JPS629562B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to an agent for controlling sea breath attached organisms. More specifically, this invention has the general formula (): [In the formula, R means an alkyl group or alkenyl group having 8 to 28 carbon atoms, and R' is

[Formula] or The present invention relates to a sea breath insect control agent containing one or more of the following as an ethylene oxide adduct of a β-hydroxy substituted aliphatic amine or an acid addition salt thereof as an active ingredient. In factories such as thermal power plants and steel mills that use seawater, sea creatures 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. Furthermore, as the aquaculture nets, ropes, and other fixed nets used in the increasingly popular aquaculture fishery for yellowtail and other fish are kept underwater for long periods of time, sea-breath organisms such as mussels attach to them, which can cause various problems. is recieving. For example, bryozoans, barnacles, sea squirts, diatoms, etc. adhere to these nets and ropes, but if a large amount of fast-growing mussels adhere to them, the passage of seawater is obstructed, resulting in a lack of dissolved oxygen for farmed fish. This may also cause nets to sink or be cut, resulting in damage such as loss of farmed fish. Alternatively, the damage caused by sea bream beetles to imported logs stored in seawater storage is severe. Funaku beetles are wood-boring marine organisms, and there are ovoviviparous and oviparous species. Both lead a planktonic life for a period of time before attaching to the wood surface, and then invade the wood by digging a long cone-shaped hole. death,
The only communication with the outside world is through a water pipe protruding from a small hole. When external conditions become unfavorable, the water pipe is withdrawn into the hole, and the hole is closed with a calcareous pallet to protect against intrusion of foreign substances and attacks by other organisms.
It is highly resistant, and once it burrows into wood, it is difficult to exterminate. This time, in order to solve this problem,
It has been found that the ethylene oxide adduct of the β-hydroxy substituted aliphatic amine represented by the above general formula or its acid addition salt significantly inhibits the growth of the above-mentioned sea breath organisms. Ethylene oxide adducts of β-hydroxy-substituted aliphatic amines or their acid addition salts have traditionally been used as surfactants; Its effects are completely unknown. In the definition of the general formula () for the ethylene oxide adduct of β-hydroxy substituted aliphatic amine or the acid addition salt thereof to be contained as an active ingredient in the sea breath insect control agent of this invention, R has 8 to 28 carbon atoms. It is an alkyl group or an alkenyl group, and may be either linear or branched, but a linear one is preferable. Preferred specific examples of ethylene oxide adducts of β-hydroxy-substituted aliphatic amines that can be used in the present invention include β-hydroxy-decylamine, β-hydroxy-dodecylamine,
-Hydroxy-hexadecylamine, β-hydroxy-octadecylamine, β-hydroxy-eicosylamine, β-hydroxy-triacontylamine, β-hydroxy-eicosylenamine, β-hydroxy-hexadecylethylenediamine, β-hydroxy- Examples thereof include octadecylethylenediamine and ethylene oxide adducts of these mixed alkylamines. In this invention, the number of moles of ethylene oxide added is m+n in the general formula () above.
= 1 to 20 and x+y+z = 1 to 20 have an antifouling effect, but preferably when one hydrogen atom is bonded to the nitrogen atom in the chemical formula, an even higher effect is exhibited. Therefore, an ethylene oxide adduct in which either m or n is 0 and the other is 1, or one or both of x, y, and z is 0, and x+y+z is 1 to 2 is preferable. However, in this case, although the compound is poorly soluble in water, it can be used as an acid addition salt. Examples of the acid addition salt of the ethylene oxide adduct of β-hydroxy-substituted aliphatic amine include inorganic or organic acid addition salts of the compound of general formula (). Specifically, the compound of general formula () and hydrochloric acid, nitric acid, nitrous acid, sulfuric acid, phosphoric acid, formic acid, butyric acid,
Examples include addition salts with acetic acid, oleic acid, naphthenic acid, adipic acid, lactic acid or citric acid. It is also possible to use a mixture of compounds in which R has a different number of carbon atoms in the general formula (), ie, an ethylene oxide adduct of β-hydroxy-mixed alkylamine or an acid addition salt thereof. Furthermore, the compounds described above may be used as a mixture of two or more. Thus, the present invention provides a composition suitable for various purposes such as liquid, gel, paste, etc., containing the compound of the general formula () as an active ingredient. For example, by adding it to a seawater cooling system as a solution, it is possible to prevent the above-mentioned problems caused by sea breath-fouling organisms, and as a liquid preparation, fishing nets can be dipped and applied to prevent the adhesion of aquatic organisms. You can prevent this from happening. In addition, as a gel-like preparation with elasticity and flexibility, this can be suspended in water in a lumber yard to gradually elute the active ingredient to prevent wood beetles from attacking the wood, or it can be used as a paste. It can be applied to wood or pressure-injected to prevent the adhesion of sea bream beetles. When using the above compound in a seawater cooling water system,
