Antifouling paint composition

Abstract

The antifouling coating composition comprises (A) a binder comprising (i) a (meth)acrylic copolymer containing 0.5 to 10% by weight of (meth)acrylic acid monomers relative to the total weight of monomers in the (meth)acrylic copolymer, and / or (ii) a metal-containing (meth)acrylic copolymer containing a metal selected from Zn or Cu; (B) 1.0 to 25% by volume of cuprous oxide in terms of solids; and (C) 1.0 to 65% by volume of hollow spheres in terms of solids.

Description

[Technical Field]

[0001] The present invention relates to an antifouling coating composition containing a (meth)acrylic copolymer and / or a metal-containing (meth)acrylic copolymer containing a (meth)acrylic acid monomer, cuprous oxide, and hollow spheres. The composition may further contain a silyl ester 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. [Overview of the Initiative] [Problems that the invention aims to solve]

[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.

[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 describing paint compositions that reduce the amount of cuprous oxide using hollow spheres.

[0011] British Patent No. 2099444 describes an antifouling composition comprising a binder resin, a biocide, a solvent, and hollow particles. The object 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.

[0012] 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.

[0013] The present invention aims to provide a low-density antifouling coating composition that offers good antifouling performance and is more environmentally friendly, sustainable, 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.

[0014] [Overview of the prefecture] In one aspect, the present invention is (A) Binder, (i) A (meth)acrylic copolymer containing 0.5 to 10% by weight, for example 0.5 to 5.0% by weight, of (meth)acrylic acid monomers relative to the total weight of monomers in the (meth)acrylic copolymer, and / or (ii) A binder comprising a metal-containing (meth)acrylic copolymer containing a metal selected from Zn or Cu, (B) Cuprous oxide in solid content of 1.0 to 25 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 1.0 to 65% by volume.

[0015] Viewed in another aspect, the present invention is (A) Binder, (i) A binder comprising a (meth)acrylic copolymer containing 0.5 to 10% by weight, for example 0.5 to 5.0% by weight, of (meth)acrylic acid monomers relative to the total weight of monomers in the (meth)acrylic copolymer, (B) Cuprous oxide in solid content of 1.0 to 25 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 1.0 to 65% by volume.

[0016] Viewed in another aspect, the present invention is (A) Binder, (i) A (meth)acrylic copolymer containing 0.5 to 10% by weight, for example 0.5 to 5.0% by weight, of (meth)acrylic acid monomers relative to the total weight of monomers in the (meth)acrylic copolymer, and / or (ii) Metal-containing (meth)acrylic copolymer containing a metal selected from Zn or Cu, (iii) A binder comprising a monocarboxylic acid or a metal salt thereof, (B) Cuprous oxide in solid content of 1.0 to 25 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 1.0 to 65% by volume.

[0017] Viewed in another aspect, the present invention is (A) Binder, (i) A (meth)acrylic copolymer containing 0.5 to 10% by weight, for example 0.5 to 5.0% by weight, of (meth)acrylic acid monomers relative to the total weight of monomers in the (meth)acrylic copolymer, and / or (ii) A binder comprising a metal-containing (meth)acrylic copolymer containing a metal selected from Zn or Cu, (B) 7.0-40% by weight of cuprous oxide, (C) Provides an antifouling coating composition containing 0.2 to 12% by weight of hollow spheres.

[0018] In one aspect, the present invention is (A) Binder, (i) A (meth)acrylic copolymer containing 0.5 to 10% by weight, for example 0.5 to 5.0% by weight, of (meth)acrylic acid monomers relative to the total weight of monomers in the (meth)acrylic copolymer, and / or (ii) Metal-containing (meth)acrylic copolymer containing a metal selected from Zn or Cu, (iii) A binder comprising a monocarboxylic acid or a metal salt thereof, (B) 7.0-40% by weight of cuprous oxide, (C) Provides an antifouling coating composition containing 0.2 to 12% by weight of hollow spheres.

[0019] Viewed in another aspect, the present invention is (A) Binder, (i) A (meth)acrylic copolymer containing 0.5 to 10% by weight, for example 0.5 to 5.0% by weight of (meth)acrylic acid monomer relative to the total weight of monomers in the (meth)acrylic copolymer, and (iv) A binder containing (meth)acrylic polymer, (B) Cuprous oxide in solid content of 1.0 to 25 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 1.0 to 65% by volume.

[0020] Viewed in another aspect, the present invention is (A) Binder, (i) A (meth)acrylic copolymer containing 0.5 to 10% by weight, for example 0.5 to 5.0% by weight, of (meth)acrylic acid monomer relative to the total weight of monomers in the (meth)acrylic copolymer. (iii) monocarboxylic acids or their metal salts, (iv) A binder containing (meth)acrylic polymer, (B) Cuprous oxide in solid content of 1.0 to 25 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 1.0 to 65% by volume.

[0021] 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.

[0022] [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.

[0023] 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.

[0024] 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.

[0025] As used herein, the term "alkyl" refers to a saturated linear group, a saturated branched group, or a saturated cyclic group.

[0026] As used herein, the term "cycloalkyl" refers to a cyclic alkyl group.

[0027] 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.

[0028] The term "(meth)acrylic polymer" refers to a polymer containing repeating units derived from (meth)acrylate monomers. Generally, a "(meth)acrylic polymer" will contain at least 50% by weight of repeating units derived from (meth)acrylate monomers, i.e., acrylate monomers and / or methacrylate monomers.

[0029] 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.

[0030] The term “binder” defines a portion of composition (A) comprising a (meth)acrylic copolymer and / or a metal-containing (meth)acrylic copolymer containing a (meth)acrylic acid monomer, 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 a binder comprising a (meth)acrylic copolymer (i) and / or a metal-containing (meth)acrylic copolymer group (ii) together with any monocarboxylic acid (iii) and optionally a (meth)acrylic polymer (iv), as defined herein.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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: %SV = (Volume of solid components) / (Total volume of wet paint) × 100

[0035] Solids volume is a parameter commonly used in the paint industry.

[0036] The term "volatile organic compound (VOC)" refers to compounds with a boiling point of 250°C or lower at standard atmospheric pressure (1 atm).

[0037] The terms "antifouling agent" or "biocide" refer to a bioactive compound or mixture of bioactive compounds that prevents the attachment and / or growth of marine organisms on a surface.

[0038] [Detailed description of the invention] The present invention relates to a novel antifouling coating composition containing a binder (A). The binder (A) contains (i) a (meth)acrylic copolymer containing 0.5 to 10% by weight, preferably 0.5 to 5.0% by weight, of (meth)acrylic acid monomer, and / or (ii) a (meth)acrylic copolymer containing a Zn-containing group or a Cu-containing group.

[0039] The binder (A) preferably further contains (iii) a monocarboxylic acid or a metal salt thereof, and optionally (iv) a (meth)acrylic polymer.

[0040] These binder components are used in combination with cuprous oxide and hollow spheres in a specific solid content volume ratio to form the antifouling coating composition of the present invention.

[0041] The use of hollow spheres in coating compositions reduces the amount of cuprous oxide, resulting in more 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.

[0042] 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 significant. Reducing the coating weight allows for a reduction in the fuel costs of such vessels.

[0043] 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. 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.

[0044] [Binder (A)] The binder (A) of the coating composition of the present invention contains (i) a (meth)acrylic copolymer containing 0.5 to 10% by weight, for example 0.5 to 5.0% by weight, of (meth)acrylic acid monomer, and / or (ii) a metal-containing (meth)acrylic copolymer containing a metal selected from Zn or Cu.

[0045] The binder (A) preferably further contains (iii) a monocarboxylic acid or a metal salt thereof, and optionally (iv) an (meth)acrylic polymer. In a preferred embodiment, binder A contains (i) a (meth)acrylic copolymer containing 0.5 to 10% by weight of (meth)acrylic acid monomer.

[0046] In a second preferred embodiment, binder A contains (ii) a metal-containing (meth)acrylic copolymer containing a metal selected from Zn or Cu.

