JPS5819644B2 - Suichi Yubou Ozai - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a low-fish toxicity, long-acting underwater antifouling paint for preventing the adhesion of underwater organisms such as seaweed, molluscs, and shellfish to ship bottoms, fishing nets, etc. Our objective is to provide fishing net antifouling agents.

That is, the present invention uses, as an active ingredient, a compound having the general formula -- (wherein R1 represents an alkyl group having 1 to 5 carbon atoms, R2 represents hydrogen, methyl or methoxy, and R3 represents nitro, methyl or mesyl.

) and one or more salicylanilide compounds represented by the general formula (wherein X1 represents chlorine or phenyl, and X2 represents chlorine, di-lower alkylamino, benzylamino, mesyl or chloromethylsulfonyl).

The present invention relates to an underwater antifouling agent characterized by containing as an active ingredient one or more of the 1,2-dithiol-3-one compounds represented by the following formulas.

Marine organisms such as Fujibo, mussels, oysters, bryozoans, sea lettuce, sea squirts, etc. adhere to ship bottoms, bridge piers, submarine communication cables, industrial water intake pipes that use the sea as cooling water, heat exchangers, drainage pipes, drainage channels, etc. This is causing various obstacles.

In ships, this causes serious problems such as a decrease in speed and an increase in fuel consumption, and in places where seawater is used as cooling water, it prevents the introduction of seawater and reduces the function of heat exchangers.

These obstacles require a huge amount of effort, money, and time to remove, repaint, and repair the infestations.

In addition, the Thai and Nomachi aquaculture industry, which has become popular in recent years, is also causing problems due to the attachment of marine organisms.

In other words, marine organisms such as Fujitbo, Ulva, sea squirts, and bryozoans attach to aquaculture nets, blocking the nets and blocking the inflow of seawater, resulting in a lack of oxygen, which causes great damage to aquaculture fish, and facilitates the development of parasites. ing.

For this reason, in the summer, the screens are changed every one to two weeks.

Considering the labor and expense involved in re-netting, and the negative impact it will have on farmed fish, it will be a huge loss.

Conventionally, cuprous oxide, mercury oxide, etc. tend to separate and precipitate during storage due to their physical and chemical properties.In recent times, in contaminated seawater, they turn black due to the hydrogen sulfide they contain, and have a remarkable antifouling effect. However, it is selective and effective against underwater species such as barnacles and oysters, but cannot be expected to be sufficiently effective against seaweed.

Furthermore, they have the disadvantage of being highly irritating to the skin and harmful to the human body.

In order to solve these drawbacks, the present inventors have conducted extensive research on various biologically active compounds, and as a result have discovered a new salicylanilide compound represented by the general formula CI No. 43-20595, German Patent No. 1126668 and German Patent No. 1128432, with the 1,2-dithiol-3-one compound represented by the general formula (n), which is known to be effective as a fungicide. It was discovered that the mixture has excellent storage stability, maintains its antifouling effect for a long time against fouling organisms such as marine organisms and seaweed, and has low toxicity to fish.

As the antifouling active ingredient according to the present invention, the new salicylanilite compound represented by the general formula CI) includes, for example, 2',5-dimethyl-4'-dirosalicylanilide melting point 216-216.5°C 3';5-Dimethyl-4'-nitrosalicylanilide Melting point 202-203°C 2',5-dimethyl-5'-dirosalicylanilide Melting point 210-211°C 5-Methyl-4'-nitrosalicyl Anilide melting point 23
6.5-237°C 2'-methoxy-5-methyl-4'-nitrosalicylanilide Melting point 218-219°C 3'-Mesyl-5-methylsalicylanilide Melting point 19
Pale yellow crystals of 4-196.5°C 5-ethyl-27-medoxy-4'-nitrosalicylanilide Melting point 186-187°C 5-ethyl-/-methyl-4'-nitrosalicylanilide Melting point 173-174 °C 5-ethyl-2'-methyl-5'-nitrosalicylanilide Melting point 167.5-168.5 °C5-ethyl-
4'-nitrosalicylanilide melting point 208-209°
G 5-Ethyl-2/, 3/-dimethylsalicylanilide Axis 129.5-130.5°C 2'-Methyl-57-nitro-5-improvilsalicylanilide Melting point 126-127°C 2'-Methyl −
47-nitro-5-improvil salicylanilide
Melting point: 175-176°C 4'-Nitro-5-isoprobylsalicylanilide Melting point: 193.5-194.5°C 2'-Mexy-4'-Nitro-5-isoprobylsalicylanilide Melting point: 183.5- 184.5°C5-Second 7"thyl-27-methyl-5'-nitrosalicylanilide Melting point 136-138°C5-Second-butyl-
2'-Methyl-4'-nitrosalicylanilide Melting point 154-156°C 5-Sec-Butyl-2'-methoxy-
4'-Nitrosalicylanilide Melting point 152-154
°C5-Tertiary butyl-2'-methyl-4'-nitrosalicylanilide Pale yellow with melting point 202-204°C 5-i tertiary 7"thyl-4'-methoxy-21-nitrosalicylanilide Melting point 153 ~154°C Yellow needle crystals 5-tertiary 7"thyl-4'-methyl-3'-nitrosalicylanilide Pale yellow crystals 5-tert-butyl-3, mp 219-221'C '-Methyl-2'-nitrosalicylanilide Yellow needle-like crystals with a melting point of 129-131°C. Yellow needle-shaped crystals 5-tert-butyl-2'-methoxy-5'-nitrosalicylanilide Pale yellow crystals 5-tert-butyl-4'-nitrosalicylanilide, melting point 188-190 °C (from benzene) Salicylanilide
Pale yellow crystals of 5-tertiary butyl with a melting point of 218-219°C
3'-Dirosalicylanilide Melting point 191-193
Pale yellow crystals of 5-tert-butyl-2'-methoxy-4 at °C.
'-nitrosalicylanilide Melting point 213-214℃
Pale yellow crystals of 5-tert-butyl-2'-methyl-57-nidrosalicylanilide, melting point 169-171 'C5-tert-butyl-7,3'-dimethylsalicylanilide, melting point 1
75-176.5°G5-Tertiary butyl-3'-mesylsalicylanilide Pale yellow crystals with a melting point of 161-164°C White crystals of 5-tertiary amyl-2'-methyl-4'-nitrosalicylanilide Melting point 150-151°C3-i Tertiary amyl-2'-methyl-57-nitrosalicylanilide
Melting point 161-162°C5-Tertiary amyl-4'-nitrosalicylanilide Melting point 200-202°C 5-Tertiary 7mil-2'-methoxy4'-nitrosalicylanilide Melting point 175-176° C5-Tertiary amyl-3'-methyl-4'-nitrosalicylanilide Melting point 102-104°C5-Tertiary amyl-3'-
Mesylsalicylanilide Examples include pale yellow crystals with a melting point of 131 to 134°C, but are not limited thereto.

