JP2000001410A - Composition for preventing attachment of marine life, and antifouling coating material containing the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for preventing the attachment of marine life to a fishing net or the bottom of a ship, and capable of being readily suspended in a solvent, and further to obtain an antifouling coating material containing the composition. SOLUTION: This powdery composition applicable to a fishing net or the bottom of a ship contains a subaqueous antifouling component hardly soluble in a solvent, a surfactant, an oil-absorber and a hydrophobic thickener, and has 0.5-10 μm average particle diameter. The suspension composition for the fishing net and the bottom of the ship contains the powdery composition and the solvent, or contains the solvent, the subaqueous antifouling component hardly soluble in the solvent, the surfactant and the hydrophobic thickener, and has 200-1,500 mPa.s viscosity (at 10 s-1 shear rate) at 25 deg.C. The antifouling coating material for the fishing net, or the antifouling coating material for the bottom of the ship contains the suspension composition as a constituent component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powdery composition for preventing marine organisms from adhering, which is applied to or dipped on the surface of fishing nets or applied to the surface of the bottom of ships, to prevent the adhesion of marine organisms, fishing nets or ship bottoms. The present invention relates to an antifouling paint for fishing nets and an antifouling paint for ship bottoms, which comprises a suspension composition for preventing marine organisms from adhering to the sea, and a composition containing the composition as a component.

[0002]

2. Description of the Related Art In the sea, a wide variety of marine organisms such as barnacles, algae, bivalves, and hydroids adhere to fishing nets or the bottom of ships. Such adhesion of marine organisms causes problems in fishing nets, such as clogging of the nets and significantly shortening the service life.
Also, the adhesion of these underwater organisms to the bottom of the ship causes an increase in fluid resistance, resulting in a decrease in navigation speed, an increase in fuel consumption, a cost for cleaning the bottom of the ship, and a cost for stopping the operation for cleaning. Incurs a loss.

As an antifouling component in water for preventing the adhesion of marine organisms, organotin compounds and the like have hitherto been used, but because of their toxicity, their safety to fish and shellfish and human bodies has been problematic. The development of an antifouling agent having high water content is being carried out.

[0004] As a method for use in fishing nets, antifouling components for fishing nets prepared by dispersing or dissolving an antifouling component in water in an aromatic or aliphatic hydrocarbon solvent, industrial gasoline or a petroleum fraction, and preparing the same in a conventional manner. The agent is applied to a fishing net and dried, or the fishing net is immersed in a fishing net antifouling agent and then taken out and dried to perform an antifouling treatment.

[0005] In addition, as a method of using the antifouling component in water, an antifouling component in water is dispersed or dissolved in an aromatic or aliphatic hydrocarbon solvent, industrial gasoline or petroleum distillate, and is prepared by a conventional method. Antifouling treatment is performed by applying or spraying antifouling paint on the ship bottom and drying.

However, the antifouling components in water that are insoluble or hardly soluble in aromatic or aliphatic hydrocarbon solvents, industrial gasoline or petroleum fractions settle out of the dispersed form within a short period of time. The underwater antifouling component hardens and hardens in a long period of time, and is not easily redispersed by ordinary stirring, resulting in so-called hard caking.

As a result, in such a state, it is difficult to efficiently remove the antifouling component in water from a drum or the like.
In addition, there is a problem that it is not possible to effectively prevent the attachment of marine organisms because it cannot be effectively adsorbed to a fishing net or a ship bottom, and the development of a suspension-stable, water-resistant antifouling preparation is desired. ing.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that a powdery composition for preventing marine organisms from being easily suspended in a solvent, and a suspension for preventing marine organisms from being adhered to a solvent for a long time. A composition and an antifouling paint for fishing nets or antifouling paint for ship bottoms which can be effectively adsorbed to a fishing net or ship bottom and prevented from adhering to marine organisms, comprising the composition as a component, and the present invention have been completed. Reached.

That is, the present invention relates to an antifouling component in water that is hardly soluble in a solvent immiscible with water, a nonionic surfactant of HLB 3 to 10, or an interface of HLB 3 to 10 in which a nonionic surfactant and an anionic surfactant are mixed. A powder composition for preventing marine organisms from adhering to fishing nets or ship bottoms, comprising an activator, an oil absorbing agent and a hydrophobic thickener, and having an average particle size of 0.5 to 10 µm; A suspension composition for preventing marine organisms from adhering to a fishing net or ship bottom, comprising a powder composition for prevention and a solvent, and an antifouling paint or bottom for fishing nets comprising the marine organisms adhesion prevention suspension composition as a component. A solvent, an antifouling component in water that is hardly soluble in the solvent, a nonionic surfactant having an HLB of 3 to 10, or a mixture of a nonionic surfactant and an anionic surfactant. Surfactant, and contain hydrophobic thickener, a viscosity of 25 ℃ 200~1,500mPa · s
(10Sec ^-1 ) Shear rate, a suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom, and an antifouling paint or bottom for fishing nets containing the suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom The present invention relates to antifouling paints.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The composition for preventing marine organisms from adhering to fishing nets or ship bottoms according to the present invention will be described in detail. In this specification, "n" is normal, "s" is symmetric, "t" is tertiary, "o" is ortho,
“P” means para. Underwater antifouling component for preventing the adhesion of marine organisms used in the present invention is a water-immiscible solvent,
For example, it may be insoluble or hardly soluble in aromatic or aliphatic hydrocarbon solvents, industrial gasoline or petroleum fractions.

Further, two or more kinds of underwater antifouling components can be used in combination. At this time, there is no problem even if they are used by mixing with the underwater antifouling components dissolved in the above-mentioned solvent. . Hereinafter, the underwater antifouling components applicable to the present invention and the underwater antifouling components that can be used in combination will be described together. Zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc ethylenebisdithiocarbamate, zinc propylenebisdithiocarbamate, zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate And dithiocarbamate-based metal compounds such as nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate, copper dimethyldithiocarbamate and iron dimethyldithiocarbamate;

Copper-based metal powders such as copper powder and copper-nickel alloy powder; cuprous oxide, cuprous thiocyanate (copper rhodan), basic copper carbonate, copper pyrophosphate, copper naphthenate, copper abietic acid; Copper compounds such as copper oxyquinoline; pyrithion metal compounds such as 2-pyridinethiol-1-oxide zinc salt and 2-pyridinethiol-1-oxide copper salt;

[0013] Tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetra-n-propylthiuram disulfide, tetraisopropylthiuram disulfide, tetra-n-butylthiuram disulfide, tetraisobutylthiuram disulfide, N, N'-ethylene Thiuram-based compounds such as bisthiocarbamoyl sulfide, N, N'-propylenebisthiocarbamoyl sulfide, N, N'-butylenebisthiocarbamoyl sulfide;

2- (4-thiazolyl) benzimidazole, 2- (methoxycarbonylamino) benzimidazole, methyl-1- (ω-cyanopentylcarbamoyl) -2-benzimidazole, zinc 2-mercaptobenzimidazole, 2-thio Benzimidazole compounds such as cyanomethylthiobenzimidazole;

2-mercaptobenzothiazole, 2-
(Thiocyanomethylthio) benzothiazole, 2- (thiocyanomethylsulfonyl) benzothiazole, 2-thiocyanoethylthio-4-chlorobenzothiazole, 2
-Thiocyanopropylthio-5,7-dichlorobenzothiazole, 2-thiocyanomethylthio-4,5,6,7
Benzothiazole compounds such as tetrachlorobenzothiazole; tetrachloroisophthalonitrile, 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile, 2,4,5,6-tetrachloroisophthalonitrile and the like Nitrile compounds;

