Chemical-free antifouling paint composition and method for forming antifouling film using the same

Abstract

The object of the present invention is to provide a novel antifouling paint composition that does not contain a marine organism repellent and that can inhibit adhesion of marine organisms and seaweed to marine materials, underwater structures, fishing nets, etc., and further to provide a method for forming an antifouling coating using said composition. [Solution] This is an antifouling paint 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 antifouling paint composition 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 300,000 or less, and comprising one or more resins selected from the group consisting of acrylic resins, acrylic silicone resins, polyester resins, alkyd resins, and alkyd rosin resins, a coating adhesion promoter, and an implantation inhibitor for suppressing the implantation of aquatic organisms on the surface of the coating, and does not contain an aquatic organism repellent.

Description

[Technical field]

[0001] The present invention relates to a novel drug-free antifouling paint composition that does not contain a marine organism repellent and that can suppress adhesion of marine organisms and seaweed to marine materials, underwater structures, fishing nets, etc., and a method for forming an antifouling coating film using the same. [Background technology]

[0002] Various marine organisms attach to the surfaces of articles such as marine materials, underwater structures, and fishing nets used in the fields of the fisheries, fishing, and marine transportation. Marine organisms such as barnacles, hydroids, bryozoans, and sea bass attach to marine materials, underwater structures, and fishing nets, and block the meshes, causing problems such as deterioration of water quality, fish diseases, and net damage. Various antifouling paints have been used to prevent the attachment of marine organisms to marine materials, underwater structures, and fishing nets, which cause such problems. In the past, antifouling paints containing organotin compounds as antifouling components 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 addition, in the fishing industry, antifouling paints containing marine life repellents have been used for fixed nets and aquaculture nets. However, in recent years, with the development of aquaculture, there has been a demand for the development of chemical-free antifouling paints that are less susceptible to chemical buildup, environmental conservation, and peeling caused by tidal changes in ocean currents.

[0004] In consideration of environmental conservation and the health of workers, etc., development of water-based antifouling paints that do not contain organic solvents is progressing. For example, Patent Document 1 discloses a water-based antifouling paint composition that contains an emulsion resin, a dispersion resin, and a marine organism repellent.

[0005] In Patent Document 2, a resin is prepared by binding an additive such as rosin, which dissolves in seawater, to the carboxyl group of a hydrolyzable resin. This resin is used to prepare an antifouling paint composition by mixing a marine organism repellent, and the antifouling effect is maintained.

[0006] Patent Document 3 discloses a coating composition that uses a sulfur-containing organopolysiloxane block vinyl copolymer to soften the coating film and prevent it from peeling off due to tidal changes. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2006-193731 A [Patent Document 2] JP 2006-152205 A [Patent Document 3] Patent No. 6859080 specification Summary of the Invention [Problem to be solved by the invention]

[0008] 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 concerns about the accumulation of chemicals due to the use of a marine organism repellent. The antifouling paint composition described in Patent Document 2 also has concerns about the accumulation of chemicals, as with the aqueous antifouling paint described in Patent Document 1. In Patent Document 3, the flexibility and peeling of the coating film are improved, but questions remain about the effects of tide differences.

[0009] In the past, antifouling paints containing marine organism repellents were used on marine materials, underwater structures, fishing nets, etc., to prevent marine organisms and seaweed from attaching to them. In recent years, with the development of aquaculture, the impact of their accumulation on marine products and environmental conservation have become issues. In addition, depending on the location of aquaculture, there is a problem of the paint film peeling off due to tidal differences.

[0010] The present invention has been made in consideration of the above circumstances, and has an object to provide a chemical-free antifouling paint composition which is capable of exerting an antifouling effect for a long period of time, does not cause the problem of chemical accumulation in marine products, and is resistant to peeling of the coating film due to tidal differences, an antifouling coating formed using the same, and marine materials, underwater structures, and fishing nets having the same coating on their surfaces. [Means for solving the problem]

[0011] In accordance with the above-mentioned object, a first aspect of the present invention provides an antifouling coating composition for forming a coating film that inhibits the attachment of aquatic organisms on a surface of an article that comes into contact with water, the antifouling coating composition 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 300,000 or less, and comprising one or more resins selected from the group consisting of poly(acrylic acid alkyl ester) resins, poly(methacrylic acid alkyl ester) resins, acrylic acid alkyl ester-acrylic acid copolymer resins, methacrylic acid alkyl ester-methacrylic acid copolymer resins, acrylic silicone resins, polyester resins, alkyd resins, and alkyd rosin resins, a coating adhesion promoter, and an implantation inhibitor for inhibiting the implantation of aquatic organisms on the surface of the coating film, and which solves the above-mentioned problems by providing a chemical-free antifouling coating composition that does not contain an aquatic organism repellent.

