethyl 4,4,4-trifluoroacetoacetate)copper, and copper and zinc compounds described in International Publication No. 2021113564A1.

[0203] Examples of organic 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 [diclofluanido], and N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide [tolylfluanido]. Examples include [D], N-(2,4,6-trichlorophenyl)maleimide, triphenylborane-pyridine [TPBP], 3-iodo-2-propynyl N-butylcarbamate [IPBC], 2,4,5,6-tetrachloroisophthalonitrile [chlorothalonyl], p-((diiodomethyl)sulfonyl)toluene, 4[1(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine], and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril].

[0204] Other examples of marine antifouling agents include tetraalkylphosphonium halides, guanidine derivatives such as dodecylguanidine hydrochloride; macrocyclic lactones including avermectins and their derivatives (such as ivermectin); spinosins and their derivatives (such as spinosad); capsaicin and its derivatives (such as phenylcapsaicin); and enzymes such as oxidases, as well as enzymes having proteolytic activity, hemicellulose degrading activity, cellulose degrading activity, lipid degrading activity, and starch degrading activity.

[0205] Suitable biocides include 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 [diclofluanide], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide [tolylfluanide], triphenylborane-pyridine [TPBP], 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine], 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril], di(ethyl 4,4,4-trifluoroacetoacetate)copper, and phenylcapsaicin. More preferred biocides include zinc pyrithione, copper pyrithione, ethylenebis(dithiocarbamate)zinc [zineb], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine], and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril].

[0206] Since different biocides affect different marine polluting organisms, mixtures of biocides can be used, as is well known in the art.

[0207] More preferably are mixtures of biocides that are active against marine invertebrates such as barnacles, mussels, bryozoans, and hydroids; plants such as seaweed, algae, and diatoms; and bacteria.

[0208] The use of cuprous oxide and copper pyrithione is particularly preferred. The total amount of biocide may constitute up to 55% by weight of the coating composition, for example, 10 to 55% by weight, or for example, 15 to 50% by weight. The total amount of biocide in the dry coating composition may constitute up to 40% by volume of the dry coating composition, for example, up to 35% by volume, or up to 30% by volume. Preferably, the total amount of biocide accounts for at least 5% by volume of the coating composition, for example, at least 10% by volume.

[0209] Some biocides may be encapsulated or adsorbed onto an inert carrier or bound to other materials for controlled release. These proportions are relative to the amount of active biocide present and therefore do not correspond to the amount of carrier used.

[0210] Viewed in another aspect, the present invention is (A) A binder comprising a (meth)acrylic copolymer (i) containing a silyl ester group, (B) Cuprous oxide in solid content of 2.0 to 30 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 2.0 to 65% by volume. Here, the total amount of cuprous oxide and hollow spheres combined is in the range of 15 to 70 volume percent in terms of solid content.

[0211] In particular, the present invention is (A) A binder comprising a (meth)acrylic copolymer (i) containing a silyl ester group, (B) Cuprous oxide in solid content of 4.0 to 25 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 4.0 to 60% by volume.

[0212] Here, the total amount of cuprous oxide and hollow spheres combined is in the range of 15 to 65 volume percent in terms of solid content.

[0213] [Pigments and fillers] The coating composition of the present invention may further contain a pigment and / or an extender.

[0214] The pigment may be any of an inorganic pigment, an organic pigment, or a mixture thereof. An inorganic pigment is 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. The pigment may optionally be surface-treated.

[0215] For the purpose of improving storage stability and improving pigment performance such as rheological properties and dispersibility in the coating composition, various inorganic or organic surface treatments can be used. For example, titanium dioxide can be surface-treated with a silicon compound, a zirconium compound, an aluminum compound, and / or a zinc compound.

[0216] The extender may be a natural mineral or a synthetic material. Examples of inorganic extenders include dolomite, plastolite, 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.

[0217] In addition to the above extenders, the coating composition may further contain reinforcing agents such as flakes and fibers, as described in, for example, WO 00 / 77102.

[0218] The use of zinc oxide is particularly preferred. However, the content in the antifouling composition of the present invention is preferably 15% by volume or less in terms of solid content.

