JPS6239125B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition for preventing aquatic biofouling. More specifically, this invention has the general formula (): [In the formula, R is an alkyl group having 1 to 4 carbon atoms, X is a halogen atom,

[Formula] (R' means an alkyl group or vinyl group having 1 to 12 carbon atoms), a lower dialkyldithiocarbamate group,
and

[Formula] (R means a group selected from the group consisting of 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. In addition, the attachment of organisms such as mussels to underwater structures causes a decrease in the speed of ships and a decrease in the amount of water flowing in seawater intake channels, causing them to become docked or stop operating at regular intervals. deposits must be removed. 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 ovoviparous and oviparous species. Both lead a planktonic life for a certain 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, which is highly resistant to invasion by foreign objects and attacks by other organisms, and once drilled into the wood. And it is not easy to exterminate. Conventionally, organic tin compounds have been widely used as so-called antifouling agents to protect against contamination caused by adhesion of such aquatic organisms. However, recently, problems of environmental pollution have been arising regarding these compounds. In other words, for example, tributyltin oxide and triphenyltin chloride, which have been conventionally used in ship bottom paints, can cause the death of sea-breathing organisms or be fatal if they come into contact with these chemical solutions. Furthermore, when these chemical solutions are actually used, they can also be toxic to adult shellfish and fish, which are not originally intended to be affected. Of course, it is known that among organic tin compounds, trialkyltin compounds are decomposed by ultraviolet rays into trialkyl forms, dialkyl forms, monoalkyl forms, and then inorganic tin and become non-toxic. There is a problem in that it exerts the above-mentioned toxicity on organisms other than those targeted for adhesion prevention. In order to solve the above problems, the inventors of this invention conducted intensive research and found that the compound represented by the above general formula () decomposes particularly quickly when exposed to ultraviolet rays, and the toxicity of the decomposition products is very low. They also discovered that it has a paralyzing effect on aquatic organisms at very low concentrations, and that there is a large difference between the concentration that causes paralysis and the concentration that is lethal. By using it at a safe concentration lower than the harmful lethal concentration, we succeeded in preventing the adhesion of aquatic organisms without polluting the environment, and thus arrived at this invention. The compound of this invention is known as an insecticide/bactericide and herbicide in JP-A-49-132038, but it is not known to have any effect on aquatic organisms such as mussels and sea breams, and especially on aquatic organisms. The paralytic effect at low concentrations and the large difference between the paralytic concentration and the lethal concentration are unexpected effects discovered for the first time by the inventors of the present invention. In the definition of the compound of general formula () which is the active ingredient of this invention, X means the following group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom and a bromine atom being preferred.

In the group represented by the formula, R' means an alkyl group having 1 to 12 carbon atoms or a vinyl group. As a lower dialkyldithiocarbamate group, sub-formula (b): R″ and R are the same or different alkyl groups having 1 to 6 carbon atoms, or phenyl groups. Preferably R″ and R
are both methyl groups.

In the group represented by the formula, R means an alkyl group having 1 to 4 carbon atoms. Specific examples of preferred compounds used as active ingredients in the composition for preventing aquatic biofouling of the present invention include di-n-octylmethyltin chloride, di-n-octylmethyltin chloride, di-n-octylmethyltin chloride,
n-octylmethyltin acetate, di-n-octylmethyltin dimethyldithiocarbamate,
Di-n-octylmethyltin bromide, di-n-
Octylmethyltin laurate, di-n-octylmethyltin acrylate, di-n-octylethyltin chloride, di-n-octyl-n-propyltin chloride, di-n-octylisopropyltin chloride, di-n-octyl -n-butyltin chloride, di-n-octylisobutyltin chloride, di-n-octyl-secbutyltin chloride, di-n-octyl-tert-butyltin chloride, di-2-ethylhexylmethyltin chloride, and the like. Regarding the production of compounds in which X is a halogen atom among the compounds of the general formula (),
Reference is made to the method described in 132038. Typical compounds used in this invention and their properties are listed in Table 1.

