JPH111407A - Aquatic pest-controlling agent - Google Patents

Abstract

(57) [Abstract] [Problem] It has low safety and health issues and environmental issues, that is, low toxicity and persistence, and does not adversely affect the ecosystem and working environment. obtain,
In particular, to provide an aquatic pest control agent which is effective as a slime control agent for papermaking. SOLUTION: The water pest controlling agent of the present invention effectively uses at least one quaternary amine compound in which a group represented by the following general formula (I) is directly bonded to a nitrogen atom. It is included as a component. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a pesticidal agent for aquatic organisms for the purpose of preventing the attachment and propagation of pests in seawater or industrial water systems.
Used to prevent the adhesion of underwater pests on the surface of underwater structures such as ships, fishing nets, buoys, seawater guide pipes,
Further, the present invention provides an underwater pesticide which can be applied as a slime control agent for papermaking.

[0002]

BACKGROUND OF THE INVENTION Underwater structures, such as ships, port facilities, buoys, pipelines,
Bridges, offshore oilfield drilling rigs, waterway pipes of power plants or coastal plants, fishing nets and rafts for aquaculture, etc. are exposed to large attached flora and fauna such as barnacles, mussels and blue seaweed, and microscopic organisms such as diatoms and bacteria, and corrode structures. Damage such as increased seawater frictional resistance of vessels, clogging of fishing nets, mass mortality of fish and shellfish, sedimentation due to increased weight, and reduced work efficiency occurs. Also, in industrial water systems such as cooling water using natural water such as river water and lake water, and in circulating cooling systems that use medium and tap water, bacteria, diatoms, cyanobacteria, blue spiders, etc., proliferate abnormally, It causes obstacles such as deterioration of cooling efficiency due to deterioration and adhesion to the vessel wall, blockage of water pipes, and decrease in flow rate.

In order to prevent such damage by pests in water, inorganic heavy metal compounds such as cuprous oxide, copper rhodanide, and mercury oxide or tributyltin oxide, triphenyltin oxide, and tributyltin (meth) acrylate copolymers are used. An antifouling agent containing an organic metal compound such as a substance is used.

However, these conventionally used compounds are extremely toxic and require not only special care in handling, but also the occurrence of malformation due to accumulation in fish bodies and environmental pollution, causing problems such as heavy metals and It has been desired to use an antifouling agent containing no organic metal.

As antifouling agents containing no heavy metals or organic metals, various compounds containing a sulfur atom such as thiuram compounds, benzothiazole compounds and thiocyan compounds have been proposed, but their effects have been insufficient. . JP-A-6-340503 proposes to use a polysulfide compound. However, even when these are used alone or in combination with other compounds described in the specification, a sufficient amount is still insufficient. No biological activity is obtained, and JP-A-7-126116 proposes an antifouling agent in water comprising a combination of dimethyldithiocarbamionate and a higher aliphatic amine compound, which is still satisfactory. Was not.

[0006] Therefore, problems in safety and health and the environment, that is, low toxicity and persistence, are not adversely affecting the ecosystem and the working environment, and are capable of exerting the effects for a long time. Control agents are desired.

[0007] In the pulp preparation process and papermaking process of pulp mills and paper mills, it is known that slime is formed due to propagation of microorganisms such as bacteria, yeasts and filamentous fungi, causing various obstacles. The slime adheres to almost all parts of the process using water, such as a channel through which the pulp slurry flows, for example, a ruffler wall, a screen, an inlet or a chest wall during a paper making process, or a white water pit, an inner wall of a recovered white water pipe, and the like. It gradually increases in thickness and eventually peels off and mixes into the pulp slurry or clogs screens and pipes. Slime lumps mixed in the pulp slurry may cause yellow or brown spots on the paper to deteriorate the quality of the product, cause the paper to run out and cause operational problems, and may cause various obstacles due to the propagation of microorganisms. It is. In particular, when a high-speed machine is used, it becomes a serious problem, resulting in a significant decrease in productivity and economic loss.

