Non-chemical type antifouling coating composition, method for forming antifouling coating film using same, and article on which antifouling coating film is formed

Abstract

The present invention provides a novel non-chemical type antifouling coating composition which is capable of suppressing adhesion of marine organisms and seaweeds to a fishery material, an undersea structure, a fishing net, and the like.　A non-chemical type antifouling coating composition according to the present invention contains: a resin (A) which has an acid value of 0 mgKOH / g to 10 mgKOH / g inclusive and a weight average molecular weight (Mw) of 50,000 to 350,000 inclusive, and which is composed of one or more resins that are selected from the group consisting of an acrylic resin, an acrylic silicone resin, a polyester resin, an alkyd resin, and an alkyd rosin resin; and a landing inhibitor (B) that is one or more compounds selected from the group consisting of a silicone compound and an aliphatic hydrocarbon compound. This non-chemical type antifouling coating composition does not contain an aquatic organism repellent that is one or more substances selected from the group consisting of cuprous oxide, bis(2-sulfidopyridin-1-olato) copper, and bis(N,N-dimethyl dithiocarbamic acid)N,N'-ethylene bis(thiocarbamoylthio zinc).

Description

Chemical-free antifouling coating composition, method for forming antifouling coating using the same, and article with antifouling coating formed thereon

[0001] The present invention relates to a novel chemical-free antifouling coating composition capable of inhibiting adhesion of marine organisms and seaweeds to marine materials, underwater structures, fishing nets, etc., a method for forming an antifouling coating using the same, and an article on which the antifouling coating is formed.

[0002] Various marine organisms attach to the surfaces of articles such as marine materials, underwater structures, and fishing nets used in the fields of aquaculture, fishing, maritime transportation, etc. Marine organisms such as barnacles, hydroids, hairy bryozoans, and sea bass attach to marine materials, underwater structures, fishing nets, etc., and block the meshes, causing problems such as deterioration of water quality, fish disease, and net damage. Various antifouling paints have been used to prevent marine organisms from attaching to marine materials, underwater structures, fishing nets, etc., which cause these problems. In the past, antifouling paints containing organotin compounds as antifouling ingredients were used as ship bottom paints, etc., but their use has been restricted in recent years due to their toxicity, and there is a demand for the development of alternative antifouling paints.

[0003] In consideration of environmental conservation and the health of workers, for example, Patent Document 1 discloses a water-based antifouling coating composition containing an emulsion resin, a dispersion resin, and a marine organism repellent.

[0004] In Patent Document 2, a resin is prepared by bonding a seawater-soluble additive such as rosin to the carboxyl group of a hydrolyzable resin, and an antifouling coating composition is prepared by mixing this resin with a marine organism repellent, thereby maintaining antifouling effects.

[0005] Patent Document 3 discloses an antifouling coating composition that uses a sulfur-containing organopolysiloxane block vinyl copolymer to soften the coating film and prevent peeling of the coating film due to tidal changes.

[0006] Japanese Patent Application Publication No. 2006-193731 Japanese Patent Application Publication No. 2006-152205 Japanese Patent No. 6859080

[0007] However, although the aqueous antifouling composition described in Patent Document 1 is designed with environmental conservation and the health of workers in mind, there are still concerns about the accumulation of chemicals because it uses a marine organism repellent.The antifouling coating composition described in Patent Document 2 and the antifouling coating composition described in Patent Document 3 also have concerns about the accumulation of chemicals, as with the aqueous antifouling paint described in Patent Document 1.

[0008] Antifouling paints containing marine organism repellents (antifouling agents) have traditionally been used to prevent the attachment of marine organisms and seaweed to fishery materials, underwater structures, fishing nets, etc. However, in recent years, from the perspective of environmental conservation and with the development of the aquaculture industry, the accumulation of chemicals in marine products has become a problem.

[0009] The present invention has been made in view of the above circumstances, and aims to provide a chemical-free antifouling paint composition that can exert an antifouling effect for a long period of time and suppress the accumulation of chemicals in marine products, an antifouling coating film formed using the same, and an article on which the coating is formed.

[0010] As a result of extensive research, the present inventors have found that the following invention can solve the above-mentioned problems, and have thus completed the present invention. That is, the present invention relates to the following inventions: <1> A chemical-free antifouling coating composition for forming a coating film that suppresses the attachment of aquatic organisms on the surface of an article that comes into contact with water, the chemical-free antifouling coating composition comprising: a resin (A) having an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less and a weight-average molecular weight (Mw) of 50,000 or more and 350,000 or less, and being one or more resins selected from the group consisting of acrylic resins, acrylic silicone resins, polyester resins, alkyd resins, and alkyd rosin resins; and an implantation inhibitor (B) being one or more selected from the group consisting of silicone compounds and aliphatic hydrocarbon compounds, and the chemical-free antifouling coating composition is free of an aquatic organism repellent being one or more selected from the group consisting of cuprous oxide, bis(2-sulfidopyridin-1-olato)copper, and bis(N,N-dimethyldithiocarbamate)N,N'-ethylenebis(thiocarbamoylthiozinc). <2> The chemical-free antifouling coating composition according to <1>, further comprising a coating adhesion promoter (C) which is one or more selected from the group consisting of rosin and a silane coupling agent. <3> The chemical-free antifouling coating composition according to <2>, comprising the rosin having an acid value of from 100 mg KOH / g to 220 mg KOH / g and a softening point of from 78°C to 100°C in a proportion of from 0.5% by mass to 10% by mass, based on the non-volatile components. <4> The chemical-free antifouling coating composition according to <2> or <3>, comprising the silane coupling agent in a proportion of from 0.2% by mass to 2.0% by mass, based on the non-volatile components.<5> The chemical-free antifouling coating composition according to any one of <1> to <4>, wherein the silicone compound comprises one or more silicone oils selected from the group consisting of polyether-modified silicone oil, alkyl-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, mercapto-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, higher fatty acid-modified silicone oil, and higher fatty acid-containing silicone oil, and the content of the silicone oil is 5% by mass to 50% by mass based on the non-volatile components; the aliphatic hydrocarbon compound is one or more selected from the group consisting of polyolefin, wax, liquid paraffin, and petrolatum; the weight-average molecular weight of the aliphatic hydrocarbon compound is 150 to 3,000; and the content of the aliphatic hydrocarbon compound is 15% by mass to 40% by mass based on the non-volatile components. <6> The chemical-free antifouling coating composition according to any one of <1> to <5>, wherein the silicone compound comprises one or more silicone powders selected from the group consisting of a silicone composite powder having an average particle size of 0.2 μm to 60 μm, a silicone rubber powder having an average particle size of 1 μm to 30 μm, and a silicone resin powder having an average particle size of 0.2 μm to 8.0 μm, and wherein the content of the silicone powder is 0.5% by mass to 2.0% by mass of the non-volatile components. <7> The chemical-free antifouling coating composition according to any one of <1> to <6>, wherein the resin (A) is one or more acrylic resins, and the implantation inhibitor (B) is a silicone oil and a polyolefin, or a silicone, a polyolefin, and a silicone powder. <8> A method for forming an antifouling coating, comprising the steps of applying the chemical-free antifouling coating composition according to any one of <1> to <7> to an article, and drying the applied coating film of the chemical-free antifouling coating composition.<9> An article having an antifouling coating formed thereon, the antifouling coating comprising: a resin (A) having an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less and a weight-average molecular weight (Mw) of 50,000 or more and 350,000 or less, the resin being one or more resins selected from the group consisting of an acrylic resin, an acrylic silicone resin, a polyester resin, and an alkyd resin; and an implantation inhibitor (B) being one or more selected from the group consisting of a silicone compound and an aliphatic hydrocarbon compound; the article not containing an aquatic organism repellent being one or more selected from the group consisting of cuprous oxide, bis(2-sulfidopyridine-1-olato)copper, and bis(N,N-dimethyldithiocarbamate)N,N'-ethylenebis(thiocarbamoylthiozinc).

