JPS6243962B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses the general formula R-(S) _o -R () ( In the formula, R represents an alkyl group having 1 to 20 carbon atoms, and n
represents an integer from 2 to 10. The present invention relates to an underwater antifouling agent characterized by containing a dialkyl sulfide compound represented by the following formula or a mixture of the present compound and tetrachloroisophthalonitrile as an active ingredient. Fouling organisms such as seaweed, barnacles, celluloids, bulrushes, and molluscs adhere to underwater contact objects such as ship bottoms, fishing nets, underwater structures, and underwater materials, impeding their efficient operation and requiring a great deal of effort to maintain them. Therefore, effective and economical measures to prevent long-term adhesion have become an important issue. For example, if fouling organisms adhere to the bottom of a ship, the propulsion efficiency will decrease and fuel consumption will increase. Also,
If fouling organisms attach to the fishing nets for aquaculture of yellowtail and sea bream, which have recently become popular, they can obstruct the flow of seawater, cause a lack of oxygen for the aquaculture fish, and harm their survival.
This causes problems such as facilitating the development of parasites. Also, regarding fixed nets, the adhesion of fouling organisms can be
It has a significant negative impact on fish catches and poses obstacles that lead to a decline in fish catches. As a countermeasure against these problems, various active ingredients of underwater antifouling agents have been proposed to prevent the attachment of fouling organisms. For example, there are heavy metal compounds such as cuprous oxide, which due to their physical or chemical properties tend to precipitate or coagulate during storage of antifouling paints. So,
There are many problems with antifouling paints containing copper compounds, such as hydrogen sulfide contained in seawater, which turns into sulfide, significantly reduces its biofouling prevention effect, and causes discoloration. In addition, although a series of recent organotin compounds (such as trialkyl- or triphenyl-tin compounds) have practical effects, they are generally highly toxic and can cause harm to humans if products containing them are handled carelessly. There are drawbacks such as the risk of The present inventors have conducted research to find a low-pollution underwater antifouling agent that does not contain heavy metals, has low toxicity, and has little risk of environmental pollution, and has developed the general formula ().
It has been found that an underwater antifouling agent containing a dialkyl sulfide compound represented by the formula or a mixture of this compound and tetrachloroisophthalonitrile as an active ingredient can provide an extremely excellent antifouling effect. These compounds have lower toxicity than organotin compounds, and possess various properties required for active ingredients in underwater antifouling agents, such as not adversely affecting the storage stability, color tone, or paint film of antifouling paint formulations. are doing. The dialkyl sulfide compound represented by the general formula () of the present invention is generally used as an extreme pressure additive for cutting oil, and contains active sulfur and has excellent antifouling effects as an active ingredient of underwater antifouling agents. The present inventors have found that. This compound has low toxicity and is non-irritating. Examples of the dialkyl sulfide compound represented by the general formula () of the present invention include, but are not limited to, the following compounds. ◎Dimethyltetrasulfide, boiling point 1.5mmHg/
60～70℃ ◎Diethylpentasulfide, boiling point 26mmHg/
119℃ ◎Diethyl hexasulfide, specific gravity 1.1622 (20
℃) ◎Dipropyl tetrasulfide, boiling point 11mm
Hg／127～127.5℃ ◎Diisopropyl trisulfide, boiling point 5mm
Hg/75~76℃ ◎Ditertiary butyl disulfide, boiling point 20mm
Hg/84~85℃ ◎Dibutyltetrasulfide, boiling point 1mmHg/
125-130℃ ◎Ditertiary butyl tetrasulfide, boiling point 0.2
mmHg/70℃ ◎Diamyltetrasulfide, boiling point 1mmHg/
100～107℃ ◎Dihexylpentasulfide, specific gravity 1.0684
(20℃) ◎Dioctyl tetrasulfide, specific gravity 1.0328
(20℃) ◎Ditertiary nonylpentasulfide, specific gravity
1.026-1.045 (15.5℃) ◎Ditertiary dodecyl pentasulfide, specific gravity
1.547 (20°C) ◎Ditetradecyltetrasulfide◎Dihexyltetrasulfide◎Dinonadecyltetrasulfide◎Dimethyloctasulfide◎Ditert-butyldecasulfide The underwater antifouling agent of the present invention The content of the dialkyl sulfide compound represented by the general formula (), which is an essential active ingredient, or this compound and tetrachloroisophthalonitrile in the antifouling agent is as follows. In either case, the mixed system can be arbitrarily changed depending on the required performance and the price of the antifouling agent, and is not particularly limited. Usually, the amount of these ingredients is 5 to 40 parts, preferably 10 to 40 parts per 100 parts (by weight) of the preparation.
There are 25 copies. In the underwater antifouling agent of the present invention, in addition to the above-mentioned essential antifouling active ingredients, known active ingredients may be used in combination as optional ingredients, and a more balanced effect against various fouling organisms can be expected. The underwater antifouling agent of the present invention can be prepared according to a conventional method. That is, a dialkyl sulfide compound represented by the general formula () or a mixture of this compound and tetrachloroisophthalonitrile is mixed with a resin such as a natural resin, an oil-based resin, a synthetic resin, or a synthetic rubber-based resin for general paints, and a solvent.
If necessary, it is dispersed or dissolved in a solvent together with pigments, plasticizers, various additives, etc. for general paints using a conventional dispersion method. For example, in the case of mixed dispersion, a pole mill or the like is used. Preferred resins include chlorinated rubber, acrylic, rosin, and vinyl chloride resin. The prepared underwater antifouling agent is applied by various coating methods suitable for the target object. The effects of the underwater antifouling agent of the present invention will be shown below using examples, but it goes without saying that the present invention is not limited to these examples. Example 1 Underwater antifouling agents were prepared according to the following formulation examples and each was coated with a polyethylene knotless net (6 knots, 400
After dipping and air-drying the net (denier/60 pieces), the net was submerged approximately 1 meter below the sea surface in Kii Tanabe Bay, Wakayama Prefecture, from late May 1973 to investigate the adhesion of fouling organisms to the net. Formulation example 1 Ditertiary nonylpentasulfide 15% Acrylic resin 8% Xylene 77% Formulation example 2 Ditertiary nonylpentasulfide 8% Tetrachloroisophthalonitrile 6% Acrylic resin 6% Xylene 80% Formulation example 3 Diamyltetrasulfide 12% Tetrachloroisophthalonitrile 3% Acrylic resin 8% Xylene 77% Formulation example 4 Ditertiary dodecylpentasulfide 15% Acrylic resin 8% Xylene 77% Formulation example 5 Dihexylpentasulfide 10% Tetrachloroisophthalonitrile 6% Polybutene 18% Xylene 66% Formulation example 6 Ditertiary nonylpentasulfide 15% Vinyl chloride resin 6% Butyl acetate 79% Formulation example 7 Dinonadecyl tetrasulfide 12% Polybutene 15% Xylene 73% Formulation Example 8 Ditert-butyl deca sulfide 12% Tetrachloroisophthalonitrile 3% Polybutene 18% Xylene 67% The results were evaluated according to the following criteria and summarized in Table 1. Fish net antifouling agent evaluation criteria rating Degree of adhesion of fouling organisms to fish net 1: No fouling organisms attached. 2: Adhesion rate of fouling organisms is less than 1% 3: Adhesion rate of fouling organisms is less than 5% 4: Adhesion rate of fouling organisms is 5% or more and less than 10% 5: Adhesion rate of fouling organisms is 10% or more and less than 20% 6: Fouling organisms are attached Adhesion rate of 20% or more but less than 50% 7: Adhesion rate of fouling organisms is 50% or more