In recent years, improvement of white water recovery rate, eutrophication by additives such as starch, polyacrylamide, sizing agent, sediment including inorganic filler, resin component of wood, adhesive and ink component derived from waste paper Due to the increased number of pitch-like deposits, the papermaking process has become an environment more suitable for the propagation of microorganisms. In particular, an improvement in the recovery rate of white water makes it easier to cause emergence of bacteria resistant to the slime control agent and a bacterial replacement phenomenon, which causes a reduction in the efficacy of the slime control agent.

For this reason, many slime control agents have heretofore been developed and used, but no slime control agent which maintains satisfactory efficacy under such conditions has yet been obtained. Was requested.

[0010] Accordingly, an object of the present invention is to provide safety and health and environmental problems, that is, low toxicity and persistence, without adversely affecting the ecosystem and the working environment, and for long-term effects. An object of the present invention is to provide an aquatic pesticide which can be exerted, and which is particularly effective as a slime control agent for papermaking.

[0011]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific quaternary amine compound can achieve the above object.

The present invention has been made based on the above-mentioned findings, and comprises a group represented by the following general formula (I) represented by the following [Chemical formula 3] (same as the above [Chemical formula 1]) directly bonded to a nitrogen atom. An object of the present invention is to provide a pesticidal agent in water containing at least one quaternary amine compound as an active ingredient.

[0013]

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[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the pest controlling agent in water of the present invention will be described in detail.

In the group represented by the above general formula (I) possessed by the quaternary amine compound used as an active ingredient of the aquatic pesticide of the present invention, the alkyl group represented by R is, for example, methyl , Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, tertiary nonyl, decyl , Isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacontyl and the like.

More specific examples of the quaternary amine compound according to the present invention include the following chemical formulas (II) -1 to (II) -3 of the following [Chemical Formula 4] (the same as the above [Chemical Formula 2]). And the like.

[0017]

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Wherein A represents a group of the above general formula (I), and Q together with N ⁺ represents a 5- or 6-membered ring which can contain an oxygen atom and / or a nitrogen atom. R ₁ and R ₂ are each independently an alkyl group, an aryl group,
Represents an arylalkyl group or an alkylaryl group,
R ₆ represents an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group, and may be bonded to Q to form an alkylene group; p, q and r represent 1 or 2; When p = 1, R ₃ represents an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group, and when p = 2, R ₃ represents an alkylene group, an arylene group or a composite group thereof. And q = 1
R ₄ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group, and q = 2
In the case of, R ₄ represents a direct bond, an alkylene group, an arylene group or a composite group thereof, and when r = 1, R ₅ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group, When r = 2, R ₅ represents an alkylene group, an arylene group or a composite group thereof;
X ₁ and X ₂ represent a halogen atom or an alkyl group;
^- represents an anion. ]

In the compounds represented by the above general formulas (II) -1 to (II) -3, examples of the ring structure which Q can form together with N ⁺ (quaternary amine) include pyrrole and
Ring structures derived from pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, piperidine, piperazine, morpholine and the like can be mentioned.
As the alkyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X ₁ and X ₂ , for example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, Groups such as nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacontyl, etc., which can be linear, branched or cyclic. Further, it may have an unsaturated bond, an ether bond, a carbamoyl bond, or the like, and may be further substituted with a hydroxyl group, a halogen atom, or the like. The aryl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ includes, for example, groups such as phenyl and naphthyl. R ₁ , R ₂ , R ₃ , R ₄ ,
Examples of the arylalkyl group represented by R ₅ and R ₆ include groups such as benzyl, α-methylbenzyl, α, α-dimethylbenzyl and the like. R ₁ , R ₂ , R ₃ , R ₄ , R ₅
And The alkyl aryl group represented by R _6, for example, the aryl group substituted in the alkyl group. Examples of the alkylene group represented by R ₃ , R ₄ and R ₅ and the alkylene group formed from R ₆ include groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. These may be linear, branched or cyclic, may have an unsaturated bond or an ether bond, and may be further substituted with a hydroxyl group or the like. Examples of the arylene group represented by R ₃ , R ₄ and R ₅ include groups such as phenylene and naphthylene. Further, as the halogen atom represented by X ₁ and X ₂ , for example, fluorine, chlorine,
Bromine, iodine and the like can be mentioned.

