Non chemical type Anti-fouling coating composition and method for forming Anti-fouling coating film using the same

Abstract

To provide a new anti-fouling coating composition which can inhibit adhesion of marine organisms and seaweeds to a fishery material, an underwater offshore structure, and a fishing net, and does not contain a marine organism repellent, and a method for forming an anti-fouling film using the composition.SOLUTION: An anti-fouling coating composition for forming a coating film for suppressing adhesion of marine organisms on a contact surface with water of an article contains one or more types of resins which 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, and 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, a coating film adhesion accelerator, and an implantation inhibitor for inhibiting implantation of marine organisms to the surface of the coating film, and does not contain a marine organism repellent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel chemical-free antifouling coating composition containing no marine organism repellent, which can suppress the 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 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 addition, the fishing industry has traditionally used antifouling paints containing marine organism repellents 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 fluctuations in ocean currents.

[0004] In consideration of environmental conservation and the health of workers, 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 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.

[0006] Patent Document 3 discloses a 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. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-193731 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-152205 [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 coating composition described in Patent Document 2 also raises concerns about the accumulation of chemicals, as with the aqueous antifouling coating described in Patent Document 1. Patent Document 3 improves the flexibility and peeling of the coating film, but questions remain about the impact of tidal differences.

[0009] In order to prevent marine organisms and seaweed from attaching to marine materials, underwater structures, fishing nets, etc., antifouling paints containing marine organism repellents have traditionally been used. With the recent development of aquaculture, the impact of these repellents on marine products and environmental conservation have become issues. In addition, depending on the aquaculture location, there is a problem of paint peeling due to tidal variations.

[0010] 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, does not cause the problem of chemical accumulation in marine products, and is resistant to peeling of the coating film due to tidal changes, an antifouling coating formed using the same, and marine materials, underwater structures, and fishing nets having the coating on their surfaces. [Means for solving the problem]

[0011] In accordance with the above-mentioned objective, 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 the 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 the above-mentioned problem is solved 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 proportion of 1% to 10% based on the non-volatile components.

[0013] The chemical-free antifouling coating composition according to the first aspect of the present invention may further contain a silane coupling agent as the coating adhesion promoter in a proportion 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 comprise 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 proportion of 5% to 50% based on the non-volatile components.

[0015] In the chemical-free antifouling coating composition according to the first aspect of the present invention, the implantation inhibitor may comprise an ethylene-α-olefin copolymer having a molecular weight of 150 or more and 3000 or less and selected from the group consisting of polybutenes, isopolybutenes, waxes, liquid paraffin, solid paraffin, laurin and petrolatum in a proportion of 15% or more and 35% or less of the non-volatile components.

[0016] The chemical-free antifouling coating composition according to the first aspect of the present invention may further contain, as the implantation inhibitor, a silicone powder 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, in a proportion of 0.5% to 2.0% relative to 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, 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. [Effects of the Invention]

[0018] According to the present invention, there are 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 sea with tidal variations, and that has a low risk of water pollution due to the release of chemicals or the accumulation of chemicals in aquatic organisms, and a method for forming an antifouling coating using the same. DETAILED DESCRIPTION OF THE INVENTION

[0019] A chemical-free antifouling coating composition according to one embodiment of the present invention (hereinafter sometimes referred to as "chemical-free antifouling coating composition" or "antifouling coating composition") comprises: (A) one or more resins having an acid value of 0 mgKOH / g or more but 10 mgKOH / g or less and a weight-average molecular weight (Mw) of 50,000 or more but 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 comprising rosin and a silane coupling agent; and (C) an implantation inhibitor comprising a silicone compound, silicone powder, and an ethylene-α-olefin copolymer. Each component is described in detail below.

[0020] (A) Resin The coating components of the chemical-free antifouling coating composition can be 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 alkyl acrylate-acrylic acid copolymer resin and the alkyl methacrylate-methacrylic acid copolymer resin may be obtained by partially hydrolyzing the alkyl carboxylate groups of a poly(alkyl acrylate ester) resin and a poly(alkyl methacrylate ester) resin, respectively.

