JP5561462B2 - Fishing net antifouling paint composition, antifouling coating film formed using the composition, method for forming the coating film, and fishing net, fishing net tool or underwater structure having the coating film on the surface - 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.

Fishing nets, fishing net tools and underwater structures are installed in the sea for a long time. 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 Proposals have been made to use active ingredients such as carbamoyl) zinc ethylenebisdithiocarbamate as antifouling agents.

  However, since there are a wide variety of varicella-stained organisms such as crustaceans, coelenterates, green algae, and red algae, antifouling agents that exert a comprehensive antifouling effect against a wide range of varicella-stained organisms are still not available. Not found. For example, triphenylborane / amine complex compounds have a low antifouling effect on coelenterates such as hydroworms and green algae, and 2-mercaptopyridine N-oxide metal salts exhibit a good antifouling effect on green algae. Antifouling effect is low for coelenterate and crustaceans. In addition, 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline exhibits a certain degree of antifouling effect on coelenterate, green algae and red algae, but has a short antifouling period and is useful for crustaceans such as barnacles. On the other hand, the antifouling effect is low. Furthermore, zinc bis (dimethylcarbamoyl) ethylenebisdithiocarbamate exhibits an excellent antifouling effect on the coelenterate, but has a disadvantage that the antifouling effect is remarkably poor against other varicella-fouling organisms.

  In addition, by using antifouling agents in combination, proposals have been made to comprehensively demonstrate antifouling effects against a wide range of water fouling organisms, but those that exhibit stable antifouling effects over a long period of time have been proposed. Not yet developed. For example, an antifouling paint composition using cuprous oxide and 2-mercaptopyridine N-oxide copper salt (Patent Document 1), an antifouling paint composition using triphenylborane / amine complex compound and tetraethylthiuram disulfide (Patent Documents 2 to 5) have been proposed. However, although both compositions show an antifouling effect against some varicella-fouling organisms, the antifouling effect on coelenterate is not satisfactory. Further, an antifouling coating composition (Patent Document 6) using zinc bis (dimethyldithiocarbamoyl) ethylenebisdithioalbamate and 2-mercaptopyridine N-oxide metal salt has been proposed. However, this composition has an improved antifouling effect on coelenterates and algae, but is not satisfactory in antifouling effect on crustaceans such as barnacles. Furthermore, an antifouling coating composition (Patent Document 2) using a triphenylborane / alkylamine complex and 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline has been proposed. However, this composition cannot comprehensively exert an antifouling effect against a wide range of water fouling fouling organisms and is not satisfactory in terms of the antifouling period.

  Therefore, in the industry related to fishing net antifouling paints, development of a fishing net antifouling paint composition capable of exhibiting a comprehensive antifouling effect against a wide variety of water fouling organisms is eagerly desired. In particular, among the waterfoil-fouling organisms, echis (a kind of red algae) and hydrangea (coelenterate), etc., once attached to the net and grow, it is easy to block the net of the net of the fishing net because it is large There is a problem, and a fishing net antifouling paint composition that exhibits a better antifouling effect on red algae such as ggies and coelenterates such as hydroworms 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

  The present invention has been made in view of the above circumstances, and exerts a comprehensive antifouling effect against a wide variety of varicella-fouling organisms, and particularly against red algae such as ggris and coelenterates such as hydroworms. It is an object of the present invention to provide a fishing net antifouling paint composition capable of exhibiting a superior antifouling effect.

  As a result of intensive studies to solve the above problems, the present inventor has found that a composition containing a specific antifouling agent can solve the above problems, and has completed the present invention.

That is, the present invention relates to a fishing net antifouling paint composition, an antifouling coating film formed using the composition, a method for forming the coating film, a fishing net having the coating film on the surface, and the like.
1. Formula (I):

(Wherein R ¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms or a phenylene group, and R ² represents a linear or branched alkyl group having 1 to 18 carbon atoms. ), A triphenylborane / alkoxy group-containing amine complex compound, 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline and / or zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate Fishing net antifouling paint composition.

  2. Formula (I):

(Wherein R ¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms or a phenylene group, and R ² represents a linear or branched alkyl group having 1 to 18 carbon atoms) Item 2. The fishing net antifouling paint composition according to Item 1, comprising a triphenylborane / alkoxy group-containing amine complex compound and 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline.

