JPS6225121B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antifouling agent for marine pests containing a sulfone derivative having a tribrominated methyl group as an active ingredient. The present invention is directed to marine harmful organisms that breed in fishing nets, underwater structures, etc. This product provides an antifouling agent in seawater for the purpose of preventing the adhesion of living things. In the fishing industry, it is well known that equipment such as aquaculture nets, fixed nets, and ropes are kept in seawater for long periods of time, so they become contaminated by the propagation of marine organisms. Adhesive propagation of these marine organisms obstructs the flow of seawater, causes a lack of oxygen in farmed fish, leads to the occurrence of parasites, and reduces the durability of fishing nets.
Furthermore, depending on the degree of adhesion of marine organisms, the net may be forced to be replaced within a short period of time. Replacement of such a net requires a great deal of effort and expense, and is economically disadvantageous. Hitherto, as economically advantageous means, antifouling agents for marine pests, for example, heavy metal compounds such as copper oxides and organotin compounds, and organochlorine compounds such as DDT and PCT have been used. However, as is well known, these antifouling agents are highly toxic to warm-blooded animals, have a tendency to accumulate, are unfavorable in terms of environmental hygiene, and are not necessarily satisfactory. Therefore, it has been desired to develop an antifouling agent that does not contain such heavy metals, has good degradability, and causes less environmental pollution. In response to this demand, the present inventors have conducted research to develop an antifouling agent that does not contain heavy metals, has good degradability, and has low environmental pollution.As a result, the specific sulfone derivatives shown above were found to be suitable for the purpose. The present invention was completed based on the discovery that it is highly effective in preventing the adhesion of marine pests. The present invention relates to a sulfone derivative having a tribrominated methyl group represented by the general formula R- _SO2 - _CBr3 (wherein R represents a phenyl group or _-CBr3 group which can be substituted with chloro, nitro, or methyl). This is a marine pest antifouling agent characterized by containing one or more of the following as an active ingredient. As the sulfone derivative as an active ingredient in the present invention, the following compounds can be specifically exemplified. (1) _Br3C − _SO2 − _CBr3bis (tribromomethyl)sulfone
mp 129-131℃ (prismatic crystal) (2) tribromomethylphenyl sulfone
mp 147-147.5℃ (acicular crystal) (3) Tribromomethyl-p-chlorophenylsulfone mp 168-169℃ (prismatic crystal) (4) Tribromomethyl-p-methylphenylsulfone mp 152-153℃ (prismatic crystal) (5) Tribromomethyl-p-nitrophenyl sulfone mp 193-195°C (small needle-like crystals) These can be used alone or in combination. These sulfone derivatives are known compounds, and their production methods and physical properties are known [Journal of Chemical Society, pages 508-513 (1956)]. However, its physiological activity, particularly its effectiveness against sessile organisms, has not been known so far, and the knowledge regarding these was discovered for the first time by the present inventors. Next, the methods and results of algicidal and insecticidal tests conducted on the active ingredient sulfone derivatives in water will be shown. Test Example 1 Since green algae such as sea lettuce and green algae are quite common as plants that adhere to fishing net materials in the sea, a test for antifouling power was conducted using chlorella, which is similar to these. The antifouling agent of the present invention was added to 200 ml of the following culture solution for chlorella (PH5.4) at a specified concentration. A certain amount of pre-cultured Chlorella ellipsoida was added to this, and 23
Aerated culture was carried out for 6 days at a constant temperature of 60°C while providing illumination with a fluorescent lamp. After 6 days, 10 ml of the cultured chlorella was placed in a centrifuge tube, centrifuged at 4000 rpm for 20 minutes, and the volumes were compared to determine the algicidal concentration. The culture solution composition is as follows. KNO ₃ 5g KH ₂ PO ₄ 1.25g MgSO _{4.7H 2} O 2.5g FeSO _{4.7H 2} O 0.003g Glucose 15g Water 1 The results are shown in Table 1.

【table】

[Table] Test Example 2 Many types of crustaceans are known to attach to fishing net materials in the sea, including barnacles, bryozoans, hydrozoans, sea squirts, and sea squirts. Brine shrimp (scientific name: Amistea) belongs to the same crustacean as barnacles.
An antifouling power test was conducted using Astemia Salina. Commercially available brine shrimp dried eggs were mixed with artificial seawater (PH
8.3) 0.2g was added to 500ml and kept at around 25°C while aerating with an air pump. After 1-2 days, the hatched larvae swam out,
This was transferred to another artificial seawater and left for 2 days in a constant temperature of 20°C with ventilation. The Astemia solids after 2 days were used for testing.
The active ingredient of the present invention was pipetted into 100 ml of artificial seawater to a specified concentration, and the mixture was kept at a constant temperature of 20°C, and the lethal dose was determined after 24 hours. The results are shown in Table 2.

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[Immersion test]

In order to conduct an evaluation (comparison) test of the present invention, polyethylene fishing nets were immersed in the antifouling agents shown in Examples 1 and 2 and Comparative Example 1, the antifouling agent was attached to the nets, the nets were taken out, and the antifouling agents were removed. A fishing net treated by drying and removing the active ingredient and fixing it together with a resin on the surface of the net, and an untreated fishing net for comparison.
Cut it into a square with a side length of 500 mm, and cut it into a square with a diameter of 18 mm.
The net was fixed to a 450 mm square frame made of vinyl chloride resin, immersed 1 m below the sea surface, and the degree of adhesion of marine organisms to the net was observed. The results are shown in Table 3 below.

[Table] From the above test results, it can be seen that the marine pest antifouling agent of the present invention has excellent effects. The active ingredient in the present invention is a sulfone derivative having a specific group called a tribrominated methyl group ( _-CBr3 ), and the effect of the present invention when this is used is a group similar to this. Compared to sulfone derivatives having a trichloromethyl group (-CCl ₃ ) (some of which are described in the specifications of U.S. Pat. No. 3,879,536), it is superior as shown in Tables 4 and 5 below. .

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Claims (1)

[Claims] 1. A tribrominated methyl group represented by the general formula R-SO ₂ -CBr ₃ (wherein R represents a phenyl group or -CBr ₃ group which can be substituted with chloro, nitro or methyl); An antifouling agent for marine pests, which contains as an active ingredient one or more sulfone derivatives. 2 A type of sulfone derivative having a tribrominated methyl group represented by the general formula R-SO ₂ -CBr ₃ (wherein R represents a phenyl group or -CBr ₃ group which can be substituted with chloro, nitro, or methyl), or The marine pest antifouling agent according to claim 1, which contains a mixed component of two or more types and an organic tin compound, particularly tributyltin oxide.