JP6186199B2 - A fishing net antifouling paint composition, a fishing net having an antifouling coating film formed using the composition, a fishing net tool, or an underwater structure. - Google Patents

Description

  The present invention provides a long-term observation that aquatic fouling organisms adhere to fishing nets for aquaculture or stationary nets, fishing net equipment such as floats and ropes, and underwater structures such as cooling water conduits of power plants. The present invention relates to a fishing net antifouling paint composition for preventing, an antifouling coating film formed using the composition, a method for forming the coating film, and a fishing net, a fishing net tool or an underwater structure having the coating film on the surface.

  Because 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 paints for fishing nets, green algae such as Aosa and Aonori, red algae such as Igis, and barnacles A variety of water fouling organisms such as crustaceans such as crustaceans, coelenterates such as hydrangea, cell plastics, bryozoans and molluscs adhere. As a result, the nets of the fishing nets are blocked and the flow of seawater becomes poor, and a large amount of cultured fish can be killed due to lack of oxygen, or infectious diseases can be caused and shipping can be seriously damaged.

  Conventionally, antifouling paint compositions for fishing nets using organotin compounds have been widely used to prevent the adhesion of these waterpox fouling organisms, but they cannot be used because of environmental considerations.

  Therefore, various studies and proposals have been made as antifouling agents to replace organic tin compounds, copper compounds such as cuprous oxide and rhodan copper, thiocarbamate compounds such as zinc and manganese salts of ethylenebisdithiocarbamic acid, tetraethylthiuram disulfide, Tetrachloroisophthalonitrile, dimethylphenyldichloromaleimide, triphenylborane / amine complex compound, 2-mercaptopyridine N-oxide metal salt, 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline, bis (dimethyl It has been proposed to use an active ingredient such as carbamoyl) ethylenebisdithiocarbamate zinc as an antifouling agent (for example, Patent Documents 1 to 6).

  However, in the industry related to fishing net antifouling paints, there is no fishing net antifouling paint composition that can exert a comprehensive antifouling effect on a wide range of water fouling fouling organisms, and its development is eagerly desired.

JP 2002-265849 A JP 11-199414 A Japanese Patent Laid-Open No. 11-322863 JP 2004-43679 A JP 2001-348532 A JP 2007-100001 A

  This invention is made | formed in view of the said situation, and makes it a subject to provide the fishing net antifouling paint composition which can exhibit the antifouling effect comprehensively with respect to a wide range of water fouling fouling organisms.

  According to the present invention, (A) 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole and (B) tetraethylthiuram disulfide, bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamic acid A fishing net antifouling paint composition containing one or more selected from the group consisting of zinc, 3- (2-ethylhexyloxy) propylamine · triphenylborane, and n-octadecylamine · triphenylborane. Provided.

  As a result of intensive studies to solve the above problems, the present inventor found that when the compound (A) and the compound (B) were used in combination, (1) both the compound (A) and the compound (B) There are two synergistic effects: a synergistic effect of exerting an antifouling effect even for organisms that do not exhibit the antifouling effect, and (2) a synergistic effect of significantly increasing the period during which the antifouling effect is exhibited. As a result, the present invention has been completed.

  In addition, the compound in which the compound (A) has a synergistic effect is limited to those listed as the compound (B), and the combined effect when combined with many compounds other than the compound (B) was also investigated. Only the antifouling effect obtained by adding the antifouling effect by the compound (A) and the antifouling effect by the compound (B) was obtained, and the synergistic effect was not exhibited (Comparative Examples 10 to 13).

  As described above, according to the present invention, there is provided a fishing net antifouling paint composition capable of comprehensively exerting an antifouling effect against a wide range of water fouling organisms.

  Moreover, according to this invention, the fishing net which has the antifouling coating film formed using the said fishing net antifouling paint composition on the surface, a fishing net tool, or an underwater structure is also provided.