【table】

[Table] Thus, the present invention provides a composition suitable for use in various forms such as liquid, gel, and paste, containing the compound of 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. can be prevented. 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,
Dissolved or emulsified in an appropriate solvent, water, alcohol, acetone, xylene, dimethylformamide, methyl cellosolve, or other organic solvent to ensure uniform dispersion in seawater, and add a surfactant as necessary to form a formulation. 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 compound according to the present invention added to the seawater cooling water system is generally 0.001 to
0.5ppm can be injected 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. It is also desirable to increase the amount if there is a particularly large amount of mussels, etc. When used as a paint for underwater structures, a ship bottom paint, or a coating agent for fishing nets, the compound of the present invention may be mixed with a natural resin, an oil-based synthetic resin vehicle, a synthetic rubber vehicle, a plasticizer, or a solvent. Alternatively, a colored pigment may be added and dissolved, dispersed or thoroughly kneaded before 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, polyolefin resins such as polybutene, and polystyrene. , various synthetic rubbers, polyurethane resins, epoxy resins, unsaturated polyester resins, phenol resins, coal tar, 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. Examples of polymeric substances that can form gels include natural hydrophilic polymeric substances such as gelatin, glue, starch, carboxymethylcellulose, and agar, as well as poly(meth)acrylic acid, acrylic acid-maleic acid copolymers, and acrylic acid-acrylamide. Polyacrylic acid polymers such as polymers or salts thereof, and synthetic polymer substances such as polyvinyl alcohol and polyethylene oxide are used. A formulation containing mainly natural polymeric substances provides a preferable gel-like preparation that is non-sticky and elastic. Examples of organic solvents include methanol, acetone, xylene, kerosene, dimethylformamide, methyl cellosolve, and ethylene glycol. Examples of the surfactant used here include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene polyoxypropylenes, alkyltrimethylammonium salts, alkylbetaines, and the like. Furthermore, in order to reinforce the gel body, cotton, or rather organic fibers such as wood fibers, or inorganic fibers such as glass fibers and asbestos, may be mixed. Additionally, color pigments and the like may be added as appropriate. By making the above formulation, when suspended in seawater, the active ingredient will elute from the gel body.
A concentration of 0.001 to 0.5 ppm can be maintained at all times, and adhesion of sea bream beetles can be effectively prevented. 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 optionally a color pigment are added, and a solution is used which is dissolved, dispersed, emulsified, or thoroughly kneaded. The natural resin, oil-based synthetic resin, or synthetic rubber vehicle mentioned here includes those disclosed in the above-mentioned paint or coating agent. The organic tin compound as the active ingredient of this invention may be used in combination with an effective control agent that can be used in the field, for example, an agent that is highly effective against sea-breath organisms such as barnacles. . Examples of sea breath insect control agents other than the active ingredient of the present invention include copper naphthenate, organic acid copper such as copper oleate, dithiocarbamate salts, and dithiocarbamate compounds such as tetramethylthiuram disulfide. . Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Compound numbers in the following examples are from Table 1. Example 1 In order to determine the rate of decomposition of the compound of the present invention by ultraviolet rays, the following test was conducted. The test method was conducted in accordance with the Research Report of the Institute of Public Health, Vol. 19, No. 3 (1970) and the same journal, Vol. 20, No. 1 (1971). That is, 30 mg of each compound was placed in a watch glass and placed under an ultraviolet lamp, and every 4 hours, a certain amount of tetrahydrofuran was added to dissolve it, and the certain amount was spotted on a thin layer chroma plate and benzene-acetone-acetic acid ( 20:2:1), and color was developed using a 0.1% dithizone acetone solution. Table 2 shows the results of determining the time required for the trialkyl compound to become undetectable.

[Table] Example 2 The following test was conducted to examine the paralysis effect and toxicity level on mussel larvae. That is, 5 parts of each compound was formulated with 90 parts of ethanol 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 thick-walled glass tube with a diameter of 60 mm and a height of 100 mm, and NXX-10 Mueller gauze was attached to the tube. The specimens were immersed in a test solution of the same concentration for 3 hours, and the lowest concentration at which all individuals did not swim in the solution was determined under a microscope.
After that, the larvae were reared for 48 hours in a running aquarium of fresh sea water, and the toxicity to the larvae was determined by counting the number of surviving larvae and the number of dead larvae under a microscope, and the results were determined as a 50% lethal concentration, as shown in Table 3.