Further, X ^- as the anion of the quaternary amine compound represented by, for example, hydroxyl anion; fluorine,
Halogenated anions such as chlorine, bromine and iodine; fluoric acid,
Halogen acid anions such as chloric acid, bromic acid and iodic acid; perhalic acid anions such as perfluorinated acid, perchloric acid, perbronic acid and periodic acid; thiocyanate anion, hexafluorophosphate anion and hexafluoride Inorganic acid anions such as antimony anion, sulfonate anion and sulfate anion, organic acid anion and the like.

The method for producing the quaternary amine compound includes, for example, reacting a halogenated methyl alkyl polysulfide with a tertiary amine compound or a nitrogen-containing aromatic compound in a solvent to form a halogen anion. A quaternary amine compound can be easily obtained, and if necessary, a quaternary amine compound of another anion can be easily obtained by anion exchange according to a conventional method. Also,
Since this reaction proceeds relatively easily, it is possible in some cases to form them by mixing them during storage or during use.

Examples of the tertiary amine compound capable of forming the quaternary amine compound include octyldimethylamine, dodecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine,
Coconut alkyldimethylamine, tallowalkyldimethylamine, hardened tallowalkyldimethylamine, didodecylmethylamine, dioctadecylmethylamine, ditallowalkylmethylamine, dicocoalkylmethylamine, dodecyltetradecylmethylamine, dodecyloctadecylmethylamine, tetra Decylhexadecylmethylamine, dodecylmethylpropylamine, hexadecylmethylamine, tallowalkylethylpropylamine, tallowalkyldiethylamine, tallowalkyldipropylamine, tallowalkyldibutylamine, cocoalkyldihexylamine, trioctylamine, tridecylamine,
β-hydroxydodecyldimethylamine, β-hydroxyhexadecyldimethylamine, β-hydroxyoctadecyldimethylamine, di (β-hydroxyhexadecyl) methylamine, di (β-hydroxyoctadecyl)
Methylamine, tallowalkyloxypropyldimethylamine, tallowalkyloxypropyldiethylamine, 3
-(2-ethylhexyloxy) propyldimethylamine, 3- (2-ethylhexyloxy) propyldiethylamine, 3-dodecyloxyethyldimethylamine,
Aliphatic tertiary amine compounds such as 3-dodecyloxyethyldiethylamine, 3-cocoalkyloxypropyldimethylamine and 3-cocoalkyloxypropyldiethylamine; aromatic aliphatic tertiary compounds such as benzyldimethylamine, benzyldiethylamine and dibenzylmethylamine Amine compounds; pyridine, bipyridyl, α-collidine,
Aromatic tertiary amine compounds such as β-collidine, γ-collidine, and pyrimidine; and heterocyclic tertiary amine compounds such as triethylenediamine, N-methylmorpholine, and N-methylpiperidine. That is, the quaternary amine compound according to the present invention is selected from the group consisting of aliphatic tertiary amine compounds, araliphatic tertiary amine compounds, aromatic tertiary amine compounds, and heterocyclic tertiary amine compounds. A quaternary amine compound having a structure obtained from at least one kind is exemplified.

Accordingly, the quaternary amine compound used in the present invention includes, for example, the following [Chemical Formula 5] to [Chemical Formula 1].
5].

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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As described above, the water pest control agent of the present invention comprises, as an active ingredient, at least one quaternary amine compound having a specific group (group represented by the above general formula (I)). Things. And the water pest control agent of the present invention can be used in combination with one or more types of conventionally used antifouling agents (bioactive antifouling components). Can also be played.

