JPH0881308A - Biojelly forming agent - Google Patents

Abstract

PURPOSE: To obtain a new biojelly forming agent free from disadvantageous effect against a useful aquatic life, free from danger of the accumulation of harmful materials in fishes and shellfishes and useful for preventing the adherence of an aquatic fouling life. CONSTITUTION: This biojelly forming agent contains a benzylideneaniline derivative of the formula (X is H, a halogen, OH, or NO2 ; Y is H, Cl or a methyl; Z is H or OH; at least two of X, Y and Z are H at the same time), e.g. benzylidene-4-chloroaniline. A structure is treated e.g. by being coated with a coating material containing the compound, impregnating the compound or being mixed and kneaded with the compound. The treated structure is immersed into water to form a slime layer on its surface. This slime layer prevents the adherence of an aquatic fouling life. A formed slime layer having a jelly-like thickness of >=0.3mm, especially about 1-5mm is effective for preventing the adherence of a large aquatic fouling life such as barnacle, sea lettuce, oyster, serpula and hard-shelled mussel.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing aquatic fouling organisms from adhering to the surface of ships, bridges and the like. In the present specification, aquatic fouling organisms are attached organisms that attach to artificial structures in water and cause industrial and economic disadvantages, and are large attached organisms that grow to a size that can be visually observed by individuals. , For example, barnacles, mussels, oysters, hydroids, bryozoans, ascidians, serplas and other animals, sea lions,
It refers to plants such as Shio Midoro.

[0002]

BACKGROUND ART When aquatic organisms such as barnacles, serpra, squirts, bryozoans, oysters, and oysters adhere to the bottom of ships, problems such as increased weight, increased water flow resistance, and reduced cruising speed will occur, resulting in reduced ship life. It causes industrial problems such as increased fuel consumption. Methods for preventing adhesion of these aquatic organisms have been studied for a long time, and biological methods using natural enemies of organisms causing adhesion, use of structural materials that are difficult to attach (e.g. use of copper alloys, silicone-based materials) Paint, fluorine-based paint, etc., prevention of larva influx (for example, by shielding with a screen), extermination of larvae (for example, use of light, ultraviolet rays, colors, ultrasonic waves, temperature rise, oxygen deficiency, etc. Environment), mechanical removal of attached organisms (e.g. cleaning, jet cleaning, brushing, suction, etc.), chemical or biochemical methods (e.g. shellfish killing, repelling, use of antifouling agents, etc.), etc. ing. Recently, because of its wide application range, high effect, and easy processing, the method of applying ship bottom paints containing shellfish killers, repellents, antifouling agents, etc. has been widely adopted and studied. Came. However, paints containing these chemicals are designed so that the drug in the coating film gradually elutes into the water, or the paint containing this is gradually scraped and dissipated into the water, and new paint surfaces are always exposed. Therefore, it has been pointed out that there is a concern that it will have an adverse effect on the marine environment. In particular, when it was pointed out that the tin compounds, which are the most representative antifouling agents in the 1980s, were contaminated by fish and shellfish, various regulations were added to tin-containing ship bottom paints in European countries and the United States, and they replaced the aquatic organisms. The development of a method for preventing biological pollution has emerged as an urgent issue. However, at present, no promising alternative to antifouling ship bottom paints containing antifouling agents has been developed. The focus of the research is on the development of low toxicity antifouling agents that replace tin compounds.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antifouling agent which prevents the adhesion of aquatic fouling organisms without using an antifouling agent.

[0004]

The present invention relates to an aquatic fouling organism adhesion preventive agent, which comprises forming a biojelly layer on the surface of a structure in water.

In the present invention, the structure means a ship bottom, a fishing net, a water conduit, a bridge and the like.

[0006] The slime layer is a slimy thin film layer formed mainly by metabolites of organisms in water.
Conventionally, thin slime layers have been studied as a type of contaminants on the bottom of ships. Therefore, there was no idea to use this actively to prevent the attachment of large-scale aquatic fouling organisms that substantially affect the life and operation of ships such as barnacles, sea lions, oysters, cellulas and mussels. When the inhibitor of the present invention is used, this slime layer is positively formed on the surface of the underwater structure, whereby adhesion of large aquatic fouling organisms can be prevented, and in such a method, No method for preventing adhesion has been known so far. The slime layer used for such a purpose has a jelly-like thickness of 0.3 mm or more, more preferably 0.5 mm to 6 mm.
mm, especially about 1 to 5 mm is suitable. Therefore, in the present invention, a slime layer having a thickness of about 0.3 mm or more is particularly called bio jelly. In the present invention, the thickness of the slime layer was determined by measuring the film thickness after allowing the test plate to be flat and leaving it at room temperature for 1 hour. As mentioned above, this slime layer or biojelly layer is a metabolite of mainly aquatic organisms, especially microorganisms, but it is a layer in which organisms such as bacteria and diatoms can live, and those organisms are actually observed. .
Chemically, it contains various sugars, polysaccharides, lipids, glycoproteins, phospholipids and the like. A jelly-like slime layer having a thickness of 0.3 mm or more is particularly useful for preventing the attachment of large aquatic fouling organisms.

The slime layer can be positively formed on the underwater structure by applying a paint containing a certain compound. Examples of such slime layer-forming substances include various benzylideneaniline derivatives. When these compounds are used, it is possible to easily form a thick slime layer, that is, biojelly, on the surface of a structure in water. Therefore, in the present specification, a compound having such properties is particularly referred to as a biojelly forming agent. To tell.

An example of a biojelly forming agent useful in the present invention is a benzylidene aniline derivative of the general formula: General formula:

Embedded image [Wherein, X represents a hydrogen atom, a halogen atom, a hydroxyl group or a nitro group; Y represents a hydrogen atom, a chlorine atom or a methyl group; and Z represents a hydrogen atom or a hydroxyl group (provided that at least two of X, Y and Z are Simultaneously represents a hydrogen atom)].