[0219] The total amount of extender and / or pigment present in the composition of the present invention is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, still more preferably 4 to 20% by weight, based on the total weight of the composition. Hollow spheres and biocides are not included here as pigments and / or fillers. The total amount of extender and / or pigment present in the composition of the present invention is in solid content, preferably 1 to 30% by volume, more preferably 2 to 20% by volume, for example 4 to 15% by volume. Those skilled in the art will understand that the contents of extender and pigment vary depending on the particle size distribution, particle shape, surface morphology, affinity between the particle surface and the resin, other components present, and the end use of the coating composition.

[0220] [Other components] The antifouling coating composition according to the present invention may further contain one or more components selected arbitrarily from additives, solvents, and diluents.

[0221] Examples of additives that can be added to the antifouling coating composition include reinforcing agents, rheology modifiers, wetting and dispersing agents, and defoaming agents.

[0222] Examples of rheology modifiers include thixotropic agents, thickeners, and anti-settling agents. Representative examples of rheology modifiers are silica such as fumed silica, organically modified clay, amide wax, polyamide wax, amide derivatives, polyethylene wax, oxidized polyethylene wax, hydrogenated castor oil wax, ethyl cellulose, aluminum stearate, and mixtures thereof. Rheology modifiers that require activation may be added directly to the coating composition and activated during the paint manufacturing process, or may be added to the coating composition in a pre-activated form, such as a solvent paste. Preferably, the rheology modifier is present in the composition of the present invention in an amount of 0 to 5.0% by weight, more preferably 0.2 to 3.0% by weight, still more preferably 0.5 to 2.0% by weight, based on the total weight of the coating composition.

[0223] Dehydrating agents improve the storage stability of antifouling coating compositions. Preferably, the dehydrating agent is a compound that removes moisture and water from the coating composition. This compound is also called a water-capturing agent, 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 anhydrous calcium sulfate, calcium sulfate hemihydrate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves, 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.

[0224] Suitable 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 tetraethoxysilane is particularly preferred.

[0225] Preferably, the dehydrating agent is added to the composition of the present invention in an amount of 0 to 5% by weight, more preferably 0.5 to 2.5% by weight, for example 1.0 to 2.0% by weight, based on the total weight of the composition.

[0226] It is highly preferable that the antifouling composition contains a solvent. This solvent is preferably volatile and preferably organic. 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 monomethyl 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.

[0227] Suitable solvents are aromatic hydrocarbon solvents, ketone solvents, and ether alcohols, particularly xylene and mixtures of aromatic hydrocarbons.

[0228] The amount of solvent is preferably as low as possible. The solvent content may be up to 45% by weight of the composition, preferably up to 40% by weight, for example up to 35% by weight, but may be as low as 15% by weight or less, for example 10% by weight or less. Furthermore, those skilled in the art will understand that some raw materials contain solvents and contribute to the total solvent content specified above, and that the solvent content will vary depending on other components present and the end use of the coating composition.

[0229] Alternatively, the coating can be dispersed in an organic non-solvent or aqueous dispersion containing the film-forming components in the coating composition.

[0230] [Coating composition] The antifouling coating composition of the present invention preferably has a solid content of more than 45% by volume, preferably more than 50% by volume, preferably more than 55% by volume, for example, 60% by volume.

[0231] The antifouling coating composition has a volatile organic compound (VOC) content of less than 500 g / L, more preferably less than 420 g / L, more preferably less than 400 g / L, for example less than 380 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. The pigment volume concentration (PVC) of the formulation containing hollow spheres is preferably 35% to 80%, for example, 40% to 65%.

[0232] The density of the paint is preferably 1 g / cm³. 3 ~1.8g / cm 3 For example, the density is 1.4 to 1.6, and the coating density is preferably 1 g / cm³. 3 ~2.6, preferably 1.2 g / cm³ 3 ~2.0g / cm 3 That is the case.

[0233] The antifouling coating composition of the present invention may have a viscosity of 150 to 2000 cP, for example, 200 to 800 cP, when measured at 23°C using a cone-plate viscometer (in accordance with ISO 2884-1:2006).