In the present invention, the antifouling agent which can be used in combination with the quaternary amine compound includes, for example,
Tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetra-n-propylthiuram disulfide, tetraisopropylthiuram disulfide, tetra-n-butylthiuram disulfide,
Tetraisobutyl thiuram disulfide, N, N'-
Ethylenebisthiocarbamoyl sulfide, N, N '
Propylene bisthiocarbamoyl sulfide, N,
Thiuram-based compounds such as N'-butylenebisthiocarbamoyl sulfide; copper-based metal powders such as copper powder and copper-nickel alloy powder; cuprous oxide, cuprous thiocyanate, basic copper carbonate, copper pyrophosphate, naphthene Copper compounds such as copper acid, copper abietate and copper oxyquinoline; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate,
Zinc dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc ethylenebisdithiocarbamate, zinc propylenebisdithiocarbamate, zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate And dithiocarbamate compounds such as copper dimethyldithiocarbamate and iron dimethyldithiocarbamate; 2- (4-thiazolyl) benzimidazole, methyl-1- (ω-cyanopentylcarbamoyl) -2-benzimidazole, 2- Benzimidazole compounds such as zinc mercaptobenzimidazole and 2-thiocyanomethylthiobenzimidazole; 2
-Mercaptobenzothiazol, 2- (thiocyanomethylthio) benzothiazole, 2- (thiocyanomethylsulfonyl) benzothiazol, 2-thiocyanoethylthio-4-chlorobenzothiazol, 2-thiocyano Benzothiazole-based compounds such as propylthio-5,7-dichlorobenzothiazole and 2-thiocyanomethylthio-4,5,6,7-tetrachlorobenzothiazole; tetrachloroisophthalonitrile, 5 Nitrile compounds such as -chloro-2,4-difluoro-6-methoxyisophthalonitrile; 4,5-dichloro-2-n-octyl-
4-isothiazolin-3-one, 2-n-octyl-4
Isothiazoline compounds such as -isothiazolin-3-one, 1,2-benzoisothiazolin-3-one; 1-
[2- (2,4-dichlorophenyl) -4-propyl-
1,3-dioxolanyl-2-methyl1-1H-1,
2,4-triazole, 4,4-dimethyl-2- (1,
2,4-triazol-1-yl) -1- (4-trifluoromethyl-2-chlorophenyl) -1-pentene-
Triazole compounds such as 2-ol; 2,3,5
6-tetrachloro-4- (methylsulfonyl) pyridine, 2,3,6-trichloro-4-propylsulfonylpyridine, 2,6-dichloro-3,5-dicyano-4-
Pyridine compounds such as phenylpyridine and triphenylboron pyridine; 2,4-dichloro-6- (α-chloroanilino) -s-triazine, 2-chloro-4-methylamino-6-isopropylamino-s-triazine,
Chloro-4,6-bis (ethylamino) -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-
Dimethyl urea, 3- (3,4-dichlorophenyl) -1
-Methoxy-1-methylurea, 1- (α, α′-dimethylbenzyl) -3-methyl-3-phenylurea, 1-
Urea compounds such as (2-methylcyclophenyl) -3-phenylurea; 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-
Tetrachloroethylthiootetrahydrophthalimide,
N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, N, N-dimethyl-
N'-phenyl-N '-(fluorodichloromethylthio) sulfurylamide, trichloromethylthiomethanesulfone-p-chloroanilide, N- (1,1,2,2,
-Tetrachloro-2-fluoroethylthio) methanesulfonanilide, N-fluorodichloromethylthio-N-
N- such as 3-chlorophenyl-N'-dimethylurea, N-fluorodichloromethylthio-N-3,4-dichlorophenyl-N'-methylurea, N-fluorodichloromethylthio-N-trissulfonyl-N-methylamine
Haloalkylthio compounds; N- (2-chlorophenyl) maleimide, N- (4-fluorophenyl) maleimide, N- (3,5-dichlorophenyl) maleimide,
N- (2,4,6-triclophenyl) maleimide, N
Maleimide-based compounds such as -4-tolylmaleimide, N-2,4-xylylmaleimide, and 2,3-dichloro-N- (2 ', 6'-dimethylphenyl) maleimide;
5-dimethyl-tetrahydro-1,3,5,2 (H)-
Thiadiazin-2-one, 3,3′-ethylenebis (tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazin-2-one, 3,5-dimethyl-2-thiotetrahydro-1,3 , 5-Thiadiazine, 3,5-dibenzyltetrahydro-1,3,5-thiadiazine {2-
Thiadiazine compounds such as thione; methyl thiocyanate, chloromethyl thiocyanate, ethyl thiocyanate,
Thiocyan compounds such as methylenebisthiocyanate, chloromethylenebisthiocyanate, ethylenebisthiocyanate, chloroethylenebisthiocyanate, isobornylthiocyanate, methylisothiocyanate, allylisothiocyanate, phenylisothiocyanate and benzylisothiocyanate; Alkyl phenol compounds such as tris (octylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono and di-mixed nonylphenyl) phosphite, etc. Alkyl phenyl phosphite compound; tris (octyl phenyl) phosphate, tris (nonyl phenyl) phosphate, tris (dinonyl phenyl) Sufeto, tris (mono-, di-mixed nonylphenyl) alkylphenyl phosphate compounds such as phosphates; octyl chloromethyl disulfide, polysulfide compounds such as decyl chloromethyl disulfide and the like.

