JPH05331007A - Attachment inhibitor for marine attaching organism - Google Patents

Abstract

PURPOSE:To obtain an effective attachment inhibitor for marine attaching organisms, comprising a specific alpha-chlorobenzaldoxime-based compound, having low toxicity to humans, animals, fishes and shellfishes and hardly causing environmental pollution. CONSTITUTION:The attachment inhibitor for marine attaching organisms comprises an alpha-chlorobenzaldoxime-based compound expressed by the formula (R<1> is H or lower acyl; R<2> is H, halogen or nitro) (preferably a- chlorobenzaldoxime or alpha-chloro-O-acetylbenzaldoxime) as an active ingredient. Hydroides norvegica Gunnerus is especially cited as the marine attaching organisms. This compound expressed by the formula is a compound mild to the environment without containing heavy metals and has excellent effects on prevention of the marine organisms from attaching. The compound expressed by the formula as an attachment inhibitor for seawater cooling systems and fishing nets and a coating for preventing attachment is capable of extremely efficiently preventing damages by the marine attaching organisms.

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 as components used for paints and fishing nets are a social problem due to their toxicity and accumulative properties, and cuprous oxide is also undesirable when used in oyster and scallop aquaculture areas. Cause a phenomenon. Furthermore, the α-chlorobenzaldoxime derivative is used as a bactericide against bacteria that cause slime in pulp and paper (Japanese Patent Publication No. 51-33171), but bacteria and marine attached organisms have a life function. It is markedly different, and the effect of this compound on marine periphyton, especially magnolia lanceolata, is completely unknown.

[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]

According to the present invention, the general formula (I):

[0008]

[Chemical 2]

(Wherein R ¹ represents a hydrogen atom or a lower acyl group and R ² represents a hydrogen atom, a halogen atom or a nitro group) and contains one or more α-chlorobenzaldoxime compounds. An agent for preventing adhesion of marine adherent organisms is provided. It was found that the compound (I) used in the present invention is an environment-friendly compound that does not contain heavy metals and has an excellent effect of preventing adhesion of marine organisms.

In the above general formula (I), the lower acyl group represented by R ¹ is a C _1-4 acyl group, for example,
Formyl, acetyl, propionyl, butyryl and the like can be mentioned, with an acetyl group being particularly preferred. Examples of the halogen atom represented by R ² in the above general formula (I) include chlorine, bromine, iodine and fluorine, with a chlorine atom being particularly preferred.

Specific examples of the compound of the above general formula (I) used in the present invention include α-chlorobenzaldoxime, α-chloro-O-acetylbenzaldoxime and α.
-Chloro-para-chlorobenzaldoxime, α-chloro-O-acetylbenzaldoxime, α-chloro-ortho-chlorobenzaldoxime, α-chloro-O-acetylbenzaldoxime, α-chloro-para-bromobenz Aldoxime, α-chloro-para-bromo-O-
Acetylbenzaldoxime, α-chloro-para-fluoro-benzaldoxime, α-chloro-para-fluoro-
Examples thereof include O-pronionylbenzaldoxime, and α-chloro-O-acetylbenzaldoxime is particularly preferable. Further, these compounds can be used in combination within the above group.

The compound represented by the above general formula (I) used in the present invention can be synthesized as follows. By reacting benzaldehydes with hydroxylamine hydrochloride under an alkali to obtain benzaldoximes, and contacting these with halogen, α-halogenated benzaldoximes can be obtained. The obtained α-halogenated benzaldoxime is acylated by a conventional method to obtain α-halogenated-O-acetylbenzaldoxime.

When the compound of the present invention is added to a seawater cooling system, the amount added is generally 0.00 based on the seawater flow rate.
It is sufficient to inject 1 ppm or more for 1 to 24 hours per day. The amount added may vary depending on the conditions of the sea area or the amount of attached organisms, but if the amount of attached organisms, especially magnolia lanceolata is large, an addition amount of 0.01 ppm or more is desirable. The upper limit of the amount added is not particularly limited, but 0.5 ppm or less is preferable in consideration of economic aspects.

When the compound of the present invention is added to the seawater cooling system, a solvent (water or ethanol, acetone, xylene, dimethylformamide, methylcellosolve) suitable for uniformly dispersing the compound (I) of the present invention in seawater. It is preferable to use it as a preparation having an appropriate concentration by dissolving it in an organic solvent (eg, etc.) or adding a surfactant as necessary and emulsifying and suspending it. As the surfactant at that time, higher fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene-polyoxypropylene copolymers, alkyltrimethylammonium salts, alkylbetaines And the like.