4,5-dichloro-2-n-octyl-4
-Isothiazolin-3-one, 2-n-octyl-4-
Isothiazoline-based compounds such as isothiazolin-3-one and 1,2-benzoisothiazolin-3-one;

1- [2- (2,4-dichlorophenyl)
-4-propyl-1,3-dioxolanyl-2-methyl] -1H-1,2,4-triazole, 4,4-dimethyl-2 (1,2,4-triazol-1-yl) -1
-(4-trifluoromethyl-2-chlorophenyl)-
Triazole compounds such as 1-penten-2-ol;

2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,3,6-trichloro-
4-propylsulfonylpyridine, 2,6-dichloro-
Pyridine compounds such as 3,5-dicyano-4-phenylpyridine;

2,4-dichloro-6- (o-chloroanilino) -s-triazine, 2-chloro-4-methylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis (ethyl Amino) -s-triazine, 2-chloro-4,6-bis (isopropylamino)
-S-triazine, 2-methylthio-4,6-bis (ethylamino) -s-triazine, 2-methylthio-4-
Triazine-based compounds such as ethylamino-6-isopropylamino-s-triazine and 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine;

3- (3,4-dichlorophenyl) -1,
1-dimethylurea, 3- (3,4-dichlorophenyl)
-1-methoxy-1-methylurea, 1- (α, α′-dimethylbenzyl) -3-methyl-3-phenylurea, 1
-(2-methylcyclohexyl) -3-phenylurea,
Urea compounds such as 3- (4-isopropylphenyl) -1,1-dimethylurea;

Quinone compounds such as 2-amino-3-chloro-1,4-naphthoquinone and 2,3-dicyano-1,4-dithiaanthraquinone;

N-trichloromethylthiotetrahydrophthalimide, N-1,1,2,2-tetrachloroethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, N, N-dimethyl-N'-phenyl-N '-
(Fluorodichloromethylthio) sulfamide, trichloromethylthiomethanesulfone-p-chloroanilide,
N- (1,1,2,2-tetrachloro-2-fluoroethylthio) methanesulfonanilide, N-fluorodichloromethylthio-N-3-chlorophenyl-N'-dimethylurea, N-fluorodichloromethylthio-N −
3,4-dichlorophenyl-N'-methylurea, N-fluorodichloromethylthio-N-trissulfonyl-N
N-haloalkylthio compounds such as -methylamine;

N- (2-chlorophenyl) maleimide,
N- (4-fluorophenyl) maleimide, N- (3
5-dichlorophenyl) maleimide, N- (2,4,6
-Trichlorophenyl) maleimide, N-4-tolylmaleimide, N-2,4-xylylmaleimide, 2,3-
Dichloro-N- (2 ', 6'-diethylphenyl) maleimide, 2,3-dichloro-N- (2'-methyl-6'-diethylphenyl) maleimide, 2,3-dichloro-N-
(2 ′, 6′-dimethylphenyl) maleimide, 2,3-
Maleimide compounds such as dichloro-N- (2 ', 4', 6'-trimethylphenyl) maleimide;

3,5-dimethyl-tetrahydro-1,
3,5,2 (H) -thiadiazin-2-one, 3,3 '
-Ethylenebis (tetrahydro-4,6-dimethyl-2
H-1,3,5-thiadiazin-2-one, 3,5-dimethyl-2-thiotetrahydro-1,3,5-thiadiazine, 3,5-dibenzyltetrahydro-1,3,5-
Thiadiazine-based compounds such as thiadiazine-2-thione;

Methyl thiocyanate, chloromethyl thiocyanate, ethyl thiocyanate, methylenebisthiocyanate, chloromethylenebisthiocyanate, ethylenebisthiocyanate, chloroethylenebisthiocyanate, isobornyl thiocyanate, methyl isothiocyanate, allyl isothiocyanate Thiocyanate compounds such as phenylisothiocyanate and benzylisothiocyanate;

Alkylphenol compounds such as caprylphenol and nonylphenol; tris (octylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixture) Alkylphenyl phosphite compounds such as nonylphenyl) phosphite;

Alkylphenyl phosphate compounds such as tris (octylphenyl) phosphate, tris (nonylphenyl) phosphate, tris (dinonylphenyl) phosphate, and tris (mono- and di-mixed nonylphenyl) phosphate;

Iodine compounds such as 3-iodo-2-propynylbutylcarbamate and diiodomethylparatolylsulfone; polysulfide compounds such as n-octylchloromethyldisulfide; boron compounds such as pyridinetriphenylborane; phenyl (bispyridyl) bismuth dichloride Bismuth compounds such as;

Among the above compounds, preferable antifouling components in water include dithiocarbamate-based metal compounds, thiuram-based compounds, pyrithion-based metal compounds, copper-based compounds, and mixtures of pyrithion-based metal compounds and copper-based compounds. Further preferred compounds include zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, tetramethylthiuram disulfide, 2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-
Mixtures of copper oxide salt, cuprous oxide, and 2-pyridinethiol-1-oxide zinc salt with cuprous oxide as a mixture of compounds and 2-pyridinethiol-1-oxide copper salt with cuprous oxide Mixtures are mentioned.

As the underwater antifouling component for fishing nets, zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate and tetramethylthiuram disulfide are particularly preferred. As the underwater antifouling component for ship bottoms,
2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide copper salt, cuprous oxide, a mixture of 2-pyridinethiol-1-oxide zinc salt and cuprous oxide and 2-
Mixtures of pyridinethiol-1-oxide copper salts and cuprous oxide are particularly preferred.

The form of the antifouling component in water that can be applied to the present invention is not particularly limited as long as a stable dispersion state can be obtained, and is usually used in the form of fine particles. The average particle size in this case is 0.5 to 10 μm, preferably 0.5 to 8 μm. The content is not particularly limited, but is preferably 3 to 90% by weight in the case of a powder composition, and 3 to 90% by weight in the case of a suspension composition.
Preferably it is used at 50% by weight.

The nonionic surfactant that can be used in the present invention is not particularly limited as long as it has an HLB of 3 to 10, but is not particularly limited. Examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyoxyethylene styrylphenyl. Ether, polyoxyethylene castor oil, polyoxyethylene-polyoxypropylene block polymer, oxyethylene alkyl ester, oxyethylene sorbitan fatty acid ester,
Polyoxyethylene sorbite fatty acid ester, sorbitan fatty acid ester, polyoxyethylene glycol fatty acid ester and the like can be mentioned.

The anionic surfactant which can be used in the present invention is mixed with a nonionic surfactant to form an HLB.
Is not particularly limited as long as it is 3 to 10, for example, polyoxyethylene alkyl ether sulfate (or phosphate), polyoxyethylene alkyl aryl ether sulfate (or phosphate), polyoxyethylene castor, etc. Oil sulfate (or phosphate), polyoxyethylene-polyoxypropylene block polymer sulfate (or,
Phosphate), alkyl sulfonates and the like.

Preferred nonionic surfactants having an HLB of 3 to 10 include polyoxyethylene glycol fatty acid esters, polyoxyethylene alkyl aryl ethers, and sorbitan fatty acid esters. Preferred anionic surfactants include alkyl sulfonates. Can be The above surfactants may be used alone or in combination of two or more.

