JPH05331008A - Attachment inhibitor for marine attaching organism - Google Patents

Abstract

PURPOSE:To obtain an effective attachment inhibitor for marine attaching organisms comprising one or more of specific glyoxime compounds as an active ingredient, having low toxicity to humans, animals, fishes and shellfishes and hardly causing environmental pollution. CONSTITUTION:The attachment inhibitor for marine attaching organisms (especially Hydroides norvegica Gunnerus) comprises one or more of glyoxime-based compounds of the formula (X is halogen; Y is H, halogen or lower alkyl) (monochloroglyoxime is especially preferred) as an active ingredient. This compound of the formula as an attachment inhibitor for seawater cooling systems and fishing nets and a coating for preventing the attachment is capable of extremely effectively preventing damages by marine attaching organisms. Furthermore, the monohalogenated glyoxime derivative of the formula can simply be synthesized by halogenating a glyoxime derivative. A dihalogenated glyoxime can be produced by further halogenating the monohalogenated derivative.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agent for preventing adhesion of marine adherent organisms. More specifically, it relates to a preparation which is effective in preventing the attachment of marine attachment organisms and has low toxicity to humans and seafood.

[0002]

2. Description of the Related Art Recently, due to the construction of large-scale marine facilities, the habitat of adhering organisms has been expanding, and there are many adhering organisms such as sticky barnacles, magnolias, and mussels. Is becoming
In factories that use seawater as cooling water, these marine adhering organisms are causing harmful effects such as impeding the passage of seawater and reducing its function.

In addition, the bottom of ships, underwater structures, aquaculture nets,
Since buoys or set nets are kept in seawater for a long period of time, many adherent organisms such as barnacles, magnolias, and mussels attach to them, causing various disorders. Conventionally, in order to prevent such adhesion of marine organisms, sodium hypochlorite or electrolytic chlorine has been used in a cooling system of seawater.

Further, anti-adhesion paints are used for ship bottoms and underwater structures, and anti-adhesion agents for fishing nets are used for aquaculture nets and stationary nets. Conventionally, cuprous oxide and organotin compounds have been used as the active ingredients of these paints and anti-adhesion agents, and cuprous oxide is still widely used. However, in the cooling water system that takes in seawater, in order to prevent the damage due to the adherent organisms, which has been increasing in recent years, it is not always possible to expect a sufficient effect only by the conventional technology, and when a chlorine agent is used, We must be concerned about the production of trihalomethanes.

Organotin compounds used as components for paints and fishing nets become a social problem due to their toxicity and accumulation, and cuprous oxide is also an undesirable phenomenon when it is used in oyster and scallop aquaculture areas. cause. Furthermore, some glyoxime compounds are known to have antibacterial activity against bacteria [Dirasat 8 (7), 185-188 (19).
86)], but the living functions of bacteria and marine adherent organisms are markedly different, and the physiological action of this compound on marine adherent organisms, among them, Haemorrhiza alba, is not known at all.

[0006] In view of the present situation and recognition, the present invention aims to provide an effective agent for preventing adhesion of marine organisms, which has low toxicity to human livestock and seafood and little environmental pollution.

[0007]

Thus, according to the present invention, the general formula (I):

[0008]

[Chemical 2] (In the formula, X represents a halogen atom and Y represents a hydrogen atom, a halogen atom or a lower alkyl group.) An anti-adhesion agent for marine adherent organisms is provided which contains one or more glyoxime compounds represented by the formula.

That is, it was found that the compound (I) of the present invention is an environment-friendly compound that does not contain heavy metals and has an excellent effect of preventing the attachment of marine attached organisms. In the general formula (I), examples of the halogen atom represented by X and Y include chlorine, bromine, iodine and fluorine atoms, and chlorine atom is particularly preferable. The lower alkyl group represented by Y is a C _1-4 alkyl group, for example,
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and the like can be mentioned, with a methyl group being preferred.

Specifically, among the compounds represented by the above general formula (I), monohalogenated glyoxime derivatives include monochloroglycoxime, monobromoglyoxime, monofluoroglyoxime, monoiodoglyoxime, 1- Chloro-2-methylglyoxime, 1-chloro-2-ethylglyoxime, 1-chloro-2-propylglyoxime, 1-chloro-2-butylglyoxime,
1-bromo-2-methylglyoxime, 1-bromo-2
-Ethyl glyoxime, 1-bromo-2-propyl glyoxime, 1-bromo-2-butyl glyoxime, 1-
Fluoro-2-methylglyoxime, 1-fluoro-2
-Ethyl glyoxime, 1-fluoro-2-propyl glyoxime, 1-fluoro-2-butyl glyoxime,
1-iodo-2-methylglyoxime, 1-iodo-2
-Ethyl glyoxime, 1-iodo-2-propyl glyoxime and 1-iodo-2-butyl glyoxime. Among these compounds, it is preferable to use monochlorotrioxime from the viewpoint of handleability and economy.

