JP7127851B2 - Fishing net antifouling coating composition, fishing net, fishing net tool or underwater structure having on its surface an antifouling coating film formed using the composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fishing net antifouling coating composition, and a fishing net, fishing net implement or underwater structure having an antifouling coating film formed using the composition on its surface.

Since fishing nets, fishing net tools, and underwater structures are installed in the sea for a long period of time, if they are used without being treated with antifouling paint for fishing nets, they may damage green algae such as sea lettuce and green laver, red algae such as gisu, and barnacles. Various aquatic fouling organisms such as crustaceans such as crustaceans, coelenterates such as hydra worms, serpra, bryozoans, and mollusks adhere. As a result, the mesh of the fishing nets is blocked and the seawater flow becomes poor, and a large number of farmed fish die due to lack of oxygen, and infectious diseases occur, making it impossible to ship them.

In order to prevent the attachment of these aquatic fouling organisms, antifouling coating compositions for fishing nets using organic tin compounds have hitherto been widely used.

Therefore, various researches and proposals have been made as antifouling coating compositions for fishing nets to replace organic tin compounds, and inorganic compounds and organic compounds are used as antifouling agents, which are blended with natural resin-based or synthetic resin-based spreading resins. antifouling coating compositions for fishing nets have been used. However, these had problems such as poor physical properties of the coating film and a short antifouling period.

In order to solve these problems, an antifouling coating composition for fishing nets has been proposed in which a specific polyether-modified silicone oil is blended with a spreading resin as an agent elution regulator (Patent Documents 1 to 4).

However, in all of the above inventions, although a good antifouling effect is exhibited at the initial stage of immersion in a fishing net, the elution of the chemical becomes unstable as the immersion period extends over a long period of time, making it difficult to obtain a good antifouling effect over a long period of time. It was difficult.

Japanese Patent Laid-Open No. 3-20370 Japanese Patent Laid-Open No. 9-176577 JP 2001-19848 JP 2009-215527

The present invention has been made in view of the above circumstances, and an antifouling fishing net that can maintain an appropriate amount of drug release over a long period of time after being immersed in water and can continuously exhibit excellent antifouling performance for a long period of time. An object of the present invention is to provide a coating composition.

According to the present invention, a fishing net antifouling paint composition containing a (meth)acrylic acid ester polymer (A), an ethylene vinyl acetate copolymer (B), a silicone oil (C), and an antifouling agent (D) goods are provided.

Means for Solving the Problems As a result of earnest research to solve the above problems, the inventors of the present invention have found that the above compositions can solve the above problems, and have completed the present invention.

The present invention will be described in detail below.

1. Fishing net antifouling paint composition The fishing net antifouling paint composition of the present invention is used for fishing nets for aquaculture or set nets, fishing net tools such as floats and ropes used in these, and underwater structures such as cooling water conduits for power plants. A composition for preventing aquatic fouling organisms from adhering to things. The composition of the present invention contains a (meth)acrylate polymer (A), an ethylene-vinyl acetate copolymer (B), a silicone oil (C), and an antifouling agent (D). A detailed description will be given below.

<(Meth)acrylic acid ester polymer (A)>
The polymer (A) is a polymer formed using a monomer containing a (meth)acrylic acid ester, and may be a homopolymer of one type of monomer. It is preferably a copolymer of monomers. The monomers for forming the polymer (A) may contain, in addition to the (meth)acrylic acid ester, an ethylenically unsaturated monomer copolymerizable with the (meth)acrylic acid ester.

The proportion of the (meth)acrylic acid ester in the monomers for forming the polymer (A) is, for example, 60% by mass or more, specifically, for example, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass, and may be within a range between any two of the numerical values exemplified here.

Examples of the (meth)acrylic acid ester forming the polymer (A) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylate, t-butyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, ( Meth) 4-methoxybutyl acrylate, 2-ethoxyethyl (meth) acrylate, propylene glycol monomethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) ) glycidyl acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, benzyl (meth)acrylate, and (meth)acrylic acid phenyl and the like.

Among these, in terms of polymerizability, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, and (meth)acrylic acid 2-ethylhexyl, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, ( 2-ethoxyethyl meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and the like are preferred.