[0011] According to the present invention, there is provided a chemical-free antifouling coating composition that can inhibit the adhesion of aquatic organisms without containing chemicals and that reduces the risk of water pollution due to the release of chemicals or the accumulation of chemicals in aquatic organisms. Also provided are a method for forming an antifouling coating using the chemical-free antifouling coating composition, and an article having the coating formed thereon.

[0012] 1 shows photographs of an ABS Compose coated with the chemical-free antifouling coating composition of the present invention after a marine immersion test. Also shown are photographs of an undyed ABS Compose (left, Comparative Example 3) and an ABS Compose coated with a chemical-free paint (right, Comparative Example 4) after a marine immersion test.

[0013] The following describes in detail an embodiment of the present invention. However, the following description of the constituent elements is an example (typical example) of an embodiment of the present invention, and the present invention is not limited to the following content unless the gist of the present invention is changed. Furthermore, in the present invention, two or more embodiments can be arbitrarily combined. In addition, when the expression "~" is used in this specification, it is used as an expression including the numerical values ​​or physical property values ​​before and after it.

[0014] <Chemical-Free Antifouling Coating Composition> The present invention relates to a chemical-free antifouling coating composition (hereinafter sometimes abbreviated as "the coating composition of the present invention") that contains: a resin (A) having an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less and a weight-average molecular weight (Mw) of 50,000 or more and 350,000 or less, the resin being one or more selected from the group consisting of acrylic resins, acrylic silicone resins, polyester resins, and alkyd resins; and an implantation inhibitor (B) being one or more selected from the group consisting of silicone compounds and aliphatic hydrocarbon compounds, and that does not contain one or more aquatic organism repellents selected from the group consisting of cuprous oxide, bis(2-sulfidopyridin-1-olato)copper, and bis(N,N-dimethyldithiocarbamate)N,N'-ethylenebis(thiocarbamoylthiozinc).

[0015] The coating composition of the present invention is used to form a coating film that inhibits the attachment of aquatic organisms to the surface of an article that comes into contact with water. Each component will be described in detail below.

[0016] <Resin (A)> The resin (A) contained in the coating composition of the present invention has an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less and a weight average molecular weight (Mw) of 50,000 or more and 350,000 or less, and is one or more types of resin selected from the group consisting of acrylic resins, acrylic silicone resins, polyester resins, alkyd resins, and alkyd rosin resins.

[0017] The resin (A) preferably contains an acrylic resin. The acrylic resin may be one type or a combination of two or more types. The acrylic resin is primarily composed of structural units derived from alkyl (meth)acrylate monomers (50 mol% or more), but is not limited to homopolymers. The acrylic resin may also be a copolymer of alkyl (meth)acrylate monomers and copolymerizable monomers. The amount of structural units derived from alkyl (meth)acrylate monomers in the acrylic resin is, for example, 80 mol% or more, 85 mol% or more, 90 mol% or more, or 95 mol% or more. Examples of acrylic resins include polyalkyl (meth)acrylate and alkyl (meth)acrylate-(meth)acrylic acid copolymers. Note that alkyl (meth)acrylate refers to at least one of alkyl acrylate or alkyl methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid or methacrylic acid.

[0018] These resins can be synthesized by any known method, such as emulsion polymerization using a radical initiator. The alkyl(meth)acrylate-(meth)acrylic acid copolymer may be obtained by partially hydrolyzing the alkyl ester groups of polyalkyl(meth)acrylate.

[0019] The acid value of the resin used as resin (A) is 0 to 10 mgKOH / g, preferably 0 to 5 mgKOH / g, from the viewpoint of long-term storage stability. As defined in JIS K5601-2-1:1999 (Testing Methods for Paint Components - Part 2: Analysis of Components in Solvent-Soluble Matter - Section 1: Acid Value (Titration Method)), the acid value refers to the "amount (mg) of KOH required to neutralize the free acid in 1 g of the nonvolatile content of the product," and is expressed in units of "mgKOH / g." The acid value can be evaluated according to the titration method described in the same standard.

[0020] In one embodiment, resin (A) may include a first acrylic resin having an acid value of 0 mgKOH / g and a second acrylic resin having an acid value of 1 mgKOH / g or more and 10 mgKOH / g or less (preferably, 1 mgKOH / g or more and 5 mgKOH / g or less). For example, resin (A) may include the first acrylic resin and the second acrylic resin in a mass ratio of 100:0 to 90:10 or 100:0 to 95:5.

[0021] In one embodiment, resin (A) can be one or more acrylic resins having an acid number of 3 to 10 mg KOH / g, or one or more acrylic resins having an acid number of 3 to 5 mg KOH / g.

[0022] The weight average molecular weight (Mw) of the resin used as resin (A) is from 50,000 to 350,000 from the viewpoint of film formation, and is preferably from 50,000 to 300,000, and more preferably from 100,000 to 250,000, in order to maintain the effect for a longer period of time. The molecular weight can be measured using any known method such as GPC (gel permeation chromatography) analysis.