[0047] In a third preferred embodiment, binder A contains (i) a (meth)acrylic copolymer containing 0.5 to 10% by weight of (meth)acrylic acid monomer, and (iii) a monocarboxylic acid or a metal salt thereof.

[0048] In a fourth preferred embodiment, binder A contains (i) a (meth)acrylic copolymer containing 0.5 to 10% by weight of (meth)acrylic acid monomer, (iii) a monocarboxylic acid or a metal salt thereof, and (iv) a (meth)acrylic polymer.

[0049] The (meth)acrylic polymers (i), (ii), and (iv) of the present invention contain repeating units derived from (meth)acrylic monomers. Preferably, the (meth)acrylic polymers (i), (ii), and (iv) contain at least 50% by weight of repeating units derived from (meth)acrylic monomers, i.e., acrylic monomers and methacrylic monomers.

[0050] More preferably, the (meth)acrylic polymers (i), (ii), and (iv) contain 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 the (meth)acrylic monomer.

[0051] In one embodiment, (meth)acrylic polymers (i), (ii), and (iv) contain 100% by weight of structural units derived from (meth)acrylic monomers, i.e., they do not contain any other types of monomers. Therefore, the term (meth)acrylic monomer encompasses (meth)acrylic acid and (meth)acrylic esters.

[0052] [(meth)acrylic copolymer(i)] The (meth)acrylic copolymer (i) contains (meth)acrylic acid monomer (a1). Suitable (meth)acrylic acid monomer (a1) is methacrylic acid or acrylic acid. The (meth)acrylic copolymer (i) preferably contains (meth)acrylic acid monomer (a1) in an amount of 0.5 to 5.0% by weight, preferably 1.0 to 4.0% by weight.

[0053] The high viscosity of (meth)acrylic copolymer (i) means that a larger amount of solvent is required when preparing and applying the paint. This is undesirable due to strict VOC regulations.

[0054] Preferably, the (meth)acrylic copolymer (i) 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.

[0055] Preferably, the (meth)acrylate monomer (a2) is present in the (meth)acrylic copolymer (i), described later, and together with the (meth)acrylic acid monomer (a1) forms a copolymer.

[0056] The (meth)acrylate monomer (a2) preferably constitutes at least 50% by weight, for example at least 75% by weight or at least 80% by weight, particularly 90 to 99.5% by weight, for example 95.0 to 99.5% by weight, of the (meth)acrylic copolymer (i).

[0057] An example of a suitable (meth)acrylate monomer (a2) is represented by formula I.

[0058] [ka]

[0059] In the formula, R 1 is H or CH3, and R 2 C1~C 20 Hydrocarbyl substituents, preferably C 1-10 alkyl substituents, for example, C 1-8 It is an alkyl group.

[0060] R 2 The group may be linear or branched. Most preferably, R 2 This is a methyl, ethyl, propyl, butyl, hexyl, octyl, or decyl group, which may be linear or branched (if possible). An ideal choice is R 2 These are methyl, ethyl, n-propyl, n-butyl, isobutyl, or isooctyl groups.

[0061] Suitable monomers of formula I as monomer (a2) in (meth)acrylic 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.

[0062] Suitable monomers of formula (I) as monomer (a2) in (meth)acrylic copolymer (i) include methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-octyl acrylate, or isooctyl acrylate.

[0063] A mixture of different monomers of formula (I) may be used in the (meth)acrylic copolymer (i). The use of two different monomers of formula (I) is particularly preferred. The use of two different monomers of formula (I) is particularly preferred when used in combination with (meth)acrylic acid.

[0064] Preferably, the (meth)acrylic copolymer (i) contains structural units derived from (meth)acrylic acid monomer (a1) and (meth)acrylate monomer (a2).

[0065] In a preferred embodiment, the (meth)acrylic copolymer (i) 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.

[0066] The (meth)acrylic copolymer (i) may further contain structural units derived from vinyl monomers, such as styrene, vinyl 2-ethylhexanoate, and other ethylenically unsaturated monomers such as vinyl neodecanoate.

[0067] The (meth)acrylic copolymer (i) 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 copolymer (i) preferably has a polydispersity index (PDI) of 1.5 to 5.0.

[0068] The (meth)acrylic copolymer (i) preferably has a Tg of less than 10.0°C, preferably less than 0°C, 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. Preferably, it is a value above -65°C, for example, a value above -55°C.

[0069] The (meth)acrylic copolymer (i) may be provided as a polymer solution, such as a solution in a solvent. The polymer solution is preferably prepared to have a solids content of 30-90% by weight, preferably 40-85% by weight, and more preferably 45-75% by weight.

[0070] The (meth)acrylic copolymer (i) may be present in an amount of 1.0 to 12% by weight, preferably 2.0 to 7.0% by weight, relative to the total weight of the entire coating composition.

[0071] The (meth)acrylic copolymer (i) may be present in an amount of 1.5 to 15% by weight, preferably 2.5 to 10% by weight, based on the total dry weight of the entire coating composition.

[0072] The (meth)acrylic copolymer (i) may be present in the entire coating in an amount of solids of preferably 1.0 to 20 vol%, for example 2.0 to 15 vol%, preferably 3.0 to 12 vol%.

[0073] [Metal-containing (meth)acrylic copolymer (ii) containing Zn or Cu] In a preferred embodiment, the binder A of the coating composition of the present invention contains a metal-containing (meth)acrylic copolymer (ii) containing Zn or Cu.

[0074] (Meth)acrylic copolymers (ii) typically have side chain groups represented by general formula (II).

[0075] [ka]

[0076] In the formula, M represents zinc or copper, and R 3 represents an organic group. Such side chains may be present in the (meth)acrylate monomer.

[0077] Group R 3 is preferably a saturated or unsaturated aliphatic group containing 2 to 50 carbon atoms, preferably 2 to 30 carbon atoms, particularly 2 to 20 carbon atoms, such as a saturated alicyclic group containing 3 to 20 carbon atoms, or R 3 is an aromatic group containing 6 to 18 carbon atoms.

[0078] In a preferred embodiment, the entire O-CO-R 3 group is derived from a monocarboxylic acid such as versatic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, naphthenic acid, etc.

[0079] In another preferred embodiment, the R 3 group contains an ethylenically unsaturated end group. The R 3 group may contain ester bonds, amide bonds, and ether bonds in the carbon chain. Suitable -OCO-R 3 groups may be derived from acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, and 3-(meth)acryloxypropanoic acid.

[0080] The metal-containing (meth)acrylic copolymer (ii) containing Zn or Cu may contain a structural unit derived from a monomer a3 containing Zn or Cu. Examples of suitable metal-containing (meth)acrylate monomers (a3) are represented by the general formula (III).

[0081]

Chemical formula

[0082] In equation (III), M represents copper or zinc. R 4 R is a monovalent group having an ethylenically unsaturated group at its terminal end. 4 It preferably contains 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms, and even more preferably 2 to 10 carbon atoms. 4 It may contain an ester group, an amide group, or an ether group in its carbon chain.

[0083] Appropriate O-CO-R 4 Examples of groups include those derived from acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, and 3-(meth)acryloxypropanoic acid. Preferred O-CO-R 4 The base is derived from acrylic acid and methacrylic acid.

[0084] R 5 R is a monovalent organic group containing 1 to 30 carbon atoms. 5 It does not contain an ethylenically unsaturated group at its terminal end. 5 Examples include aliphatic hydrocarbon groups containing 1 to 30 carbon atoms, alicyclic hydrocarbon groups containing 3 to 30 carbon atoms, and aromatic hydrocarbon groups containing 6 to 30 carbon atoms. 5 The hydrocarbon group may be linear or branched. 5 The group may contain substituents such as hydroxyl groups. 5 A hydrocarbon chain may be unsaturated as long as there are no unsaturated groups at its terminals.

[0085] Appropriate O-CO-R 5 Examples of groups include monocarboxylic acids such as versatic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, and naphthenic acid. OCO-R derived from abietic acid, versatic acid, or naphthenic acid. 5 The group is preferred, and those derived from abietic acid or versatic acid are most preferred.