[0012] In the chemical-free antifouling coating composition according to the first aspect of the present invention, the coating adhesion promoter may contain rosin having an acid value of 100 to 220 mgKOH / g and a softening point of 78 to 100°C in a ratio of 1% to 10% based on the non-volatile components.

[0013] In the chemical-free antifouling coating composition according to the first aspect of the present invention, a silane coupling agent may be further contained as the coating adhesion promoter in a ratio of 0.2% or more and 2.0% or less based on the non-volatile components.

[0014] In the drug-free antifouling coating composition according to the first aspect of the present invention, the implantation inhibitor may contain a silicone compound selected from the group consisting of methyl silicone, dimethyl silicone, methylphenyl silicone, cyclic methyl polysiloxane, alkyl-modified silicone oil, polyether-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, in a ratio of 5% to 50% based on the non-volatile components.

[0015] In the drug-free antifouling coating composition according to the first aspect of the present invention, the implantation inhibitor is selected from the group consisting of polybutenes, isopolybutenes, waxes, liquid paraffin, solid paraffin, and laurin. 、 Vaseline and Ethylene-α-olefin copolymer with a molecular weight of 150 to 3000 One or more compounds selected from the group consisting of may be contained in a ratio of 15% to 35% of the non-volatile components.

[0016] In the chemical-free antifouling coating composition according to the first aspect of the present invention, the implantation inhibitor may further comprise a silicone powder selected from the group consisting of a silicone composite powder having an average particle size of 0.2 μm or more and 60 μm or less, a silicone rubber powder having an average particle size of 1 μm or more and 30 μm or less, and a silicone resin powder having an average particle size of 0.2 μm or more and 8.0 μm or less, in a ratio of 0.5% to 2.0% based on the non-volatile components.

[0017] The second aspect of the present invention solves the above-mentioned problems by providing a method for forming an antifouling coating film, comprising the steps of applying the chemical-free antifouling coating composition according to the first aspect of the present invention and drying the applied coating film of the chemical-free antifouling coating composition. Effect of the Invention

[0018] According to the present invention, there is provided a chemical-free antifouling paint that can inhibit the attachment of aquatic organisms without containing chemicals, that is less likely to cause peeling of the coating film even when used in the ocean with tidal variations, and that has a low risk of water pollution due to the release of chemicals or accumulation of chemicals in aquatic organisms, and a method for forming an antifouling coating using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The drug-free antifouling coating composition according to one embodiment of the present invention (hereinafter, sometimes abbreviated as "drug-free antifouling coating composition" or "antifouling coating composition") is a drug-free antifouling coating composition comprising (A) one or more resins 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 300,000 or less, selected from the group consisting of poly(acrylic acid alkyl ester) resins, poly(methacrylic acid alkyl ester) resins, acrylic acid alkyl ester-acrylic acid copolymer resins, methacrylic acid alkyl ester-methacrylic acid copolymer resins, acrylic silicone resins, polyester resins, alkyd resins, and alkyd rosin resins, (B) a coating adhesion promoter of rosin and a silane coupling agent, and (C) an implantation inhibitor of a silicone compound, a silicone powder, and an ethylene-α-olefin copolymer. Each component will be described in detail below.

[0020] (A) Resin Coating components of the chemical-free antifouling coating composition are solvent-soluble, and examples of resins include acrylic resins (a general term for poly(acrylic acid alkyl ester) resins, poly(methacrylic acid alkyl ester) resins, acrylic acid alkyl ester-acrylic acid copolymer resins, and methacrylic acid alkyl ester-methacrylic acid copolymer resins), acrylic silicone resins, polyester resins, alkyd resins, and alkyd rosin resins.