[0023] In one embodiment, the resin (A) is one or more resins selected from the group consisting of an acrylic resin, an acrylic silicone resin, a polyester resin, an alkyd resin, and an alkyd rosin resin, and each resin may have an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less and a weight average molecular weight (Mw) of 50,000 or more and 300,000 or less.

[0024] In one embodiment, resin (A) is one or more acrylic resins, each of which may have an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less and a weight average molecular weight (Mw) of 50,000 or more and 350,000 or less, preferably 50,000 or more and 300,000 or less.

[0025] In one embodiment, the resin (A) is one or more acrylic resins selected from the group consisting of polyalkyl acrylate resins, polyalkyl methacrylate resins, alkyl acrylate-acrylic acid copolymer resins, and alkyl methacrylate-methacrylic acid copolymer resins, and each acrylic resin may have an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less and a weight average molecular weight (Mw) of 50,000 or more and 350,000 or less, preferably 50,000 or more and 300,000 or less.

[0026] The content of resin (A) can be, for example, 25% by mass or more and 80% by mass or less, 28% by mass or more and 75% by mass or less, 30% by mass or more and 70% by mass or less, 33% by mass or more and 60% by mass or less, or 35% by mass or more and 50% by mass or less, relative to the non-volatile components of the coating composition of the present invention (this refers to all components contained in the chemical-free antifouling coating composition excluding volatile components such as solvents; also referred to as the solid content).

[0027] <Implantation inhibitor (B)> The coating composition of the present invention contains an implantation inhibitor (B) for inhibiting the implantation of aquatic organisms on the surface of the coating film. The implantation inhibitor (B) is one or more compounds selected from the group consisting of silicone compounds and aliphatic hydrocarbon compounds. The coating composition of the present invention may contain one type of implantation inhibitor (B), or two or more types. Each component will be described in detail below.

[0028] Examples of the silicone compound include silicone oil and silicone powder.

[0029] Specific examples of silicone oils include polyether-modified silicone oils, alkyl-modified silicone oils, alcohol-modified silicone oils, fluorine-modified silicone oils, amino-modified silicone oils, mercapto-modified silicone oils, epoxy-modified silicone oils, phenyl-modified silicone oils, carboxyl-modified silicone oils, higher fatty acid-modified silicone oils, and higher fatty acid-containing silicone oils, with polyether-modified silicone oils being preferred. More specific examples include KF-351A, KF-352A, KF-353, KF354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6204, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516, KF-410, KF-412, and KF-413 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-414, KF-415, KF-4003, KF-4701, KF-4917, KF-7235B, X-22-7322, X-22-1877, KF-910, X-22-715, KF-3955, KF-50-100cs, KF-50-500cs, KF-50-1000cs, KF-50-3000cs, KF-53, KF-54, X-21-3265, KF-54SS, KF-6004, KF-889, etc. The silicone oil may be one of these, or a combination of two or more of them.

[0030] The content of the silicone oil is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 25% by mass or more and 40% by mass or less, based on the non-volatile components of the coating composition of the present invention. When two or more types of silicone oil are contained, it is preferable that the total content of the silicone oils is within the above numerical range.

[0031] The hydrophilic-lipophilic balance (HLB) of the silicone oil is preferably 1 or more and 8 or less, and more preferably 2 or more and 6 or less.

[0032] Examples of silicone powders include silicone composite powders with an average particle size of 0.2 μm to 60 μm, silicone rubber powders with an average particle size of 1 μm to 30 μm, and silicone resin powders with an average particle size of 0.2 μm to 8.0 μm. These may be used alone or in combination of any two or more. Specific examples of silicone powders include KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, KMP-402, KMP-597, KMP-598, KMP-590, KMP-706, X-52-854, and X-52-1621, manufactured by Shin-Etsu Chemical Co., Ltd.

[0033] The content of the silicone powder relative to the non-volatile components of the coating composition of the present invention is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0.5% by mass or more and 2.0% by mass or less, even more preferably 0.5% by mass or more and 1.5% by mass or less, and particularly preferably 0.5% by mass or more and 1.0% by mass or less. When two or more types of silicone powder are contained, it is preferable that the total content of the silicone powders is within the above-mentioned numerical range.

[0034] Examples of aliphatic hydrocarbon compounds include polyolefins, waxes, liquid paraffin, and petrolatum. Among these, those having a weight-average molecular weight of 150 to 3,000 are preferred. Those that are liquid at room temperature and normal pressure are also preferred. These compounds may be used alone or in combination of two or more.

[0035] Examples of polyolefins include polybutenes (polybutene, polyisobutene, etc.), ethylene-α-olefin copolymers, etc., and polybutenes are preferred. These may be used alone or in combination of two or more.

[0036] Examples of waxes include hydrocarbon waxes such as solid paraffin, animal waxes such as lanolin, etc. These may be used alone or in combination of two or more.

[0037] Examples of petrolatum include white petrolatum, yellow petrolatum, etc. These may be used alone or in combination of two or more.

[0038] Specific examples of aliphatic hydrocarbon compounds include NOF Polybutene (registered trademark, the same applies hereinafter) 0N, NOF Polybutene 015N, NOF Polybutene 3N, NOF Polybutene 10N, NOF Polybutene 30N, and NOF Polybutene 200N manufactured by NOF Corporation; Lucant (registered trademark, the same applies hereinafter) HC-40, Lucant HC-600, Lucant HC-600, Lucant HC-1100, and Lucant HC-2000 manufactured by Mitsui Chemicals, Inc.; and Nippon Seiro Co., Ltd. Examples of waxes that can be used include ParaffinWax-115, ParaffinWax-120, ParaffinWax-125, ParaffinWax-130, ParaffinWax-135, ParaffinWax-140, ParaffinWax-145, ParaffinWax-150, ParaffinWax-155, HNP-3, HNP-5, HNP-6, HNP-10, HNP-11, HNP-12, and HNP-51 manufactured by Toray Industries, Inc.

[0039] The content of the aliphatic hydrocarbon compound is preferably 15% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and even more preferably 18% by mass or more and 32% by mass or less, relative to the non-volatile components of the coating composition of the present invention. When two or more types of aliphatic hydrocarbon compounds are contained, it is preferable that the total content of the aliphatic hydrocarbon compounds is within the above-mentioned numerical range.

[0040] In one embodiment, the implantation inhibitor (B) can be a silicone oil and a polyolefin, or a silicone oil, a polyolefin, and a silicone powder.

[0041] In one embodiment, the implantation inhibitor (B) can be a polyether-modified silicone oil and a polybutene, or a polyether-modified silicone oil, a polybutene, and a silicone powder.

