JPS6129923B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to a sea breath-fouling organism control agent mainly containing mussels. More specifically, _this invention relates to the general formula: Contains as an active ingredient one or more compounds represented by a phenyl group or a benzyl group optionally substituted with a substituent selected from alkoxycarbonyl groups, and X represents an iodine or bromine atom. The present invention relates to an agent for controlling sea-breath organisms mainly composed of mussels, which is characterized by: In factories such as thermal power plants and steel mills that use seawater, sea-breeding organisms such as mussels, barnacles, hydrophiles, and bryozoans adhere to the cooling water systems, reducing their functionality. Among them, purple mussels adhere to each other in layers and grow at a fast rate. For this reason, the mussels attached to the lowest layer cannot take in sufficient nutrients and dissolved oxygen and die. As the mussels die, the byssus threads attached to the wall become weaker and fall off due to water pressure and water flow, causing blockages in the cooling tubes, preventing the passage of seawater and reducing their functionality. In addition, aquaculture nets, ropes, and other fixed nets used in aquaculture fisheries such as yellowtail, which have become popular in recent years, are kept underwater for long periods of time, so sea breath organisms such as mussels adhere to them, and these can cause various problems. suffer from a disability. For example, bryozoans, barnacles, sea squirts, silica algae, etc. adhere to these nets and ropes, but if a large amount of mussels, which grow rapidly among them, attaches in large quantities, a considerable amount of weight will be placed on the aquaculture nets, causing problems. In addition, the adhesion of these substances obstructs the flow of seawater and causes a lack of dissolved oxygen in farmed fish. Therefore, it has become an important problem to prevent these organisms from adhering to fishing nets and the like. This invention was made as a result of various studies and screenings in order to solve these problems. It was found that the adhesion of larvae and their growth were significantly suppressed. That is, by adding it to a seawater cooling system, damage caused by attached organisms can be prevented, and by immersing or coating fishing nets in this chemical solution, the purpose can be fully achieved. It is known from Japanese Patent Publication No. 41-19077 and Japanese Patent Application Publication No. 49-26419 that this type of compound is active against fungicides for industrial raw materials and products and against pathogenic bacteria for agricultural chemicals. Its living functions are also significantly different from those of mussels, etc., and, as far as the present inventors know, there is no known physiological effect on mussels or their larvae. The compound of the above general formula is Agr.Biol.Chem [Vol.
27.No.2.150-151, 1963] and Special Publication Show 39-19791
It can be made by the method described in et al. Specific examples of compounds used in this invention include pentachlorophenyl-γ-iodopropargyl ether, 2,3,4,6-tetrachlorophenyl-γ-
Iodopropargyl ether, 2,4,6-trichlorophenyl-γ-iodopropargyl ether, 2,4,5-trichlorophenyl-γ-iodopropargyl ether, 2,4,6-tribromophenyl-γ-iodopropargyl Ether, 2,6-dichlorophenyl-γ-iodopropargyl ether, 3,5-dichlorophenyl-γ-iodopropargyl ether, 3,4-dichlorophenyl-γ-iodopropargyl ether, 2,4-dichlorophenyl enyl-γ-iodopropargyl ether, 4-chlorophenyl-γ-iodopropargyl ether, 4-bromphenyl-γ-iodopropargyl ether, 4-iodophenyl-γ-iodopropargyl ether, 4-nitrophenyl-γ-iodopropargyl ether, 2- Chlorophenyl-γ-iodopropargyl ether, 3-methyl-4-chlorophenyl-γ-iodopropargyl ether, 4-carboxyphenyl-γ-iodopropargyl ether, 2-nitro-4-methylphenyl-γ-iodopropargyl ether, 4- Carbamoyl phenyl-γ-iodopropargyl ether, 2-methylphenyl-γ-iodopropargyl ether, 4-methylphenyl-γ-iodopropargyl ether, 4-chlorobenzyl-γ-iodopropargyl ether, 3,4-dichlorobenzyl-γ- Iodopropargyl ether, 2-methylbenzyl-γ-iodopropargyl ether, 3-methylbenzyl-γ-iodopropargyl ether, 4-nitrobenzyl-γ-iodopropargyl ether, 4-acetylaminophenyl-γ-iodopropargyl ether, 4-dichloroacetylaminophenyl-γ-iodopropargyl ether, 2-methyl-4,6-dichlorophenyl-γ-
Iodopropargyl ether, 4-fluorophenyl-γ-iodopropargyl ether, 4-acetylphenyl-γ-iodopropargyl ether, 4-methoxycarbonylphenyl-γ-iodopropargyl ether, 4-cyanophenyl-γ-iodopropargyl ether , 4-propargyloxyphenyl-γ-iodopropargyl ether, pentachlorophenyl-γ-bromopropargyl ether, 4-bromophenyl-γ-bromopropargyl ether, 2,4,5-trichlorophenyl-γ-bromopropargyl ether, Examples include 4-chlorophenyl-γ-bromopropargyl ether, 2,4-dichlorophenyl-γ-bromopropargyl ether, and the like. The amount of the compound according to the present invention added to the seawater cooling water system is generally 0.01 to 5 ppm relative to the seawater flow rate.
You can inject it for 1 to 24 hours a day. The amount added will vary depending on the type of compound, as it will have stronger or weaker physiological activity against mussels and the like. In addition, it is desirable to increase the amount if the amount of mussels etc. is particularly large. In addition, when using the above compound in a seawater cooling water system, use an appropriate solvent,
Preferably, it is dissolved or emulsified and suspended in an organic solvent such as water, alcohol, acetone, xylene, dimethylformamide, methyl cellosolve, etc., and a surfactant is added as necessary to form a formulation. The surfactants used in this case are higher fatty acid salts,
Examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene polyoxypropylenes, alkyltrimethylammonium salts, and alkylbetaines. When used for fishing nets, the compound of the present invention should be mixed with a natural resin, oil-based synthetic resin, or synthetic rubber vehicle, plasticizer, or solvent, or a colored pigment should be added and dissolved, dispersed, or sufficiently kneaded. use The natural resins, oil-based synthetic resins, or synthetic rubber vehicles mentioned here include rosin, boiled oil, chlorinated rubber, alkyd resins, vinyl resins such as vinyl chloride and vinyl acetate, acrylic resins,
Examples include polyolefin resins such as polybutene, polystyrene, various synthetic rubbers, polyurethane resins, epoxy resins, unsaturated polyester resins, phenol resins, and coal tar. The agent for controlling sea-breath-fouling organisms of the present invention may be used in combination with a sea-breath-fouling-fouling agent that can be used in the field; for example, it may be used in combination with a drug that is highly effective against sea-breath-fouling organisms such as barnacles. Good too. Examples of sea breath insect control agents other than the active ingredients of this invention include tri-substituted tin compounds such as triphenyltin cloide and tributyltin oxide, organic acid copper such as copper naphthenate and copper oleate, dithiocarbamate, and tetramethyl Examples include dithiocarbamate compounds such as thiuram disulfide. Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Example 1 Examples of the compounds used in the following tests and their properties are shown in Table 1.