Dissolve or emulsify and suspend in an appropriate solvent such as water or an organic solvent such as alcohol, acetone, xylene, dimethylformamide, or methyl cellosolve so that it is uniformly dispersed in seawater, and if necessary, add a surfactant to form a formulation. is used. 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. The amount of the ethylene oxide adduct of β-hydroxy substituted aliphatic amine or its acid addition salt according to this invention is generally 0.01 to 3 ppm relative to the flow rate of seawater.
You can inject it for 1 to 24 hours a day. The amount to be added may vary depending on the type of compound, as its physiological activity against sea-breath organisms varies. In addition, if the amount of sea-breath attached organisms is particularly large, it is desirable to increase the amount. When used as a coating agent for fishing nets, etc., the compound of this invention is mixed with a natural resin, a synthetic resin or a synthetic rubber emulsion, a plasticizer, a solvent, a coloring pigment, etc. as appropriate, and then dissolved, dispersed, and kneaded. It is formulated by the following operations. The natural resin, synthetic resin or synthetic rubber emulsion mentioned here includes rosin, boiled oil,
Chlorinated rubber, vinyl resins such as vinyl chloride and vinyl acetate, synthetic resin emulsions such as acrylic resin and ethyl acrylate styrene copolymer resin, methyl acrylate-vinyl acetate copolymer resin, or styrene-butadiene copolymer rubber, Acrylonitrile
Butadiene copolymer rubber, methyl methacrylate
Examples include synthetic rubber emulsions such as butadiene copolymer rubber. Examples of plasticizers include dioctyl phthalate, dibutyl phthalate, tricresyl phosphate, trioctyl phosphate, etc., and examples of solvents used include water, alcohol, xylene, kerosene, methyl isobutyl ketone, dimethyl formamide, and methyl cellosolve. The surfactants used for dispersion or emulsification include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan esters, and polyoxyethylene-polyoxypropylene block copolymers. , alkyl betaines, alkyltrimethylammonium salts, and the like. In addition, when preparing a gel preparation, the gel containing the active ingredient of this invention may be, for example, 3 active ingredients.
~20% by weight, polymeric substance that forms a gel-like substance 5~
The formulation is formulated by containing 20% by weight of a surfactant, 0 to 10% by weight of an organic solvent, and the balance water, or further containing 0 to 10% by weight of a surfactant. Such a gel preparation can be made into any shape and size such as a rod, sphere, or cube, placed in a net, basket, plastic bag or pipe with appropriate holes, and placed in a wood storage area. It can be used by hanging or incorporating it in an appropriate place between rafts and immersing it in seawater. Next, when the compound of the present invention is injected into wood to prevent the attack of sea bream beetles, a solution prepared by dissolving or dispersing the compound of the present invention in a solvent, or a mixture of the compound of the present invention and a natural resin, oily synthetic resin, or synthetic rubber. A vehicle, a plasticizer, a surfactant, a solvent, and, if necessary, a color pigment is added, and a preparation is used which is dissolved, dispersed, emulsified, or thoroughly kneaded. The ethylene oxide adduct of β-hydroxy-substituted aliphatic amine, which is the active ingredient of the present invention, may be used in combination with effective pesticidal agents that can be used in the field, and is highly effective against sea-breath organisms such as barnacles. May be used in combination with drugs. Examples of sea breath insect control agents other than the active ingredients of the present invention include trisubstituted tin compounds, copper naphthenates, organic acid coppers such as copper oleate, dithiocarbamates, and dithiocarbamates such as tetramethylthiuram disulfide. Examples include system compounds. Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Note that in the following, % and parts mean % by weight and parts by weight, respectively. Example 1 A test plant was used in which a test net was inserted into a PVC pipe with an inner diameter of 100 mm and a length of 2 m, and seawater was passed through it for 60 days during the mussel attachment period (water flow rate of 3
Each drug was injected using a chemical pump, and the amount of attached organisms (mussels, barnacles, water bugs, and bryozoans) was compared with a blank. The results are shown in Table 1.