[Table] As can be seen from the above results, the underwater antifouling agent of the present invention exhibited an excellent effect of preventing fouling organisms from adhering to fishing nets. Example 2 An underwater antifouling agent was prepared according to the following formulation. Formulation example 1 Di-tertiary nonyl pentasulfide 20% Petal 20% Barium sulfate 10% Talc 5% Vinyl chloride resin 6% Rosin 12% Butyl acetate 27% Formulation example 2 Di-tertiary nonyl pentasulfide 10% Tetra Chloroisophthalonitrile 10% Valve handle 20% Barium sulfate 10% Talc 5% Chlorinated rubber 8% Rosin 12% Xylene 25% Formulation example 3 Ditert-butyltetrasulfide 15% Tetrachloroisophthalonitrile 5% Valve handle 20% Barium sulfate 10% Talc 5% Acrylic resin 12% Rosin 4% Xylene 29% Prescription example 4 Dihexylpentasulfide 20% Valve handle 20% Barium sulfate 10% Talc 5% Chlorinated rubber 8% Rosin 12% Xylene 25% Prescription Example 5 Dioctyl tetrasulfide 10% Tetrachloroisophthalonitrile 5% Captan 5% Petal 20% Barium sulfate 10% Talc 5% Chlorinated rubber 8% Rosin 12% Xylene 25% Formulation example 6 Dinonadecyl tetrasulfide 20% Bengara 20% Barium sulfate 10% Talc 8% Vinyl chloride resin 6% Rosin 6% Methyl isobutyl ketone 20% Xylene 10% Formulation example 7 Ditertiary nonyl pentasulfide 10% Tetrachloroisophthalonitrile 10% Talc 15% Titanium white 6% Chlorinated rubber 3% Rosin 20% Cyanine blue 4% Methyl isobutyl ketone 15% Xylene 17% Comparative formulation example 1 Cuprous oxide 55% Rosin 6% Vinyl chloride resin 6% Tricresyl phosphate 2% Xylene 20% Methyl isobutyl ketone 11% The underwater antifouling agent obtained from the above formulation was applied twice evenly with a brush to a test steel plate that had been previously coated with antirust paint, and then air-dried. The test steel plates obtained were immersed in the sea at a depth of 1.5 m in Kiitanabe Bay, Wakayama Prefecture, for one year from June 1973, and the state of adhesion of fouling organisms on each test steel plate was investigated every two months. The test results are summarized in Table 2. The numbers in the table represent the percent adhesion area.

[Table] As can be seen from Table 2, the underwater antifouling agent of the present invention exhibited excellent antifouling effects.

Claims (1)

[Claims] 1 General formula R-(S) _o -R (wherein R represents an alkyl group having 1 to 20 carbon atoms, n
represents an integer from 2 to 10. ) An underwater antifouling agent characterized by containing one or more of the compounds represented by the following as an active ingredient. 2 General formula R-(S) _o -R (wherein, R represents an alkyl group having 1 to 20 carbon atoms, n
represents an integer from 2 to 10. An underwater antifouling agent characterized by containing a mixture of one or more of the compounds represented by ) and tetrachloroisophthalonitrile as an active ingredient.