The HLB of the surfactant which can be used in the present invention is usually from 3 to 10, and a more preferred range is from 5 to 10.
８8. The content of the surfactant is not particularly limited, but is preferably 1 to 20% by weight in the case of a powder composition, and 0.5 to 10% by weight in the case of a suspension composition. Is preferred.

The solvent which can be used in the present invention may be any solvent as long as it is immiscible with water, and is not particularly limited. Examples thereof include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, industrial gasoline and petroleum distillate. And the like.

Examples of the aromatic hydrocarbon solvent include xylene, toluene, benzene, ethylbenzene, chlorobenzene, cumene, and methylnaphthalene, and examples of the aliphatic hydrocarbon solvent include n-heptane, n-hexane, and the like. Cyclohexane, methyl ethyl ketone, cyclohexanone, and the like; industrial gasoline includes petroleum ether, solvent naphtha, and the like; petroleum fractions include paraffins, kerosene, light oil, and the like, preferably xylene, cyclohexanone, and the like. Is mentioned.

The above-mentioned solvents may be used alone or as a mixture of two or more kinds. The content thereof is not particularly limited, but in the case of a suspension composition or a suspension composition obtained by adding a solvent to a powder composition. When used as a product, it is preferable to use it at 20 to 90% by weight.

Examples of the hydrophobic thickener which can be used in the present invention include organic bentonite and hydrophobic silica, which are effective alone or in combination. This organic bentonite is an organically treated clay mineral. As industrial examples, Esven, Organite (Toyojun Yoko Co., Ltd.), N
ew D ORBEN (Shiraishi Industry Co., Ltd.), Benton SD
-1, Benton SD-2 (NL Chemical Co., Ltd.), Lucentite SAN, Lucentite SPN (Corp Chemical Co., Ltd.), etc., and preferably, organoite (Toyojun Yoko Co., Ltd.) and Lucentite SAN ( Corp Chemical Co., Ltd.).

Hydrophobic silica is silica in which the surface of natural hydrophilic silica is covered with a methyl group to make it hydrophobic, and as industrial examples, Aerosil R972, Aerosil R974
(Manufactured by Nippon Aerosil Co., Ltd.), and preferably,
Aerosil R972 and the like.

When organic bentonite and hydrophobic silica are used as a mixture, the mixing ratio of organic bentonite and hydrophobic silica is usually 9: 1 to 2: 8, preferably 8: 2.
2 to 5: 5.

The content of the hydrophobic thickener is not particularly limited, but is preferably used in the range of 1 to 30% by weight in the case of a powder composition, and 1 to 30% by weight in the case of a suspension composition.
Preferably, it is used in the range of 20% by weight.

The oil absorbing agent which can be used in the powder composition of the present invention includes amorphous silica. Industrial examples of this amorphous silica include Carplex # 80 (Shionogi Pharmaceutical Co., Ltd.), Toxir NR (Tokuyama Corporation), Nipsil NS (Nippon Silica Co., Ltd.), and the like.
There is no particular limitation. The content of the oil absorbing agent is preferably used in the range of 1 to 20% by weight.

The viscosity of the suspension composition for preventing marine organisms from adhering to the sea is not particularly limited as long as the dispersion becomes uniform and a stable suspension state can be obtained.
1,500 mPa · s (10 sec ^-1 ) Shear rate, preferably 200 to 1,300 mPa · s (10 sec ^-1 ) Shear r
Prepare ate. The viscosity was measured by an E-type viscometer (EMD, manufactured by Tokyo Keiki Co., Ltd., measuring temperature: 25 ° C.).

The coating resin which can be used for the antifouling coating containing the marine organism adhesion preventing suspension composition of the present invention is a coating-forming resin for forming a coating on the surface of a substrate, and is a conventional resin. The same resins as those generally used for underwater antifouling paints can be used. For example, as the resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl isobutyl ether copolymer, styrene-butadiene copolymer, chloride rubber resin, chlorinated polypropylene resin, petroleum resin,
Alkyd resin, acrylic resin, phenolic resin,
Synthetic rubber, epoxy resin, silicone rubber, silicone resin, Teflon resin, rosin resin and the like can be mentioned.

Further, if necessary, a coloring pigment or coloring agent,
For example, titanium white, red iron, carbon, cyan blue, cyanine green, etc., or an extender such as talc, barita, zinc white, etc. can be blended, and together with the above components, if necessary, for example, a plasticizer, a preservative, a decomposition inhibitor , A fixing agent, a specific gravity adjusting agent and an antifoaming agent.

The method for producing the powdery composition for preventing marine organisms from adhering to a fishing net or the bottom of a fishing net according to the present invention is as follows.
Pulverized to about 5 to 10 µm with a dry pulverizer such as Ohmizer, and mixed with a surfactant mixed with amorphous silica as an oil absorbing agent and adsorbed with a hydrophobic thickener. And the like.

The obtained powdery composition for preventing marine organisms from adhering to the fishing net or the bottom of a boat is easily suspended in a solvent and is kept at -5 ° C to 40 ° C.
Even when stored at a temperature of ℃ for a long time, sedimentation and hard caking do not occur. By adding the above-mentioned paint resin and, if necessary, additives such as a fixing agent and a plasticizer, the fishing net protection It can be used as a fouling paint or antifouling paint for ship bottoms. In addition, in the powder composition for preventing the adhesion of marine organisms to the fishing net or the bottom of the ship, a resin for coating, and a solvent, and if necessary, a fixing agent,
By directly adding an additive such as a plasticizer, an antifouling paint for fishing nets or an antifouling paint for ship bottoms can be obtained.

The method for producing the suspension composition for preventing marine organisms from adhering to a fishing net or the bottom of a fishing net according to the present invention is as follows.
The mixture is pulverized to a size of about 5 to 10 μm with a dry pulverizer such as an Ohmizer, and added to an aromatic or aliphatic hydrocarbon solvent, industrial gasoline or a liquid obtained by mixing a petroleum fraction with a surfactant and mixed. Next, the mixture is finely pulverized by a homogenizer or a wet pulverizer such as a sand mill, and pulverized to an average particle size of 0.5 to 10 μm, preferably 0.5 to 8 μm, and is taken out. It is obtained by adding a thickener thereto and mixing uniformly.

The suspension composition for preventing marine organisms from adhering to the fishing net or ship bottom does not cause sedimentation or hard caking even when stored at a temperature of -5 ° C to 40 ° C for a long period of time. By adding a resin and a solvent, and if necessary, additives such as a fixing agent and a plasticizer, it can be used as an antifouling paint for fishing nets or an antifouling paint for ship bottoms.

Preferred powder compositions for preventing marine biofouling in a solvent according to the present invention, a suspension composition for preventing marine biofouling which is easily dispersed in a solvent for a long time, and a fishing net containing the composition as a constituent The following are examples of antifouling paints for fishing nets or antifouling paints for boat bottoms that can be effectively adsorbed to the bottom of the boat to prevent the attachment of marine organisms.

(1) An antifouling component in water that is hardly soluble in a solvent, H
A nonionic surfactant of LB 3 to 10 or a mixture of a nonionic surfactant and an anionic surfactant;
A powder composition for preventing marine organisms from adhering to fishing nets or ship bottoms, comprising a surfactant, amorphous silica and a hydrophobic thickener, and having an average particle size of 0.5 to 10 μm. object.