Fishing net antifouling paint composition The fishing net antifouling paint composition of the present invention comprises:
(A) 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole, (B) tetraethylthiuram disulfide, bis (dimethyldithiocarbamoyl) ethylenezincbisdithiocarbamate, 3- (2 1-type or 2 or more types selected from the compound group which consists of -ethylhexyloxy) propylamine * triphenylborane and n-octadecylamine * triphenylborane.

<2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (A)>
As 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole used in the present invention, a commercially available product can be used. Examples of commercially available products include Econea 028 (registered trademark, Janssen PMP).

  The content of 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole is not particularly limited, but is 5 to 200 with respect to 100 parts by mass of the spreading resin in terms of solid content. It is a mass part, Preferably, it is 10-150 mass parts, More preferably, it is 15-100 mass parts.

<Compound (B)>
Examples of the compound (B) of the present invention include tetraethylthiuram disulfide, bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, 3- (2-ethylhexyloxy) propylamine / triphenylborane, n-octadecylamine / triphenylborane. These compounds may be used alone or in combination of two or more. As the compound (B), tetraethylthiuram disulfide is preferable from the viewpoint of long-term antifouling properties.

  Although content of the said compound (B) is not specifically limited, It is 5-200 mass parts with respect to 100 mass parts of spreading resin in conversion of solid content, Preferably, it is 10-150 mass parts, More preferably. Is 15 to 100 parts by mass.

Although it does not specifically limit as a compounding ratio of the said compound (A) and the said compound (B), The mass ratio of the said compound (B) / the said compound (A) is 0.1-8 in conversion of solid content. Is preferable, and 0.3 to 4 is more preferable.
Specifically, this mass ratio is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1 .1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2 .4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3 7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3 , 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6 , 7.7, 7.8, 7.9, 8 and the numerical values exemplified here It may be a Re or the range between the two. By using the (A) component and the (B) component in combination at the above-described blending ratio, the assumed combined effect can be exhibited and a synergistic antifouling effect can be obtained.

  As the tetraethylthiuram disulfide, a commercially available product can be used. Examples of the commercially available product include TET-G (registered trademark, manufactured by Sanshin Chemical Industry Co., Ltd.).

As the bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate zinc, a commercially available product can be used. Examples of commercially available products include bisdaicene (registered trademark, manufactured by Dow Agroscience), TOC-3204F (Rohm and Haas). Manufactured) and the like.
The bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate zinc [C] has an average particle diameter of 0.01 to 20 μm, preferably 0.05 to 5 μm, from the viewpoint of dispersibility in water.

The 3- (2-ethylhexyloxy) propylamine triphenylborane can be synthesized by a known method (for example, Production Example 1 of Patent Document 3). For example, it can be obtained by reacting triphenylborane and 3- (2-ethylhexyloxy) propylamine in an organic solvent at room temperature or under heating. As the organic solvent, for example, tetrahydrofuran, benzene, toluene, xylene, mineral spirit, hexane, heptane, octane, methyl ethyl ketone, methyl isobutyl ketone, dibutyl ether, methanol, ethanol, propanol and the like can be used. The use ratio of triphenylborane and 3- (2-ethylhexyloxy) propylamine is preferably 1.0 to 1.2 as the molar ratio of triphenylborane to 3- (2-ethylhexyloxy) propylamine. 0.0 is more preferable. The reaction is preferably performed in an inert atmosphere. About the obtained reaction mixture, you may post-process as needed. In the post-treatment, for example, the organic solvent is distilled off to crystallize the desired 3- (2-ethylhexyloxy) propylamine triphenylborane. Moreover, you may refine | purify by recrystallization etc. as needed.
Moreover, a commercial item can be used and OPA (registered trademark, Nitto Kasei Co., Ltd. product) is mentioned as a commercial item, for example.