[0021] These resins can be synthesized by any known method such as solution polymerization using a radical initiator, emulsion polymerization, etc. The acrylic acid alkyl ester-acrylic acid copolymer resin and the methacrylic acid alkyl ester-methacrylic acid copolymer resin may be obtained by partially hydrolyzing the carboxylic acid alkyl ester groups of a poly(acrylic acid alkyl ester) resin and a poly(methacrylic acid alkyl ester) resin, respectively.

[0022] The acid value of the resin used in the chemical-free antifouling paint composition is preferably 0 to 10 mgKOH / g, more preferably 0 to 5 mgKOH / g, from the viewpoint of long-term storage stability. As defined in JIS K5601-2-1:1999 (Paint component test method - Part 2: Component analysis in solvent-soluble matter - Section 1: Acid value (titration method)), the acid value refers to "the amount (mg) of KOH required to neutralize free acid in 1 g of nonvolatile matter 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.

[0023] The weight average molecular weight (Mw) of the resin used in the chemical-free antifouling coating composition is 50,000 or more and 300,000 or less, preferably 100,000 or more and 250,000 or less, in order to form a film and maintain the effect for a long time. The molecular weight can be measured by any known method such as GPC (gel permeation chromatography) analysis.

[0024] (B) Coating adhesion promoter The chemical-free antifouling coating composition contains a coating adhesion promoter in order to improve the adhesion between the coating and the surface of the article, thereby preventing the coating from peeling off due to the tide in the sea. The coating adhesion promoter can be selected according to the material and shape of the object to be coated. Preferable examples of the coating adhesion promoter include rosin and silane coupling agents. These may be used alone or in combination of any two or more kinds.

[0025] The rosin can be contained in a ratio of 1% to 10% based on the non-volatile components of the chemical-free antifouling coating composition (all components contained in the chemical-free antifouling coating composition excluding volatile components such as solvents. Also referred to as solid content). The acid value of the rosin is preferably 100 mgKOH / g to 200 mgKOH / g. The softening point of the rosin is preferably 78°C to 100°C. More preferably, the acid value of the rosin is 140 mgKOH / g to 200 mgKOH / g and the softening point is 75°C to 90°C. These may be used alone or in combination of any two or more kinds. Specific examples of rosin include Haritac F-75, Haritac FG-90, and Harima T-80 manufactured by Harima Chemical Co., Ltd.

[0026] The silane coupling agent can be contained in a ratio of 0.2% to 2.0% of the non-volatile components of the drug-free antifouling coating composition, preferably 0.5% to 1.5%. Specific examples of the silane coupling agent 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, and siloxanes. These may be used alone, or any two or more of them may be used in combination. 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 manufactured by Shin-Etsu Chemical Co., Ltd. , KBM-802, KBM-803, X-12-1048, X-12-1050, X-12-9815, Examples include 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, etc. Particularly preferred are aminosilane coupling agents, acid anhydride functional group-containing butadiene polymer-modified silane coupling agents, and hydrolyzable silyl group silane coupling agents.

[0027] (C) Implantation inhibitors As an implantation inhibitor for inhibiting the implantation of aquatic organisms on the surface of the coating film, the chemical-free antifouling coating composition may use one or more compounds selected from the group consisting of silicone compounds, ethylene-α-olefin copolymers, and silicone powders. Each component will be described in detail below.

[0028] The silicone compound can be contained in an amount of 5% to 50%, more preferably 10% to 40%, more preferably 25% to 40% of the non-volatile components of the drug-free antifouling coating composition. The hydrophilic-lipophilic balance (HLB) of the silicone compound is preferably 1 to 8, more preferably 2 to 6. Specific examples of the silicone compound include methyl silicone, dimethyl silicone, methylphenyl silicone, cyclic methyl polysiloxane, alkyl-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, mercapto-modified silicone oil, epoxy-modified silicone oil, phenyl-modified silicone oil, carboxyl-modified silicone oil, higher fatty acid-modified silicone oil, and higher fatty acid-containing silicone oil. 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, KF-413, KF-414, and KF-41 manufactured by Shin-Etsu Chemical Co., Ltd. No. 5, 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. are included, and polyether modified silicone oil is more preferred.