(2) An antifouling component in water that is hardly soluble in a solvent, H
A nonionic surfactant of LB 3 to 10 or a mixture of a nonionic surfactant and an anionic surfactant;
A powder composition for preventing marine organisms from adhering to fishing nets or ship bottoms, comprising a surfactant, an oil absorbing agent and organic bentonite or hydrophobic silica, and having an average particle size of 0.5 to 10 μm.

(3) dithiocarbamate metal compounds,
A thiuram-based compound, a pyrithione-based metal compound, a copper-based compound or a mixture of a pyrithione-based metal compound and a copper-based compound, a nonionic surfactant having an HLB of 3 to 10, or a mixture of a nonionic surfactant and an anionic surfactant;
Powder composition for preventing marine organisms from adhering to fishing nets or ship bottoms, comprising 10 to 10 surfactants, an oil absorbing agent and a hydrophobic thickener, and having an average particle size of 0.5 to 10 μm. object.

(4) dithiocarbamate metal compounds,
When a thiuram-based compound, a pyrithione-based metal compound, a copper-based compound, or a mixture of a pyrithione-based metal compound and a copper-based compound is used, zinc (bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, tetramethylthiuram disulfide, and 2-pyridinethiol-1 are used. -Oxide zinc salt, 2-
Pyridinethiol-1-oxide copper salt, cuprous oxide, a mixture of 2-pyridinethiol-1-oxide zinc salt and cuprous oxide, or 2-pyridinethiol-1-oxide copper salt and cuprous oxide The powder composition for preventing marine organisms from adhering to the fishing net or ship bottom according to (3), which is a mixture.

(5) Insoluble antifouling components 3 to insoluble in solvents
90% by weight of a nonionic surfactant having a HLB of 3 to 10 or a mixture of a nonionic surfactant and an anionic surfactant,
HLB 3 to 10 surfactant 1 to 20% by weight, oil absorbent 1
A powder composition for preventing marine organisms from adhering to fishing nets or ship bottoms, comprising -20% by weight and 1-30% by weight of a hydrophobic thickener, and having an average particle size of 0.5-10 µm. object.

(6) Underwater antifouling component which is hardly soluble in a solvent, H
A nonionic surfactant of LB 3 to 10 or a mixture of a nonionic surfactant and an anionic surfactant;
Containing a surfactant, an oil absorbing agent and a hydrophobic thickener, and having an average particle size of 0.5 to 10 μm,
A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom, comprising a powder composition for preventing marine organisms from adhering to a fishing net or a ship bottom and a solvent.

(7) The average particle size of the antifouling component in water is from 0.
The suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom according to (6), which is 5 to 10 μm.

(8) Solvent, HLB3, an antifouling component in water having an average particle diameter of insoluble in the solvent of 0.5 to 10 μm.
10 to 10 nonionic surfactants or a mixture of nonionic surfactants and anionic surfactants, containing a surfactant of HLB 3 to 10, and a hydrophobic thickener, and having a viscosity of 200 to 1,500 mPa at 25 ° C. A suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms, which has an s (10 Sec ^-1 ) Shear rate.

(9) The solvent is an aromatic or aliphatic hydrocarbon solvent, industrial gasoline or a petroleum fraction.
A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom as described in

(10) Aromatic or aliphatic hydrocarbon solvents, solvents that are industrial gasoline or petroleum fractions; antifouling components in water that are hardly soluble in said solvents, nonionic surfactants of HLB 3 to 10 or nonionic interfaces It contains a surfactant having an HLB of 3 to 10 in which a surfactant and an anionic surfactant are mixed, and a hydrophobic thickener, and has a viscosity at 25 ° C of 200 to 1,50.
A suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms, which has a Shear rate of ⁰ mPa · s (10 Sec ^-1 ).

(11) The suspension composition according to (6), wherein the thickener is an organic bentonite or a hydrophobic silica, which prevents the organism from adhering to a fishing net or a ship bottom.

(12) A solvent, an antifouling component in water that is hardly soluble in the solvent, a nonionic surfactant having an HLB of 3 to 10, or an HL obtained by mixing a nonionic surfactant with an anionic surfactant.
It contains a surfactant of B3 to 10, and organic bentonite or hydrophobic silica, and has a viscosity at 25 ° C of 200 to 1,50.
A suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms, which has a Shear rate of ⁰ mPa · s (10 Sec ^-1 ).

(13) The antifouling component in water is a dithiocarbamate metal compound, a thiuram compound, a pyrithion metal compound, a copper compound or a mixture of a pyrithion metal compound and a copper compound. Suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms

(14) Solvents, dithiocarbamate-based metal compounds, thiuram-based compounds, pyrithion-based metal compounds, copper-based compounds or mixtures of pyrithion-based metal compounds and copper-based compounds which are hardly soluble in the solvent, nonionics of HLB 3 to 10 A surfactant or nonionic surfactant mixed with an anionic surfactant, containing a surfactant of HLB 3 to 10 and a hydrophobic thickener, and having a viscosity at 25 ° C of 200 to 1,50.
A suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms, which has a Shear rate of ⁰ mPa · s (10 Sec ^-1 ).

(15) Dithiocarbamate metal compound, thiuram compound, pyrithion metal compound, copper compound or a mixture of a pyrithion metal compound and a copper compound is a mixture of bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, Tetramethylthiuram disulfide, 2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide copper salt, cuprous oxide, 2-pyridinethiol-1-oxide zinc salt and cuprous oxide (13) or (14), wherein the suspension composition is a mixture of a copper salt of 2-pyridinethiol-1-oxide and cuprous oxide;

(16) 3-50% by weight of antifouling component in water
Wherein the surfactant is 1 to 10% by weight, the thickener is 1 to 20% by weight, and the solvent is 20 to 90% by weight, and the marine organism adheres to the fishing net or ship bottom according to (6). Preventive suspension composition

(17) 20 to 90% by weight of a solvent, 3 to 50% by weight of an insoluble antifouling component in water which is hardly soluble in the solvent, HLB 3 to 1
0.5 to 10% by weight of a nonionic surfactant or a nonionic surfactant and a surfactant mixed with an anionic surfactant of HLB 3 to 10, and 1 to 20% by weight of a hydrophobic thickener. , Viscosity at 25 ° C is 200 to 1,500 mPa
· S (10Sec ^-1 ) Shear rate,
A suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms.

(18) An antifouling paint for fishing nets or antifouling paints for ship bottoms, which comprises the suspension composition for preventing marine organisms from adhering to the fishing net or ship bottom as described in (6).

(19) A solvent, an antifouling component in water that is hardly soluble in the solvent, a nonionic surfactant having an HLB of 3 to 10, or a mixture of a nonionic surfactant and an anionic surfactant.
It contains a surfactant of B3 to 10 and a hydrophobic thickener, and has a viscosity of 200 to 1,500 mPa · s (10Se
c ^-1 ) An antifouling paint for fishing nets or an antifouling paint for ship bottoms, which comprises, as a constituent, a suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms, characterized by a shear rate.

(20) Aromatic or aliphatic hydrocarbon solvents, solvents that are industrial gasoline or petroleum distillates; bis (dimethyldithiocarbamoyl) that is insoluble in said solvents and has an average particle size of 0.5 to 10 μm ) Zinc ethylenebisdithiocarbamate, tetramethylthiuram disulfide, 2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide copper salt, cuprous oxide, 2-pyridinethiol-1-oxide zinc salt Antifouling component in water, which is a mixture of copper and cuprous oxide or a mixture of copper salt of 2-pyridinethiol-1-oxide and cuprous oxide; a nonionic surfactant of HLB 3 to 10 or a nonionic surfactant and an anion A surfactant mixed with a surfactant, HLB of 3 to 10; and an antifouling paint for fishing nets or an antifouling paint for ship bottoms containing organic bentonite or hydrophobic silica as a component. Fees.