Examples of the 1,2-dithiol-3-one compound represented by the general formula [■] include 5-chloro-4-phenyl-1,2-dithiol-3-
Melting point 96-98°C 4,5-dichloro-1,2-dithiol-3-one Melting point 61°C 4-chloro-5-diethyl 7mi/-1,2-dithiol-3-one Melting point 65°C 4-Chloro-5-dimethylamino-1,2-dithiol-3-one Melting point 1000C 5-Benzylamino-4-chloro-1,2-dithiol-3-one Melting point 1410C 4-chloro-5-mesyl-1, 2-dithiol-3-one Melting point 196°G 4-chloro-5-I'lolomethylsulfonyl-1°2-
Dithiol-3-one Melting point 136°C5-Mesyl-4
-Phenyl-1,2-dithiol-3-one Melting point 15
Examples include, but are not limited to, 3°C.

To achieve this purpose, the active ingredient content should be 10 to 25
% is desirable, and preferably the mixing ratio of the new salicylanilite compound represented by the general formula CI) and the 1,2-dithiol-3-one compound represented by the general formula [■] ( A mixture with a ratio of 1:0.5 to 1.1 (by weight) has extremely low selectivity to marine fouling organisms and is highly versatile.

In producing the underwater antifouling agent, the general formula C of the compound of the present invention is used.
A mixture of a novel salicylanilide compound represented by I) and a 1,2-dithiol-3-one compound represented by general formula [■], and a natural resin, oil-based, synthetic resin-based, synthetic rubber-based vehicle, etc. Add plasticizers, solvents,
It can be obtained by adding a coloring pigment if desired and thoroughly pulverizing and kneading it by dissolving, dispersing, or using a conventional method (ball mill).

Examples of the natural resin, oil-based, synthetic resin or synthetic rubber vehicle include rosin, boiled oil, chlorinated rubber alkyd resin, vinyl resin such as vinyl chloride and vinyl acetate, acrylic resin, polyolefin resin such as polybutene,
Examples include, but are not limited to, polystyrene, various synthetic rubbers, polyurethane, amino resins, epoxy resins, unsaturated polyester resins, phenol resins, asphalt, and coal tar.

In addition to the active ingredients of the invention, for example, trialkyl or triaryltin compounds, organic acid copper, inorganic acid copper compounds,
Organic chlorine compounds such as cabtane, BHC, and DDT,
Triazine compounds, carbamate compounds, organic sulfur compounds such as zinc dialkyldithiocarbamate and thiuram compounds may be used in combination.

Next, the present invention will be specifically explained using examples.