Examples of monomers other than (meth)acrylates include olefins such as propylene, isobutylene, α-octene, α-dodecene and α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, Unsaturated acids such as maleic anhydride and itaconic acid or their salts or mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, ethylenesulfonic acid, allylsulfonic acid, methallyl Olefins such as sulfonic acid or salts thereof, alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth) Allyl ether, polyoxyalkylene (meth)allyl ether such as polyoxypropylene (meth)allyl ether, polyoxyalkylene (meth)acrylate such as polyoxyethylene (meth)acrylate, polyoxypropylene (meth)acrylate, polyoxyethylene (Meth)acrylamide, polyoxyalkylene (meth)acrylamide such as polyoxypropylene (meth)acrylamide, polyoxyethylene (1-(meth)acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine and the like.

The glass transition temperature (Tg) of the polymer (A) is preferably about -65 to 50°C, more preferably about -50 to 35°C. When the Tg is within the above range, the coating film becomes too tacky after being applied to the fishing net, which does not hinder the coating work. There is no problem that the antifouling effect is lost. The above Tg value refers to a value actually measured using a differential scanning calorimeter (eg, DSC1 manufactured by METTLER TOLEDO) with reference to the measurement method of JIS K 7121.

The mass average molecular weight (Mw) of the polymer (A) is about 10,000 to 7,000,000, preferably about 50,000 to 5,000,000. When Mw is about 50,000 to 5,000,000, it is preferable from the viewpoint of toughness of the coating film. Methods for measuring Mw include, for example, gel permeation chromatography (GPC). When measuring Mw by GPC, Mw is displayed as a value (polystyrene conversion value) determined by preparing a calibration curve using polystyrene as a standard substance and measuring.

The polymer (A) is obtained by polymerizing the monomers, and is a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer. good too.

Examples of the polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. Among these, solution polymerization and emulsion polymerization are particularly preferable in that the polymer (A) can be synthesized easily and accurately.

In the case of solution polymerization, the polymer (A) is polymerized, for example, in the presence of a polymerization initiator.
Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, dimethyl-2,2'-azobisisobutyrate azo compounds such as; benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy isopropyl carbonate, t-butyl peroxy-2-ethylhexanoate and other peroxides is mentioned. These polymerization initiators can be used alone or in combination of two or more. As the polymerization initiator, 2,2′-azobisisobutyronitrile and t-butylperoxy-2-ethylhexanoate are particularly preferred. By appropriately setting the amount of the polymerization initiator used, the molecular weight of the copolymer can be adjusted.

In the polymerization reaction, water or an organic solvent may be used as necessary. Examples of organic solvents include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; alcohol solvents such as alcohol and butyl alcohol; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; Among these, aromatic hydrocarbon solvents are particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.

The reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually about 70 to 140°C, preferably about 80 to 120°C. The reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours.
The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas.

In the case of emulsion polymerization, any polymerization initiator that has been conventionally used in emulsion polymerization can be used. Examples of polymerization initiators include water-soluble polymerization initiators such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide and tert-butyl hydroperoxide; 2,2′-azobisisobutyronitrile, 2, Examples include oil-soluble polymerization initiators such as 2'-azobis-2-methylbutyronitrile, dimethyl-2,2'-azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide and the like. A water-soluble polymerization initiator is particularly preferred. It is also possible to use these polymerization initiators in combination with a reducing agent as a redox polymerization initiator.

The reaction temperature in the emulsion polymerization may be appropriately set according to the type of polymerization initiator and the like, and is usually about 40 to 80°C, preferably about 55 to 70°C. The reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually 4 to 10 hours, preferably 6 to 9 hours.
The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas.

Surfactants used in emulsion polymerization include anionic surfactants such as higher alcohol sulfates, alkylbenzenesulfonates, aliphatic sulfonates, aliphatic carboxylates, and nonionic surfactant sulfates. one or two or more nonionic surfactants such as polyethylene glycol alkyl ester type, alkylphenyl ether type, and alkyl ether type can be used. Cationic surfactants and amphoteric surfactants can also be used.