[0029] The ethylene / α-olefin copolymer preferably has a weight average molecular weight of 150 to 3000. The ethylene / α-olefin copolymer may be contained in an amount of 15% to 35%, more preferably 18% to 32%, of the non-volatile components of the chemical-free antifouling coating composition. Compounds that can be used other than Specific examples include polybutenes and isopolybutenes, waxes, liquid paraffin, solid paraffin, laurin, and vaseline. These may be used alone or in any combination of two or more. . Ingredients Specific examples include polybutene 0N, polybutene 015N, polybutene 3N, polybutene 10N, polybutene 30N, and polybutene 200N manufactured by NOF Corporation; LUCANT HC-40, LUCANT HC-600, LUCANT HC-1100, and LUCANT HC-2000 manufactured by Mitsui Chemicals, Inc.; and ParaffinWax-115, ParaffinWax-120, ParaffinWax-125, ParaffinWax-130, ParaffinWax-135, ParaffinWax-140, ParaffinWax-145, ParaffinWax-150, ParaffinWax-155, HNP-3, HPN-5, HPN-6, HPN-10, HPN-11, HPN-12, and HPN-51 manufactured by Nippon Seisakusho Co., Ltd.

[0030] Examples of silicone powder include silicone composite powder with an average particle size of 0.2 μm to 60 μm, silicone rubber powder with an average particle size of 1 μm to 30 μm, and silicone resin powder 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. The silicone powder may be contained in a ratio of 0.5% to 2.0%, preferably 0.5% to 1.0%, of the non-volatile components of the drug-free antifouling paint composition. Specific examples of silicone powder include KMP-600, KMP-601, IOIP-602, KMP-605, X-52-7030, KMP-402, KMP-597, IOIP-598, IOIP-590, IOIP-706, X-52-854, X-52-1621, etc., manufactured by Shin-Etsu Chemical Co., Ltd.

[0031] The chemical-free antifouling coating composition can be produced using any known device and method. The coating of articles such as fishery materials, underwater structures, and fishing nets can be performed using methods such as immersion, brush coating, roll coater method, and spraying method. After coating, the coating film can be dried under any conditions such as natural drying to form an antifouling coating. EXAMPLES

[0032] Next, examples carried out to confirm the effects of the present invention will be described. [I] Preparation of chemical-free antifouling paint composition by difference in resin properties In the following examples, a solvent-based (xylene) acrylic resin (40% non-volatile component) was used as the resin that serves as the base material for the chemical-free antifouling coating composition. Hereinafter, in Tables 1 and 2, these are referred to as base material resin 1 to base material resin 13. Base material resin 1 to base material resin 8 have an acid value of 0, and a weight-average molecular weight as shown in Table 1. Base material resin 9 to base material resin 13 have a weight-average molecular weight of 200,000, and an acid value as shown in Table 2.

[0033] As an example, the manufacturing procedure of the chemical-free antifouling coating composition according to Example 5 in Table 1 and Example 14 in Table 2 will be described below.

[0034] Example 5 20.5 parts by mass of polybutene 0N (implantation inhibitor) and 38.0 parts by mass of KF-6020 (implantation inhibitor) were sequentially added to 59.9 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 (polyacrylic acid alkyl ester, weight average molecular weight 200,000, acid value 0 mgKOH / g) were further added and mixed and stirred for 30 minutes. In Examples 1 to 13, the chemical-free antifouling paint composition was produced using the same production procedure. The chemical-free antifouling paint composition was used to carry out an underwater immersion test.

[0035] Example 14 20.5 parts by mass of polybutene 0N (implantation inhibitor) and 38.0 parts by mass of KF-6020 (implantation inhibitor) were sequentially added to 59.9 parts by mass of xylene under stirring, and the mixture was mixed and stirred for 10 minutes. Further, 101.2 parts by mass of base resin 5 (polyacrylic acid alkyl ester, weight average molecular weight 200,000, acid value 0 mgKOH / g) and base resin 10 (alkyl acrylate) were added. workman 2.6 parts by mass of ester-acrylic acid copolymer (weight average molecular weight 200,000, acid value 3 mgKOH / g) were added in sequence and mixed and stirred for 30 minutes. In Examples 15 and 16, chemical-free antifouling paint compositions were produced using the same production procedure. Using this chemical-free antifouling paint composition, an underwater immersion test (underwater immersion results in a Russell net cage in Sasebo City, Nagasaki Prefecture) was carried out.