The underwater pest control agent of the present invention includes:
Elution modifiers such as petrolatum, silicon, polybutene, chlorinated paraffin, and polysulfide compounds can be used together with these antifouling agents.

The underwater pesticide of the present invention includes, for example,
If necessary, a film-forming component (film-forming agent) may be blended to form an antifouling paint, which can be dipped and applied to fishing nets or the like, or applied to ships and underwater structures. It is preferable to use it because a long-term antifouling effect can be maintained. When the underwater pest control agent of the present invention is used as a paint composition or a fishing net antifoulant solution, the amount of the underwater pest control agent of the present invention is determined according to the active ingredient (the quaternary amine compound) according to the present invention. But usually 1-5
The amount is 0% by weight, preferably 5 to 30% by weight, and is appropriately selected in consideration of the purpose of use, antifouling period and the like.

The components used for preparing the coating composition or the antifouling solution are not particularly limited, and the components conventionally used for preparing these coating compositions or the antifouling solution are used as they are. be able to. For example, as a coating film forming component used as an organic solvent-based paint, vinyl chloride resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, polyester resin,
Epoxy resin, urethane resin, polyamide resin, alkyd resin, coumarone resin, petroleum resin, silicone resin, silicone rubber resin, wax, paraffin, rosin ester, rosin resin can be used alone or in combination, Further, as a coating film forming component used as an aqueous paint, an acrylic emulsion resin,
Epoxy emulsion resins, vinyl acetate resins and the like can be used.

Further, the above-mentioned coating composition or the above-mentioned antifouling agent liquid may further contain a commonly used plasticizer; a coloring pigment such as a red stalk; a filler such as talc, barium sulfate;
Solvents such as pseudocumene, solvent naphtha, butanol, isopropyl alcohol, methyl isobutyl ketone, diethylbenzene, triethylbenzene, mesitylene and the like can be contained in an arbitrary ratio.

The underwater pesticide of the present invention functions as an excellent slime control agent for papermaking, and will be described in detail below.

When used as a slime control agent for papermaking, the water pest control agent of the present invention can be formulated by dissolving or dispersing it in water or an organic solvent or a mixed solvent thereof for easy use. It is possible. In that case, various surfactants can be used to improve the solubility or dispersibility.

Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol and butanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; dichloromethane and dichloroethane. , Chloroform, carbon tetrachloride and other halogenated hydrocarbons; dioxane, tetrahydrofuran and other ethers; dimethylformamide, dimethylsulfoxide, acetonitrile and other polar solvents; ethylene glycol, diethylene glycol, polyethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
Polyols such as 3-butanediol, 1,5-pentanediol, and glycerin; ether alcohols such as methylcellosolve, ethylcellosolve, butylcellosolve, diethylene glycol monomethyl ether, carbitol, and tripropylene glycol monomethyl ether; Can be

Examples of the surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate and ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulfolicine; alkali metal salts of sulfonated paraffin; Alkyl sulfonates such as ammonium salts of paraffins;
Fatty acid salts such as sodium laurate, triethanolamine oleate and triethanolamine aviate; alkyl aryl sulfonates such as sodium benzene sulfonate and alkali metal sulfate of alkali phenol hydroxyethylene; high alkyl naphthalene sulfonate; naphthalene sulfonic acid formalin condensate Dialkyl sulfosuccinates; polyoxyethylene alkyl sulfate salts; anionic surfactants such as polyoxyethylene alkyl aryl sulfate salts, for example, polyoxyethylene alkyl ethers; polyoxyethylene alkyl aryl ethers; sorbitan fatty acid esters; polyoxyethylene Sorbitan fatty acid ester; fatty acid monoglyceride; trimethylolpropane fatty acid ester Nonionic surfactants such as polyoxyethyleneoxypropylene copolymers; condensation products of ethylene oxide with fatty acid amines, amides or acids, for example, tertiary to tertiary amine salts; pyridinium salts; quaternary ammonium salts and the like Cationic surfactants, for example, polyvinyl alcohol; sodium poly (meth) acrylate, potassium poly (meth) acrylate,
Ammonium poly (meth) acrylate, polyhydroxyethyl (meth) acrylate; high molecular surfactant such as polyhydroxypropyl (meth) acrylate, having an unsaturated bond copolymerizable with the unsaturated monomer in the molecule Nonionic, anionic or cationic reactive surfactants and the like can be mentioned.