[0042] <Coating Adhesion Promoter (C)> The coating composition of the present invention preferably contains a coating adhesion promoter (C) which is one or more selected from the group consisting of rosin and silane coupling agents. By containing the coating adhesion promoter (C), it is possible to improve the adhesion between the coating film and the surface of the article and to suppress peeling of the coating film due to tidal changes in marine areas. Therefore, the coating composition of the present invention containing the coating adhesion promoter (C) can suppress the adhesion of aquatic organisms without containing the aquatic organism repellent, is less likely to cause coating peeling even when used in marine environments with tidal changes, and has a low risk of water pollution due to the release of chemicals or accumulation of chemicals in aquatic organisms.

[0043] For example, in the past, depending on the location of aquaculture, tidal differences have sometimes caused the coating film to peel off. When used in such aquaculture locations, it is particularly preferable that the coating composition of the present invention contains a coating adhesion promoter (C).

[0044] The coating adhesion promoter (C) can be selected depending on the material and shape of the substrate to be coated. The coating adhesion promoter (C) may be used alone or in combination of any two or more kinds.

[0045] Examples of rosin include modified rosin (maleic rosin, fumaric rosin, special modified rosin, etc.), modified rosin ester (maleic rosin ester, fumaric rosin ester, etc.), unmodified rosin, etc. Specific examples include HALITAC F-75, HALITAC FG-90, and HALIMAC T-80 manufactured by Harima Chemicals Co., Ltd.

[0046] The acid value of the rosin is preferably 100 mgKOH / g or more and 200 mgKOH / g or less. The softening point of the rosin is preferably 78°C or more and 100°C or less. More preferably, the acid value of the rosin is 140 mgKOH / g or more and 200 mgKOH / g or less, and the softening point is 75°C or more and 90°C or less. These may be used alone or in any combination of two or more.

[0047] The rosin content is preferably 0.5% by mass or more and 10% by mass or less, more preferably 0.9% by mass or more and 9% by mass or less, based on the non-volatile components of the coating composition of the present invention. The rosin content may also be 1% by mass or more and 10% by mass or less, based on the non-volatile components of the coating composition. When two or more types of rosin are contained, the total content of the rosins is preferably within the above-mentioned range. In particular, it is preferable to contain rosins having an acid value of 100 mg KOH / g or more and 220 mg KOH / g or less and a softening point of 78°C or more and 100°C or less, within the above-mentioned range.

[0048] Specific examples of silane coupling agents include vinyl-modified silane coupling agents, epoxy-modified silane coupling agents, styryl-modified silane coupling agents, methacryl- and acrylic-modified silane coupling agents, amino-modified silane coupling agents, mercapto-modified silane coupling agents, butadiene polymer-modified silane coupling agents, acid anhydride functional group-containing butadiene polymer-modified silane coupling agents, styrene-butadiene polymer-modified silane coupling agents, hydrolyzable silyl group silane coupling agents, polyfunctional group-type silane coupling agents, methoxy-type silanes, ethoxy-type silanes, silazanes, siloxanes, etc. These may be used alone or in any combination of two or more. More preferred examples include X-12-1267B, X-12-1287A, X-12-1281A, X-12-5263HP, KBM-3086, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103P, KBM-573, and KBM-575, all manufactured by Shin-Etsu Chemical Co., Ltd. , KBM-802, KBM-803, X-12-1048, X-12-1050, X-12-9815, X-12-9845, X-12 -1154, X-12-1156, X-12-1159L, KBM-13, KBM-22, KBM-103, KBM-202SS, KB M-3033, KBM-3063, KBM-3103C, KBM-3066, KBM-7103, KBE-04, KBE-13, KBE -22, KBE-103, KBE-3033, KBE-3063, KBE-3083, SZ-31, KPN-3504 and the like. Particularly preferred are aminosilane coupling agents, acid anhydride functional group-containing butadiene polymer-modified silane coupling agents, and hydrolyzable silyl group silane coupling agents.

[0049] The content of the silane coupling agent is preferably 0.2% by mass or more and 2.0% by mass or less, and more preferably 0.5% by mass or more and 1.5% by mass or less, based on the non-volatile components of the coating composition of the present invention.

[0050] The coating composition of the present invention does not contain one or more aquatic organism repellents selected from the group consisting of cuprous oxide (copper(I) oxide), copper bis(2-sulfidopyridin-1-olato), and N,N'-ethylenebis(thiocarbamoylthiozinc) bis(N,N-dimethyldithiocarbamate). Cuprous oxide, copper bis(2-sulfidopyridin-1-olato), and N,N'-ethylenebis(thiocarbamoylthiozinc) bis(N,N-dimethyldithiocarbamate) are widely used as antifouling agents. However, the coating composition of the present invention surprisingly exhibits long-term antifouling effects by including the resin (A) and the implantation inhibitor (B) without including these antifouling agents.

[0051] Furthermore, it is preferable that the coating composition of the present invention does not contain any compounds used as antifouling agents other than the aquatic organism repellents (hereinafter referred to as "other antifouling agents"). As defined in JIS H 7901:2005, an antifouling agent is an agent that functions to prevent the adhesion of organisms to the bottom of a ship or a fishing net in seawater. Examples of other antifouling agents include triphenylborane-amine complex compounds, tetraalkylthiuram diyl sulfide compounds, copper powder, copper rhodanide, copper naphthenate, sodium pyrithione, soluble glass, zinc bis(2-sulfidopyridin-1-olato), bisdimethyldithiocarbamoyl, zinc ethylenebisdithiocarbamate, zinc methyldithiocarbamate, zinc ethylenedithiocarbamate, manganese ethylenebisdithiocarbamate, 2,4,5,6-tetrachloroisophthalonitrile, 2,3-dichloro-N-(2 N,N'-dimethyl-dichlorophenylurea, N-(fluorodichloromethylthio)phthalimide, N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide, and N'-dichlorofluoromethylthio-N',N'-dimethyl-N-P-trisulfamide.

[0052] In one embodiment, the coating composition of the present invention may have a total content of the resin (A) and the implantation inhibitor (B) of 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more relative to the non-volatile components of the coating composition of the present invention.

