JPS62195308A - Agent for controlling aquatic adhesive life - Google Patents

Abstract

PURPOSE:To provide an agent for controlling aquatic adhesive life such as hard-shelled mussel, barnacle, laveer, diatom, etc., containing 3,4,5,6- tetrachloropyridazine as an active component, effective in preventing the adhesion and suppressing the growth of the aquatic life and capable of keeping the effect over a long period. CONSTITUTION:The objective agent contains 3,4,5,6-tetrachloropyridazine of formula as an active component. The compound can be produced by reacting dichloromaleic anhydride with hydrazine and chlorinating the resultant 4,5- dichloropyridazine-,6-dione with phosphorus oxychloride. In the case of using the composition for the treatment of fishing net, rope, fixed net, etc., the compound is dissolved or dispersed together with a resin (vehicle) in an organic solvent, a plasticiser and an organic pigment, etc., are added to the solution or dispersion and the net, etc., is immersed in or sprayed with the solution, etc., and dried. For using the composition as an antifouling paint for ship bottom, the compound is added to and dispersed in a resin composition for ship bottom paint and the dispersion is applied to ship bottom.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an aquatic sessile organism control agent [hereinafter referred to as the composition of the present invention] characterized by containing 3,4,5,6-tetrachloropyridazine represented by the formula as an active ingredient. write down ].

Various marine organisms adhere to vessels and structures that are immersed in seawater for long periods of time, such as fishing nets, ships, industrial cooling water channels, and buoys, causing great damage and loss.

In other words, nets, ropes, and fixed nets for cultivating sea bream, yellowtail, etc., which have become popular in recent years, are immersed in seawater for long periods of time, so they can be used to fish for marine animals such as fujibo, bryozoans, sea squirts, mussels, and serpula. The adhesion of plants such as sea lettuce, blue seaweed, and diatoms is significant, which blocks the mesh and obstructs the flow of the tide, resulting in poor growth and disease in aquaculture fish in aquaculture nets, and in fixed nets, the adhesion causes a load and reduces durability. This has caused damage such as a decrease in the amount of fish caught.

In addition, in ships, animal or plant-based aquatic fouling organisms adhere to and propagate on the bottom of the ship, resulting in major damage such as a reduction in the sailing speed of the ship and an increase in fuel costs.

In addition, condensers and heat exchangers for industrial cooling water at power plants, steel mills, and other factories are also severely damaged by marine organisms such as mussels and snails, resulting in blockage of cooling tinibs, etc.
Damage has occurred, including obstruction of seawater flow and a significant decline in its functionality.

Therefore, various measures have been attempted to prevent the adhesion of these marine organisms, but at present no satisfactory results have been obtained.

As a result of various studies to solve such problems, the present inventors found that 3,4.5.6-tetrachloropyridazine is
It has been discovered that it exhibits excellent control effects such as excellent anti-fouling and anti-algae properties against these marine organisms, leading to the present invention.

3,4.5.6-Tetrachloropyridazine is obtained by chlorinating 4,5-dichloropyridazine-3,6-dione obtained by reacting dichloromaleic anhydride with hydrazine with phosphorus oxychloride, Although it is stated in U.S. Patent No. 2,846,433 that it is active against weeds, insects, molds, bacteria, etc., there is no mention of its controlling effect on marine sessile organisms such as barnacles, mussels, and bryozoans. .

, the composition of the present invention is suitable for aquatic sessile organisms such as Fujibbo,
Marine animals such as bryozoans, sea squirts, serpula, and mussels, and marine plants such as sea lettuce, blue seaweed, and diatoms, etc.
It exhibits adhesion prevention and growth suppressing effects when it adheres to industrial cooling water channels, buoys, and other vessels and structures that are immersed in seawater for long periods of time, and when they grow, and the effect is sustained over a long period of time. .

When the composition of the present invention is used for fishing nets, ropes, fixed nets, etc., the compound (1) is dissolved or dispersed together with a resin (vehicle) in an organic solvent, a plasticizer, an organic pigment, etc. are added, and then fishing nets, etc. Use by soaking or spraying, then drying.