  3. The blending ratio of the 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline with respect to 100 parts by weight of the triphenylborane / alkoxy group-containing amine complex compound in terms of solid content is 10 to 200 parts by weight, The fishing net antifouling paint composition according to Item 1, wherein the blending ratio of the bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate zinc is 10 to 600 parts by weight.

  4). Furthermore, any one of the above items 1 to 3 containing one or more selected from the group consisting of silicone oil, ethylene / α-olefin copolymers, polybutenes, paraffins, petrolatums and dialkyl sulfide compounds. The fishing net antifouling paint composition as described.

  5. The fishing net according to any one of Items 1 to 4, further comprising one or more antifouling agents selected from the group consisting of tetraethylthiuram disulfide, cuprous oxide, copper powder, copper pyrithione, and zinc pyrithione. Antifouling paint composition.

  6). Item 6. The fishing net antifouling paint composition according to any one of Items 1 to 5, wherein the silicone oil is a polyether-modified silicone oil having a hydrophilic / lipophilic balance (HLB) of 0.5 to 9.

  7). Item 7. The fishing net according to any one of Items 1 to 6, wherein the triphenylborane / alkoxy group-containing amine complex compound represented by the general formula (I) is a triphenylborane-3- (2-ethylhexyloxy) propylamine complex compound. Antifouling paint composition.

  8). The antifouling processing method which forms an antifouling coating film on the surface of a to-be-coated film formation using the fishing net antifouling paint composition in any one of said item | term 1-7.

  9. The antifouling coating film formed using the fishing net antifouling paint composition in any one of said items 1-7.

  10. A fishing net, a fishing net tool or an underwater structure having the antifouling coating film according to Item 9 on its surface.

  The fishing net antifouling paint composition of the present invention exhibits a comprehensive antifouling effect against a wide range of water fouling fouling organisms, and is particularly superior to red algae such as ggies and coelenterates such as hydroworms. An antifouling effect can be exhibited.

Fishing net antifouling coating composition The fishing net antifouling coating composition of the present invention comprises a triphenylborane / alkoxy group-containing amine complex compound [A] (hereinafter sometimes referred to as “component [A]”), 4,5- Dichloro-2-n-octyl-3 (2H) isothiazoline [B] (hereinafter sometimes referred to as “[B] component”) and / or bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate zinc [C] (hereinafter referred to as “B”) "[C] component").

<Triphenylborane / alkoxy group-containing amine complex compound [A]>
The triphenylborane / alkoxy group-containing amine complex compound [A] used in the present invention is represented by the general formula (I):

(Wherein R ¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms or a phenylene group, and R ² represents a linear or branched alkyl group having 1 to 18 carbon atoms. A triphenylborane / alkoxy group-containing amine complex compound represented by the formula:

Examples of the linear or branched alkylene group having 2 to 8 carbon atoms represented by R ¹ include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 2-methyltrimethylene group, 1,1- Examples thereof include dimethylethylene group, 1,2-dimethylethylene group, 1-ethylethylene group, pentamethylene group, hexamethylene group, 1-butylethylene group, octamethylene group, 2-ethylhexamethylene group and the like.

Examples of the linear or branched alkyl group having 1 to 18 carbon atoms represented by R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, Examples include heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, lauryl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl and the like.

  Specific examples of the triphenylborane / alkoxy group-containing amine complex compound include, for example, triphenylborane · 3-ethoxypropylamine, triphenylborane · 3-butoxypropylamine, triphenylborane · 3- (2-ethyl Xyloxy) propylamine, triphenylborane-3-lauryloxypropylamine, triphenylborane-3-stearyloxypropylamine, triphenylborane-4- (2-ethylhexyloxy) butylamine, triphenylborane-4-lauryloxybutylamine , Triphenylborane · 8-ethoxyoctylamine, triphenylborane · 8- (2-ethylhexyloxy) octylamine, triphenylborane · 2-ethylhexyloxyphenylamine, triphenylbora - lauryl oxyphenyl amine.

  Of these triphenylborane / alkoxy group-containing amine complex compounds, triphenylborane · 3- (2-ethylhexyloxy) propylamine is particularly preferred. The triphenylborane / alkoxy group-containing amine complex compounds exemplified above may be used alone or in combination of two or more.