[0053] In one embodiment, the coating composition of the present invention comprises resins (A), (B), and (C), wherein the resin (A) is one or more types of acrylic resins, and the implantation inhibitor (B) is a silicone oil and a polyolefin, or a silicone oil, a polyolefin, and a silicone powder, preferably a polyether-modified silicone oil and a polybutene, or a polyether-modified silicone oil, a polybutene, and a silicone powder, and may be free of an aquatic organism repellent that is one or more selected from the group consisting of cuprous oxide (copper(I) oxide), bis(2-sulfidopyridin-1-olato)copper, and bis(N,N-dimethyldithiocarbamate)N,N'-ethylenebis(thiocarbamoylthiozinc).

[0054] In one embodiment, the coating composition of the present invention comprises resins (A), (B), and (C), and the total content of the resin (A), implantation inhibitor (B), and coating adhesion promoter (C) can be 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more of the non-volatile components of the coating composition of the present invention.

[0055] The coating composition of the present invention may contain a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as xylene, toluene, ethylbenzene, and trimethylbenzene; aliphatic hydrocarbon solvents such as heptane; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohol solvents such as ethanol, isopropyl alcohol, and n-butanol. These may be used alone or in combination of two or more of them. Among these, aromatic hydrocarbon solvents are preferred, and xylene is more preferred.

[0056] The coating composition of the present invention can be produced using any known equipment and method.

[0057] <Method for forming an antifouling coating> The method for forming an antifouling coating of the present invention comprises the steps of applying the above-described chemical-free antifouling coating composition of the present invention to an article and drying the coating film of the applied chemical-free antifouling coating composition. Application to articles such as fishery materials, underwater structures, and fishing nets can be carried out using methods such as dipping, brushing, roll coating, and spraying. After application, the coating film can be dried under any conditions, such as natural drying, to form an antifouling coating.

[0058] Examples of the articles include fishery materials, underwater structures, and fishing nets. Examples of the fishery materials include floats, buoys, ropes, compose, and fishing gear. Examples of the underwater structures include various facilities such as submarine cables, submarine tunnels, and power generation facilities, as well as piping for various facilities and bridges. Among these, fishery materials and fishing nets are preferred.

[0059] The method for forming an antifouling coating of the present invention can provide an article having an antifouling coating formed thereon. The antifouling coating formed contains a resin (A) having an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less and a weight-average molecular weight (Mw) of 50,000 or more and 350,000 or less, and being one or more resins selected from the group consisting of acrylic resins, acrylic silicone resins, polyester resins, and alkyd resins, and an implantation inhibitor (B) being one or more selected from the group consisting of silicone compounds and aliphatic hydrocarbon compounds, but not containing an aquatic organism repellent selected from the group consisting of cuprous oxide, bis(2-sulfidopyridin-1-olato)copper, and bis(N,N-dimethyldithiocarbamate)N,N'-ethylenebis(thiocarbamoylthiozinc).

[0060] In one embodiment, the antifouling coating to be formed has a silicone oil content of 5 to 50 mass%, preferably 10 to 40 mass%, and more preferably 25 to 40 mass%, an aliphatic hydrocarbon compound content of 15 to 40 mass%, preferably 15 to 35 mass%, and more preferably 18 to 32 mass%, a silicone powder content of 0 to 2.0 mass%, preferably 0.5 to 2.0 mass%, more preferably 0.5 to 1.5 mass%, and even more preferably 0.5 to 1.0 mass%, a rosin content of 0 to 10 mass%, preferably 0.5 to 10 mass%, and more preferably 0.9 to 9 mass%, and a silane coupling agent content of 0 to 2.0 mass%, preferably 0.2 to 2.0 mass%, and more preferably 0.5 to 1.5 mass%. In one embodiment, the antifouling coating formed may have a total content of the resin (A), implantation inhibitor (B), and coating adhesion promoter (C) of 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more.

[0061] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not changed.

[0062] The following materials were used in the examples. (1) Resin (A) In the following examples, a solvent-based (xylene) acrylic resin (40% non-volatile component) was used as the base resin for the chemical-free antifouling coating composition. In the tables below, these resins are referred to as base resin 1 to base resin 13. Base resins 1 to 8 had acid values ​​of 0 mgKOH / g and weight-average molecular weights (Mw) as shown in Table 1. Base resins 9 to 13 had weight-average molecular weights (Mw) of 200,000 and acid values ​​as shown in Table 2. (2) Implantation inhibitor (B) The following was used as the implantation inhibitor (B).・Polyolefin: NOF Polybutene 0N (weight average molecular weight Mw550) ・Silicone oil: KF-6020 (polyether-modified silicone oil, HLB=4) ・Silicone powder: KMP-602 (silicone composite powder, average particle size 30 μm) ・Silicone powder: KMP-590 (silicone resin powder, average particle size 2 μm) (3) Coating adhesion promoter (C) ・Rosin: Halitack FG-90 (acid value: 140 to 150 mg KOH / g, softening point: 85 to 90°C) ・Rosin: Halimack T-80 (acid value: 140 to 150 mg KOH / g, softening point: 75°C) ・Silane coupling agent: X-12-1287A (acid anhydride functional group-containing butadiene polymer-modified silane coupling agent) ・Silane coupling agent: X-12-5263HP (polyhydrolyzable group-type silane coupling agent)

[0063] [I] Evaluation of Chemical-Free Antifouling Coating Compositions Based on Differences in Resin Properties Hereinafter, as an example, the manufacturing procedures for the chemical-free antifouling coating compositions of Example 5 in Table 1 and Example 14 in Table 2 will be described. The chemical-free antifouling coating compositions of Examples 1 to 4 and 6 to 8 were manufactured using the same manufacturing procedures as Example 5 below, except for the formulations shown in Table 1. Furthermore, the chemical-free antifouling coating compositions of Examples 9 to 13, 15, and 16 were manufactured using the same manufacturing procedures as Example 14 below, except for the formulations shown in Table 2. The resulting chemical-free antifouling coating compositions were subjected to the following marine immersion test-1 and storage stability test.

[0064] Example 5 To 59.9 parts by mass of xylene, 20.5 parts by mass of polyolefin (NOF Polybutene 0N, implantation inhibitor (B)) and 38.0 parts by mass of silicone oil (KF-6020, implantation inhibitor (B)) were sequentially added under stirring, and the mixture was mixed and stirred for 10 minutes. Further, 103.8 parts by mass of base resin 5 (polyalkyl acrylate, weight average molecular weight 200,000, acid value 0 mgKOH / g) was added, and the mixture was mixed and stirred for 30 minutes.