[0086] Suitable monomer a3s for formula (III) include zinc 3-(meth)acryloyloxypropionate abietate, zinc 3-(meth)acryloyloxypropionate versatate, zinc (meth)acrylate abietate, zinc (meth)acrylate versatate, zinc (meth)acrylate naphthenate, copper 3-(meth)acryloyloxypropionate abietate, copper 3-(meth)acryloyloxypropionate versatate, copper (meth)acrylate abietate, copper (meth)acrylate versatate, and copper (meth)acrylate naphthenate.

[0087] A suitable example of a metal-containing (meth)acrylate monomer (a3) ​​may be represented by general formula (IV).

[0088] [ka]

[0089] In the formula, M represents copper or zinc, and each R 6 R is independently selected from monovalent groups having an ethylenically unsaturated group at its terminus. 6 Each R preferably contains 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms, and even more preferably 2 to 10 carbon atoms. 6 It may contain an ester group, an amide group, or an ether group in its carbon chain.

[0090] Appropriate O-CO-R 6 Examples of groups include those derived from acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, and 3-(meth)acryloxypropanoic acid. Preferred O-CO-R 6 The base is derived from acrylic acid and methacrylic acid.

[0091] Suitable monomer a3s for formula (IV) include zinc diacrylate, zinc dimethacrylate, zinc acrylate methacrylate, zinc di(3-acryloyloxypropionate), zinc di(3-methacryloyloxypropionate), zinc di(3-acryloyloxy-2-methylpropionate), zinc di(3-methacryloyloxy-2-methylpropionate), copper diacrylate, copper dimethacrylate, copper acrylate methacrylate, copper di(3-acryloyloxypropionate), copper di(3-methacryloyloxypropionate), copper di(3-acryloyloxy-2-methylpropionate), and copper di(3-methacryloyloxy-2-methylpropionate).

[0092] Zinc diacrylate, zinc dimethacrylate, zinc acrylate methacrylate, copper diacrylate, copper dimethacrylate, and copper acrylate methacrylate are most preferred.

[0093] A mixture of monomers of formula (III) and formula (IV) may be used. The metal-containing (meth)acrylic copolymer (ii) contains monomer (a3) ​​in an amount of preferably 1.0 to 60% by weight, for example 5.0 to 40% by weight, and more preferably 10 to 30% by weight, based on the total weight of monomers in the (meth)acrylic copolymer (ii).

[0094] Preferably, the (meth)acrylate monomer (a5) is present in the (meth)acrylic copolymer (ii), described later, and together with the metal-containing monomer (a3) ​​forms a copolymer.

[0095] The (meth)acrylate monomer (a5) preferably constitutes at least 40% by weight, for example, at least 60% by weight or at least 70% by weight of the metal-containing (meth)acrylic polymer (ii).

[0096] Examples of suitable (meth)acrylate monomers (a5) include those of formula (I) as defined herein above.

[0097] [ka]

[0098] In the formula, R 1 is H or CH3, and R 2 C1~C 20 Hydrocarbyl substituents, preferably C1-C 10 These are alkyl substituents, such as C1-C8 alkyl substituents.

[0099] R 2 The group may be linear or branched. Most preferably, R 2 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 2 These are methyl, ethyl, n-propyl, n-butyl, isobutyl, or isooctyl groups.

[0100] Examples of monomers of formula (I) that are suitable as monomers (a5) in metal-containing (meth)acrylic copolymers (ii) 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, and isobornyl (meth)acrylate.

[0101] Suitable monomers of formula (I) as monomer (a5) in (meth)acrylic copolymer (ii) include methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, or isooctyl acrylate.

[0102] A mixture of different monomers of formula (I) may be used in the (meth)acrylic copolymer (ii).

[0103] Preferably, the (meth)acrylic copolymer (ii) contains structural units derived from a metal-containing monomer (a3) ​​and a (meth)acrylate monomer (a5).

[0104] (Meth)acrylic copolymer (ii) is Alkoxyalkyl (meth)acrylates, such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 3-methoxy-n-propyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, isobutoxybutyl diglycol (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth(me))acrylate, butoxypolyethylene glycol (meth)acrylate, and phenoxypolyethylene glycol (meth)acrylate; Hydroxyalkyl (meth)acrylates, such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate; Glycidyl (meth)acrylate; Organic siloxane group-containing (meth)acrylates; and The material may further contain additional monomers such as vinyl compounds, for example, styrene, α-methylstyrene, vinyl acetate, vinyl benzoate, vinyltoluene, acrylonitrile, vinylpyridine, vinylpyrrolidone, and vinyl chloride. These monomers may be used individually or in combination of two or more.

[0105] The metal-containing (meth)acrylic copolymer (ii) has a copper and / or zinc content that is preferably 0.5 to 25% by weight, more preferably 1 to 20% by weight, based on the weight of the (meth)acrylic copolymer (ii).

[0106] The metal-containing (meth)acrylic copolymer (ii) has an acid value of preferably 30 to 300 mg KOH / g, more preferably 60 to 250 mg KOH / g.

[0107] The (meth)acrylic copolymer (ii) has a number-average molecular weight (Mn) of preferably 500 to 100,000, more preferably 700 to 50,000. The (meth)acrylic copolymer (ii) has a weight-average molecular weight (Mw) of preferably 1,000 to 200,000, more preferably 1,200 to 100,000, and even more preferably 3,000 to 100,000. Mw and Mn can be measured by the method described in the examples.

[0108] (Meth)acrylic copolymer(ii) can be used alone or in combination of two or more (meth)acrylic copolymer(ii) types.

[0109] The antifouling coating composition preferably contains 3 to 50% by weight, more preferably 5 to 20% by weight, and even more preferably 7 to 15% by weight of (meth)acrylic copolymer (ii) based on the total weight of the coating composition.

[0110] [Monocarboxylic acid (iii)] 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).

[0111] The monocarboxylic acid 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.

[0112] 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.

[0113] 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.

[0114] The term resin acid refers to a mixture of monocarboxylic acids present in rosin. Resin acid is also called rosin acid.

[0115] 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. Typical examples of rosin sources include gum rosin, wood rosin, and tall oil rosin. Gum rosin, also known as corohony or corohonium, is particularly preferred. Preferred rosin contains more than 85% resin acid, more preferably more than 90% resin acid.

[0116] Commercially available grade 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 grade 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.

[0117] Typical examples of modified resin acids include dihydroabietic acid, dihydropimaric acid, and tetrahydroabietic acid, as well as modified rosins such as partially hydrogenated rosin, fully hydrogenated rosin, and disproportionated rosin.

[0118] C6~C 20 Typical examples of cyclic monocarboxylic acids include naphthenic acid and trimethylisobutylenecyclohexenecarboxylic acid.

[0119] 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 24Many 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. Preferably, the monocarboxylic acid is rosin, modified rosin, or acyclic C 10 ~C 24 Monocarboxylic acids, C6~C 20 A cyclic monocarboxylic acid, or a metal salt thereof, such as rosin, modified rosin, or a metal salt thereof.

[0120] More preferably, the monocarboxylic acid is rosin or modified rosin. More preferably, the monocarboxylic acid 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.

[0121] 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.

[0122] The amount of monocarboxylic acid or its metal salt present in binder (A) is 15 to 75% by weight, preferably 25 to 60% by weight, based on the total weight of binder (A).

[0123] The final antifouling coating composition of the present invention preferably contains 5.0 to 30% by weight, for example 8 to 25% by weight, of a monocarboxylic acid or its metal salt based on the entire coating composition.

[0124] The final antifouling coating composition of the present invention preferably contains 5.0 to 30% by weight, for example 8 to 25% by weight, of rosin, modified rosin, or a metal salt thereof, based on the entire coating composition.

[0125] The final antifouling coating composition of the present invention contains, based on the entire coating composition, preferably 8.0 to 40% by volume, for example 10 to 35% by volume, of a monocarboxylic acid or its metal salt in terms of solid content.

[0126] When a blend of monocarboxylic acids or their metal salts is used, these proportions are relative to the total amount of monocarboxylic acids present.