[0072]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but they do not limit the scope of the present invention. In the following Examples and Comparative Examples, "parts" all indicate parts by weight. Example 1 70 parts of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate (general name: polycarbamate) finely pulverized by Jet-O-Mizer (manufactured by Seishin Enterprise Co., Ltd.) to an average particle size of 4 μm, and HLB
5 parts of 5.0 surfactant SORPOL 4190 (polyoxyethylene dioleate / sorbitan monooleate combination product manufactured by Toho Chemical Industry Co., Ltd.)
0 (manufactured by Shionogi & Co., Ltd.) and 20 parts of Lucentite SAN (manufactured by Corp Chemical Co., Ltd.) were adsorbed on 5 parts of a bart mix (Nisso Engineering Co., Ltd.)
And bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate 70%
A powder composition for preventing marine organisms from adhering to a fishing net or the bottom of a ship, comprising:

Example 2 In Example 1, 5 parts of Carplex # 80 (manufactured by Shionogi & Co., Ltd.) was replaced with Tokusil NR (manufactured by Tokuyama Corporation).
A powder composition containing 70% zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate for preventing the attachment of marine organisms to the fishing net or ship bottom was obtained in the same manner as in Example 1 except that the amount was changed to 5 parts.

Example 3 In Example 1, the surfactant SOR having an HLB of 5.0 was used.
5 parts of POL 4190 (polyoxyethylene dioleate / sorbitan monooleate blended product manufactured by Toho Chemical Industry Co., Ltd.) was added to a surfactant SORPOL4 of HLB 6.8.
192 (polyoxyethylene distearate / sorbitan monolaurate product manufactured by Toho Chemical Industry Co., Ltd.) in the same manner as in Example 1 except that 5 parts were used, and zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate was used. A powder composition containing 70% for preventing the attachment of marine organisms to the fishing net or the ship bottom was obtained.

Example 4 60 parts of tetramethylthiuram disulfide finely pulverized in advance by Jet-O-Mizer (manufactured by Seishin Enterprise Co., Ltd.) to an average particle size of 3.5 μm, and HLB 5.0
Surfactant SORPOL 4190 (Toho Chemical Industry)
A mixture obtained by adsorbing 5 parts of polyoxyethylene dioleate / sorbitan monooleate (manufactured by Nippon Silica Co., Ltd.) onto a nip seal NS (manufactured by Nippon Silica Co., Ltd.), New D
ORBEN (Shiraishi Industry Co., Ltd.) 20 parts, Aerosil R9
10 parts of 72D (manufactured by Nippon Aerosil Co., Ltd.) are charged into Bert O Mix (manufactured by Nisso Engineering Co., Ltd.) and mixed for 1 hour, and tetramethylthiuram disulfide 6 is added.
A powder composition containing 0% for preventing marine organisms from adhering to the fishing net or ship bottom was obtained.

Example 5 250 parts of xylene was added to 100 parts of the powder composition for preventing marine organisms from adhering to the fishing net or the bottom of a boat containing 70% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate of Example 1, and a homogenizer (100 parts). Toyo Seiki Co., Ltd.
The mixture was mixed at 1,000 rpm for 15 minutes, and the viscosity at 25 ° C. containing 20% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate was 990.
A suspension composition for preventing marine organisms from adhering to the fishing net or the bottom of the boat at a shear rate of mPa · s (10 Sec ^-1 ) was obtained.

Example 6 250 parts of xylene was added to 100 parts of the powder composition for preventing marine organisms from adhering to the fishing net or the bottom of a boat containing 70% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate of Example 3, and a homogenizer ( Toyo Seiki Co., Ltd.
The mixture was mixed at 1,000 rpm for 15 minutes, and the viscosity at 25 ° C containing 20% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate was 975.
A suspension composition for preventing marine organisms from adhering to the fishing net or the bottom of the boat at a shear rate of mPa · s (10 Sec ^-1 ) was obtained.

Example 7 Tetramethylthiuram disulfide of Example 4 60%
200 parts of xylene was added to 100 parts of the powdery composition for preventing marine organisms from adhering to a fishing net or the bottom of a boat containing
Mix for 20 minutes and add tetramethylthiuram disulfide 20
% And a viscosity at 25 ° C of 1,010 mPa · s (10
c- ¹ ) A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a shear rate was obtained.

Example 8 20 parts of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate (generic name: polycarbamate) finely pulverized to an average particle size of 4 μm with Jet-O-Mizer (manufactured by Seishin Enterprise) in advance. 65 parts of xylene, 7 parts of organite (manufactured by Toyojun Yoko Co., Ltd.), 3 parts of Aerosil R972D (manufactured by Nippon Aerosil Co., Ltd.), HLB
5.0 parts of a surfactant SORPOL 4190 (polyoxyethylene dioleate / sorbitan monooleate combination product manufactured by Toho Chemical Industry Co., Ltd.) was added, and the mixture was subjected to 1,000 rpm with a homogenizer (manufactured by Toyo Seiki Co., Ltd.). At 1
Mix for 5 minutes, containing 20% zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate
The viscosity at 5 ° C is 1,080 mPa · s (10 Sec ^-1 )
A suspension composition for preventing marine organisms from adhering to the fishing net or the bottom of the ship was obtained.

Example 9 20 parts of tetramethylthiuram disulfide finely pulverized to a mean particle size of 3.5 μm with Jet-O-Mizer (manufactured by Seishin Enterprise), 65 parts of cyclohexanone, and an organoite (( 6 parts, Aerosil R972D (manufactured by Nippon Aerosil Co., Ltd.), 4 parts, HL
5 parts of a surfactant SORPOL4190 of B5.0 (polyoxyethylene dioleate / sorbitan monooleate combination product manufactured by Toho Chemical Industry Co., Ltd.) was added, and the mixture was subjected to 1,000 rpm with a homogenizer (manufactured by Toyo Seiki Co., Ltd.). At 1
Mix for 5 minutes and add tetramethylthiuram disulfide 2
The viscosity at 25 ° C. containing 0% is 980 mPa · s (10 sec.
^-1 ) A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a Shear rate was obtained.

Example 10 In Example 8, a surfactant SOR having an HLB of 5.0 was used.
5 parts of POL 4190 (polyoxyethylene dioleate / sorbitan monooleate blended product manufactured by Toho Chemical Industry Co., Ltd.) was added to a surfactant SORPOL4 of HLB 6.8.
192 (polyoxyethylene distearate / sorbitan monolaurate product manufactured by Toho Chemical Industry Co., Ltd.), except that bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate 20% was used in the same manner as in Example 8. Containing 1,120 mPa · s (1
0Sec ^-1 ) A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a Shear rate was obtained.