Examples of the polymer (A) include commercially available products such as Banstar X1290B11 (manufactured by Chubu Saiden Co., Ltd.), Polysol (R) AP-4650N (manufactured by Showa Denko Co., Ltd.), and Polysol (R) AP-4780N. (manufactured by Showa Denko KK) and the like.

The content of the polymer (A) is not particularly limited, but is 1 to 50% by mass, preferably 3 to 30% by mass, in terms of solid content in the coating composition.

<Ethylene vinyl acetate copolymer (B)>
Copolymer (B) is a copolymer formed using monomers containing ethylene and vinyl acetate. The monomers for forming the copolymer (B) may contain, in addition to ethylene and vinyl acetate, ethylenically unsaturated monomers copolymerizable therewith.

The total ratio of ethylene and vinyl acetate in the monomers for forming the copolymer (B) is, for example, 60% by mass or more, specifically, for example, 60, 65, 70, 75, 80 , 85, 90, 95, 100 mass %, and may be within a range between any two of the numerical values exemplified here.

Examples of monomers other than ethylene and vinyl acetate include those described above as monomers other than (meth)acrylic acid esters.

The mass average molecular weight (Mw) of the copolymer (B) is about 10,000 to 7,000,000, preferably about 50,000 to 5,000,000. When Mw is about 50,000 to 5,000,000, it is preferable from the viewpoint of toughness of the coating film.

The copolymer (B) is obtained by polymerizing the monomers, and is a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer. may

As for the polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, etc., the methods described above for the polymer (A) can be applied.

Examples of the copolymer (B) include commercially available products such as Polysol (R) EVA P-3N (manufactured by Showa Denko K.K.), Novatec (TM) EVA LV-211A (manufactured by Japan Polyethylene Co., Ltd.), and the like. is mentioned.

The content of the copolymer (B) is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, based on the total mass of the polymer (A) and the copolymer (B), Particularly preferred is 50 to 80% by mass. When it is within the above range, a good antifouling effect can be maintained for a long period of time, and the physical properties of the coating film when immersed in seawater are significantly improved, especially for materials such as nylon mesh, which are relatively difficult to form a coating film. Good physical properties of the coating film can be maintained even for nets.

<Silicone oil (C)>
Examples of the silicone oil (C) include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether-modified polydimethylsiloxane, polyether-modified polyalkyl(methyl)siloxane, and polyester-modified polydimethylsiloxane. Examples include siloxane, long-chain alkyl-modified polydimethylsiloxane, aralkyl-modified polydimethylsiloxane, polyether long-chain alkylaralkyl-modified dimethylsilicone oil, fluorosilicone oil, amino-modified silicone oil, and other functional group-modified silicone oils. In particular, a polyether-modified silicone oil having a hydrophilic-lipophilic balance (HLB value) of 0.5 to 9 is preferable, specifically a polyether-modified polydimethylsiloxane or a polyether long-chain alkylaralkyl-modified dimethyl of 0.5 to 9. Silicone oil is preferred. More preferred are polyether-modified polydimethylsiloxanes or polyether long-chain alkylaralkyl-modified dimethylsilicone oils having a hydrophilic-lipophilic balance (HLB value) in the range of 1-5. By using a silicone oil with an HLB value within the range of 0.5 to 9, sufficient antifouling performance can be obtained.
In the present invention, these silicone oils may be used alone, or two or more of them may be used in combination.

The viscosity of the silicone oil is preferably 1000 poise or less, more preferably 100 poise or less, from the viewpoint of coating performance and coating film properties.

The content of the silicone oil (C) is not particularly limited, but is preferably 1 to 150 parts by mass based on 100 parts by mass of the total amount of the polymer (A) and the copolymer (B) in terms of solid content. is 5 to 100 parts by mass, more preferably 10 to 50 parts by mass.

When the silicone oil (C) is used in the water-based antifouling composition, it is emulsified with an emulsifier, dispersant, or the like. In this case, the silicone oil is preferably dispersed as particles having an average particle size of 0.01 to 100 μm, preferably 0.1 to 50 μm, from the viewpoint of dispersibility and storage stability.

As the method of emulsification, for example, silicone oil and an emulsifier are charged, then distilled water is added while stirring with a stirrer, and stirring is performed while appropriately setting so that emulsified particles in the desired particle size range are obtained. should be done.