[0127] Viewed in another aspect, the present invention is an antifouling coating composition, (A) Binder, (i) A (meth)acrylic copolymer containing 0.5 to 10% by weight of (meth)acrylic acid monomer relative to the total weight of monomers present in the (meth)acrylic copolymer, (iii) comprising a monocarboxylic acid or a metal salt thereof, The above antifouling coating composition contains a binder comprising 8.0 to 40% by volume of component (iii) and 1.0 to 20% by volume of component (i) in terms of solid content, (B) Cuprous oxide in solid content of 2.0 to 25 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 2.0 to 65% by volume.

[0128] [(meth)acrylic polymer (iv)] In one embodiment, the binder A of the coating composition of the present invention may further contain (meth)acrylic polymer (iv), which is different from (meth)acrylic copolymer (i) or (ii).

[0129] In one particularly preferred embodiment, the binder A of the coating composition of the present invention comprises a combination of (meth)acrylic copolymer (i) and (meth)acrylic polymer (iv) as defined herein.

[0130] (Meth)acrylic polymer (iv) does not contain metal-containing monomer units, such as metal (meth)acrylate monomer (a3). (Meth)acrylic polymer (iv) does not contain acid monomer (a1).

[0131] The (meth)acrylic polymer (iv) preferably contains at least one (meth)acrylate monomer (a5).

[0132] Examples of suitable (meth)acrylate monomers (a5) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isodecyl (meth)acrylate, and cyclohexyl (meth)acrylate. 3,5,5-Trimethylcyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, Benzyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, Oligo(ethylene glycol)(meth)acrylate, Poly(ethylene glycol)(meth)acrylate, 2-Methoxyethyl (meth)acrylate, 2-Ethoxyethyl (meth)acrylate, 2-Butoxyethyl (meth)acrylate, 2-(2-Ethoxyethoxy)ethyl (meth)acrylate )Acrylate, Oligo(ethylene glycol) methyl ether (meth)acrylate, Poly(ethylene glycol) methyl ether (meth)acrylate, Methoxycarbonylmethyl (meth)acrylate, Ethoxycarbonylmethyl (meth)acrylate, 2-(2-methoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, 2-(2-ethoxy-2-oxoethoxy)-2-oxoethyl (meth)acrylate, Oligo(oxycarbonylmethyl) Examples include methyl (meth)acrylate, oligo(oxycarbonylmethyl)ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycerol formal (meth)acrylate, isopropylideneglycerol (meth)acrylate, glycerol carbonate (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycidyl (meth)acrylate, and 4-glycidyloxybutyl (meth)acrylate.

[0133] A more preferred example of the (meth)acrylate monomer (a5) is that of formula (I), defined above for the (meth)acrylic copolymer (i).

[0134] Suitable monomers of formula (I) for monomer (a5) include methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, and isobutyl methacrylate.

[0135] A mixture of different monomers (a5) may be used. The (meth)acrylate polymer (iv) is particularly preferably composed of two monomers of formula (I). The (meth)acrylate monomer (a5) may further contain hydrophilic groups. Examples of suitable monomers include those represented by the following formula (V).

[0136] [ka]

[0137] In the formula, R 7 is H or CH3, and R 8 This is a C3-C atom containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom. 40 substituents, for example, C3~C 20 It is a substituent of R 8 represents a poly(alkylene glycol) group.

[0138] (Meth)acrylic copolymer (iv) may contain at least one monomer of formula (V) above. 8 The base is (CH2CH2O) n -R 9 It is 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 an integer in the range of 1 to 5, preferably 1 to 3. Preferably R 8 The formula is (CH2CH2O) n -R 9 It is expressed as, in the formula, R 9 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.

[0139] 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.

[0140] Preferably, the (meth)acrylic polymer (iv) contains one or more of 2-methoxyethyl acrylate or 2-(2-ethoxyethoxy)ethyl acrylate.

[0141] (Meth)acrylic polymer (iv) may contain at least one monomer of the above formula (V), where R 8 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 9 or (CH2CH(CH3)O) m -R 10 It may have R 10 C1~C 10 Hydrocarbyl substituents, preferably C1-C 10 alkyl or C6~C 10is an aryl substituent, and m is an integer in the range of 5 to 25, preferably 5 to 15. 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 suitable monomers have a number average molecular weight (Mn) of 300 to 1000, more preferably 300 to 550.

[0142] (Meth)acrylic polymer (iv) may further contain at least one monomer of the above formula (V). The R 8 group is of the formula (CH2C(O)O) p -R 11 or (CH(CH3)C(O)O) p -R 11 wherein, in the formula, R 11 is a C1-C 10 hydrocarbyl substituent, preferably a C1-C 10 alkyl or a C6-C 10 aryl substituent, and p is an integer in the range of 1 to 10, preferably 1 to 4.

[0143] 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.

[0144] (Meth)acrylic polymer (iv) may contain at least one monomer of the above formula (V), wherein the R 8 group is a cyclic group containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom. More preferably, R 8 is a group W-R containing up to 40 carbon atoms 12And in the formula, R 12 The monomer is a cyclic ether such as oxirane, furan, oxolane, oxane, dioxolane, or dioxane, which may optionally be 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. More preferably are tetrahydrofurfuryl acrylate and isopropylidene glycerol methacrylate.

[0145] The monomer of formula (V) is preferably 2-methoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, or poly(ethylene glycol)methyl ether methacrylate.

[0146] The monomer of formula (V) preferably constitutes at least 15% by weight of the (meth)acrylic polymer (iv). A particularly preferred amount of the monomer of formula (V) 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 (V) is present, their content is related to the total weight fraction of the monomer of formula (V) in the copolymer.

[0147] The monomer of formula (I) preferably constitutes at least 15% by weight of the (meth)acrylic polymer (iv). A particularly preferred amount of the monomer of formula (I) 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 (I) is present, their content is related to the total weight fraction of the monomer of formula (I) in the copolymer.

[0148] In a preferred embodiment, the (meth)acrylic polymer (iv) contains at least one monomer of formula (I) and at least one monomer of formula (V).

[0149] In a preferred embodiment, the (meth)acrylic polymer component (iv) consists only of monomers of formula (I) and formula (V).

[0150] 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.

[0151] 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 particularly preferably 20,000 to 50,000. Mw is measured by the method described in the Examples section. The (meth)acrylic polymer (iv) preferably has a polydispersity index (PDI) of 1.5 to 5.0.

[0152] 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. Preferably, a value of less than 80°C, for example less than 70°C, for example less than 55°C is preferred.

[0153] 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 1.5 to 20% by weight, preferably 2.5 to 15% by weight, relative to the total dry weight of the coating composition.

[0154] (Meth)acrylic polymer (iv) may be present in the antifouling coating composition in an amount of 3.0 to 30% by volume, preferably 5.0 to 25% by volume, in terms of solid content.

[0155] Viewed in another aspect, the present invention is an antifouling coating composition, (B) Binder, (i) A (meth)acrylic copolymer containing 0.5 to 10% by weight of (meth)acrylic acid monomer relative to the total weight of monomers present in the (meth)acrylic copolymer, (iii) monocarboxylic acids or their metal salts, (iv) A (meth)acrylic polymer comprising preferably at least one monomer of formula (I) as defined above, The above antifouling coating composition contains a binder comprising: component (iii) at 8.0 to 40% by volume in terms of solid content, component (iv) at 3.0 to 30% by volume in terms of solid content, and component (i) at 1.0 to 20% by volume in terms of solid content. (B) Cuprous oxide in solid content of 2.0 to 25 volume%, (C) Provides an antifouling coating composition containing hollow spheres with a solid content of 2.0 to 65% by volume.

[0156] [Preparation of (meth)acrylic copolymers (i), (ii), and (iv)] (Meth)acrylic copolymers (i) and (meth)acrylic polymers (iv) can be prepared using polymerization reactions known in the art. The polymers are 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. Optionally, a chain transfer agent may be used to control the chain length during free radical polymerization. In the preparation of coating compositions 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, solution polymerization is desirable. In the case of copolymers, the polymer may be a random copolymer, an alternating copolymer, a gradient copolymer, or a block copolymer.

[0157] 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.