  The triphenylborane / alkoxy group-containing amine complex compound can be synthesized by a known method. For example, it can be obtained by reacting triphenylborane with an alkoxy group-containing amine 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, ethyl isobutyl ketone, dibutyl ether, methanol, ethanol, propanol and the like can be used. The use ratio of triphenylborane and alkoxy group-containing amine is preferably 1.0 to 1.2, more preferably 1.0 as the molar ratio of triphenylborane to alkoxy group-containing amine. 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 target triphenylborane / alkoxy group-containing amine complex compound. Moreover, you may refine | purify by recrystallization etc. as needed.

  The content of the triphenylborane / alkoxy group-containing amine complex compound is not particularly limited, but in terms of solid content, it is 1 to 300 parts by weight, preferably 1 to 200 parts by weight with respect to 100 parts by weight of the spreading resin. Part, more preferably 10 to 100 parts by weight.

<4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B]>
The 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B] used in the present invention has the general formula (II):

It is a compound represented by these.

  The 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B] has an average particle diameter of 0.01 to 20 μm, preferably 0.05 to 5 μm from the viewpoint of dispersibility in water. Used.

  As the 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B], a commercially available product can be used. Examples of commercially available products include Cine Nine 211 (registered trademark, manufactured by Rohm and Haas), Caisson 930 (registered trademark, manufactured by Rohm and Haas), and the like.

  The content of the 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B] is not particularly limited, but is 1 to 150 parts by weight with respect to 100 parts by weight of the spreading resin in terms of solid content. 10 to 75 parts by weight is more preferable.

<Zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate [C]>
The zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate [C] used in the present invention has the general formula (III):

It is a compound represented by these.

  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.

  A commercially available product can be used as zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate [C]. Examples of commercially available products include bisdaisen (registered trademark, manufactured by Dow Agroscience), TOC3204F (made by Rohm and Haas), and the like.

  The content of the zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate [C] is not particularly limited, but is preferably 1 to 300 parts by weight and 10 to 150 parts by weight in terms of solid content with respect to 100 parts by weight of the spreading resin. Part by weight is more preferred.

  The fishing net antifouling coating composition of the present invention contains triphenylborane / alkoxy group-containing amine complex compound [A] and 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B]. A composition comprising a triphenylborane-alkoxy group-containing amine complex compound [A] and bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate zinc [C]; and a triphenylborane-alkoxy group-containing amine complex Includes a composition containing compound [A], 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B] and zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate [C] It is.

  Since zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate [C] does not dissolve in solvents such as xylene, it tends to settle at the bottom of the container when stored for a long period of time, and it is necessary to stir the paint during the coating operation. In contrast, triphenylborane / alkoxy group-containing amine complex compound [A] and 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B] are dissolved in a solvent such as xylene. Stirring is not required. Therefore, among these compositions, from the viewpoint of excellent coating workability, triphenylborane / alkoxy group-containing amine complex compound [A] and 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [ B] is preferred.

  In the case of a composition comprising a triphenylborane / alkoxy group-containing amine complex compound [A] and 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B], Although it does not specifically limit as a compounding ratio with a [B] component, A [B] component is 10-200 weight part with respect to 100 weight part of [A] component in conversion of solid content, Preferably it is 30-150 weight. Part, more preferably 50 parts by weight to 100 parts by weight. By combining the [A] component and the [B] component in the above-mentioned blending ratio, it is possible to exert the assumed combined effect and to prevent the coating film from being weakened by the plasticity of the [B] component itself. The antifouling period can be extended.

  In the case of a composition containing a triphenylborane / alkoxy group-containing amine complex compound [A] and zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate [C], the components [A] and [C] Although it does not specifically limit as a mixture ratio, [C] component is 10-600 weight part with respect to 100 weight part of [A] component in conversion of solid content, Preferably it is 30-500 weight part, Furthermore, Preferably, it is 50 to 350 parts by weight. By combining the [A] component and the [C] component in the above blending ratio, the expected combined effect can be exhibited, and the [C] component precipitates during long-term storage, and hard caking occurs at the bottom of the container. Etc. can be prevented.