[0036] The results of the underwater immersion, the cleaning test after 6 months of immersion, and the 6-month storage stability test of the chemical-free antifouling paint are shown in Tables 1 and 2.

[0037] (Results of underwater immersion) The evaluation results showed that all aquatic organisms (barnacles, serpula, hydra, moss worms, and squirrels, etc.) degree ) and evaluated based on the area ratio where aquatic organisms were found to be attached. In Tables 1 and 2, "○" means less than 10%, "○△" means between 10 and 20%, and "△" means 20% or more (same below).

[0038] (washed after soaking for 6 months) The adhesion strength of aquatic organisms to the coating surface was evaluated by a cleaning test after immersion for six months. In Tables 1 and 2, "○" means that it can be removed immediately by hand, "○△" means that it can be removed by hand but some force is required, "△" means that it can be removed by hand but it takes a long time, and "×" means that it cannot be removed by hand (the same applies below).

[0039] (Storage stability test) The storage stability was evaluated for six consecutive months in a thermostatic chamber, with two consecutive weeks at 50°C and two consecutive weeks at 8°C as one set. The evaluation results are as follows: "○" indicates that neither precipitation nor 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 below).

[0040] [Table 1]

[0041] [Table 2]

[0042] [Effect of rosin as a paint adhesion promoter] An example of a method for producing and adjusting a chemical-free antifouling coating composition containing rosin will be described with reference to the compositions shown in Example 17 of Table 3 and Example 27 of Table 4.

[0043] (Example 17) 20.7 parts by mass of polybutene 0N (implantation inhibitor) and 38.4 parts by mass of KF-6020 (implantation inhibitor) were added to 61.9 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 1.0 part by mass of Hamatack FG-90 was added and mixed and stirred for 30 minutes. The ratio of rosin to non-volatile components is shown in Table 3.

[0044] Example 27 20.7 parts by mass of polybutene 0N (polybutene: implantation inhibitor) and 38.4 parts by mass of KF-6020 (ethylene-α-olefin copolymer: implantation inhibitor) were added to 61.9 parts by mass of xylene under stirring, and mixed and stirred for 10 minutes. 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 added to the mixture, and mixed and stirred for 10 minutes. 1.0 part by mass of Hamatack FG-90 was added and mixed and stirred for 30 minutes. The ratio of rosin to non-volatile components is shown in Table 4.

[0045] In order to study the effect of paint peeling caused by tidal differences, an ABS Compose (diameter 47 mm, length 2 m) was painted and subjected to an underwater immersion test at Mukaishima, Hofu City, Yamaguchi Prefecture. The results of the underwater immersion (6-month results, washing after 6-month immersion, and 6-month storage stability test results for chemical-free antifouling paint) are shown in Tables 3 and 4.

[0046] The evaluation results of the peeling state of the coating film are shown as the area ratio of the peeled part of the coating film. In Tables 3 and 4, "○" indicates less than 10%, "○△" indicates 10% to less than 20%, and "△" indicates 20% or more.

[0047] [Table 3]

[0048] [Table 4]

[0049] A field test was conducted using the compositions of Examples 27 to 36 on monofilament cages used in oyster farming in the Sasebo area of ​​Nagasaki Prefecture and scallop farming in the Rausu area of ​​Hokkaido, and a 3-month immersion test was conducted. The test results and the results of the growth tests of oysters and scallops are shown in Tables 5 and 6.

[0050] [Table 5]

[0051] [Table 6]

[0052] [Effect of silane coupling agents as tidal separation inhibitors] An example of a method for preparing a chemical-free antifouling coating composition containing a silane coupling agent will be described with reference to the compositions shown in Example 36 of Table 7 and Example 47 of Table 8.

[0053] (Example 37) 20.7 parts by mass of polybutene 0N (implantation inhibitor) and 38.4 parts by mass of KF-6020 (implantation inhibitor) were added to 61.9 parts by mass of xylene under stirring, and the mixture was stirred for 10 minutes. 103.8 parts by mass of base resin 5 (weight average molecular weight 200,000) was added, and the mixture was stirred for 10 minutes. 0.2 parts by mass of X-12-1287A (silane coupling agent) was added, and the mixture was stirred for 30 minutes. The ratio of the silane coupling agent to the non-volatile components is as shown in Table 7.