The n-octadecylamine / triphenylborane can be synthesized by a known method (for example, see Comparative Production Example 2 in Patent Document 3). For example, it can be obtained by reacting triphenylborane and n-octadecylamine in an organic solvent at room temperature or under heating. As the organic solvent, for example, tetrahydrofuran, benzene, toluene, xylene, mineral spirit, hexane, heptane, octane, methyl ethyl ketone, methyl isobutyl ketone, dibutyl ether, methanol, ethanol, propanol and the like can be used. The use ratio of triphenylborane and n-octadecylamine is preferably 1.0 to 1.2, more preferably 1.0 as the molar ratio of triphenylborane to n-octadecylamine. The reaction is preferably performed in an inert atmosphere. About the obtained reaction mixture, you may post-process as needed. In the post-treatment, for example, the organic solvent is distilled off to crystallize the desired n-octadecylamine / triphenylborane. Moreover, you may refine | purify by recrystallization etc. as needed.
Moreover, a commercial item can be used, As an example of a commercial item, ODA (trademark, the product made from Benitoyama) is mentioned.

  The composition of this invention can be made to contain the following components as needed.

<Silicone oil>
Silicone oil can serve as an elution modifier. That is, by containing silicone oil, the elution rate of the coating film can be suitably suppressed, and the antifouling effect can be exhibited for a long period of time.

Examples of the silicone oil include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether-modified polydimethylsiloxane, polyether-modified polyalkyl (methyl) siloxane, polyester-modified polydimethylsiloxane, long Examples include chain alkyl-modified polydimethylsiloxane, aralkyl-modified polydimethylsiloxane, polyether long-chain alkylaralkyl-modified dimethyl silicone oil, fluorosilicone oil, amino-modified silicone oil, and other modified silicone oils with various functional groups. In particular, a polyether-modified silicone oil having a hydrophilic / lipophilic balance (HLB value) of 0.5 to 9 is preferred. Specifically, a polyether-modified polydimethylsiloxane or polyether long-chain alkylaralkyl-modified dimethyl having a viscosity of 0.5 to 9 is used. Silicone oil is preferred. More preferable examples include polyether-modified polydimethylsiloxane or polyether long-chain alkylaralkyl-modified dimethylsilicone oil having a hydrophilic / lipophilic balance (HLB value) in the range of 1 to 5. Sufficient antifouling performance can be obtained by using a silicone oil having an HLB value in the range of 0.5 to 9.
In the present invention, these silicone oils may be used alone or in combination of two or more.

The viscosity of the silicone oil is preferably 1000 poises or less, more preferably 100 poises or less, from the viewpoint of coating performance and coating film properties.
The content of the silicone oil is not particularly limited, but is 0.5 to 150 parts by mass, preferably 0.5 to 100 parts by mass, and more preferably in terms of solid content with respect to 100 parts by mass of the spreading resin. Is 1-50 parts by mass.

<Ethylene / α-olefin copolymer>
The ethylene / α-olefin copolymer can serve as an elution regulator. That is, by containing the ethylene / α-olefin copolymer, the elution rate of the coating film can be suitably suppressed, and the antifouling effect can be exhibited for a long period of time.
Examples of the ethylene / α-olefin copolymer include a general formula (1):

(Wherein R ¹ represents a linear or branched alkyl group having 1 to 10 carbon atoms, and x, y and p are the same or different and each represents an integer of 1 or more) An α-olefin copolymer may be mentioned.
Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R ¹ include 1 carbon atom such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. An alkyl group of ˜4 is preferred, and a methyl group is more preferred.
The ethylene / α-olefin copolymer represented by the general formula (1) is a copolymer obtained by copolymerizing ethylene and α-olefin. The ethylene / α-olefin copolymer may be a random copolymer, a block copolymer, or a graft copolymer.
A commercially available product can be used as the ethylene / α-olefin copolymer. Examples of commercially available products include Lucant HC-10, Lucant HC-20, Lucant HC-40, Lucant HC-100, Lucant HC-150, Lucant HC-600, Lucant HC-2000 (all are registered trademarks, Mitsui Chemicals, Inc.) Company-made). These ethylene / α-olefin copolymers may be used alone or in combination of two or more.