Example 11 In Example 8, 30 parts of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate finely pulverized to an average particle size of 4 μm, 30 parts of xylene and 5 parts of xylene were added.
8 parts, 7 parts Organite (manufactured by Toyojun Yoko Co., Ltd.) and 5 parts, Aerosil R972D (manufactured by Nippon Aerosil Co., Ltd.)
In the same manner as in Example 8, except that the parts were changed to 2 parts, the viscosity at 25 ° C containing 30% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate was 1,3.
A suspension composition for preventing adhesion of marine organisms to the fishing net or the bottom of the boat at a shear rate of 00 mPa · s (10 Sec ^-1 ) was obtained.

Example 12 In Example 8, the surfactant SOR having an HLB of 5.0 was used.
5 parts of POL 4190 (a blend of polyoxyethylene dioleate / sorbitan monooleate manufactured by Toho Chemical Industry Co., Ltd.) was used as an HLB 6.5 surfactant SORPOL41 in which a nonionic surfactant and an anionic surfactant were mixed.
98 (polyoxyethylene alkyl allyl ether / polyoxyethylene monostearate / alkyl allyl sulfonate compound manufactured by Toho Chemical Industry Co., Ltd.) in the same manner as in Example 8, except that 5 parts of bis (dimethyldithiocarbamoyl) were used. ) Zinc ethylenebisdithiocarbamate 2
The viscosity at 25 ° C. containing 0% is 995 mPa · s (10 sec.
^-1 ) A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a Shear rate was obtained.

Example 13 In Example 8, 35 parts of 20 parts of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate finely pulverized to an average particle size of 4 μm, and
Except that 7 parts of Organite (manufactured by Toyoko Yoko Co., Ltd.) and 3 parts of Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) were replaced with 7 parts of Lucentite SAN (manufactured by Corp Chemical). As in Example 8, the viscosity at 25 ° C. containing 35% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate was 1250 mPa · s (1
0Sec ^-1 ) A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a Shear rate was obtained.

Example 14 Zinc 2-pyridinethiol-1-oxide zinc salt (generic names zinc pyrithione, finely divided to an average particle size of 6 μm by Jet-O-Mizer (manufactured by Seishin Enterprise Co., Ltd.)
Zinc Omazine) 25 parts, Xylene 60 parts, Organite (manufactured by Toyoko Yoko Co., Ltd.) 7 parts, Aerosil R972D
3 parts of Nippon Aerosil Co., Ltd. and 5 parts of HLB 5.0 surfactant SORPOL 4190 (polyoxyethylene dioleate / sorbitan monooleate blended product of Toho Chemical Industry Co., Ltd.) were added, and a homogenizer (Toyo) Precision machine
(Manufactured by Co., Ltd.) at 1,000 rpm for 15 minutes,
Shear having a viscosity of 1,150 mPa · s (10 Sec ⁻¹ ) containing 25% of 2-pyridinethiol-1-oxide zinc salt at 25 ° C.
A suspension composition for preventing marine organisms from adhering to the fishing net or the bottom of the ship was obtained.

Example 15 A copper powder of 2-pyridinethiol-1-oxide (common name: copper pyrithione, finely pulverized to an average particle size of 5 μm in advance by Jet-O-Mizer (manufactured by Seishin Enterprise Co., Ltd.)
Copper Omazine) 30 parts, xylene 59 parts, Lucentite SAN (manufactured by Corp Chemical Co., Ltd.) 6 parts, HL
5 parts of a surfactant SORPOL4190 of B5.0 (polyoxyethylene dioleate / sorbitan monooleate combination product manufactured by Toho Chemical Industry Co., Ltd.) was added, and the mixture was subjected to 1,000 rpm with a homogenizer (manufactured by Toyo Seiki Co., Ltd.). At 1
Mix for 5 minutes and add 2-pyridinethiol-1-oxide copper salt 3
The viscosity at 25 ° C containing 0% is 1,280 mPa · s (10
A suspension composition for preventing marine organisms from adhering to the fishing net or the bottom of the boat at a Sec ^-1 ) Shear rate was obtained.

Example 16 30 parts of cuprous oxide finely ground to an average particle size of 5.5 μm, 58 parts of xylene, and Lucentite SAN by Jet-O-Mizer (manufactured by Seishin Enterprise)
7 parts of (Corp Chemical Co., Ltd.) and 5 parts of HLB 6.8 surfactant SORPOL 4192 (polyoxyethylene distearate / sorbitan monolaurate product of Toho Chemical Industry Co., Ltd.) were added, and a homogenizer ( The mixture was mixed at 1,000 rpm for 15 minutes by using Toyo Seiki Co., Ltd., and the viscosity at 25 ° C. containing 30% cuprous oxide was 1,2.
A suspension composition for preventing adhesion of marine organisms to the fishing net or the bottom of the boat at a shear rate of 00 mPa · s (10 Sec ^-1 ) was obtained.

Example 17 Copper powder of 2-pyridinethiol-1-oxide (common name: copper pyrithione, finely pulverized to an average particle size of 5 μm with Jet-O-Mizer (manufactured by Seishin Enterprise Co., Ltd.)
Copper Omazine (15 parts), cuprous oxide 20 finely pulverized to an average particle size of 5.5 μm, xylene (53 parts), Lucentite SAN (manufactured by Corp Chemical Co.) 7 parts, HL
B 5.0 5.0 parts of surfactant SORPOL 4190 (polyoxyethylene dioleate / sorbitan monooleate combination product manufactured by Toho Chemical Industry Co., Ltd.) was added, and the mixture was treated with a homogenizer (manufactured by Toyo Seiki Co., Ltd.). Mixing at 000 rpm for 15 minutes, fishing net containing 15% 2-pyridinethiol-1-oxide copper salt and 20% cuprous oxide and having a viscosity at 25 ° C. of 1,270 mPa · s (10 Sec ⁻¹ ) Shear rate or A suspension composition for preventing marine organisms from adhering to the bottom of the ship was obtained.

Comparative Example 1 (Example of Powder Composition Using Surfactant of HLB13) In Example 1, the surfactant SOR of HLB 5.0 was used.
In the same manner as in Example 1 except that 5 parts of POL 4190 (polyoxyethylene dioleate / sorbitan monooleate compound manufactured by Toho Chemical Industry Co., Ltd.) was replaced with 5 parts of polyoxyethylene alkyl allyl ether of HLB13. Thus, a powder composition for preventing the adhesion of marine organisms to a fishing net or a ship bottom containing 70% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate was produced.

Comparative Example 2 (Example of a powder composition without using an oil absorbing agent) In Example 1, 5 parts of Carplex # 80 (manufactured by Shionogi & Co., Ltd.), Lucentite SAN (manufactured by Corp Chemical Co., Ltd.) 20 parts of HLB 5.0 surfactant S
ORPOL 4190 (polyoxyethylene dioleate / sorbitan monooleate blended product manufactured by Toho Chemical Industry Co., Ltd.) was replaced with 25 parts in the same manner as in Example 1, except that
A powder composition containing 70% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate for preventing the attachment of marine organisms to fishing nets or ship bottoms was produced.

Comparative Example 3 (Example of a suspension composition using the powder composition of Comparative Example 1) A fishing net or sea bottom containing 70% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate of Comparative Example 1 250 parts of xylene was added to 100 parts of the powder composition for preventing biofouling, and a homogenizer (Toyo Seiki Co., Ltd.)
The mixture was mixed at 1,000 rpm for 15 minutes, and the viscosity at 25 ° C containing 20% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate was 810.
A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a mPa · s (10 Sec ⁻¹ ) Shear rate was produced.