[Table] Example 2 Next, a formulation with the following formulation was prepared as an antifouling agent for fishing nets. Formulation example 1 Addition of β-hydroxy-dotecylamine with 1 mole of 15 parts ethylene oxide Polybutene 5 parts Rosin 20 parts Copper naphthenate 5 parts Xylene 55 parts Formulation example 2 Addition of β-hydroxy-C _16-18 alkyl 15 parts with 1 mole of ethylene oxide Polybutene 10 parts Rosin 5 parts Coumarone resin 5 parts Dioctylphthanate 5 parts Xylene 60 parts Formulation example 3 β-Hydroxy-C _12-14 alkyl 15 parts 2 mole adduct of amine with ethylene oxide Polyoxyethylene fatty acid monoester 2 parts Terpolyoxy Ethylene alkyl ether 2 parts Lurosine 20 parts Polybutene 3 parts Xylene 18 parts Water 40 parts Formulation example 4 β-hydroxy-hexadecyl ethyl 20 parts Ethylene oxide 1 mole adduct of diamine Oleate Rosin 10 parts Vinyl resin 5 parts Butyl acetate 20 parts Toluene 45 parts Formulation example 5 β-Hydroxy-C _16-18 alkyl 15 parts 2 mole adduct of amine with ethylene oxide dioctyl phthalate 2 parts polyoxyethylene sorbitan S 5 parts terpolyoxyethylene nonylphenyl 3 parts ether xylene 20 parts acrylonitrile Butadiene latte 50 parts Tux water 5 parts Polyethylene aquaculture net was immersed in the above five types of antifouling agents, dried, and then at a depth of 1.5 m.
were immersed in the sea to examine the adhesion of fouling organisms. The results are shown in Table 2.

【table】

[Table] Example 3 10 parts of the compound of the present invention, 5 parts of methanol, 1 part of surfactant, and 15 parts of polyacrylamide were mixed, and 69
10kg of the gelatinized material was placed in a plastic basket and hung in a seawater lumber yard during the attaching season for sea bream beetles. In other words, four 4m square rafts are built vertically.
2 rows with 0.5m spacing, and 3 rows with 4m spacing between them.
Hanging the jelly product of the present invention on a book, 1m from the position
The test panel was hung at a distance of 1.5 m and the degree of penetration of the adhesive zone by the sea bream was examined using X-ray photographs two months later, and the results are shown in Table 3.

【table】

[Table] Example 4 A formulation example for injecting the compound of the present invention into wood is as follows. Formulation example 6 β-hydroxy-dodecylamine 10 parts ethylene oxide 1 molar adduct Polybutene 5 parts rosin 3 parts xylene 82 parts Formulation example 7 β-hydroxy-C _16-18 alkyl 10 parts amine 2 molar adduct copper naphthenate 5 parts polybutene 3 parts xylene 82 parts Formulation example 8 β-hydroxy-hexadecyl ethyl 10 parts ethylene oxide 1 mole adduct of diamine Acetic acid 5 parts Butylcellosolve 20 parts Copper acetate 5 parts Water 60 parts The above chemical solution was processed according to JIS-A9301 method. After injecting it into a piece of wood (30 cm x 6 cm x 2 cm) and immersing it in the sea for one year, the effectiveness against sea bream beetles was determined to be X.
Observed with line photographs. The effectiveness against bark beetles was visually determined. The results are shown in Table 4.

[Comparative example]

Using a test plant with a test net installed in a vinyl chloride pipe with an inner diameter of 100 mm and a length of 2 m, seawater was passed in a one-time flow (water flow rate of 3 tons/hour each) for 60 days during the attachment period of mussels and barnacles. , each drug is injected with a chemical pump, and the attached organisms (mussels, barnacles, hydroids,
The amount of bryozoan (bryozoa) was compared to a blank and a comparison compound. The results are shown in Table 5.

【table】

【table】

Claims (1)

[Claims] 1 General formula (): [In the formula, R means an alkyl group or alkenyl group having 8 to 28 carbon atoms, and R' is [Formula] or A sea breath insect control agent containing one or more of the following as an ethylene oxide adduct of a β-hydroxy substituted aliphatic amine or an acid addition salt thereof as an active ingredient.