When used as a slime control agent for papermaking, the aquatic pest control agent of the present invention may further contain other antibacterial components, such as 5-chloroform. -2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octylisothiazolin-3-one, 1,2-benzisothiazoline-3 Isothiazolone compounds such as -one, 2-n-octylisothiazolin-3-one and metal salts or metal complexes thereof; 2,2-dibromo-2-nitroethanol,
1,1-dibromo-1-nitropropanol, 2-bromo-2-nitro-1,3-propanediol, 3-bromo-3-nitro-2,4-pentanediol, 2-bromo-2-nitro-1 , 3-butanediol, 3-bromo-3-nitro-2-butanol, 2-bromo-2-nitro-2-butanol, 2-bromo-2-nitro-1,3
-Diacetoxypropane, 2,2-dibromo-2-nitro-1-acetoxyethane, 3-bromo-3-nitro-
4-caprinoyloxy-2-pentanol, 2-bromo-2-nitro-1-phenylethanol, 2-bromo-2-nitro-1- (o-chlorophenyl) ethanol, 2-bromo-2-nitro-1 -Phenylpropanol methylene bisthiocyanate, 4,5-dichloro-
1,2-dithiol-3-one, 2,2-dibromo-2
-Nitriloamide, 5-chloro-2,4,6-trifluoroisophthalonitrile, 1,2-bis (bromoacetoxy) ethane, 1,4-bis (bromoacetoxy) propane, α-bromo-3-nitroacetophenone, Dichloroglyoxime, 2,2-dibromo-2-cyanoacetamide, tetrachlorotetrahydrothiophene-1,1-
Dioxide; pyridine compounds, hypochlorites and the like.

Further, various additives can be added to the underwater pesticide of the present invention when used as a slime control agent for papermaking, if necessary.

The water pest control agent of the present invention when used as a slime control agent for papermaking varies depending on the water source, the paper, and the like used in the pulp preparation or papermaking process. The effective ingredient (the quaternary amine compound) according to (1) is effective when it is added in an amount of 0.1 to 100 ppm, preferably 0.5 to 50 ppm. (Note that ppm is based on weight.)

[0048]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following examples.

First, a production example of the quaternary amine compound according to the present invention will be described. Other quaternary amine compounds used in Examples were prepared in the same manner.

Production Example 1 (Compound 1-chlorine anion) 53.1 g of octyl chloromethyl disulfide, N,
63.2 g of N-dimethyl.n-hexadecylamine and 58 g of hexane were charged, and the mixture was stirred at room temperature for 5 hours. The mixture gradually became cloudy, and was allowed to stand overnight to filter the cloudy substance. The obtained white crystals were recrystallized with a mixed solution of chloroform / hexane to obtain 83 g of white crystals having a melting point of 157 to 167 ° C.
(Yield 71%) was obtained.

The following ¹ H NMR (hereinafter simply referred to as “NMR”)
), The formation of the desired product was confirmed. NMR (CDCl ₃ ), δ, ppm: 0.93 (6H,
_{t, -CH 3), 1.25 (} 38H, -CH 2 -), 2.2 (2
H, brs, -N-CH ₂ CH _2- ), 2.93 (2H, t, -SC
_{H 2 CH 2 -), 3.4} (8H, m, -N-CH 3, -N-CH 2 -),
5.25 (2H, s, -S- CH 2 -Cl)

Production Example 2 (Compound 6-6 Fluorophosphate Anion) 53.1 g of octyl chloromethyl disulfide, 32.5 g of pyridine and 43 g of hexane were charged, and the mixture was stirred at room temperature for 5 hours. After standing overnight, the cloudy matter was filtered. The obtained white crystals were recrystallized with a chloroform / hexane mixed solution to give a melting point of 138 to 143.
56 g (yield 65%) of white crystals at a temperature of 60.degree.