[0158] 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.

[0159] Examples of chain transfer agents include aromatic compounds such as α-methylstyrene dimer; thioglycolic acid, and thioglycolates such as methyl thioglycolate, ethyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, and isooctyl thioglycolate; mercaptopropionic acid, and ethyl 2-mercaptopropionate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, butyl 3-mercaptopropionate, isooctyl 3-mercaptopropionate, octadecyl 3-mercaptopropionate, and poly(propylene glycol) 3-mercaptopropionate. Examples include mercaptopropionates; and thiols such as 1-propanthol, 2-propanthol, 2-methyl-1-propanthol, 2-methyl-2-propanthol, 1-butanethiol, 2-butanethiol, 3-methyl-1-butanethiol, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, 1-octanthiol, sec-octanthiol, tert-octanthiol, 1-nonanethiol, tert-nonanethiol, 1-decanethiol, 1-dodecanethiol, tert-dodecanethiol, 1-tetradecanethiol, 1-hexadecanethiol, and 1-octadecanethiol. Chain transfer agents can be used alone or in combination of two or more.

[0160] The metal-containing (meth)acrylic copolymer (ii) can be produced, for example, by copolymerizing the metal-containing monomer (a3) ​​using any of the above free radical polymerization processes, preferably in the presence of a chain transfer agent. Alternatively, the metal-containing (meth)acrylic copolymer (ii) may be produced by reacting a polymer having a carboxylic acid group, a monocarboxylic acid compound, and a metal compound (for example, an inorganic metal compound, specifically including copper or zinc oxides, hydroxides, and / or organic salts of copper or zinc (e.g., zinc acetate)) to introduce a metal-containing group to the carboxylic acid group of the polymer.

[0161] Metal-containing monomers (a3) ​​can be synthesized, for example, by known methods of appropriately heating and stirring metal compounds (e.g., inorganic metal compounds, specifically including copper or zinc oxides, hydroxides, chlorides, and / or organic acid salts (e.g., zinc acetate)), methacrylic acid and / or acrylic acid, and optionally monocarboxylic acids, in the presence of an organic solvent and water.

[0162] [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: (Meth)acrylic polymers containing silyl ester monomers such as triisopropyl methacrylate or triisopropyl acrylate; 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); (Meth)acrylic homopolymers, e.g., poly(n-butyl acrylate); 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 (therefore these are not monocarboxylic acids or their salts); 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.

[0163] The presence of a (meth)acrylic polymer containing silyl ester monomers such as triisopropyl methacrylate or triisopropyl acrylate is particularly preferred.

[0164] 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 of the weight of binder (A), for example less than 10% by weight or less than 5% by weight. If no other binder components are present, it is preferable that binder (A) consists of component (i) and / or component (ii), and optionally component (iii) and / or component (iv).

[0165] [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.

[0166] It is preferable that the hollow sphere is made of an inorganic material, i.e., a hollow sphere made of ceramic or glass. Preferably, the hollow microspheres are glass spheres or ceramic spheres. 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.

[0167] Preferably, the hollow glass microspheres are produced from sodium borosilicate or soda-lime borosilicate. A suitable example of a ceramic hollow sphere is an aluminosilicate-based sphere. 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.

[0168] 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.

[0169] The antifouling coating composition contains at least 2.5 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.

[0170] To significantly reduce the cuprous oxide content, it is preferable to include hollow spheres in a minimum of 1.0 volume percent of the solid content. Expressed in weight percentage, the preferred content of hollow spheres tends to be in the range of approximately 0.1 to 15% by weight. The ratio of hollow spheres to cuprous oxide (solid content volume %) is preferably in the range of 0.1 to 20, preferably 0.1 to 10, and particularly 0.5 to 5.0.

[0171] The combined solid content volume % (vol) of the hollow sphere and cuprous oxide is preferably 8.0 to 70 vol% or 10 to 60 vol% in terms of solid content. Alternatively, the combined solid content volume % (vol) of the hollow sphere and cuprous oxide is preferably 15 to 70 vol% in terms of solid content, particularly 20 to 60 vol%. 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.

[0172] 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 0.1:1 to 12:1, preferably about 1, for example, 0.5:1 to 3:1. 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.

[0173] (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.

[0174] 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. The particle size of hollow spheres can be measured, for example, using sieving or laser diffraction analysis. The density of a hollow sphere varies depending on its properties. The density of the hollow sphere in this invention is 0.1 to 1.0 g / cm³. 3 It may also be within that range.

[0175] The compressive strength of the hollow spheres is preferably at least 1500 psi, more preferably 3000 psi or more, 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; therefore, application should be done by brush or roller.

[0176] 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 Eccospheres, and Cenostar's hollow glass. Cenospheres are available, for example, from Cenostar or Omya as Fillite.

[0177] [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.

[0178] 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.

[0179] The antifouling coating composition of the present invention may contain cuprous oxide in a solid content of 1.0 to 25% by volume, preferably 1.5 to 20% by volume, and more preferably 5.0 to 15% by volume.

[0180] The antifouling coating composition of the present invention may contain cuprous oxide in an amount of 8.0 to 47% by weight (dry), for example, 10 to 40% by dry weight. When the coating composition is based on binder (i), the coating composition may contain 10 to 30.0% by weight, for example, 10 to 28% by weight, of cuprous oxide. When the coating composition is based on binder (ii), the coating composition may contain 10 to 40% by weight, for example, 10 to 35% by weight, preferably 10 to 30% by weight, of cuprous oxide.

[0181] The coating composition of the present invention may contain additional antifouling agents. These antifouling agents may be inorganic, organometallic, or organic. Suitable antifouling agents are commercially available. Examples of inorganic antifouling agents include copper thiocyanate, copper sulfide, and metallic copper such as copper powder and copper flakes.

[0182] Examples of organometallic marine antifouling agents include zinc pyrithione, copper pyrithione, bis(dimethyldithiocarbamate)zinc [dilam] and ethylenebis(dithiocarbamate)zinc [zineb], di(ethyl 4,4,4-trifluoroacetoacetate)copper, and copper and zinc compounds described in International Publication No. 2021113564A1.

[0183] 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].

[0184] 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.

[0185] 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], 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine], 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril], di(ethyl4,4,4-trifluoroacetoacetate)copper, and phenylcapsaicin.

[0186] 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.

[0187] The use of cuprous oxide and copper pyrithione is particularly preferred. The total amount of biocides may constitute up to 55% by weight of the coating composition, for example, 10-55% by weight, or for example, 15-50% by weight.

[0188] The total amount of biocides may constitute up to 50% by volume of the coating composition in terms of solid content, for example, 2.0 to 40% by volume, or for example, 5.0 to 30% by volume. 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.

[0189] Viewed in another aspect, the present invention is an antifouling coating composition, (A) A binder comprising (i) a (meth)acrylic copolymer present in an amount of 1.0 to 12% by weight, preferably 2.0 to 7.0% by weight, relative to the total weight of the coating composition, (B) Cuprous oxide in solid content of 1.0 to 30 volume%, (C) Contains hollow spheres with a solid content of 1.0 to 65% by volume, The present invention provides an antifouling coating composition in which 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.

[0190] In particular, the present invention relates to an antifouling coating composition, (A) A binder comprising (i) a (meth)acrylic copolymer present in an amount of 1.0 to 12% by weight, preferably 2.0 to 7.0% by weight, relative to the total weight of the coating composition, and (iv) a (meth)acrylic polymer 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, (B) Cuprous oxide in solid content of 1.5 to 15 volume%, (C) Contains hollow spheres with a solid content of 5.0 to 60% by volume, The present invention provides an antifouling coating composition in which 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.

[0191] [Pigments and fillers] The coating composition of the present invention may further contain a pigment and / or an extender. The pigment may be an inorganic pigment, an organic pigment, or a mixture thereof. Inorganic pigments are preferred. Examples of inorganic pigments include titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, zinc sulfide, lithopone, and graphite. Examples of organic pigments include carbon black, phthalocyanine blue, phthalocyanine green, naphthol red, and diketopyrrolopyrrole red. The pigment may optionally be surface-treated to allow for easier dispersion in the paint composition.