[0234] The antifouling coating composition can be prepared by 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 raw material and mixing equipment suppliers.

[0235] [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). The object surface is typically the hull of a ship or the surface of a fixed marine object such as an oil platform or buoy. The coating composition can be applied by any convenient means, for example, by painting (e.g., with a brush or roller) or spraying the coating onto the object. Typically, the surface needs to be isolated from seawater to enable coating. The coating can be applied in the manner conventionally known in the art.

[0236] 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, plastic, composite, fiberglass, or carbon fiber), the entire coating system typically includes one or two layers of 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.

[0237] When applying an antifouling coating composition in two or more coats, the different coats may be antifouling coatings of different compositions.

[0238] The antifouling coating layer may vary in type, biocide amount, binder composition, and / or polishing rate.

[0239] In certain cases, for example in fitting-out applications, it is preferable to apply antifouling coating compositions having different polishing rates to respective coating layers. At this time, it is preferable that the polishing rate of the outermost layer is higher than that of the layer located thereunder.

[0240] The coating film formed from the coating composition of the present invention can also be cleaned by, for example, a robot, a remotely operated vehicle (ROV), or a manually operated device. Cleaning may be performed after fouling has occurred or may be performed to prevent fouling. Underwater cleaning can be carried out using, for example, mechanical means (brush, squeegee, etc.), high-pressure water, ultraviolet rays, lasers, and ultrasonic waves. An example of a robot used for underwater cleaning is described in International Publication No. 2019170888, International Publication No. 2020207791, and International Publication No. 2020207792. An example of a cleaning setting applicable when using a brush is described in International Publication No. 2021180588.

[0241] Hereinafter, the present invention will be described with reference to non-limiting examples.

[0242] [Examples] [Materials and Methods] [Measurement of Viscosity of Polymer Solution] The viscosity of the polymer was measured at a rotational speed of 12 rpm using a Brookfield DV-I Prime digital viscometer equipped with an LV-2 (62) spindle in accordance with ASTM D2196 test method A. The polymer solution was adjusted to 23.0°C ± 0.5°C before measurement.

[0243] [Measurement of Content of Non-Volatile Substances in Polymer Solution] The non-volatile substance (NVM) content of polymer solutions was measured in accordance with ISO 3251:2019. A 0.5g ± 0.1g test sample was taken and dried in a draft 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.

[0244] <Measurement of polymer molecular weight distribution> The properties of the polymer were determined by gel permeation chromatography (GPC). The molecular weight distribution (MWD) was measured using an Omnisec Resolve and Reveal system (Malvern) with two PLgel 5μm Mixed-D columns (Agilent) connected in series. Column calibration was performed using conventional calibration methods with narrow-distribution polystyrene standards. The analytical conditions were as follows:

[0245] [Table 1]

[0246] Samples were prepared by dissolving a polymer solution equivalent to 25 mg of dry polymer in 5 ml of THF. The samples were kept at room temperature for at least 3 hours before sampling for GPC measurement. Before analysis, the samples were filtered through a 0.45 μm nylon filter. The weight-average molecular weight (Mw) and polydispersity index (PDI) expressed as Mw / Mn are reported.

[0247] <Measurement of glass transition temperature> The glass transition temperature (Tg) was determined by differential scanning calorimetry (DSC) measurement. DSC measurements were performed using a TA Instruments DSC Q200, with an empty pan as a reference, by heating-cooling-heating within the temperature range of -80°C to 150°C at a heating rate of 10°C / min and a cooling rate of 10°C / min. Data were processed using Universal Analysis software (TA Instruments). The inflection point of the glass transition range, as defined in ISO 11357-2:2020, during the second heating cycle is reported as the polymer's Tg.

[0248] Samples were prepared by dropping and spreading each polymer solution onto individual glass panels using an applicator with a gap size of 100 μm. The glass panels were dried overnight at room temperature, and then dried in a ventilated heating chamber at 50°C for 24 hours. The dried polymer material was scraped from the glass panels, and approximately 10 mg of the dried polymer material was transferred to an aluminum pan. Before measurement, this pan was sealed with an airtight lid.