The number average molecular weight (Mn) of the ethylene / α-olefin copolymer is preferably 10,000 or less, more preferably 1,000 to 3,000, from the viewpoints of coating performance and coating film properties. The ethylene / α-olefin copolymer preferably has a viscosity at 0 ° C. of 20,000 PaS or less, and more preferably 500 PaS or less.
The content of the ethylene / α-olefin copolymer is not particularly limited, but is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, in terms of solid content, with respect to 100 parts by mass of silicone oil. More preferably, it is 50-300 mass parts.

<Polybutenes>
Polybutenes can serve as elution regulators. Examples of polybutenes include polybutene and polyisobutene. As the polybutenes, commercially available products can be used. Examples of commercially available products include polybutene LV-7, polybutene LV-10, polybutene LV-25, polybutene LV-50, polybutene LV-100, polybutene HV-35, polybutene HV-100, polybutene HV-300, polybutene HV- 1900 (all manufactured by Nippon Petrochemical Co., Ltd.); polybutene 0H, polybutene 5H, polybutene 10H, polybutene 300H, polybutene 2000H, polybutene 0R, polybutene 15R, polybutene 35R, polybutene 100R, polybutene 350R (all manufactured by Idemitsu Petrochemical Co., Ltd.) ); Polybutene 0N, polybutene 06N, polybutene 3N, polybutene 10SH, polybutene 200N (all manufactured by NOF Corporation) and the like.
Although content of polybutene is not specifically limited, It is 1-1000 mass parts with respect to 100 mass parts of silicone oil in conversion of solid content, Preferably it is 1-500 mass parts, More preferably, it is 50-300 mass parts. It is.

<Paraffins>
Examples of paraffins include n-paraffin, solid paraffin, liquid paraffin, and chlorinated paraffin.
Although content of paraffins is not specifically limited, It is 1-1000 mass parts with respect to 100 mass parts of silicone oil in conversion of solid content, Preferably it is 1-500 mass parts, More preferably, it is 50-300 mass parts. It is.

<Vaseline>
Examples of petrolatum include white petrolatum and yellow petrolatum.
The content of petrolatum is not particularly limited, but is 1 to 1000 parts by weight, preferably 1 to 500 parts by weight, and more preferably 50 to 300 parts by weight in terms of solid content with respect to 100 parts by weight of silicone oil. It is.

<Dialkyl sulfide compounds>
Dialkyl sulfide compounds include di-tert-butyl decasulfide, dipentyl tetrasulfide, dipentyl pentasulfide, dipentyl decasulfide, dioctyl tetrasulfide, dioctyl pentasulfide, dinonyl tetrasulfide, dinonyl pentasulfide, di-tert-nonyl tetra Examples thereof include sulfide, di-tert-nonyl pentasulfide, didecyl tetrasulfide, didodecyl tetrasulfide, dioctadecyl tetrasulfide, dinonadecyl tetrasulfide and the like.
Although content of a dialkyl sulfide compound is not specifically limited, It is 1-1000 mass parts with respect to 100 mass parts of silicone oil in conversion of solid content, Preferably it is 1-500 mass parts, More preferably, it is 50-300 mass. Part.

<Anti-fouling agent>
As the antifouling agent, in addition to the compound (A) and the compound (B), other inorganic antifouling agents and organic antifouling agents can be contained. Thereby, the formed coating film can exhibit a more suitable antifouling effect.
For example, copper-based inorganic antifouling agents such as copper powder, cupronickel, cuprous oxide, rhodan copper, zinc pyrithione, copper pyrithione, 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline, chloromethyl- n-octyl disulfide, N, N-dimethyldichlorophenylurea, N- (fluorodichloromethylthio) phthalimide, N, N′-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, N, N′-dimethyl- N′-tolyl- (N-fluorodichloromethylthio) sulfamide, 2,3-dichloro-N- (2,6-diethylphenyl) maleimide, 2,3-dichloro-N- (2′-ethyl, 6′-methyl Phenyl) maleimide, 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxai And organic antifouling agents such as tetrachloroisophthalonitrile.