[0022] The acid value of the resin used in the chemical-free antifouling coating 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 (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.

[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 period of 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 to improve adhesion between the coating and the surface of an article, thereby preventing the coating from peeling off due to tidal changes in marine areas. The coating adhesion promoter can be selected depending on the material and shape of the object to be coated. Preferred examples of coating adhesion promoters include rosin and silane coupling agents. These may be used alone or in combination of any two or more types.

[0025] The rosin may be contained in a proportion of 1% to 10% of 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 the 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 types. Specific examples of rosins include Haritack F-75, Haritack FG-90, and Harimac T-80 manufactured by Harima Chemicals Co., Ltd.

[0026] The silane coupling agent can be contained in a proportion of 0.2% to 2.0%, preferably 0.5% to 1.5%, of the non-volatile components of the chemical-free antifouling coating composition. 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 silane coupling agents, methoxy-type silanes, ethoxy-type silanes, silazanes, and siloxanes. These may be used alone or in combination of any two or more types. 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 can 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%, and even more preferably 25% to 40%, of the non-volatile components of the chemical-free antifouling coating composition. The hydrophilic-lipophilic balance (HLB) of the silicone compound is preferably 1 to 8, and more preferably 2 to 6. Specific examples of silicone compounds 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., and polyether-modified silicone oils are more preferred.

[0029] The ethylene-α-olefin copolymer preferably has a weight-average molecular weight of 150 to 3000. The ethylene-α-olefin copolymer can be contained in a proportion of 15% to 35%, more preferably 18% to 32%, of the non-volatile components of the chemical-free antifouling coating composition. Specific examples of ethylene-α-olefin copolymers include polybutenes and isopolybutenes, waxes, liquid paraffin, solid paraffin, laurin, and petrolatum. These may be used alone or in any combination of two or more. Specific examples of ethylene-α-olefin copolymers include Polybutene 0N, Polybutene 015N, Polybutene 3N, Polybutene 10N, Polybutene 30N, and Polybutene 200N manufactured by Nippon Oil & Fats 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.

[0030] 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 two or more. The silicone powder may be contained in an amount of 0.5% to 2.0%, preferably 0.5% to 1.0%, of the non-volatile components of the chemical-free antifouling coating composition. Specific examples of silicone powders 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, and X-52-1621 manufactured by Shin-Etsu Chemical Co., Ltd.

[0031] The chemical-free antifouling coating composition can be produced using any known device and method. Application to articles such as fishery materials, underwater structures, and fishing nets can be performed 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. [Example]

[0032] Next, examples carried out to confirm the effects of the present invention will be described. [I] Preparation of chemical-free antifouling paint compositions by differences in resin properties 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. Hereinafter, in Tables 1 and 2, these resins are referred to as base resin 1 to base resin 13. Base resins 1 to 8 have acid values ​​of 0 and weight-average molecular weights as shown in Table 1. Base resins 9 to 13 have weight-average molecular weights of 200,000 and acid values ​​as shown in Table 2.

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

[0034] Example 5 To 59.9 parts by mass of xylene, 20.5 parts by mass of polybutene 0N (implantation inhibitor) and 38.0 parts by mass of KF-6020 (implantation inhibitor) were sequentially added under stirring, and the mixture was mixed and stirred for 10 minutes. Then, 103.8 parts by mass of base resin 5 (polyacrylic acid alkyl ester, weight average molecular weight 200,000, acid value 0 mgKOH / g) was added, and the mixture was mixed and stirred for 30 minutes. In Examples 1 to 13, chemical-free antifouling coating compositions were produced using the same production procedure. Marine immersion tests were conducted using these chemical-free antifouling coating compositions.

[0035] Example 14 To 59.9 parts by mass of xylene, 20.5 parts by mass of polybutene 0N (implantation inhibitor) and 38.0 parts by mass of KF-6020 (implantation inhibitor) were sequentially added under stirring, and the mixture was mixed and stirred for 10 minutes. Then, 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 2.6 parts by mass of base resin 10 (acrylic acid alkyl ester-acrylic acid copolymer, weight-average molecular weight 200,000, acid value 3 mgKOH / g) were sequentially added, and the mixture was mixed and stirred for 30 minutes. In Examples 15 and 16, chemical-free antifouling coating compositions were produced using the same manufacturing procedure. This chemical-free antifouling coating composition was used in a marine immersion test (results of marine immersion using a Russell net cage in Sasebo City, Nagasaki Prefecture).