Examples of the emulsifier include nonionic surfactants and anionic surfactants.

Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethyleneoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethyleneoxypropylene alkylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene Ethyleneoxypropylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, etc., may be mentioned, and two or more of them may be used in combination.

Examples of anionic surfactants include sulfate ester salts and phosphate ester salts of nonionic surfactants, polyoxyethylene alkyl ether carboxylates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates. You may use it in combination of 2 or more types.

<Antifouling agent (D)>
The antifouling agent (D) is not particularly limited as long as it is a compound having a killing or repelling effect on marine fouling organisms. Examples include the following organic compounds and inorganic compounds.

Examples of organic compounds include 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc, zinc ethylene bisdithiocarbamate, bis(dimethyldithiocarbamate) zinc, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, pyridine.・Triphenylborane, n-octadecylamine ・Triphenylborane, 3-(2-ethylhexyloxy)propylamine ・Triphenylborane, 4-isopropyl-diphenylmethyl, 4-phenylpyridyl-diphenylborane, 2,4,6- trichloromaleimide, n-(2,6-diethylphenyl)2,3-dichloromaleimide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, chloromethyl-n-octyl disulfide, 4,5-dichloro-2-n- Octyl-3-isothiazolone, 3,4-dichlorophenyl-NN-dimethylurea, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroiso phthalonitrile, N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide, N-dichloromethylthio-N',N'-dimethyl-N-phenylsulfamide, 2-(4 -thiazolyl)benzimidazole, and the like.

Among the above organic compounds, n-octadecylamine/triphenylborane, tetraethylthiuram disulfide, 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc and bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate are particularly preferred. You may use together 1 type(s) or 2 or more types.

Examples of inorganic compounds include cuprous oxide, monovalent copper glass, divalent copper glass, copper thiocyanate, cupronickel, copper powder, etc. Cuprous oxide, monovalent copper glass and divalent Copper glass is particularly preferred, and may be used singly or in combination of two or more.

Among the antifouling agents (D), the solvent- or water-insoluble antifouling agent preferably has an average particle size of 10 μm or less, particularly preferably 3 μm or less, from the viewpoint of dispersibility. These average particle diameters can be measured with a particle size distribution meter manufactured by Nikkiso Co., Ltd., model Microtrac MT3300EXII (measurement principle: laser diffraction/scattering method).

Although the content of the antifouling agent (D) in the coating composition of the present invention is not limited, it is usually 1 to 300 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the copolymer (B). parts, preferably 5 to 200 parts by mass. If the amount of the antifouling agent used is less than 1 part by mass, the antifouling property is not sufficient, while if it exceeds 300 parts by mass, the coating performance and physical properties of the coating film tend to deteriorate.

<Other additive ingredients>
The coating composition used in the present invention includes other spreading resins, other elution modifiers, dyes, pigments, waxes, preservatives, plasticizers, dispersants, antifoaming agents, film-forming aids, and anti-settling agents. , an anti-sagging agent, a surfactant, a solvent, etc., can be arbitrarily contained in an arbitrary blending ratio within a range that does not impair the object of the present invention.

Other spreading resins other than the polymer (A) and copolymer (B) include vinyl resins, alkyd resins, urethane resins, polyester resins, synthetic rubbers, synthetic resins such as chlorinated polyethylene, wood rosin, gum rosin, Examples include natural resins such as modified rosin.

Other dissolution modifiers include, for example, ethylene/α-olefin copolymers, polybutenes, paraffins, petrolatums, dialkylsulfide compounds and the like.

Examples of plasticizers include phthalates, adipates, tricresyl phosphate, and the like.

Examples of dispersants include polyamide phosphoric acid-based dispersants, polyamide-based dispersants, unsaturated polycarboxylic acid-based dispersants, and polyethylene oxide-based dispersants. Examples thereof include Disparlon 6900-20X, Disparlon 4200 and Disparlon 1860 manufactured by Kusumoto Kasei Co., Ltd. These dispersants can be used alone or in combination of two or more.