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 blended with the compound (I) of the present invention, and a formulation is used by operations such as dissolution, dispersion and kneading. Examples of natural resins and synthetic resins used in the above formulation include rosin, boil oil, chlorinated rubber, polybutene, vinyl chloride resin, acrylic resin, epoxy resin, and the like, with acrylic resin being particularly preferred. 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, white titanium, yellow lead, dark blue, red iron oxide, phthalocyanine blue and the like. When this invention compound (I) is used as an anti-adhesion agent for fishing nets, this invention compound (I): 5 to 3
0% by weight, resin content: 5 to 30% by weight, plasticizer: 0 to 15
From the viewpoint of film-forming property, film-forming strength, etc., it is preferable to make a liquid preparation type in which 1% by weight or the like is dissolved or dispersed in an organic solvent and the total solid content concentration is 15 to 60% by weight. I): 10 to 25% by weight, resin content: 10 to 20% by weight, plasticizer: 3 to 10% by weight, and more preferably a liquid preparation having a total solid content concentration of 20 to 50% by weight.

The above-mentioned preparation is applied to a fishing net by a usual method, that is, a dipping method or the like. When this invention compound (I) is applied to a seawater structure, this invention compound (I): 5 to 30% by weight, resin content: 5 to 30% by weight, plasticizer: 0 to 15% by weight, pigment content: 10 to 35% by weight is kneaded with an organic solvent to prepare a formulation to obtain a coating composition, preferably the invention compound (I): 10 to 25% by weight, plasticizer: 1
A formulation comprising 0 to 20% by weight and a pigment content of 15 to 30% by weight 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-isothiazolin-3-one, thiocyanomethylthiobenzothiazole, tetrachloroisophthalonitrile and the like, which may be used in combination as appropriate. it can.

[0020]

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 organism of Hawthorn sol. Was collected, a living tube was removed, a soft body part was taken out, and the soft body part was left 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 liters of filtered seawater containing a test solution so as to have a predetermined concentration was put in 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 put into one of the NXX-25. The mulle gauze of the above was put in the equipment, and then 10 trochophore larvae of Kahane hawthorn were put in each. After leaving it in a thermostat at 22 ± 1 ℃ for 6 hours, replace it with filtered seawater, and put it in the thermostat for 2 hours.
After rearing for 4 hours, count the number of swimming larvae under a microscope,
The efficacy of each drug was determined. When the number of swimming individuals is 0, it means that all of them have been killed. The results are shown in Table 1.

The test solution was prepared by preparing 5 parts of the compound, 90 parts of dimethylformamide and 5 parts of polyoxyethylene sorbitan monooleate (HLB15) and diluting them with filtered seawater to prepare a test solution.

[0023]

[Table 1]

Test Example 2 Seawater was pumped up from a seawater headrace of a steel mill, which has many troubles due to mussels, barnacles, maggots, etc., into 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 the water for 40 days transiently (water flow rate of 3 tons / hour each) during the period of adhesion of the magnolia japonicus, and each mixed drug was injected with a chemical pump, At that time, the number of Hawthorn squirrels and other attached organisms attached was counted. The results are shown in Table 2.

The chemicals were prepared by dissolving each compound in dimethylformamide and adding polyoxyethylene sorbitan monooleate (HLB15) to form an emulsion.

[0026]

[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 antifouling agent to the net and air-dried for 3 days. Then, during the three months from May to July, it is hung at a depth of 1.0 to 1.5 m below the sea level from the raft in the Isaura Bay, Mie Prefecture, to prevent adhesion to Kasane lanceolata and other attached organisms.
Observed after a month. 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 composition ratio (%) of attached organisms.

[0028]

[Table 3]

[0029]

[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.

[0031]

[Table 5]

[0032]

[Table 6]

[0033]

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, R ¹ represents a hydrogen atom or a lower acyl group, and R ² represents a hydrogen atom, a halogen atom or a nitro group.) Marine adhesion of one or more α-chlorobenzaldoxime compounds Anti-biological agent. 2. The anti-adhesion agent according to claim 1, wherein the compound (I) is α-chlorobenzaldoxime. 3. The anti-adhesion agent according to claim 1, wherein the compound (I) is α-chloro-O-acetylbenzaldoxime. 4. The anti-adhesion agent according to claim 1, wherein the marine adherent organism is Magnolia solium.