Example CI) Underwater antifouling paint Example 1 5-tertiary butyl-2'-methyl-47-nitrosalicylanilide 12% 3-one
6φ triphenyltin acetate 2 talc
20 Titanium White 4 Dioctyl Phthalate 3 Chloride GoL2 0 Jin 22 Phthalocyanine Blue NC-13 Methyl In Butyl Ketone 1O Xylene
20100% Example 8 5-tertiary butyl-4'-nitrosalicylanilide
10thi-5-chloro-4-phenyl-1,2-dithiol-3-one
5N-Trichloromethylthio-4-cyclohexene-1,2-dicarboximide 5 Talc
18 titanium white
4 dioctyl phthalate 3 chloride rubber 20 gin
20 Phthalocyanine Blue NC-13 Methyl isobutyl ketone IO xylene
20100 Example 9 2', lhxy-5-methyl-47-nitrosalicylanilide 10 5-benzylamino-4-chloro-1,2-dithiol-3-one
55-chloro-4-phenyl-1,
2-dithiol-3-one
5 talc 15 titanium white 4 dioctyl phthalate 3 chloride rubber
30 gin
22 Phthalocyanine Blue NC-13 Butyl acetate lOxy1/n
20ioo% Comparative Example 1 Cuprous oxide 25% Bengara
12 Talc 10 Rosin
22 boil oil
8 methyl isobutyl ketone
23100 Comparative Example 2 Bistributyltin, oxide 10%DDT
5 titanium white
6 talc
230 gin
15 vinyl resin
8 Butyl acetate i.

Xylene 20 Phthalocyanine Blue NC-13 ioo% Antifouling paints having the formulations described in Examples 1 to 9 and Comparative Example 1.2 above were each applied twice to test mesh plates.

Then, they were immersed in the sea at a depth of 1.5 m in Tsukumi Bay in the Oita system for one year from October 1970 to October 1970, and after 6 and 12 months, each test net plate was checked for fouling organisms. We investigated the situation.

The results are shown in Table 1. Numbers in the table indicate percent adhesion area.

As is clear from the above results, the mixture of the novel salicylanilide compound and 1,2-dithyel-3-one compound of the present invention exhibits an excellent antifouling effect on marine organisms for a long period of time. .

[■] Fishing net antifouling agent Example 1 5-tertiary amyl-2'-methyl-47-nidrosalicylanilide 8 5-chloro-4
-phenyl-1,2-dithiol-3-one
6 titanium white
2 Talc 5 Chlorinated Rubber 20 Gin
11 Epoxidized soybean oil
8Butyl acetate
28 xylene 3
0100 Example 2 5-tert-butyl-2'-methyl-4'-nitrosalicylanilide 601) 4-chloro-5-mesyl-1,2-dithiol-3-one
45-chloro-4-phenyl-
1,2-dithiol-3-one
2 titanium white 1.5
Talc 50 gin
12 chloride rubber
2 Epoxidized soybean oil
8 Phthalocyanine Blue NC-11,
5 Butyl acetate 28 xylene
30100 Example 3 5-tertiary butyl-4'-nitrosalicylanilide
4% 5-tertiary amyl-2'-methyl-5'-nitrosalicylanilide 54-chloro-5-
Dimethylamino-1,2-dithiol-3-one
4 talc
5 titanium white 1.5
Chlorinated rubber 1st stage rosin
12 Epoxidized soybean oil
8 Phthalocyanine Blue NC-
11,5 Butyl acetate 28
-phenyl-1,2-dithiol-3-one
4N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide 4
Talc 3 titanium white
dichloride rubber
20 gin
11 Epoxidized soybean oil
8 carbon black 4
Butyl acetate 28xylene/3
0 100% Polyethylene 6-node (knotless) aquaculture nets (400 denier, 60 nets or more) were applied by dipping into the antifouling agents of Examples 1 to 4 above, and then air-dried and applied to the depth of Tsukumi Bay in the Oita system. 1m
It was kept immersed in the sea for 6 months from July 1970 to January 1975, and the adhesion status was investigated every month.

The results are shown in Table 2.

The ox, +, ±, and - in the table indicate the degree of adhesion of fouling organisms.

+: Fouling organisms are significantly attached.

+: Fouling organisms have adhered to the net, making it no longer usable as an aquaculture net.

±: There is no problem in practical use as an aquaculture net even if there is only a slight amount of fouling organisms attached.

-2 No fouling organisms attached.

As is clear from the results in Table 2 above, the mixture of the novel salicylanilide compound and 1,2-dithiol-3-one compound of the present invention has an excellent antifouling effect for a long period of time against fouling organisms. I can see that it will work.

A 6m small split net made of 6-section polyethylene net (knotless 400 denier, 60 nets) was dipped in the antifouling agent of Example 1, air-dried, and then immersed in the sea in Tsukumi Bay in the Oita system to collect 500 Japanese yellowtail. The fish were introduced and cultured for four months from July 1970 to November 1970.

During that time, we looked at the effects on yellowtail and found that there were no deaths.

There was no practical problem with the net except for a small amount of sea lettuce attached near the sea surface.

Claims (1)

[Scope of Claims] 1 Salicylaniline represented by the general formula (wherein R1 represents an alkyl group having 1 to 5 carbon atoms, R2 represents hydrogen, methyl or methoxy, and R3 represents nitro, methyl or mesyl) One or more ride compounds and 1,2-dithiol- represented by the general formula (wherein X1 represents chlorine or phenyl, and X2 represents chlorine, di-lower alkylamino, benzylamino, mesyl or chloromethylsulfonyl). An underwater antifouling agent characterized by containing one or more 3-one compounds as an active ingredient.