[0065] (Example 14) To 59.9 parts by mass of xylene, 20.5 parts by mass of polyolefin (NOF polybutene 0N, implantation inhibitor (B)) and 38.0 parts by mass of silicone oil (KF-6020, implantation inhibitor (B)) were sequentially added under stirring, and the mixture was mixed and stirred for 10 minutes. Further, 101.2 parts by mass of base resin 5 (polyalkyl acrylate, weight average molecular weight 200,000, acid value 0 mg KOH / g) and 2.6 parts by mass of base resin 10 (alkyl acrylate-acrylic acid copolymer, weight average molecular weight 200,000, acid value 3 mg KOH / g) were sequentially added, and the mixture was mixed and stirred for 30 minutes.

[0066] [Undersea Immersion Test-1] In Sasebo City, Nagasaki Prefecture, a Russell net cage (35 cm square x 20 cm high, quadrangular pyramidal shape) was coated with a chemical-free antifouling coating composition and allowed to dry. The coated Russell net cage was immersed in the sea, and the degree of adhesion of aquatic organisms was evaluated after 1 month, 2 months, 3 months, and 6 months.

[0067] (Attachment of aquatic organisms) The degree of attachment of aquatic organisms was evaluated comprehensively for all aquatic organisms (barnacles, serpula, hydra, moss worms, ascidians, etc.) and was evaluated as the area ratio of the part where attachment of aquatic organisms was observed to the surface area of ​​the net cage. In Tables 1 and 2, "○" means that the area of ​​attachment of aquatic organisms is less than 10%, "○△" means that the area of ​​attachment of aquatic organisms is 10% or more but less than 20%, and "△" means that the area of ​​attachment of aquatic organisms is 20% or more.

[0068] (Washing after 6 months of immersion) After immersion in the sea for 6 months, the adhesion strength of aquatic organisms to the surface of the coating film was evaluated by a washing test. In Tables 1 and 2, "○" indicates that the attached aquatic organisms could be removed immediately by hand, "○△" indicates that the attached aquatic organisms could be removed by hand but required some force, "△" indicates that the attached aquatic organisms could be removed by hand but required a long time, and "×" indicates that the attached aquatic organisms could not be removed by hand.

[0069] [Storage Stability Test] Storage stability was evaluated for six consecutive months in a thermostatic chamber, with one set consisting of two consecutive weeks at 50° C. and two consecutive weeks at 8° C. In Tables 1 and 2, "○" indicates that neither precipitation nor an increase in viscosity was observed, "○△" indicates that some precipitation occurred but the mixture returned to a uniform state upon stirring, "△" indicates that the mixture returned to a uniform state upon stirring, but particle formation was observed, and "×" indicates that aggregation and hardening were observed (the same applies hereinafter).

[0070] The results of the marine immersion test-1 and the storage stability test are shown in Tables 1 and 2. Furthermore, as Comparative Example 1, the marine immersion test-1 and the storage stability test were carried out using a commercially available copper-based antifouling paint instead of the chemical-free antifouling coating composition of the present invention. The results are also shown in Table 1.

[0071]

[0072]

[0073] [II] Effect of Rosin as Coating Adhesion Promoter (C) (Example 17) 20.7 parts by mass of polyolefin (NOF Polybutene 0N, implantation inhibitor (B)) and 38.4 parts by mass of silicone oil (KF-6020, implantation inhibitor (B)) were sequentially added to 61.9 parts by mass of xylene with stirring, and the mixture was mixed and stirred for 10 minutes. 103.8 parts by mass of Base Resin 5 (weight average molecular weight 200,000) was then added, and the mixture was mixed and stirred for 10 minutes. 1.0 part by mass of rosin (Hamatack FG-90) was then added, and the mixture was mixed and stirred for 30 minutes. The ratio of rosin to non-volatile components is as shown in Table 3.

[0074] (Example 27) To 61.9 parts by mass of xylene, 20.7 parts by mass of polyolefin (NOF polybutene 0N, implantation inhibitor (B)) and 38.4 parts by mass of silicone oil (KF-6020, implantation inhibitor (B)) were sequentially added under stirring, and mixed and stirred for 10 minutes. Further, 98.6 parts by mass of base resin 5 (weight average molecular weight 200,000) and 5.2 parts by mass of base resin 10 (acid value 3 mgKOH / g) were sequentially added, and mixed and stirred for 10 minutes. 1.0 part by mass of rosin (Hamatack FG-90) was added, and mixed and stirred for 30 minutes. The ratio of rosin to non-volatile components is as shown in Table 4.

[0075] Chemical-free antifouling coating compositions of Examples 18 to 26 were produced using the same production procedure as in Example 17 above, except for the formulations shown in Table 3. Chemical-free antifouling coating compositions of Examples 28 to 36 were produced using the same production procedure as in Example 27 above, except for the formulations shown in Table 4. The resulting chemical-free antifouling coating compositions were subjected to the following marine immersion test-2 and the above-mentioned storage stability test. The results are shown in Tables 3 and 4. Furthermore, as Comparative Example 2, a commercially available copper-based antifouling paint was used instead of the chemical-free antifouling coating composition of the present invention, and the marine immersion test-2 and storage stability test were also performed. The results are also shown in Table 3.

[0076] [Marine Immersion Test-2] To investigate the effect of tidal variations on coating peeling, a chemical-free antifouling coating composition was applied to an ABS Compose (47 mm diameter, 2 m length) at Mukojima, Hofu City, Yamaguchi Prefecture, and then allowed to dry. The coated ABS Compose was immersed in the sea to conduct a marine immersion test. The adhesion of aquatic organisms was evaluated by calculating the area ratio of the area where adhesion of aquatic organisms was observed to the surface area of ​​the ABS Compose, using the same criteria as in Marine Immersion Test-1. Cleaning after 6 months of immersion was evaluated using the same criteria as in Marine Immersion Test-1. The state of coating peeling was also evaluated using the following criteria.

[0077] (Paint peeling state) The paint peeling state was evaluated as the area ratio of the peeled paint to the surface area of ​​the ABS Compose. In Tables 3 and 4, "○" indicates that the peeled area was less than 10%, "○△" indicates that the peeled area was 10% or more but less than 20%, and "△" indicates that the peeled area was 20% or more.

[0078]

[0079]

[0080] The following Field Test-1 and Field Test-2 were carried out using the chemical-free antifouling coating compositions of Examples 27 to 36. Table 5 shows the results of Field Test-1. Table 6 shows the results of Field Test-2.