  Triphenylborane / alkoxy group-containing amine complex compound [A], 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B], and bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate zinc [C The mixing ratio of the [A] component, the [B] component, and the [C] component is not particularly limited, but is 100 parts by weight of the [A] component in terms of solid content. On the other hand, the [B] component is 10 to 200 parts by weight, preferably 30 to 150 parts by weight, more preferably 50 to 100 parts by weight, and the [C] component is 10 to 600 parts by weight. Part, preferably 30 to 500 parts by weight, and more preferably 50 parts to 350 parts by weight. By combining the [A] component, the [B] component, and the [C] component in the above blending ratio, the expected combined effect can be exhibited, and the [B] component itself has a weakness due to plasticity. By preventing the contamination, the antifouling period can be extended, and further, it is possible to prevent the [C] component from precipitating during long-term storage and causing hard caking at the bottom of the container.

  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 weight, preferably 0.5 to 100 parts by weight, and more preferably in terms of solid content with respect to 100 parts by weight of the spreading resin. Is 1 to 50 parts by weight.

<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, for example, the general formula (IV):

(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. The alkyl group of -4 is preferable and a methyl group is more preferable.

  The ethylene / α-olefin copolymer represented by the general formula (IV) is a copolymer obtained by copolymerizing ethylene and an 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 weight, preferably 1 to 500 parts by weight, in terms of solid content, with respect to 100 parts by weight of silicone oil. More preferably, it is 50-300 weight part.

<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.

  The content of polybutene is not particularly limited, but is 1 to 1000 parts by weight, preferably 1 to 500 parts by weight, 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.

<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 weight part with respect to 100 weight part of silicone oil in conversion of solid content, Preferably it is 1-500 weight part, More preferably, it is 50-300 weight part It is.

<Vaseline>
Examples of petrolatum include white petrolatum and yellow petrolatum.

  Although the content of petrolatum is not particularly limited, it is 1 to 1000 parts by weight, preferably 1 to 500 parts by weight, more preferably 50 to 300 parts by weight, based on 100 parts by weight of silicone oil in terms of solid content. 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 weight part with respect to 100 weight part of silicone oil in conversion of solid content, Preferably it is 1-500 weight part, More preferably, it is 50-300 weight. Part.

<Anti-fouling agent>
As an antifouling agent, the triphenylborane-alkoxy group-containing amine complex compound [A], 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B] and bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamine In addition to zinc acid [C], the following inorganic antifouling agents and organic antifouling agents can be contained. Thereby, the formed coating film can exhibit a more suitable antifouling effect.

  Examples of the inorganic antifouling agent include copper-based inorganic compounds such as copper powder, cupronickel, cuprous oxide, and rhodan copper.

  As the organic antifouling agent, both metal-containing organic antifouling agents and metal-free organic antifouling agents can be used.

  Examples of the metal-containing organic antifouling agent include copper-based organic compounds and zinc-based organic compounds.

  Examples of the copper-based organic compound include copper pyrithione.

  Examples of the zinc-based organic compound include zinc pyrithione.

  Examples of the metal-free organic antifouling agent include tetraalkylthiuram disulfide compounds such as tetramethylthiuram disulfide and tetraethylthiuram disulfide. In addition, 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′-methylphenyl) maleimide, 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide, 2- (p-chlorophenyl) -3-cyano -4-Bromo-5-trifluoromethylpyrrole, tetrachloroisophthalonitrile, etc. can also be used.

  Triphenylborane / alkoxy group-containing amine complex compound [A], 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline [B] and bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate zinc [C] As the antifouling agent used in combination, at least one antifouling agent selected from the group consisting of tetraethylthiuram disulfide, cuprous oxide, copper powder, copper pyrithione, and zinc pyrithione is particularly preferable.

  Although content of the said antifouling chemical | medical agent is not specifically limited, 0.1-80 weight part is preferable with respect to 100 weight part of non volatile matters in the composition of this invention, and 1-50 weight part is more preferable.

<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.

  The weight average molecular weight (Mw) of the spreading resin is preferably 5,000 to 1,000,000, and more preferably 10,000 to 500,000.

  The content of the spreading resin is not particularly limited, but is 1 to 50% by weight, preferably 5 to 30% by weight in the antifouling coating composition in terms of solid content.

<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-mentioned components [A] to [C] and, if necessary, the above-mentioned components. 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 product 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 adhesion amount of the dried coating film is preferably 1 to 30 parts by weight, more preferably 4 to 15 parts by weight with respect to 100 parts by weight 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.

Examples 1-6 and Comparative Examples 1-7
A fishing net antifouling paint composition was obtained by mixing the components described in Table 1 in the proportions (% by weight) described in Table 1.

