JPH05339110A - Water pest control agent - Google Patents

Abstract

PURPOSE:To provide a water pest control agent containing a benzoxathiol compound as an active ingredient, free from the problems on the fields of safety, hygiene and environment, namely low in toxicity and residual property, not affecting ecological systems and working environments, and having its effect for a long period. CONSTITUTION:The water pest control agent contains on or more kinds of benzoxathiol compounds of formula I (R1-R4 are H, halogen, OH, alkyl, alkenyl, alkoxy, acyl, acyloxy) (e.g. 5-methylbenzoxathiol-2-one or 5-nonylbenzoxathiol-2- one of formula II) as an active ingredient. The benzoxathiol compound of formula I can simply be synthesized by heating a corresponding substituted phenol compound together with a thiocyanate salt with stirring. Damages caused by the adhesion and propagation of pests in sea water or industrial water systems can be prevented with the control agent over a long period of time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater pest control agent for the purpose of preventing damages caused by the attachment and reproduction of pests in seawater or industrial water systems, and more specifically, ships, fish nets, buoys, and seawater inducers. The present invention relates to an underwater pest control agent used for preventing adhesion of underwater pests on the surface of underwater structures such as pipes.

[0002]

2. Description of the Related Art Underwater structures such as ships, harbor facilities, buoys, pipelines, bridges, offshore oilfield drilling facilities, waterway pipes of power plants or coastal plants, fishnets and rafts for aquaculture use barnacles, mussels. , Large adherent flora and fauna such as sea lettuce, and microscopic organisms such as diatoms and bacteria adhere,
Damages such as corrosion of structures, increase of seawater friction resistance of ships, large amount of hay death of seafood due to clogging of fishnets, sedimentation due to increase in weight and reduction of work efficiency will occur. In addition, in industrial water systems such as cooling water that uses natural water such as river water and lake water, and circulation type cooling devices that use medium and tap water, bacteria, diatoms, cyanobacteria, and red-green algae grow abnormally Cause deterioration of cooling efficiency and deterioration of cooling efficiency due to adhesion to the vessel wall, blockage of water pipe, decrease in flow rate, etc.

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 polymerization. It is practiced to use an antifouling agent containing an organometallic compound such as a product.

[0004]

However, these conventionally used compounds are extremely toxic and require special care in handling, and also cause malformation due to accumulation in fish bodies and environmental pollution. Therefore, it has been demanded to use an antifouling agent containing neither heavy metal nor organic metal.

Alkylphenols (Japanese Patent Laid-Open No. 3-183030) are used as antifouling agents containing neither heavy metals nor organic metals.
No. 2) or dichloro-N-phenylmaleimides (Japanese Examined Patent Publication No. 24242/1990), but these compounds are not sufficient in their effects, and in a short period of time. At present, it is not practical because the effect is lost.

Therefore, the object of the present invention is that there are no problems in terms of safety and health and the environment, that is, toxicity and persistence are low, and there is no adverse effect on the ecosystem and working environment.
Moreover, it is to provide an aquatic pest control agent capable of exerting its effect for a long period of time.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to achieve the above object, an aquatic pesticide containing a benzoxathiol compound achieves the above object. I found a thing.

That is, the present invention provides a pest in water containing one or more compounds represented by the general formula (I) of the following [Chemical formula 2] (the same as [Chemical formula 1]) as an active ingredient. A control agent is provided.

[0009]

[Chemical 2]

Hereinafter, the aquatic pest control agent of the present invention having the above-mentioned gist will be described in more detail.