[0192] Various inorganic or organic surface treatments can be used to improve storage stability and enhance pigment performance, such as rheological properties and dispersibility in coating compositions. For example, titanium dioxide can be surface-treated with silicon compounds, zirconium compounds, aluminum compounds, and / or zinc compounds.

[0193] The bulking agent may be a natural or synthetic mineral. Examples of bulking agents include dolomite, plastrite, calcite, quartz, barite, magnesite, silica, nepheline syenite, wollastonite, talc, chlorite, mica, kaolin, pyrophyllite, feldspar, calcium carbonate, magnesium carbonate, barium sulfate, zinc oxide, zinc phosphate, calcium silicate, and silica. In addition to the bulking agents described above, the coating composition may further contain reinforcing agents such as flakes and fibers, as described, for example, in International Publication No. 00 / 77102.

[0194] The use of zinc oxide is particularly preferred. However, the content of zinc oxide in the antifouling composition of the present invention is preferably 10% by volume or less in terms of solid content. Preferably, the total amount of fillers and / or pigments present in the composition of the present invention is 1 to 40% by weight, more preferably 2 to 30% by weight, and even 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 fillers and / or pigments present in the composition of the present invention is preferably 1 to 30% by volume, more preferably 2 to 20% by volume, for example 3 to 15% by volume, in terms of solids. Those skilled in the art will understand that the content of fillers and pigments will vary depending on the particle size distribution, particle shape, surface morphology, affinity between the particle surface and the resin, other components present, and the final use of the coating composition.

[0195] [Other ingredients] The antifouling coating composition according to the present invention may optionally further contain one or more components selected from additives, solvents, and diluents. Examples of additives that can be added to antifouling coating compositions include rheological modifiers, wetting and dispersing agents, and defoaming agents.

[0196] Examples of rheological modifiers include thixotropic agents, thickeners, and anti-settling agents. Typical examples of rheological modifiers include silica such as fumed silica, organically modified clay, amide wax, polyamide wax, amide derivatives, polyethylene wax, oxidized polyethylene wax, cured castor oil wax, ethylcellulose, aluminum stearate, and mixtures thereof. Rheological modifiers that require activation may be added directly to the coating composition and activated during the paint manufacturing process, or they may be added to the coating composition in a pre-activated form, such as a solvent paste. Each rheological modifier is present in the composition of the present invention in an amount of preferably 0 to 5.0% by weight, more preferably 0.2 to 3.0% by weight, and even more preferably 0.5 to 2.0% by weight, based on the total weight of the coating composition.

[0197] The dehydrating agent improves the storage stability of the antifouling coating composition containing a hydrolyzable binder component such as (meth)acrylic silyl ester copolymer. The dehydrating agent is preferably a compound that removes moisture and water from the coating composition. This compound is also called a water scavenger, drying agent, or desiccant. Examples of dehydrating agents include alkoxysilanes such as tetraethoxysilane, as well as inorganic desiccants such as anhydrous calcium sulfate, calcium sulfate hemihydrate, and zeolite powder. The use of tetraethoxysilane is particularly preferred. The dehydrating agent is added to the composition of the present invention in an amount of preferably 0 to 5% by weight, more preferably 0.5 to 2.5% by weight, and even more preferably 1.0 to 2.0% by weight, based on the total weight of the composition.

[0198] 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.

[0199] Suitable solvents are aromatic solvents, hydrocarbon solvents, and ketone solvents, particularly xylene and mixtures of aromatic hydrocarbons.

[0200] 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.

[0201] Alternatively, the coating can be dispersed in an organic non-solvent or aqueous dispersion containing the film-forming components in the coating composition.

[0202] [Coating composition] The antifouling coating composition of the present invention preferably has a solid content of more than 40% by volume, for example, more than 45% by volume, for example, more than 50% by volume, preferably more than 55% by volume.

[0203] More preferably, the antifouling coating composition has a volatile organic compound (VOC) content of less than 500 g / L, preferably less than 420 g / L, more preferably less than 400 g / L, for example, less than 380 g / L. 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 30-80%, for example, 40-65%. The density of the antifouling coating is, for example, 0.9-2.2 g / cm³. 3 It may also be the case that the coating density is, for example, 1.0 to 2.5 g / cm³. 3 For example, 1.2~1.8 g / cm³ 3 That's fine.

[0204] 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). The antifouling coating composition can be prepared by any method 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.

[0205] [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.

[0206] 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.

[0207] When applying the antifouling coating composition in two or more coats, the different coats may be antifouling coatings of different compositions. The antifouling coating layer may vary in type, biocide amount, binder composition, and / or polishing rate.

[0208] In certain cases, such as in fitting 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.

[0209] The coating film formed from the coating composition of the present invention can be cleaned, for example, by a robot, a remotely operated vehicle (ROV), or a manually operated device. Cleaning may be performed after dirt occurs or may be performed to prevent dirt. Underwater cleaning can be carried out using, for example, mechanical means (brush, squeegee, etc.), high-pressure water, ultraviolet rays, lasers, or ultrasonic waves. An example of a robot used for underwater cleaning is described in International Publication No. 2019 / 170888, International Publication No. 2020 / 207791, and International Publication No. 2020 / 207792. An example of a cleaning setting applicable when using a brush is described in International Publication No. 2021 / 180588. Hereinafter, the present invention will be described with reference to non-limiting examples.

[0210] [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.

[0211] <Measurement of Content of Non-Volatile Substances in Polymer Solution> The non-volatile matter content of the polymer solution was measured as described in ISO 3251:2019. A test sample of 0.5 g ± 0.1 g was taken out and dried in a ventilated oven at 105 °C for 3 hours. The weight of the residue was regarded as the non-volatile matter (NVM). The non-volatile matter content was expressed as a weight fraction %. The values shown are the average values of three parallel measurements.

[0212] <Measurement of Polymer Molecular Weight Distribution> The properties of the polymer were identified by gel permeation chromatography (GPC) measurement. The molecular weight distribution (MWD) was measured by connecting two PLgel 5μm Mixed-D columns (manufactured by Agilent) in series to an Omnisec Resolve and Reveal system (manufactured by Malvern). The calibration of the column was performed by conventional calibration using a narrow-distribution polystyrene standard substance. The analysis conditions were as follows.

[0213]

Table 1

[0214] A sample was prepared by dissolving a polymer solution corresponding to 25 mg of the dry polymer in 5 ml of tetrahydrofuran (THF). The sample was held at room temperature for at least 3 hours before sampling for GPC measurement. Before analysis, the sample was filtered through a 0.45 μm nylon filter. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were reported. The polydispersity index (PDI) was expressed as Mw / Mn.

[0215] <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.

[0216] 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.

[0217] <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.

[0218] <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 III, 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.

[0219] 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.

[0220] 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.

[0221] [Table 2]

[0222] Unless otherwise specified, antifouling performance is based on a 4-month exposure test in Singapore.

[0223] <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.

[0224] <Accelerated cracking test of coating film> The polyvinyl chloride (PVC) panel was coated with an appropriate anticorrosive primer. The antifouling coating was applied onto the panel using a film applicator with a gap size of 800 μm. After drying the panel at 52°C for 72 hours, it was immersed in seawater at 40°C. At regular intervals, the panel was taken out for evaluation. After drying the panel at room temperature, cracks were evaluated visually and at 10-fold magnification, and then evaluated again after drying at 52°C for 24 hours. Thereafter, the panel was re-immersed. The evaluation results after drying at 52°C are shown in a table together with the examples of the paint. The panel was evaluated as follows.

[0225] [Table 3]

[0226] <Accelerated blistering test of coating film> The polyvinyl chloride (PVC) panel was coated with an appropriate anticorrosive primer. The antifouling coating was applied onto the panel using a film applicator with a gap size of 800 μm. After drying the panel at 52°C for 72 hours, it was immersed in fresh water at 30°C. At regular intervals, the panel was taken out for evaluation. The panel was evaluated for blistering visually. Thereafter, the panel was re-immersed. The evaluation results are shown in a table together with the examples of the paint. The panel was evaluated as follows.