[0036] The results of the underwater immersion test, the results of the cleaning test after 6 months of immersion, and the results of 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 were based on a comprehensive assessment of all aquatic organisms (barnacles, serpula, hydra, moss worms, and ascidians) and were evaluated based on the percentage of the area where aquatic organisms were found to be attached. In Tables 1 and 2, "○" means less than 10%, "○△" means 10% to less than 20%, and "△" means 20% or more (the same applies below).

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

[0039] (Storage stability test) The storage stability was evaluated for six months in a constant temperature bath, with one set consisting of two consecutive weeks at 50°C and two consecutive weeks at 8°C. 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 below with reference to the compositions shown in Example 17 of Table 3 and Example 27 of Table 4.

[0043] Example 17 To 61.9 parts by mass of xylene, 20.7 parts by mass of polybutene 0N (implantation inhibitor) and 38.4 parts by mass of KF-6020 (implantation inhibitor) were added in that order while stirring, and mixed and stirred for 10 minutes. 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 To 61.9 parts by mass of xylene, 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 in that order while stirring, and mixed and stirred for 10 minutes. Next, 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 in that order, and mixed and stirred for 10 minutes. Then, 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] To investigate the effect of tidal variations on paint peeling, an ABS Compose (47 mm diameter, 2 m length) was painted and subjected to an underwater immersion test at Mukaishima Island in Hofu City, Yamaguchi Prefecture. The results of the underwater immersion (6-month results, results of cleaning after 6 months of immersion, and results of a 6-month storage stability test of a chemical-free antifouling paint) are shown in Tables 3 and 4.

[0046] The evaluation results of the peeling state of the coating film are expressed 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] The compositions of Examples 27 to 36 were applied to monofilament cages used in oyster farming in the Sasebo area of ​​Nagasaki Prefecture and scallop farming in the Rausu area of ​​Hokkaido, and a three-month immersion test was carried out. 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] Examples of methods for preparing chemical-free antifouling coating compositions containing a silane coupling agent will be described with reference to the compositions shown in Example 36 in Table 7 and Example 47 in Table 8.

[0053] Example 37 61.9 parts by mass of xylene was mixed with 20.7 parts by mass of polybutene 0N (implantation inhibitor) and 38.4 parts by mass of KF-6020 (implantation inhibitor), and the mixture was 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 stirred for 10 minutes. 0.2 parts by mass of X-12-1287A (silane coupling agent) was then added, and the mixture was stirred for 30 minutes. The ratio of silane coupling agent to non-volatile components is shown in Table 7.

[0054] Example 47 61.9 parts by weight of xylene was stirred, and 20.7 parts by weight of polybutene 0N (implantation inhibitor) and 38.4 parts by weight of KF-6020 (implantation inhibitor) were added in sequence, and mixed and stirred for 10 minutes. 98.6 parts by weight of base resin 5 (weight average molecular weight 200,000) and 5.2 parts by weight of base resin 10 (acid value 3 mg KOH / g) were added in sequence, and mixed and stirred for 10 minutes. 0.2 parts by weight of X-12-1287A (silane coupling agent) was added and mixed and stirred for 30 minutes. The ratio of silane coupling agent to non-volatile components is shown in Table 8.

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

[0056] [Table 7]

[0057] [Table 8]

[0058] The compositions of Examples 47 to 56 were applied to monofilament cages used in oyster farming in the Sasebo area of ​​Nagasaki Prefecture and scallop farming in the Rausu area of ​​Hokkaido, and a three-month immersion test was carried out. The test results and the results of the growth tests 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 To 10.8 parts by mass of xylene, 12.3 parts by mass of polybutene 0N (implantation inhibitor) and 5.0 parts by mass of KF-6020 (implantation inhibitor) were added in turn under stirring, and mixed and stirred for 10 minutes. 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. Then, 1.0 part by mass of Halimacc T-80 was added, and mixed and stirred for 30 minutes. The ratio of silicone compound to non-volatile components is shown in Table 11.