In the above general formula (I) representing the benzoxathiol compound used in the aquatic pest control agent of the present invention, the halogen atom represented by R _{1 to} R ₄ is chlorine, bromine, fluorine or iodine. Examples of the alkyl group represented by R _{1 to} R ₄ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, heptyl, octyl, isooctyl, 2- Examples include linear or branched alkyl groups such as ethylhexyl, tertiary octyl, nonyl, isononyl, tertiary nonyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, and triacontyl. the alkenyl group represented by R ₁ to R ₄ For example, vinyl, allyl, hexenyl, octenyl, decenyl, dodecenyl, etc. octadecenyl and the like. Further, the alkoxy group represented by R ₁ to R _4, be mentioned an alkoxy group derived from the alkyl group, the acyl group represented by R ₁ to R _4, for example, acetyl, propionyl, butyroyl,
Hexanoyl, octanoyl, lauroyl, stearoyl and the like can be mentioned, and examples of the acyloxy group represented by R _{1 to} R ₄ include the acyloxy groups derived from the above acyl groups.

Therefore, examples of the benzoxathiol compound represented by the above general formula (I) used in the aquatic pest control agent of the present invention include 5-methylbenzoxathiol-2-one and 5-nonylbenzo. Oxathiol-2-one, 6-hydroxybenzoxathiol-2
-One, 5,6-dihydroxybenzoxathiol-
2-one, 6-acetylbenzooxathiol-2-one, 6-methoxybenzooxathiol-2-one, 6
-Stearoyloxybenzoxathiol-2-one,
6-chlorobenzooxathiol-2-one, 6-hydroxy-4-methylbenzooxathiol-2-one,
7-Hydroxybenzoxitithiol-2-one and the like can be mentioned.

The benzoxathiol compound represented by the general formula (I) is prepared by converting the corresponding substituted phenol compound into
It can be easily synthesized by heating and stirring with thiocyanate.

Next, specific synthesis examples of the benzooxathiol compound represented by the above general formula (I) will be shown, but the present invention is not limited by the following synthesis examples.

Synthesis Example (Synthesis of 5-nonylbenzooxathiol-2-one)

[0016]

[Chemical 3]

While stirring a mixture of 8.8 g of nonylphenol, 20 g of copper sulfate pentahydrate and 100 ml of water, a 50 ml aqueous solution of 12 g of ammonium thiocyanate was added dropwise over 1 hour at room temperature. After the dropping was completed, the temperature was raised to 50 ° C. and the mixture was stirred for 3 hours. After completion of the reaction, chloroform was added, insoluble matter was filtered and washed with water, and the filtrate was desolvated to obtain 9.1 g of a crude product. Further, a pale yellow oily substance was obtained by subjecting to a silica gel column treatment using n-hexane as a developing solvent.
2 g was obtained.

As a result of infrared spectroscopic analysis (IR) and nuclear magnetic resonance analysis (NMR), the obtained reaction product (the above pale yellow oily matter) has the following characteristic absorption and is a desired product. It was confirmed.

IR (film): 2952 cm ^-1 , 2924 cm ^-1 , 2866 cm ^-1 , 1758
^{cm -1, 1472cm -1, 1240cm -1} , 1009cm -1, 8
15 cm ^-1 NMR (CDCl ₃ , ppm): 7.5-6.7 3H 2.0-0.4 19H

The present invention relates to an aquatic pesticide containing one or more benzoxathiol compounds represented by the above general formula (I) as an active ingredient, which is conventionally used. One type or two or more types of soiling agents can be used in combination, and in that case, depending on the type of the controlling agent used in combination, a longer-term effect can be achieved.