Comparative Example 4 (Example of a suspension composition using the powder composition of Comparative Example 2) A fishing net or sea bottom containing 70% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate of Comparative Example 2 250 parts of xylene was added to 100 parts of the powder composition for preventing biofouling, and a homogenizer (Toyo Seiki Co., Ltd.)
The mixture was mixed at 1,000 rpm for 15 minutes, and the viscosity at 25 ° C. containing 20% zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate was 55 mP.
A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at an a · s (10 Sec ⁻¹ ) Shear rate was produced.

Comparative Example 5 (Example of a suspension composition using a hydrophilic thickener) In Example 8, an organoite (manufactured by Toyoko Yoko Co., Ltd.) 7
Part, Aerosil R972D (Nippon Aerosil Co., Ltd.) 3
Parts were replaced with 10 parts of hydrophilic silica Tokuseal GUN (manufactured by Tokuyama Corporation) in the same manner as in Example 8, except that the composition contained 20% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate at 25 ° C. Has a viscosity of 25
A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a shear rate of ⁰ mPa · s (10 Sec ^-1 ) was produced.

Comparative Example 6 (Example of suspension composition using nonionic surfactant of HLB13) In Example 9, the surfactant SOR of HLB 5.0 was used.
POL 4190 (polyoxyethylene dioleate / sorbitan monooleate blended product of Toho Chemical Industry Co., Ltd.) was replaced with polyoxyethylene alkyl allyl ether of HLB13 in the same manner as in Example 9 to obtain tetramethyl 2 containing 20% thiuram disulfide
A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom having a viscosity of 850 mPa · s (10 Sec ^-1 ) at 5 ° C. was produced.

Comparative Example 7 (Example of a suspension composition without using a thickener and a surfactant) In Example 8, 65 parts of xylene, 7 parts of organoite (manufactured by Toysun Yoko Co., Ltd.), Aerosil R972D ( 3 parts of Nippon Aerosil Co., Ltd.) and 5 parts of HLB 5.0 surfactant SORPOL 4190 (polyoxyethylene dioleate / sorbitan monooleate blended product of Toho Chemical Industry Co., Ltd.) in 80 parts of xylene Except having changed, in the same manner as in Example 8, the viscosity at 25 ° C containing 20% of zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate was 30 mPa · s (10 Sec ^-1 ).
A suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms, which was te, was produced.

Comparative Example 8 (viscosity at 25 ° C. is 3,800 mPa
Example of suspension composition having s (10 Sec ^-1 ) Shear rate) In Example 9, 65 parts of cyclohexanone, 6 parts of organoite (manufactured by Toyojun Yoko Co., Ltd.), Aerosil R972D
4 parts (manufactured by Nippon Aerosil Co., Ltd.), 50 parts of xylene, 15 parts of organoite (manufactured by Toyojun Yoko Co., Ltd.), Aerosil R9
Except that 10 parts of 72D (manufactured by Nippon Aerosil Co., Ltd.) was used, the viscosity was increased to 3,800 at 25 ° C containing 20% of tetramethylthiuram disulfide in the same manner as in Example 9.
A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a mPa · s (10 Sec ⁻¹ ) Shear rate was produced.

Comparative Example 9 (viscosity at 25 ° C. is 120 mPa · s
(Example of suspension composition having (10 Sec ^-1 ) Shear rate) In Example 9, 65 parts of cyclohexanone, 6 parts of organoite (manufactured by Toyojun Yoko Co., Ltd.), Aerosil R972D
(Nippon Aerosil Co., Ltd.) 4 parts, xylene 71 parts, Organite (Toyojun Yoko Co., Ltd.) 2 parts, Aerosil R97
Except that 2 parts of 2D (manufactured by Nippon Aerosil Co., Ltd.) were replaced with 2 parts, the viscosity at 25 ° C. containing 20% of tetramethylthiuram disulfide was 120 mPa · s (1
0Sec ^-1 ) A suspension composition for preventing marine organisms from adhering to a fishing net or the bottom of a ship at a Shear rate was produced.

Comparative Example 10 (Example of a suspension composition without using a thickener and a surfactant) In Example 14, 60 parts of xylene, 7 parts of organoite (manufactured by Toysun Yoko Co., Ltd.), Aerosil R972D ( 3 parts of Nippon Aerosil Co., Ltd.) and 5 parts of HLB 5.0 surfactant SORPOL 4190 (polyoxyethylene dioleate / sorbitan monooleate blended product of Toho Chemical Industry Co., Ltd.) in 75 parts of xylene Except having changed, the viscosity at 25 ° C containing 25% of 2-pyridinethiol-1-oxide zinc salt was 80 mPa · s in the same manner as in Example 14.
A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a (10 Sec ^-1 ) Shear rate was produced.

Comparative Example 11 (Example of a suspension composition without using a thickener and a surfactant) In Example 15, 59 parts of xylene, 6 parts of Lucentite SAN (manufactured by Corp Chemical Co., Ltd.), 5 parts of HLB
Surfactant SORPOL 4190 (Toho Chemical Industry)
2-pyridinethiol-1-oxide copper salt 30 in the same manner as in Example 15 except that 5 parts of polyoxyethylene dioleate / sorbitan monooleate (manufactured by Co., Ltd.) was changed to 70 parts of xylene. % At 25 ° C. is 5
A suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom at a shear rate of ⁰ mPa · s (10 Sec ^-1 ) was produced.

Comparative Example 12 (Example of a suspension composition without using a thickener and a surfactant) In Example 16, 58 parts of xylene, 7 parts of Lucentite SAN (manufactured by Corp Chemical Co., Ltd.), and HLB 6.
8 surfactant SORPOL 4192 (Toho Chemical Industry)
Copper oxide 30 was prepared in the same manner as in Example 16 except that 5 parts of polyoxyethylene distearate / sorbitan monolaurate (manufactured by Co., Ltd.) was changed to 70 parts of xylene.
% At 25 ° C has a viscosity of 25 mPa · s (10 Sec ^-1 ) S
A suspension composition for preventing the attachment of marine organisms to the fishing net or the bottom of the ship at a hear rate was produced.

Comparative Example 13 (Example of a suspension composition not using a thickener and a surfactant) In Example 17, 53 parts of xylene, 7 parts of Lucentite SAN (manufactured by Corp Chemical Co., Ltd.), and HLB 5.
Surfactant SORPOL 4190 (Toho Chemical Industry)
2-pyridinethiol-1-oxide copper salt 15 in the same manner as in Example 17 except that 5 parts of polyoxyethylene dioleate / sorbitan monooleate (produced by Co., Ltd.) was changed to 65 parts of xylene. % And 20% cuprous oxide have a viscosity of 30 mPa · s (10 Sec ^-1 ) at 25 ° C.
A suspension composition for preventing marine organisms from adhering to the fishing net or the bottom of the boat, which was te, was produced.

Test Method The physicochemical properties of the suspension composition for preventing marine organisms from adhering to the fishing net or ship bottom of the present invention and the marine organism adhesion test were carried out by the following test methods. 1) Average particle size measurement: A centrifugal sedimentation type particle size distribution analyzer (manufactured by Shimadzu Corporation) was used. 2) Viscosity measurement: E-type viscometer (Tokyo Keiki Co., Ltd.) was used. 3) Suspension / dispersion stability: A 100 ml glass bottle (inner diameter 40 mm, height 70 mm) is charged with 100 ml of the suspension composition for preventing marine organisms from adhering to a fishing net or the bottom of a ship, and sealed to 40 ° C.
In a constant temperature bath, settled and separated, and observed for hard caking. The separation state was calculated by the following equation.