<Spreading resin>
By including the spreading resin, workability in forming the coating film is improved. Moreover, the coating film excellent in adhesiveness with a to-be-coated-film formation object can be formed.
Synthetic resins and natural resins are used as the spreading resin.
As the synthetic resin, for example, vinyl resin, alkyd resin, acrylic resin, urethane resin, polyester resin, synthetic rubber, chlorinated polyethylene and the like can be used. Examples of the vinyl resin include vinyl chloride-vinyl acetate copolymer, vinyl chloride-alkyl vinyl ether copolymer, vinyl chloride resin and the like.
Examples of the natural resin include wood rosin, gum rosin, and modified rosin.
In particular, the spreading resin preferably contains an acrylic resin.
The glass transition temperature (Tg) of the spreading resin is preferably -100 to 100 ° C, more preferably -50 to 80 ° C. If the Tg is too low, the coating film has a large tack after being applied to the fishing net, which hinders the application operation. Moreover, when Tg is too high, the said range is preferable at the point that the softness | flexibility of a coating film will be impaired, a crack, a crack, etc. will be produced and it will become the cause of reducing an antifouling effect. The value of Tg refers to a value measured by using a differential scanning calorimeter (eg, DSC1 manufactured by METTTLER TOLEDO) with reference to the measurement method of JIS K7121.
The weight average molecular weight (Mw) of the spreading resin is preferably 5,000 to 1,000,000, and more preferably 7,000 to 500,000. Examples of the method for measuring Mw include gel permeation chromatography (GPC). When Mw is measured by GPC, Mw is displayed as a value (polystyrene conversion value) obtained by creating and measuring a calibration curve using polystyrene as a standard substance.
Although content of the said spreading resin is not specifically limited, 1-50 mass% is used in an antifouling coating composition in conversion of solid content, Preferably it is 5-30 mass%.

<Others>
You may make the composition of this invention contain a well-known additive as needed.
Known additives include, for example, dyes, pigments, dispersants (eg, polyamide phosphate dispersants, polyamide dispersants, unsaturated polycarboxylic acid dispersants), plasticizers (eg, phthalate esters, adipine) Acid esters, tricresyl phosphate, etc.), antifoaming agents, sagging inhibitors, surfactants and the like.
About these additives, it can be made to contain by the arbitrary mixture ratios which do not prevent the effect of this invention.

The composition of the present invention is usually dissolved or dispersed in water or an organic solvent. Thereby, it can use suitably as a coating material.
Examples of the organic solvent include aromatic solvents such as xylene, toluene, Solvesso 100 and Solvesso 150 (all 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 isoamyl acetate can be used.

In addition, organic solvents considering low toxicity, low odor, and low environmental load can be used. For example, Pegasol AN45, Pegasol AS100 (all registered trademarks, manufactured by ExxonMobil), LAWS, HAWS (all manufactured by Shell Chemicals) ) And other aromatic / alicyclic / aliphatic hydrocarbon mixed solvents; glycol ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethylcyclohexane, dimethylcyclohexane, Ricasolve (registered trademark) 900 (C9) Aromatic hydrocarbon solvents such as aromatic hydrogenated product), Ricasolve (registered trademark) 1000 (C10 aromatic hydrogenated product); Shellsol D40 (registered trademark, manufactured by Shell Chemicals), Exol D30, Exol D40 (all Also registered trademark, made by ExxonMobil Alicyclic-aliphatic hydrocarbon solvent mixture and the like; Isopar G, Isopar H (both registered trademarks, manufactured by Exxon Mobil), such as aliphatic hydrocarbon mixture solvent, and the like may also be used.
These organic solvents can be used alone or in admixture of two or more.

  The composition of the present invention can be used for the formation of antifouling coatings for various fishing equipment, underwater structures and the like. In particular, the composition of the present invention can be suitably used as an antifouling paint composition for fishing nets.