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

[0064] [Table 11]

[0065] The compositions of Examples 57 to 66 were applied to monofilament cages used in oyster farming in the Sasebo area of ​​Nagasaki Prefecture and scallop farming in the Rausu area of ​​Hokkaido, and a three-month immersion test was carried out. 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 an 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 To 54.0 parts by mass of xylene, 14.3 parts by mass of polybutene 0N (implantation inhibitor) and 38.4 parts by mass of KF-6020 (implantation inhibitor) were added in that order with stirring, and mixed and stirred for 10 minutes. 103.8 parts by mass of base resin 5 (weight average molecular weight 200,000) was then added, followed by 1.0 part by mass of Halimaq T-80, and mixed and stirred for 30 minutes, resulting in 1% rosin, 40.3% silicone compound, and 15.0% ethylene-α-olefin copolymer, based on the nonvolatile components. The ratio of ethylene-α-olefin copolymer to the nonvolatile components is shown in Table 14.

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

[0071] [Table 14]

[0072] The compositions of Examples 67 to 76 were applied to monofilament cages used in oyster farming in the Sasebo area of ​​Nagasaki Prefecture and scallop farming in the Rausu area of ​​Hokkaido, and a three-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 weight of xylene was stirred with 21.9 parts by weight of polybutene 0N (implantation inhibitor) and 40.7 parts by weight of KF-6020 (implantation inhibitor), and the mixture was stirred for 10 minutes. 103.8 parts by weight of base resin 5 (weight average molecular weight 200,000) and 0.5 parts by weight of KBM-590 (silicone powder) were added, and the mixture was stirred for 10 minutes. 1.0 part by weight of Halima T-80 was added and the mixture was stirred for 30 minutes. The ratio of silicone powder to non-volatile components is shown in Table 17.

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

[0078] In Table 17, the ABS resin adhesion test was conducted using a 1 mm thick, 6 cm x 8 cm board (Japan Test Panel (wood)) in accordance with 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-cuts made on the surface of the coating, "100 / 100" indicates that no peeling was observed after removal of the adhesive tape in any of the 100 cross-cut squares, and "50 / 50" indicates that no peeling was observed after removal of the adhesive tape in any of the 50 cross-cut squares.

[0079] [Table 17]

[0080] The compositions of Examples 77 to 86 were applied to monofilament cages used in oyster farming in Sasebo, Nagasaki Prefecture, and scallop farming in Rausu, Hokkaido, and then immersed in the mixture for three months. 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 the 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, 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 anti-implantation agent for inhibiting the implantation of aquatic organisms on the surface of the coating film, A chemical-free antifouling paint composition that does not contain any aquatic organism repellents.

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 proportion of 1% to 10% of the non-volatile components.

3. 3. The chemical-free antifouling coating composition according to claim 2, further comprising a silane coupling agent as the coating adhesion promoter in a proportion of 0.2% to 2.0% based on the nonvolatile components.

4. 2. The chemical-free antifouling coating composition according to claim 1, wherein the implantation inhibitor is a silicone compound selected from the group consisting of methyl silicone, dimethyl silicone, methylphenyl silicone, cyclic methylpolysiloxane, 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 proportion of 5% to 50% based on the non-volatile components.

5. 2. The chemical-free antifouling coating composition according to claim 1, wherein the implantation inhibitor is an ethylene-α-olefin copolymer having a molecular weight of 150 to 3,000 selected from the group consisting of polybutenes, isopolybutenes, waxes, liquid paraffin, solid paraffin, laurin, and petrolatum, in a proportion of 15% to 35% of the non-volatile components.

6. 6. The chemical-free antifouling coating composition according to claim 4 or 5, further comprising, as the implantation inhibitor, a silicone powder 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, in an amount of 0.5% to 2.0% based on the non-volatile components.

7. 7. 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 6; and drying the applied coating film of the chemical-free antifouling coating composition.

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