(Equation 1)

4) Adhesion test for marine organisms: An antifouling paint for fishing nets or an antifouling paint for ship bottoms was prepared according to the following formulation, and after evaluating the suspension and dispersion stability by the above-mentioned method, the following method was used.
evaluated.

Table 1 Formulation 1 The marine antifouling suspension composition prepared in any of Examples 5 to 13 and Comparative Examples 3 to 50 50% acrylic resin (50% xylene solution) 40% xylene 10% ─ 100%

[0104]

Table 2 Formulation 2 The marine antifouling suspension composition prepared in any of Examples 14-17 and Comparative Examples 10-13 50% Chloride rubber resin 25% Plasticizer 3% Xylene 22% 100%

The antifouling paint for fishing nets or antifouling paint for ship bottoms prepared according to the above-mentioned formulation was applied to a hard vinyl chloride plate,
The test piece was dried for 4 hours. The test piece was immersed at a depth of 1 m in the sea at Yomune Fishing Port in Shizuoka Prefecture, and the degree of fouling by attached organisms was observed over time to measure the ratio of the attached area to the painted area.

[0106]

[Table 3] The results were evaluated in four stages based on the following criteria. A: No adhesion was observed at all. B: Adhesion was observed in a portion of 50% or less. C: Adhesion was observed in 50% or more. D: Adhered to the whole, and the coating surface was completely covered. The test results are shown in Tables 1 to 4.

[0107]

[Table 4] Table 1

2 in Table 1

[Table 5]

3 in Table 1

[Table 6]

4 in Table 1

[Table 7]

[0111]

The powder composition for preventing marine organisms from adhering to fishing nets or ship bottoms according to the present invention can be easily suspended in a solvent. , Sedimentation, hard caking, etc. are hardly observed, and the antifouling paint for fishing nets or antifouling paint for ship bottoms containing the composition as a component has good fixation to fishing nets or ship bottoms. The adhesion of marine organisms is extremely small and effective, and the suspension composition for preventing marine organisms from adhering to the fishing net or ship bottom and the antifouling paint for fishing nets or antifouling paint for ship bottoms of the present invention are practical.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 59/16 A01N 59/16 Z 59/20 59/20 Z C09D 5/16 C09D 5/16 (72) Inventor Fumiko Kondo 722-1, Tsuboi-cho, Funabashi-shi, Chiba Pref. In the Central Research Laboratory of Nissan Chemical Industry Co., Ltd. (72) Kenji Okada 3-12-19, Okamura, Isogo-ku, Yokohama-shi

Claims (16)

[Claims] 1. An HL in which a water-immiscible component hardly soluble in a solvent immiscible with water, a nonionic surfactant having an HLB of 3 to 10, or a nonionic surfactant mixed with an anionic surfactant is used.
A powder for preventing marine organisms from adhering to fishing nets or ship bottoms, comprising a surfactant of B3 to 10, an oil absorbing agent and a hydrophobic thickener, and having an average particle size of 0.5 to 10 µm. Composition. 2. The powder composition according to claim 1, wherein the oil absorbing agent is amorphous silica. 3. The powder composition according to claim 1, wherein the thickener is organic bentonite or hydrophobic silica. 4. The fishing net according to claim 1, wherein the underwater antifouling component is a dithiocarbamate-based metal compound, a thiuram-based compound, a pyrithion-based metal compound, a copper-based compound, or a mixture of a pyrithion-based metal compound and a copper-based compound. Or a powder composition for preventing marine organisms from adhering to the bottom of ships. 5. The antifouling component in water is zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, tetramethylthiuram disulfide, zinc salt of 2-pyridinethiol-1-oxide, copper salt of 2-pyridinethiol-1-oxide. A salt, cuprous oxide, a mixture of zinc 2-pyridinethiol-1-oxide and cuprous oxide or a mixture of copper 2-pyridinethiol-1-oxide and cuprous oxide. A powder composition for preventing marine organisms from adhering to fishing nets or ship bottoms. 6. An antifouling component in water of 3 to 90% by weight, a nonionic surfactant or 1 to 20% by weight of a surfactant obtained by mixing a nonionic surfactant and an anionic surfactant,
The powder composition according to claim 1, which contains 20% by weight and 1 to 30% by weight of a thickener. 7. A suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms, which comprises the powdery composition for preventing marine organisms from attaching to fishing nets or ship bottoms according to claim 1. 8. An HLB3 obtained by mixing a solvent, an antifouling component in water that is hardly soluble in said solvent, a nonionic surfactant having an HLB of 3 to 10, or a mixture of a nonionic surfactant and an anionic surfactant.
10 to 10 surfactants and a hydrophobic thickener,
The viscosity at 5 ° C is 200 to 1,500 mPa · s (10 Sec ^-1 ) S
A suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms, which has a hear rate. 9. The antifouling component in water has an average particle size of 0.5 to 0.5.
The suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms according to claim 7 or 8, which is 10 µm. 10. The solvent is an aromatic or aliphatic hydrocarbon solvent, industrial gasoline or petroleum fraction.
Or the suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom according to claim 8. 11. The suspension composition according to claim 7, wherein the thickener is organic bentonite or hydrophobic silica. 12. The antifouling component in water is a dithiocarbamate metal compound, a thiuram compound, a pyrithion metal compound, a copper compound or a mixture of a pyrithion metal compound and a copper compound. 8. The suspension composition for preventing marine organisms from adhering to a fishing net or a ship bottom according to 8. 13. The antifouling component in water is zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, tetramethylthiuram disulfide, zinc salt of 2-pyridinethiol-1-oxide, copper salt of 2-pyridinethiol-1-oxide. 13. A salt, cuprous oxide, a mixture of zinc 2-pyridinethiol-1-oxide and cuprous oxide or a mixture of copper 2-pyridinethiol-1-oxide and cuprous oxide. A suspension composition for preventing marine organisms from adhering to fishing nets or ship bottoms. 14. A solvent comprising 20 to 90% by weight of a solvent, 3 to 50% by weight of an insoluble antifouling component in water which is hardly soluble in the solvent, a nonionic surfactant or a surfactant obtained by mixing a nonionic surfactant and an anionic surfactant. 0.5-10% by weight, and thickener 1-2
9. The suspension composition according to claim 7, wherein the suspension composition contains 0% by weight. 15. An antifouling paint for fishing nets or an antifouling paint for ship bottoms, comprising the suspension composition for preventing marine organisms from adhering according to claim 7 or 8. 16. An aromatic or aliphatic hydrocarbon solvent, a solvent which is industrial gasoline or a petroleum fraction; bis (dimethyldithiocarbamoyl) which is insoluble in said solvent and has an average particle size of 0.5 to 10 μm. Zinc ethylenebisdithiocarbamate, tetramethylthiuram disulfide, 2-
Pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide copper salt, cuprous oxide, a mixture of 2-pyridinethiol-1-oxide zinc salt and cuprous oxide or 2-pyridinethiol-1 An antifouling component in water, which is a mixture of an oxide copper salt and cuprous oxide; a nonionic surfactant having an HLB of 3 to 10 or a surfactant having an HLB of 3 to 10 obtained by mixing a nonionic surfactant and an anionic surfactant; And an antifouling paint for fishing nets or an antifouling paint for ship bottoms containing organic bentonite or hydrophobic silica as a component.