[0249] <Measurement of paint viscosity using a cone-plate viscometer> The viscosity of the antifouling coating composition was determined in accordance with 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.

[0250] <Raft antifouling performance test in Singapore> This test used polyvinyl chloride (PVC) panels (20 x 30 cm) that had been degreased with a solvent and sanded to improve coating adhesion. Each panel was primed with commercially available Tiecoat (Safeguard Plus, a two-component polyamide-curable vinyl epoxy coating, manufactured by Chokwang Jotun Ltd. (South Korea)) using an airless spray. After drying at room temperature for a minimum of 24 hours, an intermediate coat was applied with commercially available antifouling paint (SeaQuantum Ultra S, a one-component silyl acrylate antifouling paint, 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.

[0251] After drying at room temperature for at least 24 hours, the antifouling coating composition of the present invention was directly applied as a topcoat to the pre-coated PVC panels using a film applicator with a gap size of 300 μm. The test area of ​​the coating film was approximately 6 cm x 20 cm. The edges of each panel were sealed with a commercially available antifouling product.

[0252] Each panel was exposed on a raft installed in Singapore. The panels were submerged to a depth of 0.5–1.5 m below the sea surface. Micro-fouling organisms such as biofilms and slime, which could be easily removed by hand, were not included in the evaluation. Each panel was evaluated by visual inspection and rated according to the following scale. The score is based on the total area of ​​animal fouling, including barnacles, tubifex worms, mussels, sponges, and hydroids.

[0253] [Table 2]

[0254] Unless otherwise specified, antifouling performance is based on a 4-month exposure test in Singapore.

[0255] <Calculation of volatile organic compound (VOC) content in antifouling coating compositions> The volatile organic compound (VOC) content of the antifouling coating composition is calculated in accordance with ASTM D5201-01.

[0256] <Measuring water absorption rate by gravimetric method in freshwater / deionized water> The water absorption rate of the coating film was measured by gravimetric method. The coating was applied to pre-weighed and numbered sandblasted glass panels (5.0 × 7.5 cm) using a film applicator with a gap size of 300 μm. The coating film was dried for at least one day under normal environmental conditions, then overnight at 50°C, and finally dried for 24 hours in a vacuum desiccator. After drying, the coated glass panels were weighed and immersed in a container filled with distilled water. During measurement, the panel and coating surface were rapidly dried with compressed air. The panel was then weighed (m²). そのまま After that, it was dried for 2 days under normal environmental conditions, held in a vacuum desiccator for 24 hours, and then reweighed (m 乾燥 The difference in weight before and after drying relative to the dry weight of the coating after exposure is expressed as the water absorption rate (%).

[0257] Water absorption amount (weight%) = (m そのまま -m 乾燥 ) / (m 乾燥 -m パネルのみ ) × 100

[0258] Measurements were taken at 5 weeks and 15 weeks, and the final measurements are shown in the table. A water absorption rate of less than 50% by weight at 15 weeks is considered acceptable.

[0259] <Accelerated cracking test of coating film> Polyvinyl chloride (PVC) panels were coated with a suitable anti-corrosion primer. The anti-fouling coating was applied to the panels using a film applicator with a gap size of 800 μm. The panels were dried at 52°C for 72 hours and then immersed in 40°C seawater (SW). Panels were removed and evaluated at regular intervals. After drying at room temperature, the panels were evaluated for cracks visually and under 10x magnification, and then again after drying at 52°C for 24 hours. The panels were then re-immersed. The evaluation results after drying at 52°C are shown in the table along with examples of coatings. The panel evaluated the results as follows:

[0260] [Table 3]

[0261] <Accelerated blistering test of coating film> Polyvinyl chloride (PVC) panels were coated with a suitable anti-corrosion primer. The anti-fouling coating was applied to the panels using a film applicator with a gap size of 800 μm. The panels were dried at 52°C for 72 hours, and then immersed in fresh water (FW) at 30°C. Panels were removed and evaluated at regular intervals. The panels were visually inspected for blistering at room temperature. The panels were then re-immersed. The evaluation results, along with examples of coatings, are shown in the table. The panel evaluated the results as follows:

[0262] [Table 4]

[0263] <Measurement of polishing speed of antifouling coatings using a rotating disc in seawater> The polishing rate was determined by measuring the amount by which the coating thickness decreased over time. A polyvinyl chloride (PVC) disc was used for this test. The coating composition was applied to the disc as radial stripes using a film applicator with a gap size of 600 μm. The thickness of the dried coating was measured using a surface profiler. Typically, the initial dried film thickness depends on the solid content and application speed of the applied antifouling coating composition. The typical initial film thickness of the coating tested in this example was 220 ± 20 μm. The PVC disc was mounted on a shaft and rotated in a container through which seawater flowed. The shaft rotation speed was set to simulate an average speed of 16 knots on the disc. The seawater (SW) used was filtered natural seawater temperature-adjusted to 30°C ± 2°C. The PVC disc was removed at regular intervals and the film thickness was measured. After washing, the disc was dried overnight at room temperature before the film thickness was measured. The results are shown as the amount of coating thickness reduction, i.e., the difference between the initial film thickness and the film thickness at each measurement point. A coating is considered fully polished if a thin, non-abrasive leaching layer (usually 10-20 μm thick) remains on the surface, or if the film is completely removed by polishing. In the table, this is indicated as PT (if applicable).

[0264] <Measurement of swelling degree in freshwater> The degree of swelling in freshwater (FW) was determined by measuring the change in coating film thickness over time. Polyvinyl chloride (PVC) discs were used for this test. The coating composition was applied to the disc as radial stripes using a film applicator with a gap size of 300 μm. The film thickness of the dried coating was measured using a surface profiler. Typically, the initial dried film thickness depends on the solid content and application rate of the applied antifouling coating composition. The typical initial dried film thickness of the coating tested in the examples was 100 ± 10 μm. The PVC discs were immersed in freshwater heated to 30°C ± 2°C. The PVC discs were removed after 4 and 8 weeks, and the film thickness was measured. After washing, the discs were dried overnight at room temperature before the film thickness was measured again. The results are shown as the difference between the initial film thickness and the film thickness at each measurement point. An increase in film thickness was observed when the coating swelled. Since the solid content and dry film thickness (DFT) differ for each coating, the degree of swelling was evaluated as the swelling rate (%) relative to the dry film thickness. Swelling was evaluated according to the following criteria.

[0265] [Table 5]

[0266] <Example of binder fabrication> <Procedure for preparing 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 90.0 parts n-butyl acrylate, 7.0 parts n-butyl methacrylate, 3.0 parts methacrylic acid, and 1.40 parts t-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 t-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".

[0267] Copolymer solution A1 had the following properties. NVM66.0wt%; Viscosity 369cP; Mw 22.1k; PDI 2.93; Tg -41℃

[0268] <Preparation procedure for copolymer solution A2> 48.5 parts xylene and 11.5 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 95°C. A premix was prepared consisting of 40.0 parts 2-methoxyethyl acrylate, 60.0 parts methyl methacrylate, and 1.60 parts 2,2'-azobis(2-methylbutyronitrile). This premix was added to the reaction vessel at a constant rate over 2.5 hours using a metering pump under a nitrogen atmosphere. After reacting for a further 1 hour, a boost initiator solution of 0.40 parts 2,2'-azobis(2-methylbutyronitrile) and 7.5 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 hour, and then cooled to room temperature. All "parts" mentioned above are "parts by weight".