When the white crystals obtained above were gradually added to water in which an equivalent amount or more of potassium hexafluorophosphate was dissolved while stirring, crystals insoluble in water were obtained.

The formation of the target compound was confirmed from the following NMR results. NMR (CDCl ₃ ), δ, ppm: 0.85 (3H,
_{t, -CH 3), 1.10~1.85 (} 12H, m, -CH 2 -
), 2.8 (2H, t, SS-CH 2 -), 6.5 (2H,
_{s, SS -CH 2 -N-),} 8.1 (2H, t, N-CH -CH-),
8.5 (1H, t, N-CHCH- CH- ), 9.7 (2H, d,
N- CH- )

Production Example 3 (Compound 7-chlorine anion) 53.1 g of octyl chloromethyl disulfide, 4,
61.1 g of 4'-bipyridine and 57 g of hexane were charged, and the mixture was stirred at room temperature for 5 hours. The mixture gradually became cloudy, and was allowed to stand overnight to filter the cloudy substance. The obtained white crystals were recrystallized with a mixed solution of chloroform / hexane to give a melting point of 1.
87 g (yield 67%) of white crystals at 78 to 182 ° C were obtained.

The formation of the target compound was confirmed from the following NMR results. NMR (CDCl ₃ ), δ, ppm: 0.85 (6H,
_{t, -CH 3), 1.10~1.85 (} 24H, m, -CH 2 -
), 2.8 (4H, t, SS-CH 2 -), 6.5 (4H,
_{s, SS -CH 2 -N-),} 8.1 (4H, t, N-CH -CH-),
9.7 (4H, d, N- CH- )

Production Example 4 (Compound 10-chlorine anion) 53.1 g of octyl chloromethyl disulfide, 26.3 g of triethylenediamine and 40 g of hexane were charged, and the mixture was stirred at room temperature for 5 hours. Then the cloudy matter was filtered. The obtained white crystals were recrystallized with a mixed solution of chloroform / hexane to give a melting point of 1.
47 g (yield 59%) of white crystals of 51 to 157 ° C were obtained.

The formation of the target compound was confirmed from the following NMR results. NMR (CDCl ₃ ), δ, ppm: 0.85 (6H,
_{t, -CH 3), 1.10~1.85 (} 24H, m, -CH 2 -
), 2.8 (4H, t, SS-CH 2 -), 6.5 (4H,
_{s, SS -CH 2 -N-),} 9.7 (12H, d, N- CH-)

Example 1 The blends (see Tables 1 and 2 below) (blending units; parts by weight) were thoroughly mixed with a high-speed homomixer to prepare antifouling paints for fishing nets. Using this antifouling paint for fishing nets, a polyethylene test net (60 knotless knots 20 cm × 30
cm) was dyed by dipping and air-dried for 2 days.

The test net was immersed in a test raft in Yokosuka City, Kanagawa Prefecture, Shizuoka City, Shizuoka Prefecture and Kita-Uwa County, Ehime Prefecture at a depth of 1 m in the sea from April, and the degree of contamination by attached organisms was observed over time. Then, the ratio of the adhesion area to the coating area was measured. The results were evaluated in five steps according to the following criteria. The results are shown in [Table 1] and [Table 2] below. A: No adhesion is observed. B: Slight adhesion was observed. C: Adhesion was observed in a portion of less than 25%. D: Adhesion was observed in 25% or more. E: Adhered to the entire surface, and the painted surface was completely covered.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

Embedded image

[0064]

Embedded image

* 5: Dimethylbenzylamine

Embodiment 2

Test compounds (Tables 3 and 4 below)
(Refer to) (composition unit; part by weight) was dissolved in diethylene glycol to prepare a slime control agent.