In the aquatic pest control agent of the present invention, examples of the antifouling agent which can be used in combination with the compound represented by the general formula (I) are, for example, tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetra. -N-propyl thiuram disulfide, tetraisopropyl thiuram disulfide, tetra-n-butyl thiuram disulfide, tetraisoptyl thiuram disulfide, N, N'-ethylenebisthiocarbamoyl sulfide, N, N'-propylenebisthiocarbamoyl sulfide Thiuram-based compounds such as sulfide and N, N'-butylene bisthiocarbamoyl sulfide; copper-based metal powders such as copper powder and copper-nickel alloy powder; cuprous oxide, cuprous thiocyanate, basic copper carbonate, pyrroline Acid copper, copper naphthenate, abieti Copper, copper compounds such as copper oxyquinoline; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, ethylphenyl dithiocarbamate, zinc,
Zinc ethylenebisdithiocarbamate, zinc propylenebisdithiocarbamate, zinc bis (dimethyldithiocarbamoyl) zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, etc. Dithiocarbamate compound; 2
-(4-thiazolyl) benzimidazole, methyl-1
-(Ω-cyanopentylcarbamoyl) -2-benzimidazole, 2-mercaptobenzimidazole zinc,
Benzimidazole compounds such as 2-thiocyanomethylthiobenzimidazole; 2-mercaptobenzothiazole, 2- (thiocyanomethylthio) benzothiazol
2, 2- (thiocyanomethylsulfonyl) benzothiazole, 2-thiocyanoethylthio-4-chlorobenzothiazole, 2-thiocyanopropylthio-5,7-dichlorobenzothiazole, 2-thio Cyanomethylthio-
Benzothiazole compounds such as 4,5,6,7-tetrachlorobenzothiazole; Nitrile compounds such as tetrachloroisophthalonitrile and 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile 4,5
-Dichloro-2-n-octyl-4-isothiazoline-
3-one, 2-n-octyl-4-isothiazoline-3
-One, isothiazoline compounds such as 1,2-benzisothiazolin-3-one; 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolanyl-2-methyl 1-1H-1 , 2,4-triazole,
4,4-dimethyl-2- (1,2,4-triazole-
1-yl) -1- (4-trifluoromethyl-2-chlorophenyl) -1-penten-2-ol and other triazole compounds; 2,3,5,6-tetrachloro-4-
Pyridine compounds such as (methylsulfonyl) pyridine, 2,3,6-trichloro-4-propylsulfonylpyridine and 2,6-dichloro-3,5-dicyano-4-phenylpyridine; 2,4-dichloro-6- ( α-chloroanilino) -s-triazine, 2-chloro-4-methylamino-6-isopropylamino-s-triazine, 2-
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 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-
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-
Tetrachloroethylthiotetrahydrophthalimide, N
-Trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, N, N-dimethyl-
N'-phenyl-N '-(fluorodichloromethylthio) sulfurylamide, trichloromethylthiomethanesulfone-p-chloroanilide, N- (1,1,2,2,2)
-Tetrachloro-2-fluoroethylthio) methanesulfonanilide, N-fluorodichloromethylthio-N-
N- such as 3-chlorophenyl-N'-dimethylurea, N-fluorodichloromethylthio-N-3,4-dichlorophenyl-N'-methylurea and 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-trichlorophenyl) maleimide, N
Maleimide compounds such as -4-tolylmaleimide and N-2,4-xylylmaleimide; 3,5-dimethyl-tetrahydro-1,3,5,2 (H) -thiadiazine-2
-One, 3,3'-ethylenebis (tetrahydro-4,
6-Dimethyl-2H-1,3,5-thiadiazine-2-
On, 3,5-dimethyl-2-thiotetrahydro-1,
Thiadiazine-based compounds such as 3,5-thiadiazine, 3,5-dibenzyltetrahydro-1,3,5-thiadiazine-2-thione; methyl thiocyanate, chloromethyl thiocyanate, ethyl thiocyanate, methylenebisthiocyanate, chloromethylene. A thiocyan compound such as bisthiocyanate, ethylene bisthiocyanate, chloroethylene bisthiocyanate, isobornyl thiocyanate, methyl isothiocyanate, allyl isothiocyanate, phenyl isothiocyanate, benzyl isothiocyanate; caprylphenol, nonylphenol, etc. Alkylphenol compounds of

The aquatic pest control agent of the present invention is a high concentration solution of the benzoxathiol compound represented by the above general formula (I), for example, a solution of about 80% by weight, and a fish net or the like is dipped and applied thereto. Alternatively, it can be incorporated into a paint and applied as antifouling paint to ships, underwater structures and the like. When the aquatic pesticide of the present invention is used as a coating composition or an antifouling solution for fishnets, the amount of the benzoxathiol compound in the coating composition or the antifouling agent for fishnets is usually preferably 0.5-90% by weight,
More preferably, it is 5 to 80% by weight, and is appropriately selected in consideration of the purpose of use, antifouling period and the like.