【table】

[Table] 5 parts of the compounds listed in Table 1 were formulated with 90 parts of dimethylformamide and 5 parts of polyethylene glycol fatty acid ester, and diluted with seawater to prepare a test solution. Next, 20 to 30 mussel larvae collected from seawater using a plankton net were placed in a 60 mm x 100 mm high walled glass tube with NXX-10 Müller gauze attached, and each concentration of each compound was determined. 50% of each compound was immersed in the test solution for 8 hours, and then reared for 48 hours in a running clear sea water tank.The number of live and dead larvae was counted under a microscope.
The results of determining the lethal concentration are shown in Table 2.

[Table] Example 2 Using a test plant in which a test net was inserted into a PVC pipe with an inner diameter of 100 mm and a length of 2 m, seawater was passed in a one-shot manner for 30 days during the mussel attachment period (water flow rate approximately 5 tons/hour). ), each drug was injected using a chemical pump, and the amount of attached organisms (mussaki mussels, barnacles, water bugs, and bryozoans) was compared with a blank. The results are shown in Table 3.

[Table] As shown in Table 3, the addition of the drug according to the present invention suppressed the growth of each type of sea breath adhering organisms and also reduced the number of adhering organisms. Example 3 Two formulations were prepared and tested for effectiveness as antifouling agents for fish nets.

【table】

[Table] Rolide
xylene 60%
xylene 71%
Cremona net (manufactured by Kuraray) 50cm x above antifouling chemical solution
A 50cm piece was immersed for 30 minutes, pulled out and air-dried in the shade for 1 day, then immersed again in the antifouling chemical solution for 30 minutes.
Air dry in the sun, shade, and dry during the mussel attachment period.
Table 4 shows the results of investigating the state of adhesion by immersing the sample at a depth of 1 m below the sea surface for several months.

[Table] In the table, 〓, 〓, +, - indicate the degree of mussel attachment. 〓: Significant adhesion. 〓: Cannot be used for aquaculture due to adhesion. +: Slight adhesion and can be used for aquaculture. −: No adhesion.

Claims (1)

[Claims] ₁ General formula:
represents a phenyl group optionally substituted with a substituent selected from an acylamino group and an alkoxycarbonyl group, and X represents an iodine or bromine atom)
An agent for controlling sea-breath organisms mainly composed of mussels, characterized by containing one or more of the compounds represented by the following as an active ingredient. 2. The sea breath-fouling organism control agent according to claim 1, wherein the halogen atom in R is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. 3. The sea breath-fouling organism control agent according to claim 1, wherein the lower alkyl group in R is a methyl group. 4. The sea breath-fouling organism control agent according to claim 1, wherein the acyl group in R is an acetyl group. 5. The sea breath insect control agent according to claim 1, wherein the acylamino group in R is an acetylamino group. 6. The sea breath-fouling organism control agent according to claim 1, wherein the alkoxycarbonyl group in R is a methoxycarbonyl group. 7 The compounds contained as active ingredients are 4-bromphenyl-γ-iodopropargyl ether, 2,4-dichlorophenyl-γ-iodopropargyl ether, 2,4,5-trichlorophenyl-γ-iodopropargyl ether, penta Chlorophenyl-γ-iodopropargyl ether, 4-nitrophenyl-γ-iodopropargyl ether, 4-acetylphenyl-γ-iodopropargyl ether, 4-chlorophenyl-γ-iodopropargyl ether, 2,4-dichlorophenyl-γ -Iodopropargyl ether, 4-carboxyphenyl-γ-iodopropargyl ether, 4-cyanophenyl-γ-iodopropargyl ether, 2-nitro-4-methylphenyl-γ-iodopropargyl ether, 4-iodophenyl-γ-iodopropargyl ether , 4-fluorophenyl-γ-iodopropargyl ether, 4-acetylaminophenyl-γ-iodopropargyl ether, or 4-methoxycarbonylphenyl-γ-bromopropargyl ether. Breath-fouling biological control agent.