[0054] (Example 47) 20.7 parts by mass of polybutene 0N (implantation inhibitor) and 38.4 parts by mass of KF-6020 (implantation inhibitor) were added to 61.9 parts by mass of xylene under stirring, and mixed and stirred for 10 minutes. 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 added to the mixture, and mixed and stirred for 10 minutes. 0.2 parts by mass of X-12-1287A (silane coupling agent) were added and mixed and stirred for 30 minutes. The ratio of the silane coupling agent to the non-volatile components is as shown in Table 8.

[0055] The coating was applied to an ABS Compose (47 mm in diameter, 2 m in length) at Mukaishima, Hofu City, Yamaguchi Prefecture. The results of immersion in the ocean (6-month results, washing after 6-month immersion, and 6-month storage stability test results for the chemical-free antifouling paint) are shown in Tables 7 and 8.

[0056] [Table 7]

[0057] [Table 8]

[0058] A field test was carried out using the compositions of Examples 47 to 56. The monofilament cages used in oyster farming in Sasebo, Nagasaki Prefecture, and scallop farming in Rausu, Hokkaido, were painted with the compositions and immersed for three months. The test results and the growth test results of oysters and scallops are shown in Tables 9 and 10.

[0059] [Table 9]

[0060] [Table 10]

[0061] [Effect of silicone compounds as implantation inhibitors] An example of a method for preparing a chemical-free antifouling coating composition using a silicone compound will be described with reference to the composition shown in Example 57 of Table 11.

[0062] (Example 57) 10.8 parts by mass of xylene was mixed with 12.3 parts by mass of polybutene 0N (implantation inhibitor) and 5.0 parts by mass of KF-6020 (implantation inhibitor) in order, 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 1.0 part by mass of Halimaq T-80 was added and mixed and stirred for 30 minutes. The ratio of silicone compounds to non-volatile components is as shown in Table 11.

[0063] The paint was applied to an ABS Compose (diameter 47 mm, length 2 m) at Mukaishima, Hofu City, Yamaguchi Prefecture. The results of immersion in the ocean (6-month results, washing after 6-month immersion, and 6-month storage stability test results of the chemical-free antifouling paint) are shown in Table 11.

[0064] [Table 11]

[0065] A field test was conducted using the compositions of Examples 57 to 66 on monofilament cages used in oyster farming in the Sasebo area of ​​Nagasaki Prefecture and scallop farming in the Rausu area of ​​Hokkaido, and a 3-month immersion test was conducted. The test results and the results of the growth tests of oysters and scallops are shown in Tables 12 and 13.

[0066] [Table 12]

[0067] [Table 13]

[0068] [Effect of ethylene-α-olefin copolymer as implantation inhibitor] An example of a method for producing and adjusting a chemical-free antifouling coating composition using an ethylene-α-olefin copolymer will be described with reference to the composition shown in Example 67 of Table 14.

[0069] (Example 67) 14.3 parts by mass of polybutene 0N (implantation inhibitor) and 38.4 parts by mass of KF-6020 (implantation inhibitor) were added to 54.0 parts by mass of xylene under stirring, and the mixture was mixed and stirred for 10 minutes. Further, 103.8 parts by mass of base resin 5 (weight average molecular weight 200,000) was added and mixed for 10 minutes. Mix together and 1.0 part by mass of Halimac T-80 was added and mixed and stirred for 30 minutes, extracting 1% rosin, 40.3% silicone compound, and 15.0% ethylene-α-olefin copolymer from the non-volatile components. The ratio of ethylene-α-olefin copolymer to the non-volatile components is shown in Table 14.

[0070] The coating was applied to an ABS Compose (diameter 47 mm, length 2 m) at Mukaishima, Hofu City, Yamaguchi Prefecture. The results of immersion in the ocean (6-month results, washing after 6-month immersion, and 6-month storage stability test results of the chemical-free antifouling paint) are shown in Table 14.

[0071] [Table 14]

[0072] A field test was carried out using the compositions of Examples 67 to 76 on monofilament cages used in oyster farming in the Sasebo area of ​​Nagasaki Prefecture and scallop farming in the Rausu area of ​​Hokkaido, and a 3-month immersion test was carried out. The test results and the results of the growth tests of oysters and scallops are shown in Tables 15 and 16.