The components (components other than the above-mentioned benzoxathiol compound) used for preparing the above-mentioned coating composition or antifouling liquid are not particularly limited, and conventionally, these coatings or antifouling liquids are prepared. The components used for this purpose can be used as they are. For example, as a resin vehicle 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,
Polyamide resin, petroleum resin, silicone resin, silicone rubber resin, wax, paraffin, rosin ester, rosin resin and the like can be used alone or in combination, and as a resin vehicle used as an aqueous paint, Acrylic emulsion resin, epoxy emulsion resin, vinyl acetate resin and the like can be used.

Further, a known antifouling agent may be added to the coating composition or the antifouling agent solution together with a benzoxathiol compound represented by the general formula (I) as an antifouling agent. It is possible, and in addition to this, a plasticizer, a coloring pigment, a filler, a solvent and the like which are usually used can be contained in an arbitrary ratio.

[0025]

[Examples] Hereinafter, the aquatic pest control agent of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 Chlorinated rubber having a chlorine content of 65% (CR-2 manufactured by Asahi Denka Kogyo Co., Ltd.
20 parts by weight of a sample compound (see [Table 1]) was added to 100 parts by weight of a 30% xylene solution of 0), thoroughly stirred, and then coated on a hard vinyl chloride plate, dried for 24 hours, and tested. It was a piece.

These test pieces were dipped at a depth of 1 m in the sea with a test raft installed offshore in Yokosuka City, Kanagawa Prefecture, and the degree of fouling by adherent organisms was observed over time, and the ratio of adhered area to painted area was measured. Was measured. The measurement results were evaluated according to the following [evaluation criteria] in four levels. The results are shown in [Table 1] below.
Shown in. [Evaluation Criteria] A: No adhesion is observed. B: Adhesion was recognized in the area of 50% or less. C: Adhesion was observed on 50% or more of the portion. D: It adhered to the entire surface and the coated surface was completely covered.

[0028]

[Table 1]

Example 2 [Composition] wt% Sample compound (see [Table 2]) 10 Acrylic resin (50% xylene solution) ^{* 1} 20 Chlorinated paraffin ^{* 2} 1 Xylene 69 * 1: Nitto Kasei Co., Ltd. NT-100 * 2: Adeka Sizer E-430 manufactured by Asahi Denka Co., Ltd.

The above-mentioned [composition] was thoroughly mixed with a high-speed homomixer to prepare an antifouling agent for fishnets. A polyethylene test net (no knot 6
A 0-twist node (20 cm × 30 cm) was subjected to a dyeing net by dipping, air-dried for 2 days, and then the degree of fouling by attached organisms was examined in the same manner as in Example 1. The results are shown in [Table 2] below.
Shown in.

[0031]

[Table 2]

From the results shown in the above [Table 1] and [Table 2], when cuprous oxide is used as a pest control agent in water, the effect is lost in a short period of time, whereas the above benzo When the oxathiol compound is used, it is clear that the effect lasts for a long time. In addition, the above-mentioned benzoxathiol compound is considered to have no properties such as toxicity and teratogenicity that adversely affect the ecosystem. It is clear that it is extremely useful as a biocontrol agent.

[0033]

INDUSTRIAL APPLICABILITY The agent for controlling aquatic pests of the present invention has no problems in terms of safety and hygiene and environment, that is, has low toxicity and persistence, and does not adversely affect the ecosystem and working environment. , That effect can be exerted for a long period of time.

Claims (1)

[Claims] 1. An aquatic pest control agent containing, as an active ingredient, one or more compounds represented by the following general formula (I) represented by the general formula (I):