Examples of the resin (vehicle) used here include natural resins such as rosin and boiled oil, synthetic resins such as vinyl chloride, alkyd, vinyl acetate, and acrylic, and synthetic rubbers such as chlorinated rubber and chloroprene. Further, as the organic solvent, benzene, xylene, inpropatol, cellosolve, etc. are used, and as the plasticizer, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. are used. In addition, dimethyl sulfoxide, dimethyl acetamide, isophorone, methyl ethyl ketone, etc. can be used as a solubilizing agent.

There are no particular restrictions on the materials of fishing nets and the like that can be treated with the composition of the present invention, but usually natural fibers such as cotton and hemp, synthetic fibers such as polyethylene, polypropylene, nylon, vinylon, and Tetron, and in special cases, A metal mesh made of iron, copper, etc. is used.

When the composition of the present invention is used in the above-mentioned fishing nets, etc., it is necessary to contain at least 0.1% by weight of Compound CI) as an active ingredient, but from the viewpoint of efficacy and stability of the preparation. 1 to 10% or more is preferable.

In addition, the active ingredient according to the present invention can be used in combination with active ingredients of antifouling agents conventionally used in fishing nets, such as tributyltin oxide, triphenyltin oxide, organic acid copper, and acrylic organic tin-containing resin. It is also expected that the effect will be enhanced.

When the composition of the present invention is used for a ship bottom antifouling paint, the compound (1
) to contain organic solvents, plasticizers, coloring pigments, etc.
The mixture is mixed and dispersed using a common dispersion machine such as a sand mill or a ball mill to form a formulation.

When the composition of the present invention is used in the above-mentioned antifouling paint, it is necessary to contain compound [I) as an active ingredient in a weight ratio of at least 0.1, but from the viewpoint of efficacy and formulation stability, 1 to 10% is preferred.

It is also expected that the effects of the present invention will be enhanced by mixing the active ingredients of this invention with the active ingredients of conventional ship bottom antifouling paints, such as triphenyl compounds, cuprous oxide, organic nitrogen, and sulfur compounds. can.

When the composition of the present invention is used for the purpose of preventing biofouling in cooling water systems, it may be dissolved in an appropriate organic solvent and added to the seawater so as to be uniformly dispersed, or it may be added as an emulsion using a surfactant or the like. Add it to the formulation. Examples of heavy organic solvents used include evaporated ethanol, acetone, dimethylformamide cellosolve, etc., and examples of surfactants include higher fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, and sorbitan alkyl esters. , alkyltrimethylammonium salts, alkylbetaines, and the like.

In this case, the compound that is the active ingredient of the composition of the present invention [■]
The amount of addition is generally o, ot to seawater flow rate.
5 ppm may be injected for 1 to 24 hours a day. It is desirable to increase or decrease the amount added depending on the amount of attached organisms such as mussels generated.

In addition, in order to maintain the above effect for a long period of time, compound CI
) can also be made into a paint and applied to the cooling water system intake, etc. Oil varnish, synthetic resin, artificial rubber, etc. are used as the coating film forming agent for this process, and pigments and the like are added as necessary to prepare the paint.

In this case, the coating agent contains compound 1"I) as an active ingredient.
A weight ratio of 10 to 50% is required.

Hereinafter, the present invention will be explained in detail using specific examples, but the present invention is not limited to these examples.

In addition, 3.4.5.6-tetrachloropyridazine is written as compound CI), and parts indicate parts by weight.

Example 1 Basic efficacy test (preparation of test solution) Compound [I] was mixed and dissolved in the following proportions to form an emulsion, and the emulsion was sequentially diluted with seawater to prepare a test solution.

Compound [I] 5 parts Tsurpol 5M-200 (manufactured by Toho Chemical Industry Co., Ltd. 35 parts xylene)
90 parts (Efficacy against Fujibbo larvae) Release 30 or more naublius stage larvae obtained from Fujibbo collected from natural seawater into a beaker containing 100 cc of diluted test solution, observe the survival or death of the larvae after 24 hours, The 50% lethal concentration was determined. As a control, a diluted mixed emulsifier/solvent solution containing no active ingredient was used. , the results are shown in Table 1.