[0269] Copolymer solution A2 had the following properties. NVM55.9wt%; Viscosity 1515cP; Mw 24.5k; PDI 2.37; Tg 29℃

[0270] <Procedure for preparing copolymer solution S1> 60.0 parts xylene were added to a temperature-controlled reaction vessel equipped with a stirrer, condenser, nitrogen inlet, and supply port. The reaction vessel was heated and maintained at a reaction temperature of 85°C. A premix was prepared consisting of 50.0 parts triisopropylsilyl methacrylate, 30.0 parts 2-methoxyethyl methacrylate, 10.0 parts n-butyl acrylate, 10.0 parts methyl methacrylate, and 1.00 part 2,2'-azobis(2-methylbutyronitrile). This premix was added to the reaction vessel at a constant rate over 2 hours using a metering pump under a nitrogen atmosphere. After reacting for a further 30 minutes, a boost initiator solution of 0.20 parts 2,2'-azobis(2-methylbutyronitrile) and 7.4 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. Subsequently, the reactor was heated to 110°C and maintained at that temperature for 1 hour. Finally, the reactor was cooled to room temperature. All "parts" mentioned above refer to "parts by weight".

[0271] The copolymer solution S1 had the following properties. NVM60.0wt%; Viscosity 1790cP; Mw 42.3k; PDI 3.11; Tg 37℃

[0272] Copolymer solutions S2 and S3 were prepared using the same process as described above for copolymer solution S1.

[0273] <Procedure for preparing copolymer solution S4> 41.6 parts of methyl amyl ketone (2-heptanone) were added to a temperature-controlled reaction vessel equipped with a stirrer, 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 55.0 parts of triisopropylsilyl methacrylate (TIPSMA), 20.0 parts of n-butyl acrylate (n-BA), 25.0 parts of methyl methacrylate (MMA), and 1.85 parts of 2,2'-azobis(2-methylbutyronitrile) (AMBN). This premix was added to the reaction vessel at a constant rate over 3.0 hours using a metering pump under a nitrogen atmosphere. Next, a boost initiator solution consisting of 0.25 parts of 2,2'-azobis(2-methylbutyronitrile) and 2.2 parts of methyl amyl ketone was supplied to the reaction vessel at a constant rate over 10 minutes. The reaction vessel was maintained at the reaction temperature for a further 2.0 hours. Finally, the reactor was cooled to room temperature. All "parts" mentioned above refer to "parts by weight".

[0274] The copolymer solution S4 had the following properties. NVM69.4wt%; Viscosity 4099cP; Mw 16.3k; PDI 2.20; Tg 36℃

[0275] The ratios of each component in examples A1, A2, and S1-S4 are shown in Table 2 below.

[0276] <Preparation of zinc rosinate solution> 150 parts of a Portuguese gum rosin solution (containing 60% rosin in xylene; acid value of the solution 110 mg KOH / g), 12 parts of zinc oxide, and 8 g of xylene were placed in a temperature-controlled reaction vessel equipped with a stirrer and reflux condenser. The reaction mixture was slowly heated to 70°C and maintained at that temperature for 2 hours. The reaction contents were cooled to room temperature while stirring to obtain a homogeneous solution.

[0277] The zinc rosinate solution contains 62.1% by weight of non-volatile substances and has a density of 1.04 g / cm³. 3 That was the case. Table 3 shows the other components used in the examples. Table 4 shows the hollow spheres used in the examples.

[0278] [Table 6]

[0279] [Table 7]

[0280] The present invention uses the following hollow spheres. The properties of the hollow spheres are described, for example, in the technical data sheet from the supplier.

[0281] [Table 8]

[0282] <General paint preparation protocol> The ingredients were mixed in the ratios shown in Tables 5 to 12. The mixing order of the raw materials and the preparation of the premix of the selected raw materials were carried out according to the guidelines of the raw material supplier. The raw materials, with glass beads (approximately 3-4 mm in diameter) added, were dispersed and crushed in a 250 ml paint can using a vibrating shaker.

[0283] Hollow spheres can be added before or after the grinding process, but it was confirmed that their presence during the grinding process improved mixability and grinding fineness. When comparing paint samples with and without added hollow spheres, no signs of sphere failure were observed. Adding hollow spheres after grinding did not affect storage stability compared to adding them before grinding (if the spheres were to break, an increase in viscosity over time would be expected). When both wet and dry paint films were observed under a microscope (70x magnification), the spheres remained intact. In these examples, hollow spheres were added before grinding.