[0081] [Field Test-1] In the Sasebo area of ​​Nagasaki Prefecture, a monofilament mesh cage (upper: 40 cm diameter, 17 cm from the top; lower: 44 cm diameter, 12 cm from the top to the bottom) used in oyster farming was painted with a chemical-free antifouling paint composition, dried, and subjected to a three-month field test. The adhesion of aquatic organisms to the cage was evaluated one month, two months, and three months after immersion in the sea. The adhesion of aquatic organisms was evaluated using the same criteria as in the marine immersion test-1. In addition, the mortality rate and growth (weight and size) of oysters after three months were evaluated.

[0082] [Field Test-2] The same procedure as in Field Test-1 was conducted, except that the chemical-free antifouling coating composition was applied to monofilament mesh cages (upper section: diameter 40 cm, 17 cm from the top; lower section: diameter 44 cm, 12 cm from the top to the bottom) used for scallop culture in the Rausu area of ​​Hokkaido instead of the monofilament mesh cages used for oyster culture in the Sasebo area of ​​Nagasaki Prefecture. The mortality rate and growth (weight and size) of the scallops after 3 months were evaluated.

[0083]

[0084]

[0085] [III] Effect of silane coupling agent as coating adhesion promoter (C) (Example 37) 61.9 parts by mass of xylene was stirred, and 20.7 parts by mass of polyolefin (NOF polybutene 0N, implantation inhibitor (B)), 38.4 parts by mass of silicone oil (KF-6020, implantation inhibitor (B)) were sequentially added, and mixed and stirred for 10 minutes, and then 103.8 parts by mass of base resin 5 (weight average molecular weight 200,000) was added, and mixed and stirred for 10 minutes, and 0.2 parts by mass of silane coupling agent (X-12-1287A) was added and mixed and stirred for 30 minutes. The ratio of silane coupling agent to non-volatile components is as shown in Table 7.

[0086] (Example 47) To 61.9 parts by weight of xylene under stirring, polyolefin (NOF polybutene 0N, implantation inhibitor (B)) 20.7 parts by weight, silicone oil (KF-6020, implantation inhibitor (B)) 38.4 parts by weight were sequentially added, mixed and stirred for 10 minutes, further base resin 5 (weight average molecular weight 200,000) 98.6 parts by weight, base resin 10 (acid value 3 mg KOH / g) 5.2 parts by weight were sequentially added, mixed and stirred for 10 minutes, silane coupling agent (X-12-1287A) 0.2 parts by weight was added and mixed and stirred for 30 minutes. The ratio of silane coupling agent to non-volatile components is as shown in Table 8.

[0087] The chemical-free antifouling coating compositions of Examples 38 to 46 were produced using the same production procedure as in Example 37 above, except for the formulations shown in Table 7. The chemical-free antifouling coating compositions of Examples 48 to 56 were produced using the same production procedure as in Example 47 above, except for the formulations shown in Table 8. The obtained chemical-free antifouling coating compositions were subjected to the above-mentioned marine immersion test-2 and storage stability test. The results are shown in Tables 7 and 8.

[0088]

[0089]

[0090] The above-mentioned Field Test-1 and Field Test-2 were carried out using the chemical-free antifouling coating compositions of Examples 37 to 46. Table 9 shows the results of Field Test-1. Table 10 shows the results of Field Test-2.

[0091]

[0092]

[0093] [IV] Effect of silicone oil as implantation inhibitor (B) (Example 57) 12.3 parts by mass of polyolefin (NOF Polybutene 0N (implantation inhibitor (B)) and 5.0 parts by mass of silicone oil (KF-6020, implantation inhibitor (B)) were sequentially added to 10.8 parts by mass of xylene under stirring, and mixed and stirred for 10 minutes, and then 103.8 parts by mass of base resin 5 (weight average molecular weight 200,000) was added, and mixed and stirred for 10 minutes, and then 1.0 part by mass of rosin (Halima T-80) was added, and mixed and stirred for 30 minutes. The ratio of silicone oil to non-volatile components is as shown in Table 11.

[0094] The chemical-free antifouling coating compositions of Examples 58 to 66 were produced using the same production procedure as in Example 57 above, except for the formulations shown in Table 11. The obtained chemical-free antifouling coating compositions were subjected to the above-mentioned marine immersion test-2 and storage stability test. The results are shown in Table 11.

[0095]

[0096] The above-mentioned Field Test-1 and Field Test-2 were carried out using the chemical-free antifouling coating compositions of Examples 57 to 66. Table 12 shows the results of Field Test-1. Table 13 shows the results of Field Test-2.

[0097]

[0098]

[0099] [V] Effect of Aliphatic Hydrocarbon Compound as Implantation Inhibitor (B) (Example 67) 14.3 parts by mass of polyolefin (NOF Polybutene 0N, implantation inhibitor (B)) and 38.4 parts by mass of silicone oil (KF-6020, implantation inhibitor (B)) were sequentially added to 54.0 parts by mass of xylene under stirring, and the mixture was mixed and stirred for 10 minutes. 103.8 parts by mass of Base Resin 5 (weight average molecular weight 200,000) was then added, and the mixture was mixed and stirred for 10 minutes. 1.0 part by mass of rosin (Halima T-80) was then added, and the mixture was mixed and stirred for 30 minutes. The ratio of polyolefin to non-volatile components is shown in Table 14.

[0100] The chemical-free antifouling coating compositions of Examples 68 to 76 were produced using the same production procedures as in Example 67 above, except for the formulations shown in Table 14. The obtained chemical-free antifouling coating compositions were subjected to the above-mentioned marine immersion test-2 and storage stability test. The results are shown in Table 14.

[0101]

[0102] The above-mentioned Field Test-1 and Field Test-2 were carried out using the chemical-free antifouling coating compositions of Examples 67 to 76. Table 15 shows the results of Field Test-1. Table 16 shows the results of Field Test-2.

[0103]

[0104]

[0105] [VI] Effect of silicone powder as implantation inhibitor (B) (Example 77) 66.8 parts by mass of xylene was stirred, and 21.9 parts by mass of polyolefin (NOF polybutene 0N, implantation inhibitor (B)), 40.7 parts by mass of silicone oil (KF-6020, implantation inhibitor (B)) were sequentially added, and mixed and stirred for 10 minutes, and then 103.8 parts by mass of base resin 5 (weight average molecular weight 200,000) and 0.5 parts by mass of silicone powder (KBM-590) were added, and mixed and stirred for 10 minutes, and 1.0 parts by mass of rosin (Halima T-80) were added and mixed and stirred for 30 minutes. The ratio of silicone powder to non-volatile components is as shown in Table 17.