Examples of solvents include organic solvents and water. Examples of organic solvents include aromatic solvents such as xylene, toluene, Solvesso 100 and Solvesso 150 (both registered trademarks, manufactured by ExxonMobil); ketone solvents such as isobutyl methyl ketone (MIBK) and diisobutyl ketone (DIBK). ; Ester solvents such as butyl acetate, isobutyl acetate and isopentyl acetate can be used.

In addition, organic solvents with low toxicity, low odor, and low environmental load can also be used. ) and other aromatic/alicyclic/aliphatic hydrocarbon mixed solvents; propylene glycol monomethyl ether acetate, glycol ester solvents such as propylene glycol monoethyl ether acetate; ethylcyclohexane, dimethylcyclohexane, Likasolve (registered trademark) 900 (C9 aromatic hydrogenated), alicyclic hydrocarbon solvents such as Likasolve (registered trademark) 1000 (C10 aromatic hydrogenated); Shellsol D40 (registered trademark, manufactured by Shell Chemicals), Exsol D30, Exsol D40 Alicyclic and aliphatic hydrocarbon mixed solvents such as (registered trademark, manufactured by ExxonMobil); and aliphatic hydrocarbon mixed solvents such as Isopar G and Isopar H (both registered trademarks, manufactured by ExxonMobil) can.
These organic solvents can be used alone or in combination of two or more.

The composition of the present invention can be used to form antifouling coating films for various fishing tools, underwater structures and the like. In particular, the composition of the present invention can be suitably used as an antifouling coating composition for fishing nets.

The fishing net antifouling coating composition of the present invention can be prepared by mixing the above components (A) to (D) and, if necessary, the above additive components. The amount of each component to be added at the time of mixing may be appropriately adjusted so as to achieve the above blending amount and content. There are no particular restrictions on the order in which the components are mixed. As for the mixing method, a known method such as mixing using a stirring device may be adopted.

2. Method for Forming Fishing Net Antifouling Coating Film, Antifouling Coating Film, and Coated Object The method for forming a fishing net antifouling coating film of the present invention comprises applying the above fishing net antifouling coating composition to the surface of a coating film forming object. It is characterized by forming a coating film. The antifouling coating film obtained by the forming method of the present invention gradually dissolves from the surface and constantly renews the coating film surface, thereby preventing adhesion of aquatic fouling organisms. Further, by topcoating the above composition after dissolving the coating film, the antifouling effect can be exhibited continuously.

Examples of coated film-forming objects include fishing tools, underwater structures, and the like. Examples of fishing tools include fishing nets for aquaculture or stationary use, fishing net attachments such as floats and ropes used for the fishing nets, and the like. Underwater structures include, for example, power plant water pipes, bridges, port facilities, and the like.

The fishing net antifouling coating film of the present invention can be formed by applying the above fishing net antifouling coating composition to the surface (entirely or partially) of a coating film forming object.

Application methods include, for example, a brush coating method, a spray method, a dipping method, a flow coating method, a spin coating method, and the like. These may be used singly or in combination of two or more. For example, when the fishing net antifouling coating composition of the present invention is applied to a fishing net, it is preferable to employ a dipping method as the coating method.

After application, dry. The drying temperature may be room temperature. The drying time may be appropriately set according to the adhesion amount of the fishing net antifouling paint.

The adhesion amount of the fishing net antifouling paint may be appropriately set according to the type of the coating film-forming material. For example, when the object to be coated with a film is a fishing net, the amount of the dry coating film deposited is preferably 1 to 30 parts by weight, more preferably 4 to 15 parts by weight, per 100 parts by weight of the fishing net.

The coated article of the present invention has the antifouling coating film on its surface. The coated article of the present invention may have the antifouling coating film on the entire surface or on a part of the surface.

Examples and the like are shown below to further clarify the features of the present invention. However, the present invention is not limited to the examples and the like.

1. Analysis method <Molecular weight analysis method>
The weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC. The conditions for GPC are as follows.
Apparatus: HLC-8220GPC manufactured by Tosoh Corporation
Guard column: TSKguardcolumn SuperHZ-L (manufactured by Tosoh Corporation)
Column ... TSKgel SuperHZM-M (manufactured by Tosoh Corporation) 2 series connection Flow rate ... 0.35 mL / min
Detector... RI
Column constant temperature bath temperature: 40°C
Developing solvent: THF (manufactured by Wako Pure Chemical Industries; reagent grade)
Standard sample: TSK standard polystyrene (manufactured by Tosoh Corporation)

<Method for analyzing heating residue>
The heating residue is a value determined according to JIS K5601-1-2 (heated at 125° C. for 1 hour).