A stainless steel water tank having a diameter of 30 cm and a depth of 30 cm was equipped with a temperature controller, a stirrer, a thermometer, and two lauan materials 5 cm wide, 30 cm long and 1.0 cm thick for slime measurement. After adding 1% of pulp and a white water culture solution to a 1000-fold diluted Waxman liquid medium (a culture liquid obtained by culturing white water collected from a newsprint papermaking process in a Waxman liquid medium) at a rate of 0.1 ml / liter, Artificial white water adjusted to pH 5 with aluminum sulfate was supplied to this tank at a flow rate of 2 liter / hour, and the same amount of artificial white water was discharged. The slime control agent was added by a pump three times a day for three hours once a day so as to be 5 ppm (by weight) based on the artificial white water supplied. White water temperature 3
Stirring was continued at 0 ° C., and the state of slime generation was confirmed after 20 days and 40 days. The evaluation was performed in the following three stages. The results are shown in [Table 3] and [Table 4] below. A: No slime adhered. B: Slime adhered thinly on the entire surface. C: Slime adhered thickly on the entire surface.

[0069]

[Table 3]

[0070]

[Table 4]

As is clear from the results of the above examples, the effect of the polysulfide compound was insufficient when used as an antifouling agent for fish nets or when used as a slime control agent (Comparative Example 1-1, 2-1), a tertiary amine compound or a quaternary amine compound having no specific group according to the present invention has little effect (Comparative Example 1-2)
~ 1-4, 2-2 ~ 2-4).

On the other hand, the water pest control agent of the present invention containing the quaternary amine compound having a specific group according to the present invention as an active ingredient can be used as a slime control agent even when used as a fish net antifouling agent. It is evident that even when used as (1), remarkably excellent effects are exhibited (Examples 1-1 to 1-16, 2-1 to 2-16). Further, even when the polysulfide compound capable of providing a specific group according to the present invention is mixed with a tertiary amine compound, the quaternary amine compound according to the present invention is partially formed to exhibit a synergistic effect (Example 1). 1
6, 2-16).

[0073]

EFFECT OF THE INVENTION The underwater pesticide of the present invention is used as an antifouling agent so that it does not cause environmental pollution and can be used on the surface of underwater pests on ships, fish nets, buoys, seawater guide tubes and the like. It is possible to prevent the adhesion of slime, and by using it as a slime control agent, it is possible to effectively suppress the generation of slime in the pulp adjusting step or the paper making step.

Claims (5)

[Claims] 1. A pesticidal agent in water comprising, as an active ingredient, at least one quaternary amine compound having a group represented by the following general formula (I) directly bonded to a nitrogen atom. Embedded image 2. The method according to claim 1, wherein the quaternary amine compound is at least one selected from the group consisting of an aliphatic tertiary amine compound, an araliphatic tertiary amine compound, an aromatic tertiary amine compound, and a heterocyclic tertiary amine compound. The pesticidal agent according to claim 1, which is a quaternary amine compound having a structure obtained from a seed. 3. The method according to claim 1, wherein the quaternary amine compound is at least one selected from compounds represented by the following general formulas (II) -1 to (II) -3. Pest control agent in water. Embedded image [Wherein, A represents a group of the above general formula (I), Q represents a 5- or 6-membered ring which can contain an oxygen atom and / or a nitrogen atom together with N ⁺ , ₁ and R ₂
Each independently represents an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group, R ₆ represents an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group, and is bonded to Q to form an alkylene group P, q and r represent 1 or 2, s and t represent 0 to 4, and when p = 1, R ₃ represents an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group; When p = 2, R ₃ represents an alkylene group, an arylene group or a composite group thereof, and when q = 1, R ₄ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group; = when 2, R ₄ is a direct bond, an alkylene group, an arylene group or a composite group thereof, R ₅ is a hydrogen atom when r = 1, an alkyl group, an aryl group, a Indicates Ruarukiru group or alkylaryl group, when r = 2, R ₅ represents an alkylene group, an arylene group or a composite group, X ₁ and X ₂ represents a halogen atom or an alkyl group, X ^- is an anion Represent. ] 4. The underwater pesticide according to claim 1, which is used as a slime control agent for papermaking. 5. The pesticidal agent according to claim 1, further comprising a film-forming agent.