  The fishing net antifouling paint composition of the present invention can be prepared by mixing the above components (A) and (B) and the respective components as necessary. What is necessary is just to adjust suitably about the addition amount of each component at the time of mixing so that it may become the said compounding quantity and content. The order of mixing the components is not particularly limited. About a mixing method, what is necessary is just to employ | adopt a well-known method, such as mixing using a stirring apparatus.

Method for forming fishing net antifouling coating film, antifouling coating film, and coated article The method for forming a fishing net antifouling coating film according to the present invention uses the above-mentioned fishnet antifouling coating composition to prevent fouling on the surface of an object to be coated A coating film is formed. The antifouling coating film obtained by the forming method of the present invention is gradually dissolved from the surface and the coating film surface is constantly renewed, thereby preventing the adhesion of chickenpox fouling organisms. Moreover, after dissolving a coating film, the antifouling effect can be exhibited continuously by overcoating the said composition.
Examples of the coating film formation include fishery tools and underwater structures. Examples of the fishery tools include aquaculture or stationary fishing nets, fishing net accessories such as floats and ropes used in the fishing nets, and the like. Examples of the underwater structure include a power plant conduit, a bridge, a port facility, and the like.

The fishing net antifouling coating film of the present invention can be formed by applying the above-mentioned fishing net antifouling coating composition to the surface (entirely or partly) of the coating film forming object.
Examples of the application method include brush coating, spraying, dipping, flow coating, and spin coating. These may be used alone or in combination of two or more. For example, when the fishing net antifouling paint composition of the present invention is applied to a fishing net, it is preferable to employ a dipping method as the application method.
After application, dry. The drying temperature may be room temperature. What is necessary is just to set drying time suitably according to the adhesion amount of a fishing net antifouling paint.

  What is necessary is just to set suitably the adhesion amount of the said fishing net antifouling paint according to the kind etc. of a coating-film formation thing. For example, when the coating film formation is a fishing net, the amount of the dry coating film is preferably 1 to 30 parts by mass, and more preferably 4 to 15 parts by mass with respect to 100 parts by mass of the fishing net.

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

  Examples and the like will be described below to further clarify the features of the present invention. However, the present invention is not limited to the examples.

Production Example 1 (Production of metal carboxylate-containing copolymer)
After adding 50 g of butyl acetate and 50 g of n-butanol to a flask equipped with a thermometer, a reflux condenser, a stirrer, a nitrogen introducing tube and a dropping funnel and heating to 90 to 100 ° C., acrylic acid 10 was added in a nitrogen atmosphere. A mixed solution of .8 g, ethyl acrylate 64.2 g, methyl methacrylate 75 g, and azobisisobutyronitrile 3 g was added dropwise over 4 hours. The mixture was kept at 100 ° C. until 1 hour after the completion of the dropwise addition, and a mixed solution of 30 g of butyl acetate and 0.5 g of azobisisobutyronitrile was added dropwise over 1 hour. Next, 12 g of zinc oxide, 20 g of butanol and 1.5 g of deionized water were added and reacted at 120 ° C. for 10 hours to obtain a metal carboxylate-containing copolymer solution. The resulting copolymer solution had a heating residue of 50.5% and Mw of 7,500.

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

<Heating residue analysis method>
The heating residue is a value determined by JIS K5601-1-2 (125 ° C., 1 hour heating).

Examples 1-12 and Comparative Examples 1-14
A fishing net antifouling paint composition was obtained by mixing the components described in Tables 1 and 2 in proportions (mass%) described in Tables 1 and 2.