[0227] [Table 4]

[0228] <Measurement of swelling degree in fresh water> The degree of swelling in freshwater was determined by measuring the change in coating film thickness 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 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 dry film thickness (DFT) of the coatings tested in the examples was 100 ± 10 μm. The PVC discs were immersed in freshwater adjusted to 30°C ± 2°C. The PVC discs were removed after 4 weeks and 10 weeks, and the film thickness was measured. After washing, the discs were dried overnight at room temperature before the film thickness was measured. 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 DFT differed for each coating, the degree of swelling was evaluated as the swelling rate (%) relative to the DFT. Swelling was evaluated according to the following criteria.

[0229] [Table 5]

[0230] <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 tert-amylperoxy-2-ethylhexanoate. This premix was added to the reaction vessel at a constant rate over 3 hours using a metering pump under a nitrogen atmosphere. After reacting for a further 30 minutes, a boost initiator solution of 0.40 parts tert-amylperoxy-2-ethylhexanoate and 5.0 parts xylene was supplied to the reaction vessel at a constant rate over 20 minutes. The reaction vessel was maintained at the reaction temperature for a further 1.5 hours, and then cooled to room temperature. All "parts" mentioned above are "parts by weight".

[0231] Copolymer solution A1 had the following properties: NVM:66.0wt%;Viscosity 369cP;Mw 22.1k;PDI 2.93;Tg -41℃

[0232] <Preparation procedure for copolymer solution A2> 54 parts xylene and 13 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 20 parts n-butyl acrylate, 60 parts methyl methacrylate, 20 parts 2-(2-ethoxyethoxy)ethyl acrylate, 11 parts xylene, 6 parts 1-methoxy-2-propanol, and 1.5 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 0.4 parts 2,2'-azobis(2-methylbutyronitrile) and 9 parts xylene was added 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 of the "parts" mentioned above refer to "weight parts".

[0233] Copolymer solution A2 had the following properties. NVM52.4wt%; Viscosity 654cP; Mw 24.4k; PDI 2.63; Tg 20℃

[0234] <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".

[0235] The copolymer solution S1 had the following properties. NVM60.0wt%; Viscosity 1790cP; Mw 42.3k; PDI 3.11; Tg 37℃

[0236] <Preparation of Zinc Rosinate Solution Z1> 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. Zinc rosinate solution Z1 contains 62.1% by weight of non-volatile substances and has a density of 1.04 g / cm³.3 That was the case.

[0237] <Synthesis of zinc acrylate monomers ZnM1 to ZnM3> <Procedure for preparing copolymer solution ZnM1> 16.0 parts xylene, 80.0 parts 1-methoxy-2-propanol, and 34.0 parts zinc oxide 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 65°C. A premix was prepared consisting of 30.1 parts acrylic acid, 35.9 parts methacrylic acid, and 4.0 parts deionized water. This premix was added to the reaction vessel at a constant rate over 3 hours using a metering pump under a nitrogen atmosphere. The reaction vessel was maintained at the reaction temperature for a further 2 hours, and then cooled to room temperature. All "parts" mentioned above are "parts by weight". NVM: 43.6% by weight

[0238] <Procedure for preparing the copolymer solution ZnM2> 86.8 parts of 1-methoxy-2-propanol and 27.6 parts of zinc oxide 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 75°C. A premix was prepared consisting of 17.1 parts of acrylic acid, 20.4 parts of methacrylic acid, and 35.0 parts of versatic acid. This premix was added to the reaction vessel at a constant rate over 3 hours using a metering pump under a nitrogen atmosphere. The reaction vessel was maintained at the reaction temperature for a further 2 hours, and then cooled to room temperature. 13.2 parts of 1-methoxy-2-propanol were added. All "parts" mentioned above are "parts by weight". NVM: 55.8% by weight

[0239] <Procedure for preparing the copolymer solution ZnM3> 96.0 parts of 1-methoxy-2-propanol and 33.9 parts of zinc oxide 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 65°C. A premix was prepared consisting of 30.1 parts of acrylic acid, 36.0 parts of methacrylic acid, and 4.0 parts of deionized water. This premix was added to the reaction vessel at a constant rate over 3 hours using a metering pump under a nitrogen atmosphere. The reaction vessel was maintained at the reaction temperature for a further 2 hours, and then cooled to room temperature. All "parts" mentioned above are "parts by weight". NVM: 44.9% by weight

[0240] <Synthesis of zinc acrylate copolymers M1-M3> <Preparation procedure for zinc acrylate copolymer solution M1> 61.3 parts xylene and 16.13 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 of 68.7 parts ethyl acrylate, 5.4 parts 2-methoxyethyl acrylate, 25.9 parts ZnM1, 10.8 parts xylene, 0.98 parts 2,4-diphenyl-4-methyl-1-pentene, 2.5 parts 2,2'-azobis(2-methylpropionitrile), and 6.9 parts 2,2'-azoddi(2-methylbutyronitrile) was added to the reaction vessel at a constant rate over 4 hours using a metering pump under a nitrogen atmosphere. A boost initiator solution consisting of 0.49 parts of tert-butyl 2-ethyl peroxyhexanoate and 7.5 parts of xylene was supplied to the reaction vessel at a constant rate over 30 minutes. The reaction vessel was held at the reaction temperature for a further 1.5 hours, after which it was cooled to room temperature. The copolymer solution was diluted with 3.9 parts of xylene. All "parts" mentioned above refer to "parts by weight".

[0241] Copolymer solution M1 had the following properties. NVM:47.0wt%;Viscosity 8748cP;Mw 5.4k;PDI 2.49;Tg 2℃

[0242] <Preparation procedure for zinc acrylate copolymer solution M2> 63.0 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 of 8.8 parts methyl methacrylate, 59.7 parts ethyl acrylate, 31.5 parts ZnM2, 10.0 parts 1-methoxy-2-propanol, and 4.9 parts 2,2'-azodi(2-methylbutyronitrile) was prepared. This premix was added to the reaction vessel at a constant rate over 4 hours using a metering pump under a nitrogen atmosphere. A boost initiator solution of 0.49 parts tert-butyl 2-ethyl peroxyhexanoate and 7.0 parts xylene was supplied to the reaction vessel at a constant rate over 30 minutes. The reaction vessel was maintained at the reaction temperature for a further 1.5 hours, after which it was cooled to room temperature. The copolymer solution was diluted with 9.8 parts xylene. All of the "parts" mentioned above refer to "weight parts".

[0243] Copolymer solution M2 had the following properties. NVM:45.8wt%;Viscosity 1532cP;Mw 5.0k;PDI 2.23;Tg 8℃

[0244] <Preparation Procedure for Zinc Acrylate Copolymer Solution M3> 60.0 parts xylene, 15.0 parts 1-methoxy-2-propanol, and 3.9 parts ethyl acrylate 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 of 14.8 parts methyl methacrylate, 47.3 parts ethyl acrylate, 14.8 parts n-butyl acrylate, 19.3 parts ZnM3, 10.0 parts xylene, 1.2 parts 2,4-diphenyl-4-methyl-1-pentene, 2.5 parts 2,2'-azobis(2-methylpropionitrile), and 6.4 parts 2,2'-azoddi(2-methylbutyronitrile) was added to the reaction vessel at a constant rate over 6 hours using a metering pump under a nitrogen atmosphere. A boost initiator solution consisting of 0.49 parts of tert-butyl 2-ethyl peroxyhexanoate and 7.0 parts of xylene was supplied to the reaction vessel at a constant rate over 30 minutes. The reaction vessel was held at the reaction temperature for a further 1.5 hours, after which it was cooled to room temperature. The copolymer solution was diluted with 8.0 parts of xylene. All "parts" mentioned above refer to "parts by weight". Copolymer solution M3 had the following properties.

[0245] NVM:47.5wt%;Viscosity 10348cP;Mw 7.2k;PDI 2.97;Tg 4℃

[0246] Table 2a shows the copolymer monomer ratios of the acrylic polymer, and Table 2b shows the ratios used in the preparation of zinc acrylate monomers ZnM1-3. Table 2c shows the monomer ratios used in the preparation of copolymers M1-M3. Table 3 shows other components used in the examples. Table 4 shows the hollow spheres used in the examples.