Among the compounds represented by the above general formula (I), examples of the dihalogenated glyoxime include dichloroglyoxime, dibromoglyoxime, difluoroglyoxime and diiodoglyoxime, with dichloroglyoxime being particularly preferred. .. These compounds are 2
One or more species can be used in combination. The monohalogenated glyoxime derivative represented by the general formula (I) can be easily synthesized by halogenating the glyoxime derivative. Further, a dihalogenated glyoxime can be produced by further halogenating the monohalogenated product produced here.

When the compound (I) of the present invention is added to a seawater cooling system, the addition amount thereof is generally 0.
It is sufficient to inject 001 ppm or more per day for 1 to 24 hours. The amount added may vary slightly depending on the conditions of the sea area or the amount of attached organisms, but if the amount of magnolia stag beetle is large among the attached organisms, the amount added is preferably 0.01 ppm or more. The upper limit of the amount added is not particularly limited, but 0.5 ppm or less is preferable in consideration of economic aspects.

The compound (I) of the present invention can be used in a seawater cooling system.
When the compound (I) is added, the compound (I) of the present invention is dissolved in a suitable solvent (water or an organic solvent such as ethanol, acetone, xylene, dimethylformamide, methylcellosolve) so that the compound (I) can be uniformly dispersed in seawater, or if necessary, an interface is added. It is preferable to add an active agent and emulsify and suspend it to use as a preparation having an appropriate concentration. As the surfactant at that time, higher fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene polyoxypropylene copolymers, alkyl trimethyl ammonium salts, alkyl betaines Etc.

Next, when the compound (I) of the present invention is applied to prevent the adhesion of marine organisms such as fishing nets and ship bottoms, it is usually used in the form of a liquid preparation. That is, a natural resin, a synthetic resin, a plasticizer, a solvent, a pigment and the like are appropriately selected and mixed with the compound (I) of the present invention, and the compound (I) is made into a formulation by operations such as dissolution, dispersion and kneading, and then used. Examples of natural resins and synthetic resins used in the above formulations include rosin, boil oil, chlorinated rubber, polybutene, vinyl chloride resin, acrylic resin, epoxy resin and the like. Examples of the plasticizer include dioctyl phthalate, dioctyl adipate, tricresyl phosphate, trioctyl phosphate and the like.

Examples of the solvent include ethanol, xylene, toluene, cyclohexanone, kerosene, methyl isobutyl ketone, butyl acetate, dimethylformamide, naphtha, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, and the like. Also, various solvents used in the field of paints can be used, and some water may be contained. Moreover, you may use these solvents in mixture of 2 or more types.

Further, examples of the pigment include talc, titanium white, yellow lead, navy blue, red iron oxide, phthalocyanine blue and the like. When this invention compound (I) is applied to fishing nets, this invention compound (I): 5 to 30% by weight, resin content: 5 to 30% by weight, plasticizer: 0 to 15% by weight, etc. in an organic solvent. From the viewpoint of film-forming property and film-forming strength, it is preferable to use a dissolved or dispersed liquid formulation and to set the total solid content concentration to 15 to 60% by weight. In particular, the compound (I): 10-2
5% by weight, resin content: 10 to 20% by weight, plasticizer: 3-1
It is more preferable that the solid content is 0 wt% and the solid content is 20 to 50 wt%.

When the above-mentioned preparation is applied to a fishing net, it is carried out by an ordinary method, that is, an immersion method or the like. On the other hand, when the compound (I) of the present invention is applied to an underwater structure, the invention compound (I): 5 to 30% by weight, resin content: 5 to 30% by weight, plasticizer: 0 to 15% by weight, pigment Min: 10 to 35% by weight is kneaded with the above solvent to prepare a formulation, which is preferably a compound (I) of the invention: 10 to 25% by weight, resin content: 10 to 20% by weight, plasticizer: 3 A formulation consisting of -10 wt% and pigment content: 15-30 wt% is used as a paint.

This anti-adhesion paint is useful for various seawater-based structures, and is preferably applied by brushing, spraying or the like. The anti-adhesion agent of the present invention thus applied to the anti-adhesion target forms a film by drying and exerts an anti-adhesion effect for a long period of time. As the anti-adhesive agent other than the compound (I) of the present invention, higher aliphatic amine compounds, copper naphthenate, copper oleate, dimethyldithiocarbamate, tetraethylthiuram disulfide, zinc pyrithione, 2,3-dichloro-N-
(2 ', 6'-diethylphenyl) maleimide, 4,5-
Dichloro-2-n-octyl-4-isothiazoline-3
-One, thiocyanomethylthiobenzothiazole, tetrachloroisophthalonitrile and the like, which can be appropriately used in combination.