Product name “Nittor HN”: Acrylic resin xylene solution (solid content 40%, Tg = about 20 ° C., Mw = about 230,000, manufactured by Nitto Kasei Corporation)
Product name "OPA" ... Triphenylborane 3- (2-ethylhexyloxy) propylamine (Nitto Kasei Co., Ltd. purity 99%)
Product name "Sea Nine 211" (solid content 30% xylene solution, manufactured by Rohm and Haas)
Product name “TOC-3204F”: zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate (Rohm and Haas)
Product name "TET-G" ... tetraethylthiuram disulfide (manufactured by Sanshin Chemical Co., Ltd.)
Product name “PK Boron”… pyridine / triphenylborane (made by Hokuko Chemical Co., Ltd.)
Product name “YN-18-20”: n-octadecylamine triphenylborane (manufactured by Benitoyama Co., Ltd.)
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.)
Product name “Lucant HC-40”: ethylene / α-olefin copolymer (Mn = 1600, manufactured by Mitsui Chemicals, Inc.)
Product name "Polybutene 0N" ... Polybutene (manufactured by NOF Corporation)
Product name “DAF-1”: Di-tert-nonylpentasulfide (Dainippon Ink Co., Ltd.)
Product name "Disparon 4200-20X" ... polyethylene oxide (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: First grade reagent manufactured 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 6 and Comparative Examples 1 to 7, and the amount of dry coating adhered to the fishing net of 100 weight. The coating was dip coated and dried to 8 parts by weight. The fishing net on which the coating film was formed was fixed to a frame of 40 × 60 cm SUS, and was immersed in 1 m below the sea surface with a stationary net at the destination of Ofuna, Iwate Prefecture, and the contamination of the fishing net due to attached organisms was observed for 6 months.

  The results are shown in Table 2.

  The numbers in Table 2 represent the surface area (%) of fouling organisms. In addition, the adhesion surface area (%) of fouling organisms was obtained by taking a picture of a fishing net from above the sea surface after the test period (1, 2, 4 or 6 months) and visually evaluating the area occupied by fouling organisms in the fishing net.

  In addition, the blank for attached organisms in Table 2 indicates that the corresponding organism was not confirmed after 6 months.

  From Table 2, compared with the coating film formed using the fishing net antifouling paint composition of Comparative Examples 1 to 7, the coating formed using the fishing net antifouling paint composition of the present invention (Examples 1 to 6). It can be seen that, even after a long period of time, the membrane is hardly attached with water fouling organisms.

Claims (10)

Formula (I):

(Wherein R ¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms or a phenylene group, and R ² represents a linear or branched alkyl group having 1 to 18 carbon atoms. ) triphenyl borane alkoxy group-containing amine complex and the compound represented by bi scan (dimethyl dithiocarbamoyl) fishing net antifouling paint composition containing ethylene bis dithiocarbamate zinc. Further, 4,5-dichloro -2-n-octyl -3 (2H) Isochiazori emissions fishing net antifouling coating composition according to claim 1 containing. In solid estimate for the triphenyl borane alkoxy group-containing amine complex compound 100 parts by weight, and pre-Symbol-bis (dimethyl dithiocarbamoyl) proportion of ethylene bis dithiocarbamate zinc 10 to 600 parts by weight, according to claim 1 Fishing net antifouling paint composition. 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. The fishing net according to any one of claims 1 to 4, further comprising one or more antifouling agents selected from the group consisting of tetraethylthiuram disulfide, cuprous oxide, copper powder, copper pyrithione, and zinc pyrithione. Antifouling paint composition. The fishing net antifouling paint composition according to any one of claims 1 to 5, wherein the silicone oil is a polyether-modified silicone oil having a hydrophilic / lipophilic balance (HLB) of 0.5 to 9. The fishing net according to any one of claims 1 to 6, wherein the triphenylborane / alkoxy group-containing amine complex compound represented by the general formula (I) is a triphenylborane · 3- (2-ethylhexyloxy) propylamine complex compound. Antifouling paint composition. The antifouling processing method which forms an antifouling coating film on the surface of a coating-film formation object using the fishing net antifouling paint composition in any one of Claims 1-7. The antifouling coating film formed using the fishing net antifouling paint composition in any one of Claims 1-7. A fishing net, a fishing net tool or an underwater structure having the antifouling coating film according to claim 9 on its surface.