[0284] [Table 9] JPEG2026522943000015.jpg248132

[0285] [Table 10]

[0286] [Table 11]

[0287] [Table 12]

[0288] [Table 13]

[0289] [Table 14]

[0290] [Table 15]

[0291] [Table 16]

[0292] <Result> Table 5: Comparative Example 1 shows a high copper content, containing approximately 50% by weight of cuprous oxide, similar to several commercially available antifouling coatings. This corresponds to 30% by volume (%SV) of cuprous oxide with silyl copolymer and rosinic acid as binders.

[0293] In Examples 1 to 6, the total %SV of cuprous oxide and hollow spheres was kept at the same level as the comparative example (30 vol%), while the ratio of spheres to cuprous oxide was varied from 0.2 to 5. As expected, the viscosity of the paint decreased as the content of hollow spheres increased. The advantage obtained here is that the introduction of hollow spheres makes it possible to increase the solid content volume (leading to a reduction in VOCs). Despite the decrease in copper content, good to excellent levels of antifouling performance were maintained, as is evident from the 4-month raft exposure test in Singapore. In none of the examples in Table 5 were any undesirable effects observed during immersion in freshwater or seawater, and no significant swelling, blistering, or cracking was observed. Example 6 demonstrates that hollow ceramic spheres can be used as well as glass spheres.

[0294] Table 6: It is possible to increase the sum of the %SV of the spheres and the %SV of cuprous oxide while maintaining excellent antifouling performance and good freshwater / seawater properties. These examples demonstrate that VOC reduction is possible by increasing the solid content volume in the paint formulation while decreasing viscosity. These examples show that it is possible to have hollow glass spheres make up to 50%, and in some cases up to 60%, of the solid content volume. Comparative Example 2 shows that the degree of fouling increases when the hollow sphere content is too high.

[0295] Tables 7 and 8: Multiple grades of cuprous oxide are available, with larger or smaller particle sizes, while still maintaining the desired antifouling performance. Combinations with the biocide medetomidine for barnacle fouling are also shown. As is evident from Example 22, zinc oxide cannot be used alone as a substitute for cuprous oxide because its viscosity increases when used in large quantities. Experiments have shown that both rosin acid and metal rosin salts are usable in the present invention, with or without the addition of zinc oxide to the formulation (Examples 23 and 24). The zinc oxide level can be varied, even to less than 1% by weight in the formulation. Different hollow spheres (glass or ceramic) are available (Example 19). In Example 25, silyl copolymer S4 was used, the solvent was changed to MAK, and the VOC was set to 300 g / L.

[0296] Table 9: This result shows silyl acrylate copolymers combined with (meth)acrylate copolymers in addition to rosin. Good antifouling performance can be maintained even when the cuprous oxide content is reduced. Comparative Example 3 is a formulation example with a cuprous oxide %SV of 20% and no hollow spheres. The inventive example shows performance equivalent to this example. Comparative Example 4 did not contain cuprous oxide, and after one month of raft exposure in Singapore, the coating became completely fouled. Therefore, the use of cuprous oxide is essential.

[0297] Tables 10-12: These results demonstrate that antifouling performance is maintained even when using various types of hollow spheres (treated / untreated hollow glass spheres and hollow ceramic spheres). In these examples, the cuprous oxide level in the formulation was maintained at 35% by weight. As is evident from the amount of polishing of the rotating disc after 21 months, the choice of sphere does not significantly affect the polishing speed.

[0298] In the examples of this invention, the ratio of the solid content volume of the hollow sphere to the solid content volume of cuprous oxide ranges from 0.1:1 to 10:1, demonstrating a wide range of performance.

Claims

1. (A) A binder comprising a (meth)acrylic copolymer (i) containing a silyl ester group, (B) Cuprous oxide in a solid content of 2.0 to 30 volume%, for example, 5.0 to 20 volume%, (C) An antifouling coating composition containing 2.0 to 65 volume percent, for example 10 to 55 volume percent, of hollow spheres in terms of solid content.

2. The aforementioned hollow sphere is an antifouling coating composition according to any one of the preceding claims, comprising ceramic or glass.