[0019]

EXAMPLES The present invention will be described below with reference to test examples and formulation examples, but the present invention is not limited thereto.

Test Example 1 A living body of Kale scutellariae was collected, a living tube was removed, a soft body part was taken out, and the soft body part was allowed to stand in filtered seawater to induce spawning / fertilization to obtain eggs and sperm. This egg and sperm were fertilized in filtered seawater, excess sperm was washed with filtered seawater, and the fertilized egg was placed in a thermostat at 22 ± 1 ° C. and left for 24 hours. The trochophore larvae thus obtained were used to test the killing efficacy of each compound against them by the following procedure. That is, 30 l of filtered seawater containing a test solution so as to have a predetermined concentration was put into a petri dish having a diameter of 90 mm and a height of 15 mm, and the thick glass tube having a diameter of 60 mm and a height of 20 mm was placed in one of the NXX-25. A device attached with mueller gauze was put in, and then 10 trochophore larvae of Hawthorn hawkweed were put in each. After leaving it in a thermostat at 22 ± 1 ° C for 6 hours, it was replaced with filtered seawater, and after breeding for 24 hours in the thermostat, the number of swimming larvae was counted under a microscope to determine the effect of each Example solution. It was judged. When the number of swimming individuals is 0, it means that all of them have been killed. The results are shown in Table 1. In addition,
Example liquid was prepared by formulating 5 parts of the compound with 90 parts of dimethylformamide and 5 parts of polyoxyethylene sorbitan monooleate (HLB15), and diluting with filtered seawater to give an example liquid.

[0021]

[Table 1]

Test Example 2 Seawater was pumped from a seawater headrace of a steelworks where there were many troubles due to mussels, barnacles, maggots, etc., to a PVC pipe with an inner diameter of 75 mm and a length of 2 m.
Using a test waterway containing a test net, seawater was passed through for 40 days temporarily during the adhesion period of Kasengakuenshi (water flow rate of 3 tons / hour), and each example solution was injected by a chemical pump at that time. The number of attached Hawthorn and other attached organisms was counted. The results are shown in Table 2. The preparation of the example liquid was carried out by dissolving each compound in dimethylformamide to obtain polyoxyethylene sorbitan monooleate (HLB).
15) was added to emulsify.

[0023]

[Table 2]

Test Example 3 A test net made of polyethylene (100 pieces, 4 sections, 40 pieces)
(cm × 60 cm) using a net for aquaculture. A test net was dipped in each anti-adhesion agent to attach the anti-adhesion agent to the net and air-dried for 3 days. Then, during the three months from May to July, it was hung at a depth of 1.0 to 1.5 m below the sea level from the raft in the Isaura Bay in Mie Prefecture, and the adhesion prevention effect against magpie scorpion and other adherent organisms was observed after 3 months. did. Examples of anti-adhesive formulations are shown in Table 3 and the test results are shown in Table 4. That is, Table 4
Shows the weight of attached organisms (wet weight) and the proportion of attached organisms (%).

[0025]

[Table 3]

[0026]

[Table 4]

Test Example 4 A 7 cm × 20 cm hard PVC plate was used as a test plate. The coating amount of each paint formulation was 1.5-2.
It was applied twice so as to obtain 0 kg / m ² . From May, one year below the sea level from the raft within Isaura Bay in Mie Prefecture for one year.
Suspended at a depth of 0 m, the effect of preventing adhesion to magnolia lanceolata and other adherent organisms was observed after 6 months and 12 months. Formulation examples of the anti-adhesive paint are shown in Table 5, and the test results are shown in Table 6. That is, in Table 6, the weight of attached organisms (wet weight) and the composition ratio (%) of attached organisms are shown.

[0028]

[Table 5]

[0029]

[Table 6]

[0030]

INDUSTRIAL APPLICABILITY According to the present invention, the compound of the present invention can very effectively prevent damage caused by organisms adhering to marine organisms for seawater cooling systems, fishing net anti-adhesion agents and anti-adhesion paints.

Claims (4)

[Claims] 1. A compound represented by the general formula (I): (In the formula, X represents a halogen atom, Y represents a hydrogen atom, a halogen atom or a lower alkyl group.) An agent for preventing the adhesion of marine organisms, which comprises one or more glyoxime compounds. 2. The anti-adhesion agent according to claim 1, wherein Y in the general formula (I) is a halogen atom. 3. The anti-adhesion agent according to claim 1, wherein X and Y in the general formula (I) are chlorine atoms. 4. The anti-adhesion agent according to claim 1, wherein the marine adherent organism is Magnolia solium.