[0247] [Table 6]

[0248] [Table 7]

[0249] [Table 8]

[0250] [Table 9]

[0251] 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.

[0252] [Table 10]

[0253] <General paint preparation protocol> The components were mixed in the ratios shown in Tables 5 to 9. 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 pulverized in a 250 ml paint can using a vibrating shaker. Hollow spheres can be added before or after the pulverization process, but it was confirmed that their presence during the pulverization process improved mixability and pulverization fineness. When paint samples with and without hollow spheres were compared, no signs of sphere breakage were observed. Adding hollow spheres after pulverization did not affect storage stability compared to adding them before pulverization (if the spheres were broken, an increase in viscosity over time would be expected). When both wet paint and dry paint films were observed under a microscope (70x magnification), the spheres were found to be intact. In these examples, hollow spheres were added before grinding.

[0254] [Table 11]

[0255] [Table 12]

[0256] [Table 13]

[0257] [Table 14]

[0258] [Table 15]

[0259] [Table 16]

[0260] <Result> Table 5: Comparative Example 1 shows an antifouling coating with a binder system based on rosin and an acrylic binder, containing 32% by weight of cuprous oxide, which corresponds to approximately 17% by volume in the dry coating (%SV). Examples 1 to 6 demonstrate that it is possible to replace a portion of the cuprous oxide with hollow glass spheres (Cu2O (%SV) replaced with hollow spheres (%SV)) while still maintaining sufficient antifouling performance and mechanical properties.

[0261] Examples 1 and 2 show cases where cuprous oxide is 15% SV and hollow glass spheres are 2% SV and 5% SV, respectively. Examples 5 and 6 show cases where cuprous oxide is 5% SV and hollow glass spheres are 20% SV and 25% SV, respectively. Lightweight hollow spheres usually reduce viscosity, so increasing the amount of spheres can increase the volume of solids in the formulation; for example, Example 5 achieves 58% volume of solids. As is clear from Table 5, the coating density decreases as the amount of hollow spheres used increases, and the coating weight becomes lighter when the same dry film thickness (DFT) is applied.

[0262] Table 6 shows examples where the cuprous oxide content was reduced to 2.5% SV (Example 9). Hollow cenospheres can also be used, with Examples 10 and 11 showing 15% SV and 10% SV, respectively.

[0263] The examples in Table 7 demonstrate that the volume of the spheres can be further increased (e.g., 50% SV or 60% SV in Examples 14 to 17) without affecting the antifouling performance or mechanical properties. The solid content volume of the formulations increased to over 60%, which means that the calculated VOCs are 292 to 333 g / L. Comparative Example 2, which did not contain cuprous oxide in the formulation, shows poor antifouling performance after a one-month exposure test in Singapore. Furthermore, this formulation also showed somewhat low blister resistance after four weeks of immersion in freshwater.

[0264] Table 8 shows several variations of the binder system. It is possible to contain silyl acrylate (Example 19) and / or zinc rosinate (Examples 20 and 21) while maintaining antifouling performance. Experiments have shown that both rosinate and metal rosinate salts can be used in the present invention.

[0265] Table 8 shows examples of the use of hollow glass spheres H38HS and iM30K, as well as the larger-grained Cenosphere Fillite 160. The results demonstrate that antifouling performance is maintained when using a variety of different hollow spheres, including both coated and uncoated hollow glass spheres and hollow ceramic spheres. The sum of the %SV of cuprous oxide and the %SV of the hollow sphere is shown in the range of 17%SV to 65%SV.

[0266] Using cuprous oxide of different particle sizes demonstrates that the effect is not limited to a specific grade / particle size of cuprous oxide. The color of cuprous oxide serves as an indicator of particle size, with smaller particles exhibiting a brighter orange color and larger particles exhibiting a darker purple color. Cu orange was used in Example 10 in Table 6, while LoLo Tint was used in Example 5 in Table 5 and Example 23 in Table 9.

[0267] The examples in Table 10 demonstrate that different metal-containing (meth)acrylic polymers and rosin-based binder systems can be used while maintaining good mechanical properties and antifouling performance. These can be used alone or in combination with, for example, a silyl acrylic copolymer (Example 27). In Examples 26 to 30, the cuprous oxide level was varied from 15% SV to 5% SV while the glass sphere level was 5% SV to 25% SV. Examples 29 and 30 showed good antifouling performance at a cuprous oxide level of 5% SV.

Claims

1. (A) A binder, (i) A (meth)acrylic copolymer containing 0.5 to 10% by weight of (meth)acrylic acid monomer relative to the total weight of monomers in the (meth)acrylic copolymer, and / or (ii) A binder comprising a metal-containing (meth)acrylic copolymer containing a metal selected from Zn or Cu, (B) Cuprous oxide in solid content of 1.0 to 25 volume%, (C) An antifouling coating composition containing hollow spheres with a solid content of 1.0 to 65% by volume.

2. 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 (iii), preferably rosin, hydrogenated rosin or a metal salt thereof.

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

4. 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 8.0 to 70% by volume, for example 15 to 70% by volume, or for example 15 to 60% by volume, in terms of solid content, based on the entire antifouling coating composition.

5. 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.

6. (B) Cuprous oxide in solid content of 1.5 to 15 volume percent, (C) The antifouling coating composition according to any one of the preceding claims, comprising 5.0 to 60% by volume of hollow spheres in terms of solid content.

7. The antifouling coating composition according to any one of the preceding claims, wherein the binder (A) further contains (meth)acrylic polymer (iv).

8. The (meth)acrylic polymer (iv) is, as a monomer, i. Equation (I) 【Transformation 7】 [In the formula, R 1 is H or CH 3 And R 2 C 1 ~C 20 Hydrocarbyl substituents, preferably C 1-10 Alkyl substituents, for example, C 1-8 It is an alkyl group. The antifouling coating composition according to claim 7, comprising at least one, for example, at least two (meth)acrylates.

9. The (meth)acrylic polymer (iv) is of formula (V) 【Transformation 8】 [Wherein, R 7 is H or CH 3 , and R 8 is a C 3-40 substituent containing at least one oxygen atom or nitrogen atom, for example a C 3 to C 20 substituent.] The antifouling coating composition according to claim 8, comprising at least one monomer.

10. The (meth)acrylic copolymer (i) is present, and as a monomer, Equation (I) 【Chemistry 9】 [In the formula, R 1 is H or CH 3 And R 2 C 1 ~C 20 Hydrocarbyl substituents, preferably C 1-10 Alkyl substituents, for example, C 1-8 It is an alkyl group. (Meth)acrylates of at least one, for example, at least two, and (meth)acrylic acid, Contains An antifouling coating composition according to any one of the prior claims.

11. (A) A binder comprising a (meth)acrylic copolymer (i) present in an amount of 1.0 to 12% by weight, preferably 2.0 to 7.0% by weight, based on the total weight of the entire coating composition, (B) Cuprous oxide in solid content of 1.0 to 25 volume%, (C) Contains hollow spheres with a solid content of 1.0 to 65% by volume, The antifouling coating composition according to any one of claims 1 to 10, wherein the total amount of the cuprous oxide and the hollow spheres combined is in the range of 15 to 70 volume percent in terms of solid content.

12. The metal-containing (meth)acrylic copolymer contains a monomer, and the monomer is of formula (II) 【Chemistry 10】 [In the formula, M represents zinc or copper, and R 3 This represents an organic group. An antifouling coating composition according to any one of the preceding claims, wherein the (meth)acrylate monomer contains a side chain.

13. 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.

14. 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.

15. If the coating composition is based on binder component (i), the coating composition contains 10 to 30.0% by weight of cuprous oxide, for example, 10 to 28% by weight, or The antifouling coating composition according to any one of the preceding claims, wherein the coating composition is based on a binder component (ii), and the coating composition contains 10 to 40% by weight, for example 10 to 35% by weight, preferably 10 to 30% by weight, of cuprous oxide.

16. 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 15.

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

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