Details of each component in Tables 1 and 2 are as follows.
Product name “Nittor HN”: Acrylic resin xylene solution (solid content 40%, Tg = about 20 ° C., Mw = about 230,000, manufactured by Nitto Kasei Co., Ltd.)
Product name "Econea 028" ... 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
Product name "TET-G" ... tetraethylthiuram disulfide (manufactured by Sanshin Chemical Industry Co., Ltd.)
Product name "OPA" ... Triphenylborane 3- (2-ethylhexyloxy) propylamine (Nitto Kasei Co., Ltd. purity 99%)
Product name “TOC-3204F” ... zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate (Rohm and Haas)
Product name "ODA" ... n-octadecylamine triphenylborane (manufactured by Benitoyama Co., Ltd.)
Product name "PK": pyridine, triphenylborane (manufactured by Hokuko Chemical Co., Ltd.)
Product name "Sea Nine 211" ... 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline (solid content 30% xylene solution, manufactured by Rohm and Haas)
Product name "ZnPT" ... zinc pyrithione (manufactured by Arch Chemical Co., Ltd.)
Product name "CuPT" ... Copper pyrithione (Arch Chemical Co., Ltd.)
Product name "X-22-2516" ... Polyether long chain alkyl aralkyl modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
Product name “KF-6020”: Polyether-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
Product name “Lucanto HC-40”: ethylene / α-olefin copolymer (Mn = 1600, manufactured by Mitsui Chemicals, Inc.)
Product name "Polybutene 0N" ... Polybutene (Nippon Yushi)
Product name "DAF-1" ... Di-tert-nonyl pentasulfide (Dainippon Ink Co., Ltd.)
Product name "Disparon 4200-20X" ... polyethylene oxide (20% solids, manufactured by Enomoto Kasei Co., Ltd.)
Product name "DISPARON 6900-20X" ... fatty acid amide (solid content 20%, manufactured by Enomoto Kasei Co., Ltd.)
Product name "Disparon FA-62" ... A mixture of acrylic polymer and silicone (solid content 35%, manufactured by Enomoto Kasei Co., Ltd.)
Xylene ... Made by Kishida Chemical Co., Ltd.

Test Example 1 (Anti-fouling effect confirmation test)
Polyethylene fishing nets (400 denier, 40, 8 sections) were applied to each of the fishing net antifouling paint compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 14, and the amount of dry coating adhered to the fishing net of 100 mass. The coating was dip coated and dried to 8 parts by mass. The fishing net on which the coating film was formed was fixed to a frame of 40 × 60 cm SUS, and immersed in 1 m below the sea surface with a stationary net at the destination of the Ofuna Iwate prefecture.
The results are shown in Tables 3-4.
The numbers in Tables 3 to 4 represent the surface area (%) of fouling organisms. In addition, the adhesion surface area (%) of the fouling organism was obtained by taking a picture of the fishing net from the sea surface after the test period (1, 2, 4, 6 or 8 months) and visually evaluating the area occupied by the fouling organism in the fishing net. .
In addition, “◯” in the column of antifouling effect in Tables 3 to 4 indicates that the corresponding organism was not confirmed after 8 months, and “×” indicates that the corresponding organism was confirmed after 8 months. It has been shown. Further, “◯ S” indicates that the antifouling effect was exerted on the corresponding organism by the synergistic effect of the combination of two or more types of antifouling agents.

<Discussion>
Referring to Comparative Example 1, it can be seen that Econia is effective for crustaceans but does not have a sufficient antifouling effect for other organisms. Referring to Comparative Example 2, it can be seen that TET-G is effective against green algae but does not have a sufficient antifouling effect against other organisms. Considering these results, it is predicted that the antifouling coating film of Example 1 using both Econia and TET-G exhibits an antifouling effect only on crustaceans and green algae. However, in fact, the antifouling effect was also exhibited for red algae in addition to crustaceans and green algae. Moreover, the period until the organism started to attach was 2 to 4 months in Comparative Examples 1 and 2, whereas it was 8 months in Example 1. Thus, in Example 1, (1) the point that the antifouling effect was exerted even on a living organism that did not exhibit the antifouling effect with a single antifouling agent, and (2) the period until the start of attachment of the organism The synergistic effect of the combination of antifouling chemicals was obtained at two points:

  Referring to Comparative Example 3, it can be seen that TOC-3204F is effective only for coelenterate animals. Therefore, the antifouling coating film of Example 2 in which Econia and TOC-3204F are used in combination is expected to be effective only for crustaceans and coelenterate animals. Demonstrated. Moreover, the period until the start of biofouling has increased significantly.