(Efficacy against larvae of bulrushes) Release at least 30 naublius stage larvae obtained from larvae collected from natural seawater into a beaker containing 100 cc of diluted test solution, and observe whether the larvae are alive or dead after 24 sowing intervals. The lethal concentration was determined. As a control, a diluted mixed emulsifier/solvent solution containing no active ingredient was used. Results (Efficacy against Ulva Ulva) Approximately 4 circular leaf pieces with a diameter of 0.8 cm were taken from the leaves of Ulva in natural seawater in a beaker containing 100 cc of the diluted test liquid.
0 pieces were immersed and left in a room with ventilation at 1500 lux, and after 24 hours, the presence or absence of damage to the leaf pieces was observed, and the 50% damage concentration was determined. As a control, a diluted mixed emulsifier/solvent solution containing no active ingredient was used. The results are shown in Table 3.

As described above, the composition of the present invention showed a remarkable control effect against Fujitbo, Psyllium vulgare, and Ulva algae.

Example 2 Field test (preparation of test liquid) Compound (1) was mixed and dissolved in the following ratio to prepare a test liquid as a viscous liquid antifouling agent for fishing nets.

(Note 1) Rosin WW Manufactured by Arayo Kogyo Kagaku Co., Ltd. (Note 2) Super Chron Manufactured by Idesumi Kokusaku Pulp Co., Ltd. (Note 3) Manufactured by S-LEC Class C Water Chemical Co., Ltd. (Note 4) Dianal LW-106 Mitsubishi Rayon Co., Ltd. Manufactured by (Note 5) OMF (contains 10% tin) Manufactured by Shinto Paint Co., Ltd. (immersion test) Polyethylene oil 1! (Verse 7.

60X60CIIl), and after drying, fixed it on a stainless steel frame, and immersed it for 4 months at a depth of 1 m below the sea surface of the Wakayama community's ura during the season for marine organisms to attach to it (summer), to check the status of the attachment of organisms to the net. observed. An untreated net was used as a control. The results are shown in Table 4.

Efficacy Judgment Criteria: Static A large amount of adhesion on the entire net + A small amount of adhesion on the entire net A small amount of adhesion on some parts - No adhesion vs. Teru (untreated net) has a large amount of adhesion on the entire net + a small amount of adhesion on the net after one month The adhesion of bryozoans and fujibushi was observed, and after 2 months, a large amount of bryozoans, serpura, sea squirts, etc. were observed in addition to algae, but the compositions of the present invention (formulation examples 1 to 4) had almost no adhesion organisms. Only after 4 months, the adhesion of algae and bryozoans was observed in Formulation Example 1, which showed a remarkable control effect.

Example 3 Field test (preparation of test liquid) Compound CI) was mixed in the following proportions and uniformly dispersed using a ball mill to prepare a test ship bottom paint.

(Immersion test) Soft rope board (300
The board was painted twice with a brush on both sides (300 x 32+ mm), and after drying, it was immersed 1 meter below the sea surface in Toba Bay, Mie Prefecture during the season for marine organisms to attach (summer), and the status of organisms attached to the board was observed. .

The results are shown in Table 5.

Effect Judgment Criteria
6) No adhesion was observed on the test boards used, and the pest control effect was remarkable.

Example 4 Field test (immersion test) During the attachment period of purple mussels in a seawater cooling water system for power generation equipment,
A 0-day adhesion test was conducted. The waterway was of a one-time type with a water flow rate of 3 tons/hour, and the emulsion obtained in Example 1 was added to the flowing water so that the active ingredient concentration was 0.1-lppm. To determine the effectiveness, place 100 in the center of the waterway.
A slate plate of 100 mm in diameter was immersed, and the number of organisms attached to it was observed. As a control, chlorine gas addition and non-addition were set. The results are shown in Table 6.

A large number of mussels and barnacles were observed adhering to the additive-free board, but only a small number of mussels and fujibo were attached to the board adding the composition of the present invention.
The control effect was remarkable.

Claims (1)

[Claims] A water-fouling organism control agent containing 3,4,5,6-tetrachloropyridazine as an active ingredient.