2. Production Example <Production Example 1 (Production of Polymer Solution A-1)>
A 300 ml flask equipped with a thermometer, condenser, stirrer and dropping funnel was charged with 41 g xylene, 17 g methyl methacrylate, 21 g butyl acrylate, 2 g stearyl methacrylate, and 0.02 g t-butyl peroxy 2-ethylhexanoate (initial Addition) was charged, and the mixture was stirred at 95±5° C. for 1 hour while introducing nitrogen gas. Thereafter, at the same temperature, 40 g of xylene, 17 g of methyl methacrylate, 21 g of butyl acrylate, 2 g of stearyl methacrylate, and 0.02 g of t-butylperoxy-2-ethylhexanoate were added dropwise from the dropping funnel over 30 minutes. After that, after stirring for 1 hour at the same temperature, a total of 0.4 g of t-butyl peroxy 2-ethylhexanoate (post-addition amount) was added in 3 portions every hour to complete the polymerization reaction. , and 40 g of xylene were added and dissolved to obtain a polymer solution A-1. The polymer solution A-1 had an Mw of 128000 and a heating residue of 39.8%.

<Production Example 2 (Production of polymer solution A-2)>
29.0 g xylene, 60 g isobutyl methacrylate, 19 g butyl acrylate, and 0.02 g t-butyl peroxy 2-ethylhexanoate (initial addition) to a 300 ml flask equipped with a thermometer, condenser, stirrer and dropping funnel. and stirred at 95±5° C. for 1 hour while introducing nitrogen gas. Then, at the same temperature, 0.02 g of t-butylperoxy-2-ethylhexanoate was added, 20.2 g of xylene was added dropwise from the dropping funnel over 20 minutes, and the mixture was stirred for 40 minutes. Then, at the same temperature, 0.04 g of t-butylperoxy-2-ethylhexanoate was added, 20.2 g of xylene was added dropwise from the dropping funnel over 20 minutes, and the mixture was stirred for 40 minutes. Then, at the same temperature, 0.21 g of t-butylperoxy-2-ethylhexanoate was added, 30.6 g of xylene was added dropwise from the dropping funnel over 20 minutes, and the mixture was stirred for 40 minutes. Then, at the same temperature, 0.16 g of t-butylperoxy-2-ethylhexanoate was added and stirred for 60 minutes. After completing the polymerization reaction, 21 g of xylene was added and dissolved to obtain a polymer solution A-2. Polymer solution A-2 had an Mw of 259000 and a heating residue of 39.8%.

3. Production of antifouling coating composition for fishing net - A fishing net antifouling coating composition was produced as a comparative example.
Tables 1 to 7 show water-based antifouling paints, and Tables 8 to 11 show oil-based antifouling paints.

Details of each component in Tables 1 to 11 are as follows.

((Meth) acrylic acid ester polymer (A))
Trade name “Banstar X1290B11”: acrylic acid ester/methacrylic acid ester copolymer emulsion (manufactured by Chubu Saiden Co., Ltd.)
Product name “Polysol (R) AP-4650N”: acrylic acid ester copolymer emulsion (manufactured by Showa Denko K.K.)
Product name “Polysol (R) AP-4780N”: acrylic acid ester copolymer emulsion (manufactured by Showa Denko K.K.)

(Ethylene vinyl acetate copolymer (B))
Product name “Polysol (R) EVA P-3N”: ethylene-vinyl acetate resin emulsion (manufactured by Showa Denko K.K.)
Trade name “Novatec (TM) EVA LV-211A”: ethylene/vinyl acetate copolymer resin (manufactured by Japan Polyethylene Co., Ltd.)

(Other spreading resins)
Product name “Polysol (R) S-65”: vinyl acetate resin emulsion (manufactured by Showa Denko K.K.)