[0073] [Table 15]

[0074] [Table 16]

[0075] [Effect of silicone powder as an implantation inhibitor] An example of a method for producing and adjusting a chemical-free antifouling coating composition using silicone powder will be described with reference to the composition shown in Example 77 of Table 17.

[0076] (Example 77) 66.8 parts by mass of xylene was mixed with 21.9 parts by mass of polybutene 0N (implantation inhibitor) and 40.7 parts by mass of KF-6020 (implantation inhibitor) in order, and mixed and stirred for 10 minutes. 103.8 parts by mass of base resin 5 (weight average molecular weight 200,000) and 0.5 parts by mass of KBM-590 (silicone powder) were added, and mixed and stirred for 10 minutes. 1.0 part by mass of Halimaq T-80 was added and mixed and stirred for 30 minutes. The ratio of silicone powder to non-volatile components is as shown in Table 17.

[0077] The coating was applied to an ABS Compose (diameter 47 mm, length 2 m) at Mukaishima, Hofu City, Yamaguchi Prefecture. The results of immersion in the ocean (6-month results, washing after 6-month immersion, and 6-month storage stability test results of the chemical-free antifouling paint) are shown in Table 17.

[0078] In Table 17, the ABS resin adhesion test was performed using a 1 mm thick, 6 cm x 8 cm board (Japan Test Panel (wood)) in accordance with the method of 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, "100 / 100" indicates that no peeling was observed after removal of the adhesive tape for all 100 squares formed by cross-cutting, and "50 / 50" indicates that no peeling was observed after removal of the adhesive tape for all 50 squares formed by cross-cutting.

[0079] [Table 17]

[0080] A field test was carried out using the compositions of Examples 77 to 86, by coating monofilament cages used in oyster farming in the Sasebo area of ​​Nagasaki Prefecture and scallop farming in the Rausu area of ​​Hokkaido, and a 3-month immersion test was carried out. The test results and the results of the growth tests of oysters and scallops are shown in Tables 18 and 19.

[0081] [Table 18]

[0082] [Table 19]

Claims

1. An antifouling coating composition for forming a coating film that inhibits adhesion of aquatic organisms on a surface of an article that comes into contact with water, comprising: one or more resins 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 300,000 or less, selected from the group consisting of poly(acrylic acid alkyl ester) resins, poly(methacrylic acid alkyl ester) resins, acrylic acid alkyl ester-acrylic acid copolymer resins, and methacrylic acid alkyl ester-methacrylic acid copolymer resins; a coating adhesion promoter which is a rosin and / or a silane coupling agent; and an implantation inhibitor which is polyether-modified silicone oil and polybutene, or polyether-modified silicone oil, polybutene, and silicone powder; A chemical-free antifouling coating composition that does not contain an aquatic organism repellent, which is an antifouling agent as defined in JIS H 7901:2005.

2. 2. The chemical-free antifouling coating composition according to claim 1, characterized in that the coating adhesion promoter contains rosin having an acid value of 100 to 220 mg KOH / g and a softening point of 78 to 100°C in a ratio of 1% to 10% based on the non-volatile components.

3. 2. The chemical-free antifouling coating composition according to claim 1, characterized in that the coating adhesion promoter comprises a silane coupling agent in an amount of 0.2% or more and 2.0% or less based on the non-volatile components.

4. 2. The chemical-free antifouling coating composition according to claim 1, characterized in that the composition contains, as the implantation inhibitor, polyether-modified silicone oil in a ratio of 5% to 50% based on the non-volatile components.

5. 2. The chemical-free antifouling coating composition according to claim 1, characterized in that the composition contains polybutene as the implantation inhibitor in a ratio of 15% to 35% based on the non-volatile components.

6. 2. The chemical-free antifouling coating composition according to claim 1, characterized in that the implantation inhibitor contains a silicone powder selected from the group consisting of a silicone composite powder having an average particle size of 0.2 μm or more and 60 μm or less, a silicone rubber powder having an average particle size of 1 μm or more and 30 μm or less, and a silicone resin powder having an average particle size of 0.2 μm or more and 8.0 μm or less, in a ratio of 0.5% to 2.0% based on the non-volatile components.

7. A drug-free antifouling paint composition as described in claim 1, characterized in that it contains the resin, the coating adhesion promoter, the implantation inhibitor, and xylene.

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

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