【table】

[Table] Example 3 In order to investigate the paralyzing effect and degree of toxicity on the larvae of the funaku beetles collected from the aquarium for breeding them using a plankton net, the complete minimum paralyzing concentration of each compound was determined using the same test solution and test method as in Example 2. The results of determining the 50% lethal concentration are shown in Table 4.

【table】

[Table] Example 4 The following test was conducted to examine the degree of toxicity to adult shellfish. 5 parts of each compound was formulated with 90 parts of ethanol and 5 parts of polyethylene glycol fatty acid ester and diluted with seawater to prepare a test solution. Next, we collected adult clams from the sea (shell length: approx. 25 mm).
mm) 10 individuals were brought into contact with the test solution of each concentration of each compound for 8 hours, and then reared in flowing fresh seawater for 96 hours, the number of surviving and dead individuals was counted, and the toxicity of each compound was determined by The results obtained as % lethal concentration are shown in Table 5.

【table】

[Table] Example 5 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 was 3 tons/hour each). ), 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 6.

[Table] - indicates no adhesion. + indicates the degree of adhesion.
Example 6 Next, a formulation example for use as an antifouling agent for fishing nets is as follows. Formulation example 1 Compound number 4 10% Rosin 10% Chlorinated rubber 5% Xylene 75% Formulation example 2 Compound number 10 8% Dioctyl phthalate 10% Polybutene 10% Copper oleate 5% Xylene 67% The above antifouling agent is used for polyethylene aquaculture. After the net was dip-coated, it was dried and immersed in the sea at a depth of 1.5 m, and the adhesion of fouling organisms was examined. The results are shown in Table 7.

[Table] Example 7 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 perforation by the funaku beetles was examined using X-ray photographs after two months. The results are shown in Table 8.

[Table] Example 8 Next, a formulation example for injecting the compound of the present invention into wood is as follows. Formulation example 1 Compound No. 1 10% Polybutene 5% Rosin 5% Xylene 80% Formulation example 2 Compound No. 4 10% Xylene 90% Formulation example 3 Compound No. 10 10% Copper naphthenate 5% Xylene 85% The above chemical solution was prepared according to JIS-A9301. After injecting it into a piece of wood (30cm x 6cm x 2cm) and soaking it in the sea for one year according to the method of
Observed with line photographs. The effectiveness against bark beetles was visually determined. The results are shown in Table 9.

[Table] Comparative Example By the same test method as in Example 2, the minimum complete paralysis concentration and 50% lethal concentration of monooctyldiethyltin chloride and trioctyltin chloride against mussel larvae were investigated. This result is
Shown in Table 10.

【table】

Claims (1)

[Claims] 1 General formula (): [In the formula, R is an alkyl group having 1 to 4 carbon atoms, X is a halogen atom, [Formula] (R' means an alkyl group or vinyl group having 1 to 12 carbon atoms), lower dialkyldithiocarbamate base,
and [Formula] (R means a group selected from the group consisting of: 2 The lower dialkyldithiocarbamate group in formula () is sub-formula (b): The composition according to claim 1, wherein the composition is a group represented by the following formula: ) are di-n-octylmethyltin chloride, di-n-octylmethyltin acetate, di-n-octylmethyltin dimethyldithiocarbamate, di-n-octylmethyltin bromide, di-n-octylmethyl Tin laurate, di-n-octylmethyltin acrylate, di-n-octylethyltin chloride, di-n-octyl-n-propyltin chloride, di-n-octylisopropyltin chloride, di-n-octyl-n -butyltin chloride, di-n-octylisobutyltin chloride,
The composition according to claim 1, which is di-n-octyl-sec-butyltin chloride, di-n-octyl-tert-butyltin chloride or di-2-ethylhexylmethyltin chloride.