[0106] Chemical-free antifouling coating compositions of Examples 78 to 86 were produced using the same production procedure as in Example 77 above, except for the formulations shown in Table 17. The resulting chemical-free antifouling coating compositions were subjected to the above-mentioned Marine Immersion Test-2, and the adhesion of aquatic organisms and cleaning after 6 months of immersion were evaluated. Furthermore, a storage stability test was also carried out using the resulting chemical-free antifouling coating compositions. The results are shown in Table 17.

[0107] [ABS Resin Adhesion Test] The ABS resin adhesion test was carried out using a 1 mm thick, 6 cm x 8 cm board (Japan Test Panel (wood)) in accordance with the method described in JIS K5600-5-6: General Test Methods for Paints, Part 5: Mechanical Properties of Coatings, Section 6: Adhesion (Cross-Cut Method). In Table 17, "1 mm width" and "2 mm width" indicate the width of the cross-cut formed on the surface of the coating film, "100 / 100" indicates that no peeling was observed after removal of the adhesive tape in any of the 100 squares formed by the cross-cut, and "50 / 50" indicates that no peeling was observed after removal of the adhesive tape in any of the 50 squares formed by the cross-cut.

[0108]

[0109] The above-mentioned Field Test-1 and Field Test-2 were carried out using the chemical-free antifouling coating compositions of Examples 77 to 86. Table 18 shows the results of Field Test-1. Table 19 shows the results of Field Test-2.

[0110]

[0111]

[0112] [VII] Example 87, Comparative Examples 3 and 4 In Example 87, the chemical-free antifouling coating composition of Example 79 was applied to an ABS compose (diameter 47 mm, length 2 m), dried, and then immersed in the sea for 6 months. In Comparative Example 3, the ABS compose was immersed in the sea for 6 months without being coated with any coating material. In Comparative Example 4, a coating material with a composition in which the antifouling agents (cuprous oxide and bis-2-pyridinethiol copper salt) were removed from the antifouling agent-containing coating material (Boussel Chemical's Boumou (registered trademark) CU#1500) was applied to an ABS compose, dried, and then immersed in the sea for 6 months.

[0113] Figure 1 shows a photograph of the ABS compose of Example 87 after the marine immersion test. Figure 2 shows a photograph of the ABS compose of Comparative Example 3 (left) and a photograph of the ABS compose of Comparative Example 4 (right) after the marine immersion test. As shown in Figure 1, no adhesion of aquatic organisms was observed in Example 87. On the other hand, as shown in Figure 2, adhesion of aquatic organisms was suppressed in Comparative Example 4 compared to Comparative Example 3, where no paint was applied, but adhesion of aquatic organisms was still observed. Figures 1 and 2 show that application of the chemical-free antifouling coating composition of the present invention exhibits excellent antifouling effects.

Claims

1. A chemical-free antifouling coating composition for forming a coating film that inhibits the attachment of aquatic organisms on the surface of an article that comes into contact with water, comprising: resin (A) having an acid value of 0 mgKOH / g to 10 mgKOH / g and a weight-average molecular weight (Mw) of 50,000 to 350,000, and being one or more resins selected from the group consisting of acrylic resin, acrylic silicone resin, polyester resin, alkyd resin, and alkyd rosin resin; and implantation inhibitor (B) being one or more selected from the group consisting of silicone compounds and aliphatic hydrocarbon compounds, said chemical-free antifouling coating composition not containing one or more aquatic organism repellents selected from the group consisting of cuprous oxide, bis(2-sulfidopyridin-1-olato)copper, and bis(N,N-dimethyldithiocarbamate)N,N'-ethylenebis(thiocarbamoylthiozinc).

2. The chemical-free antifouling coating composition according to claim 1, further comprising a coating adhesion promoter (C) which is one or more selected from the group consisting of rosin and silane coupling agents.

3. A chemical-free antifouling coating composition according to claim 2, containing the rosin having an acid value of 100 mgKOH / g or more and 220 mgKOH / g or less and a softening point of 78°C or more and 100°C or less in an amount of 0.5% by mass or more and 10% by mass or less relative to the non-volatile components.

4. A chemical-free antifouling coating composition according to claim 2, containing the silane coupling agent in a proportion of 0.2% by mass or more and 2.0% by mass or less based on the non-volatile components.

5. The chemical-free antifouling coating composition according to claim 1, wherein the silicone compound comprises one or more silicone oils selected from the group consisting of polyether-modified silicone oil, alkyl-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, mercapto-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, higher fatty acid-modified silicone oil, and higher fatty acid-containing silicone oil, the content of the silicone oil is 5% by mass or more and 50% by mass or less based on the non-volatile components, the aliphatic hydrocarbon compound is one or more selected from the group consisting of polyolefin, wax, liquid paraffin, and petrolatum, the weight-average molecular weight of the aliphatic hydrocarbon compound is 150 or more and 3,000 or less, and the content of the aliphatic hydrocarbon compound is 15% by mass or more and 40% by mass or less based on the non-volatile components.

6. A chemical-free antifouling coating composition according to claim 5, wherein the silicone compound comprises one or more silicone powders selected from the group consisting of silicone composite powders having an average particle size of 0.2 μm to 60 μm, silicone rubber powders having an average particle size of 1 μm to 30 μm, and silicone resin powders having an average particle size of 0.2 μm to 8.0 μm, and the content of the silicone powder is 0.5% by mass to 2.0% by mass of the non-volatile components.

7. A chemical-free antifouling coating composition according to claim 2, wherein the resin (A) is one or more types of acrylic resin, and the implantation inhibitor (B) is silicone oil and polyolefin, or silicone, polyolefin, and silicone powder.

8. A method for forming an antifouling coating, comprising the steps of applying the chemical-free antifouling coating composition described in any one of claims 1 to 7 to an article and drying the coating film of the applied chemical-free antifouling coating composition.

9. An article having an antifouling coating formed thereon, wherein the antifouling coating comprises: a resin (A) having an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less and a weight average molecular weight (Mw) of 50,000 or more and 350,000 or less, and being one or more resins selected from the group consisting of acrylic resins, acrylic silicone resins, polyester resins, and alkyd resins; and an implantation inhibitor (B) being one or more selected from the group consisting of silicone compounds and aliphatic hydrocarbon compounds; and the article does not contain an aquatic organism repellent being one or more selected from the group consisting of cuprous oxide, bis(2-sulfidopyridine-1-olato)copper, and bis(N,N-dimethyldithiocarbamate)N,N'-ethylenebis(thiocarbamoylthiozinc).

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