3. The antifouling coating composition according to any one of the preceding claims, wherein the total amount of the cuprous oxide and the hollow spheres combined is in the range of 15 to 70 volume percent, for example 15 to 60 volume percent, in terms of solid content based on the entire antifouling coating composition.

4. The antifouling coating composition according to any one of the preceding claims, wherein the hollow sphere is a hollow microsphere, preferably having a d50 of 10 to 100 μm.

5. The antifouling coating composition according to any one of the preceding claims, wherein the (meth)acrylic copolymer (i) containing the silyl ester group contains a triisopropylsilyl (meth)acrylate monomer.

6. The (meth)acrylic silyl ester copolymer (i) is (a) Equation (I) 【Transformation 6】 [In the formula, R 1 is H or CH 3 And, R 2 Each of them is independent of C 1 ~C 8 Selected from hydrocarbyl groups, preferably triisopropylsilyl acrylate or triisopropylsilyl methacrylate. Silyl ester monomers, (b) Formula (II) 【Transformation 7】 [Wherein, R 4 is H or CH 3 , R 5 is C 1 to C 20 hydrocarbyl substituent, preferably C 1-10 alkyl substituent.] 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 (meth)acrylic copolymer (i) containing the silyl ester group contains one or more of 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, and tetrahydrofurfuryl acrylate.

8. The antifouling coating composition according to any one of the preceding claims, wherein the (meth)acrylic copolymer (i) containing the silyl ester group contains one or more of methyl methacrylate and n-butyl (meth)acrylate.

9. The antifouling coating composition according to any one of the preceding claims, wherein the binder (A) further comprises a monocarboxylic acid or a metal salt thereof (ii), preferably rosin or a metal salt thereof.

10. The binder (A) further contains a meth(acrylic) polymer (iii), The aforementioned meth(acrylic) polymer (iii) has a Tg of less than 10°C and contains 0.5 to 10% by weight of (meth)acrylic acid monomer and formula (II) 【Transformation 8】 [In the formula, R 4 is H or CH 3 And R 5 C 1 ~C 20 Hydrocarbyl substituents, preferably C 1-10 Alkyl substituents, for example, C 1-8 It is an alkyl group. An antifouling coating composition according to any one of the preceding claims, comprising a (meth)acrylate monomer.

11. The binder (A) further contains a meth(acrylic) polymer (iv), The meth(acrylic) polymer (iv) has a glass transition temperature (Tg) of at least 10°C and comprises at least one monomer of formula (II) as defined in claim 10, and optionally, formula (IV) 【Chemistry 9】 [In the formula, R 8 is H or CH 3 And R 9 C contains at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom. 3-40 substituents, for example, C 3 ~C 20 It is a substituent, or R 9 This represents a poly(alkylene glycol) group. An antifouling coating composition according to any one of the preceding claims, comprising one or more monomers.

12. The antifouling coating composition according to any one of the preceding claims, further comprising copper pyrithione, zinc pyrithione, zineb, and at least one additional biocide such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, preferably copper pyrithione.

13. An antifouling coating composition according to any one of the preceding claims, comprising a silane such as tetraethoxysilane.

14. (A) A binder comprising a (meth)acrylic copolymer (i) containing a silyl ester group, (B) Cuprous oxide in solid content of 5.0 to 25 volume percent, (C) Contains hollow spheres with a solid content of 5.0 to 60% by volume, The antifouling coating composition according to any one of the preceding claims, wherein the total amount of cuprous oxide and the hollow spheres combined is in the range of 15 to 65 volume percent in terms of solid content.

15. Liquid acyclic saturated C 12-24 Monocarboxylic acid or its salt, or liquid acyclic branched C 12-24 An antifouling coating composition according to any one of the preceding claims, containing less than 1.0% by weight of a monocarboxylic acid or a salt thereof, or, for example, not containing such a substance.

16. An antifouling coating composition according to any one of the preceding claims, comprising only one (meth)acrylic copolymer containing a silyl ester group.

17. 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 described in any one of claims 1 to 16.

18. A substrate coated with the antifouling coating composition according to any one of claims 1 to 16.

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