Particularly preferred biojelly forming agents are benzylideneaniline, benzylidene-4-chloroaniline, benzylidene-4-bromoaniline, benzylidene-4-nitroaniline, benzylidene-4-hydroxyaniline, 4'-methylbenzylideneaniline, 4'-methylbenzylideneaniline, and 4'-methylbenzylideneaniline. Examples include'-chlorobenzylideneaniline and 2'-hydroxybenzylideneaniline.

In the present invention, the biojelly-forming agent is blended in a suitable coating composition and dipped in water to coat the surface of the structure to be used. It can be used as a paint for fishing nets by dissolving or dispersing it in an appropriate solvent and adding a polymer if necessary.

The slime layer, particularly the biojelly layer is formed by immersing the structure, which has been treated by coating, impregnating, or kneading a coating containing a biojelly-forming agent, in water. Just do it. Less than,
The present invention will be described with reference to examples.

Examples 1 to 8 A butyral resin (20 g), xylene (25 g), n-butanol (5 g) and a biojelly forming agent (15 g) shown in Table 1 were uniformly mixed to prepare a biojelly forming paint. This paint was applied and dried on a commercially available acrylic plate (300 mm x 100 mm x 2 mm) to a dry coating film thickness of about 200 µm, and this was dipped in the sea at a water temperature of about 12 to 18 ° C to form a biojelly layer. The thickness and the adhered state of fouling organisms were observed over time. The results are shown in Table 1.

Comparative Example 1 In the same manner as in Example 1 except that a tin-based antifouling agent (TBTO) was used in place of the biojelly forming agent, the biojelly layer forming property and the adhered state of fouling organisms were observed with time. . The results are also shown in Table 1.

Comparative Example 2 Instead of the biojelly forming agent, a copper-based antifouling agent (cuprous oxide) 15
In the same manner as in Example 1 except that g and rosin (5 g) were used, the formability of the biojelly layer and the adhered state of fouling organisms were observed over time. The results are shown in Table 1.

Comparative Example 3 20 g of butyral resin, 15 g of xylene and 5 g of n-butanol were mixed, and this was mixed with a commercially available acrylic plate (300 mm × 100 mm).
X 2 mm) to a dry coating film thickness of 200 μm and dried, and then immersed in seawater at a water temperature of about 12 to 18 ° C. to determine the thickness of the formed biojelly layer and the adhered state of fouling organisms over time. I observed. The results are shown in Table 1.

Comparative Example 4 20 g of butyral resin was uniformly dissolved in 40 g of xylene,
Dry coating thickness of about 2 on an acrylic plate with the same dimensions as in Comparative Example 1.
It is coated and dried so that it becomes 00 μm, and the water temperature is about 12 to 1
The thickness of the formed bio-jelly layer and the adhered state of fouling organisms were observed with time by immersing in the sea at 8 ° C. The results are shown in Table 1.

Comparative Example 5 An acrylic plate having the same dimensions as in Comparative Example 1 was used as it was at a water temperature of about 12
The thickness of the formed bio-jelly layer and the adhered state of fouling organisms were observed with time by immersing in the sea at -18 ° C. The results are shown in Table 1.

[0018]

[Table 1]

Examples 9 to 16 (antibacterial test) (1) Preparation of medium: 2% aqueous solution of a detection disk medium (manufactured by Kyokuto Co., Ltd.) was sterilized at 120 ° C. for 30 minutes, and 5 parts by weight of Bacillus seeds were used. ( Bacillus sp ), Vibrio spp. ( V
ibrio sp ) and 1 part by weight of mixed culture broth medium of Salmonella sp. ( Salmonella sp ) were added and poured into a sterile petri dish to prepare an agar flat medium. (2) Preparation of paper disk: The biojelly forming agent used in Example 1 as a test substance was dissolved in acetone. Toyo filter paper No. 7 with a diameter of 7 mm A 53-made disc was immersed in this solution, impregnated with 25 mg of the test substance, and dried to prepare a test substance-impregnated paper disc. (3) Place the paper disk of (2) on the agar flat medium of (1), incubate at 30 ° C for 5 days, and measure the diameter of the part (inhibition circle) where growth of bacteria is not observed, evaluated.
Table 2 shows the results.

Comparative Example 6 The antibacterial property was evaluated in the same manner as in Example 9 except that the biojelly forming agent was not added. Table 2 shows the results.

Comparative Example 7 The antibacterial property was evaluated in the same manner as in Example 9 except that an antifouling agent (bistributyltin oxide (TBTO)) was used instead of the biojelly forming agent. Table 2 shows the results.

Comparative Example 8 The antibacterial property was evaluated in the same manner as in Example 9 except that a copper-based antifouling agent (cuprous oxide) was used as the test substance. Table 2 shows the results.

[0023]

[Table 2]

[0024]

By intentionally forming a bio-jelly layer on an underwater structure, adhesion of aquatic fouling organisms such as barnacles, cellulas, oysters and ascidians can be effectively prevented.

[Chemical 3] When the benzylideneaniline compound represented by the formula (wherein X, Y and Z have the same meanings as described above) is used, the biojelly layer can be formed thick and quickly. By thickening the slime layer, the attachment of large-scale aquatic fouling organisms can be performed even more effectively.

Claims (1)

[Claims] 1. A general formula: [Wherein, X represents a hydrogen atom, a halogen atom, a hydroxyl group or a nitro group; Y represents a hydrogen atom, a chlorine atom or a methyl group; and Z represents a hydrogen atom or a hydroxyl group (provided that at least two of X, Y and Z are Represents a hydrogen atom at the same time)].