(Silicone oil (C))
Product name “KF-6020”: polyether-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
Product name “X-22-2516”: polyether long-chain alkylaralkyl-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Antifouling agent (D))
Product name “NC-301”: Cuprous oxide (manufactured by Nissin Chemco Co., Ltd.)
Product name “Copper Omadine Powder”: copper pyrithione “bis(2-sulfidopyridine-1-orato)copper” (manufactured by Lonza Japan Co., Ltd.)
Product name “TOC-3204F”: bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate (manufactured by Rohm and Haas)
Product name “OPA”: 3-(2-ethylhexyloxy) propylamine/triphenylborane (manufactured by Nitto Kasei Co., Ltd.)
Product name “ODA”: n-octadecylamine/triphenylborane Product name “Noccellar TET-G”: Tetraethylthiuram disulfide (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)

(pigment)
Product name “Talc MS”: Talc [hydrous magnesium silicate] (manufactured by Nippon Talc Co., Ltd.)
Product name “AF Black E-2B”: water-based pigment dispersion (manufactured by Dainichiseika Co., Ltd.)
Product name “Carbon Black #44”: black pigment (manufactured by Mitsubishi Chemical Corporation)

(Waxes)
Product name “EMUSTAR-0001”: Microcrystalline wax emulsion (manufactured by Nippon Seiro Co., Ltd.)

(Preservative)
Product name “Delltop 100N”: antiseptic (manufactured by Osaka Gas Chemicals Co., Ltd.)

(Plasticizer)
Product name “Emawet 30E”: polybutene emulsion (manufactured by NOF Corporation)
Product name "Polybutene 0N": Plasticizer (manufactured by NOF)
Product name “Lucant HC-40”: plasticizer (Mitsui Chemicals, Inc.)
Product name “DAF-1”: plasticizer (DIC Corporation)

(dispersant)
Product name “OPTIGEL WM”: rheology additive (manufactured by Vic-Chemie Japan Co., Ltd.)
Product name “Disparlon 630-20X”: Polyamide wax (manufactured by Kusumoto Kasei Co., Ltd.)
Product name “Disparon 4200-20”: Polyethylene oxide wax (manufactured by Kusumoto Kasei Co., Ltd.)

(Antifoaming agent)
Product name “Anti-Floss S110”: Defoamer (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Product name “Disparon FA-62”: Silicone antifoaming agent (manufactured by Kusumoto Kasei Co., Ltd.)

(Film-forming aid)
Product name "Texanol": film-forming aid (manufactured by EASTMAN CHEMICAL)

4. Evaluation of fishing net antifouling paint composition The obtained fishing net antifouling paint composition was subjected to an antifouling effect confirmation test by the following method. The results are shown in Tables 12-18.

As shown in Tables 12 to 18, all examples gave better results than all comparative examples.

<Antifouling effect confirmation test>
The fishing net antifouling paint compositions of Examples and Comparative Examples were applied to polyethylene fishing nets (400 denier, 40 nets, 8 nodes) and nylon fishing nets (210 denier, 48 nets, 10 nodes). It was dip-coated and dried so that the adhesion amount was 15 parts by mass with respect to 100 parts by mass of the fishing net. A fishing net with a coating film was fixed to a 40 x 60 cm SUS frame and immersed in the draft of a raft in Owase, Mie Prefecture, a sea area where aquatic fouling organisms are strongly active, and the antifouling evaluation was performed for 10 and 12 months. observed periodically throughout the period.

Evaluation was performed by the following methods. In addition, the adhesion area (%) of aquatic organisms was determined by taking a photograph of the fishing net from above after the test period (2, 4, 6, 8, 10 or 12 months) and visually evaluating the area occupied by aquatic organisms in the fishing net. .
◎: Attachment area of aquatic organisms is 0%
○: Attachment area of aquatic organisms is more than 0 and less than 10% △: Attachment area of aquatic organisms is 10 or more and less than 50% ×: Attachment area of aquatic organisms is 50% or more

Claims (2)

(Meth)acrylic acid ester polymer (A), ethylene vinyl acetate copolymer (B), silicone oil (C), and antifouling agent (D). Except when the ethylene-vinyl acetate copolymer (B) is a chloride) . Fishing nets, fishing net implements and underwater structures having on their surfaces an antifouling coating film formed using the fishing net antifouling coating composition according to claim 1.