  Referring to Comparative Examples 4-5, it can be seen that OPA and ODA are not effective against red algae. Since econia is not effective against red algae, the antifouling coating film of Examples 3 to 4 using both econia and OPA or ODA is expected to be ineffective against red algae. The antifouling effect was also demonstrated. Moreover, the period until the start of biofouling has increased significantly.

  In Example 5, the combination of antifouling agents is the same as in Example 1, but the ratio of econia is larger than that in Example 1. In Example 5, the antifouling effect was exhibited by a synergistic effect on the coelenterate animals, red algae and other organisms, and an extremely excellent result was obtained that there was no organism adhesion even after 8 months.

  In Example 6, the combination of antifouling agents is the same as in Example 2, but the ratio of econia is larger than that in Example 2. In Example 6, the antifouling effect was exhibited by a synergistic effect against green algae and other organisms.

  In Example 7, the combination of antifouling agents is the same as in Example 3, but the ratio of econia is larger than that in Example 3. In Example 7, the types of organisms that exhibit the antifouling effect are the same as in Example 3, but the results are superior to Example 3 in that the area of biological attachment after 8 months is smaller than in Example 3. was gotten.

  In Example 8, the combination of antifouling agents is the same as that in Example 1, but the amount of antifouling agents is larger than that in Example 1. In Example 8, the antifouling effect was exhibited by the synergistic effect on the coelenterate animals, red algae and other organisms, and an extremely excellent result was obtained that there was no organism adhesion even after 8 months.

  In Example 9, three types of econia, TET-G, and TOC-3204F were used in combination. As a result, the antifouling effect was exhibited by a synergistic effect against other organisms that did not exhibit the antifouling effect in any of Examples 1 and 2, and extremely excellent in that there was no organism adhesion even after 8 months. Results were obtained.

  In Example 10, three types of econia, TET-G, and OPA were used in combination. As a result, the antifouling effect was exhibited by a synergistic effect on the coelenterate animals that did not exhibit the antifouling effect in any of Examples 1 and 3, and there was no biofouling even after 8 months. Excellent results were obtained.

  In Examples 11 to 12, the type and blending amount of the antifouling agent are the same as in Example 1, and the type of spreading resin is different from that in Example 1. In Examples 11 to 12, as in Example 1, excellent results due to a synergistic effect were obtained.

  Comparative Examples 10 to 13 are a combination of Econia and PK, Sea Nine 211, ZnPT, or CuPT, but only the antifouling effect predicted from Comparative Example 1 and Comparative Examples 6 to 9 was obtained. There was no synergistic effect of the combination.

Claims (5)

(A) 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole;
(B) Selected from the compound group consisting of tetraethylthiuram disulfide, zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, 3- (2-ethylhexyloxy) propylamine • triphenylborane, n-octadecylamine • triphenylborane 1 type or 2 types or more,
A fishing net antifouling paint composition containing a polyether- modified silicone oil.   The fishing net antifouling paint composition according to claim 1, wherein the compound (B) is tetraethylthiuram disulfide.   The fishing net antifouling paint composition according to claim 1 or 2, wherein a mass ratio of the compound (B) / the compound (A) is 0.1 to 8 in terms of solid content.   Furthermore, one or more selected from the group consisting of silicone oil, ethylene / α-olefin copolymer, polybutenes, paraffins, petrolatums and dialkyl sulfide compounds are contained. The fishing net antifouling paint composition as described.   A fishing net, a fishing net tool, or an underwater structure having an antifouling coating film formed on the surface thereof using the fishing net antifouling paint composition according to claim 1.